Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025846/hk2259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025846/hk2259Isup2.hkl |
CCDC reference: 654851
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.057
- wR factor = 0.152
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Compound (I) was prepared by refluxing 3-methoxyphenyl isothiocyanate (1.65 g, 10 mmol) with absolute ethanol (50 ml) using a literature procedure (Ho et al., 2005). The white precipitate, which was obtained upon concentration of the reaction solution, was dissolved in hot dichloromethane and layered with ethanol, which resulted in the formation of colorless crystals (yield: 1.32 g, 80%, m.p. 425–427 K).
H atom of NH group was located in difference syntheses and refined isotropically [N—H = 0.87 (3) Å and Uiso(H) = 0.059 (8) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93, 0.96 and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
The title compound, (I), was investigated as a part of a study of related O-alkyl thiocarbamate molecules (Ho et al., 2005) and their phosphine gold(I) complexes (Ho et al., 2006).
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar A (O2/C6/C10) and B (S1/O1/N1/C1—C4) moieties and benzene ring C (C1—C6) are A/B = 8.72 (3)°, A/C = 3.12 (3)° and B/C = 11.47 (2)°. The C3—S1 [1.663 (2) Å] bond distance indicates that the molecule is in the thione form; the conformation about the central C—N bond is E.
The intramolecular C—H···O and intermolecular N—H···S hydrogen bonds (Table 1) may be effective in the stabilization of the crystal structure.
For general backgroud, see: Allen et al. (1987). For related literature, see: Ho et al. (2005, 2006).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick,1997); program(s) used to refine structure: SHELXL97 (Sheldrick,1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003)..
C10H13NO2S | F(000) = 448 |
Mr = 211.27 | Dx = 1.305 Mg m−3 |
Monoclinic, P21/n | Melting point: 425(2) K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 14.931 (3) Å | Cell parameters from 1520 reflections |
b = 4.866 (1) Å | θ = 2.7–24.9° |
c = 15.538 (3) Å | µ = 0.28 mm−1 |
β = 107.75 (3)° | T = 294 K |
V = 1075.2 (4) Å3 | Block, colorless |
Z = 4 | 0.46 × 0.26 × 0.20 mm |
Bruker APEX II diffractometer | 2089 independent reflections |
Radiation source: fine-focus sealed tube | 1596 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = 0→18 |
Tmin = 0.879, Tmax = 0.946 | k = 0→5 |
2170 measured reflections | l = −19→18 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0832P)2 + 0.1652P] where P = (Fo2 + 2Fc2)/3 |
2089 reflections | (Δ/σ)max = 0.001 |
133 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C10H13NO2S | V = 1075.2 (4) Å3 |
Mr = 211.27 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.931 (3) Å | µ = 0.28 mm−1 |
b = 4.866 (1) Å | T = 294 K |
c = 15.538 (3) Å | 0.46 × 0.26 × 0.20 mm |
β = 107.75 (3)° |
Bruker APEX II diffractometer | 2089 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1596 reflections with I > 2σ(I) |
Tmin = 0.879, Tmax = 0.946 | Rint = 0.022 |
2170 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.38 e Å−3 |
2089 reflections | Δρmin = −0.46 e Å−3 |
133 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6768 (2) | 1.1857 (7) | 0.39864 (18) | 0.0726 (8) | |
H1A | 0.6188 | 1.2469 | 0.4067 | 0.109* | |
H1B | 0.7273 | 1.3002 | 0.4333 | 0.109* | |
H1C | 0.6885 | 0.9988 | 0.4187 | 0.109* | |
C2 | 0.67037 (17) | 1.2031 (6) | 0.30106 (17) | 0.0558 (6) | |
H2A | 0.6543 | 1.3885 | 0.2787 | 0.067* | |
H2B | 0.7299 | 1.1531 | 0.2923 | 0.067* | |
C3 | 0.56958 (16) | 1.0016 (5) | 0.16453 (15) | 0.0472 (6) | |
C4 | 0.44867 (16) | 0.6494 (5) | 0.17244 (16) | 0.0473 (6) | |
C5 | 0.46054 (18) | 0.6384 (5) | 0.26386 (17) | 0.0557 (6) | |
H5 | 0.5033 | 0.7549 | 0.3032 | 0.067* | |
C6 | 0.40873 (18) | 0.4539 (5) | 0.29714 (18) | 0.0548 (6) | |
C7 | 0.34422 (18) | 0.2818 (6) | 0.2405 (2) | 0.0613 (7) | |
H7 | 0.3093 | 0.1585 | 0.2630 | 0.074* | |
C8 | 0.3328 (2) | 0.2977 (6) | 0.1490 (2) | 0.0705 (8) | |
H8 | 0.2888 | 0.1843 | 0.1096 | 0.085* | |
C9 | 0.38430 (19) | 0.4755 (6) | 0.11432 (18) | 0.0624 (7) | |
H9 | 0.3762 | 0.4795 | 0.0526 | 0.075* | |
C10 | 0.3885 (3) | 0.2534 (7) | 0.4304 (2) | 0.0796 (9) | |
H10A | 0.3212 | 0.2683 | 0.4096 | 0.119* | |
H10B | 0.4106 | 0.2764 | 0.4948 | 0.119* | |
H10C | 0.4068 | 0.0757 | 0.4149 | 0.119* | |
N1 | 0.49870 (15) | 0.8261 (4) | 0.13049 (15) | 0.0520 (5) | |
O1 | 0.59723 (11) | 1.0119 (4) | 0.25404 (10) | 0.0557 (5) | |
O2 | 0.42811 (17) | 0.4596 (5) | 0.38897 (14) | 0.0848 (7) | |
S1 | 0.61763 (5) | 1.18383 (16) | 0.09943 (4) | 0.0622 (3) | |
H1 | 0.4762 (19) | 0.813 (6) | 0.072 (2) | 0.059 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0718 (17) | 0.095 (2) | 0.0482 (14) | −0.0156 (17) | 0.0135 (13) | −0.0013 (15) |
C2 | 0.0533 (13) | 0.0623 (16) | 0.0503 (13) | −0.0124 (12) | 0.0134 (11) | 0.0039 (12) |
C3 | 0.0488 (12) | 0.0462 (13) | 0.0456 (12) | 0.0041 (11) | 0.0126 (9) | 0.0063 (10) |
C4 | 0.0500 (12) | 0.0399 (13) | 0.0509 (12) | 0.0040 (10) | 0.0136 (10) | 0.0069 (10) |
C5 | 0.0599 (14) | 0.0531 (15) | 0.0545 (14) | −0.0074 (12) | 0.0181 (11) | 0.0019 (12) |
C6 | 0.0584 (14) | 0.0501 (14) | 0.0593 (14) | 0.0019 (12) | 0.0230 (12) | 0.0057 (12) |
C7 | 0.0529 (14) | 0.0526 (16) | 0.0768 (18) | −0.0034 (12) | 0.0175 (12) | 0.0162 (14) |
C8 | 0.0651 (17) | 0.0644 (19) | 0.0716 (18) | −0.0197 (14) | 0.0052 (14) | 0.0072 (15) |
C9 | 0.0656 (15) | 0.0607 (17) | 0.0528 (14) | −0.0098 (13) | 0.0059 (12) | 0.0093 (13) |
C10 | 0.100 (2) | 0.078 (2) | 0.0716 (19) | −0.0127 (18) | 0.0423 (17) | 0.0170 (16) |
N1 | 0.0602 (12) | 0.0513 (13) | 0.0428 (11) | −0.0061 (10) | 0.0134 (9) | 0.0024 (9) |
O1 | 0.0588 (10) | 0.0622 (11) | 0.0434 (9) | −0.0128 (8) | 0.0116 (7) | 0.0052 (8) |
O2 | 0.1115 (16) | 0.0883 (16) | 0.0626 (12) | −0.0362 (14) | 0.0383 (12) | 0.0054 (11) |
S1 | 0.0624 (4) | 0.0757 (5) | 0.0499 (4) | −0.0128 (3) | 0.0190 (3) | 0.0094 (3) |
N1—H1 | 0.87 (3) | C5—C6 | 1.384 (3) |
C1—C2 | 1.492 (4) | C5—H5 | 0.9300 |
C1—H1A | 0.9600 | C6—O2 | 1.367 (3) |
C1—H1B | 0.9600 | C6—C7 | 1.374 (4) |
C1—H1C | 0.9600 | C7—C8 | 1.381 (4) |
C2—O1 | 1.451 (3) | C7—H7 | 0.9300 |
C2—H2A | 0.9600 | C8—C9 | 1.372 (4) |
C2—H2B | 0.9600 | C8—H8 | 0.9300 |
C3—O1 | 1.326 (3) | C9—H9 | 0.9300 |
C3—N1 | 1.337 (3) | C10—O2 | 1.415 (3) |
C3—S1 | 1.663 (2) | C10—H10A | 0.9600 |
C4—C5 | 1.378 (3) | C10—H10B | 0.9600 |
C4—C9 | 1.388 (4) | C10—H10C | 0.9600 |
C4—N1 | 1.421 (3) | ||
O1—C2—C1 | 106.3 (2) | O2—C6—C5 | 114.3 (2) |
O1—C3—N1 | 113.3 (2) | C7—C6—C5 | 121.2 (2) |
O1—C3—S1 | 124.31 (18) | C6—C7—C8 | 117.9 (2) |
N1—C3—S1 | 122.42 (18) | C9—C8—C7 | 122.1 (3) |
C5—C4—C9 | 119.5 (2) | C8—C9—C4 | 119.3 (3) |
C5—C4—N1 | 125.2 (2) | C3—N1—C4 | 131.9 (2) |
C9—C4—N1 | 115.3 (2) | C6—N1—H1B | 82.0 |
C4—C5—C6 | 120.0 (2) | C3—O1—C2 | 119.90 (18) |
O2—C6—C7 | 124.4 (2) | C6—O2—C10 | 118.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.87 (3) | 2.60 (3) | 3.464 (2) | 170.0 (3) |
C5—H5···O1 | 0.93 | 2.18 | 2.772 (3) | 120 |
Symmetry code: (i) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H13NO2S |
Mr | 211.27 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 14.931 (3), 4.866 (1), 15.538 (3) |
β (°) | 107.75 (3) |
V (Å3) | 1075.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.46 × 0.26 × 0.20 |
Data collection | |
Diffractometer | Bruker APEX II |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.879, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2170, 2089, 1596 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.152, 1.14 |
No. of reflections | 2089 |
No. of parameters | 133 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.46 |
Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXS97 (Sheldrick,1997), SHELXL97 (Sheldrick,1997), SHELXTL (Bruker, 1999), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003)..
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.87 (3) | 2.60 (3) | 3.464 (2) | 170.0 (3) |
C5—H5···O1 | 0.93 | 2.18 | 2.772 (3) | 120 |
Symmetry code: (i) −x+1, −y+2, −z. |
The title compound, (I), was investigated as a part of a study of related O-alkyl thiocarbamate molecules (Ho et al., 2005) and their phosphine gold(I) complexes (Ho et al., 2006).
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar A (O2/C6/C10) and B (S1/O1/N1/C1—C4) moieties and benzene ring C (C1—C6) are A/B = 8.72 (3)°, A/C = 3.12 (3)° and B/C = 11.47 (2)°. The C3—S1 [1.663 (2) Å] bond distance indicates that the molecule is in the thione form; the conformation about the central C—N bond is E.
The intramolecular C—H···O and intermolecular N—H···S hydrogen bonds (Table 1) may be effective in the stabilization of the crystal structure.