O-Methyl N-phenyl­thio­carbamate

The central CNC(=S)O entity in MeOC(=S)N(H)Ph, C₈H₉NOS, is effectively planar and shows that the mol­ecule exists as a thione. In the crystal structure, mol­ecules related by a centre of symmetry are associated via N—H...S interactions, forming thio­amide dimers.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.108
• Data-to-parameter ratio = 23.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHEXLTL.

(I)

Crystal data

C8H9NOS	Z = 2
Mr = 167.22	F(000) = 176
Triclinic, P1	Dx = 1.342 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.8261 (4) Å	Cell parameters from 2429 reflections
b = 8.3209 (5) Å	θ = 2.4–30.0°
c = 9.6602 (6) Å	µ = 0.33 mm^−1
α = 65.216 (2)°	T = 223 K
β = 76.823 (2)°	Block, colourless
γ = 84.066 (3)°	0.55 × 0.42 × 0.30 mm
V = 413.97 (5) Å^3

Data collection

Bruker AXS SMART CCD diffractometer	2128 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 30.0°, θmin = 2.4°
ω scans	h = −4→8
3446 measured reflections	k = −11→11
2365 independent reflections	l = −12→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.0605P] where P = (Fo^2 + 2Fc^2)/3
2365 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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. The H atoms were introduced at calculated positions as riding atoms, with bond lengths of 0.87(N—H), 0.94(CH-aromatic), and 0.97(CH₃) Å. The displacement parameters were made equal to 1.2(CH, NH) or 1.5(CH₃) times thoses of the parent atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.30544 (5)	0.13898 (4)	0.32984 (3)	0.03933 (12)
O1	0.43584 (15)	0.30771 (11)	0.47978 (10)	0.0368 (2)
N1	0.10424 (18)	0.15787 (14)	0.59683 (12)	0.0359 (2)
H1	−0.0064	0.0946	0.5976	0.043*
C1	0.28310 (19)	0.20305 (14)	0.47483 (13)	0.0301 (2)
C2	0.07654 (19)	0.20352 (14)	0.72708 (12)	0.0307 (2)
C3	0.2424 (2)	0.15048 (17)	0.81988 (14)	0.0375 (2)
H3	0.3776	0.0873	0.7959	0.045*
C4	0.2082 (2)	0.19096 (18)	0.94856 (14)	0.0421 (3)
H4	0.3212	0.1557	1.0116	0.051*
C5	0.0104 (3)	0.28228 (19)	0.98431 (15)	0.0450 (3)
H5	−0.0118	0.3097	1.0715	0.054*
C6	−0.1556 (3)	0.3337 (2)	0.89220 (18)	0.0511 (3)
H6	−0.2917	0.3953	0.9174	0.061*
C7	−0.1234 (2)	0.29514 (19)	0.76248 (16)	0.0427 (3)
H7	−0.2364	0.3310	0.6994	0.051*
C8	0.6471 (2)	0.35787 (19)	0.36045 (16)	0.0442 (3)
H8A	0.7408	0.4338	0.3791	0.066*
H8B	0.6051	0.4210	0.2594	0.066*
H8C	0.7376	0.2526	0.3625	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.04375 (19)	0.0494 (2)	0.03336 (18)	−0.00461 (13)	−0.00479 (12)	−0.02573 (14)
O1	0.0395 (4)	0.0402 (4)	0.0342 (4)	−0.0124 (3)	0.0010 (3)	−0.0202 (3)
N1	0.0343 (5)	0.0464 (5)	0.0356 (5)	−0.0095 (4)	−0.0017 (4)	−0.0256 (4)
C1	0.0327 (5)	0.0308 (5)	0.0301 (5)	−0.0003 (4)	−0.0074 (4)	−0.0152 (4)
C2	0.0332 (5)	0.0326 (5)	0.0290 (5)	−0.0071 (4)	−0.0007 (4)	−0.0163 (4)
C3	0.0380 (6)	0.0430 (6)	0.0350 (6)	0.0028 (5)	−0.0063 (4)	−0.0205 (5)
C4	0.0491 (7)	0.0486 (7)	0.0316 (6)	−0.0032 (5)	−0.0091 (5)	−0.0182 (5)
C5	0.0576 (8)	0.0479 (7)	0.0331 (6)	−0.0068 (6)	0.0005 (5)	−0.0235 (5)
C6	0.0501 (8)	0.0590 (8)	0.0493 (8)	0.0100 (6)	−0.0020 (6)	−0.0336 (7)
C7	0.0379 (6)	0.0523 (7)	0.0424 (6)	0.0045 (5)	−0.0076 (5)	−0.0249 (6)
C8	0.0408 (6)	0.0494 (7)	0.0403 (6)	−0.0151 (5)	0.0034 (5)	−0.0190 (5)

Geometric parameters (Å, º)

S1—C1	1.6708 (11)	C4—C5	1.372 (2)
O1—C1	1.3293 (13)	C4—H4	0.9400
O1—C8	1.4400 (15)	C5—C6	1.377 (2)
N1—C1	1.3288 (15)	C5—H5	0.9400
N1—C2	1.4314 (13)	C6—C7	1.3877 (19)
N1—H1	0.8700	C6—H6	0.9400
C2—C7	1.3814 (17)	C7—H7	0.9400
C2—C3	1.3810 (17)	C8—H8A	0.9700
C3—C4	1.3867 (16)	C8—H8B	0.9700
C3—H3	0.9400	C8—H8C	0.9700
C1—O1—C8	118.72 (9)	C6—C5—C4	119.88 (12)
C1—N1—C2	126.10 (10)	C6—C5—H5	120.1
C1—N1—H1	116.9	C4—C5—H5	120.1
C2—N1—H1	116.9	C5—C6—C7	120.49 (12)
S1—C1—O1	124.48 (8)	C5—C6—H6	119.8
S1—C1—N1	122.98 (9)	C7—C6—H6	119.8
O1—C1—N1	112.51 (9)	C2—C7—C6	119.27 (12)
N1—C2—C7	119.02 (11)	C2—C7—H7	120.4
N1—C2—C3	120.52 (10)	C6—C7—H7	120.4
C3—C2—C7	120.41 (11)	O1—C8—H8A	109.5
C4—C3—C2	119.60 (11)	O1—C8—H8B	109.5
C4—C3—H3	120.2	H8A—C8—H8B	109.5
C2—C3—H3	120.2	O1—C8—H8C	109.5
C3—C4—C5	120.35 (12)	H8A—C8—H8C	109.5
C3—C4—H4	119.8	H8B—C8—H8C	109.5
C5—C4—H4	119.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.87	2.51	3.3587 (12)	165

Symmetry code: (i) −x, −y, −z+1.