3-Acetyl-4-benzoyl-2-methyl-5-phenyl-3,3a-di­hydro­pyrazolo­[2,3-c]pyrimidine-7(6H)-thione

The mol­ecule of the title compound, C₂₂H₁₉N₃O₂S, is not planar. The dihedral angle between the two phenyl rings is 27.46 (7)° and in the di­hydro­pyrazolo­pyrimidine ring the total puckering amplitude Q_T is 0.526 (3) Å. The structure is stabilized by both intra- and intermolecular C-H...O interaction, and by an intermolecular N-H...S hydrogen bond.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); software used to prepare material for publication: PARST (Nardelli, 1995).

3-Acetyl-4-benzoyl-2-methyl-5-phenyl-3,3a-dihydropyrazolo[2,3-c]pyrimidine- 7(6H)-thione

Crystal data

C22H19N3O2S	F(000) = 816
Mr = 389.46	Dx = 1.333 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.9505 (3) Å	Cell parameters from 4312 reflections
b = 21.8820 (8) Å	θ = 1.9–28.4°
c = 12.9619 (5) Å	µ = 0.19 mm^−1
β = 100.239 (1)°	T = 293 K
V = 1939.99 (13) Å^3	Needle, yellow
Z = 4	0.38 × 0.12 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	4769 independent reflections
Radiation source: fine-focus sealed tube	2422 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
ω scans	θmax = 28.4°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.931, Tmax = 0.985	k = −28→28
13631 measured reflections	l = −8→17

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.152	H-atom parameters constrained
S = 0.95	Calculated w = 1/[σ^2(Fo^2) + (0.0609P)^2] where P = (Fo^2 + 2Fc^2)/3
4769 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. By using a Siemens SMART CCD area detector diffractometer and graphite monochromator, the data was collected over a hemisphere of reciprocal space by a combination of four sets of exposures. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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
S1	0.25488 (11)	0.56433 (3)	0.03406 (6)	0.0491 (2)
N1	0.2420 (3)	0.44883 (8)	0.0935 (2)	0.0407 (6)
H1A	0.1193	0.45014	0.0675	0.049*
N2	0.5123 (3)	0.49947 (8)	0.1689 (2)	0.0389 (5)
N3	0.6484 (3)	0.54688 (9)	0.1832 (2)	0.0435 (6)
O1	0.7263 (3)	0.33795 (8)	0.3089 (2)	0.0652 (7)
O2	0.7993 (3)	0.45741 (10)	0.4482 (2)	0.0639 (6)
C1	0.1992 (3)	0.34024 (11)	0.0794 (2)	0.0359 (6)
C2	0.1503 (4)	0.33388 (12)	−0.0286 (2)	0.0508 (8)
H2A	0.1874	0.36356	−0.0725	0.061*
C3	0.0469 (5)	0.28345 (15)	−0.0701 (3)	0.0630 (9)
H3A	0.0148	0.27874	−0.1424	0.076*
C4	−0.0091 (4)	0.24016 (14)	−0.0053 (3)	0.0605 (9)
H4A	−0.0770	0.20573	−0.0339	0.073*
C5	0.0337 (4)	0.24707 (13)	0.1007 (3)	0.0547 (8)
H5A	−0.0072	0.21771	0.1440	0.066*
C6	0.1372 (4)	0.29726 (11)	0.1443 (2)	0.0422 (7)
H6A	0.1650	0.30213	0.2167	0.051*
C7	0.5754 (3)	0.27283 (10)	0.1762 (2)	0.0366 (6)
C8	0.5511 (4)	0.26470 (12)	0.0693 (2)	0.0429 (7)
H8A	0.5482	0.29839	0.0254	0.052*
C9	0.5310 (4)	0.20657 (14)	0.0274 (3)	0.0589 (9)
H9A	0.5132	0.20116	−0.0448	0.071*
C10	0.5372 (5)	0.15670 (14)	0.0924 (3)	0.0701 (10)
H10A	0.5208	0.11768	0.0637	0.084*
C11	0.5672 (5)	0.16405 (13)	0.1985 (3)	0.0684 (10)
H11A	0.5746	0.13002	0.2420	0.082*
C12	0.5865 (4)	0.22183 (12)	0.2413 (2)	0.0513 (8)
H12A	0.6070	0.22678	0.3137	0.062*
C13	0.6048 (4)	0.33366 (11)	0.2279 (2)	0.0386 (6)
C14	0.4964 (4)	0.38898 (10)	0.1891 (2)	0.0335 (6)
C15	0.3226 (4)	0.39217 (10)	0.1238 (2)	0.0336 (6)
C16	0.3435 (4)	0.50283 (11)	0.1018 (2)	0.0365 (6)
C17	0.8048 (4)	0.52567 (11)	0.2390 (2)	0.0400 (6)
C18	0.9806 (4)	0.56480 (12)	0.2706 (2)	0.0567 (8)
H18A	0.9522	0.60568	0.2456	0.085*
H18B	1.0872	0.54873	0.2410	0.085*
H18C	1.0158	0.56523	0.3457	0.085*
C19	0.7957 (4)	0.45852 (10)	0.2648 (2)	0.0360 (6)
H19A	0.8610	0.43433	0.2176	0.043*
C20	0.5758 (4)	0.44763 (10)	0.2404 (2)	0.0351 (6)
H20A	0.5224	0.45331	0.3048	0.042*
C21	0.8872 (4)	0.44533 (11)	0.3794 (2)	0.0440 (7)
C22	1.0900 (4)	0.41983 (14)	0.3985 (3)	0.0681 (10)
H22A	1.1325	0.41337	0.4723	0.102*
H22B	1.1767	0.44809	0.3733	0.102*
H22C	1.0912	0.38164	0.3621	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0583 (5)	0.0379 (4)	0.0470 (5)	0.0087 (3)	−0.0013 (4)	0.0054 (3)
N1	0.0352 (12)	0.0367 (12)	0.0459 (14)	0.0020 (9)	−0.0043 (10)	0.0012 (10)
N2	0.0441 (13)	0.0285 (11)	0.0407 (13)	−0.0014 (9)	−0.0020 (11)	0.0002 (10)
N3	0.0537 (14)	0.0340 (11)	0.0407 (14)	−0.0078 (10)	0.0029 (12)	−0.0034 (10)
O1	0.0819 (15)	0.0463 (11)	0.0505 (13)	−0.0064 (10)	−0.0346 (12)	0.0099 (10)
O2	0.0727 (15)	0.084 (2)	0.0327 (12)	−0.0172 (12)	0.0024 (11)	−0.0054 (11)
C1	0.0312 (13)	0.0370 (13)	0.0360 (15)	0.0032 (11)	−0.0036 (11)	−0.0019 (12)
C2	0.058 (2)	0.049 (2)	0.038 (2)	0.0038 (14)	−0.0135 (14)	0.0025 (14)
C3	0.062 (2)	0.069 (2)	0.048 (2)	0.005 (2)	−0.018 (2)	−0.019 (2)
C4	0.043 (2)	0.057 (2)	0.076 (2)	−0.0063 (14)	−0.006 (2)	−0.029 (2)
C5	0.040 (2)	0.049 (2)	0.074 (2)	−0.0124 (13)	0.009 (2)	−0.007 (2)
C6	0.0386 (15)	0.046 (2)	0.042 (2)	−0.0050 (12)	0.0057 (13)	−0.0051 (13)
C7	0.0322 (13)	0.0340 (13)	0.040 (2)	0.0015 (11)	−0.0026 (12)	0.0048 (12)
C8	0.0383 (15)	0.045 (2)	0.045 (2)	0.0018 (12)	0.0053 (13)	−0.0009 (13)
C9	0.050 (2)	0.063 (2)	0.063 (2)	−0.001 (2)	0.007 (2)	−0.020 (2)
C10	0.064 (2)	0.043 (2)	0.098 (3)	−0.002 (2)	0.001 (2)	−0.019 (2)
C11	0.067 (2)	0.035 (2)	0.096 (3)	−0.0028 (15)	−0.005 (2)	0.011 (2)
C12	0.051 (2)	0.046 (2)	0.052 (2)	−0.0011 (13)	−0.0053 (14)	0.0102 (14)
C13	0.0410 (15)	0.0389 (14)	0.0318 (15)	−0.0039 (11)	−0.0048 (12)	0.0086 (12)
C14	0.0394 (14)	0.0324 (13)	0.0272 (13)	−0.0018 (11)	0.0015 (11)	0.0018 (11)
C15	0.0384 (14)	0.0320 (13)	0.0286 (13)	0.0005 (11)	0.0011 (11)	0.0001 (11)
C16	0.0425 (15)	0.0342 (13)	0.0328 (15)	0.0041 (11)	0.0065 (12)	−0.0007 (11)
C17	0.049 (2)	0.0400 (14)	0.0303 (14)	−0.0079 (12)	0.0045 (13)	−0.0057 (12)
C18	0.061 (2)	0.055 (2)	0.049 (2)	−0.0201 (15)	−0.001 (2)	0.001 (2)
C19	0.0381 (14)	0.0381 (13)	0.0295 (14)	−0.0025 (11)	−0.0006 (11)	−0.0019 (11)
C20	0.0389 (14)	0.0347 (13)	0.0300 (14)	−0.0024 (11)	0.0013 (11)	−0.0003 (11)
C21	0.048 (2)	0.041 (2)	0.038 (2)	−0.0112 (13)	−0.0052 (14)	−0.0008 (13)
C22	0.062 (2)	0.066 (2)	0.065 (2)	0.001 (2)	−0.019 (2)	0.005 (2)

Geometric parameters (Å, º)

S1—C16	1.664 (2)	C7—C8	1.377 (4)
N1—C16	1.371 (3)	C7—C12	1.393 (3)
N1—C15	1.388 (3)	C7—C13	1.488 (3)
N2—C16	1.333 (3)	C8—C9	1.380 (4)
N2—N3	1.394 (3)	C9—C10	1.374 (4)
N2—C20	1.481 (3)	C10—C11	1.364 (5)
N3—C17	1.281 (3)	C11—C12	1.377 (4)
O1—C13	1.228 (3)	C13—C14	1.467 (3)
O2—C21	1.197 (3)	C14—C15	1.348 (3)
C1—C6	1.380 (4)	C14—C20	1.504 (3)
C1—C2	1.387 (4)	C17—C18	1.489 (3)
C1—C15	1.477 (3)	C17—C19	1.511 (3)
C2—C3	1.374 (4)	C19—C20	1.524 (3)
C3—C4	1.367 (5)	C19—C21	1.535 (4)
C4—C5	1.362 (5)	C21—C22	1.496 (4)
C5—C6	1.378 (3)
C16—N1—C15	124.9 (2)	C14—C13—C7	124.2 (2)
C16—N2—N3	122.9 (2)	C15—C14—C13	127.3 (2)
C16—N2—C20	125.5 (2)	C15—C14—C20	116.8 (2)
N3—N2—C20	111.6 (2)	C13—C14—C20	115.2 (2)
C17—N3—N2	107.0 (2)	C14—C15—N1	119.7 (2)
C6—C1—C2	120.0 (2)	C14—C15—C1	126.7 (2)
C6—C1—C15	120.6 (2)	N1—C15—C1	113.5 (2)
C2—C1—C15	119.4 (2)	N2—C16—N1	112.6 (2)
C3—C2—C1	119.5 (3)	N2—C16—S1	126.1 (2)
C4—C3—C2	120.1 (3)	N1—C16—S1	121.2 (2)
C5—C4—C3	120.5 (3)	N3—C17—C18	121.3 (2)
C4—C5—C6	120.4 (3)	N3—C17—C19	114.4 (2)
C5—C6—C1	119.3 (3)	C18—C17—C19	124.2 (2)
C8—C7—C12	119.3 (2)	C17—C19—C20	100.7 (2)
C8—C7—C13	123.4 (2)	C17—C19—C21	111.8 (2)
C12—C7—C13	117.1 (2)	C20—C19—C21	113.5 (2)
C7—C8—C9	120.1 (3)	N2—C20—C14	109.4 (2)
C10—C9—C8	120.0 (3)	N2—C20—C19	100.7 (2)
C11—C10—C9	120.5 (3)	C14—C20—C19	120.1 (2)
C10—C11—C12	120.0 (3)	O2—C21—C22	123.4 (3)
C11—C12—C7	120.1 (3)	O2—C21—C19	120.1 (3)
O1—C13—C14	117.6 (2)	C22—C21—C19	116.5 (3)
O1—C13—C7	118.2 (2)
C16—N2—N3—C17	−169.7 (2)	C6—C1—C15—C14	56.5 (4)
C20—N2—N3—C17	12.9 (3)	C2—C1—C15—C14	−121.6 (3)
C6—C1—C2—C3	−2.5 (4)	C6—C1—C15—N1	−122.5 (3)
C15—C1—C2—C3	175.6 (3)	C2—C1—C15—N1	59.4 (3)
C1—C2—C3—C4	0.6 (4)	N3—N2—C16—N1	174.0 (2)
C2—C3—C4—C5	1.2 (5)	C20—N2—C16—N1	−9.0 (4)
C3—C4—C5—C6	−1.2 (5)	N3—N2—C16—S1	−6.7 (4)
C4—C5—C6—C1	−0.7 (4)	C20—N2—C16—S1	170.2 (2)
C2—C1—C6—C5	2.6 (4)	C15—N1—C16—N2	−18.4 (4)
C15—C1—C6—C5	−175.5 (2)	C15—N1—C16—S1	162.3 (2)
C12—C7—C8—C9	2.3 (4)	N2—N3—C17—C18	−179.1 (2)
C13—C7—C8—C9	177.9 (2)	N2—N3—C17—C19	3.2 (3)
C7—C8—C9—C10	−0.6 (4)	N3—C17—C19—C20	−16.8 (3)
C8—C9—C10—C11	−1.4 (5)	C18—C17—C19—C20	165.6 (3)
C9—C10—C11—C12	1.7 (5)	N3—C17—C19—C21	−137.7 (3)
C10—C11—C12—C7	0.0 (5)	C18—C17—C19—C21	44.7 (4)
C8—C7—C12—C11	−2.0 (4)	C16—N2—C20—C14	32.9 (3)
C13—C7—C12—C11	−177.8 (3)	N3—N2—C20—C14	−149.8 (2)
C8—C7—C13—O1	−138.7 (3)	C16—N2—C20—C19	160.3 (2)
C12—C7—C13—O1	36.9 (4)	N3—N2—C20—C19	−22.5 (3)
C8—C7—C13—C14	42.0 (4)	C15—C14—C20—N2	−31.8 (3)
C12—C7—C13—C14	−142.3 (3)	C13—C14—C20—N2	156.5 (2)
O1—C13—C14—C15	−158.3 (3)	C15—C14—C20—C19	−147.4 (2)
C7—C13—C14—C15	20.9 (4)	C13—C14—C20—C19	40.9 (3)
O1—C13—C14—C20	12.3 (4)	C17—C19—C20—N2	21.4 (2)
C7—C13—C14—C20	−168.4 (2)	C21—C19—C20—N2	141.1 (2)
C13—C14—C15—N1	−178.9 (2)	C17—C19—C20—C14	141.4 (2)
C20—C14—C15—N1	10.6 (4)	C21—C19—C20—C14	−98.9 (3)
C13—C14—C15—C1	2.1 (5)	C17—C19—C21—O2	76.4 (3)
C20—C14—C15—C1	−168.4 (2)	C20—C19—C21—O2	−36.7 (3)
C16—N1—C15—C14	17.6 (4)	C17—C19—C21—C22	−101.0 (3)
C16—N1—C15—C1	−163.3 (2)	C20—C19—C21—C22	145.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1^i	0.86	2.72	3.565 (2)	170
C4—H4A···O1^ii	0.93	2.44	3.245 (4)	145
C20—H20A···O2	0.98	2.43	2.869 (3)	107

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