5-(4-tert-Butyl-benzyl-sulfan-yl)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde.

The title compound, C(22)H(24)N(2)OS, has been synthesized as a potent fungicidal agent and its crystal structure determined. In the crystal structure, weak inter-molecular C-H⋯O inter-actions are observed. The dihedral angles between the planes of the pyrazole and phenyl rings, and between the benzene and pyrazole rings are 54.2 (2) and 25.0 (3)°, respectively. The methyl groups of the tert-butyl group are disordered over two positions; the site occupancies are ca 0.65 and 0.35.

Related literature

For related literature, see: Becher et al. (1986 ▶); Bekhit & Abdel-Aziem (2004 ▶); Comber et al. (1991 ▶); Dannhardt & Kiefer (2001 ▶); Gamage et al. (2002 ▶); Goekan-Kelekci et al. (2007 ▶); Hashizume et al. (2004 ▶); Park et al. (2005 ▶).

Experimental

Crystal data

C22H24N2OS

M = 364.49

Orthorhombic,

a = 11.129 (3) Å

b = 16.181 (4) Å

c = 22.429 (6) Å

V = 4039.0 (18) Å3

Z = 8

Mo Kα radiation

μ = 0.17 mm−1

T = 294 (2) K

0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.945, T max = 0.973

19461 measured reflections

3568 independent reflections

1788 reflections with I > 2σ(I)

R int = 0.087

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.146

S = 1.01

3568 reflections

271 parameters

57 restraints

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1997 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706597X/em2002sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706597X/em2002Isup2.hkl

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

C22H24N2OS	F000 = 1552
Mr = 364.49	Dx = 1.199 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2619 reflections
a = 11.129 (3) Å	θ = 2.4–23.4º
b = 16.181 (4) Å	µ = 0.17 mm−1
c = 22.429 (6) Å	T = 294 (2) K
V = 4039.0 (18) Å3	Orthorhombic, colourless
Z = 8	0.24 × 0.20 × 0.16 mm

Bruker SMART 1000 diffractometer	3568 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.087
T = 294(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001)	h = −12→13
Tmin = 0.945, Tmax = 0.973	k = −16→19
19461 measured reflections	l = −26→21

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)] = 0.048	H-atom parameters constrained
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0543P)2 + 1.5678P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.002
3568 reflections	Δρmax = 0.19 e Å−3
271 parameters	Δρmin = −0.21 e Å−3
57 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0053 (5)

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	Occ. (<1)
S1	0.56005 (9)	0.18185 (6)	0.52594 (4)	0.0692 (3)
O1	0.7233 (2)	−0.07664 (16)	0.52505 (12)	0.0888 (9)
N1	0.4568 (2)	0.09456 (16)	0.61696 (12)	0.0539 (7)
N2	0.4616 (3)	0.02084 (17)	0.64732 (13)	0.0622 (8)
C1	0.5704 (4)	−0.1109 (2)	0.63859 (17)	0.0809 (12)
H1A	0.5296	−0.1218	0.6755	0.121*
H1B	0.6556	−0.1146	0.6447	0.121*
H1C	0.5461	−0.1507	0.6093	0.121*
C2	0.5388 (3)	−0.0253 (2)	0.61720 (16)	0.0589 (9)
C3	0.5853 (3)	0.0175 (2)	0.56780 (14)	0.0520 (8)
C4	0.5313 (3)	0.09467 (19)	0.56915 (13)	0.0503 (8)
C5	0.6746 (3)	−0.0098 (2)	0.52514 (16)	0.0676 (10)
H5	0.6964	0.0273	0.4953	0.081*
C6	0.3817 (3)	0.1594 (2)	0.63937 (14)	0.0535 (9)
C7	0.3931 (3)	0.1839 (2)	0.69794 (15)	0.0651 (10)
H7	0.4507	0.1598	0.7224	0.078*
C8	0.3183 (4)	0.2443 (3)	0.71983 (18)	0.0787 (12)
H8	0.3249	0.2607	0.7594	0.094*
C9	0.2340 (4)	0.2806 (3)	0.6837 (2)	0.0861 (13)
H9	0.1839	0.3216	0.6987	0.103*
C10	0.2239 (4)	0.2559 (3)	0.6255 (2)	0.0875 (13)
H10	0.1668	0.2806	0.6010	0.105*
C11	0.2967 (3)	0.1955 (2)	0.60299 (16)	0.0704 (10)
H11	0.2890	0.1789	0.5635	0.084*
C12	0.6681 (3)	0.2339 (2)	0.57569 (17)	0.0752 (11)
H12A	0.7027	0.2808	0.5550	0.090*
H12B	0.6257	0.2546	0.6104	0.090*
C13	0.7670 (3)	0.17787 (19)	0.59573 (16)	0.0594 (9)
C14	0.7591 (3)	0.1360 (2)	0.64906 (15)	0.0621 (10)
H14	0.6952	0.1469	0.6746	0.075*
C15	0.8436 (3)	0.0784 (2)	0.66528 (15)	0.0655 (10)
H15	0.8356	0.0516	0.7018	0.079*
C16	0.9402 (3)	0.0589 (2)	0.62918 (15)	0.0588 (9)
C17	0.9495 (3)	0.1031 (2)	0.57631 (17)	0.0720 (11)
H17	1.0145	0.0932	0.5512	0.086*
C18	0.8651 (4)	0.1614 (2)	0.55988 (17)	0.0709 (11)
H18	0.8745	0.1900	0.5242	0.085*
C19	1.0287 (3)	−0.0081 (2)	0.64643 (16)	0.0720 (11)
C20	0.9655 (8)	−0.0873 (4)	0.6579 (6)	0.115 (3)	0.655 (12)
H20A	1.0227	−0.1284	0.6699	0.172*	0.655 (12)
H20B	0.9256	−0.1051	0.6222	0.172*	0.655 (12)
H20C	0.9073	−0.0796	0.6890	0.172*	0.655 (12)
C21	1.1021 (7)	0.0212 (5)	0.7014 (3)	0.073 (2)	0.655 (12)
H21A	1.0489	0.0298	0.7345	0.110*	0.655 (12)
H21B	1.1424	0.0720	0.6921	0.110*	0.655 (12)
H21C	1.1605	−0.0201	0.7117	0.110*	0.655 (12)
C22	1.1279 (8)	−0.0210 (6)	0.5970 (3)	0.094 (3)	0.655 (12)
H22A	1.1839	−0.0624	0.6100	0.141*	0.655 (12)
H22B	1.1697	0.0300	0.5904	0.141*	0.655 (12)
H22C	1.0905	−0.0386	0.5606	0.141*	0.655 (12)
C20'	0.9620 (13)	−0.0696 (9)	0.6921 (7)	0.087 (5)	0.345 (12)
H20D	0.8867	−0.0868	0.6753	0.130*	0.345 (12)
H20E	0.9480	−0.0415	0.7291	0.130*	0.345 (12)
H20F	1.0116	−0.1172	0.6990	0.130*	0.345 (12)
C21'	1.1392 (14)	0.0222 (13)	0.6765 (9)	0.132 (9)	0.345 (12)
H21D	1.1231	0.0745	0.6952	0.197*	0.345 (12)
H21E	1.2022	0.0288	0.6477	0.197*	0.345 (12)
H21F	1.1638	−0.0170	0.7063	0.197*	0.345 (12)
C22'	1.0496 (18)	−0.0659 (9)	0.5928 (5)	0.101 (6)	0.345 (12)
H22D	1.1070	−0.1076	0.6035	0.151*	0.345 (12)
H22E	1.0797	−0.0344	0.5598	0.151*	0.345 (12)
H22F	0.9751	−0.0916	0.5818	0.151*	0.345 (12)

	U11	U22	U33	U12	U13	U23
S1	0.0791 (7)	0.0673 (6)	0.0612 (6)	0.0141 (5)	0.0036 (5)	0.0218 (5)
O1	0.100 (2)	0.0657 (18)	0.101 (2)	0.0241 (16)	−0.0006 (17)	−0.0163 (16)
N1	0.0617 (18)	0.0461 (16)	0.0538 (16)	0.0022 (14)	−0.0019 (15)	0.0038 (13)
N2	0.069 (2)	0.0478 (17)	0.0697 (19)	−0.0030 (15)	−0.0048 (16)	0.0110 (15)
C1	0.091 (3)	0.050 (2)	0.102 (3)	0.000 (2)	−0.007 (3)	0.014 (2)
C2	0.061 (2)	0.046 (2)	0.070 (2)	−0.0044 (19)	−0.008 (2)	0.0021 (18)
C3	0.053 (2)	0.049 (2)	0.054 (2)	0.0004 (17)	−0.0086 (18)	−0.0034 (16)
C4	0.056 (2)	0.051 (2)	0.0435 (18)	0.0005 (16)	−0.0050 (17)	0.0027 (15)
C5	0.072 (3)	0.063 (2)	0.067 (2)	0.004 (2)	−0.009 (2)	−0.008 (2)
C6	0.057 (2)	0.048 (2)	0.055 (2)	0.0002 (17)	0.0020 (18)	0.0028 (16)
C7	0.074 (2)	0.066 (2)	0.055 (2)	−0.004 (2)	−0.0009 (19)	0.0041 (19)
C8	0.103 (3)	0.072 (3)	0.061 (2)	−0.005 (3)	0.014 (3)	−0.009 (2)
C9	0.097 (3)	0.073 (3)	0.088 (3)	0.015 (2)	0.022 (3)	−0.007 (2)
C10	0.089 (3)	0.090 (3)	0.083 (3)	0.030 (3)	0.000 (2)	−0.009 (3)
C11	0.079 (3)	0.072 (3)	0.061 (2)	0.014 (2)	−0.006 (2)	−0.003 (2)
C12	0.089 (3)	0.043 (2)	0.094 (3)	−0.002 (2)	0.009 (2)	0.008 (2)
C13	0.065 (2)	0.0383 (19)	0.075 (2)	−0.0072 (18)	0.003 (2)	0.0000 (18)
C14	0.068 (2)	0.067 (2)	0.051 (2)	−0.003 (2)	0.0059 (19)	−0.0109 (19)
C15	0.081 (3)	0.066 (2)	0.050 (2)	−0.001 (2)	−0.002 (2)	0.0011 (18)
C16	0.065 (2)	0.056 (2)	0.055 (2)	−0.0014 (19)	−0.003 (2)	−0.0115 (17)
C17	0.065 (3)	0.076 (3)	0.075 (3)	0.000 (2)	0.018 (2)	0.001 (2)
C18	0.074 (3)	0.066 (3)	0.073 (3)	−0.011 (2)	0.015 (2)	0.014 (2)
C19	0.082 (3)	0.067 (3)	0.068 (3)	0.013 (2)	−0.005 (2)	−0.011 (2)
C20	0.110 (6)	0.058 (4)	0.175 (8)	−0.011 (4)	−0.029 (6)	−0.012 (5)
C21	0.053 (4)	0.095 (5)	0.072 (4)	0.011 (3)	−0.006 (4)	0.001 (4)
C22	0.101 (6)	0.100 (6)	0.082 (4)	0.033 (5)	−0.001 (4)	−0.015 (4)
C20'	0.101 (9)	0.059 (7)	0.100 (9)	0.018 (6)	−0.013 (7)	−0.001 (6)
C21'	0.113 (11)	0.123 (11)	0.158 (13)	−0.008 (9)	0.001 (9)	−0.008 (9)
C22'	0.120 (10)	0.085 (8)	0.098 (8)	0.017 (7)	0.014 (7)	−0.001 (7)

S1—C4	1.741 (3)	C14—H14	0.9300
S1—C12	1.844 (4)	C15—C16	1.382 (5)
O1—C5	1.210 (4)	C15—H15	0.9300
N1—C4	1.355 (4)	C16—C17	1.389 (5)
N1—N2	1.375 (3)	C16—C19	1.515 (5)
N1—C6	1.432 (4)	C17—C18	1.381 (5)
N2—C2	1.324 (4)	C17—H17	0.9300
C1—C2	1.507 (4)	C18—H18	0.9300
C1—H1A	0.9600	C19—C20	1.485 (6)
C1—H1B	0.9600	C19—C21'	1.487 (9)
C1—H1C	0.9600	C19—C22'	1.541 (8)
C2—C3	1.406 (4)	C19—C21	1.554 (6)
C3—C4	1.386 (4)	C19—C22	1.578 (6)
C3—C5	1.448 (4)	C19—C20'	1.609 (8)
C5—H5	0.9300	C20—H20A	0.9600
C6—C7	1.378 (4)	C20—H20B	0.9600
C6—C11	1.380 (4)	C20—H20C	0.9600
C7—C8	1.375 (5)	C21—H21A	0.9600
C7—H7	0.9300	C21—H21B	0.9600
C8—C9	1.371 (5)	C21—H21C	0.9600
C8—H8	0.9300	C22—H22A	0.9600
C9—C10	1.371 (5)	C22—H22B	0.9600
C9—H9	0.9300	C22—H22C	0.9600
C10—C11	1.366 (5)	C20'—H20D	0.9600
C10—H10	0.9300	C20'—H20E	0.9600
C11—H11	0.9300	C20'—H20F	0.9600
C12—C13	1.495 (5)	C21'—H21D	0.9600
C12—H12A	0.9700	C21'—H21E	0.9600
C12—H12B	0.9700	C21'—H21F	0.9600
C13—C14	1.378 (4)	C22'—H22D	0.9600
C13—C18	1.382 (5)	C22'—H22E	0.9600
C14—C15	1.372 (5)	C22'—H22F	0.9600
C4—S1—C12	98.81 (15)	C15—C14—H14	119.3
C4—N1—N2	111.6 (3)	C13—C14—H14	119.3
C4—N1—C6	129.3 (3)	C14—C15—C16	122.2 (3)
N2—N1—C6	119.0 (3)	C14—C15—H15	118.9
C2—N2—N1	105.2 (3)	C16—C15—H15	118.9
C2—C1—H1A	109.5	C15—C16—C17	116.1 (3)
C2—C1—H1B	109.5	C15—C16—C19	121.3 (3)
H1A—C1—H1B	109.5	C17—C16—C19	122.6 (3)
C2—C1—H1C	109.5	C18—C17—C16	121.9 (3)
H1A—C1—H1C	109.5	C18—C17—H17	119.0
H1B—C1—H1C	109.5	C16—C17—H17	119.0
N2—C2—C3	111.3 (3)	C17—C18—C13	120.9 (3)
N2—C2—C1	120.5 (3)	C17—C18—H18	119.6
C3—C2—C1	128.2 (3)	C13—C18—H18	119.6
C4—C3—C2	105.5 (3)	C20—C19—C16	110.7 (5)
C4—C3—C5	125.9 (3)	C21'—C19—C16	114.7 (9)
C2—C3—C5	128.6 (3)	C16—C19—C22'	109.5 (6)
N1—C4—C3	106.4 (3)	C20—C19—C21	112.0 (5)
N1—C4—S1	123.6 (2)	C16—C19—C21	109.0 (4)
C3—C4—S1	129.6 (3)	C20—C19—C22	109.8 (5)
O1—C5—C3	125.5 (4)	C16—C19—C22	111.8 (4)
O1—C5—H5	117.3	C21—C19—C22	103.3 (4)
C3—C5—H5	117.3	C16—C19—C20'	107.8 (6)
C7—C6—C11	120.3 (3)	C19—C20—H20A	109.5
C7—C6—N1	119.5 (3)	C19—C20—H20B	109.5
C11—C6—N1	120.2 (3)	C19—C20—H20C	109.5
C8—C7—C6	119.3 (4)	C19—C21—H21A	109.5
C8—C7—H7	120.3	C19—C21—H21B	109.5
C6—C7—H7	120.3	C19—C21—H21C	109.5
C9—C8—C7	120.5 (4)	C19—C22—H22A	109.5
C9—C8—H8	119.7	C19—C22—H22B	109.5
C7—C8—H8	119.7	C19—C22—H22C	109.5
C8—C9—C10	119.7 (4)	C19—C20'—H20D	109.5
C8—C9—H9	120.2	C19—C20'—H20E	109.5
C10—C9—H9	120.2	H20D—C20'—H20E	109.5
C11—C10—C9	120.7 (4)	C19—C20'—H20F	109.5
C11—C10—H10	119.6	H20D—C20'—H20F	109.5
C9—C10—H10	119.6	H20E—C20'—H20F	109.5
C10—C11—C6	119.5 (3)	C19—C21'—H21D	109.5
C10—C11—H11	120.3	C19—C21'—H21E	109.5
C6—C11—H11	120.3	H21D—C21'—H21E	109.5
C13—C12—S1	112.7 (2)	C19—C21'—H21F	109.5
C13—C12—H12A	109.1	H21D—C21'—H21F	109.5
S1—C12—H12A	109.1	H21E—C21'—H21F	109.5
C13—C12—H12B	109.1	C19—C22'—H22D	109.5
S1—C12—H12B	109.1	C19—C22'—H22E	109.5
H12A—C12—H12B	107.8	H22D—C22'—H22E	109.5
C14—C13—C18	117.4 (3)	C19—C22'—H22F	109.5
C14—C13—C12	120.8 (3)	H22D—C22'—H22F	109.5
C18—C13—C12	121.6 (3)	H22E—C22'—H22F	109.5
C15—C14—C13	121.4 (3)
C4—N1—N2—C2	−0.9 (3)	C9—C10—C11—C6	−0.4 (6)
C6—N1—N2—C2	−178.7 (3)	C7—C6—C11—C10	0.1 (5)
N1—N2—C2—C3	0.5 (4)	N1—C6—C11—C10	178.4 (3)
N1—N2—C2—C1	178.1 (3)	C4—S1—C12—C13	50.4 (3)
N2—C2—C3—C4	0.1 (4)	S1—C12—C13—C14	−94.5 (4)
C1—C2—C3—C4	−177.3 (3)	S1—C12—C13—C18	80.7 (4)
N2—C2—C3—C5	177.6 (3)	C18—C13—C14—C15	−1.8 (5)
C1—C2—C3—C5	0.2 (6)	C12—C13—C14—C15	173.6 (3)
N2—N1—C4—C3	1.0 (3)	C13—C14—C15—C16	−0.4 (5)
C6—N1—C4—C3	178.5 (3)	C14—C15—C16—C17	2.2 (5)
N2—N1—C4—S1	−172.5 (2)	C14—C15—C16—C19	−176.7 (3)
C6—N1—C4—S1	5.0 (5)	C15—C16—C17—C18	−1.9 (5)
C2—C3—C4—N1	−0.6 (3)	C19—C16—C17—C18	177.0 (3)
C5—C3—C4—N1	−178.2 (3)	C16—C17—C18—C13	−0.3 (6)
C2—C3—C4—S1	172.3 (3)	C14—C13—C18—C17	2.1 (5)
C5—C3—C4—S1	−5.3 (5)	C12—C13—C18—C17	−173.3 (3)
C12—S1—C4—N1	78.5 (3)	C15—C16—C19—C20	55.1 (7)
C12—S1—C4—C3	−93.3 (3)	C17—C16—C19—C20	−123.7 (6)
C4—C3—C5—O1	178.3 (3)	C15—C16—C19—C21'	−96.3 (11)
C2—C3—C5—O1	1.2 (6)	C17—C16—C19—C21'	84.9 (11)
C4—N1—C6—C7	−125.0 (4)	C15—C16—C19—C22'	132.1 (9)
N2—N1—C6—C7	52.4 (4)	C17—C16—C19—C22'	−46.8 (9)
C4—N1—C6—C11	56.7 (5)	C15—C16—C19—C21	−68.6 (5)
N2—N1—C6—C11	−126.0 (3)	C17—C16—C19—C21	112.6 (5)
C11—C6—C7—C8	0.4 (5)	C15—C16—C19—C22	177.9 (5)
N1—C6—C7—C8	−177.9 (3)	C17—C16—C19—C22	−1.0 (6)
C6—C7—C8—C9	−0.6 (6)	C15—C16—C19—C20'	23.1 (8)
C7—C8—C9—C10	0.4 (6)	C17—C16—C19—C20'	−155.8 (7)
C8—C9—C10—C11	0.1 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2i	0.97	2.54	3.486 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2i	0.97	2.54	3.486 (3)	165

Symmetry code: (i) .