Bis[methyl 2-(2-pyridylmethyl-idene)hydrazinecarbodithio-ato]zinc(II).

In the title compound, [Zn(C(8)H(8)N(3)S(2))(2)], the Zn atom is coordinated by the two ligands in a tridentate manner, via the pyridyl N, the azomethine N and the thiol-ate S atom; the coordination geometry is distorted octa-hedral, with the two ligands in the mer configuration (two S atoms and two pyridyl N atoms are cis with respect to each other and the azomethine N atoms is trans). The mol-ecules are linked by C-H⋯S hydrogen bonds, forming a three-dimensional network structure.

Related literature

For general background, see: Akbar Ali et al. (2001 ▶); Casas et al. (2000 ▶); Kasuga et al. (2001 ▶); Tarafder et al. (2003 ▶). For related structures, see: Chen et al. (2003a ▶,b ▶); Lin et al. (2007 ▶).

Experimental

Crystal data

[Zn(C8H8N3S2)2]

M = 487.97

Orthorhombic,

a = 18.630 (7) Å

b = 9.160 (3) Å

c = 12.457 (4) Å

V = 2125.8 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.56 mm−1

T = 293 (2) K

0.25 × 0.22 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.745, T max = 0.777

11500 measured reflections

4584 independent reflections

3257 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.079

S = 1.04

4584 reflections

244 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Flack (1983 ▶), 2122 Friedel pairs

Flack parameter: 0.013 (12)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Bruker, 1998 ▶); software used to prepare material for publication: SHELXTL and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068493/wn2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068493/wn2230Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(C8H8N3S2)2]	F000 = 1000
Mr = 487.97	Dx = 1.525 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P2c-2n	Cell parameters from 5120 reflections
a = 18.630 (7) Å	θ = 2.8–26.8º
b = 9.160 (3) Å	µ = 1.56 mm−1
c = 12.457 (4) Å	T = 293 (2) K
V = 2125.8 (13) Å3	Block, colorless
Z = 4	0.25 × 0.22 × 0.17 mm

Bruker SMART CCD area-detector diffractometer	4584 independent reflections
Radiation source: fine-focus sealed tube	3257 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.028
T = 293(2) K	θmax = 27.1º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −23→13
Tmin = 0.745, Tmax = 0.777	k = −11→11
11500 measured reflections	l = −15→15

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0305P)2 + 0.1243P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.079	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.25 e Å−3
4584 reflections	Δρmin = −0.30 e Å−3
244 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 2122 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.013 (12)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
Zn1	0.056290 (19)	0.37624 (4)	−0.00480 (4)	0.05017 (12)
S1	0.06703 (6)	0.16722 (11)	−0.12754 (9)	0.0649 (3)
S2	0.16269 (7)	0.12965 (14)	−0.30631 (10)	0.0782 (4)
S3	0.15974 (5)	0.33863 (11)	0.11758 (9)	0.0641 (3)
S4	0.16648 (8)	0.15980 (16)	0.30963 (11)	0.0885 (4)
N1	0.05862 (16)	0.6151 (3)	0.0248 (2)	0.0548 (9)
N2	0.11660 (15)	0.4672 (3)	−0.1347 (2)	0.0494 (7)
N3	0.14624 (17)	0.3833 (4)	−0.2142 (2)	0.0587 (8)
H3A	0.1757	0.4172	−0.2611	0.070*
N4	−0.06136 (14)	0.3920 (3)	−0.0321 (2)	0.0527 (8)
N5	0.00813 (14)	0.2761 (3)	0.1317 (2)	0.0468 (7)
N6	0.04532 (16)	0.2141 (3)	0.2144 (2)	0.0563 (8)
H6A	0.0252	0.1636	0.2642	0.068*
C1	0.0304 (2)	0.6883 (5)	0.1059 (4)	0.0695 (11)
H1A	−0.0021	0.6405	0.1504	0.083*
C2	0.0468 (3)	0.8328 (5)	0.1276 (4)	0.0782 (13)
H2A	0.0268	0.8802	0.1864	0.094*
C3	0.0925 (3)	0.9028 (5)	0.0616 (4)	0.0806 (13)
H3B	0.1043	0.9998	0.0746	0.097*
C4	0.1219 (2)	0.8307 (4)	−0.0255 (4)	0.0708 (12)
H4A	0.1532	0.8780	−0.0723	0.085*
C5	0.1034 (2)	0.6868 (4)	−0.0407 (3)	0.0519 (9)
C6	0.13319 (19)	0.6008 (4)	−0.1282 (3)	0.0540 (9)
H6B	0.1638	0.6431	−0.1783	0.065*
C7	0.1259 (2)	0.2492 (5)	−0.2121 (3)	0.0513 (10)
C8	0.2232 (3)	0.2385 (6)	−0.3797 (5)	0.123 (2)
H8A	0.2461	0.1801	−0.4337	0.185*
H8B	0.2589	0.2776	−0.3320	0.185*
H8C	0.1976	0.3172	−0.4133	0.185*
C9	−0.0957 (2)	0.4483 (5)	−0.1153 (4)	0.0715 (11)
H9A	−0.0695	0.4984	−0.1670	0.086*
C10	−0.1684 (2)	0.4357 (5)	−0.1283 (4)	0.0832 (14)
H10A	−0.1906	0.4778	−0.1876	0.100*
C11	−0.2080 (2)	0.3619 (5)	−0.0549 (4)	0.0846 (15)
H11A	−0.2573	0.3521	−0.0632	0.102*
C12	−0.1735 (2)	0.3019 (5)	0.0324 (4)	0.0729 (12)
H12A	−0.1993	0.2519	0.0848	0.087*
C13	−0.09986 (19)	0.3174 (4)	0.0405 (3)	0.0529 (9)
C14	−0.05961 (18)	0.2558 (4)	0.1289 (3)	0.0543 (9)
H14A	−0.0826	0.2026	0.1824	0.065*
C15	0.1136 (2)	0.2385 (4)	0.2107 (3)	0.0535 (10)
C16	0.1042 (3)	0.0692 (7)	0.3960 (4)	0.131 (2)
H16A	0.1298	0.0223	0.4533	0.197*
H16B	0.0781	−0.0027	0.3558	0.197*
H16C	0.0713	0.1393	0.4253	0.197*

	U11	U22	U33	U12	U13	U23
Zn1	0.0438 (2)	0.0553 (2)	0.0514 (2)	−0.00346 (17)	0.0087 (2)	0.0044 (2)
S1	0.0754 (7)	0.0579 (6)	0.0615 (6)	−0.0133 (5)	0.0076 (6)	−0.0041 (5)
S2	0.0750 (8)	0.0874 (9)	0.0721 (7)	0.0010 (6)	0.0107 (6)	−0.0295 (6)
S3	0.0393 (5)	0.0865 (7)	0.0665 (6)	0.0000 (5)	0.0002 (5)	−0.0022 (6)
S4	0.0793 (9)	0.0942 (9)	0.0921 (9)	0.0049 (7)	−0.0400 (8)	0.0142 (7)
N1	0.0497 (16)	0.0497 (16)	0.065 (3)	0.0043 (15)	0.0092 (15)	−0.0022 (14)
N2	0.0492 (16)	0.053 (2)	0.0462 (16)	−0.0006 (14)	0.0097 (14)	0.0008 (15)
N3	0.0558 (19)	0.071 (2)	0.0496 (18)	−0.0080 (16)	0.0192 (15)	−0.0006 (16)
N4	0.0441 (16)	0.0578 (18)	0.056 (2)	−0.0011 (14)	0.0030 (14)	0.0111 (14)
N5	0.0418 (17)	0.0534 (17)	0.0451 (15)	−0.0013 (13)	0.0030 (14)	0.0051 (14)
N6	0.057 (2)	0.065 (2)	0.0474 (17)	−0.0068 (15)	−0.0047 (15)	0.0106 (15)
C1	0.066 (3)	0.073 (3)	0.070 (3)	0.007 (2)	0.016 (2)	−0.002 (2)
C2	0.097 (3)	0.068 (3)	0.070 (3)	0.021 (2)	0.008 (3)	−0.011 (2)
C3	0.101 (4)	0.058 (3)	0.083 (3)	0.007 (3)	−0.005 (3)	−0.009 (2)
C4	0.080 (3)	0.057 (2)	0.076 (4)	−0.004 (2)	0.002 (2)	0.005 (2)
C5	0.051 (2)	0.044 (2)	0.060 (2)	0.0033 (17)	−0.0019 (17)	0.0037 (16)
C6	0.056 (2)	0.052 (2)	0.055 (2)	−0.0081 (17)	0.0097 (19)	0.0076 (18)
C7	0.051 (2)	0.058 (3)	0.045 (2)	−0.0007 (19)	−0.0046 (16)	−0.0083 (18)
C8	0.119 (4)	0.148 (5)	0.103 (4)	−0.015 (4)	0.053 (4)	−0.024 (4)
C9	0.060 (3)	0.079 (3)	0.076 (3)	0.000 (2)	−0.003 (2)	0.026 (3)
C10	0.066 (3)	0.089 (3)	0.095 (3)	0.001 (2)	−0.026 (3)	0.032 (3)
C11	0.047 (2)	0.093 (4)	0.114 (4)	−0.004 (2)	−0.018 (3)	0.023 (3)
C12	0.048 (2)	0.090 (3)	0.080 (3)	−0.019 (2)	0.002 (2)	0.016 (2)
C13	0.039 (2)	0.060 (2)	0.059 (2)	0.0024 (17)	0.0026 (17)	0.0065 (18)
C14	0.045 (2)	0.069 (2)	0.049 (2)	−0.0080 (17)	0.0058 (19)	0.0063 (18)
C15	0.051 (2)	0.056 (3)	0.054 (2)	0.0061 (19)	−0.0101 (19)	−0.0152 (17)
C16	0.158 (6)	0.146 (5)	0.090 (4)	−0.045 (4)	−0.054 (4)	0.052 (4)

Zn1—N5	2.130 (3)	C1—H1A	0.9300
Zn1—N2	2.139 (3)	C2—C3	1.346 (7)
Zn1—N1	2.219 (3)	C2—H2A	0.9300
Zn1—N4	2.223 (3)	C3—C4	1.384 (6)
Zn1—S1	2.4584 (13)	C3—H3B	0.9300
Zn1—S3	2.4814 (13)	C4—C5	1.376 (5)
S1—C7	1.697 (4)	C4—H4A	0.9300
S2—C7	1.744 (4)	C5—C6	1.456 (5)
S2—C8	1.761 (5)	C6—H6B	0.9300
S3—C15	1.710 (4)	C8—H8A	0.9600
S4—C15	1.735 (4)	C8—H8B	0.9600
S4—C16	1.786 (6)	C8—H8C	0.9600
N1—C1	1.321 (5)	C9—C10	1.368 (5)
N1—C5	1.339 (4)	C9—H9A	0.9300
N2—C6	1.264 (4)	C10—C11	1.356 (6)
N2—N3	1.370 (4)	C10—H10A	0.9300
N3—C7	1.286 (5)	C11—C12	1.377 (6)
N3—H3A	0.8600	C11—H11A	0.9300
N4—C9	1.323 (5)	C12—C13	1.384 (5)
N4—C13	1.341 (4)	C12—H12A	0.9300
N5—C14	1.276 (4)	C13—C14	1.447 (5)
N5—N6	1.365 (4)	C14—H14A	0.9300
N6—C15	1.293 (4)	C16—H16A	0.9600
N6—H6A	0.8600	C16—H16B	0.9600
C1—C2	1.385 (6)	C16—H16C	0.9600
N5—Zn1—N2	173.15 (11)	C5—C4—C3	117.7 (4)
N5—Zn1—N1	107.46 (11)	C5—C4—H4A	121.1
N2—Zn1—N1	74.43 (11)	C3—C4—H4A	121.1
N5—Zn1—N4	74.61 (10)	N1—C5—C4	122.9 (4)
N2—Zn1—N4	112.15 (11)	N1—C5—C6	115.4 (3)
N1—Zn1—N4	88.90 (11)	C4—C5—C6	121.7 (4)
N5—Zn1—S1	101.26 (8)	N2—C6—C5	118.6 (3)
N2—Zn1—S1	77.89 (8)	N2—C6—H6B	120.7
N1—Zn1—S1	150.43 (8)	C5—C6—H6B	120.7
N4—Zn1—S1	92.05 (8)	N3—C7—S1	128.7 (3)
N5—Zn1—S3	77.11 (8)	N3—C7—S2	118.1 (3)
N2—Zn1—S3	96.37 (9)	S1—C7—S2	113.2 (2)
N1—Zn1—S3	91.11 (8)	S2—C8—H8A	109.5
N4—Zn1—S3	150.32 (8)	S2—C8—H8B	109.5
S1—Zn1—S3	102.17 (4)	H8A—C8—H8B	109.5
C7—S1—Zn1	95.42 (14)	S2—C8—H8C	109.5
C7—S2—C8	104.2 (2)	H8A—C8—H8C	109.5
C15—S3—Zn1	95.79 (13)	H8B—C8—H8C	109.5
C15—S4—C16	104.6 (2)	N4—C9—C10	122.6 (4)
C1—N1—C5	117.7 (3)	N4—C9—H9A	118.7
C1—N1—Zn1	128.3 (3)	C10—C9—H9A	118.7
C5—N1—Zn1	113.2 (2)	C11—C10—C9	120.0 (4)
C6—N2—N3	119.4 (3)	C11—C10—H10A	120.0
C6—N2—Zn1	117.2 (2)	C9—C10—H10A	120.0
N3—N2—Zn1	122.7 (2)	C10—C11—C12	118.6 (4)
C7—N3—N2	113.8 (3)	C10—C11—H11A	120.7
C7—N3—H3A	123.1	C12—C11—H11A	120.7
N2—N3—H3A	123.1	C11—C12—C13	118.6 (4)
C9—N4—C13	117.9 (3)	C11—C12—H12A	120.7
C9—N4—Zn1	128.5 (3)	C13—C12—H12A	120.7
C13—N4—Zn1	113.0 (2)	N4—C13—C12	122.3 (4)
C14—N5—N6	117.5 (3)	N4—C13—C14	115.8 (3)
C14—N5—Zn1	117.2 (2)	C12—C13—C14	122.0 (4)
N6—N5—Zn1	124.6 (2)	N5—C14—C13	118.5 (3)
C15—N6—N5	113.6 (3)	N5—C14—H14A	120.8
C15—N6—H6A	123.2	C13—C14—H14A	120.8
N5—N6—H6A	123.2	N6—C15—S3	127.7 (3)
N1—C1—C2	123.1 (4)	N6—C15—S4	117.5 (3)
N1—C1—H1A	118.5	S3—C15—S4	114.8 (2)
C2—C1—H1A	118.5	S4—C16—H16A	109.5
C3—C2—C1	118.4 (4)	S4—C16—H16B	109.5
C3—C2—H2A	120.8	H16A—C16—H16B	109.5
C1—C2—H2A	120.8	S4—C16—H16C	109.5
C2—C3—C4	120.2 (4)	H16A—C16—H16C	109.5
C2—C3—H3B	119.9	H16B—C16—H16C	109.5
C4—C3—H3B	119.9

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Sli	0.93	2.94	3.715 (3)	142
C12—H12A···S3ii	0.93	2.79	3.526 (4)	138

Zn1—N5	2.130 (3)
Zn1—N2	2.139 (3)
Zn1—N1	2.219 (3)
Zn1—N4	2.223 (3)
Zn1—S1	2.4584 (13)
Zn1—S3	2.4814 (13)

N5—Zn1—N2	173.15 (11)
N5—Zn1—N1	107.46 (11)
N2—Zn1—N1	74.43 (11)
N5—Zn1—N4	74.61 (10)
N2—Zn1—N4	112.15 (11)
N1—Zn1—N4	88.90 (11)
N5—Zn1—S1	101.26 (8)
N2—Zn1—S1	77.89 (8)
N1—Zn1—S1	150.43 (8)
N4—Zn1—S1	92.05 (8)
N5—Zn1—S3	77.11 (8)
N2—Zn1—S3	96.37 (9)
N1—Zn1—S3	91.11 (8)
N4—Zn1—S3	150.32 (8)
S1—Zn1—S3	102.17 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Sli	0.93	2.94	3.715 (3)	142
C12—H12A⋯S3ii	0.93	2.79	3.526 (4)	138

Symmetry codes: (i) ; (ii) .