5-Hy-droxy-3-methyl-5-phenyl-4,5-di-hydro-1H-pyrazole-1-carbothio-amide.

In the title compound C(11)H(13)N(3)OS, the aromatic ring and the dihydro-pyrazole ring are oriented orthogonally with respect to each other, making a dihedral angle of 89.92 (9)°. An intra-molecular O-H⋯S hydrogen bond occurs. In the crystal, weak N-H⋯N and N-H⋯S hydrogen bonds link the mol-ecules into a columnar stack propagating along the b axis.

Related literature

For the biological activity of sulfur–nitro­gen ligand compounds, see: Wilder Smith (1964 ▶); Grii & Khare (1976 ▶); French & Blang (1966 ▶); Davis Parke & Co (1957 ▶); Vattum & Rao (1959 ▶); Brockaman et al. (1959 ▶). For the carcinostatics thio­semicarbazone-containing nitro­gen heterocycles, see: Freedlander & French (1958 ▶); French & Blang (1965 ▶).

Experimental

Crystal data

C11H13N3OS

M = 235.31

Monoclinic,

a = 11.6955 (6) Å

b = 7.6889 (4) Å

c = 13.7588 (10) Å

β = 111.978 (7)°

V = 1147.35 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 298 K

0.39 × 0.41 × 0.43 mm

Data collection

Oxford Diffraction Gemini E CCD diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.541, T max = 1.000

19392 measured reflections

2326 independent reflections

2161 reflections with I > 2σ(I)

R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.130

S = 1.07

2326 reflections

157 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.35 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036658/ds2131sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036658/ds2131Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811036658/ds2131Isup3.cml

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

C11H13N3OS	F(000) = 496
Mr = 235.31	Dx = 1.362 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10287 reflections
a = 11.6955 (6) Å	θ = 3.5–73.8°
b = 7.6889 (4) Å	µ = 0.26 mm−1
c = 13.7588 (10) Å	T = 298 K
β = 111.978 (7)°	Prism, white
V = 1147.35 (12) Å3	0.43 × 0.41 × 0.39 mm
Z = 4

Oxford Diffraction Gemini E CCD diffractometer	2161 reflections with I > 2σ(I)
graphite	Rint = 0.069
ω scans, thick slices	θmax = 26.3°, θmin = 1.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −14→14
Tmin = 0.541, Tmax = 1.000	k = −9→9
19392 measured reflections	l = −17→16
2326 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0808P)2 + 0.2816P] where P = (Fo2 + 2Fc2)/3
2326 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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
N1	0.38340 (12)	0.44242 (18)	0.08551 (10)	0.0382 (3)
O1	0.09679 (11)	0.29274 (18)	0.04417 (11)	0.0503 (3)
N3	0.47610 (13)	0.1959 (2)	0.22717 (13)	0.0479 (4)
C11	0.36034 (14)	0.1729 (2)	0.16030 (12)	0.0370 (3)
C10	0.36242 (19)	0.7124 (2)	−0.00962 (16)	0.0541 (5)
H10C	0.4469	0.7273	0.0363	0.081*
H10A	0.3138	0.8058	0.0008	0.081*
H10B	0.3568	0.7128	−0.081	0.081*
N2	0.31423 (12)	0.29247 (17)	0.08476 (10)	0.0392 (3)
H3B	0.504 (2)	0.124 (3)	0.2795 (18)	0.054 (6)*
H3A	0.521 (2)	0.286 (3)	0.2218 (18)	0.060 (6)*
H1O	0.114 (2)	0.194 (4)	0.086 (2)	0.068 (7)*
S1	0.27587 (4)	0.00137 (5)	0.17302 (3)	0.04557 (19)
C6	0.17249 (13)	0.1559 (2)	−0.08034 (12)	0.0379 (3)
C9	0.31586 (15)	0.5446 (2)	0.01356 (12)	0.0396 (4)
C7	0.18692 (14)	0.2977 (2)	0.00036 (13)	0.0399 (4)
C8	0.18774 (17)	0.4804 (2)	−0.04428 (16)	0.0489 (4)
H8A	0.1694	0.4756	−0.1191	0.059*
H8B	0.1278	0.5551	−0.0317	0.059*
C1	0.07051 (15)	0.0470 (2)	−0.11386 (13)	0.0444 (4)
H2	0.0119	0.0557	−0.0835	0.053*
C3	0.1390 (2)	−0.0863 (3)	−0.23965 (14)	0.0559 (5)
H4	0.1277	−0.1666	−0.293	0.067*
C5	0.25740 (16)	0.1420 (2)	−0.12829 (14)	0.0476 (4)
H6	0.3263	0.214	−0.107	0.057*
C2	0.05503 (17)	−0.0744 (3)	−0.19207 (14)	0.0527 (5)
H3	−0.0128	−0.1484	−0.2125	0.063*
C4	0.2406 (2)	0.0223 (3)	−0.20755 (17)	0.0557 (5)
H5	0.298	0.0149	−0.2394	0.067*

	U11	U22	U33	U12	U13	U23
N1	0.0370 (7)	0.0349 (7)	0.0363 (7)	−0.0034 (5)	0.0064 (5)	0.0002 (5)
O1	0.0396 (6)	0.0545 (8)	0.0526 (7)	0.0057 (5)	0.0122 (5)	−0.0049 (6)
N3	0.0386 (7)	0.0435 (8)	0.0461 (8)	0.0001 (6)	−0.0018 (6)	0.0117 (6)
C11	0.0363 (7)	0.0343 (7)	0.0348 (7)	0.0028 (6)	0.0068 (6)	−0.0003 (6)
C10	0.0601 (11)	0.0424 (9)	0.0524 (10)	−0.0035 (8)	0.0127 (9)	0.0093 (8)
N2	0.0341 (6)	0.0336 (7)	0.0376 (7)	−0.0028 (5)	−0.0007 (5)	0.0029 (5)
S1	0.0429 (3)	0.0374 (3)	0.0500 (3)	−0.00315 (15)	0.0100 (2)	0.00632 (16)
C6	0.0337 (7)	0.0356 (7)	0.0349 (8)	0.0001 (6)	0.0021 (6)	0.0054 (6)
C9	0.0431 (8)	0.0352 (7)	0.0344 (8)	0.0013 (6)	0.0077 (6)	−0.0005 (6)
C7	0.0318 (7)	0.0365 (8)	0.0398 (8)	0.0019 (6)	0.0002 (6)	0.0022 (6)
C8	0.0436 (9)	0.0357 (8)	0.0491 (10)	0.0028 (6)	−0.0036 (8)	0.0045 (7)
C1	0.0366 (8)	0.0482 (9)	0.0399 (9)	−0.0050 (7)	0.0046 (6)	0.0004 (7)
C3	0.0708 (12)	0.0495 (10)	0.0395 (9)	0.0022 (9)	0.0116 (8)	−0.0033 (8)
C5	0.0452 (8)	0.0446 (9)	0.0511 (10)	−0.0049 (7)	0.0161 (7)	0.0040 (8)
C2	0.0511 (9)	0.0516 (10)	0.0428 (9)	−0.0108 (8)	0.0031 (7)	−0.0042 (8)
C4	0.0659 (12)	0.0559 (11)	0.0502 (10)	0.0065 (9)	0.0273 (10)	0.0070 (8)

N1—C9	1.279 (2)	C6—C5	1.387 (2)
N1—N2	1.4062 (18)	C6—C7	1.520 (2)
O1—C7	1.397 (2)	C9—C8	1.493 (2)
O1—H1O	0.93 (3)	C7—C8	1.535 (2)
N3—C11	1.334 (2)	C8—H8A	0.97
N3—H3B	0.87 (2)	C8—H8B	0.97
N3—H3A	0.89 (3)	C1—C2	1.384 (3)
C11—N2	1.340 (2)	C1—H2	0.93
C11—S1	1.6958 (16)	C3—C2	1.373 (3)
C10—C9	1.481 (2)	C3—C4	1.382 (3)
C10—H10C	0.96	C3—H4	0.93
C10—H10A	0.96	C5—C4	1.384 (3)
C10—H10B	0.96	C5—H6	0.93
N2—C7	1.5077 (18)	C2—H3	0.93
C6—C1	1.387 (2)	C4—H5	0.93
C9—N1—N2	108.12 (12)	N2—C7—C6	110.55 (12)
C7—O1—H1O	105.7 (15)	O1—C7—C8	108.45 (14)
C11—N3—H3B	117.4 (14)	N2—C7—C8	100.40 (12)
C11—N3—H3A	121.5 (15)	C6—C7—C8	112.34 (14)
H3B—N3—H3A	121 (2)	C9—C8—C7	104.14 (13)
N3—C11—N2	116.99 (15)	C9—C8—H8A	110.9
N3—C11—S1	120.81 (13)	C7—C8—H8A	110.9
N2—C11—S1	122.18 (11)	C9—C8—H8B	110.9
C9—C10—H10C	109.5	C7—C8—H8B	110.9
C9—C10—H10A	109.5	H8A—C8—H8B	108.9
H10C—C10—H10A	109.5	C2—C1—C6	120.76 (17)
C9—C10—H10B	109.5	C2—C1—H2	119.6
H10C—C10—H10B	109.5	C6—C1—H2	119.6
H10A—C10—H10B	109.5	C2—C3—C4	119.37 (18)
C11—N2—N1	119.56 (12)	C2—C3—H4	120.3
C11—N2—C7	127.61 (13)	C4—C3—H4	120.3
N1—N2—C7	112.54 (12)	C4—C5—C6	120.67 (17)
C1—C6—C5	118.38 (16)	C4—C5—H6	119.7
C1—C6—C7	121.50 (15)	C6—C5—H6	119.7
C5—C6—C7	119.93 (14)	C3—C2—C1	120.45 (17)
N1—C9—C10	122.10 (15)	C3—C2—H3	119.8
N1—C9—C8	114.56 (15)	C1—C2—H3	119.8
C10—C9—C8	123.34 (15)	C3—C4—C5	120.35 (19)
O1—C7—N2	110.74 (13)	C3—C4—H5	119.8
O1—C7—C6	113.58 (13)	C5—C4—H5	119.8
N3—C11—N2—N1	−6.3 (2)	C5—C6—C7—N2	−53.08 (19)
S1—C11—N2—N1	172.51 (12)	C1—C6—C7—C8	−116.66 (17)
N3—C11—N2—C7	−179.61 (16)	C5—C6—C7—C8	58.17 (19)
S1—C11—N2—C7	−0.8 (2)	N1—C9—C8—C7	−4.7 (2)
C9—N1—N2—C11	−173.10 (14)	C10—C9—C8—C7	175.24 (16)
C9—N1—N2—C7	1.16 (18)	O1—C7—C8—C9	120.77 (15)
N2—N1—C9—C10	−177.61 (15)	N2—C7—C8—C9	4.61 (18)
N2—N1—C9—C8	2.3 (2)	C6—C7—C8—C9	−112.86 (15)
C11—N2—C7—O1	55.5 (2)	C5—C6—C1—C2	1.1 (2)
N1—N2—C7—O1	−118.22 (15)	C7—C6—C1—C2	175.99 (15)
C11—N2—C7—C6	−71.3 (2)	C1—C6—C5—C4	−0.1 (3)
N1—N2—C7—C6	115.00 (14)	C7—C6—C5—C4	−175.07 (16)
C11—N2—C7—C8	169.90 (16)	C4—C3—C2—C1	1.1 (3)
N1—N2—C7—C8	−3.79 (18)	C6—C1—C2—C3	−1.6 (3)
C1—C6—C7—O1	6.9 (2)	C2—C3—C4—C5	−0.1 (3)
C5—C6—C7—O1	−178.28 (14)	C6—C5—C4—C3	−0.4 (3)
C1—C6—C7—N2	132.09 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S1	0.93 (3)	2.35 (3)	3.1256 (15)	141 (2)
N3—H3A···S1i	0.89 (2)	2.81 (2)	3.5827 (17)	145.9 (19)
N3—H3B···N1ii	0.87 (2)	2.30 (2)	3.158 (2)	168 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S1	0.93 (3)	2.35 (3)	3.1256 (15)	141 (2)
N3—H3A⋯S1i	0.89 (2)	2.81 (2)	3.5827 (17)	145.9 (19)
N3—H3B⋯N1ii	0.87 (2)	2.30 (2)	3.158 (2)	168 (2)

Symmetry codes: (i) ; (ii) .