The title compound, C
6H
8N
4S, crystallizes as the thione tautomer, with intramolecular N
H—N and S
H—N hydrogen bonds, and π–π stacking along the
b axis. Intermolecular N
H—N hydrogen bonds link the molecules into one-dimensional sheets stacked along the
c axis.
Supporting information
CCDC reference: 277708
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.035
- wR factor = 0.107
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT707_ALERT_1_A D...A Calc 19.064(3), Rep 3.058(2), Dev.. 5335.33 Sigma
N2 -N4 1.555 4.565
PLAT726_ALERT_1_A H...A Calc 18.83000, Rep 2.21000 Dev... 16.62 Ang.
H5 -N4 1.555 4.565
PLAT728_ALERT_1_A D-H..A Calc 105.00, Rep 169.00 Dev... 64.00 Deg.
N2 -H5 -N4 1.555 1.555 4.565
Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C6 .. 5.63 su
PLAT352_ALERT_3_C Short N-H Bond (0.87A) N4 - H7 ... 0.75 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N4 - H8 ... ?
3 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 and PLATON; software used to prepare material for publication: Please provide missing details.
N-(Pyridin-2-yl)hydrazinecarbothioamide
top
Crystal data top
C6H8N4S | F(000) = 704 |
Mr = 168.22 | Dx = 1.477 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4378 reflections |
a = 15.5846 (17) Å | θ = 2.7–28.2° |
b = 10.1592 (11) Å | µ = 0.36 mm−1 |
c = 11.1622 (12) Å | T = 293 K |
β = 121.118 (2)° | Blocks, light yellow |
V = 1513.0 (3) Å3 | 0.32 × 0.28 × 0.22 mm |
Z = 8 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 1604 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 28.2°, θmin = 2.7° |
ω scans | h = −20→16 |
4378 measured reflections | k = −13→12 |
1748 independent reflections | l = −11→14 |
Refinement top
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0614P)2 + 0.5476P] where P = (Fo2 + 2Fc2)/3 |
1748 reflections | (Δ/σ)max < 0.001 |
112 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
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 | |
S1 | 0.35725 (3) | 0.63917 (4) | 0.22149 (4) | 0.04559 (17) | |
N4 | 0.38305 (14) | 0.63960 (13) | −0.02915 (16) | 0.0474 (3) | |
N1 | 0.39857 (9) | 0.25571 (11) | 0.03824 (12) | 0.0383 (3) | |
C2 | 0.38651 (13) | 0.02148 (15) | 0.04013 (18) | 0.0500 (4) | |
H2 | 0.3916 | −0.0596 | 0.0056 | 0.060* | |
N2 | 0.37094 (9) | 0.38463 (11) | 0.18943 (12) | 0.0381 (3) | |
H5 | 0.3660 | 0.3825 | 0.2627 | 0.046* | |
C6 | 0.37261 (10) | 0.50765 (13) | 0.14174 (13) | 0.0347 (3) | |
C1 | 0.40289 (13) | 0.13602 (14) | −0.00925 (17) | 0.0464 (4) | |
H1 | 0.4179 | 0.1307 | −0.0797 | 0.056* | |
N3 | 0.38371 (10) | 0.51774 (11) | 0.03185 (13) | 0.0397 (3) | |
C5 | 0.37598 (9) | 0.26172 (13) | 0.13774 (13) | 0.0336 (3) | |
C3 | 0.36214 (12) | 0.02914 (15) | 0.14268 (17) | 0.0504 (4) | |
H3 | 0.3500 | −0.0471 | 0.1777 | 0.061* | |
C4 | 0.35599 (11) | 0.15032 (15) | 0.19251 (16) | 0.0436 (3) | |
H4 | 0.3390 | 0.1579 | 0.2608 | 0.052* | |
H8 | 0.4457 (18) | 0.672 (2) | 0.032 (3) | 0.079 (7)* | |
H7 | 0.343 (2) | 0.680 (3) | −0.029 (3) | 0.083 (8)* | |
H6 | 0.3886 (13) | 0.454 (2) | −0.005 (2) | 0.051 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0657 (3) | 0.0377 (2) | 0.0445 (3) | 0.00352 (14) | 0.0364 (2) | −0.00588 (13) |
N4 | 0.0754 (10) | 0.0318 (6) | 0.0496 (8) | −0.0037 (6) | 0.0426 (8) | 0.0021 (5) |
N1 | 0.0512 (7) | 0.0328 (6) | 0.0366 (6) | 0.0007 (5) | 0.0269 (5) | −0.0015 (5) |
C2 | 0.0604 (9) | 0.0331 (7) | 0.0477 (8) | −0.0007 (6) | 0.0218 (7) | −0.0063 (6) |
N2 | 0.0552 (7) | 0.0349 (6) | 0.0357 (6) | 0.0013 (5) | 0.0316 (5) | 0.0008 (4) |
C6 | 0.0410 (6) | 0.0349 (7) | 0.0323 (6) | −0.0004 (5) | 0.0219 (5) | −0.0017 (5) |
C1 | 0.0603 (9) | 0.0393 (8) | 0.0419 (8) | 0.0016 (6) | 0.0280 (7) | −0.0062 (6) |
N3 | 0.0630 (7) | 0.0292 (6) | 0.0397 (6) | −0.0037 (5) | 0.0357 (6) | −0.0032 (5) |
C5 | 0.0357 (6) | 0.0342 (7) | 0.0295 (6) | 0.0003 (5) | 0.0157 (5) | 0.0007 (5) |
C3 | 0.0588 (9) | 0.0347 (7) | 0.0490 (8) | −0.0050 (6) | 0.0217 (7) | 0.0055 (6) |
C4 | 0.0527 (8) | 0.0415 (8) | 0.0393 (7) | −0.0032 (6) | 0.0256 (6) | 0.0053 (6) |
Geometric parameters (Å, º) top
S1—C6 | 1.6897 (13) | N2—C5 | 1.3947 (16) |
N4—N3 | 1.4104 (16) | N2—H5 | 0.8600 |
N4—H8 | 0.92 (2) | C6—N3 | 1.3283 (17) |
N4—H7 | 0.74 (3) | C1—H1 | 0.9300 |
N1—C5 | 1.3286 (17) | N3—H6 | 0.79 (2) |
N1—C1 | 1.3420 (17) | C5—C4 | 1.3960 (19) |
C2—C1 | 1.367 (2) | C3—C4 | 1.374 (2) |
C2—C3 | 1.382 (3) | C3—H3 | 0.9300 |
C2—H2 | 0.9300 | C4—H4 | 0.9300 |
N2—C6 | 1.3639 (16) | | |
| | | |
N3—N4—H8 | 102.7 (15) | N1—C1—H1 | 118.2 |
N3—N4—H7 | 106 (2) | C2—C1—H1 | 118.2 |
H8—N4—H7 | 112 (3) | C6—N3—N4 | 122.79 (12) |
C5—N1—C1 | 117.44 (12) | C6—N3—H6 | 120.7 (14) |
C1—C2—C3 | 118.33 (14) | N4—N3—H6 | 116.4 (14) |
C1—C2—H2 | 120.8 | N1—C5—N2 | 118.87 (11) |
C3—C2—H2 | 120.8 | N1—C5—C4 | 122.98 (12) |
C6—N2—C5 | 129.97 (11) | N2—C5—C4 | 118.14 (12) |
C6—N2—H5 | 115.0 | C4—C3—C2 | 119.48 (14) |
C5—N2—H5 | 115.0 | C4—C3—H3 | 120.3 |
N3—C6—N2 | 117.96 (11) | C2—C3—H3 | 120.3 |
N3—C6—S1 | 123.16 (10) | C3—C4—C5 | 118.09 (15) |
N2—C6—S1 | 118.85 (10) | C3—C4—H4 | 121.0 |
N1—C1—C2 | 123.65 (15) | C5—C4—H4 | 121.0 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···N4i | 0.86 | 2.21 | 3.058 (2) | 169 |
N4—H7···S1 | 0.75 (3) | 2.72 (3) | 3.025 (2) | 107 (2) |
N3—H6···N1 | 0.79 (2) | 2.06 (2) | 2.6698 (16) | 134.0 (19) |
Symmetry code: (i) −x+1/2, y+3/2, −z+1/2. |