Imatinibium dipicrate.

IN THE CRYSTAL STRUCTURE OF IMATINIBIUM DIPICRATE [SYSTEMATIC NAME: 1-methyl-4-(4-{4-methyl-3-[4-(3-pyrid-yl)pyrimidin-2-yl-amino]-anilinocarbon-yl}benz-yl)piperazine-1,4-diium dipicrate], C(29)H(33)N(7)O(2+)·2C(6)H(2)N(3)O(7) (-), the imatinibium cation is proton-ated at both of the pyrimidine N atoms. Each of the two picrate anions inter-acts with the diprotonated cation through bifurcated N-H⋯O hydrogen bonds forming R(1) (2)(6) ring motifs. Also, an R(2) (2)(24) graph set is formed between the benzamidium -NH- group and the 4-pyridyl N atom inter-acting through N-H⋯N hydrogen-bond inter-actions. Additional weak C-H⋯Cg π-ring and π-π inter-molecular inter-actions are observed which also influence crystal packing.

Related literature

For related structures, see: Bindya et al. (2007 ▶); Harrison, Bindya et al. (2007 ▶); Harrison, Sreevidya et al. (2007 ▶); Jasinski et al. (2009a ▶,b ▶); Swamy et al. (2007 ▶); Szumma et al. (2000 ▶); Yathirajan et al. (2007a ▶,b ▶). For a rationally developed anticancer drug, see: Capdeville et al. (2002 ▶). For its use in chronic myeloid leukaemia, see: Moen et al. (2007 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C29H33N7O2+·2C6H2N3O7 −

M = 951.84

Triclinic,

a = 8.560 (1) Å

b = 10.734 (1) Å

c = 23.060 (1) Å

α = 96.74 (3)°

β = 92.69 (2)°

γ = 101.46 (7)°

V = 2056.9 (6) Å3

Z = 2

Cu Kα radiation

μ = 1.02 mm−1

T = 110 K

0.45 × 0.39 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.596, T max = 0.782

15890 measured reflections

8082 independent reflections

6946 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.158

S = 1.06

8082 reflections

640 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810000577/bt5129sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000577/bt5129Isup2.hkl

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

C29H33N7O2+·2C6H2N3O7−	Z = 2
Mr = 951.84	F(000) = 988
Triclinic, P1	Dx = 1.537 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 8.560 (1) Å	Cell parameters from 9389 reflections
b = 10.734 (1) Å	θ = 4.2–74.0°
c = 23.060 (1) Å	µ = 1.02 mm−1
α = 96.74 (3)°	T = 110 K
β = 92.69 (2)°	Chunk, pale yellow
γ = 101.46 (7)°	0.45 × 0.39 × 0.24 mm
V = 2056.9 (6) Å3

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector	8082 independent reflections
Radiation source: Enhance (Cu) X-ray Source	6946 reflections with I > 2σ(I)
graphite	Rint = 0.023
Detector resolution: 10.5081 pixels mm-1	θmax = 74.1°, θmin = 4.2°
ω scans	h = −10→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −13→13
Tmin = 0.596, Tmax = 0.782	l = −28→28
15890 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0615P)2 + 3.3059P] where P = (Fo2 + 2Fc2)/3
8082 reflections	(Δ/σ)max = 0.001
640 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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	0.3153 (2)	0.58462 (17)	0.49702 (9)	0.0356 (4)
N1	0.4213 (2)	0.4360 (2)	0.19545 (10)	0.0242 (4)
H1	0.465 (4)	0.514 (3)	0.2058 (13)	0.028 (8)*
N2	0.2325 (3)	0.4773 (2)	0.09313 (10)	0.0259 (5)
H2	0.182 (4)	0.397 (4)	0.0809 (15)	0.044 (9)*
C1	0.4665 (3)	0.4017 (2)	0.13475 (12)	0.0274 (5)
H1A	0.4187	0.3106	0.1211	0.033*
H1B	0.5841	0.4127	0.1349	0.033*
C2	0.4094 (3)	0.4851 (2)	0.09331 (12)	0.0291 (5)
H2A	0.4655	0.5752	0.1049	0.035*
H2B	0.4371	0.4581	0.0532	0.035*
C3	0.1853 (3)	0.5056 (2)	0.15391 (11)	0.0264 (5)
H3A	0.0675	0.4925	0.1534	0.032*
H3B	0.2307	0.5965	0.1689	0.032*
C4	0.2433 (3)	0.4209 (2)	0.19414 (11)	0.0255 (5)
H4A	0.2118	0.4431	0.2342	0.031*
H4B	0.1922	0.3303	0.1807	0.031*
C5	0.1813 (4)	0.5660 (3)	0.05447 (13)	0.0342 (6)
H5A	0.0661	0.5612	0.0558	0.051*
H5B	0.2058	0.5413	0.0142	0.051*
H5C	0.2386	0.6539	0.0680	0.051*
C6	0.4812 (3)	0.3553 (2)	0.23719 (12)	0.0294 (6)
H6A	0.4361	0.2637	0.2235	0.035*
H6B	0.5990	0.3686	0.2370	0.035*
C7	0.4370 (3)	0.3868 (2)	0.29871 (12)	0.0284 (5)
C8	0.5091 (3)	0.5012 (2)	0.33399 (12)	0.0305 (6)
H8A	0.5904	0.5608	0.3193	0.037*
C9	0.4627 (3)	0.5279 (2)	0.38995 (12)	0.0304 (6)
H9A	0.5108	0.6066	0.4130	0.036*
C10	0.3464 (3)	0.4409 (2)	0.41296 (12)	0.0276 (5)
C11	0.2752 (3)	0.3270 (2)	0.37767 (12)	0.0279 (5)
H11A	0.1957	0.2667	0.3927	0.033*
C12	0.3182 (3)	0.3006 (2)	0.32147 (12)	0.0289 (6)
H12A	0.2668	0.2233	0.2980	0.035*
C13	0.2977 (3)	0.4734 (2)	0.47391 (12)	0.0292 (5)
N14	0.2326 (3)	0.3702 (2)	0.49985 (10)	0.0290 (5)
H14	0.250 (4)	0.298 (3)	0.4857 (13)	0.030 (8)*
C15	0.1556 (3)	0.3663 (2)	0.55298 (12)	0.0276 (5)
C16	0.0846 (3)	0.4640 (3)	0.57780 (12)	0.0314 (6)
H16A	0.0945	0.5428	0.5620	0.038*
C17	−0.0012 (3)	0.4419 (3)	0.62653 (13)	0.0339 (6)
H17A	−0.0498	0.5080	0.6438	0.041*
C18	−0.0199 (3)	0.3286 (3)	0.65133 (12)	0.0315 (6)
C19	−0.1298 (4)	0.3073 (3)	0.70004 (14)	0.0437 (7)
H19A	−0.0708	0.2871	0.7340	0.066*
H19B	−0.2194	0.2357	0.6867	0.066*
H19C	−0.1708	0.3851	0.7111	0.066*
C20	0.0583 (3)	0.2345 (2)	0.62720 (11)	0.0264 (5)
C21	0.1447 (3)	0.2542 (2)	0.57814 (12)	0.0274 (5)
H21A	0.1971	0.1896	0.5617	0.033*
N22	0.0369 (3)	0.1166 (2)	0.65091 (10)	0.0295 (5)
H22	−0.053 (4)	0.098 (3)	0.6678 (15)	0.040 (9)*
C23	0.1200 (3)	0.0202 (2)	0.64192 (11)	0.0264 (5)
N24	0.0467 (3)	−0.0938 (2)	0.65697 (10)	0.0304 (5)
C25	0.1278 (3)	−0.1869 (3)	0.64831 (13)	0.0341 (6)
H25A	0.0816	−0.2684	0.6589	0.041*
C26	0.2749 (3)	−0.1733 (2)	0.62498 (13)	0.0322 (6)
H26A	0.3286	−0.2426	0.6189	0.039*
C27	0.3399 (3)	−0.0522 (2)	0.61095 (11)	0.0267 (5)
N28	0.2636 (3)	0.0452 (2)	0.62024 (9)	0.0270 (5)
C29	0.4951 (3)	−0.0229 (2)	0.58435 (11)	0.0267 (5)
C30	0.5691 (3)	−0.1204 (2)	0.56171 (12)	0.0290 (5)
H30A	0.5167	−0.2065	0.5635	0.035*
N31	0.7095 (3)	−0.1001 (2)	0.53756 (10)	0.0314 (5)
C32	0.7788 (3)	0.0217 (3)	0.53364 (12)	0.0303 (6)
H32A	0.8790	0.0380	0.5169	0.036*
C33	0.7121 (3)	0.1247 (3)	0.55272 (12)	0.0308 (6)
H33A	0.7635	0.2094	0.5479	0.037*
C34	0.5695 (3)	0.1028 (2)	0.57896 (12)	0.0291 (5)
H34A	0.5225	0.1724	0.5932	0.035*
O1A	0.1518 (2)	0.22087 (16)	0.07622 (8)	0.0291 (4)
O21A	0.3381 (2)	0.07732 (17)	0.12752 (9)	0.0346 (4)
O22A	0.3131 (2)	−0.0904 (2)	0.06313 (10)	0.0396 (5)
O41A	−0.2360 (2)	−0.33957 (17)	0.04481 (10)	0.0395 (5)
O42A	−0.4305 (2)	−0.2407 (2)	0.03722 (12)	0.0493 (6)
O61A	−0.3332 (3)	0.2150 (2)	0.07480 (12)	0.0520 (6)
O62A	−0.1032 (3)	0.32666 (18)	0.06299 (11)	0.0427 (5)
N2A	0.2595 (3)	−0.0043 (2)	0.08996 (10)	0.0287 (5)
N4A	−0.2888 (3)	−0.2408 (2)	0.04636 (10)	0.0311 (5)
N6A	−0.1906 (3)	0.2244 (2)	0.06879 (10)	0.0301 (5)
C1A	0.0479 (3)	0.1211 (2)	0.07465 (10)	0.0242 (5)
C2A	0.0909 (3)	−0.0022 (2)	0.07761 (11)	0.0253 (5)
C3A	−0.0144 (3)	−0.1176 (2)	0.06785 (11)	0.0265 (5)
H3AA	0.0223	−0.1956	0.0674	0.032*
C4A	−0.1766 (3)	−0.1186 (2)	0.05852 (11)	0.0272 (5)
C5A	−0.2330 (3)	−0.0062 (2)	0.06039 (11)	0.0261 (5)
H5AA	−0.3445	−0.0084	0.0562	0.031*
C6A	−0.1240 (3)	0.1095 (2)	0.06843 (11)	0.0259 (5)
O1B	0.4787 (2)	0.68998 (16)	0.21876 (9)	0.0303 (4)
O21B	0.2684 (2)	0.84672 (18)	0.19341 (9)	0.0348 (4)
O22B	0.3412 (3)	0.9982 (2)	0.26585 (11)	0.0493 (6)
O41B	0.8703 (3)	1.24447 (18)	0.21586 (10)	0.0441 (5)
O42B	1.0597 (2)	1.13663 (18)	0.20751 (9)	0.0363 (5)
O61B	0.9270 (2)	0.6835 (2)	0.16693 (9)	0.0392 (5)
O62B	0.7440 (2)	0.58469 (18)	0.21578 (10)	0.0405 (5)
N2B	0.3710 (3)	0.9196 (2)	0.22702 (11)	0.0316 (5)
N4B	0.9186 (3)	1.1430 (2)	0.21198 (10)	0.0327 (5)
N6B	0.8091 (3)	0.6809 (2)	0.19535 (10)	0.0285 (5)
C1B	0.5803 (3)	0.7898 (2)	0.21517 (11)	0.0248 (5)
C2B	0.5386 (3)	0.9143 (2)	0.22026 (11)	0.0267 (5)
C3B	0.6441 (3)	1.0279 (2)	0.22022 (12)	0.0298 (6)
H3BA	0.6099	1.1072	0.2255	0.036*
C4B	0.8035 (3)	1.0239 (2)	0.21222 (11)	0.0281 (5)
C5B	0.8561 (3)	0.9107 (2)	0.20437 (11)	0.0263 (5)
H5BA	0.9650	0.9103	0.1982	0.032*
C6B	0.7471 (3)	0.7972 (2)	0.20563 (11)	0.0257 (5)

	U11	U22	U33	U12	U13	U23
O1	0.0430 (11)	0.0197 (9)	0.0408 (11)	0.0000 (8)	0.0037 (9)	0.0007 (8)
N1	0.0236 (10)	0.0124 (10)	0.0347 (12)	−0.0010 (8)	0.0009 (8)	0.0036 (8)
N2	0.0293 (11)	0.0130 (10)	0.0334 (11)	0.0003 (8)	−0.0010 (9)	0.0033 (8)
C1	0.0243 (12)	0.0182 (12)	0.0379 (14)	0.0009 (9)	0.0048 (10)	0.0009 (10)
C2	0.0289 (13)	0.0207 (12)	0.0353 (14)	−0.0011 (10)	0.0052 (11)	0.0030 (10)
C3	0.0249 (12)	0.0173 (12)	0.0345 (13)	0.0006 (9)	−0.0003 (10)	0.0005 (9)
C4	0.0228 (12)	0.0179 (11)	0.0338 (13)	−0.0003 (9)	0.0027 (10)	0.0021 (9)
C5	0.0409 (16)	0.0195 (13)	0.0407 (15)	0.0019 (11)	−0.0042 (12)	0.0079 (11)
C6	0.0290 (13)	0.0189 (12)	0.0408 (15)	0.0051 (10)	−0.0005 (11)	0.0066 (10)
C7	0.0289 (13)	0.0214 (12)	0.0345 (14)	0.0037 (10)	−0.0034 (10)	0.0067 (10)
C8	0.0268 (13)	0.0197 (12)	0.0432 (15)	−0.0011 (10)	−0.0014 (11)	0.0087 (11)
C9	0.0315 (14)	0.0196 (12)	0.0361 (14)	−0.0020 (10)	−0.0058 (11)	0.0033 (10)
C10	0.0273 (13)	0.0183 (12)	0.0360 (14)	0.0027 (10)	−0.0041 (10)	0.0051 (10)
C11	0.0279 (13)	0.0176 (12)	0.0357 (14)	−0.0021 (10)	−0.0024 (10)	0.0070 (10)
C12	0.0310 (13)	0.0154 (11)	0.0373 (14)	−0.0012 (10)	−0.0064 (11)	0.0047 (10)
C13	0.0250 (12)	0.0241 (13)	0.0370 (14)	0.0040 (10)	−0.0023 (10)	0.0023 (10)
N14	0.0307 (12)	0.0198 (11)	0.0366 (12)	0.0066 (9)	0.0035 (9)	0.0011 (9)
C15	0.0225 (12)	0.0234 (12)	0.0342 (14)	0.0018 (10)	−0.0001 (10)	−0.0014 (10)
C16	0.0321 (14)	0.0206 (12)	0.0403 (15)	0.0038 (10)	0.0015 (11)	0.0026 (10)
C17	0.0354 (15)	0.0239 (13)	0.0427 (16)	0.0090 (11)	0.0077 (12)	−0.0017 (11)
C18	0.0299 (14)	0.0305 (14)	0.0329 (14)	0.0057 (11)	0.0032 (11)	−0.0001 (11)
C19	0.0502 (19)	0.0387 (17)	0.0472 (18)	0.0180 (14)	0.0163 (15)	0.0062 (13)
C20	0.0224 (12)	0.0215 (12)	0.0331 (13)	0.0004 (9)	−0.0005 (10)	0.0023 (10)
C21	0.0235 (12)	0.0221 (12)	0.0350 (14)	0.0036 (10)	0.0017 (10)	−0.0012 (10)
N22	0.0268 (11)	0.0266 (12)	0.0352 (12)	0.0034 (9)	0.0078 (9)	0.0056 (9)
C23	0.0272 (13)	0.0218 (12)	0.0278 (12)	0.0018 (10)	−0.0007 (10)	0.0004 (9)
N24	0.0291 (11)	0.0239 (11)	0.0349 (12)	−0.0015 (9)	0.0038 (9)	0.0017 (9)
C25	0.0356 (15)	0.0207 (13)	0.0420 (16)	−0.0040 (11)	0.0009 (12)	0.0055 (11)
C26	0.0339 (14)	0.0179 (12)	0.0440 (16)	0.0042 (10)	0.0013 (12)	0.0030 (11)
C27	0.0295 (13)	0.0216 (12)	0.0278 (13)	0.0046 (10)	−0.0018 (10)	0.0013 (9)
N28	0.0268 (11)	0.0213 (10)	0.0318 (11)	0.0029 (8)	0.0010 (9)	0.0026 (8)
C29	0.0270 (13)	0.0240 (13)	0.0285 (13)	0.0054 (10)	−0.0022 (10)	0.0024 (10)
C30	0.0319 (14)	0.0218 (12)	0.0333 (14)	0.0062 (10)	0.0002 (11)	0.0029 (10)
N31	0.0322 (12)	0.0281 (12)	0.0346 (12)	0.0100 (9)	0.0014 (9)	0.0011 (9)
C32	0.0258 (13)	0.0308 (14)	0.0335 (14)	0.0049 (11)	0.0008 (10)	0.0026 (11)
C33	0.0266 (13)	0.0245 (13)	0.0388 (15)	0.0014 (10)	−0.0021 (11)	0.0026 (11)
C34	0.0271 (13)	0.0217 (13)	0.0372 (14)	0.0052 (10)	−0.0009 (11)	−0.0003 (10)
O1A	0.0314 (10)	0.0166 (9)	0.0370 (10)	0.0004 (7)	0.0015 (8)	0.0026 (7)
O21A	0.0308 (10)	0.0213 (9)	0.0475 (12)	−0.0027 (8)	−0.0050 (8)	0.0048 (8)
O22A	0.0385 (11)	0.0330 (11)	0.0494 (12)	0.0142 (9)	0.0052 (9)	0.0018 (9)
O41A	0.0412 (11)	0.0168 (9)	0.0567 (13)	−0.0008 (8)	−0.0033 (9)	0.0037 (8)
O42A	0.0267 (11)	0.0258 (11)	0.0909 (18)	−0.0039 (8)	0.0026 (11)	0.0056 (11)
O61A	0.0363 (12)	0.0296 (11)	0.0924 (19)	0.0103 (9)	0.0199 (12)	0.0051 (11)
O62A	0.0376 (11)	0.0187 (10)	0.0708 (15)	0.0010 (8)	−0.0036 (10)	0.0125 (9)
N2A	0.0293 (11)	0.0201 (11)	0.0369 (12)	0.0033 (9)	0.0043 (9)	0.0073 (9)
N4A	0.0311 (12)	0.0205 (11)	0.0388 (13)	−0.0022 (9)	0.0040 (9)	0.0042 (9)
N6A	0.0331 (12)	0.0214 (11)	0.0345 (12)	0.0043 (9)	0.0013 (9)	0.0005 (9)
C1A	0.0299 (13)	0.0159 (11)	0.0250 (12)	0.0012 (10)	0.0022 (10)	0.0012 (9)
C2A	0.0272 (13)	0.0207 (12)	0.0275 (12)	0.0036 (10)	0.0026 (10)	0.0030 (9)
C3A	0.0318 (13)	0.0167 (11)	0.0304 (13)	0.0036 (10)	0.0037 (10)	0.0029 (9)
C4A	0.0324 (14)	0.0195 (12)	0.0268 (12)	−0.0014 (10)	0.0031 (10)	0.0024 (9)
C5A	0.0256 (12)	0.0223 (12)	0.0291 (13)	0.0016 (10)	0.0045 (10)	0.0029 (10)
C6A	0.0310 (13)	0.0196 (12)	0.0269 (12)	0.0043 (10)	0.0031 (10)	0.0032 (9)
O1B	0.0242 (9)	0.0149 (8)	0.0490 (11)	−0.0015 (7)	0.0018 (8)	0.0028 (7)
O21B	0.0261 (9)	0.0239 (10)	0.0516 (12)	−0.0020 (7)	−0.0013 (8)	0.0064 (8)
O22B	0.0426 (12)	0.0380 (12)	0.0659 (15)	0.0149 (10)	0.0069 (11)	−0.0120 (11)
O41B	0.0470 (13)	0.0176 (10)	0.0635 (14)	−0.0038 (9)	0.0048 (10)	0.0060 (9)
O42B	0.0337 (11)	0.0279 (10)	0.0409 (11)	−0.0099 (8)	0.0034 (8)	0.0049 (8)
O61B	0.0339 (11)	0.0346 (11)	0.0510 (12)	0.0102 (9)	0.0110 (9)	0.0052 (9)
O62B	0.0268 (10)	0.0191 (9)	0.0747 (15)	−0.0013 (8)	0.0050 (9)	0.0118 (9)
N2B	0.0314 (12)	0.0186 (11)	0.0450 (13)	0.0038 (9)	0.0050 (10)	0.0055 (9)
N4B	0.0387 (14)	0.0216 (11)	0.0326 (12)	−0.0061 (10)	0.0018 (10)	0.0033 (9)
N6B	0.0217 (10)	0.0215 (11)	0.0396 (12)	0.0005 (8)	−0.0022 (9)	0.0009 (9)
C1B	0.0266 (13)	0.0175 (12)	0.0278 (12)	0.0003 (10)	−0.0008 (10)	0.0008 (9)
C2B	0.0261 (13)	0.0200 (12)	0.0322 (13)	0.0020 (10)	0.0004 (10)	0.0010 (10)
C3B	0.0367 (14)	0.0166 (12)	0.0347 (14)	0.0035 (10)	−0.0008 (11)	0.0022 (10)
C4B	0.0323 (14)	0.0188 (12)	0.0289 (13)	−0.0047 (10)	0.0000 (10)	0.0036 (9)
C5B	0.0244 (12)	0.0241 (13)	0.0266 (12)	−0.0033 (10)	0.0002 (9)	0.0026 (9)
C6B	0.0267 (13)	0.0192 (12)	0.0289 (13)	0.0010 (10)	−0.0012 (10)	0.0015 (9)

O1—C13	1.226 (3)	C23—N28	1.339 (3)
N1—C1	1.494 (3)	C23—N24	1.352 (3)
N1—C4	1.498 (3)	N24—C25	1.328 (4)
N1—C6	1.505 (3)	C25—C26	1.380 (4)
N1—H1	0.85 (3)	C25—H25A	0.9500
N2—C3	1.490 (3)	C26—C27	1.390 (4)
N2—C5	1.491 (3)	C26—H26A	0.9500
N2—C2	1.500 (3)	C27—N28	1.341 (3)
N2—H2	0.89 (4)	C27—C29	1.482 (4)
C1—C2	1.511 (4)	C29—C30	1.391 (4)
C1—H1A	0.9900	C29—C34	1.395 (4)
C1—H1B	0.9900	C30—N31	1.338 (4)
C2—H2A	0.9900	C30—H30A	0.9500
C2—H2B	0.9900	N31—C32	1.340 (4)
C3—C4	1.506 (3)	C32—C33	1.379 (4)
C3—H3A	0.9900	C32—H32A	0.9500
C3—H3B	0.9900	C33—C34	1.378 (4)
C4—H4A	0.9900	C33—H33A	0.9500
C4—H4B	0.9900	C34—H34A	0.9500
C5—H5A	0.9800	O1A—C1A	1.245 (3)
C5—H5B	0.9800	O21A—N2A	1.226 (3)
C5—H5C	0.9800	O22A—N2A	1.228 (3)
C6—C7	1.503 (4)	O41A—N4A	1.231 (3)
C6—H6A	0.9900	O42A—N4A	1.221 (3)
C6—H6B	0.9900	O61A—N6A	1.221 (3)
C7—C12	1.399 (4)	O62A—N6A	1.225 (3)
C7—C8	1.403 (4)	N2A—C2A	1.463 (3)
C8—C9	1.383 (4)	N4A—C4A	1.452 (3)
C8—H8A	0.9500	N6A—C6A	1.457 (3)
C9—C10	1.393 (4)	C1A—C2A	1.451 (3)
C9—H9A	0.9500	C1A—C6A	1.451 (4)
C10—C11	1.397 (3)	C2A—C3A	1.367 (3)
C10—C13	1.506 (4)	C3A—C4A	1.393 (4)
C11—C12	1.377 (4)	C3A—H3AA	0.9500
C11—H11A	0.9500	C4A—C5A	1.382 (4)
C12—H12A	0.9500	C5A—C6A	1.384 (3)
C13—N14	1.356 (3)	C5A—H5AA	0.9500
N14—C15	1.419 (3)	O1B—C1B	1.252 (3)
N14—H14	0.85 (3)	O21B—N2B	1.227 (3)
C15—C21	1.385 (4)	O22B—N2B	1.228 (3)
C15—C16	1.394 (4)	O41B—N4B	1.235 (3)
C16—C17	1.389 (4)	O42B—N4B	1.232 (3)
C16—H16A	0.9500	O61B—N6B	1.226 (3)
C17—C18	1.388 (4)	O62B—N6B	1.229 (3)
C17—H17A	0.9500	N2B—C2B	1.462 (3)
C18—C20	1.396 (4)	N4B—C4B	1.451 (3)
C18—C19	1.508 (4)	N6B—C6B	1.450 (3)
C19—H19A	0.9800	C1B—C6B	1.443 (4)
C19—H19B	0.9800	C1B—C2B	1.443 (3)
C19—H19C	0.9800	C2B—C3B	1.366 (4)
C20—C21	1.394 (4)	C3B—C4B	1.394 (4)
C20—N22	1.419 (3)	C3B—H3BA	0.9500
C21—H21A	0.9500	C4B—C5B	1.373 (4)
N22—C23	1.369 (3)	C5B—C6B	1.384 (3)
N22—H22	0.87 (4)	C5B—H5BA	0.9500
C1—N1—C4	108.6 (2)	C18—C20—N22	118.4 (2)
C1—N1—C6	111.1 (2)	C15—C21—C20	121.1 (2)
C4—N1—C6	111.62 (19)	C15—C21—H21A	119.5
C1—N1—H1	107 (2)	C20—C21—H21A	119.5
C4—N1—H1	109 (2)	C23—N22—C20	129.0 (2)
C6—N1—H1	109 (2)	C23—N22—H22	116 (2)
C3—N2—C5	110.9 (2)	C20—N22—H22	113 (2)
C3—N2—C2	110.4 (2)	N28—C23—N24	125.8 (2)
C5—N2—C2	110.8 (2)	N28—C23—N22	119.1 (2)
C3—N2—H2	105 (2)	N24—C23—N22	115.2 (2)
C5—N2—H2	110 (2)	C25—N24—C23	115.0 (2)
C2—N2—H2	109 (2)	N24—C25—C26	124.4 (2)
N1—C1—C2	110.9 (2)	N24—C25—H25A	117.8
N1—C1—H1A	109.5	C26—C25—H25A	117.8
C2—C1—H1A	109.5	C25—C26—C27	116.1 (2)
N1—C1—H1B	109.5	C25—C26—H26A	121.9
C2—C1—H1B	109.5	C27—C26—H26A	121.9
H1A—C1—H1B	108.0	N28—C27—C26	121.4 (2)
N2—C2—C1	112.1 (2)	N28—C27—C29	116.0 (2)
N2—C2—H2A	109.2	C26—C27—C29	122.6 (2)
C1—C2—H2A	109.2	C23—N28—C27	117.3 (2)
N2—C2—H2B	109.2	C30—C29—C34	117.4 (2)
C1—C2—H2B	109.2	C30—C29—C27	121.1 (2)
H2A—C2—H2B	107.9	C34—C29—C27	121.5 (2)
N2—C3—C4	111.5 (2)	N31—C30—C29	123.9 (2)
N2—C3—H3A	109.3	N31—C30—H30A	118.0
C4—C3—H3A	109.3	C29—C30—H30A	118.0
N2—C3—H3B	109.3	C30—N31—C32	117.1 (2)
C4—C3—H3B	109.3	N31—C32—C33	123.3 (3)
H3A—C3—H3B	108.0	N31—C32—H32A	118.4
N1—C4—C3	111.2 (2)	C33—C32—H32A	118.4
N1—C4—H4A	109.4	C34—C33—C32	119.0 (2)
C3—C4—H4A	109.4	C34—C33—H33A	120.5
N1—C4—H4B	109.4	C32—C33—H33A	120.5
C3—C4—H4B	109.4	C33—C34—C29	119.2 (2)
H4A—C4—H4B	108.0	C33—C34—H34A	120.4
N2—C5—H5A	109.5	C29—C34—H34A	120.4
N2—C5—H5B	109.5	O21A—N2A—O22A	123.7 (2)
H5A—C5—H5B	109.5	O21A—N2A—C2A	118.4 (2)
N2—C5—H5C	109.5	O22A—N2A—C2A	117.9 (2)
H5A—C5—H5C	109.5	O42A—N4A—O41A	123.1 (2)
H5B—C5—H5C	109.5	O42A—N4A—C4A	118.6 (2)
C7—C6—N1	112.6 (2)	O41A—N4A—C4A	118.2 (2)
C7—C6—H6A	109.1	O61A—N6A—O62A	122.0 (2)
N1—C6—H6A	109.1	O61A—N6A—C6A	118.4 (2)
C7—C6—H6B	109.1	O62A—N6A—C6A	119.6 (2)
N1—C6—H6B	109.1	O1A—C1A—C2A	121.3 (2)
H6A—C6—H6B	107.8	O1A—C1A—C6A	126.9 (2)
C12—C7—C8	118.6 (3)	C2A—C1A—C6A	111.7 (2)
C12—C7—C6	119.2 (2)	C3A—C2A—C1A	124.6 (2)
C8—C7—C6	122.2 (2)	C3A—C2A—N2A	117.3 (2)
C9—C8—C7	120.4 (2)	C1A—C2A—N2A	118.0 (2)
C9—C8—H8A	119.8	C2A—C3A—C4A	118.7 (2)
C7—C8—H8A	119.8	C2A—C3A—H3AA	120.6
C8—C9—C10	120.9 (2)	C4A—C3A—H3AA	120.6
C8—C9—H9A	119.5	C5A—C4A—C3A	121.5 (2)
C10—C9—H9A	119.5	C5A—C4A—N4A	119.4 (2)
C9—C10—C11	118.4 (3)	C3A—C4A—N4A	119.1 (2)
C9—C10—C13	119.6 (2)	C4A—C5A—C6A	118.8 (2)
C11—C10—C13	122.1 (2)	C4A—C5A—H5AA	120.6
C12—C11—C10	121.2 (2)	C6A—C5A—H5AA	120.6
C12—C11—H11A	119.4	C5A—C6A—C1A	124.0 (2)
C10—C11—H11A	119.4	C5A—C6A—N6A	116.2 (2)
C11—C12—C7	120.4 (2)	C1A—C6A—N6A	119.7 (2)
C11—C12—H12A	119.8	O21B—N2B—O22B	123.7 (2)
C7—C12—H12A	119.8	O21B—N2B—C2B	118.5 (2)
O1—C13—N14	123.9 (3)	O22B—N2B—C2B	117.8 (2)
O1—C13—C10	121.8 (2)	O42B—N4B—O41B	123.7 (2)
N14—C13—C10	114.3 (2)	O42B—N4B—C4B	117.7 (2)
C13—N14—C15	129.0 (2)	O41B—N4B—C4B	118.7 (2)
C13—N14—H14	117 (2)	O61B—N6B—O62B	122.5 (2)
C15—N14—H14	113 (2)	O61B—N6B—C6B	118.1 (2)
C21—C15—C16	120.2 (2)	O62B—N6B—C6B	119.4 (2)
C21—C15—N14	116.1 (2)	O1B—C1B—C6B	126.3 (2)
C16—C15—N14	123.6 (2)	O1B—C1B—C2B	121.7 (2)
C17—C16—C15	117.5 (2)	C6B—C1B—C2B	112.0 (2)
C17—C16—H16A	121.2	C3B—C2B—C1B	125.1 (2)
C15—C16—H16A	121.2	C3B—C2B—N2B	117.4 (2)
C18—C17—C16	123.6 (2)	C1B—C2B—N2B	117.6 (2)
C18—C17—H17A	118.2	C2B—C3B—C4B	117.9 (2)
C16—C17—H17A	118.2	C2B—C3B—H3BA	121.1
C17—C18—C20	117.6 (3)	C4B—C3B—H3BA	121.1
C17—C18—C19	120.0 (3)	C5B—C4B—C3B	122.3 (2)
C20—C18—C19	122.2 (3)	C5B—C4B—N4B	118.5 (2)
C18—C19—H19A	109.5	C3B—C4B—N4B	119.3 (2)
C18—C19—H19B	109.5	C4B—C5B—C6B	118.6 (2)
H19A—C19—H19B	109.5	C4B—C5B—H5BA	120.7
C18—C19—H19C	109.5	C6B—C5B—H5BA	120.7
H19A—C19—H19C	109.5	C5B—C6B—C1B	124.1 (2)
H19B—C19—H19C	109.5	C5B—C6B—N6B	115.8 (2)
C21—C20—C18	119.8 (2)	C1B—C6B—N6B	120.1 (2)
C21—C20—N22	121.6 (2)
C4—N1—C1—C2	58.2 (2)	C27—C29—C30—N31	−179.5 (2)
C6—N1—C1—C2	−178.6 (2)	C29—C30—N31—C32	−2.2 (4)
C3—N2—C2—C1	53.6 (3)	C30—N31—C32—C33	−0.4 (4)
C5—N2—C2—C1	176.8 (2)	N31—C32—C33—C34	2.2 (4)
N1—C1—C2—N2	−56.6 (3)	C32—C33—C34—C29	−1.4 (4)
C5—N2—C3—C4	−177.2 (2)	C30—C29—C34—C33	−1.0 (4)
C2—N2—C3—C4	−54.0 (3)	C27—C29—C34—C33	−178.6 (2)
C1—N1—C4—C3	−59.2 (3)	O1A—C1A—C2A—C3A	−170.2 (2)
C6—N1—C4—C3	177.9 (2)	C6A—C1A—C2A—C3A	8.4 (4)
N2—C3—C4—N1	58.1 (3)	O1A—C1A—C2A—N2A	7.6 (4)
C1—N1—C6—C7	−179.7 (2)	C6A—C1A—C2A—N2A	−173.8 (2)
C4—N1—C6—C7	−58.3 (3)	O21A—N2A—C2A—C3A	−140.1 (2)
N1—C6—C7—C12	107.2 (3)	O22A—N2A—C2A—C3A	37.9 (3)
N1—C6—C7—C8	−71.7 (3)	O21A—N2A—C2A—C1A	41.9 (3)
C12—C7—C8—C9	−0.3 (4)	O22A—N2A—C2A—C1A	−140.1 (2)
C6—C7—C8—C9	178.6 (2)	C1A—C2A—C3A—C4A	−4.9 (4)
C7—C8—C9—C10	1.5 (4)	N2A—C2A—C3A—C4A	177.2 (2)
C8—C9—C10—C11	−1.3 (4)	C2A—C3A—C4A—C5A	−1.6 (4)
C8—C9—C10—C13	−179.5 (2)	C2A—C3A—C4A—N4A	178.2 (2)
C9—C10—C11—C12	0.0 (4)	O42A—N4A—C4A—C5A	1.1 (4)
C13—C10—C11—C12	178.1 (2)	O41A—N4A—C4A—C5A	179.9 (2)
C10—C11—C12—C7	1.2 (4)	O42A—N4A—C4A—C3A	−178.7 (3)
C8—C7—C12—C11	−1.0 (4)	O41A—N4A—C4A—C3A	0.1 (4)
C6—C7—C12—C11	−180.0 (2)	C3A—C4A—C5A—C6A	3.7 (4)
C9—C10—C13—O1	23.7 (4)	N4A—C4A—C5A—C6A	−176.1 (2)
C11—C10—C13—O1	−154.5 (3)	C4A—C5A—C6A—C1A	0.5 (4)
C9—C10—C13—N14	−156.9 (2)	C4A—C5A—C6A—N6A	178.8 (2)
C11—C10—C13—N14	25.0 (4)	O1A—C1A—C6A—C5A	172.4 (2)
O1—C13—N14—C15	8.6 (4)	C2A—C1A—C6A—C5A	−6.1 (3)
C10—C13—N14—C15	−170.8 (2)	O1A—C1A—C6A—N6A	−5.8 (4)
C13—N14—C15—C21	−160.7 (3)	C2A—C1A—C6A—N6A	175.8 (2)
C13—N14—C15—C16	23.3 (4)	O61A—N6A—C6A—C5A	15.5 (4)
C21—C15—C16—C17	−2.5 (4)	O62A—N6A—C6A—C5A	−164.3 (2)
N14—C15—C16—C17	173.3 (3)	O61A—N6A—C6A—C1A	−166.2 (3)
C15—C16—C17—C18	−0.2 (4)	O62A—N6A—C6A—C1A	14.0 (4)
C16—C17—C18—C20	2.9 (4)	O1B—C1B—C2B—C3B	176.0 (3)
C16—C17—C18—C19	−173.3 (3)	C6B—C1B—C2B—C3B	−4.2 (4)
C17—C18—C20—C21	−3.0 (4)	O1B—C1B—C2B—N2B	−2.9 (4)
C19—C18—C20—C21	173.1 (3)	C6B—C1B—C2B—N2B	176.9 (2)
C17—C18—C20—N22	−178.2 (2)	O21B—N2B—C2B—C3B	132.4 (3)
C19—C18—C20—N22	−2.1 (4)	O22B—N2B—C2B—C3B	−46.8 (4)
C16—C15—C21—C20	2.4 (4)	O21B—N2B—C2B—C1B	−48.7 (3)
N14—C15—C21—C20	−173.7 (2)	O22B—N2B—C2B—C1B	132.2 (3)
C18—C20—C21—C15	0.4 (4)	C1B—C2B—C3B—C4B	2.8 (4)
N22—C20—C21—C15	175.5 (2)	N2B—C2B—C3B—C4B	−178.3 (2)
C21—C20—N22—C23	17.2 (4)	C2B—C3B—C4B—C5B	0.2 (4)
C18—C20—N22—C23	−167.7 (3)	C2B—C3B—C4B—N4B	−180.0 (2)
C20—N22—C23—N28	18.2 (4)	O42B—N4B—C4B—C5B	−3.4 (4)
C20—N22—C23—N24	−162.5 (2)	O41B—N4B—C4B—C5B	176.1 (2)
N28—C23—N24—C25	−0.6 (4)	O42B—N4B—C4B—C3B	176.7 (2)
N22—C23—N24—C25	−179.8 (2)	O41B—N4B—C4B—C3B	−3.7 (4)
C23—N24—C25—C26	−1.0 (4)	C3B—C4B—C5B—C6B	−1.3 (4)
N24—C25—C26—C27	1.0 (4)	N4B—C4B—C5B—C6B	178.9 (2)
C25—C26—C27—N28	0.6 (4)	C4B—C5B—C6B—C1B	−0.5 (4)
C25—C26—C27—C29	−178.6 (2)	C4B—C5B—C6B—N6B	178.3 (2)
N24—C23—N28—C27	2.1 (4)	O1B—C1B—C6B—C5B	−177.2 (3)
N22—C23—N28—C27	−178.7 (2)	C2B—C1B—C6B—C5B	3.0 (4)
C26—C27—N28—C23	−2.0 (4)	O1B—C1B—C6B—N6B	4.1 (4)
C29—C27—N28—C23	177.2 (2)	C2B—C1B—C6B—N6B	−175.7 (2)
N28—C27—C29—C30	−166.7 (2)	O61B—N6B—C6B—C5B	−25.5 (3)
C26—C27—C29—C30	12.6 (4)	O62B—N6B—C6B—C5B	153.6 (2)
N28—C27—C29—C34	10.8 (4)	O61B—N6B—C6B—C1B	153.3 (2)
C26—C27—C29—C34	−170.0 (3)	O62B—N6B—C6B—C1B	−27.6 (4)
C34—C29—C30—N31	3.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1B	0.85 (3)	1.85 (3)	2.658 (3)	157 (3)
N1—H1···O62B	0.85 (3)	2.35 (3)	2.890 (3)	122 (2)
N2—H2···O1A	0.89 (4)	1.85 (4)	2.678 (3)	154 (3)
N2—H2···O62A	0.89 (4)	2.41 (4)	3.009 (3)	125 (3)
N14—H14···N31i	0.85 (3)	2.23 (3)	3.069 (3)	171 (3)
C5—H5B···O41Aii	0.98	2.48	3.258 (4)	136
C4—H4B···O42Biii	0.99	2.33	3.199 (3)	146
C3—H3A···O61Biv	0.99	2.57	3.199 (3)	121
C3—H3B···O1B	0.99	2.34	3.072 (3)	130
C12—H12A···O42Biii	0.95	2.63	3.423 (3)	142
C19—H19A···O61Bv	0.98	2.50	3.435 (4)	159
C19—H19A···N6Bv	0.98	2.65	3.541 (4)	152

D—H···A	D—H	H···A	D···A	D—H···A
C33—H33A···Cg5vi	0.95	2.90	3.545 (8)	127

Cg2···Cg7v	3.740 (4)
Cg3···Cg3v	3.496 (7)
Cg6···Cg6vii	3.396 (0)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1B	0.85 (3)	1.85 (3)	2.658 (3)	157 (3)
N1—H1⋯O62B	0.85 (3)	2.35 (3)	2.890 (3)	122 (2)
N2—H2⋯O1A	0.89 (4)	1.85 (4)	2.678 (3)	154 (3)
N2—H2⋯O62A	0.89 (4)	2.41 (4)	3.009 (3)	125 (3)
N14—H14⋯N31i	0.85 (3)	2.23 (3)	3.069 (3)	171 (3)
C5—H5B⋯O41Aii	0.98	2.48	3.258 (4)	136
C4—H4B⋯O42Biii	0.99	2.33	3.199 (3)	146
C3—H3A⋯O61Biv	0.99	2.57	3.199 (3)	121
C3—H3B⋯O1B	0.99	2.34	3.072 (3)	130
C12—H12A⋯O42Biii	0.95	2.63	3.423 (3)	142
C19—H19A⋯O61Bv	0.98	2.50	3.435 (4)	159
C19—H19A⋯N6Bv	0.98	2.65	3.541 (4)	152

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

Table 2

π-Ring hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C33—H33A⋯Cg5vi	0.95	2.90	3.545 (8)	127

Symmetry code: (vi) x + 1, y, z. Cg5 is the centroid of the C15–C21 ring.

Table 3

π–π stacking geometry (Å) for (I)

Cg2⋯Cg7v	3.740 (4)
Cg3⋯Cg3v	3.496 (7)
Cg6⋯Cg6vii	3.396 (0)

Symmetry codes: (v) −x + 1, −y + 1, −z + 1; (vii) −x + 2, −y + 2, −z. Cg2, Cg3, Cg6 and Cg7 are the centroids of the C25–C27/N28/C23/N4, C32–C34/C29//C30/N31, C1A–C6A and C1B–C6B rings, respectively.