2-Chloro-6-(2-fur­yl)-9-(4-methoxy­benz­yl)-9H-purine

The title compound, C₁₇H₁₃ClN₄O₂, displays profound and selective activity against Mycobacterium tuberculosis. In the crystal structure, there are two independent mol­ecules in the asymmetric unit. Inter­molecular hydrogen bonding between a CH group of the purine ring and the O atom of the furan ring, and also π–π stacking in another direction, builds the three-dimensional network.

S1. Comment

Tuberculosis (TB) claims ca 2 million lives every year, and infection with multidrug-resistant strains is an increasing problem, but nevertheless, no new drugs have been launched to treat TB for approximately 40 years (Dye, 2006; Tripathi et al., 2005). We have previously reported that certain 6,9-disubstituted purines are potent inhibitors of Mycobacterium tuberculosis (Mtb) in vitro. Our antimycobacterial purines display several properties which make them highly interesting as potential drugs against tuberculosis. These properties include high selectivity towards Mtb compared with other micro-organisms, activity against several drug-resistant strains of Mtb, generally low toxicity towards mammalian cells, and an ability to affect Mtb inside macrophages (Bakkestuen et al., 2000, 2005; Gundersen et al., 2002; Braendvang & Gundersen 2005). Our most active 6,9-disubstituted purine identified to date is 2-chloro-6-(2-furanyl)-9-[(4-methoxyphenyl)methyl]-9H-purine, which displays an MIC against Mtb of 0.39 µg ml^-1 (Bakkestuen et al., 2005) (MIC is defined as the minimum concentration of compound required to give 90% inhibition of bacterial growth. MIC for the currently used drug, rifampicin, is 0.25 µg ml^-1). The present work reports the X-ray crystallographic study of the potent antimycobacterial title compound, (I).

Compound (I) crystallizes as two crystallographically independent molecules, A and B, and their molecular geometries are illustrated in Fig. 1. Selected bond lengths and angles are listed in Table 1. The conformations of molecules A and B are slightly different, as revealed by a molecular fit using the quaternion transformation method (Mackay, 1984). The overlay of all atoms in molecule A with those of molecule B, except the H atoms, gives r.m.s. bond and angle fits of 0.0034 Å and 0.32°, respectively. The differences are mainly in the orientations of the methoxy and benzyl groups (Table 1). The purine ring system (C1–N9) is almost perfectly planar; the displacements of the atoms from their mean planes do not exceed 0.007 (1) Å in molecule A and 0.006 (1) Å in molecule B.

The conformations of molecules A and B in (I) very much resemble that in the previously reported crystal structure of the related antimycobacterial 9-benzyl-6-(2-thienyl)-9H-purine, (II) (Mazumdar et al., 2001). The bond lengths from the purine ring atoms to the substituents are compared in Table 1. The 6-aryl group in the title compound is nearly coplanar with the purine ring. The angles between the mean plane of the purine ring system and that of the furyl group are 2.31 (6)° in molecule A and 2.79 (5)° in molecule B, compared with 6.39 (4)° in compound (II). This coplanarity has also been reported for other 6-hetroarylpurines (Mazumdar et al., 2001; Zhong et al., 2006). The positions of the benzyl groups are slightly different in compounds (I) and (II), as seen from the torsion angles C4—N9—C10—C11 and N9—C10—C11—C12 (Table 1). The benzene ring plane is inclined at an angle of 73.64 (5)° to the purine ring plane in molecule A and at 77.80 (4)° in molecule B. In compound (II), the angle between the corresponding planes is 64.03 (5)°.

Fig. 2 shows the crystal packing of molecules A and B in the unit cell. The molecular packing appears to be stabilized by segregation of alternate hydrophobic and hydrophilic zones. In the hydrophobic region, the conformation adopted by the benzene rings allows for C—H···π interactions, viz. C19A—H19A···Cg1B and C19B—H19B···Cg1A within the asymmetric unit (Fig. 3 and Table 2) (Cg1B and Cg1A are the centroids of the C11–C16 benzene rings in molecules B and A, respectively).

In the hydrophilic region, the conformation allows for π–π interactions between the heterocycles in the asymmetric unit and these occur between the furyl and pyrimidine rings (Fig. 3). The average interplanar distance between furyl ring C17A/O18A/C19A–C21A (molecule A) and pyrimidine ring N1B/C2B/N3B/C4B–C6B (molecule B) is 3.379 Å and the centroids of the two rings are slipped by 17.2° relative to their ring normals. The corresponding interaction between furyl ring C17B/C18B/C19B–C21B and pyrimidine ring N1A/C2A/N3A/C4A–C6A results in a distance of 3.332 Å with the two ring centroids slipped by 18.6° relative to their ring normals. The Cg2A···Cg3B and Cg2B···Cg3A distances are 3.5357 (7) and 3.5160 (7) Å, respectively (Cg2 and Cg3 are the centroids of the furyl rings and pyrimidine rings, respectively), while the mean angle between the purine ring planes is 2.04 (3)°.

The crystal packing (Fig. 2) gives further π–π interactions along the c axis between the imidazole ring (C4A/C5A/N7A/C8A/N9A) in molecule A and the pyrimidine ring (N1B/C2B/N3B/C4B–C6B) in molecule Bⁱⁱⁱ [symmetry code: (iii) 3/2 - x, y, -1/2 + z]. Moving down the c axis, the ring centroid-to-centroid distance Cg4A···Cg3Bⁱⁱⁱ is 3.4516 (6) Å (Cg4A is the centroid of the imidazole ring C4A/C5A/N7A/C8A/N9A). In this interaction, the average interplanar distance is 3.28 Å and the centroids of the two rings are slipped by 18.1° relative to their ring normals, while the mean angle between the purine ring planes is 0.58 (3)°.

Finally, moving along the a axis, the two molecules A and B separately build up their own infinite chains via C8A—H8A···O18Aⁱ and C8B—H8B···O18Bⁱⁱ hydrogen bonds [Table 2 and Fig. 3; symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z]. These values are in agreement with C—H···O hydrogen bonding reported for the C-8 H atom in other purine ring systems (Trávníček & Popa, 2007).

Related literature

For related literature, see: Bakkestuen et al. (2000, 2005); Braendvang & Gundersen (2005); Dye (2006); Gundersen et al. (2002); Mackay (1984); Mazumdar et al. (2001); Trávníček & Popa (2007); Tripathi et al. (2005); Zhong et al. (2006).

S2. Experimental

The title compound was synthesized as described by Bakkestuen et al. (2005). Crystals of (I) suitable for X-ray diffraction studies were obtained by dissolving the compound (50 mg) in deuterated dichloromethane (0.6 ml) by heating, followed by slow evaporation of the solvent in a refrigerator.

S3. Refinement

Friedel pairs were not merged and the absolute structure has been determined reliably. H atoms were positioned geometrically and allowed to ride and rotate (for the CH₃ group) on their carrier atoms, with C—H = 0.95 (aromatic C—H), 0.99 (CH₂) or 0.98 Å (CH₃), and with U_iso(H) = 1.2U_eq(C) for CH₂ and aromatic C—H, or 1.5U_eq(C) for CH₃.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Version 1.08; Farrugia, 1997) and POV-RAY for Windows (Cason, 2004); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).

Figures

	Fig. 1. The two molecules, A and B, in the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. The packing of molecules A and B of (I) (with unit cell), showing the stacking of alternate molecules A and B, viewed down the a axis.
	Fig. 3. A partial packing view, showing the different intermolecular interactions (dashed lines) between molecules A and B in (I). Dashed lines labelled π–π are the intermolecular π–π interactions between the furan and pyrimidine rings in molecules A and B in the asymmetric unit. Dashed lines labelled with π are the C—H···π interactions between the C19—H19 group of one molecule and the benzyl ring (C11–C16) of the other molecule in the asymmetric unit. Dashed lines labelled with an asterisk (*) or a double astersisk (**) are the C8A—H8A···O18A^i and C8B—H8B···O18B^ii interactions, respectively. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity. [Symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z; (iv) x, y, z]. [Renumbered to avoid conflicting definitions - please double check]

2-Chloro-6-(2-furyl)-9-(4-methoxybenzyl)-9H-purine

Crystal data

C17H13ClN4O2	Dx = 1.477 Mg m^−3
Mr = 340.76	Melting point: 188 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 7767 reflections
a = 8.6963 (4) Å	θ = 2.5–39.7°
b = 24.5966 (11) Å	µ = 0.27 mm^−1
c = 14.3247 (7) Å	T = 105 K
V = 3064.0 (2) Å^3	Plate, colourless
Z = 8	0.4 × 0.3 × 0.02 mm
F(000) = 1408

Data collection

Siemens SMART CCD area-detector diffractometer	12073 reflections with I > 2σ(I)
Sets of exposures each taken over 0.3° ω rotation scans	Rint = 0.039
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	θmax = 40.2°, θmin = 1.7°
Tmin = 0.83, Tmax = 0.995	h = −14→15
49273 measured reflections	k = −44→40
17784 independent reflections	l = −23→25

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0472P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.039	(Δ/σ)max = 0.002
wR(F^2) = 0.088	Δρmax = 0.46 e Å^−3
S = 0.89	Δρmin = −0.30 e Å^−3
17784 reflections	Absolute structure: Flack (1983), with 8178 Friedel pairs
435 parameters	Absolute structure parameter: −0.01 (3)
1 restraint

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C2A	0.59897 (12)	0.84526 (4)	0.52085 (8)	0.01752 (18)
C4A	0.83104 (11)	0.81416 (4)	0.54569 (7)	0.01716 (18)
C8A	1.01781 (12)	0.75989 (5)	0.58759 (8)	0.0250 (2)
H8A	1.1192	0.7471	0.5989	0.03*
C5A	0.77394 (11)	0.76467 (4)	0.57984 (7)	0.01752 (18)
C6A	0.61351 (11)	0.75903 (4)	0.58149 (7)	0.01573 (18)
C17A	0.53788 (12)	0.71070 (4)	0.61642 (8)	0.01779 (18)
C21A	0.59340 (15)	0.66286 (5)	0.65138 (8)	0.0237 (2)
H21A	0.6984	0.6529	0.6576	0.028*
C20A	0.46366 (17)	0.63099 (5)	0.67652 (9)	0.0290 (3)
H20A	0.4646	0.5956	0.7031	0.035*
C19A	0.33829 (15)	0.66115 (5)	0.65499 (9)	0.0285 (3)
H19A	0.2351	0.6497	0.6645	0.034*
C10A	1.10090 (13)	0.85253 (5)	0.52522 (9)	0.0256 (2)
H10A	1.0683	0.8704	0.4665	0.031*
H10B	1.2023	0.8354	0.5142	0.031*
C11A	1.11604 (12)	0.89488 (5)	0.60126 (8)	0.02070 (19)
C12A	1.03108 (14)	0.94304 (5)	0.59850 (9)	0.0280 (2)
H12A	0.9655	0.95	0.5468	0.034*
C13A	1.04119 (15)	0.98076 (5)	0.67015 (10)	0.0297 (3)
H13A	0.983	1.0134	0.6673	0.036*
C14A	1.13697 (12)	0.97078 (5)	0.74650 (9)	0.0230 (2)
C15A	1.22258 (12)	0.92301 (5)	0.75040 (9)	0.0225 (2)
H15A	1.2879	0.916	0.8022	0.027*
C16A	1.21174 (12)	0.88559 (5)	0.67772 (9)	0.0219 (2)
H16A	1.2707	0.8531	0.6803	0.026*
C23A	1.25094 (17)	1.00705 (6)	0.88609 (10)	0.0321 (3)
H23B	1.2512	1.041	0.9219	0.048*
H23C	1.3523	1.0015	0.8578	0.048*
H23A	1.2273	0.9766	0.9278	0.048*
N3A	0.74811 (11)	0.85633 (4)	0.51483 (7)	0.01807 (17)
N9A	0.98807 (10)	0.81022 (4)	0.55052 (7)	0.02054 (18)
N7A	0.89430 (11)	0.73066 (4)	0.60624 (7)	0.02257 (18)
N1A	0.52548 (10)	0.80099 (4)	0.55050 (6)	0.01702 (15)
O18A	0.37981 (9)	0.71026 (3)	0.61765 (6)	0.02229 (16)
O22A	1.13690 (10)	1.01013 (4)	0.81416 (7)	0.0317 (2)
Cl2A	0.47867 (3)	0.897752 (11)	0.48363 (2)	0.02667 (6)
C2B	0.59777 (11)	0.65406 (4)	0.91328 (7)	0.01713 (18)
C4B	0.36619 (11)	0.68669 (4)	0.89193 (7)	0.01730 (18)
C8B	0.18027 (13)	0.74230 (5)	0.85371 (9)	0.0241 (2)
H8B	0.0791	0.7559	0.8444	0.029*
C5B	0.42413 (12)	0.73578 (4)	0.85669 (7)	0.01761 (18)
C6B	0.58461 (11)	0.74013 (4)	0.85200 (7)	0.01574 (17)
C17B	0.66089 (12)	0.78842 (4)	0.81701 (7)	0.01702 (17)
C21B	0.60471 (14)	0.83552 (5)	0.77956 (8)	0.0228 (2)
H21B	0.4996	0.8448	0.771	0.027*
C20B	0.73467 (16)	0.86798 (5)	0.75591 (9)	0.0267 (2)
H20B	0.7335	0.9031	0.7283	0.032*
C19B	0.85975 (14)	0.83884 (5)	0.78059 (9)	0.0263 (2)
H19B	0.9628	0.8508	0.7728	0.032*
C10B	0.09460 (13)	0.64895 (5)	0.91101 (9)	0.0242 (2)
H10D	−0.0084	0.6658	0.9168	0.029*
H10E	0.1204	0.6319	0.9716	0.029*
C11B	0.09010 (12)	0.60563 (5)	0.83611 (8)	0.02013 (19)
C12B	0.18216 (13)	0.55933 (5)	0.84251 (8)	0.0236 (2)
H12B	0.2447	0.554	0.8961	0.028*
C13B	0.18361 (13)	0.52089 (5)	0.77144 (9)	0.0241 (2)
H13B	0.2459	0.4893	0.7768	0.029*
C14B	0.09293 (12)	0.52888 (4)	0.69193 (8)	0.01968 (19)
C15B	−0.00166 (13)	0.57468 (4)	0.68475 (8)	0.02012 (19)
H15B	−0.0645	0.5799	0.6313	0.024*
C16B	−0.00234 (12)	0.61272 (5)	0.75761 (9)	0.0208 (2)
H16B	−0.0668	0.6438	0.7534	0.025*
C23B	0.00844 (15)	0.49465 (6)	0.54469 (10)	0.0294 (3)
H23D	0.0258	0.4639	0.5026	0.044*
H23E	0.0332	0.5286	0.5123	0.044*
H23F	−0.0996	0.4952	0.5641	0.044*
N3B	0.44816 (10)	0.64404 (4)	0.92208 (7)	0.01877 (17)
N9B	0.20869 (10)	0.69148 (4)	0.88961 (7)	0.02083 (18)
N7B	0.30427 (11)	0.77080 (4)	0.83311 (8)	0.02383 (19)
N1B	0.67202 (10)	0.69786 (4)	0.88118 (6)	0.01698 (15)
O18B	0.81862 (9)	0.78974 (3)	0.81841 (6)	0.02123 (15)
O22B	0.10456 (10)	0.48920 (3)	0.62503 (6)	0.02652 (17)
Cl2B	0.71778 (3)	0.601047 (11)	0.94872 (2)	0.02462 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2A	0.0144 (4)	0.0203 (5)	0.0178 (4)	0.0004 (3)	0.0019 (3)	0.0009 (4)
C4A	0.0122 (4)	0.0236 (5)	0.0157 (4)	−0.0009 (3)	0.0008 (3)	−0.0050 (3)
C8A	0.0154 (4)	0.0325 (6)	0.0271 (6)	0.0059 (4)	−0.0031 (4)	−0.0088 (5)
C5A	0.0153 (4)	0.0205 (4)	0.0168 (4)	0.0016 (3)	−0.0011 (4)	−0.0039 (3)
C6A	0.0152 (4)	0.0176 (5)	0.0144 (5)	0.0000 (3)	0.0003 (4)	−0.0023 (3)
C17A	0.0181 (4)	0.0185 (4)	0.0167 (5)	−0.0011 (3)	0.0005 (4)	−0.0016 (3)
C21A	0.0327 (6)	0.0174 (5)	0.0209 (5)	0.0021 (4)	−0.0012 (4)	−0.0004 (4)
C20A	0.0467 (7)	0.0193 (5)	0.0211 (6)	−0.0064 (5)	0.0041 (5)	0.0001 (4)
C19A	0.0342 (6)	0.0246 (6)	0.0269 (6)	−0.0117 (5)	0.0105 (5)	−0.0016 (4)
C10A	0.0148 (4)	0.0387 (6)	0.0234 (5)	−0.0071 (4)	0.0034 (4)	−0.0086 (5)
C11A	0.0133 (4)	0.0283 (5)	0.0205 (5)	−0.0037 (3)	0.0024 (4)	−0.0036 (4)
C12A	0.0215 (5)	0.0344 (6)	0.0283 (6)	0.0010 (4)	−0.0062 (5)	0.0020 (5)
C13A	0.0250 (6)	0.0259 (6)	0.0383 (7)	0.0029 (4)	−0.0031 (5)	−0.0026 (5)
C14A	0.0185 (4)	0.0231 (5)	0.0274 (5)	−0.0051 (4)	0.0031 (4)	−0.0039 (4)
C15A	0.0200 (5)	0.0240 (5)	0.0236 (5)	−0.0025 (4)	−0.0021 (4)	−0.0029 (4)
C16A	0.0176 (5)	0.0241 (5)	0.0239 (5)	0.0009 (4)	−0.0010 (4)	−0.0033 (4)
C23A	0.0318 (6)	0.0353 (7)	0.0292 (7)	−0.0138 (5)	0.0059 (5)	−0.0111 (5)
N3A	0.0153 (4)	0.0212 (4)	0.0178 (4)	−0.0016 (3)	0.0021 (3)	−0.0006 (3)
N9A	0.0120 (3)	0.0279 (5)	0.0217 (4)	−0.0005 (3)	0.0005 (3)	−0.0069 (4)
N7A	0.0179 (4)	0.0254 (5)	0.0244 (5)	0.0058 (3)	−0.0036 (3)	−0.0043 (4)
N1A	0.0141 (4)	0.0200 (4)	0.0170 (4)	−0.0007 (3)	0.0007 (3)	0.0007 (3)
O18A	0.0192 (3)	0.0217 (4)	0.0260 (4)	−0.0036 (3)	0.0047 (3)	0.0008 (3)
O22A	0.0281 (4)	0.0271 (4)	0.0398 (5)	−0.0024 (3)	−0.0005 (4)	−0.0140 (4)
Cl2A	0.01891 (11)	0.02432 (12)	0.03677 (15)	0.00315 (9)	0.00297 (10)	0.01145 (11)
C2B	0.0151 (4)	0.0188 (5)	0.0175 (4)	−0.0012 (3)	−0.0012 (4)	−0.0002 (3)
C4B	0.0125 (4)	0.0232 (5)	0.0161 (4)	−0.0021 (3)	−0.0001 (3)	−0.0039 (4)
C8B	0.0169 (5)	0.0285 (6)	0.0269 (6)	0.0049 (4)	−0.0019 (4)	−0.0047 (5)
C5B	0.0156 (4)	0.0199 (5)	0.0174 (5)	0.0006 (3)	−0.0004 (3)	−0.0034 (3)
C6B	0.0155 (4)	0.0172 (4)	0.0145 (4)	−0.0013 (3)	0.0001 (3)	−0.0023 (3)
C17B	0.0169 (4)	0.0190 (4)	0.0152 (4)	−0.0007 (3)	0.0008 (4)	−0.0016 (3)
C21B	0.0284 (5)	0.0202 (5)	0.0198 (5)	0.0017 (4)	−0.0019 (4)	−0.0013 (4)
C20B	0.0413 (7)	0.0178 (5)	0.0211 (5)	−0.0047 (4)	0.0035 (5)	0.0002 (4)
C19B	0.0295 (6)	0.0256 (6)	0.0238 (6)	−0.0101 (4)	0.0058 (5)	−0.0014 (4)
C10B	0.0160 (4)	0.0351 (6)	0.0216 (5)	−0.0066 (4)	0.0054 (4)	−0.0076 (4)
C11B	0.0143 (4)	0.0264 (5)	0.0197 (5)	−0.0049 (4)	0.0019 (4)	−0.0020 (4)
C12B	0.0183 (4)	0.0318 (6)	0.0207 (5)	−0.0025 (4)	−0.0033 (4)	0.0024 (4)
C13B	0.0211 (5)	0.0233 (5)	0.0279 (6)	0.0031 (4)	−0.0026 (4)	0.0021 (4)
C14B	0.0175 (4)	0.0195 (4)	0.0221 (5)	−0.0014 (3)	0.0014 (4)	−0.0014 (4)
C15B	0.0183 (4)	0.0222 (5)	0.0199 (5)	−0.0004 (3)	−0.0035 (4)	−0.0014 (4)
C16B	0.0160 (4)	0.0225 (5)	0.0239 (5)	0.0002 (3)	−0.0004 (4)	−0.0032 (4)
C23B	0.0278 (6)	0.0334 (6)	0.0269 (6)	0.0043 (5)	−0.0034 (5)	−0.0097 (5)
N3B	0.0152 (4)	0.0235 (4)	0.0176 (4)	−0.0033 (3)	−0.0001 (3)	−0.0013 (3)
N9B	0.0131 (4)	0.0279 (5)	0.0215 (4)	−0.0012 (3)	0.0017 (3)	−0.0062 (4)
N7B	0.0184 (4)	0.0256 (5)	0.0274 (5)	0.0035 (3)	−0.0007 (4)	−0.0035 (4)
N1B	0.0148 (3)	0.0184 (4)	0.0178 (4)	−0.0015 (3)	0.0000 (3)	0.0000 (3)
O18B	0.0177 (3)	0.0219 (4)	0.0241 (4)	−0.0044 (3)	0.0030 (3)	0.0007 (3)
O22B	0.0268 (4)	0.0230 (4)	0.0297 (4)	0.0047 (3)	−0.0048 (3)	−0.0076 (3)
Cl2B	0.01861 (11)	0.02191 (12)	0.03336 (14)	0.00040 (8)	−0.00054 (10)	0.00709 (11)

Geometric parameters (Å, º)

C2A—N3A	1.3280 (14)	C2B—N3B	1.3302 (13)
C2A—N1A	1.3320 (13)	C2B—N1B	1.3377 (14)
C2A—Cl2A	1.7453 (11)	C2B—Cl2B	1.7455 (11)
C4A—N3A	1.3385 (14)	C4B—N3B	1.3398 (14)
C4A—N9A	1.3708 (13)	C4B—N9B	1.3752 (13)
C4A—C5A	1.4027 (15)	C4B—C5B	1.4024 (15)
C8A—N7A	1.3198 (15)	C8B—N7B	1.3196 (16)
C8A—N9A	1.3717 (16)	C8B—N9B	1.3740 (16)
C8A—H8A	0.95	C8B—H8B	0.95
C5A—N7A	1.3922 (13)	C5B—N7B	1.3938 (14)
C5A—C6A	1.4022 (14)	C5B—C6B	1.4013 (14)
C6A—N1A	1.3595 (13)	C6B—N1B	1.3540 (14)
C6A—C17A	1.4479 (15)	C6B—C17B	1.4497 (15)
C17A—C21A	1.3670 (16)	C17B—C21B	1.3670 (15)
C17A—O18A	1.3748 (13)	C17B—O18B	1.3722 (12)
C21A—C20A	1.4202 (18)	C21B—C20B	1.4247 (17)
C21A—H21A	0.95	C21B—H21B	0.95
C20A—C19A	1.354 (2)	C20B—C19B	1.3500 (19)
C20A—H20A	0.95	C20B—H20B	0.95
C19A—O18A	1.3696 (14)	C19B—O18B	1.3710 (14)
C19A—H19A	0.95	C19B—H19B	0.95
C10A—N9A	1.4755 (15)	C10B—N9B	1.4740 (15)
C10A—C11A	1.5128 (16)	C10B—C11B	1.5127 (16)
C10A—H10A	0.99	C10B—H10D	0.99
C10A—H10B	0.99	C10B—H10E	0.99
C11A—C12A	1.3968 (17)	C11B—C16B	1.3932 (16)
C11A—C16A	1.3944 (17)	C11B—C12B	1.3950 (16)
C12A—C13A	1.3863 (19)	C12B—C13B	1.3895 (17)
C12A—H12A	0.95	C12B—H12B	0.95
C13A—C14A	1.3966 (18)	C13B—C14B	1.3992 (17)
C13A—H13A	0.95	C13B—H13B	0.95
C14A—O22A	1.3698 (15)	C14B—O22B	1.3715 (13)
C14A—C15A	1.3920 (16)	C14B—C15B	1.3987 (15)
C15A—C16A	1.3929 (16)	C15B—C16B	1.4017 (16)
C15A—H15A	0.95	C15B—H15B	0.95
C16A—H16A	0.95	C16B—H16B	0.95
C23A—O22A	1.4322 (18)	C23B—O22B	1.4286 (16)
C23A—H23B	0.98	C23B—H23D	0.98
C23A—H23C	0.98	C23B—H23E	0.98
C23A—H23A	0.98	C23B—H23F	0.98
N3A—C2A—N1A	131.07 (10)	N3B—C2B—N1B	130.83 (10)
N3A—C2A—Cl2A	114.44 (8)	N3B—C2B—Cl2B	114.77 (8)
N1A—C2A—Cl2A	114.49 (8)	N1B—C2B—Cl2B	114.40 (8)
N3A—C4A—N9A	127.45 (10)	N3B—C4B—N9B	127.21 (10)
N3A—C4A—C5A	126.66 (9)	N3B—C4B—C5B	126.80 (9)
N9A—C4A—C5A	105.89 (9)	N9B—C4B—C5B	105.98 (9)
N7A—C8A—N9A	114.61 (9)	N7B—C8B—N9B	114.84 (10)
N7A—C8A—H8A	122.7	N7B—C8B—H8B	122.6
N9A—C8A—H8A	122.7	N9B—C8B—H8B	122.6
N7A—C5A—C4A	110.49 (9)	N7B—C5B—C4B	110.53 (9)
N7A—C5A—C6A	133.16 (10)	N7B—C5B—C6B	133.31 (10)
C4A—C5A—C6A	116.35 (9)	C6B—C5B—C4B	116.16 (10)
N1A—C6A—C5A	118.67 (10)	N1B—C6B—C5B	119.06 (10)
N1A—C6A—C17A	118.71 (9)	N1B—C6B—C17B	118.61 (9)
C5A—C6A—C17A	122.61 (10)	C5B—C6B—C17B	122.34 (10)
C21A—C17A—O18A	109.99 (9)	C21B—C17B—O18B	110.05 (9)
C21A—C17A—C6A	132.30 (10)	C21B—C17B—C6B	131.79 (10)
O18A—C17A—C6A	117.71 (9)	O18B—C17B—C6B	118.15 (9)
C17A—C21A—C20A	106.70 (11)	C17B—C21B—C20B	106.55 (11)
C17A—C21A—H21A	126.7	C17B—C21B—H21B	126.7
C20A—C21A—H21A	126.7	C20B—C21B—H21B	126.7
C19A—C20A—C21A	106.23 (11)	C19B—C20B—C21B	106.21 (10)
C19A—C20A—H20A	126.9	C19B—C20B—H20B	126.9
C21A—C20A—H20A	126.9	C21B—C20B—H20B	126.9
C20A—C19A—O18A	111.09 (11)	C20B—C19B—O18B	111.17 (10)
C20A—C19A—H19A	124.5	C20B—C19B—H19B	124.4
O18A—C19A—H19A	124.5	O18B—C19B—H19B	124.4
N9A—C10A—C11A	111.50 (9)	N9B—C10B—C11B	111.70 (9)
N9A—C10A—H10A	109.3	N9B—C10B—H10D	109.3
C11A—C10A—H10A	109.3	C11B—C10B—H10D	109.3
N9A—C10A—H10B	109.3	N9B—C10B—H10E	109.3
C11A—C10A—H10B	109.3	C11B—C10B—H10E	109.3
H10A—C10A—H10B	108	H10D—C10B—H10E	107.9
C12A—C11A—C16A	118.48 (11)	C16B—C11B—C12B	119.10 (10)
C12A—C11A—C10A	121.17 (11)	C12B—C11B—C10B	120.90 (10)
C16A—C11A—C10A	120.31 (11)	C16B—C11B—C10B	119.96 (10)
C13A—C12A—C11A	120.88 (11)	C13B—C12B—C11B	120.84 (10)
C13A—C12A—H12A	119.6	C13B—C12B—H12B	119.6
C11A—C12A—H12A	119.6	C11B—C12B—H12B	119.6
C12A—C13A—C14A	119.99 (11)	C12B—C13B—C14B	119.71 (10)
C12A—C13A—H13A	120	C12B—C13B—H13B	120.1
C14A—C13A—H13A	120	C14B—C13B—H13B	120.1
O22A—C14A—C15A	124.63 (11)	O22B—C14B—C15B	124.41 (10)
O22A—C14A—C13A	115.44 (11)	O22B—C14B—C13B	115.29 (10)
C15A—C14A—C13A	119.92 (11)	C13B—C14B—C15B	120.30 (10)
C16A—C15A—C14A	119.45 (11)	C14B—C15B—C16B	119.03 (11)
C16A—C15A—H15A	120.3	C14B—C15B—H15B	120.5
C14A—C15A—H15A	120.3	C16B—C15B—H15B	120.5
C15A—C16A—C11A	121.28 (11)	C11B—C16B—C15B	121.00 (10)
C15A—C16A—H16A	119.4	C11B—C16B—H16B	119.5
C11A—C16A—H16A	119.4	C15B—C16B—H16B	119.5
O22A—C23A—H23B	109.5	O22B—C23B—H23D	109.5
O22A—C23A—H23C	109.5	O22B—C23B—H23E	109.5
H23B—C23A—H23C	109.5	H23D—C23B—H23E	109.5
O22A—C23A—H23A	109.5	O22B—C23B—H23F	109.5
H23B—C23A—H23A	109.5	H23D—C23B—H23F	109.5
H23C—C23A—H23A	109.5	H23E—C23B—H23F	109.5
C2A—N3A—C4A	110.22 (9)	C2B—N3B—C4B	110.17 (9)
C4A—N9A—C8A	105.73 (9)	C8B—N9B—C4B	105.44 (9)
C4A—N9A—C10A	126.89 (10)	C8B—N9B—C10B	127.04 (10)
C8A—N9A—C10A	127.32 (9)	C4B—N9B—C10B	127.20 (10)
C8A—N7A—C5A	103.27 (9)	C8B—N7B—C5B	103.21 (10)
C2A—N1A—C6A	117.03 (9)	C2B—N1B—C6B	116.98 (9)
C19A—O18A—C17A	105.99 (9)	C19B—O18B—C17B	106.02 (9)
C14A—O22A—C23A	118.12 (10)	C14B—O22B—C23B	116.93 (9)
N3A—C4A—C5A—N7A	−179.53 (10)	N3B—C4B—C5B—N7B	−179.42 (10)
N9A—C4A—C5A—N7A	0.50 (12)	N9B—C4B—C5B—N7B	0.26 (12)
N3A—C4A—C5A—C6A	0.11 (16)	N3B—C4B—C5B—C6B	0.63 (16)
N9A—C4A—C5A—C6A	−179.87 (9)	N9B—C4B—C5B—C6B	−179.70 (9)
N7A—C5A—C6A—N1A	179.57 (11)	N7B—C5B—C6B—N1B	179.91 (11)
C4A—C5A—C6A—N1A	0.04 (15)	C4B—C5B—C6B—N1B	−0.15 (14)
N7A—C5A—C6A—C17A	0.69 (19)	N7B—C5B—C6B—C17B	−0.02 (18)
C4A—C5A—C6A—C17A	−178.84 (10)	C4B—C5B—C6B—C17B	179.92 (10)
N1A—C6A—C17A—C21A	179.86 (12)	N1B—C6B—C17B—C21B	176.61 (11)
C5A—C6A—C17A—C21A	−1.25 (19)	C5B—C6B—C17B—C21B	−3.46 (18)
N1A—C6A—C17A—O18A	−1.00 (15)	N1B—C6B—C17B—O18B	−2.39 (14)
C5A—C6A—C17A—O18A	177.89 (9)	C5B—C6B—C17B—O18B	177.54 (9)
O18A—C17A—C21A—C20A	−0.50 (13)	O18B—C17B—C21B—C20B	0.24 (13)
C6A—C17A—C21A—C20A	178.70 (12)	C6B—C17B—C21B—C20B	−178.83 (11)
C17A—C21A—C20A—C19A	0.28 (14)	C17B—C21B—C20B—C19B	−0.20 (14)
C21A—C20A—C19A—O18A	0.03 (14)	C21B—C20B—C19B—O18B	0.10 (14)
N9A—C10A—C11A—C12A	−94.59 (14)	N9B—C10B—C11B—C12B	91.21 (13)
N9A—C10A—C11A—C16A	83.09 (13)	N9B—C10B—C11B—C16B	−86.23 (13)
C16A—C11A—C12A—C13A	−0.14 (18)	C16B—C11B—C12B—C13B	0.68 (17)
C10A—C11A—C12A—C13A	177.58 (12)	C10B—C11B—C12B—C13B	−176.78 (10)
C11A—C12A—C13A—C14A	−0.2 (2)	C11B—C12B—C13B—C14B	0.69 (18)
C12A—C13A—C14A—O22A	−179.00 (12)	C12B—C13B—C14B—O22B	178.80 (11)
C12A—C13A—C14A—C15A	0.21 (19)	C12B—C13B—C14B—C15B	−1.52 (17)
O22A—C14A—C15A—C16A	179.18 (11)	O22B—C14B—C15B—C16B	−179.37 (11)
C13A—C14A—C15A—C16A	0.05 (17)	C13B—C14B—C15B—C16B	0.97 (17)
C12A—C11A—C16A—C15A	0.41 (17)	C12B—C11B—C16B—C15B	−1.23 (17)
C10A—C11A—C16A—C15A	−177.33 (10)	C10B—C11B—C16B—C15B	176.25 (10)
C14A—C15A—C16A—C11A	−0.37 (17)	C14B—C15B—C16B—C11B	0.41 (17)
N1A—C2A—N3A—C4A	−0.59 (17)	N1B—C2B—N3B—C4B	0.37 (17)
Cl2A—C2A—N3A—C4A	179.34 (8)	Cl2B—C2B—N3B—C4B	−179.11 (8)
N9A—C4A—N3A—C2A	−179.91 (11)	N9B—C4B—N3B—C2B	179.70 (10)
C5A—C4A—N3A—C2A	0.12 (15)	C5B—C4B—N3B—C2B	−0.69 (15)
N7A—C8A—N9A—C4A	0.70 (13)	N7B—C8B—N9B—C4B	−0.32 (14)
N7A—C8A—N9A—C10A	178.04 (11)	N7B—C8B—N9B—C10B	−174.12 (11)
N3A—C4A—N9A—C8A	179.34 (11)	N3B—C4B—N9B—C8B	179.70 (11)
C5A—C4A—N9A—C8A	−0.69 (12)	C5B—C4B—N9B—C8B	0.02 (12)
N3A—C4A—N9A—C10A	1.99 (18)	N3B—C4B—N9B—C10B	−6.51 (18)
C5A—C4A—N9A—C10A	−178.03 (10)	C5B—C4B—N9B—C10B	173.81 (10)
C11A—C10A—N9A—C4A	78.72 (15)	C11B—C10B—N9B—C4B	−70.99 (15)
C11A—C10A—N9A—C8A	−98.07 (13)	C11B—C10B—N9B—C8B	101.50 (13)
N9A—C8A—N7A—C5A	−0.38 (13)	N9B—C8B—N7B—C5B	0.46 (14)
C6A—C5A—N7A—C8A	−179.63 (12)	C6B—C5B—N7B—C8B	179.51 (12)
C4A—C5A—N7A—C8A	−0.08 (12)	C4B—C5B—N7B—C8B	−0.43 (13)
N3A—C2A—N1A—C6A	0.77 (18)	N3B—C2B—N1B—C6B	0.02 (18)
Cl2A—C2A—N1A—C6A	−179.16 (8)	Cl2B—C2B—N1B—C6B	179.50 (7)
C5A—C6A—N1A—C2A	−0.41 (15)	C5B—C6B—N1B—C2B	−0.13 (14)
C17A—C6A—N1A—C2A	178.52 (10)	C17B—C6B—N1B—C2B	179.80 (9)
C20A—C19A—O18A—C17A	−0.33 (13)	C20B—C19B—O18B—C17B	0.04 (13)
C21A—C17A—O18A—C19A	0.51 (12)	C21B—C17B—O18B—C19B	−0.17 (12)
C6A—C17A—O18A—C19A	−178.81 (10)	C6B—C17B—O18B—C19B	179.03 (9)
C15A—C14A—O22A—C23A	11.24 (17)	C15B—C14B—O22B—C23B	−2.45 (17)
C13A—C14A—O22A—C23A	−169.59 (11)	C13B—C14B—O22B—C23B	177.22 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8A—H8A···O18A^i	0.95	2.46	3.4037 (13)	176
C8B—H8B···O18B^ii	0.95	2.44	3.3924 (14)	179
C19A—H19A···Cg1B	0.95	2.78	3.5261 (14)	136
C19B—H19B···Cg1A	0.95	2.85	3.6163 (13)	139

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.