1-(2,4-Dinitro-phenyl)-3-(4-methyl-phenyl)-4-phenyl-sulfanyl-1H-pyrazole.

In the title compound, C(22)H(16)N(4)O(4)S, the dihedral angles between the pyrazole ring and the pendant aromatic rings are 26.2 (1), 41.1 (1) and 89.5 (1)°. In the crystal structure, an intermolecular C-H⋯N bond helps to establish the packing. A short C⋯C contact of 3.110 (12) Å is observed between the C atom of the pyrazole CH group and one of the α-C atoms of the 4-methyl-phenyl ring.

Related literature

For related literature, see: Baraldi et al. (1998 ▶); Beddoes et al. (1986 ▶); Bruno et al. (1990 ▶); Cottineau et al. (2002 ▶); Londershausen (1996 ▶); Bernstein et al. (1995 ▶); Chen & Li (1998 ▶); Cordell (1981 ▶); Jin et al. (2004 ▶); Smith et al. (2001 ▶).

Experimental

Crystal data

C22H16N4O4S

M = 432.45

Monoclinic,

a = 7.3802 (3) Å

b = 26.6996 (11) Å

c = 10.6691 (4) Å

β = 106.733 (2)°

V = 2013.31 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 293 (2) K

0.25 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.951, T max = 0.963

26409 measured reflections

5987 independent reflections

4104 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.154

S = 1.05

5987 reflections

282 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803122X/bt2786sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803122X/bt2786Isup2.hkl

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

C22H16N4O4S	F(000) = 896
Mr = 432.45	Dx = 1.427 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5342 reflections
a = 7.3802 (3) Å	θ = 1.5–30.3°
b = 26.6996 (11) Å	µ = 0.20 mm−1
c = 10.6691 (4) Å	T = 293 K
β = 106.733 (2)°	Block, colorless
V = 2013.31 (14) Å3	0.25 × 0.21 × 0.19 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	5987 independent reflections
Radiation source: fine-focus sealed tube	4104 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω and φ scans	θmax = 30.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.951, Tmax = 0.963	k = −36→37
26409 measured reflections	l = −14→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H-atom parameters constrained
wR(F2) = 0.154	w = 1/[σ2(Fo2) + (0.0774P)2 + 0.3656P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.039
5987 reflections	Δρmax = 0.38 e Å−3
282 parameters	Δρmin = −0.27 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (13)

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
S1	0.24305 (7)	0.133863 (17)	0.05946 (4)	0.04676 (15)
O1	0.8025 (2)	0.24070 (6)	0.22748 (16)	0.0669 (4)
O2	0.8088 (3)	0.29587 (8)	0.37625 (14)	0.0842 (6)
O3	0.8511 (3)	0.46380 (7)	0.2362 (2)	0.0960 (7)
O4	0.7256 (4)	0.48434 (8)	0.0364 (3)	0.1256 (9)
N1	0.4753 (2)	0.25931 (5)	0.00834 (11)	0.0335 (3)
N2	0.4052 (2)	0.24683 (5)	−0.12163 (11)	0.0347 (3)
C3	0.3241 (2)	0.20272 (6)	−0.12297 (13)	0.0322 (3)
C4	0.3385 (2)	0.18664 (6)	0.00663 (14)	0.0347 (3)
C5	0.4325 (2)	0.22374 (6)	0.08542 (14)	0.0357 (4)
H5	0.4623	0.2246	0.1762	0.043*
C6	0.5566 (2)	0.30667 (6)	0.04053 (14)	0.0345 (3)
C7	0.6824 (2)	0.31920 (7)	0.16180 (15)	0.0391 (4)
C8	0.7453 (3)	0.36745 (7)	0.19047 (19)	0.0483 (4)
H8	0.8243	0.3757	0.2728	0.058*
C9	0.6891 (3)	0.40307 (7)	0.0953 (2)	0.0502 (5)
C10	0.5710 (3)	0.39244 (7)	−0.0262 (2)	0.0518 (5)
H10	0.5368	0.4172	−0.0899	0.062*
C11	0.5037 (3)	0.34446 (6)	−0.05236 (17)	0.0433 (4)
H11	0.4209	0.3371	−0.1340	0.052*
N12	0.7691 (2)	0.28207 (7)	0.26313 (15)	0.0524 (4)
N13	0.7602 (3)	0.45433 (7)	0.1245 (3)	0.0727 (6)
C14	0.2370 (2)	0.17731 (6)	−0.24803 (14)	0.0339 (3)
C15	0.1349 (2)	0.20461 (6)	−0.35568 (15)	0.0384 (4)
H15	0.1154	0.2387	−0.3474	0.046*
C16	0.0619 (3)	0.18132 (7)	−0.47542 (16)	0.0458 (4)
H16	−0.0059	0.2001	−0.5470	0.055*
C17	0.0875 (3)	0.13087 (7)	−0.49080 (16)	0.0461 (4)
C18	0.1858 (3)	0.10358 (7)	−0.38248 (17)	0.0460 (4)
H18	0.2027	0.0693	−0.3908	0.055*
C19	0.2596 (3)	0.12621 (6)	−0.26211 (15)	0.0409 (4)
H19	0.3245	0.1071	−0.1903	0.049*
C20	0.0110 (4)	0.10575 (10)	−0.62168 (19)	0.0699 (6)
H20A	−0.0225	0.0718	−0.6090	0.105*
H20B	0.1058	0.1060	−0.6672	0.105*
H20C	−0.0991	0.1234	−0.6723	0.105*
C21	0.4319 (3)	0.09067 (6)	0.09185 (15)	0.0452 (4)
C22	0.5983 (3)	0.09830 (8)	0.06220 (19)	0.0548 (5)
H22	0.6194	0.1282	0.0239	0.066*
C23	0.7352 (3)	0.06106 (9)	0.0897 (2)	0.0709 (7)
H23	0.8478	0.0658	0.0686	0.085*
C24	0.7049 (4)	0.01713 (9)	0.1480 (2)	0.0782 (7)
H24	0.7973	−0.0077	0.1669	0.094*
C25	0.5401 (5)	0.01001 (9)	0.1779 (2)	0.0788 (7)
H25	0.5206	−0.0197	0.2177	0.095*
C26	0.4027 (4)	0.04593 (7)	0.15001 (19)	0.0621 (6)
H26	0.2896	0.0405	0.1699	0.075*

	U11	U22	U33	U12	U13	U23
S1	0.0607 (3)	0.0369 (2)	0.0481 (2)	−0.0063 (2)	0.0242 (2)	0.00621 (17)
O1	0.0606 (10)	0.0587 (10)	0.0737 (10)	0.0097 (8)	0.0071 (8)	0.0176 (8)
O2	0.0954 (13)	0.1076 (14)	0.0373 (7)	−0.0208 (11)	−0.0005 (8)	0.0040 (8)
O3	0.0905 (14)	0.0649 (11)	0.1282 (17)	−0.0231 (10)	0.0248 (12)	−0.0467 (11)
O4	0.168 (2)	0.0447 (11)	0.149 (2)	−0.0344 (13)	0.0217 (18)	0.0081 (12)
N1	0.0451 (8)	0.0293 (6)	0.0273 (5)	−0.0015 (6)	0.0123 (5)	−0.0012 (5)
N2	0.0440 (8)	0.0342 (7)	0.0267 (6)	−0.0006 (6)	0.0117 (5)	0.0003 (5)
C3	0.0383 (8)	0.0296 (8)	0.0300 (6)	0.0013 (6)	0.0118 (6)	0.0005 (5)
C4	0.0464 (9)	0.0284 (8)	0.0318 (7)	0.0010 (7)	0.0154 (6)	0.0018 (5)
C5	0.0489 (10)	0.0332 (8)	0.0275 (6)	0.0026 (7)	0.0150 (6)	0.0019 (6)
C6	0.0389 (9)	0.0305 (8)	0.0359 (7)	−0.0007 (6)	0.0137 (6)	−0.0020 (6)
C7	0.0380 (9)	0.0421 (9)	0.0380 (8)	−0.0018 (7)	0.0123 (7)	−0.0010 (7)
C8	0.0429 (10)	0.0518 (11)	0.0507 (10)	−0.0090 (8)	0.0142 (8)	−0.0163 (8)
C9	0.0485 (11)	0.0332 (9)	0.0721 (12)	−0.0070 (8)	0.0226 (10)	−0.0095 (8)
C10	0.0588 (12)	0.0331 (9)	0.0629 (11)	−0.0011 (8)	0.0164 (9)	0.0051 (8)
C11	0.0511 (10)	0.0346 (9)	0.0421 (8)	−0.0013 (8)	0.0100 (7)	0.0020 (7)
N12	0.0445 (9)	0.0629 (11)	0.0452 (8)	−0.0081 (8)	0.0055 (7)	0.0086 (7)
N13	0.0709 (13)	0.0410 (10)	0.1077 (17)	−0.0137 (9)	0.0283 (12)	−0.0197 (11)
C14	0.0361 (8)	0.0354 (8)	0.0305 (7)	−0.0019 (7)	0.0101 (6)	−0.0009 (6)
C15	0.0389 (9)	0.0377 (9)	0.0380 (8)	0.0011 (7)	0.0104 (7)	0.0057 (6)
C16	0.0433 (10)	0.0562 (11)	0.0336 (7)	−0.0003 (8)	0.0043 (7)	0.0085 (7)
C17	0.0450 (10)	0.0574 (11)	0.0337 (7)	−0.0060 (9)	0.0079 (7)	−0.0058 (7)
C18	0.0543 (11)	0.0395 (9)	0.0419 (8)	−0.0010 (8)	0.0101 (8)	−0.0079 (7)
C19	0.0490 (10)	0.0371 (9)	0.0331 (7)	0.0037 (7)	0.0064 (7)	0.0001 (6)
C20	0.0766 (16)	0.0857 (17)	0.0393 (9)	−0.0105 (13)	0.0040 (10)	−0.0183 (10)
C21	0.0660 (13)	0.0320 (8)	0.0312 (7)	−0.0041 (8)	0.0037 (8)	−0.0015 (6)
C22	0.0586 (13)	0.0430 (11)	0.0522 (10)	−0.0016 (9)	−0.0009 (9)	−0.0016 (8)
C23	0.0576 (14)	0.0649 (15)	0.0721 (14)	0.0066 (11)	−0.0098 (11)	−0.0138 (12)
C24	0.0903 (16)	0.0486 (13)	0.0683 (14)	0.0214 (12)	−0.0207 (12)	−0.0075 (11)
C25	0.1190 (19)	0.0403 (12)	0.0612 (13)	0.0079 (13)	0.0006 (13)	0.0060 (10)
C26	0.0971 (18)	0.0356 (10)	0.0508 (10)	−0.0017 (11)	0.0168 (11)	0.0063 (8)

S1—C4	1.7401 (16)	C14—C15	1.386 (2)
S1—C21	1.765 (2)	C14—C19	1.388 (2)
O1—N12	1.217 (2)	C15—C16	1.383 (2)
O2—N12	1.214 (2)	C15—H15	0.9300
O3—N13	1.214 (3)	C16—C17	1.377 (3)
O4—N13	1.205 (3)	C16—H16	0.9300
N1—C5	1.3519 (19)	C17—C18	1.382 (3)
N1—N2	1.3741 (16)	C17—C20	1.505 (2)
N1—C6	1.399 (2)	C18—C19	1.381 (2)
N2—C3	1.319 (2)	C18—H18	0.9300
C3—C4	1.4223 (19)	C19—H19	0.9300
C3—C14	1.470 (2)	C20—H20A	0.9600
C4—C5	1.354 (2)	C20—H20B	0.9600
C5—H5	0.9300	C20—H20C	0.9600
C6—C11	1.389 (2)	C21—C22	1.368 (3)
C6—C7	1.399 (2)	C21—C26	1.391 (3)
C7—C8	1.374 (3)	C22—C23	1.387 (3)
C7—N12	1.470 (2)	C22—H22	0.9300
C8—C9	1.366 (3)	C23—C24	1.376 (4)
C8—H8	0.9300	C23—H23	0.9300
C9—C10	1.368 (3)	C24—C25	1.356 (4)
C9—N13	1.467 (3)	C24—H24	0.9300
C10—C11	1.373 (3)	C25—C26	1.365 (4)
C10—H10	0.9300	C25—H25	0.9300
C11—H11	0.9300	C26—H26	0.9300
C4—S1—C21	102.82 (9)	C19—C14—C3	121.15 (14)
C5—N1—N2	110.95 (12)	C16—C15—C14	120.23 (16)
C5—N1—C6	130.11 (12)	C16—C15—H15	119.9
N2—N1—C6	118.49 (12)	C14—C15—H15	119.9
C3—N2—N1	105.38 (11)	C17—C16—C15	121.31 (16)
N2—C3—C4	110.62 (13)	C17—C16—H16	119.3
N2—C3—C14	120.03 (12)	C15—C16—H16	119.3
C4—C3—C14	129.34 (14)	C16—C17—C18	118.25 (15)
C5—C4—C3	105.32 (13)	C16—C17—C20	121.27 (18)
C5—C4—S1	125.04 (11)	C18—C17—C20	120.48 (19)
C3—C4—S1	129.45 (12)	C19—C18—C17	121.21 (17)
N1—C5—C4	107.69 (13)	C19—C18—H18	119.4
N1—C5—H5	126.2	C17—C18—H18	119.4
C4—C5—H5	126.2	C18—C19—C14	120.21 (15)
C11—C6—C7	117.49 (15)	C18—C19—H19	119.9
C11—C6—N1	117.95 (14)	C14—C19—H19	119.9
C7—C6—N1	124.52 (14)	C17—C20—H20A	109.5
C8—C7—C6	121.46 (16)	C17—C20—H20B	109.5
C8—C7—N12	114.90 (16)	H20A—C20—H20B	109.5
C6—C7—N12	123.46 (15)	C17—C20—H20C	109.5
C9—C8—C7	118.47 (17)	H20A—C20—H20C	109.5
C9—C8—H8	120.8	H20B—C20—H20C	109.5
C7—C8—H8	120.8	C22—C21—C26	119.7 (2)
C8—C9—C10	122.32 (17)	C22—C21—S1	124.62 (14)
C8—C9—N13	118.6 (2)	C26—C21—S1	115.67 (17)
C10—C9—N13	119.12 (19)	C21—C22—C23	119.4 (2)
C9—C10—C11	118.73 (18)	C21—C22—H22	120.3
C9—C10—H10	120.6	C23—C22—H22	120.3
C11—C10—H10	120.6	C24—C23—C22	120.2 (3)
C10—C11—C6	121.46 (17)	C24—C23—H23	119.9
C10—C11—H11	119.3	C22—C23—H23	119.9
C6—C11—H11	119.3	C25—C24—C23	120.0 (2)
O2—N12—O1	124.99 (19)	C25—C24—H24	120.0
O2—N12—C7	117.12 (19)	C23—C24—H24	120.0
O1—N12—C7	117.82 (15)	C24—C25—C26	120.7 (2)
O4—N13—O3	124.1 (2)	C24—C25—H25	119.6
O4—N13—C9	118.2 (2)	C26—C25—H25	119.6
O3—N13—C9	117.8 (2)	C25—C26—C21	120.0 (3)
C15—C14—C19	118.75 (14)	C25—C26—H26	120.0
C15—C14—C3	120.07 (14)	C21—C26—H26	120.0
C5—N1—N2—C3	−1.74 (18)	C8—C7—N12—O2	34.3 (2)
N2—N1—N2—C3	0(64)	C6—C7—N12—O2	−150.55 (18)
C6—N1—N2—C3	−174.80 (14)	C8—C7—N12—O1	−142.78 (18)
N1—N2—C3—C4	0.97 (18)	C6—C7—N12—O1	32.4 (3)
N1—N2—C3—C14	−178.58 (14)	C8—C9—N13—O4	172.7 (2)
N2—C3—C4—C5	0.11 (19)	C10—C9—N13—O4	−6.6 (3)
C14—C3—C4—C5	179.60 (16)	C8—C9—N13—O3	−7.0 (3)
N2—C3—C4—S1	175.28 (13)	C10—C9—N13—O3	173.7 (2)
C14—C3—C4—S1	−5.2 (3)	N2—C3—C14—C15	−39.9 (2)
C21—S1—C4—C5	−89.59 (16)	C4—C3—C14—C15	140.64 (18)
C21—S1—C4—C3	96.11 (16)	N2—C3—C14—C19	138.13 (17)
N2—N1—C5—C4	1.85 (19)	C4—C3—C14—C19	−41.3 (3)
C6—N1—C5—C4	173.86 (16)	C19—C14—C15—C16	−1.8 (2)
C3—C4—C5—N1	−1.17 (18)	C3—C14—C15—C16	176.31 (15)
S1—C4—C5—N1	−176.61 (12)	C14—C15—C16—C17	0.3 (3)
C5—N1—C6—C11	−148.40 (17)	C15—C16—C17—C18	1.1 (3)
N2—N1—C6—C11	23.1 (2)	C15—C16—C17—C20	−178.87 (18)
C5—N1—C6—C7	29.1 (3)	C16—C17—C18—C19	−1.0 (3)
N2—N1—C6—C7	−159.39 (15)	C20—C17—C18—C19	178.95 (19)
C11—C6—C7—C8	2.8 (2)	C17—C18—C19—C14	−0.5 (3)
N1—C6—C7—C8	−174.74 (16)	C15—C14—C19—C18	1.9 (3)
C11—C6—C7—N12	−172.09 (16)	C3—C14—C19—C18	−176.21 (16)
N1—C6—C7—N12	10.4 (3)	C4—S1—C21—C22	−7.65 (17)
C6—C7—C8—C9	−3.0 (3)	C4—S1—C21—C26	173.29 (14)
N12—C7—C8—C9	172.26 (17)	C26—C21—C22—C23	0.5 (3)
C7—C8—C9—C10	0.9 (3)	S1—C21—C22—C23	−178.52 (15)
C7—C8—C9—N13	−178.39 (18)	C21—C22—C23—C24	−0.9 (3)
C8—C9—C10—C11	1.3 (3)	C22—C23—C24—C25	0.5 (3)
N13—C9—C10—C11	−179.38 (18)	C23—C24—C25—C26	0.4 (4)
C9—C10—C11—C6	−1.5 (3)	C24—C25—C26—C21	−0.8 (3)
C7—C6—C11—C10	−0.5 (3)	C22—C21—C26—C25	0.4 (3)
N1—C6—C11—C10	177.22 (17)	S1—C21—C26—C25	179.46 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N2i	0.93	2.44	3.2847 (18)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N2i	0.93	2.44	3.2847 (18)	152

Symmetry code: (i) .