supplementary materials


gg2112 scheme

Acta Cryst. (2013). E69, o712    [ doi:10.1107/S1600536813009409 ]

Methyl 3-(pyridin-4-ylmethylidene)dithiocarbazate

H. Wang, A.-M.-S. Hossain, S.-C. Wang and Y.-P. Tian

Abstract top

There are two independent molecules in the asymmetric unit of the title molecule, C8H9N3S2, both of which exhibit an E conformation with the pyridine ring and dithiocarbazate fragment located on opposite sides of the C=N bond. The pyridine ring and dithiocarbazate group are approximately coplanar, with dihedral angles of 4.74 (1) and 8.77 (1)° between their planes in the two molecules. In the crystal, molecules are linked to each other via N-H...N hydrogen bonds, forming zigzag chains parallel to [10-1].

Comment top

The derivatives of the title compound, (I), are often used as coordinating ligands in the metal complexes (Wu et al., 2001; Fun et al. 2001). Herewith, in this study, we report the crystal structure of the title compound (I). The dithiocarbazate moiety shows an E configuration about the C(6A)—N(2A) and N(3A)—C(7A) bonds.Through planar as whole, the molecules comprise two planar fragments, namely the pyridine moiety and dithiocarbazate moiety with dihedral angles of 4.74 (1)° and 8.77 (1)°, respectively.The bond distances of C(7A)—S(2 A) and C(7A)—S(1 A) are different compared to the bond lengths of C(7B)—S(2B) and C(7B)—S(1B). So the crystal structures of the two molecules are independent. The value for the C=S bond of two molecules is almost same with corresponding C=S bond of related compounds. Also, the pairs of centrosymmetrically related molecules are linked into dimers by pairs of N(1A)···H(3B) and N(1B)···H(3A) hydrogen bonds.

Related literature top

For related structures, see: Shan et al. (2006); Chen et al. (2007). Derivatives of the title compound are often used as coordinating ligands in the metal complexes, see for example: Wu et al. (2001); Fun et al. (2001).

Experimental top

A hot solution of S-Methyldithiocarbazate(0.488 mg, 4 mmol) in ethanol (30 mL) was mixed with a 4-formylpyridine (0.535 mg, 5 mmol) in ethanol 10 mL and the reaction mixture was reflux. After one hour, precipitated was appeared. Under cooling at room temperature the light yellow crystals were separated by filtration and recrystallized from methanol. Yield: 70%. 1H NMR (400 MHz, DMSO-d6) 13.5 (s, 1H), 8.6 (d, 2H), 8.2 (d, 2H), 7.6 (s, 2H), 2.5 (s, 3H).

Refinement top

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
[Figure 2] Fig. 2. : The H-bond diagram of the title molecule (I).
[Figure 3] Fig. 3. A packing diagram.
Methyl 3-(pyridin-4-ylmethylidene)dithiocarbazate top
Crystal data top
C8H9N3S2F(000) = 880
Mr = 211.30Dx = 1.379 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 3068 reflections
a = 7.547 (5) Åθ = 3.1–23.7°
b = 20.216 (5) ŵ = 0.48 mm1
c = 13.415 (5) ÅT = 296 K
β = 96.070 (5)°Needle, yellow
V = 2035.3 (16) Å30.30 × 0.20 × 0.20 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
3565 independent reflections
Radiation source: fine-focus sealed tube2379 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
phi and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 88
Tmin = 0.870, Tmax = 0.910k = 2423
14118 measured reflectionsl = 1515
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0609P)2 + 0.3327P]
where P = (Fo2 + 2Fc2)/3
3565 reflections(Δ/σ)max = 0.002
237 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
C8H9N3S2V = 2035.3 (16) Å3
Mr = 211.30Z = 8
Monoclinic, P21/cMo Kα radiation
a = 7.547 (5) ŵ = 0.48 mm1
b = 20.216 (5) ÅT = 296 K
c = 13.415 (5) Å0.30 × 0.20 × 0.20 mm
β = 96.070 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3565 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2379 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.910Rint = 0.035
14118 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.23 e Å3
S = 1.02Δρmin = 0.40 e Å3
3565 reflectionsAbsolute structure: ?
237 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
S1A0.35871 (10)0.85984 (3)0.66511 (5)0.0612 (2)
S2A0.61864 (10)0.86303 (4)0.85370 (5)0.0664 (2)
S2B1.13863 (10)1.12665 (4)0.84421 (6)0.0682 (2)
S1B0.88859 (11)1.12370 (4)0.65218 (6)0.0701 (3)
N2A0.4094 (3)0.72614 (10)0.67557 (13)0.0506 (5)
N3A0.5016 (2)0.75677 (10)0.75618 (13)0.0517 (5)
H3A0.56050.73370.80230.062*
N2B0.9044 (3)0.98971 (10)0.67700 (14)0.0511 (5)
C7A0.4990 (3)0.82288 (12)0.76252 (17)0.0497 (6)
C3A0.3291 (3)0.62711 (12)0.58701 (17)0.0465 (6)
N1A0.1530 (3)0.55737 (10)0.42552 (15)0.0577 (6)
C3B0.8138 (3)0.89050 (12)0.59250 (17)0.0495 (6)
C6B0.9048 (3)0.92688 (12)0.67716 (17)0.0510 (6)
H6B0.96300.90400.73120.061*
N1B0.6448 (3)0.82087 (11)0.42879 (15)0.0637 (6)
N3B0.9971 (2)1.02071 (10)0.75677 (14)0.0520 (5)
H3B1.04450.99820.80710.062*
C4B0.7214 (4)0.92342 (13)0.51193 (17)0.0644 (8)
H4B0.71520.96940.51080.077*
C7B1.0131 (3)1.08713 (12)0.75522 (18)0.0509 (6)
C6A0.4216 (3)0.66340 (12)0.67161 (16)0.0488 (6)
H6A0.48920.64060.72250.059*
C4A0.3405 (3)0.55944 (12)0.58017 (18)0.0585 (7)
H4A0.40800.53560.63000.070*
C2B0.8164 (3)0.82227 (13)0.58876 (18)0.0572 (7)
H2B0.87570.79820.64120.069*
C2A0.2238 (4)0.65942 (14)0.51115 (17)0.0662 (8)
H2A0.21050.70510.51230.079*
C5A0.2517 (3)0.52680 (13)0.49947 (18)0.0609 (7)
H5A0.26150.48100.49670.073*
C1A0.1395 (4)0.62239 (14)0.4342 (2)0.0717 (9)
H1A0.06770.64470.38450.086*
C1B0.7311 (3)0.78998 (13)0.50717 (18)0.0613 (7)
H1B0.73370.74400.50670.074*
C5B0.6397 (4)0.88672 (14)0.4341 (2)0.0726 (9)
H5B0.57640.90930.38150.087*
C8B0.9334 (4)1.20963 (13)0.6749 (3)0.0900 (10)
H8B0.90261.22130.74020.135*
H7B0.86391.23560.62520.135*
H9B1.05781.21810.67130.135*
C8A0.3883 (4)0.94601 (13)0.6945 (2)0.0754 (8)
H8A0.36110.95390.76180.113*
H9A0.31010.97180.64870.113*
H10A0.50960.95840.68870.113*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0645 (5)0.0584 (4)0.0575 (4)0.0059 (3)0.0086 (3)0.0075 (3)
S2A0.0795 (5)0.0582 (4)0.0575 (4)0.0075 (4)0.0124 (4)0.0068 (3)
S2B0.0697 (5)0.0607 (5)0.0707 (5)0.0100 (3)0.0088 (4)0.0095 (3)
S1B0.0829 (6)0.0631 (5)0.0609 (5)0.0095 (4)0.0075 (4)0.0092 (3)
N2A0.0549 (13)0.0558 (13)0.0379 (11)0.0022 (10)0.0093 (9)0.0007 (9)
N3A0.0597 (14)0.0523 (12)0.0392 (11)0.0006 (10)0.0129 (10)0.0002 (9)
N2B0.0565 (13)0.0553 (13)0.0388 (11)0.0006 (10)0.0083 (9)0.0028 (9)
C7A0.0487 (15)0.0537 (15)0.0460 (14)0.0015 (11)0.0021 (11)0.0010 (11)
C3A0.0478 (14)0.0561 (15)0.0340 (13)0.0002 (11)0.0023 (11)0.0018 (10)
N1A0.0720 (15)0.0527 (13)0.0446 (12)0.0026 (11)0.0108 (11)0.0016 (10)
C3B0.0528 (15)0.0558 (16)0.0383 (14)0.0007 (12)0.0029 (11)0.0011 (11)
C6B0.0562 (16)0.0571 (16)0.0368 (13)0.0012 (12)0.0083 (11)0.0010 (11)
N1B0.0824 (16)0.0600 (15)0.0444 (12)0.0048 (12)0.0140 (11)0.0041 (10)
N3B0.0574 (13)0.0534 (13)0.0418 (11)0.0034 (10)0.0104 (10)0.0024 (9)
C4B0.091 (2)0.0529 (16)0.0439 (15)0.0012 (14)0.0171 (14)0.0027 (12)
C7B0.0501 (15)0.0536 (15)0.0490 (14)0.0044 (12)0.0050 (12)0.0012 (11)
C6A0.0543 (15)0.0515 (15)0.0376 (13)0.0002 (12)0.0084 (11)0.0036 (11)
C4A0.0710 (18)0.0518 (16)0.0479 (15)0.0079 (13)0.0163 (13)0.0040 (12)
C2B0.0698 (18)0.0577 (17)0.0402 (14)0.0054 (13)0.0121 (12)0.0042 (11)
C2A0.096 (2)0.0478 (15)0.0481 (15)0.0069 (14)0.0244 (15)0.0006 (12)
C5A0.077 (2)0.0478 (16)0.0533 (16)0.0030 (13)0.0130 (14)0.0013 (11)
C1A0.096 (2)0.0611 (18)0.0502 (16)0.0082 (15)0.0296 (16)0.0030 (13)
C1B0.081 (2)0.0523 (16)0.0481 (16)0.0012 (13)0.0059 (14)0.0005 (12)
C5B0.106 (2)0.0561 (18)0.0479 (16)0.0010 (15)0.0256 (16)0.0024 (13)
C8B0.111 (3)0.0575 (18)0.101 (3)0.0072 (18)0.008 (2)0.0194 (17)
C8A0.085 (2)0.0578 (17)0.082 (2)0.0140 (15)0.0053 (17)0.0112 (15)
Geometric parameters (Å, º) top
S1A—C7A1.759 (2)N1B—C5B1.334 (3)
S1A—C8A1.795 (3)N3B—C7B1.348 (3)
S2A—C7A1.654 (2)N3B—H3B0.8600
S2B—C7B1.650 (3)C4B—C5B1.372 (3)
S1B—C7B1.751 (2)C4B—H4B0.9300
S1B—C8B1.790 (3)C6A—H6A0.9300
N2A—C6A1.273 (3)C4A—C5A1.379 (3)
N2A—N3A1.370 (2)C4A—H4A0.9300
N3A—C7A1.339 (3)C2B—C1B1.375 (3)
N3A—H3A0.8600C2B—H2B0.9300
N2B—C6B1.270 (3)C2A—C1A1.376 (3)
N2B—N3B1.368 (2)C2A—H2A0.9300
C3A—C4A1.375 (3)C5A—H5A0.9300
C3A—C2A1.386 (3)C1A—H1A0.9300
C3A—C6A1.465 (3)C1B—H1B0.9300
N1A—C1A1.324 (3)C5B—H5B0.9300
N1A—C5A1.329 (3)C8B—H8B0.9600
C3B—C2B1.380 (3)C8B—H7B0.9600
C3B—C4B1.392 (3)C8B—H9B0.9600
C3B—C6B1.462 (3)C8A—H8A0.9600
C6B—H6B0.9300C8A—H9A0.9600
N1B—C1B1.332 (3)C8A—H10A0.9600
C7A—S1A—C8A101.42 (13)C3A—C4A—C5A120.0 (2)
C7B—S1B—C8B101.51 (14)C3A—C4A—H4A120.0
C6A—N2A—N3A116.77 (19)C5A—C4A—H4A120.0
C7A—N3A—N2A119.44 (19)C1B—C2B—C3B119.7 (2)
C7A—N3A—H3A120.3C1B—C2B—H2B120.1
N2A—N3A—H3A120.3C3B—C2B—H2B120.1
C6B—N2B—N3B117.1 (2)C1A—C2A—C3A118.6 (3)
N3A—C7A—S2A121.75 (18)C1A—C2A—H2A120.7
N3A—C7A—S1A112.84 (17)C3A—C2A—H2A120.7
S2A—C7A—S1A125.41 (15)N1A—C5A—C4A123.4 (2)
C4A—C3A—C2A117.1 (2)N1A—C5A—H5A118.3
C4A—C3A—C6A121.5 (2)C4A—C5A—H5A118.3
C2A—C3A—C6A121.5 (2)N1A—C1A—C2A124.9 (3)
C1A—N1A—C5A116.0 (2)N1A—C1A—H1A117.5
C2B—C3B—C4B117.2 (2)C2A—C1A—H1A117.5
C2B—C3B—C6B121.6 (2)N1B—C1B—C2B123.7 (3)
C4B—C3B—C6B121.2 (2)N1B—C1B—H1B118.2
N2B—C6B—C3B120.1 (2)C2B—C1B—H1B118.2
N2B—C6B—H6B120.0N1B—C5B—C4B124.5 (3)
C3B—C6B—H6B120.0N1B—C5B—H5B117.7
C1B—N1B—C5B116.1 (2)C4B—C5B—H5B117.7
C7B—N3B—N2B118.9 (2)S1B—C8B—H8B109.5
C7B—N3B—H3B120.5S1B—C8B—H7B109.5
N2B—N3B—H3B120.5H8B—C8B—H7B109.5
C5B—C4B—C3B118.7 (3)S1B—C8B—H9B109.5
C5B—C4B—H4B120.7H8B—C8B—H9B109.5
C3B—C4B—H4B120.7H7B—C8B—H9B109.5
N3B—C7B—S2B121.11 (18)S1A—C8A—H8A109.5
N3B—C7B—S1B113.02 (18)S1A—C8A—H9A109.5
S2B—C7B—S1B125.87 (15)H8A—C8A—H9A109.5
N2A—C6A—C3A120.0 (2)S1A—C8A—H10A109.5
N2A—C6A—H6A120.0H8A—C8A—H10A109.5
C3A—C6A—H6A120.0H9A—C8A—H10A109.5
C6A—N2A—N3A—C7A177.6 (2)C4A—C3A—C6A—N2A179.6 (2)
N2A—N3A—C7A—S2A175.66 (17)C2A—C3A—C6A—N2A1.5 (4)
N2A—N3A—C7A—S1A4.1 (3)C2A—C3A—C4A—C5A1.1 (4)
C8A—S1A—C7A—N3A179.21 (18)C6A—C3A—C4A—C5A180.0 (2)
C8A—S1A—C7A—S2A0.5 (2)C4B—C3B—C2B—C1B0.6 (4)
N3B—N2B—C6B—C3B177.8 (2)C6B—C3B—C2B—C1B179.2 (2)
C2B—C3B—C6B—N2B177.9 (2)C4A—C3A—C2A—C1A0.6 (4)
C4B—C3B—C6B—N2B1.8 (4)C6A—C3A—C2A—C1A179.5 (3)
C6B—N2B—N3B—C7B174.2 (2)C1A—N1A—C5A—C4A1.6 (4)
C2B—C3B—C4B—C5B0.2 (4)C3A—C4A—C5A—N1A0.1 (4)
C6B—C3B—C4B—C5B179.5 (3)C5A—N1A—C1A—C2A2.2 (5)
N2B—N3B—C7B—S2B174.34 (17)C3A—C2A—C1A—N1A1.1 (5)
N2B—N3B—C7B—S1B6.0 (3)C5B—N1B—C1B—C2B2.0 (4)
C8B—S1B—C7B—N3B178.32 (18)C3B—C2B—C1B—N1B0.6 (4)
C8B—S1B—C7B—S2B1.3 (2)C1B—N1B—C5B—C4B2.4 (5)
N3A—N2A—C6A—C3A179.1 (2)C3B—C4B—C5B—N1B1.3 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···N1Ai0.862.042.904 (3)179
N3A—H3A···N1Bii0.862.072.909 (3)166
Symmetry codes: (i) x+1, y+3/2, z+1/2; (ii) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···N1Ai0.862.042.904 (3)179
N3A—H3A···N1Bii0.862.072.909 (3)166
Symmetry codes: (i) x+1, y+3/2, z+1/2; (ii) x, y+3/2, z+1/2.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (21071001, 21271004) and grants from the Postdoctoral Foundation of Anhui Province.

references
References top

Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, Z.-Y., Wu, G.-Q., Jiang, F.-X., Tian, Y.-L. & Shan, S. (2007). Acta Cryst. E63, o1919–o1920.

Fun, H.-K., Chantrapromma, S., Razak, I. A., Usman, A., Tang, Y. W., Ma, W., Wu, J. Y. & Tian, Y. P. (2001). Acta Cryst. E57, m519–m521.

Shan, S., Zhang, Y.-L. & Xu, D.-J. (2006). Acta Cryst. E62, o1567–o1569.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wu, J.-Y., Chantrapromma, S., Chen, D.-W., Tian, Y.-P., Yang, P. & Fun, H.-K. (2001). Acta Cryst. C57, 523–525.