Crystal structure of (4Z)-4-[(2E)-3-(4-chloro-phen-yl)-1-hy-droxy-prop-2-en-1-yl-idene]-5-methyl-2-phenyl-1H-pyrazol-5(4H)-one.

In the the asymmetric unit of the title compound, C19H15ClN2O2, there are two symmetry-independent mol-ecules, which adopt similar conformations. The largest difference is observed in the dihedral angles between the phenyl and the pyrazole fragments [17.00 (12) and 23.42 (10)°]. A strong intra-molecular O-H⋯O hydrogen bond with the S (6) motif is observed in both mol-ecules. Pairs of π-π stacking inter-actions between the phenyl groups [centroid-centroid distances = 3.6627 (13) and 3.7156 (14) Å] assemble the mol-ecules into two types of centrosymmetric dimers. Weak C-H⋯O inter-actions connect mol-ecules into chains along the b axis.

Related literature

For related structures and background, see: Chaudhry et al. (2012 ▸); Holzer et al. (1999 ▸); Malik et al. (2009 ▸).

Experimental

Crystal data

C19H15ClN2O2

M = 338.78

Triclinic,

a = 11.3207 (6) Å

b = 11.4044 (6) Å

c = 15.2839 (9) Å

α = 70.567 (3)°

β = 70.925 (3)°

γ = 62.621 (2)°

V = 1616.40 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 296 K

0.35 × 0.28 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T min = 0.919, T max = 0.963

24363 measured reflections

6925 independent reflections

4587 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.155

S = 1.02

6925 reflections

437 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500883X/gk2632sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500883X/gk2632Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S205698901500883X/gk2632fig1.tif

View of the asymmetric unit. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.

Click here for additional data file.

PLATON . DOI: 10.1107/S205698901500883X/gk2632fig2.tif

The partial packing (PLATON; Spek, 2009) showing fragments of two chains via C—H⋯O inter­actions.

CCDC reference: 1063448

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

C19H15ClN2O2	Z = 4
Mr = 338.78	F(000) = 704
Triclinic, P1	Dx = 1.392 Mg m−3
a = 11.3207 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4044 (6) Å	Cell parameters from 4689 reflections
c = 15.2839 (9) Å	θ = 1.4–27.0°
α = 70.567 (3)°	µ = 0.25 mm−1
β = 70.925 (3)°	T = 296 K
γ = 62.621 (2)°	Plate, red
V = 1616.40 (16) Å3	0.35 × 0.28 × 0.16 mm

Bruker Kappa APEXII CCD diffractometer	6925 independent reflections
Radiation source: fine-focus sealed tube	4587 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 7.80 pixels mm-1	θmax = 27.0°, θmin = 1.4°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→14
Tmin = 0.919, Tmax = 0.963	l = −18→19
24363 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0798P)2 + 0.3075P] where P = (Fo2 + 2Fc2)/3
6925 reflections	(Δ/σ)max < 0.001
437 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.32 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
Cl1	−0.47686 (7)	−0.29735 (7)	0.36338 (6)	0.0759 (2)
O1	0.30105 (14)	0.03074 (15)	0.37120 (13)	0.0633 (4)
O2	0.17939 (15)	−0.11029 (15)	0.37314 (13)	0.0627 (4)
H2A	0.2397	−0.0885	0.3718	0.094*
N1	0.15162 (16)	0.25570 (17)	0.37444 (12)	0.0473 (4)
N2	0.01106 (16)	0.33184 (17)	0.38151 (13)	0.0523 (5)
C1	0.2367 (2)	0.3144 (2)	0.37686 (14)	0.0438 (5)
C2	0.3765 (2)	0.2576 (2)	0.34316 (15)	0.0531 (5)
H2	0.4150	0.1827	0.3160	0.064*
C3	0.4570 (2)	0.3133 (3)	0.35038 (17)	0.0601 (6)
H3	0.5506	0.2752	0.3283	0.072*
C4	0.4017 (3)	0.4242 (3)	0.38966 (18)	0.0662 (7)
H4	0.4573	0.4601	0.3951	0.079*
C5	0.2636 (3)	0.4815 (2)	0.42084 (17)	0.0640 (6)
H5	0.2255	0.5579	0.4461	0.077*
C6	0.1805 (2)	0.4273 (2)	0.41528 (15)	0.0532 (5)
H6	0.0870	0.4664	0.4373	0.064*
C7	0.1839 (2)	0.1261 (2)	0.37349 (15)	0.0476 (5)
C8	0.06103 (19)	0.1169 (2)	0.37778 (14)	0.0446 (5)
C9	−0.0411 (2)	0.2509 (2)	0.38279 (15)	0.0476 (5)
C10	−0.1907 (2)	0.3019 (2)	0.38925 (18)	0.0619 (6)
H10A	−0.2325	0.3964	0.3902	0.093*
H10B	−0.2297	0.2527	0.4464	0.093*
H10C	−0.2060	0.2894	0.3354	0.093*
C11	0.0633 (2)	−0.0054 (2)	0.37681 (15)	0.0471 (5)
C12	−0.0535 (2)	−0.0281 (2)	0.37934 (15)	0.0486 (5)
H12	−0.1397	0.0394	0.3917	0.058*
C13	−0.0426 (2)	−0.1408 (2)	0.36480 (14)	0.0470 (5)
H13	0.0452	−0.2058	0.3527	0.056*
C14	−0.15161 (19)	−0.17573 (19)	0.36545 (13)	0.0411 (4)
C15	−0.2886 (2)	−0.1023 (2)	0.40044 (15)	0.0484 (5)
H15	−0.3129	−0.0279	0.4249	0.058*
C16	−0.3879 (2)	−0.1390 (2)	0.39903 (15)	0.0504 (5)
H16	−0.4789	−0.0891	0.4219	0.061*
C17	−0.3518 (2)	−0.2496 (2)	0.36372 (15)	0.0488 (5)
C18	−0.2180 (2)	−0.3242 (2)	0.32883 (15)	0.0496 (5)
H18	−0.1947	−0.3984	0.3044	0.059*
C19	−0.1191 (2)	−0.2870 (2)	0.33063 (14)	0.0469 (5)
H19	−0.0284	−0.3377	0.3079	0.056*
Cl2	1.30602 (7)	0.98559 (7)	0.13178 (6)	0.0820 (2)
N3	0.75509 (18)	0.35396 (17)	0.12243 (13)	0.0507 (4)
N4	0.68090 (19)	0.49510 (17)	0.10654 (14)	0.0556 (5)
O3	0.97609 (16)	0.20330 (14)	0.14297 (13)	0.0664 (5)
O4	1.11542 (15)	0.32575 (15)	0.14249 (13)	0.0629 (4)
H4A	1.0921	0.2649	0.1481	0.094*
C20	0.6945 (2)	0.2690 (2)	0.12269 (14)	0.0480 (5)
C21	0.5784 (2)	0.3249 (3)	0.08691 (16)	0.0592 (6)
H21	0.5397	0.4176	0.0630	0.071*
C22	0.5202 (3)	0.2425 (3)	0.08689 (19)	0.0708 (7)
H22	0.4415	0.2803	0.0632	0.085*
C23	0.5763 (3)	0.1058 (3)	0.12117 (19)	0.0739 (7)
H23	0.5369	0.0507	0.1200	0.089*
C24	0.6914 (3)	0.0508 (3)	0.15718 (17)	0.0662 (7)
H24	0.7294	−0.0420	0.1808	0.079*
C25	0.7512 (2)	0.1304 (2)	0.15898 (16)	0.0578 (6)
H25	0.8288	0.0922	0.1841	0.069*
C26	0.8828 (2)	0.3216 (2)	0.13010 (15)	0.0499 (5)
C27	0.8924 (2)	0.4451 (2)	0.12111 (15)	0.0474 (5)
C28	0.7614 (2)	0.5477 (2)	0.10651 (15)	0.0498 (5)
C29	0.7111 (3)	0.6984 (2)	0.09116 (18)	0.0636 (6)
H29A	0.6187	0.7397	0.0833	0.095*
H29B	0.7669	0.7314	0.0353	0.095*
H29C	0.7154	0.7206	0.1451	0.095*
C30	1.0133 (2)	0.4430 (2)	0.12793 (15)	0.0498 (5)
C31	1.0370 (2)	0.5599 (2)	0.12068 (15)	0.0508 (5)
H31	0.9718	0.6453	0.1022	0.061*
C32	1.1478 (2)	0.5509 (2)	0.13923 (14)	0.0492 (5)
H32	1.2114	0.4637	0.1558	0.059*
C33	1.1824 (2)	0.6600 (2)	0.13693 (14)	0.0444 (5)
C34	1.2924 (2)	0.6291 (2)	0.17330 (15)	0.0513 (5)
H34	1.3428	0.5393	0.1982	0.062*
C35	1.3295 (2)	0.7284 (2)	0.17355 (16)	0.0577 (6)
H35	1.4032	0.7061	0.1990	0.069*
C36	1.2560 (2)	0.8606 (2)	0.13566 (16)	0.0538 (5)
C37	1.1451 (2)	0.8952 (2)	0.09963 (17)	0.0586 (6)
H37	1.0956	0.9853	0.0747	0.070*
C38	1.1081 (2)	0.7963 (2)	0.10069 (16)	0.0542 (6)
H38	1.0323	0.8199	0.0770	0.065*

	U11	U22	U33	U12	U13	U23
Cl1	0.0599 (4)	0.0658 (4)	0.1194 (6)	−0.0307 (3)	−0.0291 (4)	−0.0219 (4)
O1	0.0380 (8)	0.0445 (8)	0.1090 (13)	−0.0038 (7)	−0.0233 (8)	−0.0291 (8)
O2	0.0411 (8)	0.0459 (9)	0.1043 (13)	−0.0087 (7)	−0.0231 (8)	−0.0249 (8)
N1	0.0358 (9)	0.0392 (9)	0.0648 (11)	−0.0090 (7)	−0.0129 (8)	−0.0149 (8)
N2	0.0338 (9)	0.0410 (9)	0.0739 (12)	−0.0062 (8)	−0.0120 (8)	−0.0142 (9)
C1	0.0432 (11)	0.0398 (10)	0.0479 (11)	−0.0167 (9)	−0.0102 (9)	−0.0079 (9)
C2	0.0468 (12)	0.0518 (13)	0.0585 (13)	−0.0193 (10)	−0.0050 (10)	−0.0156 (10)
C3	0.0516 (13)	0.0650 (15)	0.0670 (15)	−0.0308 (12)	−0.0108 (11)	−0.0085 (12)
C4	0.0781 (18)	0.0654 (16)	0.0728 (16)	−0.0422 (14)	−0.0256 (14)	−0.0061 (13)
C5	0.0792 (18)	0.0535 (14)	0.0684 (16)	−0.0278 (13)	−0.0195 (13)	−0.0177 (12)
C6	0.0535 (13)	0.0481 (12)	0.0564 (13)	−0.0178 (10)	−0.0073 (10)	−0.0165 (10)
C7	0.0412 (11)	0.0403 (11)	0.0605 (13)	−0.0111 (9)	−0.0139 (9)	−0.0139 (9)
C8	0.0364 (10)	0.0408 (11)	0.0571 (12)	−0.0112 (9)	−0.0157 (9)	−0.0113 (9)
C9	0.0365 (11)	0.0428 (11)	0.0591 (13)	−0.0113 (9)	−0.0128 (9)	−0.0095 (10)
C10	0.0408 (12)	0.0479 (13)	0.0874 (17)	−0.0077 (10)	−0.0162 (11)	−0.0148 (12)
C11	0.0385 (11)	0.0447 (12)	0.0584 (13)	−0.0120 (9)	−0.0152 (9)	−0.0128 (9)
C12	0.0395 (11)	0.0433 (11)	0.0620 (13)	−0.0115 (9)	−0.0151 (9)	−0.0128 (10)
C13	0.0388 (11)	0.0445 (12)	0.0552 (12)	−0.0129 (9)	−0.0122 (9)	−0.0104 (9)
C14	0.0386 (10)	0.0356 (10)	0.0467 (11)	−0.0120 (8)	−0.0124 (8)	−0.0064 (8)
C15	0.0429 (11)	0.0402 (11)	0.0624 (13)	−0.0112 (9)	−0.0114 (9)	−0.0187 (10)
C16	0.0354 (11)	0.0449 (12)	0.0672 (14)	−0.0089 (9)	−0.0120 (10)	−0.0165 (10)
C17	0.0455 (12)	0.0427 (11)	0.0610 (13)	−0.0184 (10)	−0.0199 (10)	−0.0047 (10)
C18	0.0557 (13)	0.0337 (10)	0.0603 (13)	−0.0161 (10)	−0.0151 (10)	−0.0106 (9)
C19	0.0408 (11)	0.0385 (11)	0.0560 (12)	−0.0111 (9)	−0.0085 (9)	−0.0118 (9)
Cl2	0.0742 (5)	0.0591 (4)	0.1263 (6)	−0.0358 (3)	−0.0237 (4)	−0.0197 (4)
N3	0.0475 (10)	0.0362 (9)	0.0649 (11)	−0.0116 (8)	−0.0182 (8)	−0.0075 (8)
N4	0.0510 (11)	0.0364 (9)	0.0718 (12)	−0.0076 (8)	−0.0201 (9)	−0.0095 (8)
O3	0.0548 (10)	0.0347 (8)	0.1091 (13)	−0.0077 (7)	−0.0308 (9)	−0.0159 (8)
O4	0.0520 (9)	0.0385 (8)	0.0979 (12)	−0.0100 (7)	−0.0209 (8)	−0.0205 (8)
C20	0.0513 (12)	0.0464 (12)	0.0463 (12)	−0.0206 (10)	−0.0108 (9)	−0.0071 (9)
C21	0.0584 (14)	0.0560 (14)	0.0602 (14)	−0.0151 (11)	−0.0224 (11)	−0.0100 (11)
C22	0.0643 (16)	0.083 (2)	0.0764 (17)	−0.0264 (14)	−0.0289 (13)	−0.0207 (14)
C23	0.0816 (19)	0.086 (2)	0.0763 (18)	−0.0487 (17)	−0.0184 (14)	−0.0195 (15)
C24	0.0820 (18)	0.0561 (14)	0.0696 (16)	−0.0380 (13)	−0.0227 (13)	−0.0021 (12)
C25	0.0619 (14)	0.0497 (13)	0.0643 (14)	−0.0257 (11)	−0.0241 (11)	0.0009 (11)
C26	0.0482 (12)	0.0410 (11)	0.0573 (13)	−0.0136 (10)	−0.0142 (10)	−0.0098 (9)
C27	0.0495 (12)	0.0368 (10)	0.0553 (12)	−0.0134 (9)	−0.0142 (9)	−0.0112 (9)
C28	0.0518 (13)	0.0371 (11)	0.0536 (13)	−0.0106 (10)	−0.0136 (10)	−0.0091 (9)
C29	0.0634 (15)	0.0384 (12)	0.0806 (17)	−0.0073 (11)	−0.0248 (13)	−0.0121 (11)
C30	0.0516 (13)	0.0395 (11)	0.0543 (13)	−0.0130 (10)	−0.0097 (10)	−0.0142 (9)
C31	0.0504 (13)	0.0397 (11)	0.0607 (13)	−0.0141 (10)	−0.0116 (10)	−0.0144 (10)
C32	0.0494 (12)	0.0395 (11)	0.0533 (12)	−0.0132 (9)	−0.0073 (10)	−0.0134 (9)
C33	0.0409 (11)	0.0390 (10)	0.0490 (12)	−0.0132 (9)	−0.0055 (9)	−0.0121 (9)
C34	0.0472 (12)	0.0406 (11)	0.0593 (13)	−0.0120 (9)	−0.0149 (10)	−0.0066 (10)
C35	0.0464 (13)	0.0573 (14)	0.0711 (15)	−0.0184 (11)	−0.0197 (11)	−0.0116 (11)
C36	0.0488 (13)	0.0458 (12)	0.0663 (14)	−0.0198 (10)	−0.0075 (10)	−0.0141 (10)
C37	0.0526 (13)	0.0380 (11)	0.0812 (16)	−0.0133 (10)	−0.0209 (12)	−0.0079 (11)
C38	0.0461 (12)	0.0442 (12)	0.0727 (15)	−0.0135 (10)	−0.0219 (11)	−0.0101 (11)

Cl1—C17	1.736 (2)	Cl2—C36	1.738 (2)
O1—C7	1.269 (2)	N3—C26	1.354 (3)
O2—C11	1.309 (2)	N3—N4	1.409 (2)
O2—H2A	0.8200	N3—C20	1.419 (3)
N1—C7	1.353 (3)	N4—C28	1.301 (3)
N1—N2	1.406 (2)	O3—C26	1.274 (2)
N1—C1	1.418 (2)	O4—C30	1.312 (2)
N2—C9	1.298 (3)	O4—H4A	0.8200
C1—C6	1.383 (3)	C20—C21	1.379 (3)
C1—C2	1.391 (3)	C20—C25	1.391 (3)
C2—C3	1.376 (3)	C21—C22	1.373 (3)
C2—H2	0.9300	C21—H21	0.9300
C3—C4	1.372 (4)	C22—C23	1.369 (4)
C3—H3	0.9300	C22—H22	0.9300
C4—C5	1.371 (3)	C23—C24	1.371 (4)
C4—H4	0.9300	C23—H23	0.9300
C5—C6	1.377 (3)	C24—C25	1.370 (3)
C5—H5	0.9300	C24—H24	0.9300
C6—H6	0.9300	C25—H25	0.9300
C7—C8	1.422 (3)	C26—C27	1.419 (3)
C8—C11	1.388 (3)	C27—C30	1.395 (3)
C8—C9	1.439 (3)	C27—C28	1.436 (3)
C9—C10	1.496 (3)	C28—C29	1.501 (3)
C10—H10A	0.9600	C29—H29A	0.9600
C10—H10B	0.9600	C29—H29B	0.9600
C10—H10C	0.9600	C29—H29C	0.9600
C11—C12	1.447 (3)	C30—C31	1.440 (3)
C12—C13	1.321 (3)	C31—C32	1.326 (3)
C12—H12	0.9300	C31—H31	0.9300
C13—C14	1.457 (3)	C32—C33	1.454 (3)
C13—H13	0.9300	C32—H32	0.9300
C14—C19	1.386 (3)	C33—C34	1.379 (3)
C14—C15	1.398 (3)	C33—C38	1.400 (3)
C15—C16	1.376 (3)	C34—C35	1.378 (3)
C15—H15	0.9300	C34—H34	0.9300
C16—C17	1.373 (3)	C35—C36	1.371 (3)
C16—H16	0.9300	C35—H35	0.9300
C17—C18	1.375 (3)	C36—C37	1.373 (3)
C18—C19	1.378 (3)	C37—C38	1.366 (3)
C18—H18	0.9300	C37—H37	0.9300
C19—H19	0.9300	C38—H38	0.9300
C11—O2—H2A	109.5	C26—N3—N4	110.82 (17)
C7—N1—N2	110.82 (16)	C26—N3—C20	129.58 (18)
C7—N1—C1	128.74 (17)	N4—N3—C20	119.48 (17)
N2—N1—C1	120.22 (16)	C28—N4—N3	106.55 (17)
C9—N2—N1	106.60 (16)	C30—O4—H4A	109.5
C6—C1—C2	119.7 (2)	C21—C20—C25	120.0 (2)
C6—C1—N1	119.60 (18)	C21—C20—N3	119.53 (19)
C2—C1—N1	120.64 (19)	C25—C20—N3	120.5 (2)
C3—C2—C1	119.3 (2)	C22—C21—C20	119.4 (2)
C3—C2—H2	120.4	C22—C21—H21	120.3
C1—C2—H2	120.4	C20—C21—H21	120.3
C4—C3—C2	121.1 (2)	C23—C22—C21	121.0 (2)
C4—C3—H3	119.4	C23—C22—H22	119.5
C2—C3—H3	119.4	C21—C22—H22	119.5
C5—C4—C3	119.3 (2)	C22—C23—C24	119.3 (3)
C5—C4—H4	120.3	C22—C23—H23	120.4
C3—C4—H4	120.3	C24—C23—H23	120.4
C4—C5—C6	120.9 (2)	C25—C24—C23	121.1 (2)
C4—C5—H5	119.6	C25—C24—H24	119.4
C6—C5—H5	119.6	C23—C24—H24	119.4
C5—C6—C1	119.7 (2)	C24—C25—C20	119.1 (2)
C5—C6—H6	120.2	C24—C25—H25	120.4
C1—C6—H6	120.2	C20—C25—H25	120.4
O1—C7—N1	126.47 (19)	O3—C26—N3	126.6 (2)
O1—C7—C8	126.7 (2)	O3—C26—C27	126.8 (2)
N1—C7—C8	106.78 (17)	N3—C26—C27	106.63 (18)
C11—C8—C7	119.71 (18)	C30—C27—C26	119.56 (19)
C11—C8—C9	136.05 (19)	C30—C27—C28	135.7 (2)
C7—C8—C9	104.24 (18)	C26—C27—C28	104.70 (19)
N2—C9—C8	111.55 (18)	N4—C28—C27	111.28 (19)
N2—C9—C10	119.92 (18)	N4—C28—C29	119.4 (2)
C8—C9—C10	128.53 (19)	C27—C28—C29	129.3 (2)
C9—C10—H10A	109.5	C28—C29—H29A	109.5
C9—C10—H10B	109.5	C28—C29—H29B	109.5
H10A—C10—H10B	109.5	H29A—C29—H29B	109.5
C9—C10—H10C	109.5	C28—C29—H29C	109.5
H10A—C10—H10C	109.5	H29A—C29—H29C	109.5
H10B—C10—H10C	109.5	H29B—C29—H29C	109.5
O2—C11—C8	118.66 (18)	O4—C30—C27	118.5 (2)
O2—C11—C12	115.98 (19)	O4—C30—C31	116.0 (2)
C8—C11—C12	125.37 (19)	C27—C30—C31	125.50 (19)
C13—C12—C11	122.6 (2)	C32—C31—C30	122.8 (2)
C13—C12—H12	118.7	C32—C31—H31	118.6
C11—C12—H12	118.7	C30—C31—H31	118.6
C12—C13—C14	127.80 (19)	C31—C32—C33	128.2 (2)
C12—C13—H13	116.1	C31—C32—H32	115.9
C14—C13—H13	116.1	C33—C32—H32	115.9
C19—C14—C15	118.03 (19)	C34—C33—C38	117.9 (2)
C19—C14—C13	119.07 (18)	C34—C33—C32	118.95 (19)
C15—C14—C13	122.90 (19)	C38—C33—C32	123.16 (19)
C16—C15—C14	120.7 (2)	C35—C34—C33	121.5 (2)
C16—C15—H15	119.7	C35—C34—H34	119.3
C14—C15—H15	119.7	C33—C34—H34	119.3
C17—C16—C15	119.63 (19)	C36—C35—C34	119.0 (2)
C17—C16—H16	120.2	C36—C35—H35	120.5
C15—C16—H16	120.2	C34—C35—H35	120.5
C16—C17—C18	121.2 (2)	C35—C36—C37	121.1 (2)
C16—C17—Cl1	119.67 (17)	C35—C36—Cl2	119.22 (19)
C18—C17—Cl1	119.13 (17)	C37—C36—Cl2	119.69 (18)
C17—C18—C19	118.8 (2)	C38—C37—C36	119.5 (2)
C17—C18—H18	120.6	C38—C37—H37	120.2
C19—C18—H18	120.6	C36—C37—H37	120.2
C18—C19—C14	121.62 (19)	C37—C38—C33	121.0 (2)
C18—C19—H19	119.2	C37—C38—H38	119.5
C14—C19—H19	119.2	C33—C38—H38	119.5
C7—N1—N2—C9	−1.3 (2)	C26—N3—N4—C28	−1.3 (2)
C1—N1—N2—C9	−176.40 (17)	C20—N3—N4—C28	−177.68 (18)
C7—N1—C1—C6	−153.7 (2)	C26—N3—C20—C21	−161.1 (2)
N2—N1—C1—C6	20.4 (3)	N4—N3—C20—C21	14.5 (3)
C7—N1—C1—C2	24.7 (3)	C26—N3—C20—C25	19.1 (3)
N2—N1—C1—C2	−161.22 (19)	N4—N3—C20—C25	−165.3 (2)
C6—C1—C2—C3	1.3 (3)	C25—C20—C21—C22	−0.5 (3)
N1—C1—C2—C3	−177.10 (19)	N3—C20—C21—C22	179.8 (2)
C1—C2—C3—C4	−0.4 (3)	C20—C21—C22—C23	−0.5 (4)
C2—C3—C4—C5	−1.0 (4)	C21—C22—C23—C24	0.9 (4)
C3—C4—C5—C6	1.6 (4)	C22—C23—C24—C25	−0.3 (4)
C4—C5—C6—C1	−0.7 (3)	C23—C24—C25—C20	−0.6 (4)
C2—C1—C6—C5	−0.8 (3)	C21—C20—C25—C24	1.0 (3)
N1—C1—C6—C5	177.64 (19)	N3—C20—C25—C24	−179.2 (2)
N2—N1—C7—O1	−177.3 (2)	N4—N3—C26—O3	−178.7 (2)
C1—N1—C7—O1	−2.7 (4)	C20—N3—C26—O3	−2.8 (4)
N2—N1—C7—C8	1.4 (2)	N4—N3—C26—C27	1.3 (2)
C1—N1—C7—C8	175.97 (19)	C20—N3—C26—C27	177.25 (19)
O1—C7—C8—C11	−2.0 (4)	O3—C26—C27—C30	−1.1 (4)
N1—C7—C8—C11	179.28 (19)	N3—C26—C27—C30	178.85 (19)
O1—C7—C8—C9	177.7 (2)	O3—C26—C27—C28	179.2 (2)
N1—C7—C8—C9	−1.0 (2)	N3—C26—C27—C28	−0.9 (2)
N1—N2—C9—C8	0.7 (2)	N3—N4—C28—C27	0.7 (2)
N1—N2—C9—C10	−179.56 (19)	N3—N4—C28—C29	−179.97 (19)
C11—C8—C9—N2	179.9 (2)	C30—C27—C28—N4	−179.5 (2)
C7—C8—C9—N2	0.2 (2)	C26—C27—C28—N4	0.1 (3)
C11—C8—C9—C10	0.1 (4)	C30—C27—C28—C29	1.2 (4)
C7—C8—C9—C10	−179.6 (2)	C26—C27—C28—C29	−179.2 (2)
C7—C8—C11—O2	0.8 (3)	C26—C27—C30—O4	0.1 (3)
C9—C8—C11—O2	−178.8 (2)	C28—C27—C30—O4	179.7 (2)
C7—C8—C11—C12	−179.00 (19)	C26—C27—C30—C31	−179.7 (2)
C9—C8—C11—C12	1.3 (4)	C28—C27—C30—C31	−0.1 (4)
O2—C11—C12—C13	−9.7 (3)	O4—C30—C31—C32	−8.3 (3)
C8—C11—C12—C13	170.2 (2)	C27—C30—C31—C32	171.5 (2)
C11—C12—C13—C14	180.00 (19)	C30—C31—C32—C33	−178.36 (19)
C12—C13—C14—C19	167.5 (2)	C31—C32—C33—C34	169.7 (2)
C12—C13—C14—C15	−13.0 (3)	C31—C32—C33—C38	−9.3 (3)
C19—C14—C15—C16	−0.8 (3)	C38—C33—C34—C35	−0.5 (3)
C13—C14—C15—C16	179.66 (19)	C32—C33—C34—C35	−179.59 (19)
C14—C15—C16—C17	0.6 (3)	C33—C34—C35—C36	−0.8 (3)
C15—C16—C17—C18	−0.6 (3)	C34—C35—C36—C37	1.4 (4)
C15—C16—C17—Cl1	179.14 (16)	C34—C35—C36—Cl2	−177.63 (17)
C16—C17—C18—C19	0.7 (3)	C35—C36—C37—C38	−0.6 (4)
Cl1—C17—C18—C19	−179.03 (15)	Cl2—C36—C37—C38	178.40 (18)
C17—C18—C19—C14	−0.9 (3)	C36—C37—C38—C33	−0.8 (4)
C15—C14—C19—C18	0.9 (3)	C34—C33—C38—C37	1.3 (3)
C13—C14—C19—C18	−179.52 (18)	C32—C33—C38—C37	−179.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	1.78	2.542 (2)	153
C16—H16···O1i	0.93	2.47	3.239 (2)	140
O4—H4A···O3	0.82	1.78	2.540 (2)	153
C37—H37···O3ii	0.93	2.61	3.314 (3)	133

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O2H2AO1	0.82	1.78	2.542(2)	153
C16H16O1i	0.93	2.47	3.239(2)	140
O4H4AO3	0.82	1.78	2.540(2)	153
C37H37O3ii	0.93	2.61	3.314(3)	133

Symmetry codes: (i) ; (ii) .