PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2662.
Published online 2009 October 7. doi:  10.1107/S1600536809038586
PMCID: PMC2971425

2-(Phenyl­sulfan­yl)pyridine-3-carboxylic acid

Abstract

The title compound, C12H9NO2S, belongs to the nitro­gen-containing group of heterocyclic organic compounds and crystallized with two mol­ecules per asymmetric unit. In the crystal, both molecules form inversion dimers linked by pairs of O—H—O hydrogen bonds. Weak symmetry-related C—H—O inter­actions link the carboxyl dimers along b axis. The dihedral angle between the two aromatic rings in the two mol­ecules are 55.75 (14) and 58.33 (13)°.

Related literature

For the pharmacological effects of heteroaromatic anti­tumor compounds: Denny et al. (1982 [triangle]); Fujiwara (1997 [triangle]); Antonini & Martelli (1992 [triangle]); Cholody et al. (1992 [triangle]). For the title compound as an inter­mediate for heterocycles, see: Khan et al. (2008a [triangle],b [triangle]). For the synthesis, see: Mann & Reid (1952 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2662-scheme1.jpg

Experimental

Crystal data

  • C12H9NO2S
  • M r = 231.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2662-efi1.jpg
  • a = 7.2201 (4) Å
  • b = 7.6653 (4) Å
  • c = 19.9537 (11) Å
  • α = 97.895 (3)°
  • β = 98.520 (3)°
  • γ = 91.661 (3)°
  • V = 1080.41 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 296 K
  • 0.21 × 0.09 × 0.06 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.911, T max = 0.983
  • 23200 measured reflections
  • 5397 independent reflections
  • 2766 reflections with I > 2/s(I)
  • R int = 0.063

Refinement

  • R[F 2 > 2σ(F 2)] = 0.073
  • wR(F 2) = 0.224
  • S = 1.09
  • 5397 reflections
  • 292 parameters
  • H-atom parameters constrained
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038586/hg2570sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038586/hg2570Isup2.hkl

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

Acknowledgments

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant under the project strengthening the Materials Chemistry Laboratory at GC University, Lahore.

supplementary crystallographic information

Comment

In continuation of our studies on pyridine-containing heterocyclic compounds, the title compond was synthesized. It is an intermediate for our previously reported crystal structures of 7-nitro-5H-thiochromeno[2,3-b]pyridin-5-one (Khan et al., 2008a) and 5H-thiochromeno[2,3-b]pyridin-5-one (Khan et al., 2008b). Pyridine containing compounds are widely distributed in nature. Heteroaromatic antitumor compounds have been prepared in recent years with the hope of increasing pharmacological effects (Denny et al., 1982), (Fujiwara, 1997), (Antonini & Martelli, 1992) (Cholody et al., 1992).

The title compound was crystallized with two independent molecules in the asymmetric unit (Fig 1). The dihedral angles between the two aromatic rings in molecule A and molecule B are 55.75 (14)° and 58.33 (13)° respectively. The carboxylic group present in each molecule forms dimers which are linked through weak C–H—O type interaction along the b axis to stabilize the structure Table. 1 & Fig. 2.

Experimental

A mixture of 2-chloronicotinic acid (1.57 g, 10 mmol) and thiophenol (2 ml) was heated under reflux for two hours to produce 2-(Phenylsulfanyl)pyridine-3-carboxylic acid (Mann & Reid, 1952). Suitable crystals for X-ray diffractions were obtained on cooling the saturated solution of (I) in ethanol.

Refinement

The H-atoms for aromatic carbons and carboxylic O atoms were refined geometrically and treated as riding atoms: C—H = 0.93Å with Uiso(H) = 1.2 and O—H = 0.82 with Uiso(H) = 1.5.

Figures

Fig. 1.
The molecular structure diagram of the title compound showing the atom labels. Thermal ellipsoids are drawn at the 50% probability level.
Fig. 2.
Unit cell packing diagram showing the intermolecular hydrogen bonding using dashed lines. The hydrogen atoms not involved in hydrogen bonding have been omitted.

Crystal data

C12H9NO2SZ = 4
Mr = 231.26F(000) = 480
Triclinic, P1Dx = 1.422 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2201 (4) ÅCell parameters from 3133 reflections
b = 7.6653 (4) Åθ = 2.9–23.8°
c = 19.9537 (11) ŵ = 0.28 mm1
α = 97.895 (3)°T = 296 K
β = 98.520 (3)°Needle, white
γ = 91.661 (3)°0.21 × 0.09 × 0.06 mm
V = 1080.41 (10) Å3

Data collection

Bruker Kappa APEXII CCD diffractometer5397 independent reflections
Radiation source: fine-focus sealed tube2766 reflections with I > 2/s(I)
graphiteRint = 0.063
[var phi] and ω scansθmax = 28.4°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −9→9
Tmin = 0.911, Tmax = 0.983k = −10→10
23200 measured reflectionsl = −26→26

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.224w = 1/[σ2(Fo2) + (0.1023P)2 + 0.1581P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
5397 reflectionsΔρmax = 0.59 e Å3
292 parametersΔρmin = −0.52 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.045 (5)

Special details

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)

xyzUiso*/Ueq
S10.15013 (14)−0.12613 (12)0.21464 (5)0.0407 (3)
S20.70162 (15)0.36894 (12)0.22267 (5)0.0447 (3)
O10.1649 (4)−0.2094 (3)0.07364 (13)0.0508 (7)
O20.2377 (6)−0.0151 (4)0.00790 (14)0.0709 (10)
H20.2653−0.1043−0.01550.106*
O30.7077 (5)0.2844 (3)0.08218 (13)0.0568 (8)
O40.7667 (5)0.4795 (4)0.01516 (15)0.0689 (10)
H4O0.79580.3911−0.00830.103*
N10.1813 (5)0.2239 (4)0.23401 (15)0.0422 (8)
N20.6430 (4)0.7119 (4)0.23511 (15)0.0414 (8)
C10.1727 (5)0.0818 (4)0.18659 (17)0.0341 (8)
C20.1832 (5)0.0971 (5)0.11768 (18)0.0382 (8)
C30.1939 (6)0.2639 (5)0.1002 (2)0.0496 (10)
H30.20050.27830.05510.059*
C40.1951 (6)0.4099 (5)0.1488 (2)0.0521 (11)
H40.19780.52340.13720.062*
C50.1921 (6)0.3809 (5)0.2150 (2)0.0485 (10)
H50.19810.47870.24860.058*
C60.1937 (6)−0.0559 (5)0.06520 (18)0.0413 (9)
C70.1766 (5)−0.0719 (5)0.30494 (18)0.0380 (8)
C80.3176 (6)−0.1484 (5)0.34292 (19)0.0490 (10)
H80.4002−0.21900.32140.059*
C90.3357 (7)−0.1189 (7)0.4143 (2)0.0656 (13)
H90.4306−0.17090.44030.079*
C100.2159 (8)−0.0149 (7)0.4461 (2)0.0738 (15)
H100.22900.00480.49360.089*
C110.0762 (7)0.0605 (6)0.4077 (2)0.0665 (14)
H11−0.00530.13200.42950.080*
C120.0542 (6)0.0326 (5)0.3379 (2)0.0509 (10)
H12−0.04260.08360.31250.061*
C130.6743 (5)0.5728 (5)0.19104 (18)0.0357 (8)
C140.6895 (5)0.5891 (5)0.12249 (18)0.0373 (8)
C150.6724 (6)0.7539 (5)0.1026 (2)0.0457 (10)
H150.68180.76860.05770.055*
C160.6416 (6)0.8959 (5)0.1483 (2)0.0463 (10)
H160.63171.00810.13580.056*
C170.6261 (5)0.8659 (5)0.2134 (2)0.0442 (9)
H170.60170.96120.24440.053*
C180.7230 (6)0.4371 (5)0.07237 (18)0.0416 (9)
C190.7107 (5)0.4283 (5)0.31237 (18)0.0380 (8)
C200.5879 (6)0.3405 (6)0.3442 (2)0.0492 (10)
H200.49680.26040.31840.059*
C210.5999 (7)0.3716 (7)0.4149 (2)0.0658 (13)
H210.51610.31280.43630.079*
C220.7329 (8)0.4871 (7)0.4529 (2)0.0717 (14)
H220.74150.50660.50040.086*
C230.8545 (7)0.5748 (6)0.4213 (2)0.0683 (14)
H230.94450.65520.44760.082*
C240.8463 (6)0.5467 (6)0.3516 (2)0.0528 (11)
H240.93080.60640.33080.063*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0630 (7)0.0289 (5)0.0303 (5)0.0032 (4)0.0088 (4)0.0027 (4)
S20.0728 (7)0.0313 (5)0.0326 (5)0.0075 (5)0.0147 (5)0.0060 (4)
O10.092 (2)0.0293 (15)0.0329 (15)0.0027 (13)0.0166 (14)0.0041 (12)
O20.148 (3)0.0337 (16)0.0387 (17)0.0088 (18)0.0413 (19)0.0042 (13)
O30.111 (2)0.0291 (15)0.0366 (16)0.0060 (14)0.0284 (15)0.0063 (12)
O40.137 (3)0.0358 (16)0.0428 (18)0.0118 (18)0.0420 (19)0.0057 (13)
N10.062 (2)0.0298 (17)0.0348 (18)0.0000 (14)0.0090 (15)0.0022 (14)
N20.056 (2)0.0325 (17)0.0378 (18)0.0111 (14)0.0137 (15)0.0047 (14)
C10.041 (2)0.0320 (19)0.0291 (19)0.0071 (15)0.0034 (15)0.0037 (15)
C20.054 (2)0.0300 (19)0.0309 (19)0.0066 (16)0.0075 (16)0.0034 (15)
C30.078 (3)0.034 (2)0.040 (2)0.0069 (19)0.016 (2)0.0065 (18)
C40.084 (3)0.028 (2)0.048 (3)0.0085 (19)0.016 (2)0.0099 (18)
C50.068 (3)0.029 (2)0.046 (2)0.0008 (18)0.013 (2)−0.0059 (18)
C60.065 (3)0.032 (2)0.029 (2)0.0089 (17)0.0106 (17)0.0056 (16)
C70.053 (2)0.0293 (19)0.031 (2)−0.0026 (16)0.0100 (17)0.0019 (15)
C80.063 (3)0.048 (2)0.038 (2)0.005 (2)0.0113 (19)0.0104 (19)
C90.077 (3)0.080 (3)0.041 (3)−0.003 (3)0.003 (2)0.021 (2)
C100.101 (4)0.087 (4)0.032 (2)−0.020 (3)0.020 (3)0.000 (3)
C110.087 (4)0.060 (3)0.054 (3)−0.001 (3)0.035 (3)−0.010 (2)
C120.063 (3)0.048 (2)0.045 (2)0.004 (2)0.020 (2)0.0043 (19)
C130.044 (2)0.0323 (19)0.0295 (19)0.0029 (15)0.0065 (15)0.0008 (15)
C140.052 (2)0.0310 (19)0.0305 (19)0.0016 (16)0.0122 (16)0.0042 (15)
C150.067 (3)0.032 (2)0.041 (2)0.0050 (18)0.0151 (19)0.0080 (17)
C160.064 (3)0.032 (2)0.048 (2)0.0099 (18)0.016 (2)0.0126 (18)
C170.060 (2)0.030 (2)0.043 (2)0.0088 (17)0.0143 (18)−0.0001 (17)
C180.063 (3)0.032 (2)0.032 (2)0.0039 (17)0.0154 (18)0.0047 (17)
C190.052 (2)0.033 (2)0.0301 (19)0.0079 (16)0.0102 (16)0.0056 (16)
C200.056 (3)0.053 (3)0.039 (2)−0.001 (2)0.0074 (19)0.0115 (19)
C210.074 (3)0.087 (4)0.044 (3)0.006 (3)0.023 (2)0.024 (3)
C220.093 (4)0.090 (4)0.033 (2)0.012 (3)0.014 (3)0.005 (3)
C230.079 (3)0.072 (3)0.046 (3)0.004 (3)−0.008 (2)0.001 (2)
C240.064 (3)0.053 (3)0.042 (2)−0.004 (2)0.009 (2)0.009 (2)

Geometric parameters (Å, °)

S1—C11.771 (4)C9—C101.360 (7)
S1—C71.773 (4)C9—H90.9300
S2—C131.769 (4)C10—C111.365 (7)
S2—C191.776 (4)C10—H100.9300
O1—C61.228 (4)C11—C121.365 (6)
O2—C61.306 (4)C11—H110.9300
O2—H20.8200C12—H120.9300
O3—C181.218 (4)C13—C141.411 (5)
O4—C181.308 (4)C14—C151.379 (5)
O4—H4O0.8200C14—C181.478 (5)
N1—C51.315 (5)C15—C161.367 (5)
N1—C11.334 (4)C15—H150.9300
N2—C171.315 (5)C16—C171.369 (5)
N2—C131.333 (4)C16—H160.9300
C1—C21.409 (5)C17—H170.9300
C2—C31.374 (5)C19—C201.376 (5)
C2—C61.472 (5)C19—C241.386 (5)
C3—C41.374 (5)C20—C211.386 (5)
C3—H30.9300C20—H200.9300
C4—C51.372 (5)C21—C221.354 (7)
C4—H40.9300C21—H210.9300
C5—H50.9300C22—C231.366 (7)
C7—C81.372 (5)C22—H220.9300
C7—C121.387 (5)C23—C241.371 (6)
C8—C91.397 (5)C23—H230.9300
C8—H80.9300C24—H240.9300
C1—S1—C7103.18 (16)C11—C12—C7119.9 (4)
C13—S2—C19103.20 (16)C11—C12—H12120.1
C6—O2—H2109.5C7—C12—H12120.1
C18—O4—H4O109.5N2—C13—C14121.1 (3)
C5—N1—C1118.8 (3)N2—C13—S2117.3 (3)
C17—N2—C13118.6 (3)C14—C13—S2121.6 (3)
N1—C1—C2121.4 (3)C15—C14—C13117.9 (3)
N1—C1—S1116.8 (3)C15—C14—C18119.8 (3)
C2—C1—S1121.8 (3)C13—C14—C18122.3 (3)
C3—C2—C1117.6 (3)C16—C15—C14120.5 (4)
C3—C2—C6119.1 (3)C16—C15—H15119.8
C1—C2—C6123.1 (3)C14—C15—H15119.8
C2—C3—C4120.7 (4)C15—C16—C17117.2 (3)
C2—C3—H3119.6C15—C16—H16121.4
C4—C3—H3119.6C17—C16—H16121.4
C5—C4—C3117.1 (4)N2—C17—C16124.7 (3)
C5—C4—H4121.5N2—C17—H17117.6
C3—C4—H4121.5C16—C17—H17117.6
N1—C5—C4124.3 (3)O3—C18—O4122.1 (3)
N1—C5—H5117.8O3—C18—C14123.5 (3)
C4—C5—H5117.8O4—C18—C14114.3 (3)
O1—C6—O2121.9 (3)C20—C19—C24119.4 (4)
O1—C6—C2123.8 (3)C20—C19—S2117.8 (3)
O2—C6—C2114.2 (3)C24—C19—S2122.5 (3)
C8—C7—C12119.6 (4)C19—C20—C21120.0 (4)
C8—C7—S1117.3 (3)C19—C20—H20120.0
C12—C7—S1122.9 (3)C21—C20—H20120.0
C7—C8—C9119.3 (4)C22—C21—C20120.4 (4)
C7—C8—H8120.3C22—C21—H21119.8
C9—C8—H8120.3C20—C21—H21119.8
C10—C9—C8120.6 (5)C21—C22—C23119.7 (4)
C10—C9—H9119.7C21—C22—H22120.2
C8—C9—H9119.7C23—C22—H22120.2
C9—C10—C11119.6 (4)C22—C23—C24121.3 (4)
C9—C10—H10120.2C22—C23—H23119.3
C11—C10—H10120.2C24—C23—H23119.3
C10—C11—C12121.1 (4)C23—C24—C19119.3 (4)
C10—C11—H11119.5C23—C24—H24120.4
C12—C11—H11119.5C19—C24—H24120.4
C5—N1—C1—C22.8 (5)C17—N2—C13—C140.1 (5)
C5—N1—C1—S1−177.9 (3)C17—N2—C13—S2178.6 (3)
C7—S1—C1—N1−7.2 (3)C19—S2—C13—N2−8.3 (3)
C7—S1—C1—C2172.1 (3)C19—S2—C13—C14170.2 (3)
N1—C1—C2—C3−2.9 (6)N2—C13—C14—C150.4 (6)
S1—C1—C2—C3177.8 (3)S2—C13—C14—C15−177.9 (3)
N1—C1—C2—C6173.5 (3)N2—C13—C14—C18−179.6 (3)
S1—C1—C2—C6−5.8 (5)S2—C13—C14—C182.0 (5)
C1—C2—C3—C40.2 (6)C13—C14—C15—C160.0 (6)
C6—C2—C3—C4−176.3 (4)C18—C14—C15—C16−179.9 (4)
C2—C3—C4—C52.4 (6)C14—C15—C16—C17−1.0 (6)
C1—N1—C5—C40.1 (6)C13—N2—C17—C16−1.3 (6)
C3—C4—C5—N1−2.6 (7)C15—C16—C17—N21.7 (6)
C3—C2—C6—O1−171.7 (4)C15—C14—C18—O3−166.9 (4)
C1—C2—C6—O112.0 (6)C13—C14—C18—O313.2 (6)
C3—C2—C6—O28.6 (6)C15—C14—C18—O411.6 (6)
C1—C2—C6—O2−167.8 (4)C13—C14—C18—O4−168.3 (4)
C1—S1—C7—C8−122.4 (3)C13—S2—C19—C20126.3 (3)
C1—S1—C7—C1262.3 (4)C13—S2—C19—C24−59.6 (4)
C12—C7—C8—C9−0.2 (6)C24—C19—C20—C210.3 (6)
S1—C7—C8—C9−175.7 (3)S2—C19—C20—C21174.6 (3)
C7—C8—C9—C10−0.3 (7)C19—C20—C21—C22−0.5 (7)
C8—C9—C10—C110.3 (8)C20—C21—C22—C230.7 (8)
C9—C10—C11—C120.3 (8)C21—C22—C23—C24−0.8 (8)
C10—C11—C12—C7−0.8 (7)C22—C23—C24—C190.7 (7)
C8—C7—C12—C110.8 (6)C20—C19—C24—C23−0.4 (6)
S1—C7—C12—C11176.0 (3)S2—C19—C24—C23−174.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.821.822.624 (2)168 (1)
O4—H4o···O1i0.8201.830002.642 (2)169.62 (19)
C3—H3···O4ii0.932.503.264 (5)139
C4—H4···O1iii0.932.553.458 (5)164
C15—H15···O2ii0.932.543.294 (5)138
C16—H16···O3iii0.932.583.467 (5)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2570).

References

  • Antonini, I. & Martelli, S. (1992). J. Heterocycl. Chem 29, 471-473.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cholody, W. M., Martelli, S. & Konopa, J. (1992). J. Med. Chem 25, 276–315.
  • Denny, W. A., Cain, B. F., Atwell, G. J., Hansch, C., Panthananickal, A. & Leo, A. (1982). J. Med. Chem 25, 276–315. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Fujiwara, H. (1997). Heterocycles, 45, 119–127.
  • Khan, M. N., Tahir, M. N., Khan, M. A., Khan, I. U. & Arshad, M. N. (2008a). Acta Cryst. E64, o730. [PMC free article] [PubMed]
  • Khan, M. N., Tahir, M. N., Khan, M. A., Khan, I. U. & Arshad, M. N. (2008b). Acta Cryst. E64, o1704. [PMC free article] [PubMed]
  • Mann, F. G. & Reid, J. A. (1952). J. Chem. Soc pp. 2057–2062.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography