Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045734/bv2071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045734/bv2071Isup2.hkl |
CCDC reference: 663813
Key indicators
- Single-crystal X-ray study
- T = 98 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.069
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.506 1.000 Tmin(prime) and Tmax expected: 0.898 0.995 RR(prime) = 0.561 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.56
Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. S1 .. 3.14 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H6 .. S1 .. 3.17 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported C6 .. S1 .. 4.04 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.995 Tmax scaled 0.995 Tmin scaled 0.503 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 26.50 From the CIF: _reflns_number_total 2202 Count of symmetry unique reflns 1357 Completeness (_total/calc) 162.27% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 845 Fraction of Friedel pairs measured 0.623 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of indazole (1.18 g, 10 mmol) in dry n-hexane (25 ml) was treated with solid NaH (55%, 0.44 g, 10 mmol) under an N2 atmosphere. Liberation of H2 stopped after 3 h stirring. PhNCS (1.2 ml, 10 mmol) was added to the resulting suspension of [Na][Indz] and the reaction was continued overnight at r.t. The suspension was filtered using a fritted funnel and the collected white solid, [Na][PhNCSIndz], was washed with cold n-hexane (3 x 10 ml) and dried in vacuo; yield 2.60 g, 95%. M.p. = 240 °C (melting along with colour change and decomposition). Colourless crystals of (I) were obtained unintentionally as the decomposition product of an authenticated sample of Bu2Sn(PhNCSIndz)2 during attempts to grow crystals from heptane solution in air; M.p. = 90 °C.
All C– and N-bound H atoms were included in the riding-model approximation, with C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C, N).
The preparation and crystal structures of series of compounds containing molecules related to the title compound (I), i.e. with the general formula PhNC(=S)R (R = pyrazolyl, 3,5-dimethylpyrazolyl and 3,5-diphenylpyrazolyl) and PhNC(=S)NRR' (R = alkyl or aryl) have been reported recently (Hossaini Sadr, Sardroodi et al., 2005; Hossaini Sadr, Jalili et al., 2005; Henderson et al., 2006). Compound (I) exists as a thione, C8=S1 is 1.6545 (19) Å, and the conformation about the C8—N3 bond is Z. The molecule is non-planar as the phenyl ring is twisted out of the plane of the central chromophore as manifested in the C8/N3/C9/C10 torsion angle of 51.7 (2)°. In the crystal structure, molecules related by 2-fold symmetry associate via N—H···N hydrogen bonds, Table 1. Pairs of molecules are connected by C—H···π interactions [C1—H1···Cg(C9—C14) = 2.47 Å for symmetry operation 1 - x, 1 + y, -z] on either side to form columns parallel to the b axis. Connections between columns are afforded by weak C—H···S interactions; the S1 forms two such contacts with different molecules of the adjacent chain, Table 1. A view of the unit-cell contents is shown in Fig. 2.
For related literature, see: Hossaini Sadr, Sardroodi et al. (2005); Hossaini Sadr, Jalili et al. (2005); Henderson et al. (2006).
Data collection: CrystalClear (Rigaku Americas Corporation, 2005); cell refinement: CrystalClear (Rigaku Americas Corporation, 2005); data reduction: CrystalClear (Rigaku Americas Corporation, 2005); 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) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C14H11N3S | F(000) = 528 |
Mr = 253.32 | Dx = 1.416 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: C 2y | Cell parameters from 5144 reflections |
a = 20.408 (8) Å | θ = 3.4–29.6° |
b = 5.690 (2) Å | µ = 0.26 mm−1 |
c = 11.949 (5) Å | T = 98 K |
β = 121.110 (14)° | Prism, colourless |
V = 1188.0 (8) Å3 | 0.42 × 0.12 × 0.02 mm |
Z = 4 |
Rigaku AFC12κ/SATURN724 diffractometer | 2202 independent reflections |
Radiation source: fine-focus sealed tube | 2160 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 26.5°, θmin = 2.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −25→25 |
Tmin = 0.506, Tmax = 1.000 | k = −7→6 |
6334 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.0306P)2 + 1.0876P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2202 reflections | Δρmax = 0.22 e Å−3 |
163 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 845 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (7) |
C14H11N3S | V = 1188.0 (8) Å3 |
Mr = 253.32 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 20.408 (8) Å | µ = 0.26 mm−1 |
b = 5.690 (2) Å | T = 98 K |
c = 11.949 (5) Å | 0.42 × 0.12 × 0.02 mm |
β = 121.110 (14)° |
Rigaku AFC12κ/SATURN724 diffractometer | 2202 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2160 reflections with I > 2σ(I) |
Tmin = 0.506, Tmax = 1.000 | Rint = 0.023 |
6334 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.069 | Δρmax = 0.22 e Å−3 |
S = 1.05 | Δρmin = −0.19 e Å−3 |
2202 reflections | Absolute structure: Flack (1983), 845 Friedel pairs |
163 parameters | Absolute structure parameter: 0.03 (7) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.53512 (3) | 0.82070 (8) | 0.39615 (4) | 0.02211 (12) | |
N1 | 0.45431 (9) | 1.0153 (3) | 0.15952 (14) | 0.0166 (3) | |
N2 | 0.43439 (9) | 1.0280 (3) | 0.02939 (14) | 0.0192 (3) | |
N3 | 0.55419 (8) | 0.7817 (3) | 0.19105 (13) | 0.0170 (3) | |
H3 | 0.5407 | 0.8284 | 0.1118 | 0.020* | |
C1 | 0.38502 (11) | 1.1986 (4) | −0.02293 (18) | 0.0205 (4) | |
H1 | 0.3618 | 1.2443 | −0.1119 | 0.025* | |
C2 | 0.36965 (9) | 1.3095 (4) | 0.06872 (15) | 0.0183 (4) | |
C3 | 0.32405 (11) | 1.4985 (4) | 0.0617 (2) | 0.0230 (4) | |
H3A | 0.2935 | 1.5815 | −0.0178 | 0.028* | |
C4 | 0.32458 (11) | 1.5613 (4) | 0.1736 (2) | 0.0244 (4) | |
H4 | 0.2943 | 1.6899 | 0.1717 | 0.029* | |
C5 | 0.36970 (11) | 1.4360 (4) | 0.29058 (19) | 0.0237 (4) | |
H5 | 0.3689 | 1.4827 | 0.3662 | 0.028* | |
C6 | 0.41493 (11) | 1.2485 (4) | 0.29997 (17) | 0.0215 (4) | |
H6 | 0.4448 | 1.1652 | 0.3796 | 0.026* | |
C7 | 0.41481 (10) | 1.1861 (3) | 0.18606 (17) | 0.0167 (4) | |
C8 | 0.51513 (10) | 0.8685 (3) | 0.24509 (16) | 0.0174 (4) | |
C9 | 0.61595 (10) | 0.6190 (3) | 0.25473 (16) | 0.0154 (4) | |
C10 | 0.60810 (11) | 0.4125 (4) | 0.30926 (17) | 0.0189 (4) | |
H10 | 0.5610 | 0.3779 | 0.3039 | 0.023* | |
C11 | 0.66871 (11) | 0.2582 (3) | 0.37105 (17) | 0.0205 (4) | |
H11 | 0.6635 | 0.1188 | 0.4095 | 0.025* | |
C12 | 0.73743 (10) | 0.3055 (4) | 0.37739 (16) | 0.0208 (4) | |
H12 | 0.7793 | 0.1996 | 0.4207 | 0.025* | |
C13 | 0.74437 (11) | 0.5080 (3) | 0.32012 (18) | 0.0201 (4) | |
H13 | 0.7908 | 0.5393 | 0.3226 | 0.024* | |
C14 | 0.68392 (10) | 0.6660 (3) | 0.25904 (17) | 0.0185 (4) | |
H14 | 0.6891 | 0.8054 | 0.2205 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0249 (2) | 0.0273 (3) | 0.0173 (2) | 0.0050 (2) | 0.01318 (17) | 0.0041 (2) |
N1 | 0.0174 (8) | 0.0192 (8) | 0.0148 (7) | 0.0017 (6) | 0.0094 (6) | 0.0010 (6) |
N2 | 0.0223 (8) | 0.0217 (9) | 0.0152 (7) | 0.0009 (7) | 0.0109 (6) | 0.0016 (6) |
N3 | 0.0174 (7) | 0.0209 (9) | 0.0143 (6) | 0.0022 (6) | 0.0093 (6) | 0.0031 (6) |
C1 | 0.0216 (9) | 0.0223 (10) | 0.0186 (9) | 0.0037 (8) | 0.0111 (7) | 0.0034 (8) |
C2 | 0.0162 (8) | 0.0204 (9) | 0.0195 (8) | −0.0004 (9) | 0.0101 (7) | −0.0003 (9) |
C3 | 0.0210 (10) | 0.0219 (10) | 0.0248 (10) | 0.0021 (8) | 0.0110 (8) | 0.0013 (8) |
C4 | 0.0196 (10) | 0.0234 (11) | 0.0323 (10) | 0.0033 (8) | 0.0149 (8) | −0.0027 (8) |
C5 | 0.0217 (10) | 0.0288 (11) | 0.0236 (10) | −0.0023 (9) | 0.0139 (8) | −0.0074 (8) |
C6 | 0.0201 (9) | 0.0276 (12) | 0.0203 (9) | −0.0011 (8) | 0.0129 (8) | −0.0024 (8) |
C7 | 0.0145 (9) | 0.0161 (9) | 0.0213 (9) | −0.0019 (7) | 0.0105 (7) | −0.0022 (7) |
C8 | 0.0162 (8) | 0.0189 (11) | 0.0170 (8) | −0.0020 (7) | 0.0086 (7) | −0.0004 (7) |
C9 | 0.0168 (9) | 0.0154 (9) | 0.0116 (8) | 0.0008 (7) | 0.0056 (7) | −0.0005 (7) |
C10 | 0.0191 (9) | 0.0203 (9) | 0.0168 (8) | −0.0011 (8) | 0.0091 (7) | −0.0006 (7) |
C11 | 0.0240 (10) | 0.0197 (11) | 0.0168 (8) | −0.0001 (8) | 0.0097 (7) | −0.0007 (7) |
C12 | 0.0175 (8) | 0.0219 (9) | 0.0180 (8) | 0.0024 (9) | 0.0055 (7) | −0.0035 (8) |
C13 | 0.0182 (9) | 0.0213 (10) | 0.0219 (9) | −0.0016 (8) | 0.0112 (8) | −0.0058 (8) |
C14 | 0.0199 (9) | 0.0181 (10) | 0.0182 (9) | −0.0020 (7) | 0.0104 (7) | −0.0018 (7) |
S1—C8 | 1.6545 (19) | C5—C6 | 1.377 (3) |
N1—N2 | 1.391 (2) | C5—H5 | 0.9500 |
N1—C7 | 1.399 (2) | C6—C7 | 1.405 (3) |
N1—C8 | 1.405 (2) | C6—H6 | 0.9500 |
N2—C1 | 1.303 (3) | C9—C14 | 1.387 (3) |
N3—C8 | 1.352 (2) | C9—C10 | 1.393 (3) |
N3—C9 | 1.426 (2) | C10—C11 | 1.379 (3) |
N3—H3 | 0.8800 | C10—H10 | 0.9500 |
C1—C2 | 1.432 (3) | C11—C12 | 1.391 (3) |
C1—H1 | 0.9500 | C11—H11 | 0.9500 |
C2—C3 | 1.396 (3) | C12—C13 | 1.384 (3) |
C2—C7 | 1.405 (3) | C12—H12 | 0.9500 |
C3—C4 | 1.378 (3) | C13—C14 | 1.390 (3) |
C3—H3A | 0.9500 | C13—H13 | 0.9500 |
C4—C5 | 1.407 (3) | C14—H14 | 0.9500 |
C4—H4 | 0.9500 | ||
N2—N1—C7 | 110.34 (14) | N1—C7—C2 | 106.18 (15) |
N2—N1—C8 | 118.84 (14) | N1—C7—C6 | 132.99 (17) |
C7—N1—C8 | 130.08 (15) | C2—C7—C6 | 120.82 (18) |
C1—N2—N1 | 106.36 (15) | N3—C8—N1 | 112.77 (15) |
C8—N3—C9 | 123.98 (14) | N3—C8—S1 | 125.95 (14) |
C8—N3—H3 | 118.0 | N1—C8—S1 | 121.26 (13) |
C9—N3—H3 | 118.0 | C14—C9—C10 | 120.00 (17) |
N2—C1—C2 | 112.47 (17) | C14—C9—N3 | 119.07 (16) |
N2—C1—H1 | 123.8 | C10—C9—N3 | 120.92 (17) |
C2—C1—H1 | 123.8 | C11—C10—C9 | 119.97 (18) |
C3—C2—C7 | 121.21 (16) | C11—C10—H10 | 120.0 |
C3—C2—C1 | 134.13 (17) | C9—C10—H10 | 120.0 |
C7—C2—C1 | 104.65 (17) | C10—C11—C12 | 120.40 (18) |
C4—C3—C2 | 118.07 (18) | C10—C11—H11 | 119.8 |
C4—C3—H3A | 121.0 | C12—C11—H11 | 119.8 |
C2—C3—H3A | 121.0 | C13—C12—C11 | 119.46 (18) |
C3—C4—C5 | 120.36 (19) | C13—C12—H12 | 120.3 |
C3—C4—H4 | 119.8 | C11—C12—H12 | 120.3 |
C5—C4—H4 | 119.8 | C12—C13—C14 | 120.55 (17) |
C6—C5—C4 | 122.72 (18) | C12—C13—H13 | 119.7 |
C6—C5—H5 | 118.6 | C14—C13—H13 | 119.7 |
C4—C5—H5 | 118.6 | C9—C14—C13 | 119.60 (18) |
C5—C6—C7 | 116.82 (17) | C9—C14—H14 | 120.2 |
C5—C6—H6 | 121.6 | C13—C14—H14 | 120.2 |
C7—C6—H6 | 121.6 | ||
C7—N1—N2—C1 | 0.2 (2) | C5—C6—C7—N1 | 177.58 (19) |
C8—N1—N2—C1 | −170.97 (16) | C5—C6—C7—C2 | −0.7 (3) |
N1—N2—C1—C2 | 0.3 (2) | C9—N3—C8—N1 | −176.69 (16) |
N2—C1—C2—C3 | 178.1 (2) | C9—N3—C8—S1 | 5.0 (3) |
N2—C1—C2—C7 | −0.7 (2) | N2—N1—C8—N3 | 9.0 (2) |
C7—C2—C3—C4 | 0.1 (3) | C7—N1—C8—N3 | −160.10 (18) |
C1—C2—C3—C4 | −178.5 (2) | N2—N1—C8—S1 | −172.60 (13) |
C2—C3—C4—C5 | −0.4 (3) | C7—N1—C8—S1 | 18.3 (3) |
C3—C4—C5—C6 | 0.2 (3) | C8—N3—C9—C14 | −129.93 (19) |
C4—C5—C6—C7 | 0.4 (3) | C8—N3—C9—C10 | 51.7 (2) |
N2—N1—C7—C2 | −0.61 (19) | C14—C9—C10—C11 | 2.0 (3) |
C8—N1—C7—C2 | 169.24 (17) | N3—C9—C10—C11 | −179.65 (16) |
N2—N1—C7—C6 | −179.06 (19) | C9—C10—C11—C12 | −1.1 (3) |
C8—N1—C7—C6 | −9.2 (3) | C10—C11—C12—C13 | −0.6 (3) |
C3—C2—C7—N1 | −178.21 (17) | C11—C12—C13—C14 | 1.4 (3) |
C1—C2—C7—N1 | 0.76 (19) | C10—C9—C14—C13 | −1.2 (3) |
C3—C2—C7—C6 | 0.5 (3) | N3—C9—C14—C13 | −179.58 (16) |
C1—C2—C7—C6 | 179.44 (17) | C12—C13—C14—C9 | −0.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2i | 0.88 | 2.30 | 3.097 (3) | 151 |
C5—H5···S1ii | 0.95 | 3.14 | 3.881 (2) | 136 |
C6—H6···S1iii | 0.95 | 3.17 | 4.040 (3) | 153 |
C1—H1···Cg(C9–C14)iv | 0.95 | ??? | 2.47 | ??? |
Symmetry codes: (i) −x+1, y, −z; (ii) −x+1, y+1, −z+1; (iii) −x+1, y, −z+1; (iv) −x+1, y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H11N3S |
Mr | 253.32 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 98 |
a, b, c (Å) | 20.408 (8), 5.690 (2), 11.949 (5) |
β (°) | 121.110 (14) |
V (Å3) | 1188.0 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.42 × 0.12 × 0.02 |
Data collection | |
Diffractometer | Rigaku AFC12κ/SATURN724 |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.506, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6334, 2202, 2160 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.069, 1.05 |
No. of reflections | 2202 |
No. of parameters | 163 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.19 |
Absolute structure | Flack (1983), 845 Friedel pairs |
Absolute structure parameter | 0.03 (7) |
Computer programs: CrystalClear (Rigaku Americas Corporation, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2i | 0.88 | 2.30 | 3.097 (3) | 151 |
C5—H5···S1ii | 0.95 | 3.14 | 3.881 (2) | 136 |
C6—H6···S1iii | 0.95 | 3.17 | 4.040 (3) | 153 |
C1—H1···Cg(C9–C14)iv | 0.95 | ??? | 2.47 | ??? |
Symmetry codes: (i) −x+1, y, −z; (ii) −x+1, y+1, −z+1; (iii) −x+1, y, −z+1; (iv) −x+1, y+1, −z. |
The preparation and crystal structures of series of compounds containing molecules related to the title compound (I), i.e. with the general formula PhNC(=S)R (R = pyrazolyl, 3,5-dimethylpyrazolyl and 3,5-diphenylpyrazolyl) and PhNC(=S)NRR' (R = alkyl or aryl) have been reported recently (Hossaini Sadr, Sardroodi et al., 2005; Hossaini Sadr, Jalili et al., 2005; Henderson et al., 2006). Compound (I) exists as a thione, C8=S1 is 1.6545 (19) Å, and the conformation about the C8—N3 bond is Z. The molecule is non-planar as the phenyl ring is twisted out of the plane of the central chromophore as manifested in the C8/N3/C9/C10 torsion angle of 51.7 (2)°. In the crystal structure, molecules related by 2-fold symmetry associate via N—H···N hydrogen bonds, Table 1. Pairs of molecules are connected by C—H···π interactions [C1—H1···Cg(C9—C14) = 2.47 Å for symmetry operation 1 - x, 1 + y, -z] on either side to form columns parallel to the b axis. Connections between columns are afforded by weak C—H···S interactions; the S1 forms two such contacts with different molecules of the adjacent chain, Table 1. A view of the unit-cell contents is shown in Fig. 2.