S-Phenyl 4-cyano­thio­benzoate

Mol­ecules of the title compound, C₁₄H₉NOS, exhibit a chiral non-planar structure in which the 4-cyano­phenyl and S-phenyl rings are tilted at dihedral angles of 1.81 (2) and 72.49 (1)° with respect to the central thio­carbonate unit.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.077
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...     595.80 Ang-3
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C51    ...       1.45 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14    ..  O1      ..       2.75 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H15    ..  O1      ..       2.96 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  O1      ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  N5      ..       2.88 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13    ..  N5      ..       2.99 Ang.

Alert level G
HYDTR01_ALERT_1_G  Extra text has been found in the _refine_ls_hydrogen_treatment fi
            Explanatory text should be in the _publ_section_refinement field.
            Hydrogen treatment given as constr.
            Hydrogen treatment identified as  constr
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           25.05
           From the CIF: _reflns_number_total               2068
           Count of symmetry unique reflns         1136
           Completeness (_total/calc)            182.04%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       932
           Fraction of Friedel pairs measured     0.820
           Are heavy atom types Z>Si present        yes

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

   3 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
   6 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

In previous papers on the vibrational spectra and theoretical analysis of S-phenyl 4-substituted-thiobenzoates, we have assigned and interpreted the characteristic IR bands and predicted their molecular structures using the possibilities of linear-dichroic infrared spectroscopy (Arnaudov et al., 2003; Ivanova & Arnaudov, 2003). With the goal of comparing an experimental structure with the predictions of IR–LD spectroscopic analysis and ab initio calculations, we have now determined the single-crystal X-ray structure of the title compound, (I).

Molecules of (I) are chiral due to the fact that the S-phenyl ring is twisted by 72.49 (1)° out of the plane of thiocarbonate function to minimize the O1···C16 contact. In contrast, the 4-cyanophenyl ring (C2–C7) is almost coplanar with the central thiocarbonate unit and exhibits an interplanar angle of only 1.81 (2)°. Our IR–LD spectral analysis and ab initio calculations predicted interplanar angles of 90.8 (6) and 0.0 (1)°, respectively. The experimental and theoretical metrical parameters obtained for (I) are closely similar.

Compound (I) crystallizes in the chiral monoclinic space group P2₁ and participates in very weak intermolecular hydrogen bridges (Table 1). The observed structure of (I) is in good agreement with those determined for other S-phenyl thiobenzoates (Allouchi et al., 1995; Chrusciel et al., 1995; Ganesh et al., 2005; Jovanovski et al., 1993; Karczmarcyk or Karczmarzyk et al., 2001; Low et al., 2000; Sakamoto et al., 1996; Takahashi, Sekine et al., 1998; Takahashi, Fujita et al., 1998).

S2. Experimental

The title compound was purchased as a white powder from Merck. 0.532 g were dissolved in 5 ml of methanol and the solution left (2.22 mmol) to stand to afford white crystals of (I) within 5 days. Elemental analysis for C₁₄H₉NOS found: C 70.2, H 2.8, N 5.9%; calculated: C 70.3, H 3.8, N 5.9%; FAB–MS (Fisons VG Autospec) m/z 238.3 (100%).

S3. Refinement

The H atoms were refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_iso(C). The highest peak in the final difference synthesis is 0.87 Å from atom S1 and the deepest hole is 0.80 Å from this atom.

Computing details

Data collection: R3m/V User's Guide (Siemens, 1989); cell refinement: R3m/V User's Guide; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% propability level.
	Fig. 2. Projection of the structure of (I) perpendicular to [010].

(S)-Phenyl 4-cyanothiobenzoate

Crystal data

C14H9NOS	F(000) = 248
Mr = 239.28	Dx = 1.334 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 15 reflections
a = 7.499 (5) Å	θ = 7.6–15.8°
b = 7.835 (3) Å	µ = 0.25 mm^−1
c = 10.624 (7) Å	T = 294 K
β = 107.37 (8)°	Needle, colourless
V = 595.8 (6) Å^3	0.59 × 0.26 × 0.21 mm
Z = 2

Data collection

Siemens P4 four-circle diffractometer	1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 25.1°, θmin = 2.0°
ω scans	h = −1→8
Absorption correction: psi-scan (XPREP in SHELXTL-Plus; Sheldrick, 1995)	k = −9→9
Tmin = 0.928, Tmax = 0.947	l = −12→12
2572 measured reflections	3 standard reflections every 100 reflections
2068 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 0.1314P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.18 e Å^−3
2068 reflections	Δρmin = −0.23 e Å^−3
155 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.016 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 942 Friedel Pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.05 (8)

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	0.00671 (8)	0.46646 (9)	0.95738 (6)	0.0590 (2)
O1	−0.2488 (3)	0.2794 (3)	0.79479 (18)	0.0690 (6)
C1	−0.0973 (3)	0.3421 (3)	0.8160 (2)	0.0446 (6)
C2	0.0193 (3)	0.3200 (3)	0.7239 (2)	0.0423 (5)
C3	−0.0560 (4)	0.2281 (3)	0.6093 (3)	0.0555 (7)
H3	−0.1759	0.1834	0.5908	0.067*
C4	0.0458 (4)	0.2023 (4)	0.5222 (3)	0.0594 (8)
H4	−0.0053	0.1395	0.4456	0.071*
C5	0.2223 (4)	0.2692 (3)	0.5485 (2)	0.0535 (6)
C51	0.3299 (5)	0.2384 (4)	0.4577 (3)	0.0745 (9)
N5	0.4122 (5)	0.2126 (5)	0.3861 (3)	0.1095 (12)
C6	0.2980 (3)	0.3628 (4)	0.6617 (3)	0.0572 (7)
H6	0.4170	0.4093	0.6791	0.069*
C7	0.1959 (3)	0.3873 (3)	0.7492 (2)	0.0503 (6)
H7	0.2472	0.4498	0.8259	0.060*
C11	−0.1729 (3)	0.4720 (4)	1.0344 (2)	0.0454 (5)
C12	−0.1510 (4)	0.3854 (3)	1.1498 (2)	0.0531 (6)
H12	−0.0443	0.3202	1.1858	0.064*
C13	−0.2875 (4)	0.3947 (4)	1.2132 (2)	0.0583 (7)
H13	−0.2727	0.3348	1.2912	0.070*
C14	−0.4434 (3)	0.4912 (4)	1.1617 (2)	0.0550 (6)
H14	−0.5350	0.4969	1.2043	0.066*
C15	−0.4649 (4)	0.5799 (3)	1.0466 (3)	0.0542 (6)
H15	−0.5708	0.6466	1.0120	0.065*
C16	−0.3310 (3)	0.5710 (3)	0.9820 (2)	0.0514 (6)
H16	−0.3465	0.6309	0.9038	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0491 (3)	0.0726 (4)	0.0633 (4)	−0.0142 (4)	0.0288 (3)	−0.0210 (4)
O1	0.0520 (11)	0.0935 (16)	0.0704 (12)	−0.0275 (10)	0.0318 (10)	−0.0261 (11)
C1	0.0416 (13)	0.0484 (14)	0.0470 (13)	−0.0020 (11)	0.0182 (10)	0.0013 (11)
C2	0.0423 (12)	0.0446 (13)	0.0413 (12)	0.0009 (10)	0.0143 (9)	0.0018 (10)
C3	0.0500 (14)	0.0653 (17)	0.0532 (14)	−0.0085 (13)	0.0186 (12)	−0.0071 (13)
C4	0.064 (2)	0.0669 (18)	0.0497 (17)	−0.0013 (15)	0.0208 (14)	−0.0085 (13)
C5	0.0573 (16)	0.0627 (16)	0.0477 (13)	0.0138 (13)	0.0267 (13)	0.0081 (12)
C51	0.077 (2)	0.090 (2)	0.0694 (18)	0.0110 (18)	0.0426 (17)	0.0064 (17)
N5	0.125 (3)	0.135 (3)	0.099 (2)	0.013 (2)	0.080 (2)	−0.004 (2)
C6	0.0429 (13)	0.0723 (18)	0.0600 (15)	0.0008 (13)	0.0211 (12)	0.0038 (14)
C7	0.0413 (13)	0.0662 (15)	0.0449 (12)	−0.0032 (12)	0.0149 (10)	−0.0029 (11)
C11	0.0428 (12)	0.0495 (12)	0.0475 (11)	−0.0009 (14)	0.0192 (10)	−0.0096 (13)
C12	0.0530 (14)	0.0550 (14)	0.0511 (14)	0.0079 (12)	0.0149 (12)	−0.0019 (12)
C13	0.0670 (17)	0.0646 (16)	0.0467 (14)	0.0036 (14)	0.0224 (13)	0.0013 (12)
C14	0.0541 (13)	0.0618 (17)	0.0568 (14)	−0.0034 (14)	0.0285 (11)	−0.0142 (14)
C15	0.0479 (14)	0.0556 (15)	0.0612 (16)	0.0038 (12)	0.0194 (13)	−0.0080 (12)
C16	0.0559 (15)	0.0516 (15)	0.0479 (14)	−0.0006 (12)	0.0176 (12)	−0.0024 (12)

Geometric parameters (Å, º)

S1—C1	1.765 (3)	C6—H6	0.9300
S1—C11	1.773 (2)	C7—H7	0.9300
O1—C1	1.195 (3)	C11—C12	1.368 (3)
C1—C2	1.505 (3)	C11—C16	1.387 (3)
C2—C7	1.375 (3)	C12—C13	1.385 (3)
C2—C3	1.382 (3)	C12—H12	0.9300
C3—C4	1.379 (4)	C13—C14	1.362 (4)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.373 (4)	C14—C15	1.373 (4)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.378 (4)	C15—C16	1.377 (3)
C5—C51	1.450 (4)	C15—H15	0.9300
C51—N5	1.131 (3)	C16—H16	0.9300
C6—C7	1.383 (3)
C1—S1—C11	101.68 (12)	C2—C7—H7	119.7
O1—C1—C2	122.3 (2)	C6—C7—H7	119.7
O1—C1—S1	122.74 (18)	C12—C11—C16	119.8 (2)
C2—C1—S1	114.95 (17)	C12—C11—S1	119.82 (19)
C7—C2—C3	119.2 (2)	C16—C11—S1	120.30 (19)
C7—C2—C1	122.8 (2)	C11—C12—C13	120.1 (2)
C3—C2—C1	118.0 (2)	C11—C12—H12	120.0
C4—C3—C2	120.4 (2)	C13—C12—H12	120.0
C4—C3—H3	119.8	C14—C13—C12	120.3 (2)
C2—C3—H3	119.8	C14—C13—H13	119.9
C5—C4—C3	120.1 (3)	C12—C13—H13	119.9
C5—C4—H4	120.0	C13—C14—C15	119.8 (2)
C3—C4—H4	120.0	C13—C14—H14	120.1
C4—C5—C6	120.1 (2)	C15—C14—H14	120.1
C4—C5—C51	119.7 (3)	C14—C15—C16	120.6 (2)
C6—C5—C51	120.2 (3)	C14—C15—H15	119.7
N5—C51—C5	179.0 (4)	C16—C15—H15	119.7
C5—C6—C7	119.6 (2)	C15—C16—C11	119.4 (2)
C5—C6—H6	120.2	C15—C16—H16	120.3
C7—C6—H6	120.2	C11—C16—H16	120.3
C2—C7—C6	120.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1^i	0.93	2.75	3.359 (3)	124
C15—H15···O1^i	0.93	2.96	3.472 (4)	116
C6—H6···O1^ii	0.93	2.64	3.333 (4)	132
C6—H6···N5^iii	0.93	2.88	3.626 (4)	138
C13—H13···N5^iv	0.93	2.99	3.599 (4)	125

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