4-(4-Chlorophenyl)-3,7,7-trimethyl-1-[2-(4-nitrobenzoyl)ethyl]-4,7,8,9-tetrahydro-1H-pyrazolo[3,4-b]quinolin-5(6H)-one–ethanol (1/1)

Molecules of the title compound, C₂₈H₂₇ClN₄O₄·C₂H₆O, form a C(6) chain via an N—H...O hydrogen bond along the c axis by the operation of a c-glide plane, with N...O = 2.761 (3) Å and N—H...O = 165°. The mol­ecules are further linked by a weak C—H...O interaction, with C...O = 3.344 (4) Å and C—H...O = 150°. Pendant hydrogen-bonded ethanol solvent mol­ecules are attached to the chains by O—H...N hydrogen bonds, with O...N = 2.904 (3) Å and O—H...N = 175°.

S1. Comment

Pyrazolo[3,4-b]quinolines are of interest as possible antiviral agents (Crenshaw et al., 1976, 1978; Smirnoff & Crenshaw, 1977). Some of their derivatives exhibit parasiticidic properties (Bristol-Meyers, 1973) and have been studied as potential antimalarial agents (Gein Stein et al., 1970). Other pyrazolo[3,4-b]quinolines have also shown bactericidal activity (Farghaly et al., 1989) and applications as vasodilators (Bell & Ackerman, 1990), and have even been evaluated for enzymatic inhibitory activity (Gatta et al., 1991). We have previously prepared diverse 4-aryl-3,7,7-trimethyl-4,7,8,9-tetrahydro- 2H-pyrazolo[3,4-b]quinolin-5-(6H)-ones and reported their structures (Cannon et al., 2001a,b,c,d). The present work was undertaken to expand the possible applications of such heterocycles, by using N-alkylation to prepare derivatives from azole systems. Here, we report the structure of the title compound, (I), which was prepared by the easy, efficient and regioselective method described below. \sch

Selected bond lengths and angles for (I) are given in Table 1 and are similar to those reported in the four structures cited above (Cannon et al., 2001a,b,c,d). Fig. 1 depicts a view of the molecule.

Molecules of (I) form C(6) chains (Bernstein et al., 1995) via the N9—H9···O5ⁱ hydrogen bond along the c axis by the operation of the c glide plane, as shown in Fig. 2 [symmetry code: (i) x, 1 - y, 1/2 + z]. The molecules in these chains are then linked by weak C12—H12···O12ⁱ interactions and this interaction, together with the N9—H9···O5ⁱ hydrogen bond, forms an R₂²(23) ring (Bernstein et al., 1995), as shown in Fig. 3. These linked chains are not connected to the chains related by the C-centring. Pendant hydrogen-bonded ethanol solvent molecules are attached to each molecule of (I). Details of the hydrogen bonding are given in Table 2.

There is significant π–π base-stacking between rings C131—C136 and N9/C8a/C4a/C4/C3a/C9a (at x, -y, 1/2 + z Not 1 - y?), where the distance between centres of gravity is 3.73 Å, the perpendicular distance of the centre of gravity of the former ring from the latter is 3.73 Å, the perpendicular distance of the centre of gravity of the latter from the former is 3.50 Å and the angle between the planes is 2.7°. In addition, ring C131—C136 is involved in π–π stacking with ring N1/N2/C3/C3a/C9a (at x, -y, 1/2 + z Not 1 - y?), where the distance between centres of gravity is 3.76 Å, the perpendicular distance of the centre of gravity of the former from the latter is 3.53 Å, the perpendicular distance of the centre of gravity of the latter from the former is 3.52 Å and the angle between the planes is 0.73°.

This supramolecular structure is different from those reported by Cannon et al. (2001a,b,c,d), which were all similar. This difference is due to the presence of the 2-(4-nitrobenzoyl)ethyl substituent on N1, which locks the 1H form and precludes the presence of an H atom at N2, which is involved in the formation of the supramolecular structures of the crystal structures cited above. In compound (I), the 1H configuration of the heterocyclic system results in an essentially planar pyridine ring, whereas in the published structures, it is intermediate between a boat and an envelope. Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent accessible voids in the crystal lattice apart from that occupied by the solvent molecule.

Related literature

For related literature, see: Bell & Ackerman (1990); Bernstein et al. (1995); Bristol-Meyers & Co (1973); Cannon et al. (2001a, 2001b, 2001c, 2001d); Crenshaw et al. (1976, 1978); Farghaly et al. (1989); Gatta et al. (1991); Gein Stein, Biel & Singh (1970); Smirnoff & Crenshaw (1977); Spek (2000).

S2. Experimental

A solution of 4-(4-chlorophenyl)-3,7,7-trimethyl-4,7,8,9-tetrahydro-2H- pyrazolo[3,4-b]quinolin-5(6H)-one (2.0 mmol) and 3-dimethylamino-4-nitropropiophenone (2.0 mmol) in absolute ethanol (15 ml) was refluxed for 50 min, and the resulting precipitate was filtered, washed with ethanol, dried and recrystallized from ethanol. Compound (I) was obtained as orange crystals (m.p. 466 K, yield 82%), from which suitable ones were selected for X-ray diffraction. Analysis calculated for C₂₈H₂₈ClN₄O₄: C 64.80, H 5.24, N 10.80%; found: C,64.87, H 5.16, N 10.73.

S3. Refinement

H atoms on N9 and O1A were located on a difference map; all others were placed in calculated positions. All H atoms were treated as riding, with C—H = 0.95–1.00 Å, N—H = 0.92 Å and O—H 1.05 Å. Those attached to atom C2A were calculated as six half H atoms.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the crystal structure of (I) showing the C(6) chain [symmetry code: (i) x, 1 - y, 1/2 + z]. The solvent molecule has been omitted for clarity.
	Fig. 3. A view of the crystal structure of (I) showing the R2^2(23) ring [symmetry code: (i) x, 1 - y, 1/2 + z]. The solvent molecule has been omitted for clarity.

4-(4-Chlorophenyl)-3,7,7-trimethyl-1-[2-(4-nitrobenzoyl)ethyl]-4,7,8,9- tetrahydro-1H-pyrazolo[3,4-b]quinolin-5(6H)-one-ethanol (1/1)

Crystal data

C28H27ClN4O4·C2H6O	Dx = 1.34 Mg m^−3
Mr = 565.05	Melting point: 466 K
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 23.6298 (6) Å	Cell parameters from 5677 reflections
b = 9.6215 (3) Å	θ = 3.1–27.5°
c = 14.2657 (4) Å	µ = 0.18 mm^−1
β = 120.2930 (16)°	T = 150 K
V = 2800.51 (14) Å^3	Block, orange
Z = 4	0.30 × 0.14 × 0.14 mm
F(000) = 1192

Data collection

Nonius KappaCCD area-detector diffractometer	5677 independent reflections
Radiation source: fine-focus sealed X-ray tube	4821 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.04
ϕ and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −27→30
Tmin = 0.947, Tmax = 0.975	k = −11→12
11553 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0495P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
5677 reflections	Δρmax = 0.24 e Å^−3
365 parameters	Δρmin = −0.27 e Å^−3
2 restraints	Absolute structure: Flack (1983), 3212 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.89438 (9)	0.20346 (19)	0.84225 (14)	0.0202 (4)
C11	0.89995 (12)	0.1996 (2)	0.94874 (18)	0.0216 (5)
C12	0.85271 (12)	0.3010 (2)	0.95531 (18)	0.0228 (5)
C13	0.85921 (11)	0.3050 (2)	1.06560 (17)	0.0206 (5)
O133	0.89835 (8)	0.23116 (17)	1.13971 (13)	0.0274 (4)
C131	0.81675 (12)	0.4049 (2)	1.08372 (18)	0.0217 (5)
C132	0.82133 (13)	0.4052 (2)	1.18466 (19)	0.0263 (6)
C133	0.78476 (13)	0.4981 (3)	1.20700 (18)	0.0281 (6)
C134	0.74471 (12)	0.5915 (2)	1.12706 (19)	0.0240 (5)
N13	0.70767 (10)	0.6933 (2)	1.15138 (17)	0.0305 (5)
O11	0.68257 (9)	0.79102 (19)	1.08941 (16)	0.0369 (4)
O12	0.70387 (9)	0.6748 (2)	1.23412 (14)	0.0409 (5)
C135	0.73805 (13)	0.5915 (3)	1.0259 (2)	0.0274 (6)
C136	0.77391 (12)	0.4964 (3)	1.00400 (18)	0.0257 (5)
N2	0.85070 (9)	0.1171 (2)	0.76075 (15)	0.0206 (4)
C3	0.85750 (11)	0.1469 (2)	0.67517 (17)	0.0199 (5)
C31	0.81786 (12)	0.0718 (3)	0.57003 (18)	0.0254 (5)
C3a	0.90445 (11)	0.2518 (2)	0.69987 (16)	0.0180 (5)
C4	0.93151 (11)	0.3198 (2)	0.63608 (17)	0.0178 (5)
C41	0.96523 (11)	0.2159 (2)	0.59909 (17)	0.0165 (4)
C42	1.01761 (12)	0.1363 (2)	0.67326 (18)	0.0209 (5)
C43	1.04852 (12)	0.0425 (2)	0.63972 (18)	0.0217 (5)
C44	1.02560 (11)	0.0292 (2)	0.52926 (18)	0.0198 (5)
Cl4	1.06286 (3)	−0.09124 (6)	0.48634 (4)	0.02874 (15)
C45	0.97350 (12)	0.1061 (2)	0.45389 (17)	0.0214 (5)
C46	0.94360 (12)	0.1994 (2)	0.48954 (18)	0.0207 (5)
C4a	0.97781 (11)	0.4366 (2)	0.70570 (17)	0.0178 (5)
C5	1.00230 (11)	0.5276 (2)	0.65364 (17)	0.0181 (5)
O5	0.98308 (8)	0.51332 (16)	0.55532 (11)	0.0239 (4)
C6	1.04798 (12)	0.6457 (2)	0.71622 (18)	0.0230 (5)
C7	1.08601 (12)	0.6270 (2)	0.83932 (18)	0.0230 (5)
C71	1.11769 (14)	0.7664 (3)	0.8925 (2)	0.0301 (6)
C72	1.13858 (13)	0.5163 (3)	0.8729 (2)	0.0332 (6)
C8	1.03685 (12)	0.5848 (2)	0.87447 (18)	0.0232 (5)
C8a	0.99454 (11)	0.4638 (2)	0.81104 (16)	0.0184 (5)
N9	0.97083 (10)	0.38750 (18)	0.86433 (14)	0.0196 (4)
C9a	0.92577 (11)	0.2843 (2)	0.80607 (17)	0.0182 (5)
O1A	0.79130 (9)	−0.12932 (19)	0.79244 (14)	0.0376 (5)
C1A	0.72545 (15)	−0.1122 (3)	0.7110 (2)	0.0455 (8)
C2A	0.68370 (15)	−0.2230 (3)	0.7226 (3)	0.0437 (7)
H11A	0.9454	0.2233	1.0051	0.026*
H11B	0.8906	0.1043	0.9634	0.026*
H12A	0.8607	0.3953	0.9367	0.027*
H12B	0.8073	0.2744	0.9009	0.027*
H132	0.8497	0.3414	1.2389	0.032*
H133	0.7871	0.4975	1.2755	0.034*
H135	0.7095	0.6554	0.9719	0.033*
H136	0.7692	0.4936	0.9338	0.031*
H31A	0.7891	0.0043	0.5771	0.038*
H31B	0.8472	0.0230	0.5513	0.038*
H31C	0.7912	0.1387	0.5127	0.038*
H4	0.8942	0.3627	0.5699	0.021*
H42	1.0327	0.1461	0.7485	0.025*
H43	1.0846	−0.0114	0.6912	0.026*
H45	0.9581	0.0956	0.3786	0.026*
H46	0.9076	0.2531	0.4378	0.025*
H6A	1.0220	0.7324	0.6989	0.028*
H6B	1.0798	0.6575	0.6909	0.028*
H71A	1.1422	0.7555	0.9716	0.045*
H71B	1.0835	0.8367	0.8722	0.045*
H71C	1.1476	0.7957	0.8675	0.045*
H72A	1.1183	0.4286	0.8365	0.050*
H72B	1.1609	0.5032	0.9517	0.050*
H72C	1.1705	0.5457	0.8521	0.050*
H8A	1.0612	0.5603	0.9525	0.028*
H8B	1.0084	0.6653	0.8653	0.028*
H9	0.9744	0.4044	0.9307	0.024*
H1A	0.8102	−0.0369	0.7797	0.045*
H1A1	0.7214	−0.1195	0.6387	0.055*
H1A2	0.7100	−0.0188	0.7172	0.055*
H2A1	0.6376	−0.2088	0.6672	0.066*	0.50
H2A2	0.6886	−0.2167	0.7949	0.066*	0.50
H2A3	0.6979	−0.3150	0.7132	0.066*	0.50
H2A4	0.7118	−0.2849	0.7830	0.066*	0.50
H2A5	0.6608	−0.2770	0.6553	0.066*	0.50
H2A6	0.6515	−0.1787	0.7370	0.066*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0246 (11)	0.0219 (10)	0.0182 (9)	−0.0045 (8)	0.0139 (9)	−0.0033 (8)
C11	0.0257 (13)	0.0246 (12)	0.0191 (11)	−0.0013 (10)	0.0146 (11)	0.0000 (9)
C12	0.0240 (13)	0.0291 (13)	0.0195 (11)	0.0006 (10)	0.0140 (11)	0.0001 (9)
C13	0.0197 (13)	0.0241 (12)	0.0211 (12)	−0.0056 (10)	0.0126 (11)	−0.0036 (9)
O133	0.0296 (10)	0.0308 (9)	0.0238 (8)	0.0020 (8)	0.0149 (8)	0.0024 (7)
C131	0.0233 (13)	0.0247 (12)	0.0218 (12)	−0.0077 (10)	0.0147 (11)	−0.0053 (9)
C132	0.0290 (15)	0.0274 (13)	0.0241 (12)	−0.0022 (11)	0.0147 (12)	−0.0017 (10)
C133	0.0319 (15)	0.0352 (14)	0.0218 (12)	−0.0021 (12)	0.0170 (12)	−0.0042 (10)
C134	0.0213 (13)	0.0260 (13)	0.0286 (12)	−0.0049 (10)	0.0154 (11)	−0.0076 (10)
N13	0.0225 (12)	0.0341 (13)	0.0372 (12)	−0.0053 (10)	0.0168 (10)	−0.0134 (10)
O11	0.0340 (11)	0.0293 (10)	0.0523 (12)	−0.0025 (9)	0.0254 (10)	−0.0058 (9)
O12	0.0305 (11)	0.0662 (13)	0.0313 (10)	0.0037 (10)	0.0194 (9)	−0.0107 (9)
C135	0.0263 (14)	0.0317 (14)	0.0288 (13)	−0.0001 (11)	0.0173 (12)	0.0004 (11)
C136	0.0272 (14)	0.0339 (14)	0.0207 (12)	−0.0006 (12)	0.0155 (11)	−0.0013 (10)
N2	0.0177 (10)	0.0234 (10)	0.0223 (10)	−0.0010 (8)	0.0111 (9)	−0.0051 (8)
C3	0.0195 (13)	0.0199 (11)	0.0220 (11)	0.0018 (9)	0.0117 (10)	−0.0014 (9)
C31	0.0226 (13)	0.0300 (13)	0.0217 (11)	−0.0042 (11)	0.0098 (11)	−0.0060 (10)
C3a	0.0169 (12)	0.0194 (11)	0.0204 (11)	0.0016 (9)	0.0113 (10)	−0.0003 (9)
C4	0.0196 (12)	0.0183 (11)	0.0170 (10)	0.0011 (9)	0.0104 (10)	−0.0013 (9)
C41	0.0175 (12)	0.0161 (10)	0.0191 (11)	−0.0040 (9)	0.0117 (10)	−0.0013 (8)
C42	0.0235 (13)	0.0242 (12)	0.0167 (11)	−0.0010 (10)	0.0113 (10)	−0.0017 (9)
C43	0.0188 (12)	0.0234 (12)	0.0225 (11)	0.0032 (10)	0.0102 (10)	0.0008 (9)
C44	0.0203 (13)	0.0195 (11)	0.0247 (12)	−0.0044 (10)	0.0152 (11)	−0.0053 (9)
Cl4	0.0286 (3)	0.0284 (3)	0.0332 (3)	0.0027 (3)	0.0185 (3)	−0.0073 (3)
C45	0.0261 (13)	0.0226 (12)	0.0162 (11)	−0.0037 (10)	0.0113 (11)	−0.0040 (9)
C46	0.0207 (13)	0.0226 (12)	0.0166 (10)	−0.0012 (10)	0.0079 (10)	−0.0001 (9)
C4a	0.0194 (12)	0.0184 (11)	0.0182 (10)	0.0019 (9)	0.0112 (10)	−0.0008 (8)
C5	0.0223 (12)	0.0173 (11)	0.0172 (11)	0.0044 (9)	0.0119 (10)	0.0019 (8)
O5	0.0329 (10)	0.0232 (8)	0.0191 (8)	0.0009 (7)	0.0158 (8)	0.0015 (7)
C6	0.0248 (13)	0.0233 (12)	0.0228 (12)	−0.0051 (10)	0.0134 (11)	0.0003 (10)
C7	0.0230 (13)	0.0248 (12)	0.0214 (11)	−0.0054 (10)	0.0114 (11)	−0.0023 (9)
C71	0.0360 (15)	0.0330 (14)	0.0239 (12)	−0.0110 (12)	0.0171 (12)	−0.0045 (10)
C72	0.0245 (14)	0.0376 (15)	0.0310 (13)	0.0026 (12)	0.0092 (12)	0.0040 (12)
C8	0.0295 (14)	0.0225 (12)	0.0199 (11)	−0.0047 (10)	0.0140 (11)	−0.0029 (9)
C8a	0.0200 (12)	0.0185 (11)	0.0186 (11)	0.0033 (10)	0.0111 (10)	0.0030 (9)
N9	0.0275 (11)	0.0215 (10)	0.0144 (9)	−0.0035 (8)	0.0139 (9)	−0.0025 (7)
C9a	0.0187 (12)	0.0200 (11)	0.0181 (10)	0.0005 (9)	0.0108 (10)	−0.0011 (9)
O1A	0.0351 (12)	0.0364 (10)	0.0334 (10)	−0.0086 (9)	0.0113 (9)	0.0020 (8)
C1A	0.0377 (18)	0.0539 (19)	0.0383 (16)	−0.0098 (14)	0.0143 (14)	0.0097 (13)
C2A	0.0441 (19)	0.0423 (17)	0.0548 (17)	−0.0079 (14)	0.0324 (16)	−0.0034 (14)

Geometric parameters (Å, º)

N1—N2	1.377 (3)	C43—H43	0.9500
N1—C9a	1.345 (3)	C44—C45	1.372 (3)
N1—C11	1.458 (3)	C44—Cl4	1.743 (2)
N2—C3	1.340 (3)	C45—C46	1.388 (3)
C3—C3a	1.407 (3)	C45—H45	0.9500
C3—C31	1.494 (3)	C46—H46	0.9500
C3a—C9a	1.370 (3)	C4a—C8a	1.372 (3)
N13—O11	1.220 (3)	C4a—C5	1.445 (3)
N13—O12	1.241 (3)	C5—O5	1.245 (2)
N13—C134	1.467 (3)	C5—C6	1.510 (3)
C11—C12	1.520 (3)	C6—C7	1.527 (3)
C11—H11A	0.9900	C6—H6A	0.9900
C11—H11B	0.9900	C6—H6B	0.9900
C12—C13	1.502 (3)	C7—C72	1.519 (4)
C12—H12A	0.9900	C7—C8	1.534 (3)
C12—H12B	0.9900	C7—C71	1.537 (3)
C13—O133	1.221 (3)	C71—H71A	0.9800
C13—C131	1.503 (3)	C71—H71B	0.9800
C131—C132	1.388 (3)	C71—H71C	0.9800
C131—C136	1.389 (4)	C72—H72A	0.9800
C132—C133	1.387 (3)	C72—H72B	0.9800
C132—H132	0.9500	C72—H72C	0.9800
C133—C134	1.384 (3)	C8—C8a	1.504 (3)
C133—H133	0.9500	C8—H8A	0.9900
C134—C135	1.371 (3)	C8—H8B	0.9900
C135—C136	1.386 (3)	C8a—N9	1.364 (3)
C135—H135	0.9500	N9—C9a	1.385 (3)
C136—H136	0.9500	N9—H9	0.9216
C31—H31A	0.9800	O1A—C1A	1.405 (4)
C31—H31B	0.9800	O1A—H1A	1.0514
C31—H31C	0.9800	C1A—C2A	1.518 (4)
C3a—C4	1.500 (3)	C1A—H1A1	0.9900
C4—C41	1.528 (3)	C1A—H1A2	0.9900
C4—C4a	1.534 (3)	C2A—H2A1	0.9800
C4—H4	1.0000	C2A—H2A2	0.9800
C41—C42	1.384 (3)	C2A—H2A3	0.9800
C41—C46	1.387 (3)	C2A—H2A4	0.9800
C42—C43	1.389 (3)	C2A—H2A5	0.9800
C42—H42	0.9500	C2A—H2A6	0.9800
C43—C44	1.390 (3)
C9a—N1—N2	110.40 (17)	C45—C46—H46	119.3
C9a—N1—C11	129.60 (19)	C8a—C4a—C5	118.6 (2)
N2—N1—C11	119.99 (17)	C8a—C4a—C4	124.49 (19)
N1—C11—C12	111.40 (18)	C5—C4a—C4	116.83 (18)
N1—C11—H11A	109.3	O5—C5—C4a	119.9 (2)
C12—C11—H11A	109.3	O5—C5—C6	119.67 (19)
N1—C11—H11B	109.3	C4a—C5—C6	120.29 (18)
C12—C11—H11B	109.3	C5—C6—C7	114.93 (18)
H11A—C11—H11B	108.0	C5—C6—H6A	108.5
C13—C12—C11	112.99 (18)	C7—C6—H6A	108.5
C13—C12—H12A	109.0	C5—C6—H6B	108.5
C11—C12—H12A	109.0	C7—C6—H6B	108.5
C13—C12—H12B	109.0	H6A—C6—H6B	107.5
C11—C12—H12B	109.0	C72—C7—C6	111.0 (2)
H12A—C12—H12B	107.8	C72—C7—C8	110.2 (2)
O133—C13—C12	121.6 (2)	C6—C7—C8	107.69 (19)
O133—C13—C131	120.19 (19)	C72—C7—C71	109.8 (2)
C12—C13—C131	118.16 (19)	C6—C7—C71	108.80 (19)
C132—C131—C136	119.4 (2)	C8—C7—C71	109.29 (19)
C132—C131—C13	118.0 (2)	C7—C71—H71A	109.5
C136—C131—C13	122.6 (2)	C7—C71—H71B	109.5
C133—C132—C131	120.5 (2)	H71A—C71—H71B	109.5
C133—C132—H132	119.7	C7—C71—H71C	109.5
C131—C132—H132	119.7	H71A—C71—H71C	109.5
C134—C133—C132	118.4 (2)	H71B—C71—H71C	109.5
C134—C133—H133	120.8	C7—C72—H72A	109.5
C132—C133—H133	120.8	C7—C72—H72B	109.5
C135—C134—C133	122.4 (2)	H72A—C72—H72B	109.5
C135—C134—N13	118.9 (2)	C7—C72—H72C	109.5
C133—C134—N13	118.7 (2)	H72A—C72—H72C	109.5
O11—N13—O12	123.9 (2)	H72B—C72—H72C	109.5
O11—N13—C134	118.2 (2)	C8a—C8—C7	113.04 (18)
O12—N13—C134	117.9 (2)	C8a—C8—H8A	109.0
C134—C135—C136	118.6 (2)	C7—C8—H8A	109.0
C134—C135—H135	120.7	C8a—C8—H8B	109.0
C136—C135—H135	120.7	C7—C8—H8B	109.0
C135—C136—C131	120.7 (2)	H8A—C8—H8B	107.8
C135—C136—H136	119.7	N9—C8a—C4a	122.4 (2)
C131—C136—H136	119.7	N9—C8a—C8	114.62 (18)
C3—N2—N1	104.89 (18)	C4a—C8a—C8	122.90 (19)
N2—C3—C3a	111.53 (18)	C8a—N9—C9a	117.32 (17)
N2—C3—C31	120.6 (2)	C8a—N9—H9	128.8
C3a—C3—C31	127.9 (2)	C9a—N9—H9	112.8
C3—C31—H31A	109.5	N1—C9a—C3a	109.04 (19)
C3—C31—H31B	109.5	N1—C9a—N9	126.19 (18)
H31A—C31—H31B	109.5	C3a—C9a—N9	124.74 (19)
C3—C31—H31C	109.5	C1A—O1A—H1A	98.5
H31A—C31—H31C	109.5	O1A—C1A—C2A	109.7 (2)
H31B—C31—H31C	109.5	O1A—C1A—H1A1	109.7
C9a—C3a—C3	104.13 (18)	C2A—C1A—H1A1	109.7
C9a—C3a—C4	122.7 (2)	O1A—C1A—H1A2	109.7
C3—C3a—C4	133.16 (19)	C2A—C1A—H1A2	109.7
C3a—C4—C41	112.37 (17)	H1A1—C1A—H1A2	108.2
C3a—C4—C4a	108.03 (17)	C1A—C2A—H2A1	109.5
C41—C4—C4a	112.17 (19)	C1A—C2A—H2A2	109.5
C3a—C4—H4	108.0	H2A1—C2A—H2A2	109.5
C41—C4—H4	108.0	C1A—C2A—H2A3	109.5
C4a—C4—H4	108.0	H2A1—C2A—H2A3	109.5
C42—C41—C46	118.5 (2)	H2A2—C2A—H2A3	109.5
C42—C41—C4	121.23 (19)	C1A—C2A—H2A4	109.5
C46—C41—C4	120.3 (2)	H2A1—C2A—H2A4	141.1
C41—C42—C43	121.3 (2)	H2A2—C2A—H2A4	56.3
C41—C42—H42	119.4	H2A3—C2A—H2A4	56.3
C43—C42—H42	119.4	C1A—C2A—H2A5	109.5
C42—C43—C44	118.6 (2)	H2A1—C2A—H2A5	56.3
C42—C43—H43	120.7	H2A2—C2A—H2A5	141.1
C44—C43—H43	120.7	H2A3—C2A—H2A5	56.3
C45—C44—C43	121.4 (2)	H2A4—C2A—H2A5	109.5
C45—C44—Cl4	119.71 (17)	C1A—C2A—H2A6	109.5
C43—C44—Cl4	118.84 (17)	H2A1—C2A—H2A6	56.3
C44—C45—C46	118.9 (2)	H2A2—C2A—H2A6	56.3
C44—C45—H45	120.6	H2A3—C2A—H2A6	141.1
C46—C45—H45	120.6	H2A4—C2A—H2A6	109.5
C41—C46—C45	121.4 (2)	H2A5—C2A—H2A6	109.5
C41—C46—H46	119.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···N2	1.05	1.86	2.904 (3)	175
N9—H9···O5^i	0.92	1.86	2.761 (3)	165
C12—H12B···O12^ii	0.99	2.45	3.344 (4)	150

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2.