Stoichiometric and polymorphic salts of hexa-methyl-ene-tetra-minium and 2-chloro-4-nitro-benzoate.

Four mol-ecular salts made from hexa-methyl-ene-tetra-minium and 2-chloro-4-nitro-benzoate have been synthesized and are reported, namely ammonium hexa-methyl-ene-tetra-minium bis-(2-chloro-4-nitro-benzoate), NH4+·C6H13N4+·2C7H3ClNO4-, (I), hexa-methyl-ene-tetra-minium hydrogen bis-(2-chloro-4-nitro-benzoate), 0.5C6H13N4+·C7H3.50ClNO4-, (II), hexa-methyl-ene-tetra-minium 2-chloro-4-nitro-benzoate, C6H13N4+·C7H3ClNO4-, (IIIa) and (IIIb). All four mol-ecular salts show N+-H⋯O- hydrogen bonding. Salt (I) crystallized out with an NH4+ counter-ion which came from decomposition of 50% of the hexa-methyl-ene-tetra-minium cation in solution. (II) shows an unusual asymmetric unit, with both a hexa-methyl-ene-tetra-minium cation and a partially deproton-ated 2-chloro-4-nitro-benzoate anion. Salts (IIIa) and (IIIb) are polymorphs of each other. This work shows that hexamethylenetetramine only protonates once, even in the presence of excess acid.

Chemical context

Crystal engineering, the conception and synthesis of mol­ecular solid-state structures, is fundamentally based upon the discernment and subsequent exploitation of inter­molecular inter­actions (Desiraju, 1989 ▸) Thus, primarily non-covalent bonding is used to achieve the organization of mol­ecules and ions in the solid state in order to produce materials with desired properties. One mol­ecule that has been used that has multiple acceptor sites is hexa­methyl­ene­tetra­mine (hmta), and it has been shown to act as a hydrogen-bond acceptor for alcohol or carb­oxy­lic acid donors (Lemmerer, 2011 ▸). Inter­estingly, hmta has four equivalent N atoms but there are very few reported co-crystals or salts that use all four. Examples that use all four N atoms in neutral hydrogen bonding are seen with alcohols (MacLean et al., 1999 ▸), whereas the vast majority of mol­ecular complexes with hmta show it acting as a twofold acceptor (Li et al., 2001 ▸). However, if protonation does occur, then it is usually confined to only one site being protonated (Lemmerer et al., 2012 ▸). 2-Chloro-4-nitro­benzoic (2c4nH) acid has been used extensively in making co-crystals and salts using pyridine as an acceptor (Lemmerer et al., 2010 ▸, 2015 ▸) and has been chosen to be the hydrogen-bond donor/acid. The experimental pK a of hmta is 4.89 (Cooney et al., 1986 ▸), and the calculated pK a of 2c4nH is 2.04 (Lemmerer et al., 2015 ▸). Childs et al. (2007 ▸) postulated that for 0 < ΔpK a < 3, either a neutral co-crystal or salt can form, and that the crystalline environment can influence which one is favoured. In general, however, for ΔpK a values > 3 and < 0, a salt or co-crystal, respectively, is formed (Lemmerer et al., 2015 ▸). Hence, it is postulated that proton transfer will occur for a solution containing hmta and 2c4nH. In this work, we will make mol­ecular salts using a 1:1 or 1:2 ratio of hmta with 2c4nH to see if two N atoms sites can be protonated. The four salts synthesized and reported here are: (hmtaH+)·(NH4 +)(2c4nH−)2, (I), (hmtaH+)·(2c4nH−)2, (II) and (hmtaH+)·(2c4nH−), (IIIa) and (IIIb).

Structural commentary

The asymmetric units and atom-labelling schemes are shown in Fig. 1 ▸, together with their displacement ellipsoids for all four salts. A noteworthy asymmetric unit is the one for salts (I) and (II). In salt (I), there is the expected simple hmtaH+ cation and 2c4n− pair that are hydrogen bonded to each other using a charge-assisted N+—H⋯O− hydrogen bond (Table 1 ▸). However, an NH4 + ammonium cation is included in the asymmetric unit and its charge is balanced by a second 2c4n− anion. The NH4 + cation’s appearance is not unique as it has been reported in the literature that hmta can decompose to form NH4 and formaldehyde (Lough et al., 2000 ▸), especially if the crystallization takes place slowly and in the presence of an acid. From a crystallographic standpoint, the 2:1 mol­ecular salt (II) features half of an hmtaH+ cation crystallizing along a mirror plane at y = 1/4 and a fully occupied 2c4nH anion. In the difference-Fourier map, there is clear evidence that the N1 atom on a special position (0.485286 0.250000 0.494001) is protonated and hence has a half positive charge. However, the carb­oxy­lic acid group of 2c4nH has bond lengths typical of being neutral and clearly shows an acidic H atom, H2, located near O1 in the difference-Fourier map. Combined, this means that H1 acts as a bifurcated donor to two 2-chloro-4-nitro­benzoic mol­ecules (Table 2 ▸), which themselves share the hydrogen atom H2. Mol­ecular salts (IIIa) and (IIIb) both have a 1:1 ratio and are polymorphs of each other. Both have charge-assisted N+—H⋯O− hydrogen bonds (Tables 3 ▸ and 4 ▸) between the two ions but differ in their packing as described further below.

Figure 1

Perspective views of compounds (I)–(IIIb), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms with superscript (i) are at symmetry position (x, −y + , z). The dashed lines indicate the symmetry-independent N+—H⋯O− hydrogen bonds.

Table 1

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.94 (2)	1.71 (2)	2.6564 (18)	177 (2)
N1A—H1A⋯O2	0.94 (2)	1.89 (2)	2.817 (2)	168 (2)
N1A—H2A⋯O5	0.93 (2)	1.87 (2)	2.784 (2)	167 (2)
N1A—H3A⋯O5i	0.91 (2)	1.90 (2)	2.803 (2)	171 (2)
N1A—H4A⋯O6ii	1.02 (2)	1.73 (2)	2.747 (2)	173 (2)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.92 (3)	2.12 (2)	2.7667 (15)	126 (1)

Table 3

Hydrogen-bond geometry (Å, °) for (IIIa)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	1.00 (3)	1.60 (3)	2.599 (2)	173 (3)

Table 4

Hydrogen-bond geometry (Å, °) for (IIIb)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.90 (2)	1.80 (2)	2.6911 (17)	175.7 (19)

Supra­molecular features

The packing of salt (I) consists of clearly separated layers of hydro­phobic and hydro­phillic layers. All good hydrogen-bond donors are used (Table1, Fig. 2 ▸ a). The NH4 + cation forms a hydrogen-bonded ring using two carboxyl­ate groups and this ring repeats along the b-axis direction. The ring can be described as (8) and is a common feature in ammonium carboxyl­ate salts (Lemmerer & Fernandes, 2012 ▸). This ladder is then surrounded by a 2c4n− anion that hydrogen bonds to the hmta+ cation. Overall, the hydro­philic layer consists of the cationic NH part of hmtaH+, NH4 + and the carboxyl­ate CO2 − part of 2c4n− (Fig. 3 ▸ a). Salt (II) consists only of the hmtaH+ and 2c4n− anion in a 1:2 ratio. However, it appears crystallographically that only one complete proton transfer has taken place, and that on average, each of the 2c4n anions has released half a proton each to the N atom (labelled H1) and that the other half proton (labelled as H2) is located in between the two anions. Hence, only one N atom on hmta has been protonated, and subsequently, two 2c4n− anions are behaving as acceptors from a single N—H group (Fig. 1 ▸). Overall, the same layering of hydro­philic and hydro­phobic parts occurs, where the cationic and anionic parts are located in the same ac plane. Salts (IIIa) and (IIIb) have identical asymmetric units with a 2:1 ratio of hmtaH+ and 2c4n−, in contrast to the previous two salts. The only significant difference is in the relative packing of these ion pairs. In (IIIa), the pairs pack anti-parallel (Fig. 3 ▸ c), and in (IIIb), parallel (Fig. 3 ▸ d).

Figure 2

(a) Detailed view of the five hydrogen bonds formed by the cations and anions in (I). (b) The hydrogen-bonded ladder formed between the NH4 + cation and carboxyl­ate anion forming a repeating (8) motif. Hydrogen bonds are shown as dashed red lines.

Figure 3

The packing diagrams for all four salts. Note the different packing arrangement of the two 1:1 dimorphs (IIIa) and (IIIb).

Database survey

Up to now, there are only 36 structures of singly protonated hmtaH+ mol­ecular salts in the Cambridge Structural Database (CSD, Version 5.38; Groom et al., 2016 ▸), together with any organic or inorganic counter-anion. Only one structure has the hmta doubly protonated (FOQZIW; Zaręba et al., 2014 ▸). Co-crystals of hmta in a 1:1 or 1:2 ratio with carb­oxy­lic acids are much more numerous (45). Ultimately, it has been shown that even with an excess of 2c4n, the hmta mol­ecule only allows itself to be protonated once.

Synthesis and crystallization

All chemicals were purchased from commercial sources (Sigma Aldrich) and used as received without further purification. Crystals were grown via the slow evaporation method, under ambient conditions, of alcoholic solutions. For (I) and (II), these crystals crystallized out concomitantly from a 1:2 ratio, and (IIIa) and (IIIb), concomitantly from a 1:1 molar ratio. The morphology of the yellow-tinted crystals are shown in Fig. 4 ▸. Detailed masses and volumes are as follows. For (I) and (II): hexa­methyl­ene­tetra­mine (0.050 g, 0.375 mmol) and 2-chloro-4-nitro­benzoic acid acid (0.072 g, 0.375 mmol) in methanol (5 mL); for (IIIa) and (IIIb): hexa­methyl­ene­tetra­mine (0.050 g, 0.375 mmol) and 2-chloro-4-nitro­benzoic acid acid (0.144 g, 0.750 mmol) in ethanol (5 mL).

Figure 4

The morphologies of the four title salts: (I) block, (II) plate, (IIIa) thick needles and (IIIb) prism.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. For all compounds, the C-bound H atoms were placed geometrically (C—H bond lengths of 0.99 (ethyl­ene CH2), and 0.95 (Ar—H) Å) and refined as riding with U iso(H) = 1.2U eq(C). The N–bound H atoms were located in difference-Fourier maps and their coordinates and isotropic displacement parameters allowed to refine freely. The O–bound H atom in (II) was located in the difference-Fourier map and refined as riding with U iso(H) = 1.5U eq(O).

Table 5

Experimental details

	(I)	(II)	(IIIa)	(IIIb)
Crystal data
Chemical formula	H4N+·C6H13N4 +·2C7H3ClNO4 −	0.5C6H13N4 +·C7H3.50ClNO4 −	C6H13N4 +·C7H3ClNO4 −	C6H13N4 +·C7H3ClNO4 −
M r	560.35	543.32	341.76	341.76
Crystal system, space group	Monoclinic, C2/c	Orthorhombic, P n m a	Monoclinic, C c	Monoclinic, P21/c
Temperature (K)	173	173	173	173
a, b, c (Å)	33.6032 (8), 6.0235 (1), 28.0229 (7)	8.2777 (2), 19.7942 (5), 13.5331 (4)	5.9049 (1), 21.9330 (4), 12.0194 (2)	12.0663 (2), 19.5741 (4), 6.6473 (1)
α, β, γ (°)	90, 121.007 (1), 90	90, 90, 90	90, 103.445 (1), 90	90, 105.820 (1), 90
V (Å3)	4861.56 (19)	2217.40 (10)	1514.00 (5)	1510.54 (5)
Z	8	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.33	0.36	0.28	0.28
Crystal size (mm)	0.36 × 0.19 × 0.05	0.49 × 0.22 × 0.17	0.43 × 0.36 × 0.16	0.34 × 0.34 × 0.09
Data collection
Diffractometer	Bruker D8 Venture Photon CCD area detector	Bruker D8 Venture Photon CCD area detector	Bruker D8 Venture Photon CCD area detector	Bruker D8 Venture Photon CCD area detector
Absorption correction	Integration (XPREP; Bruker, 2016 ▸)	Integration (XPREP; Bruker, 2016 ▸)	Integration (XPREP; Bruker, 2016 ▸)	Integration (XPREP; Bruker, 2016 ▸)
T min, T max	0.927, 0.986	0.887, 0.954	0.914, 0.978	0.921, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	16830, 5858, 4131	20018, 2749, 2269	19814, 3644, 3487	26282, 3650, 3027
R int	0.047	0.037	0.047	0.052
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.039, 0.093, 0.95	0.031, 0.084, 1.06	0.026, 0.066, 1.07	0.039, 0.109, 1.05
No. of reflections	5858	2749	3644	3650
No. of parameters	354	173	212	212
No. of restraints	0	0	2	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.29, −0.34	0.27, −0.23	0.15, −0.16	0.55, −0.32
Absolute structure	–	–	Flack x determined using 1663 quotients [(I +)-(I -)]/[(I +)+(I -)] (Parsons et al., 2013 ▸)	–
Absolute structure parameter	–	–	−0.010 (19)	–

Computer programs: APEX3, SAINT-Plus and XPREP (Bruker 2016 ▸), SHELXS97 (Sheldrick, 2015 ▸), SHELXL2017/1 (Sheldrick, 2015 ▸), ORTEPIII for Windows and WinGX publication routines (Farrugia, 2012 ▸) and DIAMOND (Brandenburg & Berndt, 1999 ▸).

Crystal structure: contains datablock(s) I, II, IIIa, IIIb, shelx. DOI: 10.1107/S2056989017014359/eb2001sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017014359/eb2001Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017014359/eb2001IIsup3.hkl

Structure factors: contains datablock(s) IIIa. DOI: 10.1107/S2056989017014359/eb2001IIIasup4.hkl

Structure factors: contains datablock(s) IIIb. DOI: 10.1107/S2056989017014359/eb2001IIIbsup5.hkl

CCDC references: 1578099, 1578098, 1578097, 1578096

Additional supporting information: crystallographic information; 3D view; checkCIF report

H4N+·C6H13N4+·2C7H3ClNO4−	F(000) = 2320
Mr = 560.35	Dx = 1.531 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4303 reflections
a = 33.6032 (8) Å	θ = 2.4–26.5°
b = 6.0235 (1) Å	µ = 0.33 mm−1
c = 28.0229 (7) Å	T = 173 K
β = 121.007 (1)°	Plate, yellow
V = 4861.56 (19) Å3	0.36 × 0.19 × 0.05 mm
Z = 8

Bruker D8 Venture Photon CCD area detector diffractometer	4131 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 28.0°, θmin = 1.4°
Absorption correction: integration (XPREP; Bruker, 2016)	h = −44→42
Tmin = 0.927, Tmax = 0.986	k = −7→7
16830 measured reflections	l = −34→37
5858 independent reflections

Refinement on F2	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95	(Δ/σ)max < 0.001
5858 reflections	Δρmax = 0.29 e Å−3
354 parameters	Δρmin = −0.34 e Å−3
0 restraints

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2007)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	0.12646 (7)	0.8962 (3)	0.25907 (8)	0.0436 (5)
H1B	0.124511	0.734282	0.263614	0.052*
H1C	0.15024	0.92274	0.248896	0.052*
C2	0.14211 (6)	1.2486 (3)	0.30330 (8)	0.0376 (4)
H2B	0.152064	1.326005	0.338888	0.045*
H2C	0.165633	1.27754	0.292835	0.045*
C3	0.08364 (7)	1.2276 (3)	0.20814 (7)	0.0322 (4)
H3B	0.106877	1.25849	0.197318	0.039*
H3C	0.053299	1.285973	0.178539	0.039*
C4	0.06273 (6)	1.2897 (3)	0.27554 (7)	0.0340 (4)
H4B	0.032214	1.348363	0.246406	0.041*
H4C	0.071612	1.367283	0.310805	0.041*
C5	0.10396 (8)	0.9702 (4)	0.32528 (8)	0.0538 (6)
H5A	0.101801	0.808914	0.330395	0.065*
H5B	0.113292	1.044666	0.361035	0.065*
C6	0.04479 (7)	0.9401 (3)	0.23067 (8)	0.0417 (5)
H6A	0.013988	0.994563	0.201219	0.05*
H6B	0.042317	0.778576	0.235157	0.05*
N1	0.08009 (5)	0.9820 (2)	0.21368 (6)	0.0298 (3)
N2	0.13960 (6)	1.0090 (3)	0.31095 (6)	0.0436 (4)
N3	0.09712 (5)	1.3374 (2)	0.26001 (6)	0.0293 (3)
N4	0.05840 (6)	1.0525 (3)	0.28254 (6)	0.0400 (4)
H1	0.0698 (7)	0.909 (3)	0.1795 (9)	0.055 (6)*
C7	0.06854 (5)	0.5904 (3)	0.05877 (6)	0.0239 (3)
C8	0.08353 (5)	0.3865 (3)	0.05022 (6)	0.0242 (3)
C9	0.07300 (5)	0.3194 (3)	−0.00250 (6)	0.0254 (4)
H9	0.082512	0.178213	−0.008152	0.03*
C10	0.04844 (5)	0.4631 (3)	−0.04620 (6)	0.0272 (4)
C11	0.03282 (6)	0.6669 (3)	−0.04007 (7)	0.0304 (4)
H11	0.015947	0.76348	−0.07092	0.037*
C12	0.04261 (5)	0.7252 (3)	0.01254 (7)	0.0283 (4)
H12	0.031212	0.86257	0.017342	0.034*
C13	0.08027 (6)	0.6776 (3)	0.11575 (7)	0.0263 (4)
N5	0.03893 (5)	0.3921 (3)	−0.10143 (6)	0.0344 (4)
O1	0.04796 (4)	0.7787 (2)	0.11648 (5)	0.0392 (3)
O2	0.12006 (4)	0.6506 (2)	0.15595 (5)	0.0360 (3)
O3	0.02132 (5)	0.5272 (3)	−0.13945 (5)	0.0491 (4)
O4	0.04925 (4)	0.2028 (2)	−0.10660 (5)	0.0442 (4)
Cl1	0.11490 (2)	0.19844 (7)	0.10370 (2)	0.03492 (12)
C14	0.22494 (5)	0.1024 (3)	0.09588 (6)	0.0241 (3)
C15	0.18721 (5)	0.0359 (3)	0.04462 (6)	0.0232 (3)
C16	0.17243 (6)	0.1593 (3)	−0.00290 (7)	0.0258 (4)
H16	0.146226	0.11506	−0.037342	0.031*
C17	0.19690 (6)	0.3500 (3)	0.00099 (6)	0.0268 (4)
C18	0.23531 (6)	0.4187 (3)	0.05009 (7)	0.0296 (4)
H18	0.252105	0.547679	0.051372	0.035*
C19	0.24862 (6)	0.2941 (3)	0.09738 (7)	0.0278 (4)
H19	0.274601	0.340546	0.131781	0.033*
C20	0.24019 (5)	−0.0227 (3)	0.14930 (7)	0.0279 (4)
N6	0.17928 (6)	0.4903 (3)	−0.04867 (6)	0.0377 (4)
O5	0.24220 (5)	0.0883 (2)	0.18852 (5)	0.0463 (4)
O6	0.24993 (4)	−0.22222 (19)	0.15110 (5)	0.0353 (3)
O7	0.20330 (6)	0.6416 (3)	−0.04802 (6)	0.0652 (5)
O8	0.14019 (5)	0.4528 (3)	−0.08803 (5)	0.0594 (4)
Cl2	0.15515 (2)	−0.19840 (7)	0.03935 (2)	0.03327 (12)
N1A	0.21195 (6)	0.5093 (3)	0.19658 (7)	0.0301 (3)
H1A	0.1800 (8)	0.543 (3)	0.1788 (8)	0.046 (6)*
H2A	0.2175 (7)	0.365 (4)	0.1897 (8)	0.045 (6)*
H4A	0.2269 (7)	0.617 (4)	0.1824 (8)	0.056 (6)*
H3A	0.2251 (7)	0.522 (3)	0.2341 (9)	0.046 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0376 (10)	0.0339 (10)	0.0426 (11)	0.0118 (9)	0.0088 (9)	−0.0071 (9)
C2	0.0293 (9)	0.0417 (11)	0.0359 (10)	−0.0049 (8)	0.0125 (8)	−0.0159 (8)
C3	0.0407 (10)	0.0352 (10)	0.0257 (8)	0.0047 (8)	0.0207 (8)	0.0023 (7)
C4	0.0335 (9)	0.0428 (11)	0.0288 (9)	0.0015 (8)	0.0183 (8)	−0.0080 (8)
C5	0.0782 (16)	0.0458 (13)	0.0310 (10)	−0.0021 (12)	0.0235 (11)	0.0110 (9)
C6	0.0423 (11)	0.0425 (11)	0.0428 (11)	−0.0186 (9)	0.0237 (9)	−0.0145 (9)
N1	0.0286 (7)	0.0305 (8)	0.0267 (7)	−0.0013 (6)	0.0117 (6)	−0.0103 (6)
N2	0.0404 (9)	0.0420 (10)	0.0291 (8)	0.0126 (8)	0.0040 (7)	−0.0011 (7)
N3	0.0364 (8)	0.0255 (7)	0.0299 (7)	−0.0010 (6)	0.0198 (7)	−0.0040 (6)
N4	0.0465 (9)	0.0495 (10)	0.0296 (8)	−0.0157 (8)	0.0237 (8)	−0.0066 (7)
C7	0.0206 (7)	0.0273 (9)	0.0279 (8)	−0.0059 (7)	0.0153 (7)	−0.0069 (7)
C8	0.0239 (8)	0.0257 (8)	0.0243 (8)	−0.0042 (7)	0.0135 (7)	−0.0017 (7)
C9	0.0245 (8)	0.0282 (9)	0.0266 (8)	−0.0042 (7)	0.0155 (7)	−0.0075 (7)
C10	0.0206 (8)	0.0387 (10)	0.0217 (8)	−0.0050 (7)	0.0106 (7)	−0.0063 (7)
C11	0.0234 (8)	0.0356 (10)	0.0270 (8)	−0.0008 (7)	0.0092 (7)	0.0013 (7)
C12	0.0228 (8)	0.0278 (9)	0.0334 (9)	−0.0001 (7)	0.0139 (7)	−0.0046 (7)
C13	0.0302 (9)	0.0237 (9)	0.0310 (9)	−0.0076 (7)	0.0201 (8)	−0.0086 (7)
N5	0.0237 (7)	0.0551 (10)	0.0224 (7)	−0.0012 (7)	0.0105 (6)	−0.0038 (7)
O1	0.0282 (6)	0.0513 (8)	0.0410 (7)	−0.0063 (6)	0.0198 (6)	−0.0237 (6)
O2	0.0354 (7)	0.0425 (7)	0.0260 (6)	0.0049 (6)	0.0129 (6)	−0.0074 (5)
O3	0.0473 (8)	0.0709 (10)	0.0260 (7)	0.0071 (7)	0.0166 (6)	0.0067 (7)
O4	0.0400 (8)	0.0593 (9)	0.0312 (7)	0.0072 (7)	0.0170 (6)	−0.0145 (6)
Cl1	0.0519 (3)	0.0274 (2)	0.0269 (2)	0.0028 (2)	0.0213 (2)	0.00014 (17)
C14	0.0230 (8)	0.0225 (8)	0.0256 (8)	0.0026 (7)	0.0117 (7)	−0.0020 (7)
C15	0.0234 (8)	0.0197 (8)	0.0294 (8)	−0.0030 (6)	0.0157 (7)	−0.0046 (7)
C16	0.0247 (8)	0.0294 (9)	0.0229 (8)	−0.0031 (7)	0.0119 (7)	−0.0062 (7)
C17	0.0310 (9)	0.0280 (9)	0.0232 (8)	−0.0024 (7)	0.0153 (7)	−0.0009 (7)
C18	0.0317 (9)	0.0272 (9)	0.0319 (9)	−0.0083 (7)	0.0179 (8)	−0.0023 (7)
C19	0.0230 (8)	0.0277 (9)	0.0254 (8)	−0.0040 (7)	0.0071 (7)	−0.0035 (7)
C20	0.0233 (8)	0.0273 (9)	0.0280 (9)	0.0004 (7)	0.0096 (7)	0.0024 (7)
N6	0.0480 (10)	0.0392 (9)	0.0260 (8)	−0.0087 (8)	0.0191 (7)	−0.0007 (7)
O5	0.0737 (10)	0.0317 (7)	0.0230 (6)	0.0127 (7)	0.0174 (7)	0.0018 (6)
O6	0.0391 (7)	0.0249 (6)	0.0444 (7)	0.0065 (5)	0.0233 (6)	0.0058 (6)
O7	0.0738 (11)	0.0669 (10)	0.0432 (8)	−0.0364 (9)	0.0217 (8)	0.0112 (8)
O8	0.0607 (10)	0.0618 (10)	0.0288 (7)	−0.0197 (8)	0.0039 (7)	0.0090 (7)
Cl2	0.0287 (2)	0.0269 (2)	0.0405 (2)	−0.00875 (17)	0.01514 (19)	−0.00310 (18)
N1A	0.0353 (9)	0.0268 (8)	0.0231 (8)	−0.0002 (7)	0.0114 (7)	−0.0008 (7)

C1—N2	1.452 (2)	C9—H9	0.95
C1—N1	1.507 (2)	C10—C11	1.380 (2)
C1—H1B	0.99	C10—N5	1.473 (2)
C1—H1C	0.99	C11—C12	1.380 (2)
C2—N3	1.467 (2)	C11—H11	0.95
C2—N2	1.468 (2)	C12—H12	0.95
C2—H2B	0.99	C13—O2	1.237 (2)
C2—H2C	0.99	C13—O1	1.254 (2)
C3—N3	1.441 (2)	N5—O4	1.222 (2)
C3—N1	1.498 (2)	N5—O3	1.2243 (19)
C3—H3B	0.99	C14—C19	1.391 (2)
C3—H3C	0.99	C14—C15	1.398 (2)
C4—N3	1.458 (2)	C14—C20	1.510 (2)
C4—N4	1.460 (2)	C15—C16	1.375 (2)
C4—H4B	0.99	C15—Cl2	1.7349 (16)
C4—H4C	0.99	C16—C17	1.384 (2)
C5—N4	1.461 (3)	C16—H16	0.95
C5—N2	1.465 (3)	C17—C18	1.379 (2)
C5—H5A	0.99	C17—N6	1.467 (2)
C5—H5B	0.99	C18—C19	1.382 (2)
C6—N4	1.448 (2)	C18—H18	0.95
C6—N1	1.510 (2)	C19—H19	0.95
C6—H6A	0.99	C20—O6	1.2399 (19)
C6—H6B	0.99	C20—O5	1.258 (2)
N1—H1	0.94 (2)	N6—O7	1.2113 (19)
C7—C12	1.391 (2)	N6—O8	1.2247 (19)
C7—C8	1.394 (2)	N1A—H1A	0.94 (2)
C7—C13	1.527 (2)	N1A—H2A	0.93 (2)
C8—C9	1.390 (2)	N1A—H4A	1.02 (2)
C8—Cl1	1.7357 (16)	N1A—H3A	0.91 (2)
C9—C10	1.374 (2)
N2—C1—N1	109.47 (14)	C8—C7—C13	124.12 (15)
N2—C1—H1B	109.8	C9—C8—C7	121.47 (15)
N1—C1—H1B	109.8	C9—C8—Cl1	115.88 (13)
N2—C1—H1C	109.8	C7—C8—Cl1	122.62 (12)
N1—C1—H1C	109.8	C10—C9—C8	118.11 (15)
H1B—C1—H1C	108.2	C10—C9—H9	120.9
N3—C2—N2	111.53 (14)	C8—C9—H9	120.9
N3—C2—H2B	109.3	C9—C10—C11	122.78 (15)
N2—C2—H2B	109.3	C9—C10—N5	117.32 (15)
N3—C2—H2C	109.3	C11—C10—N5	119.90 (15)
N2—C2—H2C	109.3	C12—C11—C10	117.57 (16)
H2B—C2—H2C	108	C12—C11—H11	121.2
N3—C3—N1	110.42 (14)	C10—C11—H11	121.2
N3—C3—H3B	109.6	C11—C12—C7	122.45 (16)
N1—C3—H3B	109.6	C11—C12—H12	118.8
N3—C3—H3C	109.6	C7—C12—H12	118.8
N1—C3—H3C	109.6	O2—C13—O1	125.97 (15)
H3B—C3—H3C	108.1	O2—C13—C7	118.86 (15)
N3—C4—N4	112.46 (14)	O1—C13—C7	115.12 (15)
N3—C4—H4B	109.1	O4—N5—O3	123.84 (15)
N4—C4—H4B	109.1	O4—N5—C10	118.31 (15)
N3—C4—H4C	109.1	O3—N5—C10	117.85 (16)
N4—C4—H4C	109.1	C19—C14—C15	118.09 (15)
H4B—C4—H4C	107.8	C19—C14—C20	119.18 (14)
N4—C5—N2	112.37 (15)	C15—C14—C20	122.72 (14)
N4—C5—H5A	109.1	C16—C15—C14	121.59 (15)
N2—C5—H5A	109.1	C16—C15—Cl2	117.30 (12)
N4—C5—H5B	109.1	C14—C15—Cl2	121.01 (13)
N2—C5—H5B	109.1	C15—C16—C17	117.97 (15)
H5A—C5—H5B	107.9	C15—C16—H16	121
N4—C6—N1	110.20 (14)	C17—C16—H16	121
N4—C6—H6A	109.6	C18—C17—C16	122.72 (15)
N1—C6—H6A	109.6	C18—C17—N6	119.13 (15)
N4—C6—H6B	109.6	C16—C17—N6	118.04 (14)
N1—C6—H6B	109.6	C17—C18—C19	117.93 (15)
H6A—C6—H6B	108.1	C17—C18—H18	121
C3—N1—C1	108.86 (14)	C19—C18—H18	121
C3—N1—C6	108.38 (14)	C18—C19—C14	121.64 (15)
C1—N1—C6	108.37 (15)	C18—C19—H19	119.2
C3—N1—H1	111.0 (13)	C14—C19—H19	119.2
C1—N1—H1	112.1 (13)	O6—C20—O5	125.82 (16)
C6—N1—H1	108.0 (13)	O6—C20—C14	118.14 (15)
C1—N2—C5	109.25 (17)	O5—C20—C14	116.04 (14)
C1—N2—C2	108.94 (16)	O7—N6—O8	123.31 (16)
C5—N2—C2	108.27 (16)	O7—N6—C17	118.61 (15)
C3—N3—C4	108.97 (14)	O8—N6—C17	118.03 (15)
C3—N3—C2	108.73 (14)	H1A—N1A—H2A	112.6 (17)
C4—N3—C2	108.61 (14)	H1A—N1A—H4A	108.4 (17)
C6—N4—C4	108.95 (14)	H2A—N1A—H4A	108.8 (17)
C6—N4—C5	108.66 (16)	H1A—N1A—H3A	109.6 (17)
C4—N4—C5	107.91 (15)	H2A—N1A—H3A	106.8 (17)
C12—C7—C8	117.56 (15)	H4A—N1A—H3A	110.7 (17)
C12—C7—C13	118.28 (14)
N3—C3—N1—C1	−58.93 (19)	N5—C10—C11—C12	179.91 (15)
N3—C3—N1—C6	58.74 (18)	C10—C11—C12—C7	2.2 (2)
N2—C1—N1—C3	58.6 (2)	C8—C7—C12—C11	−2.1 (2)
N2—C1—N1—C6	−59.1 (2)	C13—C7—C12—C11	175.80 (15)
N4—C6—N1—C3	−58.4 (2)	C12—C7—C13—O2	−136.62 (16)
N4—C6—N1—C1	59.64 (19)	C8—C7—C13—O2	41.1 (2)
N1—C1—N2—C5	58.9 (2)	C12—C7—C13—O1	41.0 (2)
N1—C1—N2—C2	−59.2 (2)	C8—C7—C13—O1	−141.29 (16)
N4—C5—N2—C1	−60.0 (2)	C9—C10—N5—O4	6.9 (2)
N4—C5—N2—C2	58.6 (2)	C11—C10—N5—O4	−173.10 (15)
N3—C2—N2—C1	60.8 (2)	C9—C10—N5—O3	−172.66 (15)
N3—C2—N2—C5	−57.87 (19)	C11—C10—N5—O3	7.3 (2)
N1—C3—N3—C4	−59.01 (18)	C19—C14—C15—C16	−2.5 (2)
N1—C3—N3—C2	59.21 (19)	C20—C14—C15—C16	176.37 (15)
N4—C4—N3—C3	59.83 (18)	C19—C14—C15—Cl2	−178.82 (12)
N4—C4—N3—C2	−58.46 (18)	C20—C14—C15—Cl2	0.0 (2)
N2—C2—N3—C3	−60.51 (19)	C14—C15—C16—C17	1.8 (2)
N2—C2—N3—C4	57.93 (19)	Cl2—C15—C16—C17	178.27 (12)
N1—C6—N4—C4	58.2 (2)	C15—C16—C17—C18	0.6 (3)
N1—C6—N4—C5	−59.1 (2)	C15—C16—C17—N6	−175.74 (15)
N3—C4—N4—C6	−59.57 (19)	C16—C17—C18—C19	−2.1 (3)
N3—C4—N4—C5	58.23 (19)	N6—C17—C18—C19	174.17 (16)
N2—C5—N4—C6	59.7 (2)	C17—C18—C19—C14	1.4 (3)
N2—C5—N4—C4	−58.3 (2)	C15—C14—C19—C18	0.8 (2)
C12—C7—C8—C9	−0.1 (2)	C20—C14—C19—C18	−178.03 (16)
C13—C7—C8—C9	−177.82 (15)	C19—C14—C20—O6	−124.75 (17)
C12—C7—C8—Cl1	−178.35 (12)	C15—C14—C20—O6	56.4 (2)
C13—C7—C8—Cl1	3.9 (2)	C19—C14—C20—O5	54.6 (2)
C7—C8—C9—C10	2.0 (2)	C15—C14—C20—O5	−124.17 (18)
Cl1—C8—C9—C10	−179.62 (12)	C18—C17—N6—O7	12.8 (3)
C8—C9—C10—C11	−1.9 (2)	C16—C17—N6—O7	−170.81 (17)
C8—C9—C10—N5	178.06 (14)	C18—C17—N6—O8	−164.69 (17)
C9—C10—C11—C12	−0.1 (2)	C16—C17—N6—O8	11.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.94 (2)	1.71 (2)	2.6564 (18)	177 (2)
N1A—H1A···O2	0.94 (2)	1.89 (2)	2.817 (2)	168 (2)
N1A—H2A···O5	0.93 (2)	1.87 (2)	2.784 (2)	167 (2)
N1A—H3A···O5i	0.91 (2)	1.90 (2)	2.803 (2)	171 (2)
N1A—H4A···O6ii	1.02 (2)	1.73 (2)	2.747 (2)	173 (2)

C6H13N4+·C14H7Cl2N2O8−	F(000) = 1120
Mr = 543.32	Dx = 1.627 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 7712 reflections
a = 8.2777 (2) Å	θ = 2.9–28.3°
b = 19.7942 (5) Å	µ = 0.36 mm−1
c = 13.5331 (4) Å	T = 173 K
V = 2217.40 (10) Å3	Block, yellow
Z = 4	0.49 × 0.22 × 0.17 mm

Bruker D8 Venture Photon CCD area detector diffractometer	2269 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 28.0°, θmin = 1.8°
Absorption correction: integration (XPREP; Bruker, 2016)	h = −9→10
Tmin = 0.887, Tmax = 0.954	k = −26→26
20018 measured reflections	l = −15→17
2749 independent reflections

Refinement on F2	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0459P)2 + 0.3817P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2749 reflections	Δρmax = 0.27 e Å−3
173 parameters	Δρmin = −0.23 e Å−3
0 restraints

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2016)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.5362 (2)	0.25	0.60139 (15)	0.0293 (4)
H1A	0.602402	0.209478	0.615413	0.035*	0.5
H1B	0.602403	0.290522	0.615413	0.035*	0.5
C2	0.29732 (18)	0.31010 (6)	0.64113 (11)	0.0316 (3)
H2A	0.201625	0.3107	0.684998	0.038*
H2B	0.361744	0.351156	0.655045	0.038*
C3	0.38433 (16)	0.31232 (7)	0.47447 (11)	0.0302 (3)
H3A	0.449124	0.353372	0.487692	0.036*
H3B	0.350359	0.313181	0.404342	0.036*
C4	0.1490 (2)	0.25	0.51788 (16)	0.0317 (4)
H4A	0.051092	0.249999	0.559915	0.038*
H4B	0.113777	0.25	0.447969	0.038*
N1	0.48529 (18)	0.25	0.49400 (12)	0.0266 (3)
N2	0.3952 (2)	0.25	0.66325 (12)	0.0298 (3)
N3	0.24353 (13)	0.31154 (5)	0.53769 (9)	0.0284 (2)
H1	0.575 (3)	0.25	0.4540 (19)	0.050 (7)*
C5	0.91417 (14)	0.41404 (6)	0.36290 (9)	0.0225 (2)
C6	0.84727 (14)	0.47610 (6)	0.38838 (9)	0.0224 (3)
C7	0.93805 (15)	0.53490 (6)	0.38801 (9)	0.0236 (3)
H7	0.890704	0.577243	0.403921	0.028*
C8	1.09962 (15)	0.52991 (6)	0.36376 (9)	0.0240 (3)
C9	1.17365 (15)	0.46922 (6)	0.34177 (9)	0.0259 (3)
H9	1.286207	0.46701	0.328452	0.031*
C10	1.07902 (15)	0.41200 (6)	0.33976 (9)	0.0254 (3)
H10	1.126815	0.370043	0.322226	0.03*
C11	0.82257 (15)	0.34800 (6)	0.36070 (10)	0.0263 (3)
N4	1.19475 (14)	0.59237 (5)	0.35791 (8)	0.0290 (2)
O1	0.85862 (14)	0.31125 (5)	0.28588 (7)	0.0377 (3)
H2	0.83408	0.270874	0.297686	0.057*	0.5
O2	0.72967 (12)	0.33353 (5)	0.42674 (8)	0.0413 (3)
O3	1.33995 (11)	0.58735 (5)	0.34060 (9)	0.0404 (3)
O4	1.12464 (12)	0.64612 (5)	0.36731 (9)	0.0407 (3)
Cl1	0.64344 (4)	0.48455 (2)	0.41656 (3)	0.03169 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0282 (9)	0.0237 (8)	0.0360 (10)	0	−0.0040 (8)	0
C2	0.0363 (7)	0.0243 (6)	0.0343 (7)	0.0015 (5)	0.0073 (6)	−0.0047 (5)
C3	0.0284 (7)	0.0277 (6)	0.0344 (7)	0.0016 (5)	0.0039 (5)	0.0090 (5)
C4	0.0231 (9)	0.0317 (9)	0.0404 (11)	0	0.0011 (8)	0
N1	0.0220 (7)	0.0262 (7)	0.0316 (8)	0	0.0065 (6)	0
N2	0.0383 (9)	0.0237 (7)	0.0276 (8)	0	0.0015 (7)	0
N3	0.0249 (5)	0.0251 (5)	0.0351 (6)	0.0026 (4)	0.0046 (5)	0.0028 (4)
C5	0.0238 (6)	0.0242 (6)	0.0194 (5)	0.0018 (5)	0.0011 (5)	0.0031 (5)
C6	0.0199 (6)	0.0278 (6)	0.0196 (6)	0.0041 (5)	0.0017 (4)	0.0025 (5)
C7	0.0265 (6)	0.0238 (6)	0.0207 (6)	0.0049 (5)	−0.0003 (5)	0.0013 (5)
C8	0.0261 (6)	0.0253 (6)	0.0207 (6)	−0.0015 (5)	0.0003 (5)	0.0021 (5)
C9	0.0216 (6)	0.0316 (6)	0.0244 (6)	0.0032 (5)	0.0035 (5)	0.0023 (5)
C10	0.0261 (6)	0.0237 (6)	0.0262 (6)	0.0065 (5)	0.0041 (5)	0.0015 (5)
C11	0.0265 (6)	0.0243 (6)	0.0281 (7)	0.0030 (5)	−0.0003 (5)	0.0030 (5)
N4	0.0302 (6)	0.0292 (6)	0.0277 (6)	−0.0029 (5)	0.0015 (5)	0.0026 (4)
O1	0.0618 (7)	0.0215 (5)	0.0299 (5)	−0.0019 (4)	0.0082 (5)	0.0000 (4)
O2	0.0399 (6)	0.0337 (5)	0.0503 (7)	−0.0100 (5)	0.0201 (5)	−0.0041 (5)
O3	0.0273 (5)	0.0398 (6)	0.0541 (7)	−0.0066 (4)	0.0075 (4)	0.0006 (5)
O4	0.0406 (6)	0.0248 (5)	0.0566 (7)	−0.0009 (4)	0.0045 (5)	−0.0009 (5)
Cl1	0.02016 (16)	0.03606 (19)	0.0388 (2)	0.00424 (12)	0.00556 (12)	−0.00421 (14)

C1—N2	1.436 (2)	C5—C6	1.3909 (17)
C1—N1	1.513 (2)	C5—C10	1.4006 (17)
C1—H1A	0.99	C5—C11	1.5115 (17)
C1—H1B	0.99	C6—C7	1.3854 (17)
C2—N3	1.4693 (19)	C6—Cl1	1.7378 (12)
C2—N2	1.4703 (16)	C7—C8	1.3806 (17)
C2—H2A	0.99	C7—H7	0.95
C2—H2B	0.99	C8—C9	1.3811 (17)
C3—N3	1.4460 (16)	C8—N4	1.4679 (16)
C3—N1	1.5132 (15)	C9—C10	1.3775 (18)
C3—H3A	0.99	C9—H9	0.95
C3—H3B	0.99	C10—H10	0.95
C4—N3i	1.4725 (14)	C11—O2	1.2133 (16)
C4—N3	1.4725 (14)	C11—O1	1.2820 (16)
C4—H4A	0.99	N4—O4	1.2185 (14)
C4—H4B	0.99	N4—O3	1.2286 (14)
N1—H1	0.92 (3)	O1—H2	0.84
N2—C1—N1	109.51 (14)	C1—N2—C2i	109.21 (10)
N2—C1—H1A	109.8	C2—N2—C2i	108.03 (15)
N1—C1—H1A	109.8	C3—N3—C2	108.64 (11)
N2—C1—H1B	109.8	C3—N3—C4	109.24 (12)
N1—C1—H1B	109.8	C2—N3—C4	108.57 (12)
H1A—C1—H1B	108.2	C6—C5—C10	117.96 (11)
N3—C2—N2	112.13 (11)	C6—C5—C11	124.68 (10)
N3—C2—H2A	109.2	C10—C5—C11	117.34 (11)
N2—C2—H2A	109.2	C7—C6—C5	121.67 (11)
N3—C2—H2B	109.2	C7—C6—Cl1	116.53 (9)
N2—C2—H2B	109.2	C5—C6—Cl1	121.73 (9)
H2A—C2—H2B	107.9	C8—C7—C6	117.79 (11)
N3—C3—N1	109.46 (11)	C8—C7—H7	121.1
N3—C3—H3A	109.8	C6—C7—H7	121.1
N1—C3—H3A	109.8	C7—C8—C9	122.90 (12)
N3—C3—H3B	109.8	C7—C8—N4	118.18 (11)
N1—C3—H3B	109.8	C9—C8—N4	118.88 (11)
H3A—C3—H3B	108.2	C10—C9—C8	117.86 (11)
N3i—C4—N3	111.64 (14)	C10—C9—H9	121.1
N3i—C4—H4A	109.3	C8—C9—H9	121.1
N3—C4—H4A	109.3	C9—C10—C5	121.73 (11)
N3i—C4—H4B	109.3	C9—C10—H10	119.1
N3—C4—H4B	109.3	C5—C10—H10	119.1
H4A—C4—H4B	108	O2—C11—O1	126.54 (12)
C1—N1—C3	108.75 (10)	O2—C11—C5	120.51 (12)
C1—N1—C3i	108.75 (10)	O1—C11—C5	112.92 (11)
C3—N1—C3i	109.21 (14)	O4—N4—O3	123.81 (11)
C1—N1—H1	110.0 (16)	O4—N4—C8	118.31 (10)
C3—N1—H1	110.1 (8)	O3—N4—C8	117.83 (11)
C3i—N1—H1	110.1 (8)	C11—O1—H2	109.5
C1—N2—C2	109.21 (10)
N2—C1—N1—C3	59.41 (9)	C5—C6—C7—C8	−1.59 (18)
N2—C1—N1—C3i	−59.42 (9)	Cl1—C6—C7—C8	−178.61 (9)
N3—C3—N1—C1	−59.65 (14)	C6—C7—C8—C9	−1.09 (19)
N3—C3—N1—C3i	58.89 (18)	C6—C7—C8—N4	176.73 (11)
N1—C1—N2—C2	−58.97 (10)	C7—C8—C9—C10	3.08 (19)
N1—C1—N2—C2i	58.97 (10)	N4—C8—C9—C10	−174.73 (11)
N3—C2—N2—C1	60.31 (15)	C8—C9—C10—C5	−2.47 (19)
N3—C2—N2—C2i	−58.36 (18)	C6—C5—C10—C9	−0.04 (19)
N1—C3—N3—C2	59.30 (14)	C11—C5—C10—C9	−178.59 (11)
N1—C3—N3—C4	−58.98 (15)	C6—C5—C11—O2	−43.34 (19)
N2—C2—N3—C3	−60.24 (14)	C10—C5—C11—O2	135.11 (14)
N2—C2—N3—C4	58.46 (15)	C6—C5—C11—O1	138.58 (13)
N3i—C4—N3—C3	60.40 (19)	C10—C5—C11—O1	−42.97 (16)
N3i—C4—N3—C2	−57.92 (18)	C7—C8—N4—O4	−5.45 (18)
C10—C5—C6—C7	2.13 (18)	C9—C8—N4—O4	172.47 (12)
C11—C5—C6—C7	−179.43 (11)	C7—C8—N4—O3	176.84 (12)
C10—C5—C6—Cl1	179.00 (9)	C9—C8—N4—O3	−5.24 (18)
C11—C5—C6—Cl1	−2.56 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.92 (3)	2.12 (2)	2.7667 (15)	126 (1)

C6H13N4+·C7H3ClNO4−	F(000) = 712
Mr = 341.76	Dx = 1.499 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 8081 reflections
a = 5.9049 (1) Å	θ = 2.6–28.2°
b = 21.9330 (4) Å	µ = 0.28 mm−1
c = 12.0194 (2) Å	T = 173 K
β = 103.445 (1)°	Block, yellow
V = 1514.00 (5) Å3	0.43 × 0.36 × 0.16 mm
Z = 4

Bruker D8 Venture Photon CCD area detector diffractometer	3487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 28.0°, θmin = 1.9°
Absorption correction: integration (XPREP; Bruker, 2016)	h = −7→7
Tmin = 0.914, Tmax = 0.978	k = −28→28
19814 measured reflections	l = −15→15
3644 independent reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.026	w = 1/[σ2(Fo2) + (0.0432P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.15 e Å−3
3644 reflections	Δρmin = −0.16 e Å−3
212 parameters	Absolute structure: Flack x determined using 1663 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: −0.010 (19)
0 constraints

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2007)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	1.0080 (3)	0.72838 (9)	0.47292 (17)	0.0302 (4)
H1A	1.096685	0.737124	0.551861	0.036*
H1B	1.049816	0.686893	0.452137	0.036*
C2	0.9342 (4)	0.75914 (10)	0.27795 (17)	0.0319 (4)
H2A	0.976526	0.788891	0.224231	0.038*
H2B	0.976087	0.717955	0.25558	0.038*
C3	0.6207 (3)	0.71808 (8)	0.34676 (16)	0.0286 (4)
H3A	0.658855	0.676431	0.325098	0.034*
H3B	0.451188	0.719959	0.341854	0.034*
C4	0.6238 (4)	0.82334 (9)	0.3026 (2)	0.0350 (4)
H4A	0.661827	0.853586	0.248535	0.042*
H4B	0.454371	0.825696	0.297832	0.042*
C5	1.0013 (4)	0.83387 (9)	0.4256 (2)	0.0391 (5)
H5A	1.088446	0.843625	0.504334	0.047*
H5B	1.045272	0.864199	0.3733	0.047*
C6	0.6902 (4)	0.79500 (9)	0.49725 (19)	0.0343 (4)
H6A	0.521113	0.797405	0.493412	0.041*
H6B	0.774748	0.804796	0.576425	0.041*
N1	0.7517 (3)	0.73145 (7)	0.46727 (14)	0.0260 (3)
N2	1.0680 (3)	0.77256 (8)	0.39466 (16)	0.0320 (4)
N3	0.6820 (3)	0.76185 (7)	0.26875 (14)	0.0291 (3)
N4	0.7511 (3)	0.83861 (7)	0.41911 (17)	0.0347 (4)
H1	0.701 (5)	0.7025 (12)	0.521 (3)	0.047 (7)*
C7	0.4837 (3)	0.55022 (8)	0.59523 (16)	0.0247 (4)
C8	0.5755 (3)	0.51846 (8)	0.69629 (15)	0.0235 (3)
C9	0.4580 (3)	0.47118 (8)	0.73393 (16)	0.0242 (3)
H9	0.523206	0.449697	0.802544	0.029*
C10	0.2400 (3)	0.45652 (8)	0.66667 (17)	0.0252 (4)
C11	0.1378 (3)	0.48766 (9)	0.56796 (17)	0.0317 (4)
H11	−0.014186	0.477454	0.525556	0.038*
C12	0.2629 (4)	0.53414 (9)	0.53253 (18)	0.0330 (4)
H12	0.196649	0.555527	0.463953	0.04*
C13	0.6155 (3)	0.60098 (8)	0.55257 (15)	0.0258 (4)
N5	0.1104 (3)	0.40717 (7)	0.70493 (14)	0.0282 (3)
O1	0.5964 (3)	0.65311 (6)	0.59380 (14)	0.0443 (4)
O2	0.7254 (2)	0.58844 (6)	0.48014 (12)	0.0323 (3)
O3	−0.0851 (3)	0.39514 (8)	0.64851 (16)	0.0452 (4)
O4	0.2033 (3)	0.37964 (7)	0.79287 (13)	0.0393 (4)
Cl1	0.84686 (7)	0.53900 (2)	0.77974 (4)	0.03201 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0260 (10)	0.0383 (10)	0.0253 (9)	0.0055 (8)	0.0038 (7)	0.0053 (8)
C2	0.0363 (11)	0.0347 (10)	0.0284 (10)	0.0076 (8)	0.0149 (9)	0.0089 (8)
C3	0.0262 (9)	0.0276 (9)	0.0304 (10)	−0.0036 (7)	0.0035 (7)	−0.0036 (7)
C4	0.0320 (11)	0.0278 (9)	0.0429 (11)	0.0092 (8)	0.0043 (9)	0.0053 (8)
C5	0.0335 (11)	0.0321 (10)	0.0508 (13)	−0.0118 (8)	0.0079 (10)	−0.0032 (9)
C6	0.0374 (11)	0.0320 (10)	0.0378 (11)	0.0008 (8)	0.0176 (9)	−0.0103 (8)
N1	0.0294 (8)	0.0256 (7)	0.0248 (8)	−0.0012 (6)	0.0100 (6)	−0.0006 (6)
N2	0.0205 (8)	0.0382 (8)	0.0382 (9)	0.0007 (7)	0.0087 (7)	0.0060 (7)
N3	0.0308 (9)	0.0275 (8)	0.0268 (8)	0.0046 (6)	0.0019 (7)	0.0034 (6)
N4	0.0359 (9)	0.0230 (7)	0.0457 (10)	−0.0005 (6)	0.0109 (8)	−0.0045 (7)
C7	0.0301 (10)	0.0238 (8)	0.0201 (8)	0.0006 (7)	0.0056 (7)	−0.0003 (6)
C8	0.0224 (8)	0.0240 (7)	0.0225 (8)	−0.0004 (7)	0.0015 (7)	−0.0022 (6)
C9	0.0260 (9)	0.0231 (8)	0.0220 (8)	−0.0001 (6)	0.0024 (7)	0.0014 (6)
C10	0.0271 (9)	0.0227 (8)	0.0250 (9)	−0.0025 (6)	0.0044 (7)	−0.0014 (6)
C11	0.0287 (10)	0.0369 (10)	0.0252 (9)	−0.0044 (8)	−0.0023 (8)	0.0008 (8)
C12	0.0360 (11)	0.0365 (10)	0.0225 (9)	−0.0033 (8)	−0.0012 (8)	0.0061 (7)
C13	0.0310 (9)	0.0267 (8)	0.0191 (8)	−0.0010 (7)	0.0046 (7)	0.0019 (6)
N5	0.0291 (8)	0.0235 (7)	0.0310 (8)	−0.0044 (6)	0.0048 (7)	−0.0034 (6)
O1	0.0744 (12)	0.0273 (7)	0.0427 (9)	−0.0096 (7)	0.0370 (9)	−0.0058 (6)
O2	0.0353 (8)	0.0317 (7)	0.0331 (7)	0.0026 (5)	0.0147 (6)	0.0024 (6)
O3	0.0341 (8)	0.0444 (8)	0.0503 (9)	−0.0169 (7)	−0.0039 (7)	0.0037 (7)
O4	0.0414 (9)	0.0321 (7)	0.0410 (9)	−0.0084 (6)	0.0027 (7)	0.0114 (6)
Cl1	0.0265 (2)	0.0358 (2)	0.0297 (2)	−0.00838 (18)	−0.00158 (16)	0.00365 (19)

C1—N2	1.450 (3)	C6—N1	1.505 (2)
C1—N1	1.501 (3)	C6—H6A	0.99
C1—H1A	0.99	C6—H6B	0.99
C1—H1B	0.99	N1—H1	1.00 (3)
C2—N3	1.469 (3)	C7—C12	1.392 (3)
C2—N2	1.471 (3)	C7—C8	1.396 (3)
C2—H2A	0.99	C7—C13	1.514 (2)
C2—H2B	0.99	C8—C9	1.381 (3)
C3—N3	1.445 (2)	C8—Cl1	1.7405 (18)
C3—N1	1.504 (2)	C9—C10	1.390 (3)
C3—H3A	0.99	C9—H9	0.95
C3—H3B	0.99	C10—C11	1.380 (3)
C4—N4	1.466 (3)	C10—N5	1.460 (2)
C4—N3	1.472 (3)	C11—C12	1.383 (3)
C4—H4A	0.99	C11—H11	0.95
C4—H4B	0.99	C12—H12	0.95
C5—N4	1.466 (3)	C13—O2	1.232 (2)
C5—N2	1.473 (3)	C13—O1	1.262 (2)
C5—H5A	0.99	N5—O3	1.224 (2)
C5—H5B	0.99	N5—O4	1.230 (2)
C6—N4	1.443 (3)
N2—C1—N1	109.65 (15)	C3—N1—C6	108.21 (15)
N2—C1—H1A	109.7	C1—N1—H1	113.2 (17)
N1—C1—H1A	109.7	C3—N1—H1	109.4 (17)
N2—C1—H1B	109.7	C6—N1—H1	107.9 (15)
N1—C1—H1B	109.7	C1—N2—C2	109.08 (16)
H1A—C1—H1B	108.2	C1—N2—C5	109.07 (17)
N3—C2—N2	111.95 (15)	C2—N2—C5	107.93 (17)
N3—C2—H2A	109.2	C3—N3—C2	109.06 (15)
N2—C2—H2A	109.2	C3—N3—C4	108.64 (15)
N3—C2—H2B	109.2	C2—N3—C4	108.30 (17)
N2—C2—H2B	109.2	C6—N4—C5	108.62 (17)
H2A—C2—H2B	107.9	C6—N4—C4	108.69 (16)
N3—C3—N1	110.18 (15)	C5—N4—C4	108.72 (18)
N3—C3—H3A	109.6	C12—C7—C8	118.04 (17)
N1—C3—H3A	109.6	C12—C7—C13	119.58 (16)
N3—C3—H3B	109.6	C8—C7—C13	122.38 (17)
N1—C3—H3B	109.6	C9—C8—C7	122.48 (17)
H3A—C3—H3B	108.1	C9—C8—Cl1	118.08 (14)
N4—C4—N3	111.86 (15)	C7—C8—Cl1	119.43 (14)
N4—C4—H4A	109.2	C8—C9—C10	116.82 (17)
N3—C4—H4A	109.2	C8—C9—H9	121.6
N4—C4—H4B	109.2	C10—C9—H9	121.6
N3—C4—H4B	109.2	C11—C10—C9	123.11 (17)
H4A—C4—H4B	107.9	C11—C10—N5	118.76 (17)
N4—C5—N2	112.12 (16)	C9—C10—N5	118.09 (16)
N4—C5—H5A	109.2	C10—C11—C12	118.13 (18)
N2—C5—H5A	109.2	C10—C11—H11	120.9
N4—C5—H5B	109.2	C12—C11—H11	120.9
N2—C5—H5B	109.2	C11—C12—C7	121.37 (18)
H5A—C5—H5B	107.9	C11—C12—H12	119.3
N4—C6—N1	110.32 (15)	C7—C12—H12	119.3
N4—C6—H6A	109.6	O2—C13—O1	126.16 (17)
N1—C6—H6A	109.6	O2—C13—C7	118.14 (16)
N4—C6—H6B	109.6	O1—C13—C7	115.67 (16)
N1—C6—H6B	109.6	O3—N5—O4	123.01 (17)
H6A—C6—H6B	108.1	O3—N5—C10	118.76 (16)
C1—N1—C3	108.81 (15)	O4—N5—C10	118.23 (15)
C1—N1—C6	109.14 (15)
N2—C1—N1—C3	59.36 (19)	N3—C4—N4—C5	57.9 (2)
N2—C1—N1—C6	−58.5 (2)	C12—C7—C8—C9	1.7 (3)
N3—C3—N1—C1	−59.28 (19)	C13—C7—C8—C9	−178.40 (17)
N3—C3—N1—C6	59.19 (19)	C12—C7—C8—Cl1	−177.75 (15)
N4—C6—N1—C1	59.0 (2)	C13—C7—C8—Cl1	2.2 (2)
N4—C6—N1—C3	−59.2 (2)	C7—C8—C9—C10	−0.6 (3)
N1—C1—N2—C2	−59.2 (2)	Cl1—C8—C9—C10	178.85 (14)
N1—C1—N2—C5	58.5 (2)	C8—C9—C10—C11	−1.5 (3)
N3—C2—N2—C1	59.7 (2)	C8—C9—C10—N5	−179.32 (16)
N3—C2—N2—C5	−58.7 (2)	C9—C10—C11—C12	2.5 (3)
N4—C5—N2—C1	−60.1 (2)	N5—C10—C11—C12	−179.77 (18)
N4—C5—N2—C2	58.3 (2)	C10—C11—C12—C7	−1.3 (3)
N1—C3—N3—C2	58.6 (2)	C8—C7—C12—C11	−0.7 (3)
N1—C3—N3—C4	−59.30 (19)	C13—C7—C12—C11	179.37 (18)
N2—C2—N3—C3	−59.3 (2)	C12—C7—C13—O2	−83.2 (2)
N2—C2—N3—C4	58.8 (2)	C8—C7—C13—O2	96.9 (2)
N4—C4—N3—C3	60.2 (2)	C12—C7—C13—O1	95.1 (2)
N4—C4—N3—C2	−58.1 (2)	C8—C7—C13—O1	−84.8 (2)
N1—C6—N4—C5	−58.8 (2)	C11—C10—N5—O3	−0.3 (3)
N1—C6—N4—C4	59.3 (2)	C9—C10—N5—O3	177.59 (18)
N2—C5—N4—C6	59.9 (2)	C11—C10—N5—O4	179.86 (18)
N2—C5—N4—C4	−58.2 (2)	C9—C10—N5—O4	−2.3 (3)
N3—C4—N4—C6	−60.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	1.00 (3)	1.60 (3)	2.599 (2)	173 (3)

C6H13N4+·C7H3ClNO4−	F(000) = 712
Mr = 341.76	Dx = 1.503 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8173 reflections
a = 12.0663 (2) Å	θ = 2.7–28.3°
b = 19.5741 (4) Å	µ = 0.28 mm−1
c = 6.6473 (1) Å	T = 173 K
β = 105.820 (1)°	Flint, yellow
V = 1510.54 (5) Å3	0.34 × 0.34 × 0.09 mm
Z = 4

Bruker D8 Venture Photon CCD area detector diffractometer	3027 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 28°, θmin = 1.8°
Absorption correction: integration (XPREP; Bruker, 2016)	h = −15→15
Tmin = 0.921, Tmax = 0.981	k = −25→25
26282 measured reflections	l = −7→8
3650 independent reflections

Refinement on F2	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.054P)2 + 0.5922P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3650 reflections	Δρmax = 0.55 e Å−3
212 parameters	Δρmin = −0.32 e Å−3
0 restraints

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2016)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	0.47109 (13)	0.06841 (8)	0.8298 (2)	0.0271 (3)
H1A	0.476631	0.018936	0.803213	0.033*
H1B	0.546088	0.08373	0.921587	0.033*
C2	0.37372 (14)	0.15425 (8)	0.9693 (2)	0.0276 (3)
H2A	0.313223	0.162548	1.041406	0.033*
H2B	0.447916	0.170366	1.062001	0.033*
C3	0.43573 (13)	0.18246 (7)	0.6683 (2)	0.0244 (3)
H3A	0.510444	0.199335	0.757087	0.029*
H3B	0.417076	0.208139	0.534971	0.029*
C4	0.23625 (12)	0.16842 (8)	0.6381 (2)	0.0266 (3)
H4A	0.17462	0.176786	0.707533	0.032*
H4B	0.216747	0.19411	0.50475	0.032*
C5	0.27060 (14)	0.05744 (8)	0.7927 (3)	0.0286 (3)
H5A	0.274979	0.008016	0.764242	0.034*
H5B	0.208987	0.064229	0.863228	0.034*
C6	0.32952 (12)	0.08285 (8)	0.4889 (2)	0.0243 (3)
H6A	0.310535	0.107689	0.354087	0.029*
H6B	0.333422	0.033463	0.459442	0.029*
N1	0.44482 (11)	0.10695 (6)	0.6253 (2)	0.0224 (3)
N2	0.38141 (12)	0.08021 (6)	0.9327 (2)	0.0272 (3)
N3	0.34674 (10)	0.19364 (6)	0.77319 (19)	0.0236 (3)
N4	0.24105 (10)	0.09499 (6)	0.5939 (2)	0.0253 (3)
H1	0.5012 (17)	0.0994 (10)	0.563 (3)	0.034 (5)*
C7	0.75647 (12)	0.14049 (7)	0.3243 (2)	0.0245 (3)
C8	0.86231 (13)	0.10840 (7)	0.4116 (2)	0.0250 (3)
C9	0.95324 (12)	0.11511 (8)	0.3214 (3)	0.0283 (3)
H9	1.025178	0.093435	0.380783	0.034*
C10	0.93535 (13)	0.15426 (8)	0.1431 (2)	0.0291 (3)
C11	0.83262 (14)	0.18678 (8)	0.0513 (3)	0.0312 (3)
H11	0.822882	0.213174	−0.072295	0.037*
C12	0.74455 (13)	0.17962 (8)	0.1452 (3)	0.0295 (3)
H12	0.673439	0.202156	0.085609	0.035*
C13	0.65228 (13)	0.13753 (8)	0.4116 (3)	0.0276 (3)
N5	1.03144 (12)	0.16391 (9)	0.0488 (2)	0.0407 (4)
O1	0.61912 (11)	0.08068 (6)	0.4561 (2)	0.0409 (3)
O2	0.60096 (11)	0.19263 (6)	0.4134 (2)	0.0434 (3)
O3	1.02236 (14)	0.20679 (8)	−0.0877 (3)	0.0594 (4)
O4	1.11599 (12)	0.12771 (11)	0.1120 (2)	0.0706 (6)
Cl1	0.88646 (4)	0.06116 (2)	0.64016 (6)	0.03601 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0267 (7)	0.0216 (7)	0.0312 (8)	0.0035 (6)	0.0047 (6)	0.0047 (6)
C2	0.0346 (8)	0.0249 (7)	0.0237 (7)	−0.0002 (6)	0.0088 (6)	−0.0012 (6)
C3	0.0265 (7)	0.0156 (6)	0.0333 (8)	−0.0003 (5)	0.0116 (6)	0.0010 (6)
C4	0.0223 (7)	0.0268 (7)	0.0310 (8)	0.0051 (6)	0.0076 (6)	−0.0002 (6)
C5	0.0312 (8)	0.0241 (7)	0.0346 (8)	−0.0056 (6)	0.0160 (6)	−0.0001 (6)
C6	0.0247 (7)	0.0239 (7)	0.0249 (7)	−0.0001 (6)	0.0077 (6)	−0.0021 (6)
N1	0.0216 (6)	0.0179 (6)	0.0298 (6)	0.0015 (4)	0.0110 (5)	0.0020 (5)
N2	0.0350 (7)	0.0222 (6)	0.0247 (6)	0.0002 (5)	0.0090 (5)	0.0032 (5)
N3	0.0265 (6)	0.0191 (6)	0.0269 (6)	0.0014 (5)	0.0103 (5)	0.0004 (5)
N4	0.0209 (6)	0.0260 (6)	0.0292 (6)	−0.0003 (5)	0.0072 (5)	−0.0023 (5)
C7	0.0198 (7)	0.0216 (7)	0.0329 (8)	−0.0033 (5)	0.0089 (6)	−0.0067 (6)
C8	0.0231 (7)	0.0239 (7)	0.0273 (7)	−0.0025 (6)	0.0058 (6)	−0.0041 (6)
C9	0.0181 (7)	0.0333 (8)	0.0325 (8)	0.0000 (6)	0.0054 (6)	−0.0070 (6)
C10	0.0225 (7)	0.0356 (8)	0.0317 (8)	−0.0050 (6)	0.0115 (6)	−0.0082 (7)
C11	0.0305 (8)	0.0309 (8)	0.0334 (8)	−0.0023 (6)	0.0103 (7)	0.0014 (7)
C12	0.0233 (7)	0.0280 (8)	0.0368 (8)	0.0020 (6)	0.0076 (6)	−0.0010 (6)
C13	0.0219 (7)	0.0274 (8)	0.0359 (8)	−0.0027 (6)	0.0117 (6)	−0.0060 (6)
N5	0.0271 (7)	0.0621 (10)	0.0355 (8)	−0.0076 (7)	0.0129 (6)	−0.0112 (7)
O1	0.0368 (7)	0.0242 (6)	0.0723 (9)	−0.0010 (5)	0.0331 (6)	−0.0005 (6)
O2	0.0391 (7)	0.0293 (6)	0.0702 (9)	0.0047 (5)	0.0291 (7)	0.0018 (6)
O3	0.0622 (9)	0.0590 (9)	0.0723 (11)	−0.0087 (7)	0.0443 (8)	0.0089 (8)
O4	0.0281 (7)	0.1466 (18)	0.0404 (8)	0.0219 (9)	0.0149 (6)	0.0116 (9)
Cl1	0.0355 (2)	0.0380 (2)	0.0323 (2)	−0.00006 (17)	0.00555 (16)	0.00463 (16)

C1—N2	1.448 (2)	C6—N1	1.5140 (19)
C1—N1	1.5105 (19)	C6—H6A	0.99
C1—H1A	0.99	C6—H6B	0.99
C1—H1B	0.99	N1—H1	0.90 (2)
C2—N3	1.4724 (19)	C7—C12	1.390 (2)
C2—N2	1.4766 (19)	C7—C8	1.399 (2)
C2—H2A	0.99	C7—C13	1.522 (2)
C2—H2B	0.99	C8—C9	1.393 (2)
C3—N3	1.4475 (18)	C8—Cl1	1.7340 (16)
C3—N1	1.5150 (18)	C9—C10	1.378 (2)
C3—H3A	0.99	C9—H9	0.95
C3—H3B	0.99	C10—C11	1.379 (2)
C4—N4	1.4714 (19)	C10—N5	1.473 (2)
C4—N3	1.4746 (19)	C11—C12	1.379 (2)
C4—H4A	0.99	C11—H11	0.95
C4—H4B	0.99	C12—H12	0.95
C5—N4	1.469 (2)	C13—O1	1.2454 (19)
C5—N2	1.474 (2)	C13—O2	1.2454 (19)
C5—H5A	0.99	N5—O3	1.219 (2)
C5—H5B	0.99	N5—O4	1.219 (2)
C6—N4	1.4454 (19)
N2—C1—N1	110.18 (11)	C6—N1—C3	108.36 (11)
N2—C1—H1A	109.6	C1—N1—H1	109.4 (12)
N1—C1—H1A	109.6	C6—N1—H1	111.2 (12)
N2—C1—H1B	109.6	C3—N1—H1	110.4 (12)
N1—C1—H1B	109.6	C1—N2—C5	108.64 (12)
H1A—C1—H1B	108.1	C1—N2—C2	108.84 (12)
N3—C2—N2	112.14 (12)	C5—N2—C2	108.28 (12)
N3—C2—H2A	109.2	C3—N3—C2	109.46 (12)
N2—C2—H2A	109.2	C3—N3—C4	108.80 (12)
N3—C2—H2B	109.2	C2—N3—C4	107.99 (11)
N2—C2—H2B	109.2	C6—N4—C5	108.79 (12)
H2A—C2—H2B	107.9	C6—N4—C4	109.36 (11)
N3—C3—N1	109.86 (11)	C5—N4—C4	108.80 (12)
N3—C3—H3A	109.7	C12—C7—C8	118.18 (14)
N1—C3—H3A	109.7	C12—C7—C13	116.36 (13)
N3—C3—H3B	109.7	C8—C7—C13	125.45 (14)
N1—C3—H3B	109.7	C9—C8—C7	121.08 (14)
H3A—C3—H3B	108.2	C9—C8—Cl1	117.62 (12)
N4—C4—N3	111.73 (11)	C7—C8—Cl1	121.27 (12)
N4—C4—H4A	109.3	C10—C9—C8	117.76 (14)
N3—C4—H4A	109.3	C10—C9—H9	121.1
N4—C4—H4B	109.3	C8—C9—H9	121.1
N3—C4—H4B	109.3	C9—C10—C11	123.26 (14)
H4A—C4—H4B	107.9	C9—C10—N5	118.72 (14)
N4—C5—N2	111.88 (12)	C11—C10—N5	118.00 (15)
N4—C5—H5A	109.2	C12—C11—C10	117.61 (15)
N2—C5—H5A	109.2	C12—C11—H11	121.2
N4—C5—H5B	109.2	C10—C11—H11	121.2
N2—C5—H5B	109.2	C11—C12—C7	122.11 (14)
H5A—C5—H5B	107.9	C11—C12—H12	118.9
N4—C6—N1	109.79 (12)	C7—C12—H12	118.9
N4—C6—H6A	109.7	O1—C13—O2	125.36 (14)
N1—C6—H6A	109.7	O1—C13—C7	118.49 (13)
N4—C6—H6B	109.7	O2—C13—C7	115.79 (14)
N1—C6—H6B	109.7	O3—N5—O4	123.66 (16)
H6A—C6—H6B	108.2	O3—N5—C10	118.92 (15)
C1—N1—C6	108.45 (11)	O4—N5—C10	117.42 (16)
C1—N1—C3	109.01 (11)
N2—C1—N1—C6	−58.92 (15)	N3—C4—N4—C5	58.67 (15)
N2—C1—N1—C3	58.86 (15)	C12—C7—C8—C9	−0.3 (2)
N4—C6—N1—C1	59.13 (15)	C13—C7—C8—C9	−178.99 (14)
N4—C6—N1—C3	−59.07 (14)	C12—C7—C8—Cl1	177.65 (11)
N3—C3—N1—C1	−58.31 (15)	C13—C7—C8—Cl1	−1.0 (2)
N3—C3—N1—C6	59.54 (15)	C7—C8—C9—C10	−0.2 (2)
N1—C1—N2—C5	58.93 (15)	Cl1—C8—C9—C10	−178.17 (12)
N1—C1—N2—C2	−58.77 (15)	C8—C9—C10—C11	0.1 (2)
N4—C5—N2—C1	−60.34 (15)	C8—C9—C10—N5	178.05 (14)
N4—C5—N2—C2	57.72 (16)	C9—C10—C11—C12	0.4 (2)
N3—C2—N2—C1	59.64 (16)	N5—C10—C11—C12	−177.55 (14)
N3—C2—N2—C5	−58.29 (16)	C10—C11—C12—C7	−0.9 (2)
N1—C3—N3—C2	58.23 (15)	C8—C7—C12—C11	0.9 (2)
N1—C3—N3—C4	−59.57 (15)	C13—C7—C12—C11	179.66 (14)
N2—C2—N3—C3	−59.64 (16)	C12—C7—C13—O1	131.29 (16)
N2—C2—N3—C4	58.66 (16)	C8—C7—C13—O1	−50.0 (2)
N4—C4—N3—C3	60.13 (15)	C12—C7—C13—O2	−42.2 (2)
N4—C4—N3—C2	−58.59 (15)	C8—C7—C13—O2	136.53 (17)
N1—C6—N4—C5	−59.65 (15)	C9—C10—N5—O3	−168.41 (16)
N1—C6—N4—C4	59.06 (15)	C11—C10—N5—O3	9.7 (2)
N2—C5—N4—C6	60.87 (15)	C9—C10—N5—O4	12.0 (2)
N2—C5—N4—C4	−58.19 (15)	C11—C10—N5—O4	−169.91 (17)
N3—C4—N4—C6	−60.04 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90 (2)	1.80 (2)	2.6911 (17)	175.7 (19)