Propane-1,3-diaminium-2-carboxy-pyridine-6-carboxyl-ate-pyridine-2,6-dicarboxylic acid-water (1/2/2/8).

The title proton-transfer compound, C(3)H(12)N(2) (2+)·2C(7)H(4)NO(4) (-)·2C(7)H(5)NO(4)·8H(2)O or (pnH(2))(pydcH)(2).2(pydcH(2))·8H(2)O, was obtained by the reaction of pyridine-2,6-dicarboxylic acid (pydcH(2)) and propane-1,3-diamine (pn) in aqueous solution. Both neutral and monoanionic forms of the diacid are observed in the crystal structure. The negative charge of two monoanions is balanced by the dicationic propane-1,3-diaminium species. In addition, considerable π-π stacking inter-actions between the aromatic rings of the (pydcH)(-) and (pydcH(2)) fragments [with centroid-centroid distances of 3.5108 (11)-3.5949 (11) Å] are observed. The most important feature of this crystal structure is the presence of a large number of O-H⋯O, O-H⋯N, N-H⋯O, N-H⋯N, C-H⋯O and C-H⋯N hydrogen bonds, with D⋯A ranging from 2.445 (2) to 3.485 (3) Å. These inter-actions as well as ion pairing and π-π stacking connect the various fragments into a supra-molecular structure.

Related literature

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi, Ghasemikhah & Soleimannejad (2007 ▶); Aghabozorg, Attar Gharamaleki, Ghasemikhah, Ghadermazi & Soleimannejad, 2007 ▶; Aghabozorg, Daneshvar et al. (2007 ▶).

Experimental

Crystal data

C3H12N2 2+·2C7H4NO4 −·2C7H5NO4·8H2O

M = 886.73

Monoclinic,

a = 13.5425 (2) Å

b = 13.5237 (2) Å

c = 21.7538 (3) Å

β = 99.914 (1)°

V = 3924.60 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 150 (2) K

0.26 × 0.12 × 0.12 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.967, T max = 0.985

56174 measured reflections

9031 independent reflections

6702 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.139

S = 1.02

9031 reflections

550 parameters

H-atom parameters constrained

Δρmax = 0.84 e Å−3

Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2005 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065270/bq2048sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065270/bq2048Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C3H12N22+·2C7H4NO4–·2C7H5NO4·8H2O	F000 = 1864
Mr = 886.73	Dx = 1.501 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
a = 13.5425 (2) Å	Cell parameters from 9156 reflections
b = 13.5237 (2) Å	θ = 2.4–29.1º
c = 21.7538 (3) Å	µ = 0.13 mm−1
β = 99.914 (1)º	T = 150 (2) K
V = 3924.60 (10) Å3	Block, colourless
Z = 4	0.26 × 0.12 × 0.12 mm

Bruker SMART 1000 diffractometer	9031 independent reflections
Radiation source: fine-focus sealed tube	6702 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.054
Detector resolution: 100 pixels mm-1	θmax = 27.5º
T = 150(2) K	θmin = 1.5º
ω scans	h = −17→17
Absorption correction: multi-scan(SADABS; Bruker, 1998)	k = −17→17
Tmin = 0.967, Tmax = 0.985	l = −28→28
56174 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.139	w = 1/[σ2(Fo2) + (0.0592P)2 + 3.5811P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
9031 reflections	Δρmax = 0.84 e Å−3
550 parameters	Δρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.90840 (11)	0.77843 (12)	0.54180 (7)	0.0254 (3)
O2	0.74609 (11)	0.79981 (11)	0.51063 (7)	0.0249 (3)
H2A	0.6958	0.8087	0.4748	0.030*
O3	0.60302 (12)	0.87473 (13)	0.31596 (7)	0.0307 (4)
O4	0.68349 (11)	0.88557 (12)	0.23488 (7)	0.0262 (3)
O5	0.18211 (12)	0.78608 (13)	−0.00659 (7)	0.0320 (4)
H5AA	0.2027	0.7723	−0.0453	0.038*
O6	0.33622 (12)	0.84668 (13)	0.02551 (7)	0.0292 (4)
O7	0.45325 (11)	0.89020 (13)	0.23505 (7)	0.0298 (4)
H7A	0.5096	0.8838	0.2675	0.036*
O8	0.35911 (12)	0.86950 (14)	0.30873 (7)	0.0333 (4)
O9	0.15292 (11)	0.52710 (12)	−0.01050 (6)	0.0245 (3)
H9A	0.1799	0.5233	−0.0480	0.029*
O10	0.31288 (12)	0.55101 (13)	0.03474 (7)	0.0315 (4)
O11	0.39207 (11)	0.63847 (12)	0.24320 (6)	0.0262 (3)
H11A	0.4456	0.6339	0.2776	0.031*
O12	0.28767 (11)	0.61399 (11)	0.31033 (6)	0.0235 (3)
O13	0.46668 (11)	0.12691 (14)	0.17039 (7)	0.0322 (4)
O14	0.37185 (11)	0.11228 (12)	0.24412 (6)	0.0258 (3)
O15	0.02539 (11)	0.06135 (12)	0.19062 (7)	0.0255 (3)
O16	−0.04375 (11)	0.02480 (12)	0.09246 (6)	0.0248 (3)
H16A	−0.1019	0.0061	0.1086	0.030*
O17	0.18876 (11)	0.09699 (12)	0.28868 (7)	0.0263 (3)
H17A	0.1416	0.0806	0.2525	0.032*
H17B	0.2490	0.1058	0.2726	0.032*
O18	0.85758 (12)	0.72397 (12)	0.65729 (7)	0.0276 (3)
H18B	0.8642	0.7497	0.6176	0.033*
H18A	0.8308	0.7822	0.6725	0.033*
O19	0.55978 (12)	0.80178 (13)	0.42843 (7)	0.0337 (4)
H19B	0.6221	0.8311	0.4244	0.040*
H19A	0.5239	0.7533	0.4019	0.040*
O20	0.20445 (14)	0.74513 (13)	−0.11979 (8)	0.0385 (4)
H20B	0.2437	0.7866	−0.1413	0.046*
H20A	0.2206	0.6770	−0.1216	0.046*
O21	0.42936 (12)	0.54219 (13)	−0.06159 (7)	0.0338 (4)
H21B	0.3970	0.5418	−0.0262	0.041*
H21A	0.4678	0.6011	−0.0607	0.041*
O22	0.22400 (13)	0.53350 (13)	−0.11351 (7)	0.0348 (4)
H22A	0.2948	0.5373	−0.1021	0.042*
H22B	0.2014	0.4911	−0.1479	0.042*
O23	0.42837 (14)	0.89677 (16)	−0.07328 (8)	0.0464 (5)
H23B	0.3852	0.8938	−0.0432	0.056*
H23A	0.3866	0.8866	−0.1125	0.056*
O24	−0.20133 (11)	−0.03538 (11)	0.13049 (7)	0.0236 (3)
H24B	−0.1884	−0.1000	0.1470	0.028*
H24A	−0.2294	0.0031	0.1597	0.028*
C1	0.83900 (16)	0.79459 (15)	0.49983 (9)	0.0200 (4)
C2	0.85368 (15)	0.80829 (15)	0.43368 (9)	0.0187 (4)
C3	0.94700 (16)	0.79837 (15)	0.41643 (10)	0.0213 (4)
H3	1.0049	0.7844	0.4465	0.026*
C4	0.95318 (17)	0.80945 (16)	0.35423 (10)	0.0244 (5)
H4	1.0156	0.8019	0.3405	0.029*
C5	0.86744 (16)	0.83174 (15)	0.31202 (10)	0.0222 (4)
H5	0.8702	0.8397	0.2690	0.027*
C6	0.77715 (16)	0.84232 (15)	0.33360 (9)	0.0196 (4)
C7	0.68120 (16)	0.86929 (16)	0.29052 (9)	0.0223 (4)
C8	0.25328 (15)	0.82141 (16)	0.03516 (9)	0.0207 (4)
C9	0.22600 (15)	0.82952 (15)	0.09889 (9)	0.0179 (4)
C10	0.12850 (15)	0.81571 (15)	0.10843 (9)	0.0199 (4)
H10	0.0767	0.7994	0.0747	0.024*
C11	0.10811 (15)	0.82621 (15)	0.16848 (10)	0.0215 (4)
H11	0.0417	0.8191	0.1765	0.026*
C12	0.18632 (16)	0.84712 (15)	0.21610 (10)	0.0212 (4)
H12	0.1748	0.8543	0.2577	0.025*
C13	0.28225 (15)	0.85764 (15)	0.20248 (9)	0.0193 (4)
C14	0.36955 (16)	0.87368 (16)	0.25443 (10)	0.0228 (4)
C15	0.22408 (15)	0.54705 (16)	0.03722 (9)	0.0209 (4)
C16	0.18464 (15)	0.56360 (15)	0.09693 (9)	0.0177 (4)
C17	0.08312 (15)	0.55850 (15)	0.09973 (10)	0.0204 (4)
H17	0.0350	0.5465	0.0633	0.024*
C18	0.05401 (16)	0.57144 (16)	0.15715 (10)	0.0224 (4)
H18	−0.0148	0.5680	0.1608	0.027*
C19	0.12607 (15)	0.58934 (15)	0.20898 (9)	0.0197 (4)
H19	0.1079	0.5973	0.2490	0.024*
C20	0.22577 (15)	0.59546 (14)	0.20150 (9)	0.0172 (4)
C21	0.30780 (15)	0.61719 (15)	0.25620 (9)	0.0190 (4)
C22	0.38272 (15)	0.11248 (16)	0.18930 (9)	0.0208 (4)
C23	0.29575 (15)	0.09393 (14)	0.13742 (9)	0.0178 (4)
C24	0.30923 (15)	0.08566 (15)	0.07564 (9)	0.0192 (4)
H24	0.3738	0.0925	0.0647	0.023*
C25	0.22567 (16)	0.06715 (15)	0.03039 (9)	0.0201 (4)
H25	0.2320	0.0614	−0.0123	0.024*
C26	0.13305 (16)	0.05727 (15)	0.04837 (9)	0.0197 (4)
H26	0.0746	0.0452	0.0183	0.024*
C27	0.12751 (15)	0.06546 (14)	0.11150 (9)	0.0173 (4)
C28	0.03140 (15)	0.05113 (15)	0.13594 (9)	0.0193 (4)
C29	0.57849 (17)	0.82728 (18)	0.08483 (10)	0.0278 (5)
H29A	0.6472	0.8472	0.0803	0.033*
H29B	0.5371	0.8245	0.0427	0.033*
C30	0.58164 (16)	0.72587 (18)	0.11447 (10)	0.0266 (5)
H30A	0.6195	0.7297	0.1576	0.032*
H30B	0.6176	0.6798	0.0907	0.032*
C31	0.47782 (16)	0.68576 (17)	0.11606 (10)	0.0255 (5)
H31A	0.4435	0.7295	0.1422	0.031*
H31B	0.4385	0.6861	0.0733	0.031*
N1	0.76996 (13)	0.82962 (13)	0.39359 (8)	0.0192 (4)
N2	0.30298 (13)	0.85093 (12)	0.14479 (8)	0.0185 (3)
N3	0.25553 (12)	0.58254 (12)	0.14653 (7)	0.0172 (3)
N4	0.20715 (12)	0.08387 (12)	0.15546 (7)	0.0172 (3)
N5	0.53588 (15)	0.90263 (15)	0.12309 (8)	0.0285 (4)
H5A	0.4682	0.8858	0.1245	0.034*
H5B	0.5770	0.9026	0.1631	0.034*
H5C	0.5359	0.9684	0.1078	0.034*
N6	0.48067 (13)	0.58346 (14)	0.14140 (8)	0.0230 (4)
H6A	0.5210	0.5842	0.1817	0.028*
H6B	0.5084	0.5374	0.1161	0.028*
H6C	0.4155	0.5676	0.1490	0.028*

	U11	U22	U33	U12	U13	U23
O1	0.0257 (8)	0.0309 (9)	0.0189 (7)	0.0012 (6)	0.0019 (6)	0.0031 (6)
O2	0.0228 (8)	0.0324 (9)	0.0200 (7)	0.0025 (6)	0.0051 (6)	0.0006 (6)
O3	0.0221 (8)	0.0496 (11)	0.0201 (8)	−0.0014 (7)	0.0027 (6)	−0.0003 (7)
O4	0.0266 (8)	0.0358 (9)	0.0157 (7)	−0.0062 (7)	0.0017 (6)	0.0001 (6)
O5	0.0288 (9)	0.0478 (11)	0.0183 (8)	−0.0069 (7)	0.0008 (6)	−0.0078 (7)
O6	0.0266 (8)	0.0433 (10)	0.0188 (7)	−0.0046 (7)	0.0074 (6)	−0.0021 (7)
O7	0.0195 (8)	0.0508 (11)	0.0184 (7)	−0.0055 (7)	0.0007 (6)	−0.0019 (7)
O8	0.0287 (9)	0.0554 (11)	0.0162 (8)	0.0009 (8)	0.0048 (6)	−0.0034 (7)
O9	0.0243 (8)	0.0328 (9)	0.0156 (7)	−0.0044 (6)	0.0007 (6)	−0.0031 (6)
O10	0.0249 (8)	0.0493 (11)	0.0212 (8)	−0.0053 (7)	0.0066 (6)	−0.0076 (7)
O11	0.0165 (7)	0.0465 (10)	0.0151 (7)	−0.0009 (7)	0.0014 (6)	−0.0020 (7)
O12	0.0285 (8)	0.0276 (8)	0.0153 (7)	−0.0007 (6)	0.0066 (6)	−0.0005 (6)
O13	0.0181 (8)	0.0608 (12)	0.0173 (7)	−0.0034 (7)	0.0022 (6)	0.0041 (7)
O14	0.0211 (8)	0.0402 (9)	0.0157 (7)	−0.0010 (7)	0.0022 (6)	0.0008 (6)
O15	0.0225 (8)	0.0363 (9)	0.0187 (7)	−0.0022 (6)	0.0065 (6)	−0.0048 (6)
O16	0.0193 (7)	0.0366 (9)	0.0186 (7)	−0.0064 (6)	0.0035 (6)	−0.0035 (6)
O17	0.0251 (8)	0.0379 (9)	0.0163 (7)	−0.0009 (7)	0.0050 (6)	−0.0014 (6)
O18	0.0338 (9)	0.0276 (8)	0.0234 (8)	0.0022 (7)	0.0107 (7)	0.0040 (6)
O19	0.0290 (9)	0.0442 (10)	0.0285 (9)	0.0022 (7)	0.0061 (7)	−0.0040 (7)
O20	0.0527 (11)	0.0310 (9)	0.0367 (10)	−0.0008 (8)	0.0213 (8)	0.0039 (7)
O21	0.0350 (9)	0.0400 (10)	0.0301 (9)	−0.0047 (8)	0.0156 (7)	−0.0063 (7)
O22	0.0425 (10)	0.0408 (10)	0.0223 (8)	−0.0057 (8)	0.0087 (7)	−0.0043 (7)
O23	0.0338 (10)	0.0815 (15)	0.0254 (9)	0.0036 (10)	0.0095 (7)	0.0090 (9)
O24	0.0228 (8)	0.0285 (8)	0.0205 (7)	−0.0024 (6)	0.0060 (6)	−0.0031 (6)
C1	0.0236 (11)	0.0171 (10)	0.0190 (10)	−0.0004 (8)	0.0035 (8)	0.0001 (8)
C2	0.0215 (10)	0.0160 (10)	0.0188 (10)	−0.0015 (8)	0.0043 (8)	−0.0009 (8)
C3	0.0209 (10)	0.0189 (10)	0.0237 (10)	0.0004 (8)	0.0027 (8)	0.0010 (8)
C4	0.0252 (11)	0.0234 (11)	0.0269 (11)	0.0000 (9)	0.0104 (9)	0.0010 (9)
C5	0.0275 (11)	0.0213 (11)	0.0192 (10)	−0.0028 (8)	0.0075 (8)	−0.0014 (8)
C6	0.0258 (11)	0.0158 (10)	0.0169 (9)	−0.0039 (8)	0.0033 (8)	−0.0023 (8)
C7	0.0236 (11)	0.0239 (11)	0.0188 (10)	−0.0064 (8)	0.0019 (8)	−0.0028 (8)
C8	0.0200 (10)	0.0221 (10)	0.0195 (10)	0.0009 (8)	0.0020 (8)	0.0004 (8)
C9	0.0208 (10)	0.0155 (9)	0.0176 (9)	0.0003 (8)	0.0037 (8)	0.0009 (8)
C10	0.0208 (10)	0.0174 (10)	0.0205 (10)	−0.0015 (8)	0.0002 (8)	0.0033 (8)
C11	0.0177 (10)	0.0205 (10)	0.0275 (11)	0.0004 (8)	0.0072 (8)	0.0035 (8)
C12	0.0244 (11)	0.0208 (10)	0.0195 (10)	0.0020 (8)	0.0073 (8)	0.0010 (8)
C13	0.0218 (10)	0.0183 (10)	0.0180 (10)	−0.0006 (8)	0.0034 (8)	0.0001 (8)
C14	0.0217 (11)	0.0268 (11)	0.0202 (10)	0.0008 (9)	0.0042 (8)	−0.0024 (8)
C15	0.0222 (11)	0.0224 (10)	0.0180 (10)	−0.0022 (8)	0.0030 (8)	−0.0009 (8)
C16	0.0190 (10)	0.0168 (10)	0.0172 (9)	0.0004 (8)	0.0030 (7)	0.0012 (8)
C17	0.0197 (10)	0.0174 (10)	0.0226 (10)	−0.0009 (8)	−0.0004 (8)	0.0002 (8)
C18	0.0177 (10)	0.0219 (11)	0.0288 (11)	0.0006 (8)	0.0073 (8)	0.0011 (9)
C19	0.0206 (10)	0.0192 (10)	0.0211 (10)	0.0010 (8)	0.0083 (8)	0.0001 (8)
C20	0.0198 (10)	0.0161 (10)	0.0165 (9)	0.0021 (7)	0.0051 (8)	0.0015 (7)
C21	0.0222 (10)	0.0188 (10)	0.0166 (9)	0.0027 (8)	0.0053 (8)	−0.0003 (8)
C22	0.0184 (10)	0.0261 (11)	0.0176 (10)	0.0006 (8)	0.0023 (8)	0.0032 (8)
C23	0.0198 (10)	0.0162 (10)	0.0171 (9)	0.0002 (8)	0.0023 (8)	0.0009 (8)
C24	0.0210 (10)	0.0188 (10)	0.0188 (10)	0.0000 (8)	0.0059 (8)	0.0002 (8)
C25	0.0272 (11)	0.0190 (10)	0.0146 (9)	−0.0025 (8)	0.0049 (8)	−0.0005 (8)
C26	0.0222 (10)	0.0186 (10)	0.0175 (9)	−0.0028 (8)	0.0014 (8)	−0.0008 (8)
C27	0.0192 (10)	0.0149 (9)	0.0179 (9)	0.0002 (7)	0.0036 (8)	0.0010 (7)
C28	0.0219 (10)	0.0183 (10)	0.0177 (10)	0.0014 (8)	0.0036 (8)	−0.0002 (8)
C29	0.0225 (11)	0.0417 (14)	0.0202 (10)	−0.0082 (10)	0.0064 (9)	−0.0055 (10)
C30	0.0169 (10)	0.0398 (13)	0.0235 (11)	−0.0014 (9)	0.0046 (8)	−0.0042 (10)
C31	0.0187 (10)	0.0327 (12)	0.0249 (11)	0.0005 (9)	0.0033 (8)	0.0008 (9)
N1	0.0226 (9)	0.0185 (9)	0.0168 (8)	−0.0022 (7)	0.0036 (7)	−0.0006 (7)
N2	0.0205 (9)	0.0185 (8)	0.0171 (8)	0.0006 (7)	0.0043 (7)	0.0010 (7)
N3	0.0188 (8)	0.0176 (8)	0.0160 (8)	−0.0001 (7)	0.0053 (6)	0.0001 (7)
N4	0.0183 (8)	0.0179 (8)	0.0153 (8)	0.0010 (6)	0.0028 (6)	0.0002 (6)
N5	0.0297 (10)	0.0355 (11)	0.0199 (9)	−0.0053 (8)	0.0034 (8)	−0.0007 (8)
N6	0.0186 (9)	0.0329 (10)	0.0181 (8)	0.0010 (7)	0.0052 (7)	−0.0035 (7)

O1—C1	1.212 (3)	C8—C9	1.499 (3)
O2—C1	1.321 (2)	C9—N2	1.345 (3)
O2—H2A	0.9499	C9—C10	1.384 (3)
O3—C7	1.278 (3)	C10—C11	1.388 (3)
O4—C7	1.236 (2)	C10—H10	0.9500
O5—C8	1.296 (3)	C11—C12	1.377 (3)
O5—H5AA	0.9501	C11—H11	0.9500
O6—C8	1.226 (3)	C12—C13	1.389 (3)
O7—C14	1.295 (3)	C12—H12	0.9500
O7—H7A	0.9501	C13—N2	1.335 (3)
O8—C14	1.215 (3)	C13—C14	1.504 (3)
O9—C15	1.317 (2)	C15—C16	1.504 (3)
O9—H9A	0.9499	C16—N3	1.340 (3)
O10—C15	1.214 (3)	C16—C17	1.388 (3)
O11—C21	1.255 (2)	C17—C18	1.384 (3)
O11—H11A	0.9499	C17—H17	0.9500
O12—C21	1.254 (2)	C18—C19	1.380 (3)
O13—C22	1.289 (2)	C18—H18	0.9500
O14—C22	1.227 (2)	C19—C20	1.390 (3)
O15—C28	1.214 (2)	C19—H19	0.9500
O16—C28	1.314 (2)	C20—N3	1.338 (2)
O16—H16A	0.9500	C20—C21	1.510 (3)
O17—H17A	0.9500	C22—C23	1.505 (3)
O17—H17B	0.9499	C23—N4	1.332 (3)
O18—H18B	0.9501	C23—C24	1.392 (3)
O18—H18A	0.9499	C24—C25	1.389 (3)
O19—H19B	0.9501	C24—H24	0.9500
O19—H19A	0.9500	C25—C26	1.383 (3)
O20—H20B	0.9502	C25—H25	0.9500
O20—H20A	0.9501	C26—C27	1.393 (3)
O21—H21B	0.9500	C26—H26	0.9500
O21—H21A	0.9500	C27—N4	1.336 (3)
O22—H22A	0.9500	C27—C28	1.501 (3)
O22—H22B	0.9500	C29—N5	1.493 (3)
O23—H23B	0.9500	C29—C30	1.513 (3)
O23—H23A	0.9499	C29—H29A	0.9900
O24—H24B	0.9500	C29—H29B	0.9900
O24—H24A	0.9501	C30—C31	1.513 (3)
C1—C2	1.498 (3)	C30—H30A	0.9900
C2—N1	1.337 (3)	C30—H30B	0.9900
C2—C3	1.385 (3)	C31—N6	1.487 (3)
C3—C4	1.378 (3)	C31—H31A	0.9900
C3—H3	0.9500	C31—H31B	0.9900
C4—C5	1.384 (3)	N5—H5A	0.9500
C4—H4	0.9500	N5—H5B	0.9500
C5—C6	1.391 (3)	N5—H5C	0.9500
C5—H5	0.9500	N6—H6A	0.9502
C6—N1	1.336 (3)	N6—H6B	0.9499
C6—C7	1.510 (3)	N6—H6C	0.9500
C1—O2—H2A	115.5	C19—C18—H18	120.4
C8—O5—H5AA	113.4	C17—C18—H18	120.4
C14—O7—H7A	112.3	C18—C19—C20	118.65 (18)
C15—O9—H9A	110.5	C18—C19—H19	120.7
C21—O11—H11A	114.1	C20—C19—H19	120.7
C28—O16—H16A	113.3	N3—C20—C19	123.04 (18)
H17A—O17—H17B	102.8	N3—C20—C21	115.83 (17)
H18B—O18—H18A	96.6	C19—C20—C21	121.13 (17)
H19B—O19—H19A	127.0	O12—C21—O11	124.91 (19)
H20B—O20—H20A	113.5	O12—C21—C20	118.92 (18)
H21B—O21—H21A	108.4	O11—C21—C20	116.17 (17)
H22A—O22—H22B	114.4	O14—C22—O13	124.81 (19)
H23B—O23—H23A	105.7	O14—C22—C23	121.27 (18)
H24B—O24—H24A	108.7	O13—C22—C23	113.92 (17)
O1—C1—O2	120.96 (18)	N4—C23—C24	123.43 (18)
O1—C1—C2	122.15 (19)	N4—C23—C22	115.11 (17)
O2—C1—C2	116.88 (17)	C24—C23—C22	121.44 (18)
N1—C2—C3	123.70 (18)	C25—C24—C23	118.21 (18)
N1—C2—C1	114.54 (17)	C25—C24—H24	120.9
C3—C2—C1	121.76 (18)	C23—C24—H24	120.9
C4—C3—C2	117.9 (2)	C26—C25—C24	119.01 (18)
C4—C3—H3	121.1	C26—C25—H25	120.5
C2—C3—H3	121.1	C24—C25—H25	120.5
C3—C4—C5	119.3 (2)	C25—C26—C27	118.46 (19)
C3—C4—H4	120.4	C25—C26—H26	120.8
C5—C4—H4	120.4	C27—C26—H26	120.8
C4—C5—C6	118.98 (19)	N4—C27—C26	123.16 (18)
C4—C5—H5	120.5	N4—C27—C28	114.39 (17)
C6—C5—H5	120.5	C26—C27—C28	122.43 (18)
N1—C6—C5	122.19 (19)	O15—C28—O16	124.19 (19)
N1—C6—C7	115.94 (18)	O15—C28—C27	122.74 (18)
C5—C6—C7	121.87 (18)	O16—C28—C27	113.06 (17)
O4—C7—O3	125.2 (2)	N5—C29—C30	111.50 (17)
O4—C7—C6	119.12 (19)	N5—C29—H29A	109.3
O3—C7—C6	115.69 (18)	C30—C29—H29A	109.3
O6—C8—O5	125.11 (19)	N5—C29—H29B	109.3
O6—C8—C9	121.12 (18)	C30—C29—H29B	109.3
O5—C8—C9	113.76 (18)	H29A—C29—H29B	108.0
N2—C9—C10	123.73 (18)	C29—C30—C31	112.13 (19)
N2—C9—C8	114.79 (17)	C29—C30—H30A	109.2
C10—C9—C8	121.48 (18)	C31—C30—H30A	109.2
C9—C10—C11	118.47 (19)	C29—C30—H30B	109.2
C9—C10—H10	120.8	C31—C30—H30B	109.2
C11—C10—H10	120.8	H30A—C30—H30B	107.9
C12—C11—C10	118.49 (19)	N6—C31—C30	112.15 (18)
C12—C11—H11	120.8	N6—C31—H31A	109.2
C10—C11—H11	120.8	C30—C31—H31A	109.2
C11—C12—C13	119.14 (19)	N6—C31—H31B	109.2
C11—C12—H12	120.4	C30—C31—H31B	109.2
C13—C12—H12	120.4	H31A—C31—H31B	107.9
N2—C13—C12	123.32 (19)	C6—N1—C2	117.92 (18)
N2—C13—C14	116.79 (18)	C13—N2—C9	116.79 (17)
C12—C13—C14	119.84 (18)	C20—N3—C16	117.42 (17)
O8—C14—O7	125.4 (2)	C23—N4—C27	117.72 (16)
O8—C14—C13	121.05 (19)	C29—N5—H5A	108.8
O7—C14—C13	113.53 (17)	C29—N5—H5B	106.8
O10—C15—O9	124.74 (19)	H5A—N5—H5B	112.7
O10—C15—C16	122.26 (18)	C29—N5—H5C	114.9
O9—C15—C16	113.00 (17)	H5A—N5—H5C	107.1
N3—C16—C17	123.50 (18)	H5B—N5—H5C	106.6
N3—C16—C15	114.34 (17)	C31—N6—H6A	107.8
C17—C16—C15	122.16 (18)	C31—N6—H6B	112.5
C18—C17—C16	118.13 (19)	H6A—N6—H6B	108.7
C18—C17—H17	120.9	C31—N6—H6C	108.0
C16—C17—H17	120.9	H6A—N6—H6C	104.2
C19—C18—C17	119.23 (19)	H6B—N6—H6C	115.1
O1—C1—C2—N1	−177.34 (19)	C18—C19—C20—C21	178.60 (19)
O2—C1—C2—N1	3.4 (3)	N3—C20—C21—O12	−168.41 (18)
O1—C1—C2—C3	3.2 (3)	C19—C20—C21—O12	11.4 (3)
O2—C1—C2—C3	−176.03 (18)	N3—C20—C21—O11	12.3 (3)
N1—C2—C3—C4	−1.2 (3)	C19—C20—C21—O11	−167.82 (19)
C1—C2—C3—C4	178.17 (19)	O14—C22—C23—N4	4.0 (3)
C2—C3—C4—C5	1.3 (3)	O13—C22—C23—N4	−176.68 (19)
C3—C4—C5—C6	0.0 (3)	O14—C22—C23—C24	−174.4 (2)
C4—C5—C6—N1	−1.5 (3)	O13—C22—C23—C24	4.9 (3)
C4—C5—C6—C7	178.33 (19)	N4—C23—C24—C25	0.8 (3)
N1—C6—C7—O4	177.41 (19)	C22—C23—C24—C25	179.11 (19)
C5—C6—C7—O4	−2.4 (3)	C23—C24—C25—C26	−0.3 (3)
N1—C6—C7—O3	−1.6 (3)	C24—C25—C26—C27	−0.6 (3)
C5—C6—C7—O3	178.6 (2)	C25—C26—C27—N4	1.0 (3)
O6—C8—C9—N2	−10.0 (3)	C25—C26—C27—C28	−177.05 (18)
O5—C8—C9—N2	169.95 (18)	N4—C27—C28—O15	4.3 (3)
O6—C8—C9—C10	170.0 (2)	C26—C27—C28—O15	−177.5 (2)
O5—C8—C9—C10	−10.1 (3)	N4—C27—C28—O16	−174.48 (17)
N2—C9—C10—C11	1.2 (3)	C26—C27—C28—O16	3.7 (3)
C8—C9—C10—C11	−178.76 (19)	N5—C29—C30—C31	65.6 (2)
C9—C10—C11—C12	−1.8 (3)	C29—C30—C31—N6	176.28 (17)
C10—C11—C12—C13	0.4 (3)	C5—C6—N1—C2	1.6 (3)
C11—C12—C13—N2	1.7 (3)	C7—C6—N1—C2	−178.23 (18)
C11—C12—C13—C14	−175.90 (19)	C3—C2—N1—C6	−0.2 (3)
N2—C13—C14—O8	−171.6 (2)	C1—C2—N1—C6	−179.62 (17)
C12—C13—C14—O8	6.2 (3)	C12—C13—N2—C9	−2.3 (3)
N2—C13—C14—O7	7.5 (3)	C14—C13—N2—C9	175.36 (18)
C12—C13—C14—O7	−174.77 (19)	C10—C9—N2—C13	0.8 (3)
O10—C15—C16—N3	−0.2 (3)	C8—C9—N2—C13	−179.19 (18)
O9—C15—C16—N3	179.01 (17)	C19—C20—N3—C16	0.5 (3)
O10—C15—C16—C17	−179.6 (2)	C21—C20—N3—C16	−179.69 (17)
O9—C15—C16—C17	−0.4 (3)	C17—C16—N3—C20	1.1 (3)
N3—C16—C17—C18	−1.5 (3)	C15—C16—N3—C20	−178.31 (17)
C15—C16—C17—C18	177.83 (19)	C24—C23—N4—C27	−0.4 (3)
C16—C17—C18—C19	0.4 (3)	C22—C23—N4—C27	−178.80 (17)
C17—C18—C19—C20	1.1 (3)	C26—C27—N4—C23	−0.5 (3)
C18—C19—C20—N3	−1.6 (3)	C28—C27—N4—C23	177.68 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O19	0.95	1.94	2.830 (2)	154
O5—H5AA···O20	0.95	1.67	2.592 (2)	164
O7—H7A···O3	0.95	1.51	2.455 (2)	177
O7—H7A···O4	0.95	2.57	3.119 (2)	117
O9—H9A···O22	0.95	1.64	2.588 (2)	172
O11—H11A···O13i	0.95	1.50	2.445 (2)	177
O11—H11A···O14i	0.95	2.61	3.181 (2)	119
O16—H16A···O24	0.95	1.60	2.551 (2)	174
O17—H17A···O15	0.95	1.90	2.838 (2)	167
O17—H17A···N4	0.95	2.43	2.956 (2)	115
O17—H17B···O14	0.95	1.87	2.821 (2)	175
O18—H18B···O1	0.95	1.89	2.815 (2)	164
O18—H18A···O17ii	0.95	1.88	2.809 (2)	166
O19—H19B···N1	0.95	2.22	3.092 (2)	152
O19—H19A···O13i	0.95	2.34	3.174 (2)	146
O20—H20B···O12iii	0.95	1.87	2.793 (2)	164
O20—H20A···O22	0.95	1.95	2.875 (3)	165
O21—H21B···O10	0.95	1.89	2.834 (2)	170
O21—H21A···O19iii	0.95	1.85	2.784 (2)	166
O22—H22A···O21	0.95	1.88	2.818 (2)	168
O22—H22B···O17iv	0.95	1.81	2.742 (2)	167
O23—H23B···O6	0.95	1.85	2.749 (2)	157
O23—H23A···O12iii	0.95	1.96	2.899 (2)	170
O24—H24B···O18v	0.95	1.79	2.706 (2)	161
O24—H24A···O12vi	0.95	1.86	2.761 (2)	157
N5—H5A···N2	0.95	2.40	3.342 (3)	171
N5—H5A···O6	0.95	2.61	3.227 (2)	123
N5—H5B···O4	0.95	1.95	2.879 (2)	166
N5—H5C···O23vii	0.95	2.06	2.991 (3)	166
N6—H6A···O14i	0.95	2.01	2.938 (2)	164
N6—H6B···O21viii	0.95	1.90	2.849 (2)	174
N6—H6C···N3	0.95	2.17	3.070 (2)	158
C5—H5···O18iii	0.95	2.56	3.429 (3)	153
C10—H10···O1ix	0.95	2.50	3.335 (3)	147
C11—H11···O18ix	0.95	2.52	3.427 (3)	159
C19—H19···O15x	0.95	2.46	3.266 (3)	143
C25—H25···O24xi	0.95	2.56	3.485 (3)	165
C26—H26···O16xi	0.95	2.56	3.287 (3)	134
C31—H31A···N2	0.99	2.52	3.391 (3)	146
C31—H31B···O10	0.99	2.54	3.175 (3)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O19	0.95	1.94	2.830 (2)	154
O5—H5AA⋯O20	0.95	1.67	2.592 (2)	164
O7—H7A⋯O3	0.95	1.51	2.455 (2)	177
O7—H7A⋯O4	0.95	2.57	3.119 (2)	117
O9—H9A⋯O22	0.95	1.64	2.588 (2)	172
O11—H11A⋯O13i	0.95	1.50	2.445 (2)	177
O11—H11A⋯O14i	0.95	2.61	3.181 (2)	119
O16—H16A⋯O24	0.95	1.60	2.551 (2)	174
O17—H17A⋯O15	0.95	1.90	2.838 (2)	167
O17—H17A⋯N4	0.95	2.43	2.956 (2)	115
O17—H17B⋯O14	0.95	1.87	2.821 (2)	175
O18—H18B⋯O1	0.95	1.89	2.815 (2)	164
O18—H18A⋯O17ii	0.95	1.88	2.809 (2)	166
O19—H19B⋯N1	0.95	2.22	3.092 (2)	152
O19—H19A⋯O13i	0.95	2.34	3.174 (2)	146
O20—H20B⋯O12iii	0.95	1.87	2.793 (2)	164
O20—H20A⋯O22	0.95	1.95	2.875 (3)	165
O21—H21B⋯O10	0.95	1.89	2.834 (2)	170
O21—H21A⋯O19iii	0.95	1.85	2.784 (2)	166
O22—H22A⋯O21	0.95	1.88	2.818 (2)	168
O22—H22B⋯O17iv	0.95	1.81	2.742 (2)	167
O23—H23B⋯O6	0.95	1.85	2.749 (2)	157
O23—H23A⋯O12iii	0.95	1.96	2.899 (2)	170
O24—H24B⋯O18v	0.95	1.79	2.706 (2)	161
O24—H24A⋯O12vi	0.95	1.86	2.761 (2)	157
N5—H5A⋯N2	0.95	2.40	3.342 (3)	171
N5—H5A⋯O6	0.95	2.61	3.227 (2)	123
N5—H5B⋯O4	0.95	1.95	2.879 (2)	166
N5—H5C⋯O23vii	0.95	2.06	2.991 (3)	166
N6—H6A⋯O14i	0.95	2.01	2.938 (2)	164
N6—H6B⋯O21viii	0.95	1.90	2.849 (2)	174
N6—H6C⋯N3	0.95	2.17	3.070 (2)	158
C5—H5⋯O18iii	0.95	2.56	3.429 (3)	153
C10—H10⋯O1ix	0.95	2.50	3.335 (3)	147
C11—H11⋯O18ix	0.95	2.52	3.427 (3)	159
C19—H19⋯O15x	0.95	2.46	3.266 (3)	143
C25—H25⋯O24xi	0.95	2.56	3.485 (3)	165
C26—H26⋯O16xi	0.95	2.56	3.287 (3)	134
C31—H31A⋯N2	0.99	2.52	3.391 (3)	146
C31—H31B⋯O10	0.99	2.54	3.175 (3)	122

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) .