Supramolecular hydrogen-bonded hexamers in two 5-aryl-3-methyl-1-phenyl-1,6,7,8-tetra­hydro­pyrazolo­[3,4-b][1,4]­diazepines

In both title compounds, i.e. 3-methyl-1,5-di­phenyl-1,6,7,8-tetra­hydro­pyrazolo­[3,4-b][1,4]­diazepine, C₁₉H₁₈N₄, (I), and 5-(4-chloro­phenyl)-3-methyl-1-phenyl-1,6,7,8-tetra­hydro­pyra­zolo­[3,4-b][1,4]­diazepine, C₁₉H₁₇ClN₄, (II), an N-H...N hydrogen bond links six mol­ecules to form an R(30) ring. Compound (I) crystallizes in the R space group and (II) crystallizes in P with three mol­ecules in the asymmetric unit. The mol­ecule of (I) contains a disordered seven-membered ring.

S1. Comment

Benzodiazepines are an important class of heterocyclic compounds used in psychotherapy. In recent years, analogous behaviour has reported for other heterocyclic fused diazepine systems (Chimirri et al., 1993; DeWald et al., 1981; Sharp, 1984; Sternbach, 1978). We present here the crystal structure of two pyrazolodiazepines prepared by the reaction between 4,5-diaminopyrazole and 1-aryl-2-propenones (Insuasty et al., 1999), namely 3-methyl-1,5-diphenyl-1,6,7,8-tetrahydropyrazolo[3,4-b][1,4]diazepine, (I), and tetrahydropyrazolo[3,4-b][1,4]diazepine, (II).

In (I), atoms C6 and C7 in the seven-membered ring are disordered, with the major component having a site-occupancy factor of 0.808. The torsion angles related to the major and minor components are given in Table 1. The deviations from the mean C5/N4/C3A/C8A/N8 plane are 0.534 (3) and -0.680 (8) Å for C6 and C61. The corresponding values for C7 and C71 are -0.372 (4) and 0.269 (12) Å, respectively. Thus, the twists are in the opposite directions for the major and minor components. Fig. 1 shows the major component.

The torsion angles for the seven-membered rings for the three molecules of (II) are given in Table 3. Views of the three molecules in the asymmetric unit are shown in Fig. 2.

In (I), the N—H···N hydrogen bond [N8—H8···N2(x-y, x, 1 - z)] in the structure, which by action of the 3 symmetry axis, links six molecules to form a hexamer with an R⁶₆(30) ring (Bernstein et al., 1995; Table 2 and Fig. 3). These rings are repeated at (1/3,2/3,2/3) and (2/3,1/3,1/3) by space-group symmetry. There are no other significant intermolecular contacts.

In (II), which crystallizes in the triclinic spacegroup P1, there are three molecules in the asymmetric unit which were selected such that the three molecules were linked to each other by a NI8—HI8···NJ2 hydrogen bond, (I and J denote the prefix numbers for the three molecules). The action of a centre of symmetry at (0,1/2,1) forms a hexamer with an identical R⁶₆(30) ring structure (Bernstein et al., 1995) to (I) (Fig. 4).

S2. Experimental

The title compounds were prepared as described previously by Insuasty et al. (1999).

S3. Refinement

Compound (I) crystallized in the trigonal system; space group R3 was assumed and confirmed by the analysis. H atoms were treated as riding, with C—H distances in the range 0.95–0.99 Å and an N—H distance of 0.88 Å. The minor component of the disordered seven-membered ring was constrained by use of DFIX instructions (DFIX 1.52. 005 C5/C61/C61/C71 and DFIX 1.46. 005 C71/N8), the C—C and C—N distances being based on those in the major component. The disordered atoms of the minor component were refined isotropically. The site occupancies for the disordered atoms were also refined with the site-occupancy factors being controlled by a single free variable. Compound (II) crystallized in the triclinic system; space group P1 was assumed and confirmed by the analysis. H atoms were treated as riding, with distances in the range C—H 0.95—0.99 Å. The final R factor for (II) of 0.822 is rather large; however, the crystal quality was poor, as is indicated by the value of R_int and it proved difficult to obtain better crystals. The largestest difference peaks are associated with the Cl atom.

Computing details

For both compounds, 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, 2001); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of the major component of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Views of the three molecules of the asymmetric unit of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A view of the supramolecular structure of (I) showing the R^66(30) ring. The molecules labels are at symmetry positions as follows: ($) -y, x-y, z; (?) -x + y, -x, z; (&) -x, -y, 1 - z; (#) y, -x + y, -z; (*) x-y, x, -z.
	Fig. 4. A view of the the supramolecular structure of (II) showing the R^66(30) ring. The molecules labelled with an asterisk (*) are at symmetry position (-x, 1 - y, 2 - z). The unit-cell box has been omitted for clarity.

(I) 3-methyl-1,5-diphenyl-1,6,7,8-tetrahydropyrazolo[3,4-b][1,4]diazepine

Crystal data

C19H18N4	Dx = 1.263 Mg m^−3
Mr = 302.38	Melting point: 493 K
Trigonal, R3	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3	Cell parameters from 3272 reflections
a = 30.5212 (7) Å	θ = 3.1–27.1°
c = 8.8689 (2) Å	µ = 0.08 mm^−1
V = 7154.9 (3) Å^3	T = 120 K
Z = 18	Plate, yellow
F(000) = 2880	0.25 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	3272 independent reflections
Radiation source: fine-focus sealed X-ray tube	2600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ scans and ω scans with κ offsets	θmax = 27.1°, θmin = 3.1°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −32→38
Tmin = 0.981, Tmax = 0.992	k = −39→20
40810 measured reflections	l = −8→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0676P)^2 + 6.7105P] where P = (Fo^2 + 2Fc^2)/3
3272 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.40 e Å^−3
3 restraints	Δρmin = −0.46 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

23.6197 (0.0166) x - 24.2617 (0.0157) y + 3.7543 (0.0041) z = 5.7703 (0.0035)

* -0.0643 (0.0011) N4 * 0.0294 (0.0010) C3A * 0.0209 (0.0011) C8A * -0.0269 (0.0007) N8 * 0.0410 (0.0007) C5 0.5339 (0.0030) C6 - 0.3716 (0.0037) C7

Rms deviation of fitted atoms = 0.0396

23.6197 (0.0166) x - 24.2617 (0.0157) y + 3.7543 (0.0041) z = 5.7703 (0.0035)

Angle to previous plane (with approximate e.s.d.) = 0.00 (0.11)

* -0.0643 (0.0011) N4 * 0.0294 (0.0010) C3A * 0.0209 (0.0011) C8A * -0.0269 (0.0007) N8 * 0.0410 (0.0007) C5 - 0.6803 (0.0084) C61 0.2689 (0.0121) C71

Rms deviation of fitted atoms = 0.0396

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.13804 (5)	−0.03624 (5)	0.45798 (14)	0.0232 (3)
C11	0.11700 (6)	−0.03483 (6)	0.59955 (17)	0.0233 (3)
C12	0.06534 (6)	−0.05238 (6)	0.60855 (18)	0.0274 (4)
C13	0.04368 (7)	−0.05339 (7)	0.7466 (2)	0.0352 (4)
C14	0.07371 (7)	−0.03554 (7)	0.8742 (2)	0.0396 (5)
C15	0.12520 (7)	−0.01720 (7)	0.86460 (19)	0.0370 (4)
C16	0.14719 (6)	−0.01706 (6)	0.72729 (18)	0.0296 (4)
N2	0.11100 (5)	−0.07893 (5)	0.36751 (14)	0.0253 (3)
C3	0.13898 (6)	−0.06950 (6)	0.24485 (17)	0.0241 (4)
C31	0.12383 (7)	−0.10841 (6)	0.12376 (19)	0.0327 (4)
C3A	0.18372 (6)	−0.02137 (6)	0.25082 (17)	0.0226 (3)
N4	0.21767 (5)	−0.00298 (5)	0.13112 (14)	0.0240 (3)
C5	0.26150 (6)	0.03627 (6)	0.13707 (19)	0.0327 (4)
C6	0.28581 (7)	0.06250 (8)	0.2850 (2)	0.0281 (6)	0.808 (5)
C7	0.25529 (9)	0.08274 (8)	0.3665 (3)	0.0282 (6)	0.808 (5)
C61	0.2611 (4)	0.0798 (3)	0.2286 (8)	0.041 (3)*	0.192 (5)
C71	0.2658 (2)	0.0711 (5)	0.3958 (9)	0.038 (3)*	0.192 (5)
N8	0.21482 (5)	0.04338 (5)	0.45868 (15)	0.0278 (3)
C8A	0.18198 (6)	−0.00107 (6)	0.39076 (17)	0.0225 (3)
C51	0.29130 (6)	0.05233 (6)	−0.00559 (18)	0.0264 (4)
C52	0.33314 (6)	0.10047 (6)	−0.02655 (19)	0.0286 (4)
C53	0.35800 (6)	0.11439 (6)	−0.16457 (19)	0.0304 (4)
C54	0.34152 (6)	0.08075 (7)	−0.28392 (19)	0.0314 (4)
C55	0.30032 (6)	0.03234 (7)	−0.26403 (19)	0.0311 (4)
C56	0.27582 (6)	0.01840 (6)	−0.12645 (18)	0.0272 (4)
H12	0.0450	−0.0636	0.5203	0.033*
H13	0.0082	−0.0663	0.7538	0.042*
H14	0.0589	−0.0359	0.9687	0.047*
H15	0.1456	−0.0046	0.9523	0.044*
H16	0.1825	−0.0049	0.7209	0.036*
H31A	0.0889	−0.1355	0.1409	0.049*
H31B	0.1464	−0.1226	0.1254	0.049*
H31C	0.1262	−0.0927	0.0255	0.049*
H6A	0.3203	0.0909	0.2644	0.034*	0.808 (5)
H6B	0.2891	0.0383	0.3517	0.034*	0.808 (5)
H7A	0.2782	0.1115	0.4319	0.034*	0.808 (5)
H7B	0.2403	0.0954	0.2912	0.034*	0.808 (5)
H61C	0.2898	0.1129	0.1968	0.049*	0.192 (5)
H61D	0.2292	0.0800	0.2098	0.049*	0.192 (5)
H71C	0.2833	0.0514	0.4087	0.046*	0.192 (5)
H71D	0.2857	0.1039	0.4482	0.046*	0.192 (5)
H8	0.2032	0.0568	0.5240	0.033*
H52	0.3448	0.1240	0.0544	0.034*
H53	0.3865	0.1472	−0.1770	0.037*
H54	0.3582	0.0906	−0.3787	0.038*
H55	0.2890	0.0089	−0.3451	0.037*
H56	0.2480	−0.0148	−0.1138	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0226 (7)	0.0205 (7)	0.0247 (7)	0.0094 (6)	0.0002 (5)	−0.0014 (5)
C11	0.0262 (8)	0.0180 (8)	0.0250 (8)	0.0104 (7)	0.0020 (6)	0.0025 (6)
C12	0.0251 (8)	0.0236 (8)	0.0303 (9)	0.0096 (7)	0.0006 (6)	−0.0010 (6)
C13	0.0291 (9)	0.0297 (9)	0.0393 (11)	0.0090 (8)	0.0086 (7)	−0.0030 (7)
C14	0.0445 (12)	0.0317 (10)	0.0300 (10)	0.0096 (9)	0.0112 (8)	−0.0023 (7)
C15	0.0438 (11)	0.0304 (10)	0.0257 (10)	0.0103 (8)	−0.0028 (7)	−0.0006 (7)
C16	0.0266 (9)	0.0279 (9)	0.0307 (9)	0.0110 (7)	−0.0026 (7)	0.0028 (7)
N2	0.0238 (7)	0.0208 (7)	0.0269 (7)	0.0079 (6)	−0.0022 (5)	−0.0027 (5)
C3	0.0236 (8)	0.0225 (8)	0.0259 (9)	0.0113 (7)	−0.0010 (6)	0.0001 (6)
C31	0.0313 (9)	0.0260 (9)	0.0328 (10)	0.0082 (8)	0.0013 (7)	−0.0044 (7)
C3A	0.0231 (8)	0.0210 (8)	0.0245 (8)	0.0116 (7)	−0.0001 (6)	0.0003 (6)
N4	0.0222 (7)	0.0216 (7)	0.0282 (7)	0.0110 (6)	0.0013 (5)	0.0015 (5)
C5	0.0272 (9)	0.0273 (9)	0.0328 (10)	0.0054 (8)	0.0034 (7)	−0.0046 (7)
C6	0.0198 (10)	0.0274 (11)	0.0317 (12)	0.0077 (9)	0.0004 (8)	−0.0051 (8)
C7	0.0243 (11)	0.0186 (11)	0.0349 (13)	0.0056 (9)	0.0045 (9)	−0.0048 (8)
N8	0.0243 (7)	0.0213 (7)	0.0333 (8)	0.0080 (6)	0.0048 (5)	−0.0060 (5)
C8A	0.0192 (8)	0.0206 (8)	0.0288 (9)	0.0107 (6)	−0.0008 (6)	0.0009 (6)
C51	0.0238 (8)	0.0244 (8)	0.0299 (9)	0.0112 (7)	0.0020 (6)	0.0015 (6)
C52	0.0251 (9)	0.0233 (8)	0.0360 (9)	0.0111 (7)	0.0025 (7)	−0.0028 (7)
C53	0.0225 (8)	0.0225 (8)	0.0433 (10)	0.0090 (7)	0.0069 (7)	0.0040 (7)
C54	0.0271 (9)	0.0335 (10)	0.0326 (10)	0.0143 (8)	0.0075 (7)	0.0040 (7)
C55	0.0278 (9)	0.0324 (9)	0.0308 (9)	0.0133 (8)	0.0008 (7)	−0.0031 (7)
C56	0.0230 (8)	0.0223 (8)	0.0324 (9)	0.0084 (7)	0.0010 (6)	0.0002 (6)

Geometric parameters (Å, º)

N1—C8A	1.3663 (19)	C6—C7	1.532 (3)
N1—N2	1.3954 (17)	C6—H6A	0.9900
N1—C11	1.4207 (19)	C6—H6B	0.9900
C11—C16	1.388 (2)	C7—N8	1.467 (2)
C11—C12	1.391 (2)	C7—H7A	0.9900
C12—C13	1.384 (2)	C7—H7B	0.9900
C12—H12	0.9500	C61—C71	1.526 (5)
C13—C14	1.385 (3)	C61—H61C	0.9900
C13—H13	0.9500	C61—H61D	0.9900
C14—C15	1.382 (3)	C71—N8	1.461 (5)
C14—H14	0.9500	C71—H71C	0.9900
C15—C16	1.390 (2)	C71—H71D	0.9900
C15—H15	0.9500	N8—C8A	1.359 (2)
C16—H16	0.9500	N8—H8	0.8801
N2—C3	1.323 (2)	C51—C52	1.396 (2)
C3—C3A	1.421 (2)	C51—C56	1.398 (2)
C3—C31	1.493 (2)	C52—C53	1.390 (2)
C31—H31A	0.9800	C52—H52	0.9500
C31—H31B	0.9800	C53—C54	1.382 (2)
C31—H31C	0.9800	C53—H53	0.9500
C3A—N4	1.391 (2)	C54—C55	1.392 (2)
C3A—C8A	1.400 (2)	C54—H54	0.9500
N4—C5	1.275 (2)	C55—C56	1.382 (2)
C5—C51	1.491 (2)	C55—H55	0.9500
C5—C6	1.522 (3)	C56—H56	0.9500
C5—C61	1.562 (5)
C8A—N1—N2	111.88 (12)	H6A—C6—H6B	107.8
C8A—N1—C11	129.99 (13)	N8—C7—C6	111.45 (18)
N2—N1—C11	118.12 (12)	N8—C7—H7A	109.3
C16—C11—C12	120.45 (15)	C6—C7—H7A	109.3
C16—C11—N1	120.76 (14)	N8—C7—H7B	109.3
C12—C11—N1	118.78 (14)	C6—C7—H7B	109.3
C13—C12—C11	119.75 (15)	H7A—C7—H7B	108.0
C13—C12—H12	120.1	C71—C61—C5	108.4 (7)
C11—C12—H12	120.1	C71—C61—H61C	110.0
C12—C13—C14	119.92 (17)	C5—C61—H61C	110.0
C12—C13—H13	120.0	C71—C61—H61D	110.0
C14—C13—H13	120.0	C5—C61—H61D	110.0
C15—C14—C13	120.27 (16)	H61C—C61—H61D	108.4
C15—C14—H14	119.9	N8—C71—C61	107.8 (6)
C13—C14—H14	119.9	N8—C71—H71C	110.1
C14—C15—C16	120.32 (16)	C61—C71—H71C	110.1
C14—C15—H15	119.8	N8—C71—H71D	110.1
C16—C15—H15	119.8	C61—C71—H71D	110.1
C11—C16—C15	119.26 (16)	H71C—C71—H71D	108.5
C11—C16—H16	120.4	C8A—N8—C71	116.7 (5)
C15—C16—H16	120.4	C8A—N8—C7	117.96 (14)
C3—N2—N1	104.69 (12)	C71—N8—C7	25.3 (4)
N2—C3—C3A	112.12 (13)	C8A—N8—H8	119.2
N2—C3—C31	120.59 (14)	C71—N8—H8	122.9
C3A—C3—C31	127.20 (14)	C7—N8—H8	110.9
C3—C31—H31A	109.5	N8—C8A—N1	122.35 (14)
C3—C31—H31B	109.5	N8—C8A—C3A	131.47 (14)
H31A—C31—H31B	109.5	N1—C8A—C3A	106.17 (13)
C3—C31—H31C	109.5	C52—C51—C56	118.04 (15)
H31A—C31—H31C	109.5	C52—C51—C5	123.08 (15)
H31B—C31—H31C	109.5	C56—C51—C5	118.85 (14)
N4—C3A—C8A	133.12 (14)	C53—C52—C51	120.75 (15)
N4—C3A—C3	121.72 (13)	C53—C52—H52	119.6
C8A—C3A—C3	105.13 (13)	C51—C52—H52	119.6
C5—N4—C3A	124.59 (14)	C54—C53—C52	120.46 (15)
N4—C5—C51	117.05 (14)	C54—C53—H53	119.8
N4—C5—C6	122.43 (15)	C52—C53—H53	119.8
C51—C5—C6	120.11 (14)	C53—C54—C55	119.44 (15)
N4—C5—C61	111.7 (4)	C53—C54—H54	120.3
C51—C5—C61	115.1 (4)	C55—C54—H54	120.3
C6—C5—C61	46.7 (3)	C56—C55—C54	120.07 (15)
C5—C6—C7	112.59 (18)	C56—C55—H55	120.0
C5—C6—H6A	109.1	C54—C55—H55	120.0
C7—C6—H6A	109.1	C55—C56—C51	121.21 (15)
C5—C6—H6B	109.1	C55—C56—H56	119.4
C7—C6—H6B	109.1	C51—C56—H56	119.4
C8A—N1—C11—C16	−43.4 (2)	C5—C61—C71—N8	−94.3 (9)
N2—N1—C11—C16	137.66 (15)	C61—C71—N8—C8A	55.5 (9)
C8A—N1—C11—C12	137.69 (17)	C61—C71—N8—C7	−43.9 (6)
N2—N1—C11—C12	−41.28 (19)	C6—C7—N8—C8A	−53.5 (3)
C16—C11—C12—C13	−1.7 (2)	C6—C7—N8—C71	40.4 (10)
N1—C11—C12—C13	177.22 (15)	C71—N8—C8A—N1	163.8 (5)
C11—C12—C13—C14	1.9 (3)	C7—N8—C8A—N1	−167.77 (18)
C12—C13—C14—C15	−0.7 (3)	C71—N8—C8A—C3A	−15.5 (5)
C13—C14—C15—C16	−0.8 (3)	C7—N8—C8A—C3A	13.0 (3)
C12—C11—C16—C15	0.3 (2)	N2—N1—C8A—N8	−179.18 (13)
N1—C11—C16—C15	−178.64 (15)	C11—N1—C8A—N8	1.8 (3)
C14—C15—C16—C11	1.0 (3)	N2—N1—C8A—C3A	0.21 (17)
C8A—N1—N2—C3	0.23 (17)	C11—N1—C8A—C3A	−178.81 (14)
C11—N1—N2—C3	179.38 (13)	N4—C3A—C8A—N8	−3.2 (3)
N1—N2—C3—C3A	−0.59 (17)	C3—C3A—C8A—N8	178.78 (16)
N1—N2—C3—C31	176.16 (14)	N4—C3A—C8A—N1	177.44 (16)
N2—C3—C3A—N4	−177.54 (14)	C3—C3A—C8A—N1	−0.54 (16)
C31—C3—C3A—N4	6.0 (2)	N4—C5—C51—C52	162.96 (16)
N2—C3—C3A—C8A	0.73 (18)	C6—C5—C51—C52	−24.2 (3)
C31—C3—C3A—C8A	−175.76 (16)	C61—C5—C51—C52	28.6 (5)
C8A—C3A—N4—C5	12.6 (3)	N4—C5—C51—C56	−14.7 (2)
C3—C3A—N4—C5	−169.72 (16)	C6—C5—C51—C56	158.14 (17)
C3A—N4—C5—C51	−175.91 (14)	C61—C5—C51—C56	−149.0 (4)
C3A—N4—C5—C6	11.4 (3)	C56—C51—C52—C53	1.1 (2)
C3A—N4—C5—C61	−40.2 (4)	C5—C51—C52—C53	−176.60 (16)
N4—C5—C6—C7	−61.5 (2)	C51—C52—C53—C54	0.3 (3)
C51—C5—C6—C7	125.99 (18)	C52—C53—C54—C55	−1.3 (3)
C61—C5—C6—C7	28.7 (5)	C53—C54—C55—C56	0.8 (3)
C5—C6—C7—N8	84.6 (2)	C54—C55—C56—C51	0.6 (3)
N4—C5—C61—C71	83.8 (6)	C52—C51—C56—C55	−1.6 (2)
C51—C5—C61—C71	−139.5 (5)	C5—C51—C56—C55	176.25 (16)
C6—C5—C61—C71	−30.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···N2^i	0.88	2.12	2.963 (2)	160

Symmetry code: (i) x−y, x, −z+1.

(II) 5-(4-Chlorophenyl)-3-methyl-1-phenyl-1,6,7,8- tetrahydropyrazolo[3,4-b][1,4]diazepine

Crystal data

C19H17ClN4	Z = 6
Mr = 336.82	F(000) = 1056
Triclinic, P1	Dx = 1.351 Mg m^−3
Hall symbol: -P 1	Melting point: 513 K
a = 9.0066 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 17.969 (4) Å	Cell parameters from 11212 reflections
c = 18.007 (4) Å	θ = 3.0–27.6°
α = 115.73 (3)°	µ = 0.24 mm^−1
β = 101.02 (3)°	T = 120 K
γ = 98.83 (3)°	Rod, yellow
V = 2483.1 (9) Å^3	0.48 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	11212 independent reflections
Radiation source: fine-focus sealed X-ray tube	7499 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.108
ϕ scans and ω scans with κ offsets	θmax = 27.6°, θmin = 3.0°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.894, Tmax = 0.977	k = −23→23
37371 measured reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: odirect
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.226	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1172P)^2 + 1.3813P] where P = (Fo^2 + 2Fc^2)/3
11212 reflections	(Δ/σ)max < 0.001
652 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	−0.1791 (3)	0.42914 (18)	0.68344 (18)	0.0261 (6)
C111	−0.0264 (4)	0.4293 (2)	0.7227 (2)	0.0249 (7)
C112	−0.0073 (4)	0.4004 (2)	0.7830 (2)	0.0303 (7)
C113	0.1423 (4)	0.3990 (3)	0.8201 (3)	0.0384 (9)
C114	0.2698 (5)	0.4278 (3)	0.7982 (3)	0.0448 (10)
C115	0.2511 (4)	0.4580 (3)	0.7394 (3)	0.0385 (9)
C116	0.1004 (4)	0.4570 (2)	0.7001 (2)	0.0323 (8)
N12	−0.3066 (3)	0.35926 (18)	0.65717 (19)	0.0277 (6)
C13	−0.4295 (4)	0.3807 (2)	0.6277 (2)	0.0256 (7)
C131	−0.5900 (4)	0.3189 (2)	0.5882 (3)	0.0346 (8)
C13A	−0.3891 (4)	0.4637 (2)	0.6347 (2)	0.0242 (7)
N14	−0.5015 (3)	0.50299 (18)	0.61540 (17)	0.0243 (6)
C15	−0.4677 (4)	0.5719 (2)	0.6084 (2)	0.0237 (7)
C151	−0.5970 (4)	0.6114 (2)	0.59668 (19)	0.0229 (7)
C152	−0.7524 (4)	0.5671 (2)	0.5808 (2)	0.0256 (7)
C153	−0.8756 (4)	0.6034 (2)	0.5732 (2)	0.0266 (7)
C154	−0.8457 (4)	0.6850 (2)	0.5812 (2)	0.0285 (7)
Cl15	−1.00142 (10)	0.73005 (7)	0.57008 (7)	0.0381 (2)
C155	−0.6939 (4)	0.7314 (2)	0.5981 (2)	0.0315 (8)
C156	−0.5719 (4)	0.6940 (2)	0.6050 (2)	0.0285 (7)
C16	−0.3044 (4)	0.6127 (2)	0.6132 (2)	0.0272 (7)
C17	−0.1819 (4)	0.6393 (2)	0.6981 (2)	0.0265 (7)
N18	−0.1201 (3)	0.56862 (18)	0.69495 (17)	0.0247 (6)
C18A	−0.2257 (4)	0.4930 (2)	0.6717 (2)	0.0229 (7)
N21	−0.1306 (3)	0.20189 (18)	0.77023 (17)	0.0245 (6)
C211	−0.2384 (4)	0.2438 (2)	0.8092 (2)	0.0262 (7)
C212	−0.1884 (4)	0.3032 (2)	0.8958 (2)	0.0335 (8)
C213	−0.2954 (5)	0.3425 (3)	0.9345 (3)	0.0412 (9)
C214	−0.4486 (5)	0.3234 (3)	0.8859 (3)	0.0433 (10)
C215	−0.4957 (5)	0.2653 (3)	0.7993 (3)	0.0390 (9)
C216	−0.3928 (4)	0.2238 (2)	0.7601 (2)	0.0317 (8)
N22	−0.0214 (3)	0.1794 (2)	0.81721 (18)	0.0281 (6)
C23	0.0674 (4)	0.1481 (2)	0.7668 (2)	0.0286 (7)
C231	0.1934 (4)	0.1117 (3)	0.7925 (2)	0.0350 (8)
C23A	0.0224 (4)	0.1504 (2)	0.6879 (2)	0.0250 (7)
N24	0.1060 (3)	0.12597 (18)	0.62814 (18)	0.0247 (6)
C25	0.0572 (4)	0.1131 (2)	0.5506 (2)	0.0226 (7)
C251	0.1679 (4)	0.0929 (2)	0.4972 (2)	0.0238 (7)
C252	0.1289 (4)	0.0724 (3)	0.4113 (2)	0.0347 (8)
C253	0.2358 (4)	0.0543 (3)	0.3636 (2)	0.0384 (9)
C254	0.3856 (4)	0.0590 (2)	0.4043 (2)	0.0299 (7)
C256	0.3212 (4)	0.0961 (2)	0.5351 (2)	0.0273 (7)
Cl25	0.52190 (10)	0.03544 (6)	0.34524 (6)	0.0374 (2)
C255	0.4301 (4)	0.0794 (2)	0.4894 (2)	0.0279 (7)
C26	−0.1021 (4)	0.1195 (2)	0.5130 (2)	0.0267 (7)
C27	−0.1354 (4)	0.2054 (2)	0.5671 (2)	0.0274 (7)
N28	−0.1963 (3)	0.20390 (18)	0.63598 (17)	0.0236 (6)
C28A	−0.1073 (4)	0.1862 (2)	0.6927 (2)	0.0229 (7)
N31	−0.0881 (3)	0.27320 (18)	1.07850 (17)	0.0253 (6)
C311	0.0598 (4)	0.3136 (2)	1.0771 (2)	0.0265 (7)
C312	0.0999 (4)	0.4011 (2)	1.1055 (2)	0.0323 (8)
C313	0.2450 (5)	0.4399 (3)	1.1048 (3)	0.0446 (10)
C314	0.3464 (5)	0.3913 (3)	1.0746 (3)	0.0458 (10)
C315	0.3055 (4)	0.3040 (3)	1.0459 (2)	0.0410 (9)
C316	0.1629 (4)	0.2650 (2)	1.0482 (2)	0.0324 (8)
N32	−0.1464 (3)	0.31680 (19)	1.14747 (17)	0.0270 (6)
C33	−0.2884 (4)	0.2663 (2)	1.1267 (2)	0.0272 (7)
C331	−0.3850 (4)	0.2890 (3)	1.1879 (2)	0.0346 (8)
C33A	−0.3268 (3)	0.1914 (2)	1.0451 (2)	0.0231 (7)
N34	−0.4740 (3)	0.13225 (18)	1.00902 (17)	0.0248 (6)
C35	−0.5066 (4)	0.0580 (2)	0.9430 (2)	0.0220 (6)
C351	−0.6735 (4)	0.0052 (2)	0.9093 (2)	0.0229 (7)
C352	−0.7244 (4)	−0.0783 (2)	0.8419 (2)	0.0362 (9)
C353	−0.8817 (4)	−0.1236 (3)	0.8106 (3)	0.0432 (10)
C354	−0.9896 (4)	−0.0850 (2)	0.8457 (2)	0.0309 (8)
C355	−0.9429 (4)	−0.0028 (2)	0.9141 (2)	0.0288 (7)
C356	−0.7858 (4)	0.0410 (2)	0.9453 (2)	0.0280 (7)
Cl35	−1.18825 (10)	−0.14153 (6)	0.80571 (7)	0.0439 (3)
C36	−0.3894 (4)	0.0228 (2)	0.8973 (2)	0.0283 (7)
C37	−0.2993 (4)	0.0827 (2)	0.8714 (2)	0.0280 (7)
N38	−0.1653 (3)	0.14642 (18)	0.94216 (17)	0.0240 (6)
C38A	−0.1948 (4)	0.1990 (2)	1.0162 (2)	0.0232 (7)
H112	−0.0949	0.3819	0.7988	0.036*
H113	0.1565	0.3781	0.8605	0.046*
H114	0.3714	0.4269	0.8240	0.054*
H115	0.3395	0.4793	0.7258	0.046*
H116	0.0855	0.4755	0.6578	0.039*
H13A	−0.5840	0.2661	0.5911	0.052*	0.50
H13B	−0.6291	0.3054	0.5279	0.052*	0.50
H13C	−0.6615	0.3448	0.6199	0.052*	0.50
H13D	−0.6658	0.3447	0.5682	0.052*	0.50
H13E	−0.6207	0.3055	0.6313	0.052*	0.50
H13F	−0.5882	0.2661	0.5394	0.052*	0.50
H152	−0.7731	0.5112	0.5753	0.031*
H153	−0.9797	0.5727	0.5625	0.032*
H155	−0.6740	0.7878	0.6048	0.038*
H156	−0.4682	0.7253	0.6156	0.034*
H16A	−0.3060	0.6640	0.6056	0.033*
H16B	−0.2726	0.5717	0.5651	0.033*
H17A	−0.0950	0.6876	0.7097	0.032*
H17B	−0.2305	0.6592	0.7457	0.032*
H18	−0.0296	0.5840	0.7338	0.030*
H212	−0.0826	0.3171	0.9285	0.040*
H213	−0.2631	0.3823	0.9943	0.049*
H214	−0.5211	0.3505	0.9122	0.052*
H215	−0.6002	0.2534	0.7660	0.047*
H216	−0.4268	0.1825	0.7009	0.038*
H23A	0.1896	0.1110	0.8463	0.052*	0.50
H23B	0.2959	0.1471	0.8011	0.052*	0.50
H23C	0.1775	0.0530	0.7471	0.052*	0.50
H23D	0.2524	0.0964	0.7500	0.052*	0.50
H23E	0.1461	0.0604	0.7952	0.052*	0.50
H23F	0.2645	0.1544	0.8492	0.052*	0.50
H252	0.0262	0.0707	0.3840	0.042*
H253	0.2060	0.0390	0.3042	0.046*
H256	0.3515	0.1101	0.5941	0.033*
H255	0.5337	0.0821	0.5165	0.033*
H26A	−0.1837	0.0723	0.5076	0.032*
H26B	−0.1098	0.1119	0.4544	0.032*
H27A	−0.0373	0.2522	0.5924	0.033*
H27B	−0.2127	0.2172	0.5295	0.033*
H28	−0.2352	0.2482	0.6574	0.028*
H312	0.0291	0.4340	1.1251	0.039*
H313	0.2747	0.5000	1.1250	0.054*
H314	0.4449	0.4181	1.0736	0.055*
H315	0.3751	0.2709	1.0246	0.049*
H316	0.1355	0.2053	1.0301	0.039*
H33A	−0.3229	0.3397	1.2422	0.052*	0.50
H33B	−0.4171	0.2408	1.1986	0.052*	0.50
H33C	−0.4785	0.3015	1.1630	0.052*	0.50
H33D	−0.4894	0.2483	1.1603	0.052*	0.50
H33E	−0.3952	0.3471	1.2039	0.052*	0.50
H33F	−0.3338	0.2865	1.2396	0.052*	0.50
H352	−0.6503	−0.1050	0.8168	0.043*
H353	−0.9145	−0.1810	0.7651	0.052*
H355	−1.0175	0.0232	0.9392	0.035*
H356	−0.7532	0.0973	0.9928	0.034*
H36A	−0.4455	−0.0323	0.8449	0.034*
H36B	−0.3131	0.0109	0.9354	0.034*
H37A	−0.2625	0.0484	0.8220	0.034*
H37B	−0.3707	0.1121	0.8528	0.034*
H38	−0.0972	0.1720	0.9258	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0195 (13)	0.0236 (15)	0.0371 (16)	0.0058 (11)	0.0076 (11)	0.0162 (13)
C111	0.0206 (15)	0.0221 (17)	0.0298 (17)	0.0065 (13)	0.0053 (12)	0.0109 (14)
C112	0.0279 (17)	0.0238 (18)	0.0344 (19)	0.0055 (14)	0.0061 (14)	0.0113 (15)
C113	0.0317 (19)	0.032 (2)	0.048 (2)	0.0043 (16)	−0.0017 (16)	0.0217 (18)
C114	0.0278 (19)	0.036 (2)	0.068 (3)	0.0091 (16)	0.0030 (18)	0.026 (2)
C115	0.0215 (17)	0.032 (2)	0.063 (3)	0.0076 (15)	0.0146 (16)	0.0228 (19)
C116	0.0259 (17)	0.032 (2)	0.043 (2)	0.0102 (15)	0.0133 (15)	0.0202 (17)
N12	0.0234 (14)	0.0193 (14)	0.0408 (17)	0.0038 (11)	0.0093 (12)	0.0152 (13)
C13	0.0206 (16)	0.0176 (16)	0.0339 (18)	0.0020 (12)	0.0082 (13)	0.0091 (14)
C131	0.0234 (17)	0.0227 (18)	0.052 (2)	0.0019 (14)	0.0072 (15)	0.0161 (17)
C13A	0.0198 (15)	0.0230 (17)	0.0277 (17)	0.0048 (13)	0.0060 (12)	0.0112 (14)
N14	0.0200 (13)	0.0212 (14)	0.0287 (14)	0.0033 (11)	0.0048 (10)	0.0108 (12)
C15	0.0223 (16)	0.0228 (17)	0.0225 (16)	0.0020 (13)	0.0047 (12)	0.0098 (14)
C151	0.0211 (15)	0.0236 (17)	0.0217 (16)	0.0029 (13)	0.0034 (12)	0.0111 (14)
C152	0.0260 (16)	0.0202 (17)	0.0286 (17)	0.0039 (13)	0.0097 (13)	0.0100 (14)
C153	0.0185 (15)	0.0298 (19)	0.0320 (18)	0.0066 (13)	0.0089 (13)	0.0145 (15)
C154	0.0248 (17)	0.034 (2)	0.0293 (18)	0.0095 (14)	0.0063 (13)	0.0173 (16)
Cl15	0.0276 (4)	0.0469 (6)	0.0585 (6)	0.0178 (4)	0.0170 (4)	0.0371 (5)
C155	0.0292 (18)	0.0275 (19)	0.046 (2)	0.0065 (14)	0.0116 (15)	0.0244 (17)
C156	0.0193 (15)	0.0309 (19)	0.0360 (19)	0.0027 (13)	0.0049 (13)	0.0192 (16)
C16	0.0224 (16)	0.0269 (18)	0.0347 (18)	0.0043 (13)	0.0072 (13)	0.0180 (15)
C17	0.0237 (16)	0.0197 (17)	0.0324 (18)	0.0033 (13)	0.0056 (13)	0.0109 (14)
N18	0.0176 (13)	0.0225 (15)	0.0302 (15)	0.0019 (11)	0.0010 (10)	0.0128 (12)
C18A	0.0226 (15)	0.0187 (16)	0.0258 (16)	0.0032 (12)	0.0076 (12)	0.0099 (13)
N21	0.0190 (13)	0.0258 (15)	0.0291 (15)	0.0055 (11)	0.0064 (11)	0.0139 (12)
C211	0.0259 (16)	0.0276 (18)	0.0322 (18)	0.0087 (13)	0.0103 (13)	0.0191 (15)
C212	0.037 (2)	0.037 (2)	0.034 (2)	0.0135 (16)	0.0118 (15)	0.0218 (17)
C213	0.057 (3)	0.041 (2)	0.037 (2)	0.027 (2)	0.0205 (18)	0.0217 (19)
C214	0.051 (2)	0.055 (3)	0.047 (2)	0.033 (2)	0.0279 (19)	0.033 (2)
C215	0.0316 (19)	0.051 (3)	0.049 (2)	0.0163 (18)	0.0162 (17)	0.033 (2)
C216	0.0281 (18)	0.035 (2)	0.0348 (19)	0.0083 (15)	0.0092 (14)	0.0186 (17)
N22	0.0252 (14)	0.0346 (17)	0.0299 (15)	0.0084 (12)	0.0066 (11)	0.0205 (13)
C23	0.0179 (15)	0.037 (2)	0.0346 (19)	0.0048 (14)	0.0063 (13)	0.0218 (16)
C231	0.0325 (19)	0.046 (2)	0.041 (2)	0.0177 (17)	0.0134 (15)	0.0289 (19)
C23A	0.0210 (15)	0.0265 (18)	0.0301 (17)	0.0057 (13)	0.0069 (13)	0.0161 (15)
N24	0.0246 (14)	0.0214 (14)	0.0319 (15)	0.0083 (11)	0.0086 (11)	0.0153 (12)
C25	0.0221 (15)	0.0160 (15)	0.0275 (17)	0.0034 (12)	0.0063 (12)	0.0093 (13)
C251	0.0230 (16)	0.0145 (15)	0.0289 (17)	0.0046 (12)	0.0053 (13)	0.0072 (13)
C252	0.0261 (18)	0.047 (2)	0.0338 (19)	0.0185 (16)	0.0076 (14)	0.0188 (18)
C253	0.0322 (19)	0.055 (3)	0.0249 (18)	0.0162 (18)	0.0059 (14)	0.0154 (18)
C254	0.0288 (17)	0.0236 (18)	0.0338 (19)	0.0065 (14)	0.0125 (14)	0.0096 (15)
C256	0.0226 (16)	0.0283 (18)	0.0267 (17)	0.0036 (13)	0.0042 (13)	0.0116 (15)
Cl25	0.0279 (4)	0.0428 (6)	0.0339 (5)	0.0106 (4)	0.0115 (3)	0.0103 (4)
C255	0.0182 (15)	0.0263 (18)	0.0339 (19)	0.0029 (13)	0.0049 (13)	0.0120 (15)
C26	0.0235 (16)	0.0283 (18)	0.0281 (17)	0.0072 (13)	0.0053 (13)	0.0139 (15)
C27	0.0294 (17)	0.0298 (19)	0.0298 (18)	0.0120 (14)	0.0091 (14)	0.0186 (15)
N28	0.0235 (13)	0.0219 (14)	0.0255 (14)	0.0090 (11)	0.0056 (10)	0.0111 (12)
C28A	0.0211 (15)	0.0174 (16)	0.0265 (16)	−0.0004 (12)	0.0038 (12)	0.0103 (13)
N31	0.0203 (13)	0.0236 (15)	0.0275 (14)	0.0030 (11)	0.0064 (11)	0.0094 (12)
C311	0.0225 (16)	0.0276 (18)	0.0257 (17)	0.0036 (13)	0.0037 (12)	0.0119 (14)
C312	0.0321 (18)	0.0263 (19)	0.0320 (19)	0.0047 (15)	0.0076 (14)	0.0099 (15)
C313	0.046 (2)	0.032 (2)	0.042 (2)	−0.0060 (18)	0.0146 (18)	0.0105 (18)
C314	0.037 (2)	0.044 (3)	0.042 (2)	−0.0030 (18)	0.0146 (17)	0.0115 (19)
C315	0.0238 (18)	0.045 (2)	0.037 (2)	0.0034 (16)	0.0091 (15)	0.0068 (18)
C316	0.0260 (17)	0.030 (2)	0.0323 (19)	0.0043 (14)	0.0043 (14)	0.0093 (16)
N32	0.0201 (13)	0.0269 (15)	0.0266 (14)	0.0066 (11)	0.0064 (11)	0.0064 (12)
C33	0.0218 (16)	0.0302 (19)	0.0257 (17)	0.0089 (14)	0.0052 (13)	0.0102 (15)
C331	0.0253 (17)	0.040 (2)	0.0275 (18)	0.0058 (15)	0.0092 (14)	0.0065 (16)
C33A	0.0169 (15)	0.0235 (17)	0.0257 (16)	0.0053 (12)	0.0045 (12)	0.0099 (14)
N34	0.0203 (13)	0.0258 (15)	0.0276 (14)	0.0056 (11)	0.0073 (11)	0.0122 (12)
C35	0.0212 (15)	0.0213 (17)	0.0255 (16)	0.0073 (12)	0.0071 (12)	0.0122 (14)
C351	0.0208 (15)	0.0238 (17)	0.0276 (17)	0.0055 (13)	0.0074 (12)	0.0153 (14)
C352	0.0263 (18)	0.0246 (19)	0.045 (2)	0.0070 (14)	0.0128 (15)	0.0051 (17)
C353	0.030 (2)	0.0214 (19)	0.058 (3)	0.0019 (15)	0.0139 (17)	0.0029 (18)
C354	0.0244 (17)	0.0260 (19)	0.043 (2)	0.0063 (14)	0.0104 (14)	0.0171 (16)
C355	0.0234 (17)	0.0299 (19)	0.0389 (19)	0.0111 (14)	0.0135 (14)	0.0184 (16)
C356	0.0289 (17)	0.0226 (18)	0.0314 (18)	0.0092 (14)	0.0104 (14)	0.0105 (15)
Cl35	0.0219 (4)	0.0288 (5)	0.0674 (7)	0.0024 (3)	0.0118 (4)	0.0132 (5)
C36	0.0232 (16)	0.0219 (17)	0.0363 (19)	0.0042 (13)	0.0123 (14)	0.0098 (15)
C37	0.0256 (17)	0.0273 (18)	0.0266 (17)	0.0042 (14)	0.0084 (13)	0.0097 (15)
N38	0.0202 (13)	0.0231 (15)	0.0248 (14)	0.0017 (11)	0.0071 (10)	0.0091 (12)
C38A	0.0219 (15)	0.0207 (16)	0.0246 (16)	0.0045 (12)	0.0042 (12)	0.0102 (13)

Geometric parameters (Å, º)

N11—C18A	1.364 (4)	C23A—C28A	1.417 (5)
N11—N12	1.398 (4)	N24—C25	1.285 (4)
N11—C111	1.420 (4)	C25—C251	1.492 (4)
C111—C116	1.377 (5)	C25—C26	1.508 (4)
C111—C112	1.386 (5)	C251—C252	1.382 (5)
C112—C113	1.394 (5)	C251—C256	1.399 (5)
C112—H112	0.9500	C252—C253	1.393 (5)
C113—C114	1.382 (6)	C252—H252	0.9500
C113—H113	0.9500	C253—C254	1.378 (5)
C114—C115	1.379 (6)	C253—H253	0.9500
C114—H114	0.9500	C254—C255	1.368 (5)
C115—C116	1.399 (5)	C254—Cl25	1.757 (3)
C115—H115	0.9500	C256—C255	1.384 (5)
C116—H116	0.9500	C256—H256	0.9500
N12—C13	1.318 (4)	C255—H255	0.9500
C13—C13A	1.425 (5)	C26—C27	1.539 (5)
C13—C131	1.502 (5)	C26—H26A	0.9900
C131—H13A	0.9800	C26—H26B	0.9900
C131—H13B	0.9800	C27—N28	1.457 (4)
C131—H13C	0.9800	C27—H27A	0.9900
C131—H13D	0.9800	C27—H27B	0.9900
C131—H13E	0.9800	N28—C28A	1.354 (4)
C131—H13F	0.9800	N28—H28	0.8800
C13A—N14	1.393 (4)	N31—C38A	1.362 (4)
C13A—C18A	1.404 (4)	N31—N32	1.401 (4)
N14—C15	1.295 (4)	N31—C311	1.426 (4)
C15—C151	1.482 (4)	C311—C312	1.386 (5)
C15—C16	1.508 (4)	C311—C316	1.391 (5)
C151—C156	1.403 (5)	C312—C313	1.389 (5)
C151—C152	1.408 (4)	C312—H312	0.9500
C152—C153	1.385 (5)	C313—C314	1.384 (6)
C152—H152	0.9500	C313—H313	0.9500
C153—C154	1.387 (5)	C314—C315	1.381 (6)
C153—H153	0.9500	C314—H314	0.9500
C154—C155	1.389 (5)	C315—C316	1.383 (5)
C154—Cl15	1.745 (3)	C315—H315	0.9500
C155—C156	1.386 (5)	C316—H316	0.9500
C155—H155	0.9500	N32—C33	1.328 (4)
C156—H156	0.9500	C33—C33A	1.427 (5)
C16—C17	1.529 (5)	C33—C331	1.490 (5)
C16—H16A	0.9900	C331—H33A	0.9800
C16—H16B	0.9900	C331—H33B	0.9800
C17—N18	1.447 (4)	C331—H33C	0.9800
C17—H17A	0.9900	C331—H33D	0.9800
C17—H17B	0.9900	C331—H33E	0.9800
N18—C18A	1.372 (4)	C331—H33F	0.9800
N18—H18	0.8800	C33A—N34	1.396 (4)
N21—C28A	1.364 (4)	C33A—C38A	1.396 (4)
N21—N22	1.395 (4)	N34—C35	1.284 (4)
N21—C211	1.423 (4)	C35—C351	1.497 (4)
C211—C212	1.383 (5)	C35—C36	1.509 (4)
C211—C216	1.395 (5)	C351—C352	1.390 (5)
C212—C213	1.397 (5)	C351—C356	1.395 (5)
C212—H212	0.9500	C352—C353	1.389 (5)
C213—C214	1.386 (6)	C352—H352	0.9500
C213—H213	0.9500	C353—C354	1.373 (5)
C214—C215	1.378 (6)	C353—H353	0.9500
C214—H214	0.9500	C354—C355	1.382 (5)
C215—C216	1.384 (5)	C354—Cl35	1.751 (4)
C215—H215	0.9500	C355—C356	1.381 (5)
C216—H216	0.9500	C355—H355	0.9500
N22—C23	1.324 (4)	C356—H356	0.9500
C23—C23A	1.422 (5)	C36—C37	1.532 (5)
C23—C231	1.489 (5)	C36—H36A	0.9900
C231—H23A	0.9800	C36—H36B	0.9900
C231—H23B	0.9800	C37—N38	1.453 (4)
C231—H23C	0.9800	C37—H37A	0.9900
C231—H23D	0.9800	C37—H37B	0.9900
C231—H23E	0.9800	N38—C38A	1.364 (4)
C231—H23F	0.9800	N38—H38	0.8801
C23A—N24	1.386 (4)
C18A—N11—N12	111.6 (3)	H23E—C231—H23F	109.5
C18A—N11—C111	128.4 (3)	N24—C23A—C28A	133.2 (3)
N12—N11—C111	119.8 (3)	N24—C23A—C23	121.9 (3)
C116—C111—C112	120.7 (3)	C28A—C23A—C23	104.7 (3)
C116—C111—N11	120.1 (3)	C25—N24—C23A	124.4 (3)
C112—C111—N11	119.2 (3)	N24—C25—C251	116.9 (3)
C111—C112—C113	119.1 (3)	N24—C25—C26	123.5 (3)
C111—C112—H112	120.4	C251—C25—C26	119.6 (3)
C113—C112—H112	120.4	C252—C251—C256	117.0 (3)
C114—C113—C112	120.1 (4)	C252—C251—C25	123.6 (3)
C114—C113—H113	119.9	C256—C251—C25	119.4 (3)
C112—C113—H113	119.9	C251—C252—C253	121.9 (3)
C115—C114—C113	120.7 (3)	C251—C252—H252	119.0
C115—C114—H114	119.6	C253—C252—H252	119.0
C113—C114—H114	119.6	C254—C253—C252	118.6 (3)
C114—C115—C116	119.2 (3)	C254—C253—H253	120.7
C114—C115—H115	120.4	C252—C253—H253	120.7
C116—C115—H115	120.4	C255—C254—C253	121.7 (3)
C111—C116—C115	120.1 (3)	C255—C254—Cl25	118.9 (3)
C111—C116—H116	120.0	C253—C254—Cl25	119.4 (3)
C115—C116—H116	120.0	C255—C256—C251	122.1 (3)
C13—N12—N11	104.7 (3)	C255—C256—H256	119.0
N12—C13—C13A	112.7 (3)	C251—C256—H256	119.0
N12—C13—C131	120.7 (3)	C254—C255—C256	118.7 (3)
C13A—C13—C131	126.5 (3)	C254—C255—H255	120.6
C13—C131—H13A	109.5	C256—C255—H255	120.6
C13—C131—H13B	109.5	C25—C26—C27	113.5 (3)
H13A—C131—H13B	109.5	C25—C26—H26A	108.9
C13—C131—H13C	109.5	C27—C26—H26A	108.9
H13A—C131—H13C	109.5	C25—C26—H26B	108.9
H13B—C131—H13C	109.5	C27—C26—H26B	108.9
C13—C131—H13D	109.5	H26A—C26—H26B	107.7
H13A—C131—H13D	141.1	N28—C27—C26	111.3 (3)
H13B—C131—H13D	56.3	N28—C27—H27A	109.4
H13C—C131—H13D	56.3	C26—C27—H27A	109.4
C13—C131—H13E	109.5	N28—C27—H27B	109.4
H13A—C131—H13E	56.3	C26—C27—H27B	109.4
H13B—C131—H13E	141.1	H27A—C27—H27B	108.0
H13C—C131—H13E	56.3	C28A—N28—C27	117.5 (3)
H13D—C131—H13E	109.5	C28A—N28—H28	117.2
C13—C131—H13F	109.5	C27—N28—H28	108.8
H13A—C131—H13F	56.3	N28—C28A—N21	123.4 (3)
H13B—C131—H13F	56.3	N28—C28A—C23A	130.6 (3)
H13C—C131—H13F	141.1	N21—C28A—C23A	106.0 (3)
H13D—C131—H13F	109.5	C38A—N31—N32	111.8 (3)
H13E—C131—H13F	109.5	C38A—N31—C311	128.9 (3)
N14—C13A—C18A	132.7 (3)	N32—N31—C311	118.9 (3)
N14—C13A—C13	122.6 (3)	C312—C311—C316	120.7 (3)
C18A—C13A—C13	104.3 (3)	C312—C311—N31	119.5 (3)
C15—N14—C13A	123.3 (3)	C316—C311—N31	119.7 (3)
N14—C15—C151	117.1 (3)	C311—C312—C313	119.1 (4)
N14—C15—C16	122.7 (3)	C311—C312—H312	120.5
C151—C15—C16	120.1 (3)	C313—C312—H312	120.5
C156—C151—C152	117.3 (3)	C314—C313—C312	120.1 (4)
C156—C151—C15	123.0 (3)	C314—C313—H313	119.9
C152—C151—C15	119.6 (3)	C312—C313—H313	119.9
C153—C152—C151	121.3 (3)	C315—C314—C313	120.5 (4)
C153—C152—H152	119.4	C315—C314—H314	119.7
C151—C152—H152	119.4	C313—C314—H314	119.7
C152—C153—C154	119.5 (3)	C314—C315—C316	119.8 (4)
C152—C153—H153	120.2	C314—C315—H315	120.1
C154—C153—H153	120.2	C316—C315—H315	120.1
C153—C154—C155	121.0 (3)	C315—C316—C311	119.6 (4)
C153—C154—Cl15	119.4 (3)	C315—C316—H316	120.2
C155—C154—Cl15	119.5 (3)	C311—C316—H316	120.2
C156—C155—C154	118.8 (3)	C33—N32—N31	104.3 (3)
C156—C155—H155	120.6	N32—C33—C33A	112.3 (3)
C154—C155—H155	120.6	N32—C33—C331	120.2 (3)
C155—C156—C151	122.0 (3)	C33A—C33—C331	127.4 (3)
C155—C156—H156	119.0	C33—C331—H33A	109.5
C151—C156—H156	119.0	C33—C331—H33B	109.5
C15—C16—C17	113.5 (3)	H33A—C331—H33B	109.5
C15—C16—H16A	108.9	C33—C331—H33C	109.5
C17—C16—H16A	108.9	H33A—C331—H33C	109.5
C15—C16—H16B	108.9	H33B—C331—H33C	109.5
C17—C16—H16B	108.9	C33—C331—H33D	109.5
H16A—C16—H16B	107.7	H33A—C331—H33D	141.1
N18—C17—C16	111.2 (3)	H33B—C331—H33D	56.3
N18—C17—H17A	109.4	H33C—C331—H33D	56.3
C16—C17—H17A	109.4	C33—C331—H33E	109.5
N18—C17—H17B	109.4	H33A—C331—H33E	56.3
C16—C17—H17B	109.4	H33B—C331—H33E	141.1
H17A—C17—H17B	108.0	H33C—C331—H33E	56.3
C18A—N18—C17	117.6 (3)	H33D—C331—H33E	109.5
C18A—N18—H18	118.5	C33—C331—H33F	109.5
C17—N18—H18	114.4	H33A—C331—H33F	56.3
N11—C18A—N18	121.6 (3)	H33B—C331—H33F	56.3
N11—C18A—C13A	106.7 (3)	H33C—C331—H33F	141.1
N18—C18A—C13A	131.7 (3)	H33D—C331—H33F	109.5
C28A—N21—N22	112.2 (3)	H33E—C331—H33F	109.5
C28A—N21—C211	128.4 (3)	N34—C33A—C38A	133.7 (3)
N22—N21—C211	119.2 (3)	N34—C33A—C33	121.5 (3)
C212—C211—C216	120.9 (3)	C38A—C33A—C33	104.7 (3)
C212—C211—N21	119.3 (3)	C35—N34—C33A	123.8 (3)
C216—C211—N21	119.9 (3)	N34—C35—C351	116.6 (3)
C211—C212—C213	119.2 (3)	N34—C35—C36	124.2 (3)
C211—C212—H212	120.4	C351—C35—C36	119.1 (3)
C213—C212—H212	120.4	C352—C351—C356	117.4 (3)
C214—C213—C212	120.1 (4)	C352—C351—C35	123.2 (3)
C214—C213—H213	120.0	C356—C351—C35	119.4 (3)
C212—C213—H213	120.0	C353—C352—C351	121.0 (3)
C215—C214—C213	119.9 (4)	C353—C352—H352	119.5
C215—C214—H214	120.0	C351—C352—H352	119.5
C213—C214—H214	120.0	C354—C353—C352	119.8 (3)
C214—C215—C216	120.9 (4)	C354—C353—H353	120.1
C214—C215—H215	119.6	C352—C353—H353	120.1
C216—C215—H215	119.6	C353—C354—C355	120.8 (3)
C215—C216—C211	118.9 (3)	C353—C354—Cl35	119.9 (3)
C215—C216—H216	120.5	C355—C354—Cl35	119.3 (3)
C211—C216—H216	120.5	C356—C355—C354	118.8 (3)
C23—N22—N21	104.8 (3)	C356—C355—H355	120.6
N22—C23—C23A	112.3 (3)	C354—C355—H355	120.6
N22—C23—C231	121.0 (3)	C355—C356—C351	122.1 (3)
C23A—C23—C231	126.6 (3)	C355—C356—H356	118.9
C23—C231—H23A	109.5	C351—C356—H356	118.9
C23—C231—H23B	109.5	C35—C36—C37	114.0 (3)
H23A—C231—H23B	109.5	C35—C36—H36A	108.7
C23—C231—H23C	109.5	C37—C36—H36A	108.7
H23A—C231—H23C	109.5	C35—C36—H36B	108.7
H23B—C231—H23C	109.5	C37—C36—H36B	108.7
C23—C231—H23D	109.5	H36A—C36—H36B	107.6
H23A—C231—H23D	141.1	N38—C37—C36	111.7 (3)
H23B—C231—H23D	56.3	N38—C37—H37A	109.3
H23C—C231—H23D	56.3	C36—C37—H37A	109.3
C23—C231—H23E	109.5	N38—C37—H37B	109.3
H23A—C231—H23E	56.3	C36—C37—H37B	109.3
H23B—C231—H23E	141.1	H37A—C37—H37B	107.9
H23C—C231—H23E	56.3	C38A—N38—C37	117.1 (3)
H23D—C231—H23E	109.5	C38A—N38—H38	115.0
C23—C231—H23F	109.5	C37—N38—H38	113.5
H23A—C231—H23F	56.3	N31—C38A—N38	122.4 (3)
H23B—C231—H23F	56.3	N31—C38A—C33A	106.9 (3)
H23C—C231—H23F	141.1	N38—C38A—C33A	130.7 (3)
H23D—C231—H23F	109.5
C18A—N11—C111—C116	−47.8 (5)	N24—C25—C251—C256	−5.5 (5)
N12—N11—C111—C116	137.4 (3)	C26—C25—C251—C256	173.2 (3)
C18A—N11—C111—C112	132.9 (4)	C256—C251—C252—C253	1.1 (6)
N12—N11—C111—C112	−42.0 (4)	C25—C251—C252—C253	179.7 (4)
C116—C111—C112—C113	−0.7 (5)	C251—C252—C253—C254	−1.6 (6)
N11—C111—C112—C113	178.7 (3)	C252—C253—C254—C255	1.2 (6)
C111—C112—C113—C114	1.5 (6)	C252—C253—C254—Cl25	179.4 (3)
C112—C113—C114—C115	−0.3 (6)	C252—C251—C256—C255	−0.2 (5)
C113—C114—C115—C116	−1.7 (6)	C25—C251—C256—C255	−178.9 (3)
C112—C111—C116—C115	−1.4 (5)	C253—C254—C255—C256	−0.3 (6)
N11—C111—C116—C115	179.3 (3)	Cl25—C254—C255—C256	−178.6 (3)
C114—C115—C116—C111	2.5 (6)	C251—C256—C255—C254	−0.2 (5)
C18A—N11—N12—C13	1.5 (4)	N24—C25—C26—C27	53.9 (4)
C111—N11—N12—C13	177.1 (3)	C251—C25—C26—C27	−124.7 (3)
N11—N12—C13—C13A	−1.0 (4)	C25—C26—C27—N28	−84.8 (3)
N11—N12—C13—C131	176.3 (3)	C26—C27—N28—C28A	57.3 (4)
N12—C13—C13A—N14	−173.6 (3)	C27—N28—C28A—N21	164.3 (3)
C131—C13—C13A—N14	9.3 (5)	C27—N28—C28A—C23A	−15.5 (5)
N12—C13—C13A—C18A	0.2 (4)	N22—N21—C28A—N28	−178.9 (3)
C131—C13—C13A—C18A	−176.9 (3)	C211—N21—C28A—N28	−5.3 (5)
C18A—C13A—N14—C15	19.2 (5)	N22—N21—C28A—C23A	1.0 (4)
C13—C13A—N14—C15	−169.0 (3)	C211—N21—C28A—C23A	174.6 (3)
C13A—N14—C15—C151	−173.8 (3)	N24—C23A—C28A—N28	4.0 (6)
C13A—N14—C15—C16	5.3 (5)	C23—C23A—C28A—N28	179.6 (3)
N14—C15—C151—C156	167.3 (3)	N24—C23A—C28A—N21	−175.9 (3)
C16—C15—C151—C156	−11.8 (5)	C23—C23A—C28A—N21	−0.2 (3)
N14—C15—C151—C152	−9.3 (4)	C38A—N31—C311—C312	134.3 (4)
C16—C15—C151—C152	171.6 (3)	N32—N31—C311—C312	−37.9 (4)
C156—C151—C152—C153	0.4 (5)	C38A—N31—C311—C316	−46.4 (5)
C15—C151—C152—C153	177.2 (3)	N32—N31—C311—C316	141.4 (3)
C151—C152—C153—C154	0.0 (5)	C316—C311—C312—C313	0.0 (5)
C152—C153—C154—C155	−1.0 (5)	N31—C311—C312—C313	179.3 (3)
C152—C153—C154—Cl15	179.1 (2)	C311—C312—C313—C314	1.1 (6)
C153—C154—C155—C156	1.4 (5)	C312—C313—C314—C315	−0.8 (6)
Cl15—C154—C155—C156	−178.7 (3)	C313—C314—C315—C316	−0.7 (6)
C154—C155—C156—C151	−0.9 (5)	C314—C315—C316—C311	1.8 (6)
C152—C151—C156—C155	0.1 (5)	C312—C311—C316—C315	−1.5 (5)
C15—C151—C156—C155	−176.6 (3)	N31—C311—C316—C315	179.2 (3)
N14—C15—C16—C17	−59.3 (4)	C38A—N31—N32—C33	1.7 (4)
C151—C15—C16—C17	119.8 (3)	C311—N31—N32—C33	175.2 (3)
C15—C16—C17—N18	85.9 (4)	N31—N32—C33—C33A	−1.2 (4)
C16—C17—N18—C18A	−53.4 (4)	N31—N32—C33—C331	176.3 (3)
N12—N11—C18A—N18	178.5 (3)	N32—C33—C33A—N34	−176.5 (3)
C111—N11—C18A—N18	3.3 (5)	C331—C33—C33A—N34	6.3 (5)
N12—N11—C18A—C13A	−1.4 (4)	N32—C33—C33A—C38A	0.3 (4)
C111—N11—C18A—C13A	−176.6 (3)	C331—C33—C33A—C38A	−176.9 (3)
C17—N18—C18A—N11	−166.7 (3)	C38A—C33A—N34—C35	15.5 (6)
C17—N18—C18A—C13A	13.1 (5)	C33—C33A—N34—C35	−168.8 (3)
N14—C13A—C18A—N11	173.6 (3)	C33A—N34—C35—C351	−175.9 (3)
C13—C13A—C18A—N11	0.7 (3)	C33A—N34—C35—C36	2.7 (5)
N14—C13A—C18A—N18	−6.3 (6)	N34—C35—C351—C352	−175.7 (3)
C13—C13A—C18A—N18	−179.2 (3)	C36—C35—C351—C352	5.7 (5)
C28A—N21—C211—C212	−136.1 (3)	N34—C35—C351—C356	5.5 (5)
N22—N21—C211—C212	37.1 (4)	C36—C35—C351—C356	−173.0 (3)
C28A—N21—C211—C216	44.7 (5)	C356—C351—C352—C353	1.4 (6)
N22—N21—C211—C216	−142.1 (3)	C35—C351—C352—C353	−177.4 (4)
C216—C211—C212—C213	1.0 (5)	C351—C352—C353—C354	1.0 (7)
N21—C211—C212—C213	−178.2 (3)	C352—C353—C354—C355	−2.5 (6)
C211—C212—C213—C214	−1.6 (6)	C352—C353—C354—Cl35	179.4 (3)
C212—C213—C214—C215	0.4 (6)	C353—C354—C355—C356	1.6 (6)
C213—C214—C215—C216	1.4 (6)	Cl35—C354—C355—C356	179.7 (3)
C214—C215—C216—C211	−2.0 (6)	C354—C355—C356—C351	0.9 (5)
C212—C211—C216—C215	0.8 (5)	C352—C351—C356—C355	−2.3 (5)
N21—C211—C216—C215	179.9 (3)	C35—C351—C356—C355	176.5 (3)
C28A—N21—N22—C23	−1.3 (4)	N34—C35—C36—C37	−52.1 (4)
C211—N21—N22—C23	−175.6 (3)	C351—C35—C36—C37	126.4 (3)
N21—N22—C23—C23A	1.1 (4)	C35—C36—C37—N38	83.7 (4)
N21—N22—C23—C231	−176.2 (3)	C36—C37—N38—C38A	−58.3 (4)
N22—C23—C23A—N24	175.7 (3)	N32—N31—C38A—N38	178.9 (3)
C231—C23—C23A—N24	−7.2 (5)	C311—N31—C38A—N38	6.2 (5)
N22—C23—C23A—C28A	−0.6 (4)	N32—N31—C38A—C33A	−1.5 (4)
C231—C23—C23A—C28A	176.6 (3)	C311—N31—C38A—C33A	−174.2 (3)
C28A—C23A—N24—C25	−17.1 (6)	C37—N38—C38A—N31	−163.8 (3)
C23—C23A—N24—C25	167.9 (3)	C37—N38—C38A—C33A	16.7 (5)
C23A—N24—C25—C251	176.0 (3)	N34—C33A—C38A—N31	176.9 (3)
C23A—N24—C25—C26	−2.6 (5)	C33—C33A—C38A—N31	0.7 (4)
N24—C25—C251—C252	175.9 (3)	N34—C33A—C38A—N38	−3.5 (6)
C26—C25—C251—C252	−5.4 (5)	C33—C33A—C38A—N38	−179.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N18—H18···N32^i	0.88	2.19	2.976 (4)	149
N28—H28···N12	0.88	2.19	3.000 (5)	153
N38—H38···N22	0.88	2.24	3.022 (4)	148

Symmetry code: (i) −x, −y+1, −z+2.