Bis[benzyl N′-(3-phenyl­prop-2-enyl­idene)hydrazinecarbodithio­ato-κ²N′,S]zinc(II)

In the title Zn^II complex, [Zn(C₁₇H₁₅N₂S₂)₂], the Zn^II atom lies on a twofold rotation axis. It exists in a tetra­hedral geometry, chelated by two deprotonated Schiff base ligands. The dihedral angle between each ligand is 71.48 (8)°. Mol­ecules are connected by weak C—H...S inter­molecular inter­actions into chains along the c axis. The crystal structure is further stabilized by C—H...π inter­actions involving the phenyl ring of the 3-phenyl­prop-2-enyl­idene unit.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.029
• wR factor = 0.092
• Data-to-parameter ratio = 23.5

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: M. T. H. Tarafder, M. Toihidul Islam, C. M. Zakaria and M. A. A. A. A. Islam are involved in the synthesis of the title complex. H.-K. Fun and S. Chantrapromma are involved in X-ray structure determination. All are involved in manuscript preparation.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

The coordination chemistry of the ligands derived from S-benzyldithiocarbazate (SBDTC) had been of immense interests because of their intriguing coordination chemistry as well as their increasingly important biomedical properties (Ali et al., 2001; 2002; Tarafder et al., 2001; Tarafder, Jin et al., 2002b). Synthesis (Ali & Tarafder, 1977) and structure (Shanmuga Sundara Raj et al., 2000) of SBDTC were reported. We have previously reported the Schiff bases complexes derived from dithiocarbazate derivatives (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). In continuation of our interests, we report herein the X-ray structure of the zinc(II) complex of Schiff base ligand of SBDTC which is found to be isostructural with the copper(II) analog (Tarafder et al., 2008).

The Zn^II atom of the title complex, lies on a twofold rotation axis and therefore the asymmetric unit contains one-half of a molecule (Fig. 1). The ligands coordinate to the Zn^II through the two azomethine nitrogen and the two thiolate sulfur atoms forming a distorted tetrahedral geometry (Fig. 1). Both the two nitrogen atoms (N1 and N1A) and two sulfur atoms (S1 and S1A) from the two ligands are coordinated at opposite positions. The NS chelation results in the two five membered Zn^II-bidentate rings (Zn1, N1, N2, C8, S1), atom Zn1 having a maximum deviation of 0.0839 (5) Å. The dihedral angle between these Zn^II-bidentate rings is 80.03 (4) °. The smaller angle around Zn^II is 86.96 (3) ° for N1—Zn1—S1. The N—Zn—N and S—Zn—S bond angles are 104.32 (7) ° and 134.49 (2) °, respectively. The Zn1—N1 distance of 2.0662 (12) Å is slightly longer compared to the [Zn(C₁₄H₁₈N₃OS)₂] by Latheef et al., 2007 (Zn—N = 2.026 (3) and 2.040 (3) Å) whereas the Zn1—S1 distance of 2.2636 (4) Å in the title complex is in the same range (Zn—S = 2.2597 (13) and 2.2462 (12) Å (Latheef et al., 2007)). The mean plane of the prop-2-enylidene moiety (C7/C8/C9/N1/N2) makes a dihedral angle of 12.25 (12)° with mean plane of the attached C1–C6 phenyl ring. Atoms N1, N2, C10, S1 and S2 lie on the same plane and this plane makes a dihedral angle of 76.75 (6) ° with the C12–C17 phenyl ring. The dihedral angle between the two phenhyl rings (C1–C6 and C12–C17) is 71.48 (8)°. Bond lengths and angles observed in the Schiff base ligand are of normal values.

In the crystal packing (Fig. 2), the molecules are interconnected by weak C—H···S intermolecular interactions (Table 1) into chains along the c axis. The crystal is further stabilized by C—H···π interactions (Table 1) involving the C1–C6 phenyl ring (centroid Cg₁) of the 3-phenylprop-2-enylidene moiety.

Related literature

For the synthesis and structure of S-benzyldithiocarbazates, see: Ali & Tarafder (1977); Shanmuga Sundara Raj et al. (2000). For the structures of Zn^II complexes, see: Latheef et al. (2007); Tarafder et al. (2002a). 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).

S2. Experimental

The Schiff base ligand was prepared following the literature procedure (Tarafder et al., 2008) by adding cinamaldehyde (1.32 g, 10 mmol) to a hot solution of S-benzyldithiocarbazate (SBDTC) (1.98 g, 10 mmol) in absolute ethanol (40 ml). The mixture was refluxed for 10 min. The yellow precipitate, which formed, was isolated and washed with hot ethanol. The yellow solid was recrystallized from absolute ethanol (Yield: 1.52 g, 46%). The zinc complex was synthesized by adding the solution of the Schiff base ligand (0.31 g, 1 mmol) in absolute ethanol (70 ml) to a solution of zinc nitrate hexahydrate (0.15 g, 0.5 mmol) in absolute ethanol (5 ml) and stirred under boiling condition for 10 min. A resultant yellow precipitate was separated and washed with hot ethanol (Yield: 0.29 g, 63%). Yellow single crystals of the title complex were crystallized from a mixture solution of chloroform/absolute ethanol (70:5 v/v) after 40 days at room temperature and further recrystallized from chloroform (40 ml) by slow evaporation at 296 K after 10 days, M.p 457–458 K.

S3. Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å, for CH and aromatic, 0.97 Å, for CH₂ and U_iso = 1.2U_eq(C). The highest residual electron density peak is located at 0.60 Å from C1 and the deepest hole is located at 0.54 Å from Zn1.

Computing details

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

Figures

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering. Atoms labelled with suffix A are generated by the symmetry operation (-x, y, 1/2 - z).
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Intermolecular C—H···S weak interactions are shown as dashed lines.

Bis[benzyl N'-(3-phenylprop-2-enylidene)hydrazinecarbodithioato- κ²N',S]zinc(II)

Crystal data

[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 = 1.1–30.0°
b = 9.9310 (1) Å	µ = 1.08 mm^−1
c = 8.7633 (1) Å	T = 100 K
V = 3140.83 (6) Å^3	Block, yellow
Z = 4	0.37 × 0.25 × 0.17 mm
F(000) = 1424

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	4580 independent reflections
Radiation source: fine-focus sealed tube	4071 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.33 pixels mm^-1	θmax = 30.0°, θmin = 1.1°
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 1.4067P] where P = (Fo^2 + 2Fc^2)/3
4580 reflections	(Δ/σ)max = 0.001
195 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Zn1—N1	2.0662 (12)	C6—C7	1.4616 (19)
Zn1—N1^i	2.0662 (12)	C7—C8	1.347 (2)
Zn1—S1^i	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—N1^i	104.32 (7)	C7—C8—C9	123.08 (13)
N1—Zn1—S1^i	121.84 (3)	C7—C8—H8A	118.5
N1^i—Zn1—S1^i	86.96 (3)	C9—C8—H8A	118.5
N1—Zn1—S1	86.96 (3)	N1—C9—C8	120.80 (13)
N1^i—Zn1—S1	121.84 (3)	N1—C9—H9A	119.6
S1^i—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)
N1^i—Zn1—S1—C10	98.14 (6)	N2—N1—C9—C8	−176.13 (12)
S1^i—Zn1—S1—C10	−140.35 (5)	Zn1—N1—C9—C8	7.7 (2)
N1^i—Zn1—N1—C9	64.77 (12)	C7—C8—C9—N1	−178.89 (14)
S1^i—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)
N1^i—Zn1—N1—N2	−111.33 (10)	C11—S2—C10—N2	11.23 (14)
S1^i—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)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S2^ii	0.93	2.76	3.6697 (17)	167
C11—H11B···Cg1^iii	0.97	2.98	3.5785 (17)	121

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z+1.