Bis[benzyl N'-(3-phenyl-prop-2-enyl-idene)hydrazinecarbodithio-ato-κN',S]zinc(II).

In the title Zn(II) complex, [Zn(C(17)H(15)N(2)S(2))(2)], the Zn(II) atom lies on a twofold rotation axis. It exists in a tetra-hedral geometry, chelated by two deprotonated Schiff base ligands. The dihedral angle between each ligand is 71.48 (8)°. Mol-ecules are connected by weak C-H⋯S inter-molecular inter-actions into chains along the c axis. The crystal structure is further stabilized by C-H⋯π inter-actions involving the phenyl ring of the 3-phenyl-prop-2-enyl-idene unit.

Related literature

For the synthesis and structure of S-benzyl­dithio­carbaza­tes, see: Ali & Tarafder (1977 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For the structures of ZnII complexes, see: Latheef et al. (2007 ▶); Tarafder, Chew et al. (2002 ▶). For the structures of other metal dithio­carbaza­tes, see: Ali et al. (2001 ▶, 2002 ▶, 2008 ▶); Chew et al. (2004 ▶); Crouse et al. (2004 ▶); Tarafder et al. (2001 ▶, 2008 ▶); Tarafder, Chew et al. (2002 ▶); Tarafder, Jin et al. (2002 ▶). For the bioactivity of metal S-benzyl­dithio­carbaza­tes, see, for example: Ali et al. (2001 ▶, 2002 ▶); Tarafder et al. (2001 ▶); Tarafder, Jin et al. (2002 ▶).

Experimental

Crystal data

[Zn(C17H15N2S2)2]

M = 688.23

Orthorhombic,

a = 36.0897 (4) Å

b = 9.9310 (1) Å

c = 8.7633 (1) Å

V = 3140.83 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.08 mm−1

T = 100.0 (1) K

0.37 × 0.25 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.692, T max = 0.841

82655 measured reflections

4580 independent reflections

4071 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.091

S = 1.15

4580 reflections

195 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005643/ng2427sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005643/ng2427Isup2.hkl

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

[Zn(C17H15N2S2)2]	Dx = 1.455 Mg m−3
Mr = 688.23	Melting point = 457–458 K
Orthorhombic, Pbcn	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4580 reflections
a = 36.0897 (4) Å	θ = 1.1–30.0º
b = 9.9310 (1) Å	µ = 1.08 mm−1
c = 8.7633 (1) Å	T = 100.0 (1) K
V = 3140.83 (6) Å3	Block, yellow
Z = 4	0.37 × 0.25 × 0.17 mm
F000 = 1424

Bruker SMART APEXII CCD area-detector diffractometer	4580 independent reflections
Radiation source: fine-focus sealed tube	4071 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.042
Detector resolution: 8.33 pixels mm-1	θmax = 30.0º
T = 100.0(1) K	θmin = 1.1º
ω scans	h = −50→50
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −13→13
Tmin = 0.692, Tmax = 0.841	l = −12→12
82655 measured reflections

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)] = 0.028	H-atom parameters constrained
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0478P)2 + 1.4067P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max = 0.001
4580 reflections	Δρmax = 0.49 e Å−3
195 parameters	Δρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.0000	0.42216 (2)	0.2500	0.01855 (8)
S1	−0.056843 (10)	0.51031 (4)	0.20596 (5)	0.02295 (9)
S2	−0.126368 (10)	0.40453 (4)	0.31408 (5)	0.02541 (10)
N1	−0.02538 (3)	0.29452 (12)	0.40410 (14)	0.0177 (2)
N2	−0.06402 (3)	0.29289 (12)	0.40147 (14)	0.0183 (2)
C1	0.10940 (4)	0.21479 (15)	0.60174 (17)	0.0215 (3)
H1A	0.1007	0.2854	0.5420	0.026*
C2	0.14657 (4)	0.20851 (16)	0.63939 (18)	0.0238 (3)
H2B	0.1627	0.2745	0.6040	0.029*
C3	0.16001 (4)	0.10408 (18)	0.72987 (18)	0.0251 (3)
H3A	0.1851	0.0999	0.7541	0.030*
C4	0.13595 (4)	0.00646 (18)	0.78363 (19)	0.0263 (3)
H4A	0.1448	−0.0627	0.8451	0.032*
C5	0.09847 (4)	0.01154 (17)	0.74589 (18)	0.0233 (3)
H5A	0.0824	−0.0543	0.7825	0.028*
C6	0.08479 (4)	0.11508 (15)	0.65326 (16)	0.0191 (3)
C7	0.04530 (4)	0.11779 (15)	0.61642 (17)	0.0197 (3)
H7A	0.0304	0.0534	0.6627	0.024*
C8	0.02865 (4)	0.20541 (15)	0.52127 (17)	0.0203 (3)
H8A	0.0434	0.2660	0.4676	0.024*
C9	−0.01069 (4)	0.20968 (15)	0.49886 (16)	0.0194 (3)
H9A	−0.0258	0.1509	0.5530	0.023*
C10	−0.07830 (4)	0.38814 (15)	0.31855 (16)	0.0188 (3)
C11	−0.14245 (4)	0.29477 (17)	0.46680 (18)	0.0239 (3)
H11A	−0.1382	0.2011	0.4407	0.029*
H11B	−0.1295	0.3146	0.5611	0.029*
C12	−0.18343 (4)	0.32244 (15)	0.48382 (17)	0.0216 (3)
C13	−0.19570 (4)	0.42883 (18)	0.5729 (2)	0.0300 (3)
H13A	−0.1785	0.4831	0.6226	0.036*
C14	−0.23315 (5)	0.4555 (2)	0.5890 (2)	0.0327 (4)
H14A	−0.2410	0.5265	0.6503	0.039*
C15	−0.25893 (4)	0.37653 (18)	0.51415 (19)	0.0281 (3)
H15A	−0.2841	0.3942	0.5249	0.034*
C16	−0.24710 (4)	0.27147 (19)	0.4234 (2)	0.0316 (4)
H16A	−0.2644	0.2187	0.3722	0.038*
C17	−0.20951 (4)	0.24407 (17)	0.4082 (2)	0.0281 (3)
H17A	−0.2018	0.1729	0.3470	0.034*

	U11	U22	U33	U12	U13	U23
Zn1	0.01629 (12)	0.02017 (13)	0.01920 (13)	0.000	0.00389 (8)	0.000
S1	0.02122 (17)	0.02294 (18)	0.02470 (18)	0.00512 (13)	0.00525 (14)	0.00599 (14)
S2	0.01511 (16)	0.0341 (2)	0.02701 (19)	0.00377 (14)	−0.00046 (13)	0.00913 (15)
N1	0.0135 (5)	0.0205 (5)	0.0191 (5)	0.0002 (4)	0.0008 (4)	−0.0007 (4)
N2	0.0131 (5)	0.0227 (6)	0.0191 (5)	−0.0007 (4)	−0.0003 (4)	0.0002 (5)
C1	0.0198 (6)	0.0222 (7)	0.0226 (7)	0.0018 (5)	−0.0006 (5)	0.0003 (5)
C2	0.0176 (6)	0.0265 (7)	0.0272 (7)	−0.0010 (5)	0.0016 (5)	−0.0024 (6)
C3	0.0168 (6)	0.0325 (8)	0.0260 (7)	0.0047 (6)	−0.0026 (5)	−0.0048 (6)
C4	0.0240 (7)	0.0294 (8)	0.0255 (7)	0.0061 (6)	−0.0039 (6)	0.0025 (6)
C5	0.0214 (7)	0.0241 (7)	0.0243 (7)	0.0016 (6)	−0.0001 (5)	0.0029 (6)
C6	0.0166 (6)	0.0224 (6)	0.0184 (6)	0.0019 (5)	−0.0006 (5)	−0.0011 (5)
C7	0.0163 (6)	0.0228 (7)	0.0199 (6)	−0.0003 (5)	0.0008 (5)	−0.0003 (5)
C8	0.0155 (6)	0.0235 (7)	0.0219 (6)	−0.0004 (5)	0.0011 (5)	0.0008 (5)
C9	0.0164 (6)	0.0226 (7)	0.0192 (6)	−0.0007 (5)	0.0009 (5)	0.0008 (5)
C10	0.0156 (6)	0.0227 (7)	0.0182 (6)	0.0008 (5)	0.0010 (5)	−0.0008 (5)
C11	0.0151 (6)	0.0301 (8)	0.0266 (7)	0.0006 (5)	−0.0003 (5)	0.0060 (6)
C12	0.0148 (6)	0.0268 (7)	0.0230 (7)	0.0001 (5)	−0.0011 (5)	0.0044 (6)
C13	0.0212 (7)	0.0377 (9)	0.0311 (8)	−0.0008 (6)	−0.0057 (6)	−0.0092 (7)
C14	0.0235 (8)	0.0425 (10)	0.0322 (8)	0.0068 (7)	−0.0010 (6)	−0.0106 (8)
C15	0.0153 (6)	0.0392 (9)	0.0297 (8)	0.0025 (6)	0.0009 (6)	0.0018 (7)
C16	0.0172 (7)	0.0347 (9)	0.0428 (10)	−0.0042 (6)	−0.0036 (6)	−0.0053 (7)
C17	0.0189 (7)	0.0273 (8)	0.0380 (9)	−0.0004 (6)	−0.0015 (6)	−0.0070 (7)

Zn1—N1	2.0662 (12)	C6—C7	1.4616 (19)
Zn1—N1i	2.0662 (12)	C7—C8	1.347 (2)
Zn1—S1i	2.2634 (4)	C7—H7A	0.9300
Zn1—S1	2.2636 (4)	C8—C9	1.4337 (19)
S1—C10	1.7450 (15)	C8—H8A	0.9300
S2—C10	1.7428 (14)	C9—H9A	0.9300
S2—C11	1.8210 (16)	C11—C12	1.5118 (19)
N1—C9	1.2964 (18)	C11—H11A	0.9700
N1—N2	1.3948 (15)	C11—H11B	0.9700
N2—C10	1.2994 (19)	C12—C13	1.386 (2)
C1—C2	1.383 (2)	C12—C17	1.390 (2)
C1—C6	1.405 (2)	C13—C14	1.384 (2)
C1—H1A	0.9300	C13—H13A	0.9300
C2—C3	1.393 (2)	C14—C15	1.382 (2)
C2—H2B	0.9300	C14—H14A	0.9300
C3—C4	1.384 (2)	C15—C16	1.379 (2)
C3—H3A	0.9300	C15—H15A	0.9300
C4—C5	1.393 (2)	C16—C17	1.390 (2)
C4—H4A	0.9300	C16—H16A	0.9300
C5—C6	1.400 (2)	C17—H17A	0.9300
C5—H5A	0.9300
N1—Zn1—N1i	104.32 (7)	C7—C8—C9	123.08 (13)
N1—Zn1—S1i	121.84 (3)	C7—C8—H8A	118.5
N1i—Zn1—S1i	86.96 (3)	C9—C8—H8A	118.5
N1—Zn1—S1	86.96 (3)	N1—C9—C8	120.80 (13)
N1i—Zn1—S1	121.84 (3)	N1—C9—H9A	119.6
S1i—Zn1—S1	134.50 (2)	C8—C9—H9A	119.6
C10—S1—Zn1	92.11 (5)	N2—C10—S2	118.39 (11)
C10—S2—C11	104.17 (7)	N2—C10—S1	130.26 (11)
C9—N1—N2	114.33 (12)	S2—C10—S1	111.35 (8)
C9—N1—Zn1	129.50 (10)	C12—C11—S2	105.99 (10)
N2—N1—Zn1	116.07 (9)	C12—C11—H11A	110.5
C10—N2—N1	113.42 (12)	S2—C11—H11A	110.5
C2—C1—C6	120.33 (14)	C12—C11—H11B	110.5
C2—C1—H1A	119.8	S2—C11—H11B	110.5
C6—C1—H1A	119.8	H11A—C11—H11B	108.7
C1—C2—C3	120.48 (14)	C13—C12—C17	118.62 (14)
C1—C2—H2B	119.8	C13—C12—C11	120.44 (14)
C3—C2—H2B	119.8	C17—C12—C11	120.92 (14)
C4—C3—C2	119.80 (14)	C14—C13—C12	121.01 (15)
C4—C3—H3A	120.1	C14—C13—H13A	119.5
C2—C3—H3A	120.1	C12—C13—H13A	119.5
C3—C4—C5	120.19 (15)	C15—C14—C13	120.01 (16)
C3—C4—H4A	119.9	C15—C14—H14A	120.0
C5—C4—H4A	119.9	C13—C14—H14A	120.0
C4—C5—C6	120.44 (15)	C16—C15—C14	119.63 (15)
C4—C5—H5A	119.8	C16—C15—H15A	120.2
C6—C5—H5A	119.8	C14—C15—H15A	120.2
C5—C6—C1	118.75 (13)	C15—C16—C17	120.35 (15)
C5—C6—C7	119.05 (13)	C15—C16—H16A	119.8
C1—C6—C7	122.18 (13)	C17—C16—H16A	119.8
C8—C7—C6	125.72 (14)	C12—C17—C16	120.37 (15)
C8—C7—H7A	117.1	C12—C17—H17A	119.8
C6—C7—H7A	117.1	C16—C17—H17A	119.8
N1—Zn1—S1—C10	−6.84 (6)	C6—C7—C8—C9	−174.96 (14)
N1i—Zn1—S1—C10	98.14 (6)	N2—N1—C9—C8	−176.13 (12)
S1i—Zn1—S1—C10	−140.35 (5)	Zn1—N1—C9—C8	7.7 (2)
N1i—Zn1—N1—C9	64.77 (12)	C7—C8—C9—N1	−178.89 (14)
S1i—Zn1—N1—C9	−30.62 (14)	N1—N2—C10—S2	−176.19 (9)
S1—Zn1—N1—C9	−173.11 (13)	N1—N2—C10—S1	3.1 (2)
N1i—Zn1—N1—N2	−111.33 (10)	C11—S2—C10—N2	11.23 (14)
S1i—Zn1—N1—N2	153.28 (8)	C11—S2—C10—S1	−168.22 (8)
S1—Zn1—N1—N2	10.79 (9)	Zn1—S1—C10—N2	4.50 (14)
C9—N1—N2—C10	172.96 (13)	Zn1—S1—C10—S2	−176.13 (7)
Zn1—N1—N2—C10	−10.34 (15)	C10—S2—C11—C12	171.23 (11)
C6—C1—C2—C3	−0.6 (2)	S2—C11—C12—C13	−84.45 (16)
C1—C2—C3—C4	−0.6 (2)	S2—C11—C12—C17	94.11 (16)
C2—C3—C4—C5	0.8 (2)	C17—C12—C13—C14	1.2 (3)
C3—C4—C5—C6	0.1 (2)	C11—C12—C13—C14	179.80 (16)
C4—C5—C6—C1	−1.2 (2)	C12—C13—C14—C15	−0.8 (3)
C4—C5—C6—C7	−179.72 (14)	C13—C14—C15—C16	−0.1 (3)
C2—C1—C6—C5	1.4 (2)	C14—C15—C16—C17	0.6 (3)
C2—C1—C6—C7	179.91 (14)	C13—C12—C17—C16	−0.7 (3)
C5—C6—C7—C8	−175.41 (15)	C11—C12—C17—C16	−179.28 (16)
C1—C6—C7—C8	6.1 (2)	C15—C16—C17—C12	−0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S2ii	0.93	2.76	3.6697 (17)	167
C11—H11B···Cg1iii	0.97	2.98	3.5785 (17)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯S2i	0.93	2.76	3.6697 (17)	167
C11—H11B⋯Cg1ii	0.97	2.98	3.5785 (17)	121

Symmetry codes: (i) ; (ii) .