Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015390/qa0447sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015390/qa0447Isup2.hkl |
CCDC reference: 156215
All H atoms were included in the refinement, at calculated positions, as riding models with C—H set to 0.95 Å, except for the amine H atoms, which were located on difference syntheses and both positional and displacement parameters refined.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
C7H9N3S | Dx = 1.372 Mg m−3 |
Mr = 167.23 | Melting point: 411-413 K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9231 (7) Å | Cell parameters from 6169 reflections |
b = 5.4888 (3) Å | θ = 1.0–27.5° |
c = 12.3788 (8) Å | µ = 0.33 mm−1 |
β = 91.527 (3)° | T = 150 K |
V = 809.82 (8) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
F(000) = 352 |
Enraf Nonius KappaCCD area-detector diffractometer | 1803 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 1.7° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −6→7 |
Tmin = 0.878, Tmax = 0.936 | l = −15→16 |
4691 measured reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0669P)2 + 0.3297P] where P = (Fo2 + 2Fc2)/3 |
1803 reflections | (Δ/σ)max < 0.001 |
116 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C7H9N3S | V = 809.82 (8) Å3 |
Mr = 167.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.9231 (7) Å | µ = 0.33 mm−1 |
b = 5.4888 (3) Å | T = 150 K |
c = 12.3788 (8) Å | 0.40 × 0.30 × 0.20 mm |
β = 91.527 (3)° |
Enraf Nonius KappaCCD area-detector diffractometer | 1803 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1483 reflections with I > 2σ(I) |
Tmin = 0.878, Tmax = 0.936 | Rint = 0.037 |
4691 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.24 e Å−3 |
1803 reflections | Δρmin = −0.32 e Å−3 |
116 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
Geometry. Mean plane data ex SHELXL97 ########################### Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 9.0426 (0.0063) x − 2.9114 (0.0038) y − 4.9372 (0.0091) z = 2.5340 (0.0043) * −0.0020 (0.0013) C41 * 0.0020 (0.0013) C42 * 0.0009 (0.0014) C43 * −0.0038 (0.0014) C44 * 0.0039 (0.0015) C45 * −0.0010 (0.0014) C46 Rms deviation of fitted atoms = 0.0026 − 8.1354 (0.0082) x − 3.1653 (0.0026) y + 5.7850 (0.0082) z = 0.0360 (0.0021) Angle to previous plane (with approximate e.s.d.) = 67.56 (0.05) * 0.0082 (0.0006) N4 * −0.0071 (0.0015) C3 * −0.0090 (0.0007) S3 * 0.0268 (0.0013) N2 * −0.0189 (0.0009) N1 Rms deviation of fitted atoms = 0.0160 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.14402 (15) | −0.5007 (3) | −0.06846 (14) | 0.0262 (4) | |
H11 | 0.166 (2) | −0.449 (4) | −0.131 (2) | 0.037 (7)* | |
H12 | 0.087 (2) | −0.612 (5) | −0.077 (2) | 0.044 (7)* | |
N2 | 0.10107 (14) | −0.3002 (3) | −0.01129 (12) | 0.0253 (4) | |
H2 | 0.047 (2) | −0.207 (4) | −0.0406 (18) | 0.032 (6)* | |
C3 | 0.14740 (15) | −0.2346 (3) | 0.08389 (14) | 0.0226 (4) | |
S3 | 0.09915 (5) | 0.01116 (9) | 0.15019 (4) | 0.0322 (2) | |
N4 | 0.22921 (14) | −0.3795 (3) | 0.12235 (12) | 0.0262 (4) | |
H4 | 0.225 (2) | −0.515 (5) | 0.093 (2) | 0.049 (8)* | |
C41 | 0.29000 (15) | −0.3449 (3) | 0.22171 (14) | 0.0223 (4) | |
C42 | 0.36142 (16) | −0.1471 (3) | 0.23506 (15) | 0.0264 (4) | |
H42 | 0.3684 | −0.0311 | 0.1787 | 0.033* | |
C43 | 0.42258 (16) | −0.1195 (4) | 0.33101 (16) | 0.0295 (4) | |
H43 | 0.4716 | 0.0158 | 0.3405 | 0.037* | |
C44 | 0.41248 (17) | −0.2885 (4) | 0.41313 (16) | 0.0305 (5) | |
H44 | 0.4540 | −0.2685 | 0.4791 | 0.038* | |
C45 | 0.34203 (19) | −0.4863 (4) | 0.39914 (17) | 0.0316 (5) | |
H45 | 0.3359 | −0.6033 | 0.4552 | 0.039* | |
C46 | 0.28022 (18) | −0.5144 (3) | 0.30350 (16) | 0.0269 (4) | |
H46 | 0.2313 | −0.6498 | 0.2942 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0322 (10) | 0.0280 (9) | 0.0184 (8) | −0.0009 (7) | 0.0030 (7) | −0.0051 (6) |
N2 | 0.0288 (8) | 0.0279 (8) | 0.0190 (7) | 0.0046 (7) | −0.0031 (6) | −0.0027 (6) |
S3 | 0.0430 (4) | 0.0302 (3) | 0.0229 (3) | 0.0131 (2) | −0.0104 (2) | −0.00705 (18) |
C3 | 0.0271 (9) | 0.0227 (9) | 0.0181 (8) | −0.0026 (7) | 0.0011 (7) | 0.0021 (7) |
N4 | 0.0337 (9) | 0.0233 (8) | 0.0214 (8) | 0.0045 (7) | −0.0044 (6) | −0.0056 (6) |
C41 | 0.0219 (9) | 0.0238 (9) | 0.0209 (9) | 0.0058 (7) | −0.0015 (7) | −0.0021 (7) |
C42 | 0.0279 (10) | 0.0254 (9) | 0.0259 (9) | 0.0012 (8) | 0.0020 (7) | 0.0023 (7) |
C43 | 0.0221 (9) | 0.0300 (10) | 0.0361 (11) | −0.0019 (8) | −0.0018 (8) | −0.0056 (8) |
C44 | 0.0289 (10) | 0.0360 (11) | 0.0261 (10) | 0.0057 (9) | −0.0082 (8) | −0.0044 (8) |
C45 | 0.0384 (12) | 0.0314 (11) | 0.0247 (10) | 0.0033 (9) | −0.0033 (8) | 0.0047 (8) |
C46 | 0.0302 (10) | 0.0229 (9) | 0.0275 (10) | −0.0016 (7) | −0.0015 (8) | 0.0009 (7) |
S3—C3 | 1.6882 (19) | C41—C42 | 1.387 (3) |
N4—C3 | 1.336 (2) | C42—C43 | 1.385 (3) |
N4—C41 | 1.424 (2) | C42—H42 | 0.9500 |
N4—H4 | 0.83 (3) | C43—C44 | 1.384 (3) |
N2—C3 | 1.337 (2) | C43—H43 | 0.9500 |
N2—N1 | 1.412 (2) | C44—C45 | 1.381 (3) |
N2—H2 | 0.89 (2) | C44—H44 | 0.9500 |
N1—H11 | 0.87 (3) | C45—C46 | 1.386 (3) |
N1—H12 | 0.92 (3) | C45—H45 | 0.9500 |
C41—C46 | 1.382 (3) | C46—H46 | 0.9500 |
C3—N4—C41 | 125.37 (16) | C42—C43—C44 | 120.16 (18) |
C3—N4—H4 | 110 (2) | C42—C43—H43 | 119.9 |
C41—N4—H4 | 122 (2) | C44—C43—H43 | 119.9 |
C3—N2—N1 | 120.31 (16) | C45—C44—C43 | 119.96 (17) |
C3—N2—H2 | 118.7 (15) | C45—C44—H44 | 120.0 |
N1—N2—H2 | 120.8 (15) | C43—C44—H44 | 120.0 |
N2—N1—H11 | 108.2 (17) | C44—C45—C46 | 120.16 (18) |
N2—N1—H12 | 107.0 (16) | C44—C45—H45 | 119.9 |
H11—N1—H12 | 111 (2) | C46—C45—H45 | 119.9 |
C46—C41—C42 | 120.21 (17) | C41—C46—C45 | 119.82 (18) |
C46—C41—N4 | 119.50 (17) | C41—C46—H46 | 120.1 |
C42—C41—N4 | 120.26 (16) | C45—C46—H46 | 120.1 |
C43—C42—C41 | 119.68 (17) | N2—C3—N4 | 115.74 (17) |
C43—C42—H42 | 120.2 | N2—C3—S3 | 120.36 (14) |
C41—C42—H42 | 120.2 | N4—C3—S3 | 123.86 (14) |
C3—N4—C41—C46 | 115.1 (2) | C42—C41—C46—C45 | 0.0 (3) |
C3—N4—C41—C42 | −67.0 (3) | N4—C41—C46—C45 | 177.86 (18) |
C46—C41—C42—C43 | −0.3 (3) | C44—C45—C46—C41 | 0.6 (3) |
N4—C41—C42—C43 | −178.13 (16) | N1—N2—C3—N4 | −4.4 (3) |
C41—C42—C43—C44 | 0.0 (3) | N1—N2—C3—S3 | 177.77 (13) |
C42—C43—C44—C45 | 0.5 (3) | C41—N4—C3—N2 | −179.97 (17) |
C43—C44—C45—C46 | −0.8 (3) | C41—N4—C3—S3 | −2.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1 | 0.83 (2) | 2.19 (2) | 2.6317 (17) | 113 (2) |
N2—H2···S3i | 0.89 (2) | 2.43 (2) | 3.3097 (17) | 168 (2) |
N1—H11···S3ii | 0.87 (3) | 2.83 (3) | 3.5100 (18) | 137 (2) |
N1—H12···N2iii | 0.92 (3) | 2.56 (3) | 3.296 (2) | 137 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y−1/2, z−1/2; (iii) −x, −y−1, −z. |
Experimental details
Crystal data | |
Chemical formula | C7H9N3S |
Mr | 167.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.9231 (7), 5.4888 (3), 12.3788 (8) |
β (°) | 91.527 (3) |
V (Å3) | 809.82 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.878, 0.936 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4691, 1803, 1483 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.132, 1.13 |
No. of reflections | 1803 |
No. of parameters | 116 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.32 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1 | 0.83 (2) | 2.19 (2) | 2.6317 (17) | 113 (2) |
N2—H2···S3i | 0.89 (2) | 2.43 (2) | 3.3097 (17) | 168 (2) |
N1—H11···S3ii | 0.87 (3) | 2.83 (3) | 3.5100 (18) | 137 (2) |
N1—H12···N2iii | 0.92 (3) | 2.56 (3) | 3.296 (2) | 137 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y−1/2, z−1/2; (iii) −x, −y−1, −z. |
The structure of the title compound, (I), was initially determined using data from visual estimation of photographic intensity measurements at room temperature, with refinement to R = 0.112 (Kolman et al., 1972). However, reported here is a redetermination of the structure using data collected by a modern area detector at 150 K, giving R = 0.040. The previously published value for the dihedral angle between the phenyl ring and the five-membered thiosemicarbazide was 67.5°, which can now be updated to 67.56 (5)°.