6-Amino-1-benzyl-4-(4-chloro-phen-yl)-3-(4-pyrid-yl)-1,4-dihydro-pyrano[2,3-c]pyrazole-5-carbonitrile.

The crystal structure of the title compound, C(25)H(18)ClN(5)O, was determined in the course of our studies on the synthesis of 1,4-dihydro-pyrano[2,3-c]pyrazole as an inhibitor of the p38 mitogen-activated protein kinase (MAPK). The compound was prepared via a base-catalysed synthesis from 1-benzyl-3-(4-pyrid-yl)-1H-pyrazol-5(4H)-one with p-chloro-aldehyde and malononitrile. The crystal data obtained were used to generate a three-dimensional pharmacophore model for in silico database screening. The phenyl ring is disordered over two positions, with site occupancy factors of 0.55 and 0.45. The dihedral angles between the 1,4-dihydropyrano[2,3-c]pyrazole unit and the chloro-phenyl and pyridine rings are 83.7 (1) and 16.0 (1)°, respectively. The chloro-phenyl and pyridine rings make a dihedral angle of 86.8 (2)°.

Related literature

The therapeutic potential of p38 mitogen-activated protein (MAP) kinase inhibitors for the treatment of inflammatory-associated diseases has been extensively reviewed (Kumar et al., 2003 ▶; Pargellis & Regan, 2003 ▶). The synthesis of the title compound was performed according to the published procedures (Dyachenko & Chernega, 2005 ▶; Dyachenko & Rusanov, 2004 ▶; Klokol et al., 1999 ▶).

Experimental

Crystal data

C25H18ClN5O

M = 439.89

Monoclinic,

a = 5.7021 (11) Å

b = 17.795 (3) Å

c = 21.056 (9) Å

β = 90.954 (8)°

V = 2136.2 (11) Å3

Z = 4

Cu Kα radiation

μ = 1.81 mm−1

T = 193 (2) K

0.46 × 0.12 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T min = 0.825, T max = 0.998 (expected range = 0.725–0.865)

4443 measured reflections

4018 independent reflections

2971 reflections with I > 2σ(I)

R int = 0.026

3 standard reflections frequency: 60 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.203

S = 1.07

4018 reflections

307 parameters

66 restraints

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.64 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800487X/nc2090sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800487X/nc2090Isup2.hkl

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

C25H18ClN5O	F000 = 912
Mr = 439.89	Dx = 1.368 Mg m−3
Monoclinic, P21/c	Cu Kα radiation λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 5.7021 (11) Å	θ = 30–42º
b = 17.795 (3) Å	µ = 1.81 mm−1
c = 21.056 (9) Å	T = 193 (2) K
β = 90.954 (8)º	Needle, colourless
V = 2136.2 (11) Å3	0.46 × 0.12 × 0.08 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	Rint = 0.026
Monochromator: graphite	θmax = 69.9º
T = 193(2) K	θmin = 3.3º
ω/2θ scans	h = 0→6
Absorption correction: ψ scan(CORINC; Dräger & Gattow, 1971)	k = 0→21
Tmin = 0.825, Tmax = 0.998	l = −25→25
4443 measured reflections	3 standard reflections
4018 independent reflections	every 60 min
2971 reflections with I > 2σ(I)	intensity decay: 2%

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)] = 0.067	H-atom parameters constrained
wR(F2) = 0.203	w = 1/[σ2(Fo2) + (0.0991P)2 + 1.7529P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.002
4018 reflections	Δρmax = 0.50 e Å−3
307 parameters	Δρmin = −0.64 e Å−3
66 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
N1	0.9067 (5)	0.26498 (14)	0.08891 (12)	0.0361 (6)
C2	0.7214 (5)	0.31100 (16)	0.08484 (13)	0.0336 (6)
O3	0.6666 (4)	0.34475 (12)	0.02838 (9)	0.0367 (5)
C4	0.4711 (5)	0.38996 (16)	0.03011 (13)	0.0328 (6)
C5	0.3506 (5)	0.40201 (16)	0.08494 (13)	0.0332 (6)
C6	0.4017 (5)	0.36554 (17)	0.14986 (13)	0.0327 (6)
H6	0.2635	0.3341	0.1615	0.039*
C7	0.6089 (5)	0.31463 (16)	0.14147 (13)	0.0330 (6)
C8	0.7427 (5)	0.26449 (17)	0.18021 (14)	0.0340 (7)
N9	0.9221 (5)	0.23499 (15)	0.14809 (12)	0.0372 (6)
C10	1.0661 (6)	0.2425 (2)	0.03898 (16)	0.0438 (8)
H10A	1.2188	0.2281	0.0585	0.053*	0.55
H10B	1.0933	0.2859	0.0106	0.053*	0.55
H10C	1.1120	0.2880	0.0152	0.053*	0.45
H10D	1.2100	0.2217	0.0593	0.053*	0.45
C11A	0.9722 (14)	0.1768 (3)	−0.0004 (3)	0.060 (5)	0.55
C12A	0.9179 (14)	0.1866 (3)	−0.0645 (3)	0.079 (2)	0.55
H12A	0.9415	0.2341	−0.0840	0.095*	0.55
C13A	0.8290 (16)	0.1269 (4)	−0.1000 (3)	0.106 (4)	0.55
H13A	0.7919	0.1336	−0.1438	0.127*	0.55
C14A	0.7945 (17)	0.0574 (4)	−0.0714 (4)	0.126 (5)	0.55
H14A	0.7338	0.0166	−0.0957	0.151*	0.55
C15A	0.8488 (17)	0.0477 (3)	−0.0074 (4)	0.134 (5)	0.55
H15A	0.8252	0.0002	0.0122	0.161*	0.55
C16A	0.9377 (16)	0.1074 (4)	0.0282 (2)	0.100 (3)	0.55
H16A	0.9748	0.1007	0.0719	0.120*	0.55
C11B	0.9766 (14)	0.1880 (5)	−0.0057 (4)	0.047 (4)	0.45
C12B	0.7484 (13)	0.1612 (6)	−0.0118 (4)	0.091 (4)	0.45
H12B	0.6351	0.1743	0.0189	0.110*	0.45
C13B	0.6861 (16)	0.1152 (6)	−0.0627 (5)	0.115 (5)	0.45
H13B	0.5302	0.0969	−0.0668	0.138*	0.45
C14B	0.852 (2)	0.0960 (7)	−0.1075 (5)	0.140 (7)	0.45
H14B	0.8094	0.0646	−0.1423	0.169*	0.45
C15B	1.080 (2)	0.1229 (8)	−0.1014 (6)	0.249 (14)	0.45
H15B	1.1936	0.1098	−0.1321	0.299*	0.45
C16B	1.1425 (14)	0.1689 (7)	−0.0505 (6)	0.122 (5)	0.45
H16B	1.2985	0.1872	−0.0464	0.146*	0.45
N17	0.4223 (3)	0.41620 (8)	−0.02841 (6)	0.0399 (6)
H17A	0.5116	0.3977	−0.0603	0.060*
H17B	0.2870	0.4458	−0.0355	0.060*
C18	0.1547 (3)	0.45076 (8)	0.08023 (6)	0.0361 (7)
N19	−0.0041 (3)	0.49044 (8)	0.07707 (6)	0.0465 (7)
C20	0.4394 (3)	0.42549 (8)	0.20151 (6)	0.0333 (6)
C21	0.2730 (3)	0.43846 (8)	0.24634 (6)	0.0660 (12)
H21	0.1334	0.4093	0.2462	0.079*
C22	0.3071 (9)	0.4943 (3)	0.2924 (2)	0.0825 (16)
H22	0.1897	0.5039	0.3229	0.099*
C23	0.5087 (8)	0.5345 (2)	0.29324 (17)	0.0548 (10)
C24	0.6723 (8)	0.5225 (2)	0.2495 (2)	0.0604 (10)
H24	0.8128	0.5512	0.2504	0.072*
C25	0.6371 (7)	0.4684 (2)	0.20311 (18)	0.0543 (9)
H25	0.7530	0.4610	0.1718	0.065*
Cl26	0.5572 (3)	0.60204 (7)	0.35216 (6)	0.0929 (5)
C27	0.7013 (6)	0.23447 (17)	0.24463 (14)	0.0368 (7)
C28	0.8630 (7)	0.1865 (2)	0.27282 (18)	0.0548 (9)
H28	1.0078	0.1767	0.2527	0.066*
C29	0.8138 (7)	0.1527 (2)	0.33022 (18)	0.0588 (10)
H29	0.9275	0.1196	0.3482	0.071*
N30	0.6181 (6)	0.16380 (18)	0.36153 (13)	0.0514 (8)
C31	0.4668 (7)	0.2105 (3)	0.33473 (18)	0.0625 (11)
H31	0.3261	0.2205	0.3567	0.075*
C32	0.4972 (7)	0.2462 (2)	0.27684 (18)	0.0581 (10)
H32	0.3786	0.2781	0.2598	0.070*

	U11	U22	U33	U12	U13	U23
N1	0.0401 (14)	0.0352 (13)	0.0331 (13)	−0.0005 (11)	0.0039 (10)	−0.0038 (10)
C2	0.0419 (17)	0.0304 (14)	0.0286 (14)	−0.0032 (12)	0.0020 (12)	−0.0020 (11)
O3	0.0438 (12)	0.0397 (11)	0.0268 (10)	0.0027 (9)	0.0048 (8)	−0.0002 (8)
C4	0.0413 (16)	0.0289 (14)	0.0282 (14)	−0.0028 (12)	0.0011 (12)	−0.0017 (11)
C5	0.0387 (16)	0.0333 (15)	0.0277 (14)	−0.0012 (12)	0.0030 (12)	−0.0006 (11)
C6	0.0382 (16)	0.0336 (15)	0.0265 (14)	−0.0035 (12)	0.0037 (11)	0.0002 (11)
C7	0.0377 (16)	0.0317 (14)	0.0297 (14)	−0.0038 (12)	0.0032 (12)	−0.0022 (11)
C8	0.0381 (16)	0.0321 (15)	0.0319 (15)	−0.0040 (12)	0.0010 (12)	−0.0003 (12)
N9	0.0420 (14)	0.0356 (13)	0.0341 (13)	−0.0002 (11)	0.0008 (11)	−0.0014 (10)
C10	0.0424 (18)	0.0462 (19)	0.0433 (18)	−0.0002 (15)	0.0096 (14)	−0.0066 (15)
C11A	0.096 (11)	0.045 (5)	0.040 (6)	−0.010 (5)	0.008 (5)	−0.024 (4)
C12A	0.119 (6)	0.067 (5)	0.052 (4)	0.008 (5)	−0.023 (4)	0.002 (4)
C13A	0.142 (8)	0.101 (7)	0.074 (6)	0.009 (6)	−0.036 (6)	−0.025 (6)
C14A	0.167 (9)	0.110 (8)	0.100 (7)	−0.041 (7)	−0.009 (7)	−0.030 (6)
C15A	0.187 (9)	0.098 (7)	0.116 (8)	−0.044 (7)	−0.008 (7)	−0.020 (6)
C16A	0.149 (8)	0.074 (5)	0.077 (5)	−0.039 (6)	−0.010 (5)	−0.005 (4)
C11B	0.042 (7)	0.048 (5)	0.050 (7)	0.003 (5)	0.003 (5)	0.003 (5)
C12B	0.077 (6)	0.090 (7)	0.107 (7)	−0.008 (5)	−0.003 (6)	−0.054 (6)
C13B	0.104 (8)	0.113 (8)	0.129 (9)	0.000 (7)	−0.007 (7)	−0.036 (7)
C14B	0.155 (11)	0.131 (10)	0.135 (11)	−0.040 (8)	0.000 (8)	−0.049 (8)
C15B	0.248 (16)	0.252 (16)	0.248 (16)	−0.014 (10)	0.019 (10)	−0.033 (10)
C16B	0.129 (9)	0.128 (9)	0.110 (8)	−0.033 (7)	0.036 (7)	−0.057 (7)
N17	0.0501 (16)	0.0441 (15)	0.0255 (12)	0.0034 (12)	0.0042 (11)	0.0018 (11)
C18	0.0428 (17)	0.0410 (17)	0.0248 (14)	−0.0051 (14)	0.0044 (12)	−0.0004 (12)
N19	0.0488 (17)	0.0581 (18)	0.0329 (14)	0.0104 (15)	0.0056 (12)	0.0024 (12)
C20	0.0396 (16)	0.0359 (15)	0.0244 (13)	0.0051 (13)	0.0006 (11)	−0.0005 (11)
C21	0.052 (2)	0.091 (3)	0.056 (2)	−0.008 (2)	0.0152 (18)	−0.032 (2)
C22	0.075 (3)	0.112 (4)	0.061 (3)	0.011 (3)	0.018 (2)	−0.046 (3)
C23	0.072 (3)	0.047 (2)	0.0450 (19)	0.0216 (19)	−0.0219 (18)	−0.0117 (16)
C24	0.069 (3)	0.048 (2)	0.064 (2)	−0.0149 (19)	−0.002 (2)	−0.0152 (18)
C25	0.059 (2)	0.051 (2)	0.053 (2)	−0.0166 (18)	0.0170 (17)	−0.0129 (17)
Cl26	0.1409 (12)	0.0647 (7)	0.0714 (7)	0.0405 (7)	−0.0474 (8)	−0.0352 (6)
C27	0.0437 (17)	0.0337 (15)	0.0330 (15)	−0.0048 (13)	−0.0019 (13)	0.0017 (12)
C28	0.054 (2)	0.062 (2)	0.049 (2)	0.0111 (18)	0.0050 (17)	0.0155 (17)
C29	0.065 (2)	0.062 (2)	0.049 (2)	0.008 (2)	0.0004 (18)	0.0187 (18)
N30	0.0636 (19)	0.0524 (18)	0.0380 (15)	−0.0055 (15)	−0.0010 (14)	0.0104 (13)
C31	0.061 (2)	0.081 (3)	0.046 (2)	0.008 (2)	0.0127 (18)	0.020 (2)
C32	0.058 (2)	0.070 (3)	0.047 (2)	0.015 (2)	0.0106 (17)	0.0203 (18)

N1—C2	1.338 (4)	C11B—C16B	1.3900
N1—N9	1.357 (3)	C12B—C13B	1.3900
N1—C10	1.457 (4)	C12B—H12B	0.9500
C2—O3	1.364 (3)	C13B—C14B	1.3900
C2—C7	1.365 (4)	C13B—H13B	0.9500
O3—C4	1.376 (4)	C14B—C15B	1.3900
C4—N17	1.342 (3)	C14B—H14B	0.9500
C4—C5	1.370 (4)	C15B—C16B	1.3900
C5—C18	1.416 (3)	C15B—H15B	0.9500
C5—C6	1.537 (4)	C16B—H16B	0.9500
C6—C7	1.502 (4)	N17—H17A	0.9113
C6—C20	1.536 (3)	N17—H17B	0.9442
C6—H6	1.0000	C18—N19	1.1496
C7—C8	1.422 (4)	C20—C25	1.362 (4)
C8—N9	1.342 (4)	C20—C21	1.3687
C8—C27	1.481 (4)	C21—C22	1.401 (5)
C10—C11B	1.438 (7)	C21—H21	0.9500
C10—C11A	1.524 (5)	C22—C23	1.354 (7)
C10—H10A	0.9900	C22—H22	0.9500
C10—H10B	0.9900	C23—C24	1.338 (6)
C10—H10C	0.9900	C23—Cl26	1.746 (4)
C10—H10D	0.9900	C24—C25	1.385 (5)
C11A—C12A	1.3900	C24—H24	0.9500
C11A—C16A	1.3900	C25—H25	0.9500
C12A—C13A	1.3900	C27—C32	1.373 (5)
C12A—H12A	0.9500	C27—C28	1.383 (5)
C13A—C14A	1.3900	C28—C29	1.382 (5)
C13A—H13A	0.9500	C28—H28	0.9500
C14A—C15A	1.3900	C29—N30	1.320 (5)
C14A—H14A	0.9500	C29—H29	0.9500
C15A—C16A	1.3900	N30—C31	1.318 (5)
C15A—H15A	0.9500	C31—C32	1.387 (5)
C16A—H16A	0.9500	C31—H31	0.9500
C11B—C12B	1.3900	C32—H32	0.9500
C2—N1—N9	109.8 (2)	C14A—C15A—H15A	120.0
C2—N1—C10	128.6 (3)	C15A—C16A—C11A	120.0
N9—N1—C10	121.5 (3)	C15A—C16A—H16A	120.0
N1—C2—O3	119.7 (2)	C11A—C16A—H16A	120.0
N1—C2—C7	110.8 (3)	C12B—C11B—C16B	120.0
O3—C2—C7	129.5 (3)	C12B—C11B—C10	127.8 (6)
C2—O3—C4	114.1 (2)	C16B—C11B—C10	111.8 (6)
N17—C4—C5	128.3 (3)	C13B—C12B—C11B	120.0
N17—C4—O3	109.6 (2)	C13B—C12B—H12B	120.0
C5—C4—O3	122.1 (3)	C11B—C12B—H12B	120.0
C4—C5—C18	116.3 (2)	C12B—C13B—C14B	120.0
C4—C5—C6	126.4 (3)	C12B—C13B—H13B	120.0
C18—C5—C6	117.3 (2)	C14B—C13B—H13B	120.0
C7—C6—C20	113.6 (2)	C15B—C14B—C13B	120.0
C7—C6—C5	106.7 (2)	C15B—C14B—H14B	120.0
C20—C6—C5	111.0 (2)	C13B—C14B—H14B	120.0
C7—C6—H6	108.4	C14B—C15B—C16B	120.0
C20—C6—H6	108.4	C14B—C15B—H15B	120.0
C5—C6—H6	108.4	C16B—C15B—H15B	120.0
C2—C7—C8	102.5 (3)	C15B—C16B—C11B	120.0
C2—C7—C6	120.9 (3)	C15B—C16B—H16B	120.0
C8—C7—C6	136.6 (3)	C11B—C16B—H16B	120.0
N9—C8—C7	111.2 (3)	C4—N17—H17A	116.2
N9—C8—C27	117.1 (3)	C4—N17—H17B	119.7
C7—C8—C27	131.3 (3)	H17A—N17—H17B	123.3
C8—N9—N1	105.7 (2)	N19—C18—C5	179.30 (13)
C11B—C10—N1	116.0 (4)	C25—C20—C21	118.13 (16)
C11B—C10—C11A	8.3 (5)	C25—C20—C6	120.9 (2)
N1—C10—C11A	112.7 (4)	C21—C20—C6	120.99 (12)
C11B—C10—H10A	113.4	C20—C21—C22	120.5 (2)
N1—C10—H10A	109.1	C20—C21—H21	119.7
C11A—C10—H10A	109.1	C22—C21—H21	119.7
C11B—C10—H10B	100.8	C23—C22—C21	119.4 (3)
N1—C10—H10B	109.1	C23—C22—H22	120.3
C11A—C10—H10B	109.1	C21—C22—H22	120.3
H10A—C10—H10B	107.8	C24—C23—C22	120.6 (3)
C11B—C10—H10C	108.3	C24—C23—Cl26	119.6 (3)
N1—C10—H10C	108.3	C22—C23—Cl26	119.8 (3)
C11A—C10—H10C	116.4	C23—C24—C25	120.1 (4)
H10A—C10—H10C	100.5	C23—C24—H24	119.9
H10B—C10—H10C	8.5	C25—C24—H24	119.9
C11B—C10—H10D	108.3	C20—C25—C24	121.2 (3)
N1—C10—H10D	108.3	C20—C25—H25	119.4
C11A—C10—H10D	103.3	C24—C25—H25	119.4
H10A—C10—H10D	7.3	C32—C27—C28	116.5 (3)
H10B—C10—H10D	114.5	C32—C27—C8	123.2 (3)
H10C—C10—H10D	107.4	C28—C27—C8	120.0 (3)
C12A—C11A—C16A	120.0	C29—C28—C27	120.0 (4)
C12A—C11A—C10	120.2 (4)	C29—C28—H28	120.0
C16A—C11A—C10	119.8 (4)	C27—C28—H28	120.0
C11A—C12A—C13A	120.0	N30—C29—C28	123.8 (4)
C11A—C12A—H12A	120.0	N30—C29—H29	118.1
C13A—C12A—H12A	120.0	C28—C29—H29	118.1
C12A—C13A—C14A	120.0	C31—N30—C29	115.7 (3)
C12A—C13A—H13A	120.0	N30—C31—C32	125.0 (4)
C14A—C13A—H13A	120.0	N30—C31—H31	117.5
C13A—C14A—C15A	120.0	C32—C31—H31	117.5
C13A—C14A—H14A	120.0	C27—C32—C31	118.9 (4)
C15A—C14A—H14A	120.0	C27—C32—H32	120.5
C16A—C15A—C14A	120.0	C31—C32—H32	120.5
C16A—C15A—H15A	120.0
N9—N1—C2—O3	−177.1 (2)	C13A—C14A—C15A—C16A	0.0
C10—N1—C2—O3	−1.6 (5)	C14A—C15A—C16A—C11A	0.0
N9—N1—C2—C7	1.2 (3)	C12A—C11A—C16A—C15A	0.0
C10—N1—C2—C7	176.6 (3)	C10—C11A—C16A—C15A	179.0 (7)
N1—C2—O3—C4	179.3 (3)	N1—C10—C11B—C12B	8.6 (10)
C7—C2—O3—C4	1.4 (4)	C11A—C10—C11B—C12B	76 (4)
C2—O3—C4—N17	−175.7 (2)	N1—C10—C11B—C16B	−178.7 (6)
C2—O3—C4—C5	2.8 (4)	C11A—C10—C11B—C16B	−111 (4)
N17—C4—C5—C18	−2.8 (4)	C16B—C11B—C12B—C13B	0.0
O3—C4—C5—C18	179.0 (2)	C10—C11B—C12B—C13B	172.3 (10)
N17—C4—C5—C6	174.6 (3)	C11B—C12B—C13B—C14B	0.0
O3—C4—C5—C6	−3.5 (5)	C12B—C13B—C14B—C15B	0.0
C4—C5—C6—C7	0.2 (4)	C13B—C14B—C15B—C16B	0.0
C18—C5—C6—C7	177.6 (2)	C14B—C15B—C16B—C11B	0.0
C4—C5—C6—C20	124.6 (3)	C12B—C11B—C16B—C15B	0.0
C18—C5—C6—C20	−58.0 (3)	C10—C11B—C16B—C15B	−173.4 (9)
N1—C2—C7—C8	−1.2 (3)	C4—C5—C18—N19	−160 (100)
O3—C2—C7—C8	176.8 (3)	C6—C5—C18—N19	22 (11)
N1—C2—C7—C6	177.1 (3)	C7—C6—C20—C25	48.8 (3)
O3—C2—C7—C6	−4.8 (5)	C5—C6—C20—C25	−71.5 (3)
C20—C6—C7—C2	−119.2 (3)	C7—C6—C20—C21	−132.64 (18)
C5—C6—C7—C2	3.6 (4)	C5—C6—C20—C21	107.0 (2)
C20—C6—C7—C8	58.5 (4)	C25—C20—C21—C22	−0.1 (3)
C5—C6—C7—C8	−178.8 (3)	C6—C20—C21—C22	−178.7 (3)
C2—C7—C8—N9	0.9 (3)	C20—C21—C22—C23	−1.4 (6)
C6—C7—C8—N9	−177.0 (3)	C21—C22—C23—C24	1.7 (7)
C2—C7—C8—C27	−171.3 (3)	C21—C22—C23—Cl26	−177.8 (3)
C6—C7—C8—C27	10.8 (6)	C22—C23—C24—C25	−0.4 (7)
C7—C8—N9—N1	−0.2 (3)	Cl26—C23—C24—C25	179.1 (3)
C27—C8—N9—N1	173.2 (2)	C21—C20—C25—C24	1.4 (5)
C2—N1—N9—C8	−0.6 (3)	C6—C20—C25—C24	180.0 (3)
C10—N1—N9—C8	−176.4 (3)	C23—C24—C25—C20	−1.2 (6)
C2—N1—C10—C11B	−75.7 (6)	N9—C8—C27—C32	−164.6 (3)
N9—N1—C10—C11B	99.3 (6)	C7—C8—C27—C32	7.2 (5)
C2—N1—C10—C11A	−84.0 (5)	N9—C8—C27—C28	9.2 (5)
N9—N1—C10—C11A	91.0 (4)	C7—C8—C27—C28	−179.0 (3)
C11B—C10—C11A—C12A	0(3)	C32—C27—C28—C29	0.5 (6)
N1—C10—C11A—C12A	115.3 (5)	C8—C27—C28—C29	−173.7 (3)
C11B—C10—C11A—C16A	−179 (4)	C27—C28—C29—N30	−0.7 (7)
N1—C10—C11A—C16A	−63.8 (6)	C28—C29—N30—C31	−0.3 (6)
C16A—C11A—C12A—C13A	0.0	C29—N30—C31—C32	1.6 (7)
C10—C11A—C12A—C13A	−179.0 (7)	C28—C27—C32—C31	0.6 (6)
C11A—C12A—C13A—C14A	0.0	C8—C27—C32—C31	174.6 (4)
C12A—C13A—C14A—C15A	0.0	N30—C31—C32—C27	−1.7 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17A···N30i	0.91	2.08	2.955 (3)	162
N17—H17B···N19ii	0.94	2.15	3.068 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N17—H17A⋯N30i	0.91	2.08	2.955 (3)	162
N17—H17B⋯N19ii	0.94	2.15	3.068 (3)	165

Symmetry codes: (i) ; (ii) .