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The structure of the title compound, C7H9N3S, comprises twisted mol­ecules that associate via N-H...N and N-H...S hydrogen-bonding interactions. The dihedral angle between the phenyl ring and the five-membered thio­semicarbazide plane is 67.56 (5)°. This structure was previously determined using data from visual estimation of photographic intensity (measurements at room temperature, with R = 0.112).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015390/qa0447sup1.cif
Contains datablocks I, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015390/qa0447Isup2.hkl
Contains datablock I

CCDC reference: 156215

Comment top

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)°.

Experimental top

Crystals of (I) were obtained from Spa Contract Synthesis.

Refinement top

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.

Computing details top

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.

4-(Phenyl)thiosemicarbazide top
Crystal data top
C7H9N3SDx = 1.372 Mg m3
Mr = 167.23Melting point: 411-413 K K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.9231 (7) ÅCell parameters from 6169 reflections
b = 5.4888 (3) Åθ = 1.0–27.5°
c = 12.3788 (8) ŵ = 0.33 mm1
β = 91.527 (3)°T = 150 K
V = 809.82 (8) Å3Block, colourless
Z = 40.40 × 0.30 × 0.20 mm
F(000) = 352
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
1803 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode1483 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 1.7°
ϕ and ω scansh = 1515
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 67
Tmin = 0.878, Tmax = 0.936l = 1516
4691 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H 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 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C7H9N3SV = 809.82 (8) Å3
Mr = 167.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.9231 (7) ŵ = 0.33 mm1
b = 5.4888 (3) ÅT = 150 K
c = 12.3788 (8) Å0.40 × 0.30 × 0.20 mm
β = 91.527 (3)°
Data collection top
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 = 0.936Rint = 0.037
4691 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.24 e Å3
1803 reflectionsΔρmin = 0.32 e Å3
116 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.14402 (15)0.5007 (3)0.06846 (14)0.0262 (4)
H110.166 (2)0.449 (4)0.131 (2)0.037 (7)*
H120.087 (2)0.612 (5)0.077 (2)0.044 (7)*
N20.10107 (14)0.3002 (3)0.01129 (12)0.0253 (4)
H20.047 (2)0.207 (4)0.0406 (18)0.032 (6)*
C30.14740 (15)0.2346 (3)0.08389 (14)0.0226 (4)
S30.09915 (5)0.01116 (9)0.15019 (4)0.0322 (2)
N40.22921 (14)0.3795 (3)0.12235 (12)0.0262 (4)
H40.225 (2)0.515 (5)0.093 (2)0.049 (8)*
C410.29000 (15)0.3449 (3)0.22171 (14)0.0223 (4)
C420.36142 (16)0.1471 (3)0.23506 (15)0.0264 (4)
H420.36840.03110.17870.033*
C430.42258 (16)0.1195 (4)0.33101 (16)0.0295 (4)
H430.47160.01580.34050.037*
C440.41248 (17)0.2885 (4)0.41313 (16)0.0305 (5)
H440.45400.26850.47910.038*
C450.34203 (19)0.4863 (4)0.39914 (17)0.0316 (5)
H450.33590.60330.45520.039*
C460.28022 (18)0.5144 (3)0.30350 (16)0.0269 (4)
H460.23130.64980.29420.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0322 (10)0.0280 (9)0.0184 (8)0.0009 (7)0.0030 (7)0.0051 (6)
N20.0288 (8)0.0279 (8)0.0190 (7)0.0046 (7)0.0031 (6)0.0027 (6)
S30.0430 (4)0.0302 (3)0.0229 (3)0.0131 (2)0.0104 (2)0.00705 (18)
C30.0271 (9)0.0227 (9)0.0181 (8)0.0026 (7)0.0011 (7)0.0021 (7)
N40.0337 (9)0.0233 (8)0.0214 (8)0.0045 (7)0.0044 (6)0.0056 (6)
C410.0219 (9)0.0238 (9)0.0209 (9)0.0058 (7)0.0015 (7)0.0021 (7)
C420.0279 (10)0.0254 (9)0.0259 (9)0.0012 (8)0.0020 (7)0.0023 (7)
C430.0221 (9)0.0300 (10)0.0361 (11)0.0019 (8)0.0018 (8)0.0056 (8)
C440.0289 (10)0.0360 (11)0.0261 (10)0.0057 (9)0.0082 (8)0.0044 (8)
C450.0384 (12)0.0314 (11)0.0247 (10)0.0033 (9)0.0033 (8)0.0047 (8)
C460.0302 (10)0.0229 (9)0.0275 (10)0.0016 (7)0.0015 (8)0.0009 (7)
Geometric parameters (Å, º) top
S3—C31.6882 (19)C41—C421.387 (3)
N4—C31.336 (2)C42—C431.385 (3)
N4—C411.424 (2)C42—H420.9500
N4—H40.83 (3)C43—C441.384 (3)
N2—C31.337 (2)C43—H430.9500
N2—N11.412 (2)C44—C451.381 (3)
N2—H20.89 (2)C44—H440.9500
N1—H110.87 (3)C45—C461.386 (3)
N1—H120.92 (3)C45—H450.9500
C41—C461.382 (3)C46—H460.9500
C3—N4—C41125.37 (16)C42—C43—C44120.16 (18)
C3—N4—H4110 (2)C42—C43—H43119.9
C41—N4—H4122 (2)C44—C43—H43119.9
C3—N2—N1120.31 (16)C45—C44—C43119.96 (17)
C3—N2—H2118.7 (15)C45—C44—H44120.0
N1—N2—H2120.8 (15)C43—C44—H44120.0
N2—N1—H11108.2 (17)C44—C45—C46120.16 (18)
N2—N1—H12107.0 (16)C44—C45—H45119.9
H11—N1—H12111 (2)C46—C45—H45119.9
C46—C41—C42120.21 (17)C41—C46—C45119.82 (18)
C46—C41—N4119.50 (17)C41—C46—H46120.1
C42—C41—N4120.26 (16)C45—C46—H46120.1
C43—C42—C41119.68 (17)N2—C3—N4115.74 (17)
C43—C42—H42120.2N2—C3—S3120.36 (14)
C41—C42—H42120.2N4—C3—S3123.86 (14)
C3—N4—C41—C46115.1 (2)C42—C41—C46—C450.0 (3)
C3—N4—C41—C4267.0 (3)N4—C41—C46—C45177.86 (18)
C46—C41—C42—C430.3 (3)C44—C45—C46—C410.6 (3)
N4—C41—C42—C43178.13 (16)N1—N2—C3—N44.4 (3)
C41—C42—C43—C440.0 (3)N1—N2—C3—S3177.77 (13)
C42—C43—C44—C450.5 (3)C41—N4—C3—N2179.97 (17)
C43—C44—C45—C460.8 (3)C41—N4—C3—S32.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N10.83 (2)2.19 (2)2.6317 (17)113 (2)
N2—H2···S3i0.89 (2)2.43 (2)3.3097 (17)168 (2)
N1—H11···S3ii0.87 (3)2.83 (3)3.5100 (18)137 (2)
N1—H12···N2iii0.92 (3)2.56 (3)3.296 (2)137 (2)
Symmetry codes: (i) x, y, z; (ii) x, y1/2, z1/2; (iii) x, y1, z.

Experimental details

Crystal data
Chemical formulaC7H9N3S
Mr167.23
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)11.9231 (7), 5.4888 (3), 12.3788 (8)
β (°) 91.527 (3)
V3)809.82 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerEnraf Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.878, 0.936
No. of measured, independent and
observed [I > 2σ(I)] reflections
4691, 1803, 1483
Rint0.037
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.132, 1.13
No. of reflections1803
No. of parameters116
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.32

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N10.83 (2)2.19 (2)2.6317 (17)113 (2)
N2—H2···S3i0.89 (2)2.43 (2)3.3097 (17)168 (2)
N1—H11···S3ii0.87 (3)2.83 (3)3.5100 (18)137 (2)
N1—H12···N2iii0.92 (3)2.56 (3)3.296 (2)137 (2)
Symmetry codes: (i) x, y, z; (ii) x, y1/2, z1/2; (iii) x, y1, z.
 

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