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The title compound, C6H7N3S, crystallizes with two essentially planar molecules in the asymmetric unit (r.m.s. deviation for all non-H atoms = 0.055 and 0.006 Å), which are held together by two N—H
S hydrogen bonds. The two molecules are almost identical (r.m.s. deviation for all non-H atoms = 0.066 Å). An intramolecular N—HN hydrogen bond stabilizes the synperiplanar conformations between the pyridine N atom and the thiocarbonyl C atom, as well as between the pivot C atom of the pyridine ring and the NH2 group [torsion angles: N—C—N—C = 7.3 (3) and −1.0 (3)°, C—N—C—N = −4.1 (3) and −0.4 (3)°].
S hydrogen bonds. The two molecules are almost identical (r.m.s. deviation for all non-H atoms = 0.066 Å). An intramolecular N—HN hydrogen bond stabilizes the synperiplanar conformations between the pyridine N atom and the thiocarbonyl C atom, as well as between the pivot C atom of the pyridine ring and the NH2 group [torsion angles: N—C—N—C = 7.3 (3) and −1.0 (3)°, C—N—C—N = −4.1 (3) and −0.4 (3)°].Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057388/at2476sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057388/at2476Isup2.hkl |
CCDC reference: 672921
![[sigma]](http://journals.iucr.org/logos/entities/sigma_rmgif.gif){kind=small}
(C-C)= 0.003 Å
Experimental top
Single crystals of title compound were obtained from recrystallization of the commercially available 1-(pPyridin-2-yl)thiourea from acetonitril at room temperature.
Refinement top
All H atoms were initially located by difference Fourier synthesis. Subsequently the positions of those bonded to C atoms were idealized and constrained to ride on their parent atoms with C—H = 0.95 Å and fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C)]. H atoms bonded to N were refined isotropically.
Computing details top
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Figures top
![[Figure 1]](http://journals.iucr.org/e/issues/2007/12/00/at2476/at2476fig1thm.gif)
| Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level. Hydrogen bonds shown as dashed lines. |
![[Figure 2]](http://journals.iucr.org/e/issues/2007/12/00/at2476/at2476fig2thm.gif)
| Fig. 2. Partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
1-(Pyridin-2-yl)thiourea top
Crystal data top
| C6H7N3S | F(000) = 640 |
| Mr = 153.21 | Dx = 1.403 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 11901 reflections |
| a = 14.0116 (13) Å | θ = 3.5–25.9° |
| b = 6.1820 (4) Å | µ = 0.37 mm−1 |
| c = 16.8726 (15) Å | T = 173 K |
| β = 97.140 (7)° | Block, colourless |
| V = 1450.2 (2) Å3 | 0.52 × 0.40 × 0.28 mm |
| Z = 8 |
Data collection top
| Stoe IPDS II two-circle diffractometer | 2700 independent reflections |
| Radiation source: fine-focus sealed tube | 2307 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.075 |
| ω scans | θmax = 25.6°, θmin = 3.5° |
| Absorption correction: multi-scan [MULABS (Spek, 2003; Blessing, 1995)] | h = −16→15 |
| Tmin = 0.832, Tmax = 0.904 | k = −7→7 |
| 11661 measured reflections | l = −20→20 |
Refinement top
| 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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0536P)2 + 0.3005P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 2700 reflections | Δρmax = 0.25 e Å−3 |
| 206 parameters | Δρmin = −0.21 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.019 (2) |
Crystal data top
| C6H7N3S | V = 1450.2 (2) Å3 |
| Mr = 153.21 | Z = 8 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.0116 (13) Å | µ = 0.37 mm−1 |
| b = 6.1820 (4) Å | T = 173 K |
| c = 16.8726 (15) Å | 0.52 × 0.40 × 0.28 mm |
| β = 97.140 (7)° |
Data collection top
| Stoe IPDS II two-circle diffractometer | 2700 independent reflections |
| Absorption correction: multi-scan [MULABS (Spek, 2003; Blessing, 1995)] | 2307 reflections with I > 2σ(I) |
| Tmin = 0.832, Tmax = 0.904 | Rint = 0.075 |
| 11661 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
| wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | Δρmax = 0.25 e Å−3 |
| 2700 reflections | Δρmin = −0.21 e Å−3 |
| 206 parameters |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.13558 (11) | 0.0118 (2) | 0.67619 (8) | 0.0223 (3) | |
| C2 | 0.12387 (15) | −0.1750 (3) | 0.71483 (11) | 0.0267 (4) | |
| H2 | 0.1749 | −0.2226 | 0.7533 | 0.032* | |
| C3 | 0.04226 (14) | −0.3015 (3) | 0.70201 (10) | 0.0256 (4) | |
| H3 | 0.0375 | −0.4326 | 0.7306 | 0.031* | |
| C4 | −0.03333 (14) | −0.2315 (3) | 0.64587 (10) | 0.0236 (4) | |
| H4 | −0.0908 | −0.3140 | 0.6359 | 0.028* | |
| C5 | −0.02313 (13) | −0.0402 (3) | 0.60495 (10) | 0.0210 (4) | |
| H5 | −0.0735 | 0.0119 | 0.5668 | 0.025* | |
| C6 | 0.06331 (13) | 0.0744 (2) | 0.62123 (9) | 0.0175 (3) | |
| N61 | 0.07537 (11) | 0.2636 (2) | 0.57712 (8) | 0.0188 (3) | |
| H61 | 0.0270 (16) | 0.303 (3) | 0.5476 (12) | 0.024 (5)* | |
| C62 | 0.15552 (12) | 0.3890 (3) | 0.57543 (9) | 0.0169 (3) | |
| S62 | 0.15173 (3) | 0.59971 (7) | 0.50991 (2) | 0.02136 (15) | |
| N63 | 0.23412 (11) | 0.3401 (3) | 0.62421 (9) | 0.0239 (3) | |
| H63A | 0.2874 (18) | 0.420 (4) | 0.6260 (13) | 0.034 (6)* | |
| H63B | 0.2320 (16) | 0.220 (3) | 0.6586 (13) | 0.034 (6)* | |
| N1' | 0.40042 (12) | 1.2425 (2) | 0.49260 (9) | 0.0287 (4) | |
| C2' | 0.39561 (15) | 1.3748 (3) | 0.42865 (12) | 0.0338 (5) | |
| H2' | 0.4304 | 1.5070 | 0.4342 | 0.041* | |
| C3' | 0.34342 (15) | 1.3303 (3) | 0.35574 (11) | 0.0333 (5) | |
| H3' | 0.3415 | 1.4296 | 0.3126 | 0.040* | |
| C4' | 0.29375 (15) | 1.1354 (3) | 0.34738 (11) | 0.0323 (5) | |
| H4' | 0.2580 | 1.0983 | 0.2977 | 0.039* | |
| C5' | 0.29658 (14) | 0.9956 (3) | 0.41174 (10) | 0.0267 (4) | |
| H5' | 0.2626 | 0.8624 | 0.4074 | 0.032* | |
| C6' | 0.35137 (12) | 1.0571 (3) | 0.48370 (10) | 0.0212 (4) | |
| N61' | 0.35356 (11) | 0.9141 (2) | 0.54900 (9) | 0.0220 (3) | |
| H61' | 0.3152 (16) | 0.804 (4) | 0.5417 (12) | 0.027 (5)* | |
| C62' | 0.40118 (12) | 0.9316 (3) | 0.62462 (10) | 0.0206 (4) | |
| S62' | 0.38933 (3) | 0.72820 (7) | 0.69093 (3) | 0.02639 (16) | |
| N63' | 0.45425 (12) | 1.1059 (3) | 0.64362 (11) | 0.0290 (4) | |
| H63C | 0.4538 (17) | 1.207 (4) | 0.6090 (14) | 0.035 (6)* | |
| H63D | 0.485 (2) | 1.118 (4) | 0.6931 (16) | 0.046 (7)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0221 (8) | 0.0209 (7) | 0.0232 (7) | 0.0018 (6) | 0.0004 (6) | 0.0045 (6) |
| C2 | 0.0319 (10) | 0.0243 (9) | 0.0239 (9) | 0.0054 (8) | 0.0037 (7) | 0.0066 (7) |
| C3 | 0.0371 (11) | 0.0168 (8) | 0.0251 (9) | 0.0022 (8) | 0.0121 (8) | 0.0025 (7) |
| C4 | 0.0315 (10) | 0.0180 (8) | 0.0227 (9) | −0.0058 (7) | 0.0081 (7) | −0.0030 (6) |
| C5 | 0.0245 (9) | 0.0188 (8) | 0.0193 (8) | −0.0015 (7) | 0.0010 (7) | −0.0018 (6) |
| C6 | 0.0216 (9) | 0.0150 (8) | 0.0162 (7) | 0.0006 (7) | 0.0037 (6) | −0.0015 (6) |
| N61 | 0.0175 (8) | 0.0182 (7) | 0.0193 (7) | −0.0014 (6) | −0.0032 (6) | 0.0032 (5) |
| C62 | 0.0174 (8) | 0.0173 (8) | 0.0162 (7) | −0.0003 (6) | 0.0025 (6) | −0.0026 (6) |
| S62 | 0.0198 (2) | 0.0209 (2) | 0.0225 (2) | −0.00443 (16) | −0.00109 (17) | 0.00586 (15) |
| N63 | 0.0179 (8) | 0.0251 (8) | 0.0271 (8) | −0.0034 (7) | −0.0033 (6) | 0.0059 (6) |
| N1' | 0.0265 (9) | 0.0281 (8) | 0.0306 (8) | −0.0096 (7) | 0.0003 (7) | 0.0047 (6) |
| C2' | 0.0342 (12) | 0.0292 (10) | 0.0387 (11) | −0.0077 (9) | 0.0071 (9) | 0.0089 (8) |
| C3' | 0.0351 (11) | 0.0375 (11) | 0.0286 (10) | −0.0005 (9) | 0.0093 (8) | 0.0122 (8) |
| C4' | 0.0351 (11) | 0.0404 (11) | 0.0207 (9) | −0.0017 (9) | 0.0006 (8) | 0.0043 (8) |
| C5' | 0.0269 (10) | 0.0306 (10) | 0.0221 (9) | −0.0069 (8) | 0.0008 (7) | 0.0022 (7) |
| C6' | 0.0161 (9) | 0.0249 (9) | 0.0225 (9) | −0.0026 (7) | 0.0019 (7) | 0.0019 (7) |
| N61' | 0.0216 (8) | 0.0226 (8) | 0.0204 (7) | −0.0082 (6) | −0.0035 (6) | 0.0023 (6) |
| C62' | 0.0146 (8) | 0.0248 (9) | 0.0213 (8) | 0.0007 (7) | −0.0014 (6) | −0.0012 (6) |
| S62' | 0.0258 (3) | 0.0291 (3) | 0.0218 (2) | −0.00563 (19) | −0.00690 (18) | 0.00572 (17) |
| N63' | 0.0285 (9) | 0.0294 (9) | 0.0261 (8) | −0.0099 (7) | −0.0089 (7) | 0.0028 (7) |
Geometric parameters (Å, º) top
| N1—C6 | 1.342 (2) | N1'—C6' | 1.335 (2) |
| N1—C2 | 1.346 (2) | N1'—C2' | 1.349 (2) |
| C2—C3 | 1.380 (3) | C2'—C3' | 1.379 (3) |
| C2—H2 | 0.9500 | C2'—H2' | 0.9500 |
| C3—C4 | 1.399 (3) | C3'—C4' | 1.390 (3) |
| C3—H3 | 0.9500 | C3'—H3' | 0.9500 |
| C4—C5 | 1.386 (2) | C4'—C5' | 1.385 (3) |
| C4—H4 | 0.9500 | C4'—H4' | 0.9500 |
| C5—C6 | 1.401 (2) | C5'—C6' | 1.406 (2) |
| C5—H5 | 0.9500 | C5'—H5' | 0.9500 |
| C6—N61 | 1.408 (2) | C6'—N61' | 1.410 (2) |
| N61—C62 | 1.368 (2) | N61'—C62' | 1.369 (2) |
| N61—H61 | 0.83 (2) | N61'—H61' | 0.87 (2) |
| C62—N63 | 1.325 (2) | C62'—N63' | 1.326 (2) |
| C62—S62 | 1.7051 (16) | C62'—S62' | 1.7047 (18) |
| N63—H63A | 0.89 (3) | N63'—H63C | 0.86 (2) |
| N63—H63B | 0.95 (2) | N63'—H63D | 0.89 (3) |
| C6—N1—C2 | 117.08 (15) | C6'—N1'—C2' | 117.17 (16) |
| N1—C2—C3 | 123.97 (17) | N1'—C2'—C3' | 124.12 (18) |
| N1—C2—H2 | 118.0 | N1'—C2'—H2' | 117.9 |
| C3—C2—H2 | 118.0 | C3'—C2'—H2' | 117.9 |
| C2—C3—C4 | 118.29 (16) | C2'—C3'—C4' | 117.84 (17) |
| C2—C3—H3 | 120.9 | C2'—C3'—H3' | 121.1 |
| C4—C3—H3 | 120.9 | C4'—C3'—H3' | 121.1 |
| C5—C4—C3 | 119.01 (17) | C5'—C4'—C3' | 119.77 (18) |
| C5—C4—H4 | 120.5 | C5'—C4'—H4' | 120.1 |
| C3—C4—H4 | 120.5 | C3'—C4'—H4' | 120.1 |
| C4—C5—C6 | 118.31 (16) | C4'—C5'—C6' | 117.90 (17) |
| C4—C5—H5 | 120.8 | C4'—C5'—H5' | 121.1 |
| C6—C5—H5 | 120.8 | C6'—C5'—H5' | 121.1 |
| N1—C6—C5 | 123.31 (15) | N1'—C6'—C5' | 123.19 (16) |
| N1—C6—N61 | 118.37 (15) | N1'—C6'—N61' | 119.29 (15) |
| C5—C6—N61 | 118.32 (15) | C5'—C6'—N61' | 117.52 (15) |
| C62—N61—C6 | 129.40 (15) | C62'—N61'—C6' | 129.79 (15) |
| C62—N61—H61 | 115.7 (15) | C62'—N61'—H61' | 114.5 (14) |
| C6—N61—H61 | 114.9 (15) | C6'—N61'—H61' | 115.4 (14) |
| N63—C62—N61 | 118.61 (15) | N63'—C62'—N61' | 118.90 (16) |
| N63—C62—S62 | 122.24 (13) | N63'—C62'—S62' | 122.56 (14) |
| N61—C62—S62 | 119.14 (12) | N61'—C62'—S62' | 118.55 (13) |
| C62—N63—H63A | 121.6 (14) | C62'—N63'—H63C | 118.2 (15) |
| C62—N63—H63B | 118.2 (14) | C62'—N63'—H63D | 118.9 (16) |
| H63A—N63—H63B | 120.2 (19) | H63C—N63'—H63D | 123 (2) |
| C6—N1—C2—C3 | −1.0 (3) | C6'—N1'—C2'—C3' | 0.2 (3) |
| N1—C2—C3—C4 | −0.4 (3) | N1'—C2'—C3'—C4' | −0.9 (3) |
| C2—C3—C4—C5 | 0.6 (3) | C2'—C3'—C4'—C5' | 1.1 (3) |
| C3—C4—C5—C6 | 0.6 (2) | C3'—C4'—C5'—C6' | −0.7 (3) |
| C2—N1—C6—C5 | 2.3 (2) | C2'—N1'—C6'—C5' | 0.3 (3) |
| C2—N1—C6—N61 | −176.99 (15) | C2'—N1'—C6'—N61' | −179.53 (17) |
| C4—C5—C6—N1 | −2.1 (3) | C4'—C5'—C6'—N1' | −0.1 (3) |
| C4—C5—C6—N61 | 177.19 (15) | C4'—C5'—C6'—N61' | 179.78 (17) |
| N1—C6—N61—C62 | 7.3 (3) | N1'—C6'—N61'—C62' | −1.0 (3) |
| C5—C6—N61—C62 | −172.06 (16) | C5'—C6'—N61'—C62' | 179.15 (18) |
| C6—N61—C62—N63 | −4.1 (3) | C6'—N61'—C62'—N63' | 0.4 (3) |
| C6—N61—C62—S62 | 174.97 (13) | C6'—N61'—C62'—S62' | −179.88 (15) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N61—H61···S62i | 0.83 (2) | 2.64 (2) | 3.4401 (16) | 163.3 (19) |
| N63—H63A···S62′ | 0.89 (3) | 2.55 (2) | 3.3383 (16) | 148.3 (19) |
| N63—H63B···N1 | 0.95 (2) | 1.91 (2) | 2.664 (2) | 134.4 (19) |
| N61′—H61′···S62 | 0.87 (2) | 2.61 (2) | 3.4273 (16) | 157.1 (18) |
| N63′—H63C···N1′ | 0.86 (2) | 2.02 (2) | 2.701 (2) | 135 (2) |
| N63′—H63D···S62′ii | 0.89 (3) | 2.56 (3) | 3.4127 (17) | 161 (2) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2. |
Experimental details
| Crystal data | |
| Chemical formula | C6H7N3S |
| Mr | 153.21 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 173 |
| a, b, c (Å) | 14.0116 (13), 6.1820 (4), 16.8726 (15) |
| β (°) | 97.140 (7) |
| V (Å3) | 1450.2 (2) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.37 |
| Crystal size (mm) | 0.52 × 0.40 × 0.28 |
| Data collection | |
| Diffractometer | Stoe IPDS II two-circle diffractometer |
| Absorption correction | Multi-scan [MULABS (Spek, 2003; Blessing, 1995)] |
| Tmin, Tmax | 0.832, 0.904 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11661, 2700, 2307 |
| Rint | 0.075 |
| (sin θ/λ)max (Å−1) | 0.607 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.091, 1.03 |
| No. of reflections | 2700 |
| No. of parameters | 206 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N61—H61···S62i | 0.83 (2) | 2.64 (2) | 3.4401 (16) | 163.3 (19) |
| N63—H63A···S62' | 0.89 (3) | 2.55 (2) | 3.3383 (16) | 148.3 (19) |
| N63—H63B···N1 | 0.95 (2) | 1.91 (2) | 2.664 (2) | 134.4 (19) |
| N61'—H61'···S62 | 0.87 (2) | 2.61 (2) | 3.4273 (16) | 157.1 (18) |
| N63'—H63C···N1' | 0.86 (2) | 2.02 (2) | 2.701 (2) | 135 (2) |
| N63'—H63D···S62'ii | 0.89 (3) | 2.56 (3) | 3.4127 (17) | 161 (2) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2. |
1-(Pyridin-2-yl)thiourea crystallizes with two essentially planar molecules in the asymmetric unit (r.m.s. deviation for all non-H atoms 0.055 Å and 0.006 Å), which are held together by two N—H···S hydrogen bonds. The two molecules are almost identical (r.m.s. deviation for all non-H atoms 0.066 Å). An intramolecular N—H···N hydrogen bond stabilizes the syn-periplanar conformations between the pyridine N atom and the thiocarbonyl C atom, as well as between the C6 atom and the NH2 group [torsion angle N1—C6—N61—C62: 7.3 (3)°, N1'—C6'—N61'—C62': -1.0 (3)°, C6—N61—C62—N63: -4.1 (3)°, C6'—N61'—C62'—N63': -0.4 (3)°]. The crystal packing shows a network of intermolecular N—H···S hydrogen bonds resulting in corrugated layers.