2-Amino-4-(2-chloro-phen-yl)-7,7-di-methyl-5-oxo-5,6,7,8-tetra-hydro-4H-chromene-3-carbonitrile hemihydrate.

The asymmetric unit of the title compound, C(18)H(17)ClN(2)O(2)·0.5H(2)O, contains two organic mol-ecules and one solvent water mol-ecule. In each organic mol-ecule, the cyclo-hexene ring adopts an envelope conformation with the C atom connecting the two methyl groups on the flap; the 4H-pyran ring is nearly planar [maximum deviation = 0.113 (3) Å in one mol-ecule and 0.089 (3) Å in the other mol-ecule] and is approximately perpendicular to the chloro-phenyl ring [dihedral angle = 86.43 (15)° in one mol-ecule and 89.73 (15)° in the other mol-ecule]. Inter-molecular N-H⋯N, N-H⋯O, O-H⋯O and O-H⋯Cl hydrogen bonding is present in the crystal.

Related literature

For background to 2-amino-4H-benzopyran-3-carbonitriles, see: Gao et al. (2001 ▶); Xu et al. (2011 ▶); Luan et al. (2011 ▶). For the synthesis of 2-amino-4H-benzopyran-3-carbonitriles, see: Shi et al. (2003 ▶); Bao et al. (2007 ▶).

Experimental

Crystal data

C18H17ClN2O2·0.5H2O

M = 337.80

Monoclinic,

a = 31.431 (6) Å

b = 9.3230 (19) Å

c = 25.079 (5) Å

β = 111.24 (3)°

V = 6850 (2) Å3

Z = 16

Mo Kα radiation

μ = 0.24 mm−1

T = 291 K

0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.945, T max = 0.959

15314 measured reflections

6243 independent reflections

3806 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.168

S = 1.00

6243 reflections

428 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003807/xu5439sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003807/xu5439Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812003807/xu5439Isup3.cml

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

C18H17ClN2O2·0.5H2O	F(000) = 2832
Mr = 337.80	Dx = 1.310 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3715 reflections
a = 31.431 (6) Å	θ = 2.1–23.9°
b = 9.3230 (19) Å	µ = 0.24 mm−1
c = 25.079 (5) Å	T = 291 K
β = 111.24 (3)°	Prism, colorless
V = 6850 (2) Å3	0.20 × 0.20 × 0.20 mm
Z = 16

Bruker SMART APEX CCD diffractometer	6243 independent reflections
Radiation source: sealed tube	3806 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
φ and ω scans	θmax = 25.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −37→31
Tmin = 0.945, Tmax = 0.959	k = −9→11
15314 measured reflections	l = −25→30

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0954P)2] where P = (Fo2 + 2Fc2)/3
6243 reflections	(Δ/σ)max < 0.001
428 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.50 e Å−3

Experimental. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)- 12.7873 (0.0387) x - 4.5876 (0.0107) y + 21.6869 (0.0196) z = 2.4952 (0.0356)* -0.0054 (0.0022) C1 * 0.0083 (0.0024) C2 * -0.0071 (0.0025) C3 * 0.0030 (0.0023) C4 * -0.0001 (0.0020) C5 * 0.0014 (0.0020) C6Rms deviation of fitted atoms = 0.005211.1322 (0.0507) x + 7.9044 (0.0087) y + 6.0068 (0.0449) z = 18.4619 (0.0327)Angle to previous plane (with approximate e.s.d.) = 75.07 (12)* -0.0232 (0.0025) C10 * 0.0250 (0.0019) C11 * -0.0262 (0.0019) C13 * 0.0290 (0.0024) C14 * -0.0045 (0.0022) C15Rms deviation of fitted atoms = 0.0233- 6.9377 (0.0455) x + 5.2108 (0.0111) y + 20.6895 (0.0225) z = 5.0012 (0.0397)Angle to previous plane (with approximate e.s.d.) = 44.67 (16)* -0.0049 (0.0022) C19 * 0.0034 (0.0025) C20 * 0.0014 (0.0027) C21 * -0.0045 (0.0027) C22 * 0.0029 (0.0025) C23 * 0.0018 (0.0022) C24Rms deviation of fitted atoms = 0.00341.7021 (0.0460) x - 8.5297 (0.0071) y + 8.8582 (0.0381) z = 6.0421 (0.0321)Angle to previous plane (with approximate e.s.d.) = 78.25 (11)* 0.0432 (0.0021) C28 * -0.0437 (0.0016) C29 * 0.0442 (0.0017) C31 * -0.0470 (0.0023) C32 * 0.0032 (0.0020) C33Rms deviation of fitted atoms = 0.0399

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
C1	0.87769 (10)	0.7977 (4)	0.80107 (13)	0.0404 (7)
C2	0.87215 (12)	0.9275 (4)	0.82590 (15)	0.0495 (8)
H2	0.8973	0.9748	0.8516	0.059*
C3	0.82914 (13)	0.9840 (4)	0.81178 (15)	0.0531 (9)
H3	0.8251	1.0715	0.8271	0.064*
C4	0.79199 (11)	0.9116 (3)	0.77502 (14)	0.0453 (8)
H4	0.7629	0.9499	0.7664	0.054*
C5	0.79701 (11)	0.7834 (3)	0.75071 (13)	0.0395 (7)
H5	0.7714	0.7367	0.7256	0.047*
C6	0.84100 (10)	0.7219 (3)	0.76370 (12)	0.0335 (6)
C7	0.84471 (9)	0.5760 (3)	0.73737 (12)	0.0319 (6)
H7	0.8135	0.5475	0.7140	0.038*
C8	0.86352 (9)	0.4584 (3)	0.78183 (12)	0.0322 (6)
C9	0.90599 (10)	0.3998 (3)	0.79355 (12)	0.0379 (7)
C10	0.91149 (10)	0.5090 (4)	0.71063 (12)	0.0405 (7)
C11	0.93956 (11)	0.5026 (4)	0.67499 (15)	0.0499 (9)
H11A	0.9348	0.4110	0.6554	0.060*
H11B	0.9715	0.5087	0.6994	0.060*
C12	0.92855 (10)	0.6222 (4)	0.63111 (13)	0.0395 (7)
C13	0.87805 (11)	0.6376 (5)	0.60281 (15)	0.0527 (9)
H13A	0.8664	0.5554	0.5782	0.063*
H13B	0.8717	0.7223	0.5787	0.063*
C14	0.85235 (10)	0.6499 (3)	0.64347 (13)	0.0381 (7)
C15	0.87098 (9)	0.5780 (3)	0.69802 (12)	0.0335 (6)
C16	0.94814 (13)	0.7637 (4)	0.66638 (15)	0.0546 (9)
H16A	0.9448	0.8423	0.6405	0.082*
H16B	0.9799	0.7504	0.6890	0.082*
H16C	0.9316	0.7840	0.6910	0.082*
C17	0.95296 (13)	0.6054 (5)	0.59000 (14)	0.0586 (10)
H17A	0.9409	0.5238	0.5659	0.088*
H17B	0.9850	0.5916	0.6109	0.088*
H17C	0.9486	0.6900	0.5668	0.088*
C18	0.83765 (10)	0.4130 (3)	0.81353 (13)	0.0365 (7)
C19	0.94532 (11)	0.1569 (4)	0.51895 (14)	0.0454 (8)
C20	0.96005 (16)	0.2732 (4)	0.49501 (17)	0.0634 (11)
H20	0.9910	0.2864	0.5024	0.076*
C21	0.92824 (18)	0.3689 (4)	0.46015 (17)	0.0686 (12)
H21	0.9379	0.4462	0.4440	0.082*
C22	0.88321 (17)	0.3500 (5)	0.44952 (17)	0.0701 (12)
H22	0.8619	0.4138	0.4259	0.084*
C23	0.86889 (13)	0.2357 (4)	0.47387 (15)	0.0539 (9)
H23	0.8379	0.2247	0.4665	0.065*
C24	0.89882 (10)	0.1381 (3)	0.50843 (12)	0.0349 (6)
C25	0.88120 (9)	0.0083 (3)	0.53129 (11)	0.0324 (6)
H25	0.9078	−0.0417	0.5581	0.039*
C26	0.85659 (9)	−0.0962 (3)	0.48349 (11)	0.0319 (6)
C27	0.81138 (9)	−0.1227 (3)	0.46640 (12)	0.0349 (6)
C28	0.80578 (9)	0.0119 (3)	0.54358 (12)	0.0333 (6)
C29	0.77329 (10)	0.0455 (3)	0.57239 (14)	0.0376 (7)
H29A	0.7681	−0.0404	0.5910	0.045*
H29B	0.7443	0.0739	0.5438	0.045*
C30	0.79024 (10)	0.1653 (3)	0.61691 (12)	0.0359 (7)
C31	0.83979 (12)	0.1330 (4)	0.65379 (13)	0.0514 (9)
H31A	0.8517	0.2110	0.6807	0.062*
H31B	0.8409	0.0464	0.6757	0.062*
C32	0.86993 (11)	0.1136 (4)	0.61901 (13)	0.0422 (7)
C33	0.85047 (10)	0.0454 (3)	0.56274 (12)	0.0347 (6)
C34	0.78655 (12)	0.3096 (3)	0.58672 (15)	0.0493 (8)
H34A	0.8034	0.3059	0.5616	0.074*
H34B	0.7989	0.3837	0.6147	0.074*
H34C	0.7551	0.3299	0.5649	0.074*
C35	0.76102 (14)	0.1704 (4)	0.65389 (17)	0.0600 (10)
H35A	0.7717	0.2460	0.6816	0.090*
H35B	0.7632	0.0804	0.6733	0.090*
H35C	0.7298	0.1881	0.6301	0.090*
C36	0.88196 (9)	−0.1639 (3)	0.45490 (12)	0.0341 (6)
Cl1	0.93301 (3)	0.73422 (10)	0.82028 (4)	0.0497 (2)
Cl2	0.98615 (3)	0.04182 (10)	0.56223 (4)	0.0535 (3)
N1	0.81581 (8)	0.3730 (3)	0.83876 (11)	0.0437 (7)
N2	0.92876 (9)	0.3135 (3)	0.83506 (11)	0.0517 (7)
H2A	0.9171	0.2864	0.8596	0.062*
H2B	0.9553	0.2836	0.8378	0.062*
N3	0.90360 (9)	−0.2218 (3)	0.43262 (11)	0.0510 (7)
N4	0.78563 (9)	−0.2024 (3)	0.42255 (12)	0.0490 (7)
H4A	0.7979	−0.2469	0.4018	0.059*
H4B	0.7569	−0.2109	0.4154	0.059*
O1	0.93091 (7)	0.4299 (3)	0.75980 (9)	0.0469 (6)
O2	0.81516 (6)	0.7103 (2)	0.62866 (8)	0.0404 (5)
O3	0.78475 (6)	−0.0620 (2)	0.49361 (9)	0.0394 (5)
O4	0.91002 (8)	0.1490 (3)	0.63733 (10)	0.0601 (7)
O1W	1.00378 (11)	0.1570 (4)	0.68730 (14)	0.0858 (9)
H1X	0.9740	0.1980	0.6788	0.103*
H1Y	1.0031	0.0925	0.6572	0.103*

	U11	U22	U33	U12	U13	U23
C1	0.0300 (14)	0.0491 (19)	0.0441 (16)	0.0001 (14)	0.0158 (13)	0.0035 (15)
C2	0.058 (2)	0.0449 (18)	0.0470 (19)	−0.0052 (16)	0.0202 (16)	−0.0037 (15)
C3	0.065 (2)	0.0428 (18)	0.056 (2)	0.0084 (17)	0.0263 (18)	−0.0032 (16)
C4	0.0401 (17)	0.0422 (18)	0.057 (2)	0.0121 (14)	0.0216 (16)	0.0047 (16)
C5	0.0461 (17)	0.0383 (16)	0.0427 (16)	0.0056 (14)	0.0264 (14)	0.0090 (14)
C6	0.0379 (15)	0.0331 (15)	0.0311 (14)	0.0011 (13)	0.0144 (12)	0.0079 (12)
C7	0.0257 (13)	0.0305 (14)	0.0398 (16)	0.0047 (11)	0.0122 (12)	0.0083 (12)
C8	0.0358 (15)	0.0309 (15)	0.0332 (15)	0.0051 (12)	0.0165 (12)	0.0032 (12)
C9	0.0427 (16)	0.0400 (17)	0.0365 (16)	0.0123 (13)	0.0212 (13)	0.0135 (13)
C10	0.0361 (15)	0.0556 (19)	0.0319 (15)	0.0101 (14)	0.0147 (12)	0.0134 (14)
C11	0.0471 (18)	0.062 (2)	0.0499 (19)	0.0162 (16)	0.0293 (16)	0.0167 (17)
C12	0.0362 (15)	0.0515 (19)	0.0375 (16)	−0.0008 (14)	0.0213 (13)	0.0072 (14)
C13	0.0431 (18)	0.077 (3)	0.0424 (18)	0.0100 (17)	0.0210 (15)	0.0091 (18)
C14	0.0357 (16)	0.0418 (17)	0.0389 (16)	0.0047 (13)	0.0160 (13)	0.0054 (14)
C15	0.0321 (14)	0.0389 (15)	0.0325 (15)	0.0048 (12)	0.0155 (12)	0.0022 (12)
C16	0.056 (2)	0.058 (2)	0.050 (2)	−0.0085 (17)	0.0193 (17)	−0.0055 (17)
C17	0.058 (2)	0.092 (3)	0.0316 (17)	0.007 (2)	0.0230 (16)	0.0071 (18)
C18	0.0351 (15)	0.0315 (15)	0.0446 (17)	−0.0005 (12)	0.0166 (13)	0.0109 (13)
C19	0.0461 (18)	0.0511 (19)	0.0476 (18)	−0.0146 (15)	0.0274 (15)	−0.0103 (15)
C20	0.089 (3)	0.060 (2)	0.067 (2)	−0.030 (2)	0.059 (2)	−0.014 (2)
C21	0.114 (4)	0.050 (2)	0.058 (2)	−0.032 (2)	0.051 (2)	−0.0052 (19)
C22	0.101 (3)	0.063 (3)	0.048 (2)	−0.023 (2)	0.028 (2)	−0.0009 (19)
C23	0.059 (2)	0.055 (2)	0.0469 (19)	−0.0096 (17)	0.0180 (17)	0.0055 (17)
C24	0.0441 (16)	0.0340 (15)	0.0318 (15)	−0.0084 (13)	0.0199 (13)	−0.0054 (13)
C25	0.0294 (14)	0.0376 (15)	0.0284 (14)	−0.0032 (12)	0.0084 (11)	−0.0006 (12)
C26	0.0340 (14)	0.0311 (15)	0.0313 (14)	−0.0050 (12)	0.0126 (12)	−0.0013 (12)
C27	0.0330 (15)	0.0351 (15)	0.0376 (16)	0.0028 (12)	0.0138 (13)	−0.0013 (13)
C28	0.0307 (14)	0.0344 (15)	0.0374 (15)	−0.0007 (12)	0.0153 (12)	−0.0027 (13)
C29	0.0359 (15)	0.0325 (16)	0.0514 (18)	−0.0008 (12)	0.0242 (14)	−0.0031 (13)
C30	0.0470 (17)	0.0296 (15)	0.0389 (16)	−0.0066 (13)	0.0252 (14)	0.0006 (12)
C31	0.059 (2)	0.064 (2)	0.0319 (17)	0.0008 (17)	0.0175 (16)	−0.0021 (15)
C32	0.0450 (18)	0.0496 (19)	0.0319 (15)	−0.0044 (15)	0.0138 (14)	−0.0021 (14)
C33	0.0375 (15)	0.0338 (15)	0.0373 (15)	−0.0058 (12)	0.0191 (13)	0.0002 (12)
C34	0.065 (2)	0.0283 (16)	0.064 (2)	−0.0015 (14)	0.0340 (18)	−0.0024 (15)
C35	0.071 (2)	0.059 (2)	0.066 (2)	−0.0012 (19)	0.045 (2)	−0.0007 (19)
C36	0.0286 (14)	0.0431 (17)	0.0284 (14)	−0.0043 (12)	0.0076 (12)	−0.0027 (12)
Cl1	0.0312 (4)	0.0594 (5)	0.0549 (5)	0.0005 (3)	0.0112 (3)	0.0006 (4)
Cl2	0.0403 (4)	0.0652 (6)	0.0657 (6)	−0.0023 (4)	0.0321 (4)	0.0019 (4)
N1	0.0330 (13)	0.0491 (16)	0.0484 (16)	0.0086 (12)	0.0141 (12)	0.0181 (13)
N2	0.0412 (14)	0.068 (2)	0.0434 (15)	0.0124 (14)	0.0122 (12)	0.0155 (14)
N3	0.0418 (15)	0.070 (2)	0.0426 (15)	−0.0052 (14)	0.0167 (13)	−0.0163 (14)
N4	0.0450 (15)	0.0532 (17)	0.0496 (16)	−0.0059 (13)	0.0181 (13)	−0.0095 (14)
O1	0.0421 (12)	0.0658 (15)	0.0399 (12)	0.0231 (11)	0.0234 (10)	0.0228 (11)
O2	0.0289 (10)	0.0487 (12)	0.0405 (11)	0.0057 (9)	0.0086 (9)	0.0075 (10)
O3	0.0291 (10)	0.0435 (12)	0.0474 (12)	−0.0045 (9)	0.0159 (9)	−0.0140 (10)
O4	0.0471 (14)	0.0865 (19)	0.0428 (13)	−0.0122 (13)	0.0117 (11)	−0.0204 (13)
O1W	0.0741 (19)	0.089 (2)	0.085 (2)	−0.0176 (17)	0.0176 (17)	0.0101 (18)

C1—C6	1.387 (4)	C20—C21	1.388 (6)
C1—C2	1.401 (5)	C20—H20	0.9300
C1—Cl1	1.732 (3)	C21—C22	1.354 (6)
C2—C3	1.372 (5)	C21—H21	0.9300
C2—H2	0.9300	C22—C23	1.382 (5)
C3—C4	1.375 (5)	C22—H22	0.9300
C3—H3	0.9300	C23—C24	1.369 (5)
C4—C5	1.377 (4)	C23—H23	0.9300
C4—H4	0.9300	C24—C25	1.526 (4)
C5—C6	1.421 (4)	C25—C33	1.492 (4)
C5—H5	0.9300	C25—C26	1.521 (4)
C6—C7	1.535 (4)	C25—H25	0.9800
C7—C15	1.499 (4)	C26—C27	1.350 (4)
C7—C8	1.523 (4)	C26—C36	1.401 (4)
C7—H7	0.9800	C27—N4	1.331 (4)
C8—C9	1.372 (4)	C27—O3	1.379 (3)
C8—C18	1.393 (4)	C28—C33	1.346 (4)
C9—N2	1.305 (4)	C28—O3	1.372 (3)
C9—O1	1.374 (3)	C28—C29	1.482 (4)
C10—C15	1.358 (4)	C29—C30	1.532 (4)
C10—O1	1.376 (3)	C29—H29A	0.9700
C10—C11	1.467 (4)	C29—H29B	0.9700
C11—C12	1.516 (4)	C30—C35	1.524 (4)
C11—H11A	0.9700	C30—C31	1.526 (5)
C11—H11B	0.9700	C30—C34	1.527 (4)
C12—C13	1.493 (4)	C31—C32	1.513 (4)
C12—C17	1.500 (4)	C31—H31A	0.9700
C12—C16	1.583 (5)	C31—H31B	0.9700
C13—C14	1.517 (4)	C32—O4	1.220 (4)
C13—H13A	0.9700	C32—C33	1.464 (4)
C13—H13B	0.9700	C34—H34A	0.9600
C14—O2	1.227 (3)	C34—H34B	0.9600
C14—C15	1.443 (4)	C34—H34C	0.9600
C16—H16A	0.9600	C35—H35A	0.9600
C16—H16B	0.9600	C35—H35B	0.9600
C16—H16C	0.9600	C35—H35C	0.9600
C17—H17A	0.9600	C36—N3	1.158 (4)
C17—H17B	0.9600	N2—H2A	0.8599
C17—H17C	0.9600	N2—H2B	0.8600
C18—N1	1.151 (4)	N4—H4A	0.8600
C19—C20	1.397 (5)	N4—H4B	0.8599
C19—C24	1.399 (4)	O1W—H1X	0.9600
C19—Cl2	1.723 (4)	O1W—H1Y	0.9599
C6—C1—C2	122.3 (3)	C19—C20—H20	120.2
C6—C1—Cl1	121.3 (2)	C22—C21—C20	120.3 (4)
C2—C1—Cl1	116.5 (2)	C22—C21—H21	119.9
C3—C2—C1	119.1 (3)	C20—C21—H21	119.9
C3—C2—H2	120.4	C21—C22—C23	119.9 (4)
C1—C2—H2	120.4	C21—C22—H22	120.1
C2—C3—C4	120.2 (3)	C23—C22—H22	120.1
C2—C3—H3	119.9	C24—C23—C22	122.2 (4)
C4—C3—H3	119.9	C24—C23—H23	118.9
C3—C4—C5	121.2 (3)	C22—C23—H23	118.9
C3—C4—H4	119.4	C23—C24—C19	117.9 (3)
C5—C4—H4	119.4	C23—C24—C25	120.3 (3)
C4—C5—C6	120.5 (3)	C19—C24—C25	121.7 (3)
C4—C5—H5	119.8	C33—C25—C26	108.9 (2)
C6—C5—H5	119.8	C33—C25—C24	114.0 (2)
C1—C6—C5	116.8 (3)	C26—C25—C24	111.2 (2)
C1—C6—C7	124.6 (3)	C33—C25—H25	107.5
C5—C6—C7	118.6 (3)	C26—C25—H25	107.5
C15—C7—C8	109.3 (2)	C24—C25—H25	107.5
C15—C7—C6	114.7 (2)	C27—C26—C36	118.9 (3)
C8—C7—C6	113.1 (2)	C27—C26—C25	122.9 (3)
C15—C7—H7	106.3	C36—C26—C25	118.1 (2)
C8—C7—H7	106.3	N4—C27—C26	128.3 (3)
C6—C7—H7	106.3	N4—C27—O3	110.0 (2)
C9—C8—C18	118.7 (3)	C26—C27—O3	121.7 (3)
C9—C8—C7	122.2 (2)	C33—C28—O3	122.5 (3)
C18—C8—C7	119.0 (2)	C33—C28—C29	126.2 (3)
N2—C9—C8	128.7 (3)	O3—C28—C29	111.3 (2)
N2—C9—O1	110.3 (2)	C28—C29—C30	113.0 (2)
C8—C9—O1	121.0 (2)	C28—C29—H29A	109.0
C15—C10—O1	122.5 (3)	C30—C29—H29A	109.0
C15—C10—C11	126.7 (3)	C28—C29—H29B	109.0
O1—C10—C11	110.8 (2)	C30—C29—H29B	109.0
C10—C11—C12	112.5 (3)	H29A—C29—H29B	107.8
C10—C11—H11A	109.1	C35—C30—C31	110.2 (3)
C12—C11—H11A	109.1	C35—C30—C34	108.6 (3)
C10—C11—H11B	109.1	C31—C30—C34	110.6 (3)
C12—C11—H11B	109.1	C35—C30—C29	109.8 (3)
H11A—C11—H11B	107.8	C31—C30—C29	107.9 (3)
C13—C12—C17	113.8 (3)	C34—C30—C29	109.7 (2)
C13—C12—C11	109.9 (3)	C32—C31—C30	112.9 (2)
C17—C12—C11	112.5 (3)	C32—C31—H31A	109.0
C13—C12—C16	108.5 (3)	C30—C31—H31A	109.0
C17—C12—C16	106.2 (3)	C32—C31—H31B	109.0
C11—C12—C16	105.5 (3)	C30—C31—H31B	109.0
C12—C13—C14	114.9 (3)	H31A—C31—H31B	107.8
C12—C13—H13A	108.5	O4—C32—C33	119.6 (3)
C14—C13—H13A	108.5	O4—C32—C31	121.8 (3)
C12—C13—H13B	108.5	C33—C32—C31	118.5 (3)
C14—C13—H13B	108.5	C28—C33—C32	117.5 (3)
H13A—C13—H13B	107.5	C28—C33—C25	123.3 (3)
O2—C14—C15	121.0 (3)	C32—C33—C25	119.1 (2)
O2—C14—C13	120.8 (3)	C30—C34—H34A	109.5
C15—C14—C13	118.0 (3)	C30—C34—H34B	109.5
C10—C15—C14	117.7 (3)	H34A—C34—H34B	109.5
C10—C15—C7	122.3 (3)	C30—C34—H34C	109.5
C14—C15—C7	119.9 (2)	H34A—C34—H34C	109.5
C12—C16—H16A	109.5	H34B—C34—H34C	109.5
C12—C16—H16B	109.5	C30—C35—H35A	109.5
H16A—C16—H16B	109.5	C30—C35—H35B	109.5
C12—C16—H16C	109.5	H35A—C35—H35B	109.5
H16A—C16—H16C	109.5	C30—C35—H35C	109.5
H16B—C16—H16C	109.5	H35A—C35—H35C	109.5
C12—C17—H17A	109.5	H35B—C35—H35C	109.5
C12—C17—H17B	109.5	N3—C36—C26	178.1 (3)
H17A—C17—H17B	109.5	C9—N2—H2A	120.0
C12—C17—H17C	109.5	C9—N2—H2B	120.0
H17A—C17—H17C	109.5	H2A—N2—H2B	120.0
H17B—C17—H17C	109.5	C27—N4—H4A	119.9
N1—C18—C8	178.4 (3)	C27—N4—H4B	120.1
C20—C19—C24	120.2 (4)	H4A—N4—H4B	120.0
C20—C19—Cl2	117.9 (3)	C9—O1—C10	119.6 (2)
C24—C19—Cl2	122.0 (2)	C28—O3—C27	118.7 (2)
C21—C20—C19	119.6 (4)	H1X—O1W—H1Y	109.5
C21—C20—H20	120.2
C6—C1—C2—C3	−1.7 (5)	C21—C22—C23—C24	−0.7 (6)
Cl1—C1—C2—C3	179.2 (3)	C22—C23—C24—C19	0.1 (5)
C1—C2—C3—C4	1.9 (5)	C22—C23—C24—C25	−176.1 (3)
C2—C3—C4—C5	−1.4 (5)	C20—C19—C24—C23	0.6 (4)
C3—C4—C5—C6	0.7 (5)	Cl2—C19—C24—C23	179.4 (2)
C2—C1—C6—C5	1.0 (4)	C20—C19—C24—C25	176.8 (3)
Cl1—C1—C6—C5	−180.0 (2)	Cl2—C19—C24—C25	−4.4 (4)
C2—C1—C6—C7	−177.1 (3)	C23—C24—C25—C33	−54.9 (4)
Cl1—C1—C6—C7	1.9 (4)	C19—C24—C25—C33	129.0 (3)
C4—C5—C6—C1	−0.5 (4)	C23—C24—C25—C26	68.7 (4)
C4—C5—C6—C7	177.7 (3)	C19—C24—C25—C26	−107.4 (3)
C1—C6—C7—C15	−64.6 (4)	C33—C25—C26—C27	12.9 (4)
C5—C6—C7—C15	117.3 (3)	C24—C25—C26—C27	−113.5 (3)
C1—C6—C7—C8	61.8 (4)	C33—C25—C26—C36	−169.2 (3)
C5—C6—C7—C8	−116.3 (3)	C24—C25—C26—C36	64.3 (3)
C15—C7—C8—C9	18.8 (4)	C36—C26—C27—N4	−3.6 (5)
C6—C7—C8—C9	−110.4 (3)	C25—C26—C27—N4	174.2 (3)
C15—C7—C8—C18	−164.1 (3)	C36—C26—C27—O3	178.5 (3)
C6—C7—C8—C18	66.7 (3)	C25—C26—C27—O3	−3.7 (4)
C18—C8—C9—N2	−7.1 (5)	C33—C28—C29—C30	19.0 (4)
C7—C8—C9—N2	170.0 (3)	O3—C28—C29—C30	−161.9 (2)
C18—C8—C9—O1	173.3 (3)	C28—C29—C30—C35	−167.1 (3)
C7—C8—C9—O1	−9.6 (5)	C28—C29—C30—C31	−47.0 (3)
C15—C10—C11—C12	20.3 (5)	C28—C29—C30—C34	73.6 (3)
O1—C10—C11—C12	−161.7 (3)	C35—C30—C31—C32	175.0 (3)
C10—C11—C12—C13	−44.9 (4)	C34—C30—C31—C32	−64.9 (4)
C10—C11—C12—C17	−172.9 (3)	C29—C30—C31—C32	55.1 (4)
C10—C11—C12—C16	71.8 (4)	C30—C31—C32—O4	147.2 (3)
C17—C12—C13—C14	178.1 (3)	C30—C31—C32—C33	−35.1 (4)
C11—C12—C13—C14	50.9 (4)	O3—C28—C33—C32	−174.9 (3)
C16—C12—C13—C14	−63.9 (4)	C29—C28—C33—C32	4.1 (5)
C12—C13—C14—O2	154.8 (3)	O3—C28—C33—C25	1.2 (4)
C12—C13—C14—C15	−30.5 (5)	C29—C28—C33—C25	−179.8 (3)
O1—C10—C15—C14	−176.0 (3)	O4—C32—C33—C28	−178.1 (3)
C11—C10—C15—C14	1.8 (5)	C31—C32—C33—C28	4.1 (4)
O1—C10—C15—C7	1.4 (5)	O4—C32—C33—C25	5.6 (5)
C11—C10—C15—C7	179.2 (3)	C31—C32—C33—C25	−172.1 (3)
O2—C14—C15—C10	177.6 (3)	C26—C25—C33—C28	−11.7 (4)
C13—C14—C15—C10	2.9 (5)	C24—C25—C33—C28	113.1 (3)
O2—C14—C15—C7	0.2 (5)	C26—C25—C33—C32	164.3 (3)
C13—C14—C15—C7	−174.5 (3)	C24—C25—C33—C32	−70.9 (3)
C8—C7—C15—C10	−14.7 (4)	C27—C26—C36—N3	−117 (10)
C6—C7—C15—C10	113.6 (3)	C25—C26—C36—N3	65 (10)
C8—C7—C15—C14	162.6 (3)	N2—C9—O1—C10	174.3 (3)
C6—C7—C15—C14	−69.1 (4)	C8—C9—O1—C10	−6.0 (5)
C9—C8—C18—N1	−92 (12)	C15—C10—O1—C9	10.3 (5)
C7—C8—C18—N1	91 (12)	C11—C10—O1—C9	−167.8 (3)
C24—C19—C20—C21	−0.8 (5)	C33—C28—O3—C27	9.9 (4)
Cl2—C19—C20—C21	−179.6 (3)	C29—C28—O3—C27	−169.2 (2)
C19—C20—C21—C22	0.2 (6)	N4—C27—O3—C28	173.2 (3)
C20—C21—C22—C23	0.5 (6)	C26—C27—O3—C28	−8.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3i	0.86	2.11	2.957 (4)	167
N2—H2B···O1Wii	0.86	2.01	2.793 (4)	152
N4—H4A···N1iii	0.86	2.20	3.048 (4)	169
N4—H4B···O2iv	0.86	2.13	2.957 (3)	161
O1W—H1X···O4	0.96	1.95	2.754 (4)	139
O1W—H1Y···Cl2	0.96	2.29	3.168 (4)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N3i	0.86	2.11	2.957 (4)	167
N2—H2B⋯O1Wii	0.86	2.01	2.793 (4)	152
N4—H4A⋯N1iii	0.86	2.20	3.048 (4)	169
N4—H4B⋯O2iv	0.86	2.13	2.957 (3)	161
O1W—H1X⋯O4	0.96	1.95	2.754 (4)	139
O1W—H1Y⋯Cl2	0.96	2.29	3.168 (4)	151

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