3'-(Methyl­sulfan­yl)biphenyl-4-carbo­nitrile

In the title compound, C₁₄H₁₁NS, the two benzene rings make a dihedral angle of 22.0 (2)°. The cyano group and the S atom are coplanar with their corresponding benzene rings.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.097
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C11    -   C14    ...       1.44 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            C10 -C11 -C14 -N1    -58.00 11.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         22
            C12 -C11 -C14 -N1    121.00 11.00   1.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.88
           From the CIF: _reflns_number_total               2670
           Count of symmetry unique reflns         1553
           Completeness (_total/calc)            171.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1117
           Fraction of Friedel pairs measured     0.719
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Aryl compounds with a methylthio group are of interest as pesticide and synthetic intermediates used in the preparation of many pharmaceuticals (Robbins, et al., 2003). The methylthio group can be easily oxidized to form sulfinyl or sulfonyl groups, which are useful groups in pharmaceuticals (Gans, et al., 1990; Khanna, et al., 2000). Here, we report the synthesis and crystal structure of the title compound, (I).

The title compound of (I), contains two benzene rings and they make a dihedral angle of 22.0 (2)°. the torsion angles of C1—S1—C2—C3 and C1—S1—C2—C7 are 5.6 (2) and 174.60 (15)°, respectively, indicating that S atom don't significantly deviate from the benzene ring plane (C2—C7). The p-π conjugation of S atom with the benzene ring affect the bond distance S1—C2 [1.767 (2) Å] which is shorter than S1—C1 [1.7991 (19) Å].

Related literature

For related literature, see: Gans et al. (1990); Khanna et al. (2000); Robbins et al. (2003).

S2. Experimental

A mixture of 3-methylthiophenylboronic acid (1.327 mmol), 4-bromobenzonitrile (0.8845 mmol), K₂CO₃ (2.657 mmol) and POPd (0.00177 mmol, 0.2 mol %) was stirred and refluxed in 2 ml of dioxane for 3 h. The reaction mixture was allowed to cool to room temperature, quenched with water, and extracted with EtOAc. The combined organic layers were washed with brine and dried over MgSO₄, and the solvents were removed under vacuum. The residue was purified by chromatography on silica gel eluting with hexane/EtOAc (60:1 v/v) to give the target product as white acicular crystal in 99.7% yield (m.p.337 K). Spectroscopic analysis: IR (KBr): 2230 cm^{-1. 1}H NMR (500 MHz, Chloroform-d1, TMS): δ 2.54 (s, 3H), 7.31 (d, 1H, J= 7.8 Hz), 7.34 (d, 1H, J= 7.8 Hz), 7.39–7.42 (t, 1H, J= 7.8 Hz), 7.45 (s, 1H), 7.67 (d, 2H, J= 8.4 Hz), 7.73 (d, 2H, J= 8.3 Hz). ¹³C NMR (125 MHz, TMS): δ 15.8, 124., 125.4, 126.7, 127.9, 129.6, 139.5, 139.9, 147.2, 147.3; HRMS (EI): M⁺, found 225.0616. C₁₄H₁₁NS requires 225.0612. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1 v/v).

S3. Refinement

All H atoms were positioned geometrically and refined using a riding on their parent atoms, with C—H = 0.95–0.98 Å and U_iso(H) = 1.2 or 1.5U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2004); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.

3'-(Methylsulfanyl)biphenyl-4-carbonitrile

Crystal data

C14H11NS	Dx = 1.340 Mg m^−3
Mr = 225.30	Melting point: 337 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3597 reflections
a = 7.2200 (14) Å	θ = 2.3–27.8°
b = 11.961 (2) Å	µ = 0.26 mm^−1
c = 12.936 (3) Å	T = 113 K
V = 1117.2 (4) Å^3	Prism, colourless
Z = 4	0.14 × 0.12 × 0.08 mm
F(000) = 472

Data collection

Rigaku Saturn diffractometer	2670 independent reflections
Radiation source: rotating anode	2539 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.046
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.3°
ω and ϕ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
Tmin = 0.965, Tmax = 0.980	l = −16→17
14124 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0426P)^2 + 0.3196P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
2670 reflections	Δρmax = 0.22 e Å^−3
146 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1118 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (10)

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.24370 (8)	0.21096 (4)	0.38537 (4)	0.02390 (14)
C6	0.1139 (2)	0.30649 (16)	0.09659 (14)	0.0174 (4)
C2	0.1735 (3)	0.29709 (17)	0.28158 (15)	0.0190 (4)
N1	0.1321 (3)	0.04988 (16)	−0.37872 (15)	0.0304 (4)
C13	0.1450 (3)	0.31419 (16)	−0.09653 (15)	0.0209 (4)
H13	0.1649	0.3925	−0.0914	0.025*
C11	0.1171 (3)	0.14894 (18)	−0.20058 (15)	0.0203 (4)
C8	0.1125 (3)	0.25204 (17)	−0.00672 (16)	0.0179 (4)
C12	0.1485 (3)	0.26366 (17)	−0.19279 (16)	0.0218 (4)
H12	0.1721	0.3068	−0.2530	0.026*
C5	0.0609 (3)	0.41861 (16)	0.10827 (16)	0.0211 (4)
H5	0.0211	0.4604	0.0499	0.025*
C9	0.0812 (3)	0.13761 (17)	−0.01641 (16)	0.0199 (4)
H9	0.0587	0.0942	0.0438	0.024*
C1	0.2520 (4)	0.30445 (16)	0.49421 (15)	0.0274 (4)
H1A	0.3363	0.3665	0.4789	0.041*
H1B	0.2966	0.2639	0.5552	0.041*
H1C	0.1277	0.3338	0.5079	0.041*
C4	0.0664 (3)	0.46838 (17)	0.20489 (16)	0.0243 (5)
H4	0.0320	0.5447	0.2119	0.029*
C7	0.1708 (3)	0.24753 (16)	0.18386 (15)	0.0184 (4)
H7	0.2086	0.1719	0.1767	0.022*
C14	0.1240 (3)	0.09457 (18)	−0.30001 (16)	0.0231 (4)
C10	0.0824 (3)	0.08612 (16)	−0.11220 (16)	0.0219 (4)
H10	0.0595	0.0081	−0.1176	0.026*
C3	0.1214 (3)	0.40857 (17)	0.29177 (16)	0.0219 (4)
H3	0.1234	0.4436	0.3577	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0307 (3)	0.0233 (2)	0.0177 (2)	0.0006 (2)	−0.0026 (2)	−0.00141 (19)
C6	0.0115 (9)	0.0194 (9)	0.0211 (10)	−0.0031 (7)	0.0002 (7)	−0.0002 (8)
C2	0.0162 (9)	0.0209 (9)	0.0199 (9)	−0.0020 (8)	0.0001 (7)	−0.0022 (8)
N1	0.0353 (11)	0.0311 (10)	0.0248 (10)	0.0022 (8)	−0.0014 (9)	−0.0029 (8)
C13	0.0210 (10)	0.0188 (10)	0.0230 (11)	−0.0006 (8)	−0.0012 (8)	−0.0001 (8)
C11	0.0157 (10)	0.0247 (10)	0.0203 (10)	0.0027 (8)	−0.0020 (8)	−0.0014 (8)
C8	0.0145 (9)	0.0210 (9)	0.0181 (10)	0.0003 (7)	−0.0015 (8)	−0.0010 (8)
C12	0.0205 (11)	0.0238 (10)	0.0210 (10)	0.0004 (8)	−0.0017 (8)	0.0032 (8)
C5	0.0192 (10)	0.0195 (9)	0.0247 (10)	0.0005 (8)	0.0001 (9)	0.0012 (9)
C9	0.0196 (10)	0.0203 (10)	0.0199 (10)	0.0005 (8)	0.0002 (8)	0.0014 (8)
C1	0.0327 (11)	0.0308 (11)	0.0186 (9)	−0.0034 (11)	0.0009 (10)	−0.0038 (8)
C4	0.0222 (11)	0.0191 (10)	0.0315 (12)	0.0024 (9)	−0.0004 (9)	−0.0038 (9)
C7	0.0146 (9)	0.0208 (9)	0.0198 (10)	−0.0017 (8)	0.0016 (7)	−0.0012 (8)
C14	0.0205 (10)	0.0247 (10)	0.0241 (11)	0.0032 (8)	−0.0030 (8)	0.0009 (9)
C10	0.0231 (10)	0.0182 (9)	0.0243 (10)	0.0019 (8)	−0.0005 (9)	−0.0019 (9)
C3	0.0211 (10)	0.0224 (10)	0.0221 (10)	0.0020 (8)	0.0011 (8)	−0.0055 (8)

Geometric parameters (Å, º)

S1—C2	1.767 (2)	C8—C9	1.393 (3)
S1—C1	1.7991 (19)	C12—H12	0.9500
C6—C7	1.393 (3)	C5—C4	1.385 (3)
C6—C5	1.403 (3)	C5—H5	0.9500
C6—C8	1.487 (3)	C9—C10	1.384 (3)
C2—C3	1.392 (3)	C9—H9	0.9500
C2—C7	1.396 (3)	C1—H1A	0.9800
N1—C14	1.151 (3)	C1—H1B	0.9800
C13—C12	1.384 (3)	C1—H1C	0.9800
C13—C8	1.399 (3)	C4—C3	1.390 (3)
C13—H13	0.9500	C4—H4	0.9500
C11—C10	1.391 (3)	C7—H7	0.9500
C11—C12	1.394 (3)	C10—H10	0.9500
C11—C14	1.442 (3)	C3—H3	0.9500
C2—S1—C1	104.00 (10)	C10—C9—C8	121.13 (19)
C7—C6—C5	118.50 (18)	C10—C9—H9	119.4
C7—C6—C8	120.58 (17)	C8—C9—H9	119.4
C5—C6—C8	120.91 (18)	S1—C1—H1A	109.5
C3—C2—C7	119.26 (19)	S1—C1—H1B	109.5
C3—C2—S1	124.36 (15)	H1A—C1—H1B	109.5
C7—C2—S1	116.39 (15)	S1—C1—H1C	109.5
C12—C13—C8	121.20 (18)	H1A—C1—H1C	109.5
C12—C13—H13	119.4	H1B—C1—H1C	109.5
C8—C13—H13	119.4	C5—C4—C3	121.11 (19)
C10—C11—C12	120.09 (19)	C5—C4—H4	119.4
C10—C11—C14	119.72 (19)	C3—C4—H4	119.4
C12—C11—C14	120.18 (19)	C6—C7—C2	121.52 (18)
C9—C8—C13	118.33 (19)	C6—C7—H7	119.2
C9—C8—C6	120.83 (18)	C2—C7—H7	119.2
C13—C8—C6	120.83 (17)	N1—C14—C11	178.7 (2)
C13—C12—C11	119.45 (19)	C9—C10—C11	119.78 (18)
C13—C12—H12	120.3	C9—C10—H10	120.1
C11—C12—H12	120.3	C11—C10—H10	120.1
C4—C5—C6	120.01 (19)	C4—C3—C2	119.58 (19)
C4—C5—H5	120.0	C4—C3—H3	120.2
C6—C5—H5	120.0	C2—C3—H3	120.2
C1—S1—C2—C3	−5.6 (2)	C6—C8—C9—C10	−179.06 (18)
C1—S1—C2—C7	174.60 (15)	C6—C5—C4—C3	−1.0 (3)
C12—C13—C8—C9	−0.8 (3)	C5—C6—C7—C2	0.8 (3)
C12—C13—C8—C6	178.35 (19)	C8—C6—C7—C2	179.90 (17)
C7—C6—C8—C9	30.4 (3)	C3—C2—C7—C6	−1.2 (3)
C5—C6—C8—C9	−150.53 (19)	S1—C2—C7—C6	178.57 (15)
C7—C6—C8—C13	−148.74 (19)	C10—C11—C14—N1	−58 (11)
C5—C6—C8—C13	30.3 (3)	C12—C11—C14—N1	121 (11)
C8—C13—C12—C11	0.7 (3)	C8—C9—C10—C11	0.7 (3)
C10—C11—C12—C13	0.1 (3)	C12—C11—C10—C9	−0.8 (3)
C14—C11—C12—C13	−178.76 (19)	C14—C11—C10—C9	178.1 (2)
C7—C6—C5—C4	0.3 (3)	C5—C4—C3—C2	0.6 (3)
C8—C6—C5—C4	−178.81 (18)	C7—C2—C3—C4	0.5 (3)
C13—C8—C9—C10	0.1 (3)	S1—C2—C3—C4	−179.27 (16)