Supra-molecular architecture in a co-crystal of the N(7)-H tautomeric form of N (6)-benzoyl-adenine with adipic acid (1/0.5).

The asymmetric unit of the title co-crystal, C12H9N5O·0.5C6H10O4, consists of one mol-ecule of N (6)-benzoyl-adenine (BA) and one half-mol-ecule of adipic acid (AA), the other half being generated by inversion symmetry. The dihedral angle between the adenine and phenyl ring planes is 26.71 (7)°. The N (6)-benzoyl-adenine mol-ecule crystallizes in the N(7)-H tautomeric form with three non-protonated N atoms. This tautomeric form is stabilized by intra-molecular N-H⋯O hydrogen bonding between the carbonyl (C=O) group and the N(7)-H hydrogen atom on the Hoogsteen face of the purine ring, forming an S(7) ring motif. The two carboxyl groups of adipic acid inter-act with the Watson-Crick face of the BA mol-ecules through O-H⋯N and N-H⋯O hydrogen bonds, generating an R 2 (2)(8) ring motif. The latter units are linked by N-H⋯N hydrogen bonds, forming layers parallel to (10-5). A weak C-H⋯O hydrogen bond is also present, linking adipic acid mol-ecules in neighbouring layers, enclosing R (2) 2(10) ring motifs and forming a three-dimensional structure. C=O⋯π and C-H⋯π inter-actions are also present in the structure.

Chemical context

Adipic acid has been widely used in controlled-release formulations of many drugs and food additives (Roew et al., 2009 ▸). N 6-benzoyl­adenine is a synthetic analogue of a group of naturally occurring N 6-substituted adenines having plant-growth-stimulating activity (cytokinins) (McHugh & Erxleben, 2011 ▸). A number of co-crystals involving adipic acid have been reported in the literature (Lemmerer et al., 2012 ▸; Lin et al., 2012 ▸; Matulková et al., 2014 ▸; Thanigaimani et al., 2012 ▸). This paper deals with a co-crystal formed between N 6-benzoyl­adenine and adipic acid (I).

Structural commentary

The asymmetric unit of (I) contains one N 6-benzoyl­­adenine (BA) mol­ecule and a half-mol­ecule of adipic acid (AA). As evident from the angles at N7 [C8—N7—C5 = 106.82 (11)°] and N9 [C8—N9—C4 = 103.90 (11)°], the N 6-benzoyl­adenine moiety exists in the N(7)—H tautomeric form with non-protonated N1, N3 and N9 atoms. In addition, the C8—N7 bond [1.3415 (17) Å)] is longer than C8—N9 [1.3175 (19) Å]. These values are similar to those in neutral N 6-benzoyl­adenine (Raghunathan & Pattabhi, 1981 ▸). An intra­molecular hydrogen bond in the Hoogsteen face between N7—H7 and the benzoyl oxygen atom O1 forms a S(7) ring motif. The dihedral angle between the adenine and phenyl ring plane is 26.71 (7)° and the C6—N6—C10—C11 torsion angle is 173.08 (14)°. The bond lengths and bond angles of AA are in the range of values reported (Srinivasa Gopalan et al., 1999 ▸; 2000 ▸). The values for the torsion angles C18—C19—C19a—C18a [180.00 (13)°] and C17—C18—C19—C19a [–176.09 (14)°] indicate that the carbon chain of AA is fully extended.

In the crystal structures of N 6-benzyl­adenine (Raghunathan & Pattabhi, 1981 ▸), N 6-furfuryladenine (Soriano-Garcia & Parthasarathy, 1977 ▸), N 6-benzyl­adenine hydro­bromide (Umadevi et al., 2001 ▸), N 6-furfuryladenine hydro­chloride (Stanley et al., 2003 ▸), N 6-benzyl­adeninium p-toluene­sulfonate (Tamilselvi & Mu­thiah, 2011 ▸), N 6-benzyl­adeninium nitrate, N 6-benzyl­adeninium 3-hy­droxy picolinate (Nirmalram et al., 2011 ▸) and the hydrate adduct of N 6-benzyl­adenine-5-sulfo­sali­cylic acid (Xia et al., 2010 ▸), the N 6-substituent is distal to the N7 position, whereas in the crystal structures of N 6-benzoyl­adenine (Raghunathan et al., 1983 ▸), N 6-benzoyl­adenine-3-hy­droxy­pyridinium-2-carboxyl­ate (1:1), N 6-benz­oyl­adenine-dl-tartaric acid (1:1) (Karthikeyan et al., 2015 ▸), N 6-benzoyl­adeninium nitrate (Karthikeyan et al., 2015 ▸) and the title compound, the N 6-substituent is distal to N1 and syn to adenine nitrogen atom N7. In the present structure, this may be attributed to the presence of the N7—H7⋯O1A intra­molecular hydrogen bond (Table 1 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C11–C16 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1i	0.82	1.92	2.7327 (19)	175
N6—H6⋯O3A ii	0.86	2.09	2.904 (11)	157
N7—H7⋯O1A	0.86	2.04	2.616 (16)	124
N7—H7⋯N9iii	0.86	2.17	2.9271 (17)	146
C19—H19B⋯O3A iv	0.97	2.54	3.481 (11)	164
C2—H2⋯Cg3v	0.93	2.94	3.4611 (16)	117

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Supra­molecular features

Each of the two carboxyl groups of adipic acid inter­acts with the Watson–Crick face (atoms N1 and N6) of the corres­ponding BA through O—H⋯N and N—H⋯O hydrogen bonds, generating an (8) ring motif (Fig. 1 ▸). Thus each adipic acid mol­ecule bridges two BA mol­ecules. The latter units are linked by N7—H7⋯N9iii hydrogen bonds (Table 1 ▸) forming layers parallel to plane (10). A weak C—H⋯O hydrogen bond (C19—H19B⋯O3A iv) is also present (Table 1 ▸ and Fig. 2 ▸), linking adipic acid mol­ecules in neighbouring layers, enclosing (10) ring motifs and forming a three-dimensional structure. Thus atom O3A functions as a bifurcated hydrogen-bond acceptor whereas N7—H is a bifurcated hydrogen-bond donor.

Figure 1

A Mercury (Macrae et al., 2008 ▸) view of the title compound (I), showing the atom-numbering scheme. Disordered oxygen atoms are omitted for clarity. H atoms not involved in hydrogen bonding have been omitted for clarity. Unlabelled atoms are related by the symmetry operation 1 − x, 1 − y, −z.

Figure 2

A view of the sheet-like supra­molecular architecture generated via C19—H19B⋯O3A hydrogen bonds (black dotted lines). Phenyl rings are indicated as yellow balls. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes are as given in Table 1 ▸.

The crystal structure also features C2—H2⋯π inter­actions between purine and phenyl rings (Fig. 3 ▸ a) and C10=O1B⋯π inter­actions between the carbonyl oxygen O1B and the centroid of the (N1/C2/N3/C4/C5/C6) pyrimidine ring [O⋯centroid = 3.407 (10) Å; symmetry code: 1 − x,  + y,  − z; Fig. 3 ▸ b] (Safaei-Ghomi et al., 2009 ▸).

Figure 3

(a) A view of the C—H⋯π inter­action in compound (I). Cg3 is the centroid of the phenyl ring of the BA mol­ecule (symmetry code: x, −1 + y, z). (b) A view of the C=O⋯π inter­action. Cg2 is the centroid of the pyrimidine ring of the BA mol­ecule (symmetry code: 1 − x,  + y,  − z).

Database survey

The neutral mol­ecule N 6-benzoyl­adenine was reported by Raghunathan & Pattabhi (1981 ▸). Co-crystals have also been reported: N 6-benzoyl­adenine-3-hy­droxy­pyridinium-2-carb­oxyl­ate (1:1), N 6-benzoyl­adenine-dl-tartaric acid (1:1) (Karthikeyan et al., 2015 ▸) and N 6-benzoyl­adeninium nitrate (Karthikeyan et al., 2016 ▸). Similarly, co-crystals of adipic acid with pyrimidine derivatives [adenine (Byres et al., 2009 ▸), caffeine (Bučar et al., 2007 ▸), cytosine (Das & Baruah, 2011 ▸), bis-pyrimidine-amine-linked xylene spacer (Goswami et al., 2010 ▸)] have also been reported.

Synthesis and crystallization

The title co-crystal was synthesized by mixing a DMF solution of N 6-benzoyl­adenine (30 mg) and adipic acid (19 mg) (total volume = 10 mL). The mixture was warmed in a water bath for 20 min. After cooling to room temperature, colourless plate-like crystals were collected from the mother liquor after a few days (m.p. 438 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Atoms O1 and O3 are disordered over two positions with refined occupancy ratios of 0.57 (3):0.43 (3) and 0.63 (3):0.37 (3), respectively. Hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 (aromatic) or 0.97 (methyl­ene), N—H = 0.86, and O—H = 0.82 Å, and with U iso(H) = kU eq(C,N,O), where k = 1.5 for hy­droxy and 1.2 for all other H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C12H9N5O·0.5C6H10O4
M r	312.31
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	293
a, b, c (Å)	6.1776 (4), 9.2296 (4), 25.7480 (15)
β (°)	97.117 (6)
V (Å3)	1456.76 (14)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.10
Crystal size (mm)	0.60 × 0.60 × 0.40
Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 ▸)
T min, T max	0.756, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9480, 3325, 2755
R int	0.020
(sin θ/λ)max (Å−1)	0.649
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.122, 1.05
No. of reflections	3325
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.25, −0.22

Computer programs: CrysAlis PRO (Agilent, 2013 ▸), SUPERFLIP (Palatinus & Chapuis, 2007 ▸), SHELXL2014 (Sheldrick, 2015 ▸), PLATON (Spek, 2009 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016007581/hg5474sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016007581/hg5474Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016007581/hg5474Isup3.cml

CCDC reference: 1478504

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

C12H9N5O·0.5C6H10O4	F(000) = 652
Mr = 312.31	Dx = 1.424 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1776 (4) Å	Cell parameters from 4139 reflections
b = 9.2296 (4) Å	θ = 3.3–30.1°
c = 25.7480 (15) Å	µ = 0.10 mm−1
β = 97.117 (6)°	T = 293 K
V = 1456.76 (14) Å3	Prism, colorless
Z = 4	0.60 × 0.60 × 0.40 mm

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3325 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2755 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.020
Detector resolution: 10.4933 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→11
Tmin = 0.756, Tmax = 1.000	l = −33→31
9480 measured reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.0541P)2 + 0.3295P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.122	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.25 e Å−3
3325 reflections	Δρmin = −0.22 e Å−3
230 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0130 (18)

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)
O1A	0.7104 (15)	0.6427 (14)	0.1669 (8)	0.094 (4)	0.57 (3)
O1B	0.6582 (19)	0.6621 (6)	0.1877 (4)	0.054 (2)	0.43 (3)
N1	0.3308 (2)	0.27081 (12)	0.16588 (5)	0.0415 (3)
N3	0.5648 (2)	0.09828 (13)	0.21438 (5)	0.0477 (3)
N6	0.39990 (19)	0.51100 (12)	0.15270 (5)	0.0391 (3)
H6	0.2702	0.5109	0.1361	0.047*
N7	0.85319 (19)	0.42515 (12)	0.22672 (5)	0.0402 (3)
H7	0.8790	0.5157	0.2226	0.048*
N9	0.9054 (2)	0.19667 (13)	0.25397 (5)	0.0470 (3)
C2	0.3848 (3)	0.13827 (15)	0.18545 (6)	0.0468 (4)
H2	0.2811	0.0660	0.1774	0.056*
C4	0.7054 (2)	0.20808 (14)	0.22480 (5)	0.0389 (3)
C5	0.6683 (2)	0.35149 (13)	0.20707 (5)	0.0352 (3)
C6	0.4717 (2)	0.38085 (13)	0.17619 (5)	0.0347 (3)
C8	0.9855 (3)	0.32896 (15)	0.25376 (6)	0.0451 (4)
H8	1.1219	0.3535	0.2709	0.054*
C10	0.5100 (3)	0.63803 (16)	0.15283 (7)	0.0493 (4)
C11	0.4104 (2)	0.75951 (14)	0.11985 (6)	0.0412 (3)
C12	0.5550 (3)	0.86137 (17)	0.10534 (7)	0.0544 (4)
H12	0.7028	0.8527	0.1173	0.065*
C13	0.4831 (3)	0.97575 (19)	0.07333 (8)	0.0627 (5)
H13	0.5825	1.0423	0.0630	0.075*
C14	0.2660 (3)	0.99109 (19)	0.05686 (7)	0.0628 (5)
H14	0.2168	1.0681	0.0353	0.075*
C15	0.1208 (3)	0.8931 (2)	0.07213 (8)	0.0655 (5)
H15	−0.0274	0.9047	0.0611	0.079*
C16	0.1909 (3)	0.77622 (18)	0.10389 (7)	0.0538 (4)
H16	0.0908	0.7102	0.1142	0.065*
O2	0.9399 (2)	0.25032 (13)	0.10377 (6)	0.0694 (4)
H2A	1.0565	0.2620	0.1223	0.104*
O3A	1.0228 (15)	0.4644 (11)	0.0753 (5)	0.072 (2)	0.63 (3)
O3B	0.951 (3)	0.4828 (6)	0.0985 (9)	0.070 (5)	0.37 (3)
C17	0.8870 (3)	0.36824 (17)	0.07825 (6)	0.0494 (4)
C18	0.6762 (3)	0.36172 (16)	0.04285 (6)	0.0491 (4)
H18A	0.5619	0.3312	0.0631	0.059*
H18B	0.6882	0.2888	0.0162	0.059*
C19	0.6100 (3)	0.50345 (16)	0.01626 (6)	0.0494 (4)
H19A	0.6069	0.5781	0.0427	0.059*
H19B	0.7188	0.5308	−0.0060	0.059*

	U11	U22	U33	U12	U13	U23
O1A	0.047 (3)	0.085 (4)	0.138 (8)	−0.023 (2)	−0.033 (4)	0.071 (4)
O1B	0.052 (3)	0.028 (2)	0.073 (4)	−0.0097 (15)	−0.024 (2)	0.011 (2)
N1	0.0423 (6)	0.0333 (6)	0.0467 (7)	−0.0045 (5)	−0.0037 (5)	0.0046 (5)
N3	0.0559 (8)	0.0299 (6)	0.0536 (7)	−0.0047 (5)	−0.0074 (6)	0.0067 (5)
N6	0.0365 (6)	0.0308 (6)	0.0470 (6)	0.0002 (4)	−0.0071 (5)	0.0062 (5)
N7	0.0399 (6)	0.0269 (5)	0.0503 (7)	0.0015 (5)	−0.0079 (5)	0.0000 (5)
N9	0.0495 (7)	0.0310 (6)	0.0561 (7)	0.0051 (5)	−0.0108 (6)	0.0036 (5)
C2	0.0519 (9)	0.0325 (7)	0.0528 (8)	−0.0091 (6)	−0.0060 (7)	0.0062 (6)
C4	0.0444 (8)	0.0292 (6)	0.0412 (7)	0.0023 (5)	−0.0023 (6)	0.0017 (5)
C5	0.0381 (7)	0.0280 (6)	0.0383 (7)	0.0015 (5)	−0.0002 (6)	−0.0008 (5)
C6	0.0380 (7)	0.0290 (6)	0.0362 (6)	0.0006 (5)	0.0007 (6)	0.0015 (5)
C8	0.0423 (8)	0.0341 (7)	0.0550 (8)	0.0045 (6)	−0.0101 (7)	−0.0007 (6)
C10	0.0461 (8)	0.0357 (7)	0.0611 (9)	−0.0047 (6)	−0.0131 (7)	0.0124 (7)
C11	0.0472 (8)	0.0303 (6)	0.0441 (7)	0.0017 (6)	−0.0019 (6)	0.0044 (5)
C12	0.0510 (9)	0.0398 (8)	0.0710 (11)	−0.0011 (7)	0.0017 (8)	0.0131 (7)
C13	0.0716 (12)	0.0437 (9)	0.0746 (12)	0.0012 (8)	0.0155 (10)	0.0202 (8)
C14	0.0809 (13)	0.0479 (9)	0.0590 (10)	0.0163 (9)	0.0061 (9)	0.0205 (8)
C15	0.0542 (10)	0.0617 (11)	0.0771 (12)	0.0142 (9)	−0.0059 (9)	0.0204 (9)
C16	0.0464 (9)	0.0455 (8)	0.0672 (10)	0.0021 (7)	−0.0019 (8)	0.0146 (7)
O2	0.0568 (7)	0.0461 (6)	0.0963 (10)	−0.0026 (5)	−0.0264 (7)	0.0128 (6)
O3A	0.061 (3)	0.072 (2)	0.076 (4)	−0.026 (2)	−0.024 (3)	0.027 (2)
O3B	0.069 (5)	0.037 (2)	0.092 (8)	−0.006 (2)	−0.035 (5)	0.002 (2)
C17	0.0477 (9)	0.0428 (8)	0.0544 (9)	−0.0017 (7)	−0.0073 (7)	0.0029 (7)
C18	0.0472 (8)	0.0408 (8)	0.0558 (9)	−0.0017 (6)	−0.0071 (7)	−0.0016 (7)
C19	0.0481 (9)	0.0411 (8)	0.0554 (9)	−0.0023 (6)	−0.0070 (7)	0.0023 (7)

O1A—C10	1.247 (6)	C12—C13	1.378 (2)
O1B—C10	1.221 (6)	C12—H12	0.9300
N1—C6	1.3424 (17)	C13—C14	1.363 (3)
N1—C2	1.3489 (17)	C13—H13	0.9300
N3—C2	1.3125 (19)	C14—C15	1.365 (3)
N3—C4	1.3401 (18)	C14—H14	0.9300
N6—C10	1.3551 (18)	C15—C16	1.390 (2)
N6—C6	1.3926 (16)	C15—H15	0.9300
N6—H6	0.8600	C16—H16	0.9300
N7—C8	1.3415 (17)	O2—C17	1.2923 (18)
N7—C5	1.3712 (17)	O2—H2A	0.8200
N7—H7	0.8601	O3A—C17	1.230 (4)
N9—C8	1.3175 (19)	O3B—C17	1.223 (6)
N9—C4	1.3684 (18)	C17—C18	1.495 (2)
C2—H2	0.9300	C18—C19	1.509 (2)
C4—C5	1.4096 (17)	C18—H18A	0.9700
C5—C6	1.3931 (18)	C18—H18B	0.9700
C8—H8	0.9300	C19—C19i	1.506 (3)
C10—C11	1.4924 (18)	C19—H19A	0.9700
C11—C16	1.376 (2)	C19—H19B	0.9700
C11—C12	1.380 (2)
C6—N1—C2	119.23 (11)	C13—C12—H12	119.6
C2—N3—C4	112.56 (12)	C11—C12—H12	119.6
C10—N6—C6	127.77 (11)	C14—C13—C12	119.81 (17)
C10—N6—H6	116.0	C14—C13—H13	120.1
C6—N6—H6	116.2	C12—C13—H13	120.1
C8—N7—C5	106.82 (11)	C13—C14—C15	119.86 (15)
C8—N7—H7	126.7	C13—C14—H14	120.1
C5—N7—H7	126.5	C15—C14—H14	120.1
C8—N9—C4	103.90 (11)	C14—C15—C16	121.01 (16)
N3—C2—N1	128.29 (13)	C14—C15—H15	119.5
N3—C2—H2	115.9	C16—C15—H15	119.5
N1—C2—H2	115.9	C11—C16—C15	119.12 (16)
N3—C4—N9	124.79 (12)	C11—C16—H16	120.4
N3—C4—C5	124.74 (12)	C15—C16—H16	120.4
N9—C4—C5	110.47 (12)	C17—O2—H2A	109.5
N7—C5—C6	137.86 (12)	O3B—C17—O2	117.6 (6)
N7—C5—C4	104.56 (11)	O3A—C17—O2	120.5 (3)
C6—C5—C4	117.57 (12)	O3B—C17—C18	120.5 (3)
N1—C6—N6	113.77 (11)	O3A—C17—C18	122.7 (2)
N1—C6—C5	117.61 (11)	O2—C17—C18	114.98 (13)
N6—C6—C5	128.60 (12)	C17—C18—C19	114.09 (13)
N9—C8—N7	114.25 (12)	C17—C18—H18A	108.7
N9—C8—H8	122.9	C19—C18—H18A	108.7
N7—C8—H8	122.9	C17—C18—H18B	108.7
O1B—C10—N6	119.4 (5)	C19—C18—H18B	108.7
O1A—C10—N6	120.7 (5)	H18A—C18—H18B	107.6
O1B—C10—C11	120.0 (3)	C19i—C19—C18	112.99 (16)
O1A—C10—C11	117.6 (3)	C19i—C19—H19A	109.0
N6—C10—C11	118.50 (12)	C18—C19—H19A	109.0
C16—C11—C12	119.33 (13)	C19i—C19—H19B	109.0
C16—C11—C10	125.15 (14)	C18—C19—H19B	109.0
C12—C11—C10	115.52 (13)	H19A—C19—H19B	107.8
C13—C12—C11	120.82 (16)
C4—N3—C2—N1	0.6 (3)	C6—N6—C10—O1B	−23.5 (8)
C6—N1—C2—N3	−0.5 (3)	C6—N6—C10—O1A	13.7 (14)
C2—N3—C4—N9	−179.85 (15)	C6—N6—C10—C11	173.08 (14)
C2—N3—C4—C5	−0.1 (2)	O1B—C10—C11—C16	−138.8 (8)
C8—N9—C4—N3	179.82 (16)	O1A—C10—C11—C16	−175.5 (14)
C8—N9—C4—C5	0.06 (18)	N6—C10—C11—C16	24.5 (3)
C8—N7—C5—C6	−179.15 (18)	O1B—C10—C11—C12	40.7 (9)
C8—N7—C5—C4	−0.01 (16)	O1A—C10—C11—C12	4.0 (14)
N3—C4—C5—N7	−179.79 (15)	N6—C10—C11—C12	−156.02 (16)
N9—C4—C5—N7	−0.03 (17)	C16—C11—C12—C13	−2.8 (3)
N3—C4—C5—C6	−0.4 (2)	C10—C11—C12—C13	177.68 (17)
N9—C4—C5—C6	179.31 (13)	C11—C12—C13—C14	1.8 (3)
C2—N1—C6—N6	178.40 (13)	C12—C13—C14—C15	0.0 (3)
C2—N1—C6—C5	−0.2 (2)	C13—C14—C15—C16	−0.7 (3)
C10—N6—C6—N1	−175.34 (15)	C12—C11—C16—C15	2.0 (3)
C10—N6—C6—C5	3.0 (3)	C10—C11—C16—C15	−178.52 (16)
N7—C5—C6—N1	179.62 (16)	C14—C15—C16—C11	−0.3 (3)
C4—C5—C6—N1	0.6 (2)	O3B—C17—C18—C19	26.0 (16)
N7—C5—C6—N6	1.3 (3)	O3A—C17—C18—C19	−19.2 (10)
C4—C5—C6—N6	−177.74 (14)	O2—C17—C18—C19	176.05 (16)
C4—N9—C8—N7	−0.08 (19)	C17—C18—C19—C19i	−176.11 (18)
C5—N7—C8—N9	0.06 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ii	0.82	1.92	2.7327 (19)	175
N6—H6···O3Aiii	0.86	2.09	2.904 (11)	157
N7—H7···O1A	0.86	2.04	2.616 (16)	124
N7—H7···N9iv	0.86	2.17	2.9271 (17)	146
C19—H19B···O3Av	0.97	2.54	3.481 (11)	164
C2—H2···Cg3vi	0.93	2.94	3.4611 (16)	117