1,3-Dimethyl-4-phenyl­sulfanyl-1H-pyrazol-5-ol

Shahani, T.; Fun, H.-K.; Ragavan, R.V.; Vijayakumar, V.; Sarveswari, S.

doi:10.1107/S1600536811004922

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o633

doi:10.1107/S1600536811004922

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1,3-Dimethyl-4-phenylsulfanyl-1H-pyrazol-5-ol

Tara Shahani,^a Hoong-Kun Fun,^a ^*‡ R. Venkat Ragavan,^b V. Vijayakumar ^b and S. Sarveswari ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India
^*Correspondence e-mail: hkfun@usm.my

(Received 8 February 2011; accepted 9 February 2011; online 16 February 2011)

In the title compound, C₁₁H₁₂N₂OS, the pyrazole ring makes a dihedral angle of 85.40 (8)° with the phenyl ring. In the crystal, intermolecular N—H⋯O and C—H⋯O hydrogen bonds link molecules into a two-dimensional network parallel to the bc plane.

Related literature

For pyrazole derivatives and their microbial activity, see: Ragavan et al. (2009 , 2010 ). For related structures, see: Shahani et al. (2009 , 2010a ,b ,c ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₁H₁₂N₂OS
M_r = 220.30
Orthorhombic, P b c a
a = 10.9479 (2) Å
b = 11.3470 (3) Å
c = 17.7392 (4) Å
V = 2203.67 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.33 × 0.13 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.917, T_max = 0.971
12209 measured reflections
3027 independent reflections
2406 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 1.04
3027 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.94 (2)	1.71 (2)	2.6446 (16)	173 (2)
C3—H3A⋯O1ⁱⁱ	0.93	2.53	3.2549 (19)	135
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004922/is2676sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004922/is2676Isup2.hkl

checkCIF report

Comment top

Antibacterial and antifungal activities of the azoles are most widely studied and some of them are in clinical practice as anti-microbial agents. However, the azole-resistant strain had led to the development of new antimicrobial compounds. In particular pyrazole derivatives are extensively studied and used as antimicrobial agents. Pyrazole is an important class of heterocyclic compounds and many pyrazole derivatives are reported to have the broad spectrum of biological properties, such as anti-inflammatory, antifungal, herbicidal, anti-tumour, cytotoxic, molecular modelling, and antiviral activities. Pyrazole derivatives also act as antiangiogenic agents, A3 adenosine receptor antagonists, neuropeptide YY5 receptor antagonists, kinase inhibitor for treatment of type 2 diabetes, hyperlipidemia, obesity, and thrombopiotinmimetics. Recently urea derivatives of pyrazoles have been reported as potent inhibitors of p38 kinase. Since the high electronegativity of halogens (particularly chlorine and fluorine) in the aromatic part of the drug molecules play an important role in enhancing their biological activity, we are interested to have 4-fluoro or 4-chloro substitution in the aryls of 1,5-diaryl pyrazoles. As part of our on-going research aiming the synthesis of new antimicrobial compounds, we have reported the synthesis of novel pyrazole derivatives and their microbial activities (Ragavan et al., 2009, 2010). The structure of the title compound is presented here.

In the title compound, (Fig. 1), the 1H-pyrazol ring (C7–C9/N1/N2) [maximum deviation of 0.00117 (14) Å] makes a dihedral angle of 85.40 (8)° with the phenyl ring (C1–C6). The bond lengths (Allen et al., 1987) and angles are within normal ranges and comparable to those closely related structures (Shahani et al., 2009, 2010a,b,c).

In the crystal packing (Fig. 2), pairs of intermolecular N1—H1N1···O1 and C3—H3A···O1 hydrogen bonds (Table 1) link the molecules into two-dimensional networks parallel to the bc plane.

Related literature top

For pyrazole derivatives and their microbial activity, see: Ragavan et al. (2009, 2010). For related structures, see: Shahani et al. (2009, 2010a,b,c). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

The compound has been synthesized using the method available in the literature (Ragavan et al., 2009) and recrystallized using the ethanol-chloroform 1:1 mixture (yield 60%, m.p. 444 K).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008; molecular graphics: SHELXTL (Sheldrick, 2008; software used to prepare material for publication: SHELXTL (Sheldrick, 2008 and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
	Fig. 2. The crystal structure of the title compound viewed approximately along the b axis. Intermolecular interactions are shown in dashed lines. Hydrogen bond not involved in intermolecular interactions are omitted for clarity.

1,3-Dimethyl-4-phenylsulfanyl-1H-pyrazol-5-ol top

Crystal data top

C₁₁H₁₂N₂OS	F(000) = 928
M_r = 220.30	D_x = 1.328 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2873 reflections
a = 10.9479 (2) Å	θ = 2.8–29.1°
b = 11.3470 (3) Å	µ = 0.27 mm⁻¹
c = 17.7392 (4) Å	T = 100 K
V = 2203.67 (9) Å³	Block, colourless
Z = 8	0.33 × 0.13 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3027 independent reflections
Radiation source: fine-focus sealed tube	2406 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 29.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→15
T_min = 0.917, T_max = 0.971	k = −15→15
12209 measured reflections	l = −16→24

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0481P)² + 0.8061P] where P = (F_o² + 2F_c²)/3
3027 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₁H₁₂N₂OS	V = 2203.67 (9) Å³
M_r = 220.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.9479 (2) Å	µ = 0.27 mm⁻¹
b = 11.3470 (3) Å	T = 100 K
c = 17.7392 (4) Å	0.33 × 0.13 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3027 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2406 reflections with I > 2σ(I)
T_min = 0.917, T_max = 0.971	R_int = 0.041
12209 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
3027 reflections	Δρ_min = −0.31 e Å⁻³
142 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.09449 (3)	0.31932 (3)	0.09298 (2)	0.01802 (11)
O1	0.32686 (10)	0.34450 (8)	−0.02532 (6)	0.0207 (2)
N1	0.20240 (12)	0.61926 (10)	0.00845 (8)	0.0202 (3)
N2	0.28173 (12)	0.54374 (10)	−0.02791 (7)	0.0192 (3)
C1	0.28747 (15)	0.36136 (13)	0.19278 (9)	0.0225 (3)
H1A	0.3057	0.4285	0.1649	0.027*
C2	0.35663 (15)	0.33304 (13)	0.25590 (9)	0.0254 (3)
H2A	0.4211	0.3816	0.2700	0.031*
C3	0.33066 (15)	0.23327 (14)	0.29808 (9)	0.0236 (3)
H3A	0.3766	0.2154	0.3407	0.028*
C4	0.23531 (15)	0.16043 (13)	0.27606 (9)	0.0243 (3)
H4A	0.2180	0.0929	0.3037	0.029*
C5	0.16551 (14)	0.18758 (13)	0.21304 (9)	0.0212 (3)
H5A	0.1019	0.1382	0.1986	0.025*
C6	0.19092 (13)	0.28904 (12)	0.17148 (8)	0.0173 (3)
C7	0.16428 (13)	0.43840 (11)	0.04922 (8)	0.0166 (3)
C8	0.26321 (13)	0.43076 (11)	−0.00304 (8)	0.0164 (3)
C9	0.13144 (14)	0.55679 (12)	0.05474 (8)	0.0178 (3)
C10	0.38173 (15)	0.58669 (13)	−0.07387 (10)	0.0239 (3)
H10A	0.4171	0.5222	−0.1013	0.036*
H10B	0.4427	0.6217	−0.0420	0.036*
H10C	0.3517	0.6446	−0.1087	0.036*
C11	0.03683 (15)	0.61354 (14)	0.10271 (9)	0.0248 (3)
H11A	0.0198	0.6912	0.0839	0.037*
H11B	0.0661	0.6189	0.1536	0.037*
H11C	−0.0365	0.5672	0.1016	0.037*
H1N1	0.1983 (19)	0.700 (2)	−0.0036 (13)	0.047 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01876 (19)	0.01847 (18)	0.0168 (2)	−0.00372 (13)	−0.00109 (13)	0.00267 (13)
O1	0.0267 (6)	0.0139 (4)	0.0215 (6)	0.0008 (4)	0.0046 (4)	0.0000 (4)
N1	0.0264 (7)	0.0129 (5)	0.0212 (7)	0.0017 (5)	−0.0005 (5)	−0.0006 (5)
N2	0.0240 (6)	0.0131 (5)	0.0206 (7)	−0.0002 (5)	0.0034 (5)	0.0007 (5)
C1	0.0273 (8)	0.0198 (7)	0.0204 (8)	−0.0046 (6)	−0.0027 (6)	0.0034 (6)
C2	0.0285 (8)	0.0257 (7)	0.0221 (9)	−0.0037 (6)	−0.0065 (7)	−0.0002 (6)
C3	0.0255 (8)	0.0298 (8)	0.0155 (8)	0.0053 (6)	−0.0012 (6)	0.0006 (6)
C4	0.0247 (8)	0.0260 (7)	0.0222 (8)	0.0015 (6)	0.0032 (6)	0.0082 (6)
C5	0.0197 (7)	0.0213 (7)	0.0225 (8)	−0.0015 (6)	0.0013 (6)	0.0043 (6)
C6	0.0196 (7)	0.0188 (6)	0.0134 (7)	0.0007 (5)	0.0019 (5)	0.0003 (5)
C7	0.0193 (7)	0.0148 (6)	0.0156 (7)	−0.0014 (5)	−0.0003 (5)	0.0005 (5)
C8	0.0224 (7)	0.0127 (6)	0.0141 (7)	−0.0017 (5)	−0.0018 (6)	0.0001 (5)
C9	0.0207 (7)	0.0179 (6)	0.0149 (7)	0.0009 (5)	−0.0035 (6)	−0.0002 (5)
C10	0.0283 (8)	0.0184 (7)	0.0250 (8)	−0.0043 (6)	0.0050 (7)	0.0032 (6)
C11	0.0248 (8)	0.0250 (7)	0.0245 (9)	0.0071 (6)	−0.0008 (6)	−0.0021 (6)

Geometric parameters (Å, º) top

S1—C7	1.7356 (14)	C3—H3A	0.9300
S1—C6	1.7809 (15)	C4—C5	1.389 (2)
O1—C8	1.2648 (17)	C4—H4A	0.9300
N1—C9	1.3343 (19)	C5—C6	1.395 (2)
N1—N2	1.3801 (17)	C5—H5A	0.9300
N1—H1N1	0.94 (2)	C7—C9	1.3942 (19)
N2—C8	1.3708 (17)	C7—C8	1.428 (2)
N2—C10	1.4494 (19)	C9—C11	1.487 (2)
C1—C2	1.389 (2)	C10—H10A	0.9600
C1—C6	1.391 (2)	C10—H10B	0.9600
C1—H1A	0.9300	C10—H10C	0.9600
C2—C3	1.387 (2)	C11—H11A	0.9600
C2—H2A	0.9300	C11—H11B	0.9600
C3—C4	1.388 (2)	C11—H11C	0.9600

C7—S1—C6	103.83 (7)	C1—C6—S1	123.32 (11)
C9—N1—N2	108.92 (11)	C5—C6—S1	117.02 (11)
C9—N1—H1N1	129.0 (13)	C9—C7—C8	107.44 (12)
N2—N1—H1N1	121.9 (13)	C9—C7—S1	127.24 (12)
C8—N2—N1	109.70 (12)	C8—C7—S1	125.24 (10)
C8—N2—C10	127.39 (13)	O1—C8—N2	122.79 (13)
N1—N2—C10	121.97 (11)	O1—C8—C7	131.88 (13)
C2—C1—C6	119.79 (14)	N2—C8—C7	105.33 (12)
C2—C1—H1A	120.1	N1—C9—C7	108.57 (13)
C6—C1—H1A	120.1	N1—C9—C11	121.85 (13)
C3—C2—C1	120.80 (15)	C7—C9—C11	129.57 (14)
C3—C2—H2A	119.6	N2—C10—H10A	109.5
C1—C2—H2A	119.6	N2—C10—H10B	109.5
C2—C3—C4	119.26 (15)	H10A—C10—H10B	109.5
C2—C3—H3A	120.4	N2—C10—H10C	109.5
C4—C3—H3A	120.4	H10A—C10—H10C	109.5
C3—C4—C5	120.56 (14)	H10B—C10—H10C	109.5
C3—C4—H4A	119.7	C9—C11—H11A	109.5
C5—C4—H4A	119.7	C9—C11—H11B	109.5
C4—C5—C6	119.92 (14)	H11A—C11—H11B	109.5
C4—C5—H5A	120.0	C9—C11—H11C	109.5
C6—C5—H5A	120.0	H11A—C11—H11C	109.5
C1—C6—C5	119.66 (14)	H11B—C11—H11C	109.5

C9—N1—N2—C8	−1.48 (17)	N1—N2—C8—O1	−177.46 (13)
C9—N1—N2—C10	−171.15 (14)	C10—N2—C8—O1	−8.5 (2)
C6—C1—C2—C3	0.0 (2)	N1—N2—C8—C7	2.10 (16)
C1—C2—C3—C4	0.9 (2)	C10—N2—C8—C7	171.06 (14)
C2—C3—C4—C5	−0.8 (2)	C9—C7—C8—O1	177.55 (16)
C3—C4—C5—C6	−0.2 (2)	S1—C7—C8—O1	−5.6 (2)
C2—C1—C6—C5	−1.0 (2)	C9—C7—C8—N2	−1.96 (16)
C2—C1—C6—S1	178.43 (12)	S1—C7—C8—N2	174.91 (11)
C4—C5—C6—C1	1.1 (2)	N2—N1—C9—C7	0.18 (17)
C4—C5—C6—S1	−178.38 (12)	N2—N1—C9—C11	179.36 (13)
C7—S1—C6—C1	7.87 (15)	C8—C7—C9—N1	1.12 (17)
C7—S1—C6—C5	−172.70 (12)	S1—C7—C9—N1	−175.67 (11)
C6—S1—C7—C9	−100.38 (14)	C8—C7—C9—C11	−177.97 (15)
C6—S1—C7—C8	83.36 (14)	S1—C7—C9—C11	5.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.94 (2)	1.71 (2)	2.6446 (16)	173 (2)
C3—H3A···O1ⁱⁱ	0.93	2.53	3.2549 (19)	135

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂OS
M_r	220.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	10.9479 (2), 11.3470 (3), 17.7392 (4)
V (Å³)	2203.67 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.33 × 0.13 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.917, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	12209, 3027, 2406
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.104, 1.04
No. of reflections	3027
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008 and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.94 (2)	1.71 (2)	2.6446 (16)	173 (2)
C3—H3A···O1ⁱⁱ	0.93	2.53	3.2549 (19)	135

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and TSH thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSH also thanks USM for the award of a research fellowship.

References

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