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The title compound, C18H18N4S4·2C3H7NO, crystallizes with the dibenzyl dihydrazinecarbodithioate mol­ecule residing on a crystallographic inversion centre. The mol­ecule adopts a trans conformation with respect to the central C-C single bond. The dihedral angle between the phenyl group and the thio­thio­semicarbazone unit is 74.1 (1)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102011411/bj1039sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011411/bj1039Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270102011411/bj1039sup3.pdf
Supplementary material

CCDC reference: 164378

Comment top

Over the past three decades, metal complexes of SN chelating agents have been extensively studied because of their pronounced antibacterial, antiviral and anticancer biological activity (Ali & Livingstone, 1974). The majority of ligands studied have been focused on either bidentate NS or tridentate NNS donor sequences. The observation that the quadridentate SN ligand 3-ethoxy-2-oxobutyraldehyde bis(thiosemicarbazone) and its copper(II) chelate possess antineoplastic activities (Winkelmann et al., 1974; Petering, 1974; Chan-Stier et al., 1976; Minkel et al., 1976, 1978; Minkel & Petering, 1978) provided an impetus to the study of quadridentate SN ligands and transition metal complexes of thiosemicarbazone. A number of nickel(II), copper(II) and zinc(II) chelates have been synthesized and characterized. Recently, the title compound, (I), and the corresponding nickel(II), copper(II), cadmium(II) and zinc(II) chelates, have been reported to present biological activity (Ali et al., 1992). We have obtained a single-crystal of the title compound, (I), and report herein its molecular and crystal structure. \sch

The structure of (I), along with the atom-labelling scheme, is shown in Fig. 1. The two thiosemicarbazone moieties adopt a trans configuration with respect to the C9—C9A bond, which minimizes the steric crowding in the molecule. No intramolecular hydrogen bonding is observed. The molecule sits on a crystallographic centre of symmetry which resides at the midpoint of the C9—C9A bond. There are three nearly planar groupings of atoms in the molecule: the two symmetry-related phenyl planes, with a mean deviation of 0.0025 Å, and the central plane consisting of atoms C7, S1, C8, S2, N1, N2, C9 and their symmetry-related atoms at (-1 - x, 1 - y, 1 - z), with a mean-plane deviation of 0.0110 Å. The dihedral angle between the phenyl ring and the central plane is 74.1°.

Selected bond lengths and angles are listed in Table 1. The C9—N2 [1.275 (3) Å] and C8—S2 [1.647 (3) Å] bonds both exhibit double-bond character. The C8—N1 [1.337 (3) Å] and C8—S1 [1.746 (2) Å] bond distances are shorter than the accepted covalent single-bond values (N—C 1.47 Å and C—S 1.81 Å; Xu, 1993; Lydon et al., 1982), indicating their partial double-bond character due to delocalization of the electrons in the π-system of S1—C8—S2—N1.

The bond angles around C8 illustrate the steric effect of the bulky benzyl substituent, with the result that the S2—C8—S1 angle is 125.44 (15)°, compared with 112.78 (18)° for N1—C8—S1 and 121.78 (18)° for N1—C8—S2. There are weak intermolecular C9—H9A···O1 and N1—H1A···O1 hydrogen bonds between (I) and dimethylformamide solvent molecules, as shown in Table 2. There are no other significant interactions such as ππ stacking found in the crystal structure.

Experimental top

The title compound was prepared by refluxing S-benzyldithiocarbazate and 30% aqueous solution of glyoxal (mole ratio 2:1) in absolute ethanol for ca 5 min (Ali et al., 1992). Diffraction-quality crystals of (I) were obtained by recrystallization from dimethylformamide.

Refinement top

Atom H12 was located from a difference map. The remaining H atoms were located geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and N—H = 0.86 Å. Are these the correct constraints?

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii and atoms with the suffix A are at (-1 - x, 1 - y, 1 - z).
Dibenzyl 2,2'-(ethane-1,2-diylidene)dihydrazinecarbodithioate dimethylformamide disolvate top
Crystal data top
C18H18N4S4·2C3H7NOZ = 1
Mr = 564.84F(000) = 298
Triclinic, P1Dx = 1.273 Mg m3
a = 6.104 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.3202 (18) ÅCell parameters from 1445 reflections
c = 11.960 (2) Åθ = 2.8–25.9°
α = 94.863 (3)°µ = 0.35 mm1
β = 94.078 (3)°T = 293 K
γ = 99.867 (3)°Prism, pale yellow
V = 736.8 (2) Å30.25 × 0.22 × 0.17 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
3156 independent reflections
Radiation source: fine-focus sealed tube1900 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
Detector resolution: 8.33 pixels mm-1θmax = 27.9°, θmin = 1.7°
ω scansh = 78
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 1311
Tmin = 0.913, Tmax = 0.942l = 1512
4486 measured reflections
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.063P)2]
where P = (Fo2 + 2Fc2)/3
3156 reflections(Δ/σ)max < 0.001
168 parametersΔρmax = 0.41 e Å3
38 restraintsΔρmin = 0.28 e Å3
Crystal data top
C18H18N4S4·2C3H7NOγ = 99.867 (3)°
Mr = 564.84V = 736.8 (2) Å3
Triclinic, P1Z = 1
a = 6.104 (1) ÅMo Kα radiation
b = 10.3202 (18) ŵ = 0.35 mm1
c = 11.960 (2) ÅT = 293 K
α = 94.863 (3)°0.25 × 0.22 × 0.17 mm
β = 94.078 (3)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3156 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1900 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.942Rint = 0.013
4486 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04838 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.41 e Å3
3156 reflectionsΔρmin = 0.28 e Å3
168 parameters
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
S10.06846 (11)0.48333 (7)0.73835 (6)0.0675 (3)
S20.29519 (12)0.76296 (7)0.71832 (7)0.0838 (3)
N10.0813 (3)0.64299 (19)0.61019 (18)0.0619 (6)
H1A0.08470.71400.57780.074*
N20.2509 (3)0.53704 (19)0.58523 (18)0.0567 (6)
N30.0951 (4)0.9085 (2)0.3510 (2)0.0713 (7)
O10.1690 (3)0.83568 (18)0.46605 (19)0.0757 (6)
C10.4482 (7)0.2978 (4)0.8648 (3)0.1134 (13)
H1B0.54630.31610.80980.136*
C20.4449 (8)0.1843 (4)0.9171 (4)0.1406 (17)
H2B0.54030.12670.89700.169*
C30.3044 (8)0.1555 (4)0.9974 (4)0.1126 (13)
H3A0.30220.07811.03230.135*
C40.1715 (7)0.2374 (4)1.0257 (3)0.1089 (12)
H4A0.07440.21891.08110.131*
C50.1766 (6)0.3509 (3)0.9729 (3)0.0969 (11)
H5A0.08170.40840.99430.116*
C60.3124 (5)0.3830 (3)0.8917 (2)0.0632 (7)
C70.3178 (5)0.5079 (3)0.8359 (3)0.0770 (9)
H7A0.45060.52570.79570.092*
H7B0.31840.58200.89150.092*
C80.0897 (4)0.6368 (2)0.6846 (2)0.0571 (7)
C90.4083 (4)0.5536 (2)0.5149 (2)0.0579 (7)
H9A0.40420.63330.48350.069*
C100.1541 (7)0.9937 (4)0.2642 (4)0.1284 (15)
H10A0.02581.02840.23790.193*
H10B0.20480.94410.20270.193*
H10C0.27101.06520.29430.193*
C110.2628 (5)0.8451 (4)0.4030 (3)0.0967 (11)
H11A0.19860.79150.45840.145*
H11B0.38330.91100.43870.145*
H11C0.31830.79030.34670.145*
C120.1032 (5)0.8977 (3)0.3898 (3)0.0715 (9)
H120.187 (5)0.946 (3)0.352 (2)0.076 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0620 (4)0.0629 (5)0.0737 (5)0.0001 (3)0.0164 (3)0.0251 (4)
S20.0667 (5)0.0697 (5)0.1040 (7)0.0127 (4)0.0280 (4)0.0272 (4)
N10.0522 (12)0.0534 (12)0.0758 (15)0.0025 (10)0.0143 (11)0.0237 (10)
N20.0462 (11)0.0546 (12)0.0669 (14)0.0009 (10)0.0077 (10)0.0189 (10)
N30.0601 (15)0.0716 (16)0.0831 (18)0.0076 (12)0.0130 (13)0.0151 (12)
O10.0609 (11)0.0695 (12)0.1010 (15)0.0067 (9)0.0080 (10)0.0424 (11)
C10.138 (3)0.118 (3)0.103 (3)0.056 (2)0.034 (2)0.036 (2)
C20.164 (3)0.129 (3)0.153 (3)0.079 (2)0.032 (3)0.027 (2)
C30.150 (3)0.094 (3)0.104 (3)0.040 (2)0.012 (2)0.033 (2)
C40.123 (3)0.115 (3)0.101 (3)0.032 (2)0.027 (2)0.043 (2)
C50.104 (2)0.094 (2)0.111 (3)0.0469 (19)0.031 (2)0.039 (2)
C60.0631 (17)0.0722 (18)0.0554 (17)0.0174 (14)0.0079 (13)0.0132 (13)
C70.0692 (18)0.082 (2)0.077 (2)0.0052 (15)0.0204 (15)0.0262 (15)
C80.0511 (14)0.0589 (15)0.0606 (16)0.0068 (12)0.0033 (12)0.0151 (12)
C90.0485 (14)0.0537 (15)0.0712 (18)0.0046 (11)0.0044 (12)0.0227 (13)
C100.127 (3)0.141 (3)0.128 (3)0.018 (3)0.056 (2)0.051 (3)
C110.0622 (19)0.123 (3)0.105 (3)0.021 (2)0.0022 (18)0.005 (2)
C120.0624 (19)0.0604 (18)0.093 (2)0.0111 (15)0.0023 (17)0.0249 (16)
Geometric parameters (Å, º) top
S1—C81.746 (2)C3—H3A0.9300
S1—C71.818 (3)C4—C51.374 (5)
S2—C81.647 (3)C4—H4A0.9300
N1—C81.337 (3)C5—C61.347 (4)
N1—N21.367 (3)C5—H5A0.9300
N1—H1A0.8600C6—C71.498 (4)
N2—C91.275 (3)C7—H7A0.9700
N3—C121.317 (4)C7—H7B0.9700
N3—C111.439 (4)C9—C9i1.434 (5)
N3—C101.442 (4)C9—H9A0.9300
O1—C121.211 (3)C10—H10A0.9600
C1—C61.343 (3)C10—H10B0.9600
C1—C21.371 (3)C10—H10C0.9600
C1—H1B0.9300C11—H11A0.9600
C2—C31.351 (5)C11—H11B0.9600
C2—H2B0.9300C11—H11C0.9600
C3—C41.309 (5)C12—H120.89 (3)
C8—S1—C7101.86 (12)C6—C7—H7A110.4
C8—N1—N2120.34 (19)S1—C7—H7A110.4
C8—N1—H1A119.8C6—C7—H7B110.4
N2—N1—H1A119.8S1—C7—H7B110.4
C9—N2—N1115.60 (19)H7A—C7—H7B108.6
C12—N3—C11119.8 (3)N1—C8—S2121.78 (18)
C12—N3—C10120.8 (3)N1—C8—S1112.77 (18)
C11—N3—C10119.1 (3)S2—C8—S1125.44 (15)
C6—C1—C2121.2 (4)N2—C9—C9i118.5 (3)
C6—C1—H1B119.4N2—C9—H9A120.8
C2—C1—H1B119.4C9i—C9—H9A120.8
C3—C2—C1120.6 (4)N3—C10—H10A109.5
C3—C2—H2B119.7N3—C10—H10B109.5
C1—C2—H2B119.7H10A—C10—H10B109.5
C4—C3—C2119.4 (4)N3—C10—H10C109.5
C4—C3—H3A120.3H10A—C10—H10C109.5
C2—C3—H3A120.3H10B—C10—H10C109.5
C3—C4—C5119.4 (4)N3—C11—H11A109.5
C3—C4—H4A120.3N3—C11—H11B109.5
C5—C4—H4A120.3H11A—C11—H11B109.5
C6—C5—C4123.2 (3)N3—C11—H11C109.5
C6—C5—H5A118.4H11A—C11—H11C109.5
C4—C5—H5A118.4H11B—C11—H11C109.5
C1—C6—C5116.2 (3)O1—C12—N3127.3 (3)
C1—C6—C7121.3 (3)O1—C12—H12122.6 (18)
C5—C6—C7122.5 (3)N3—C12—H12110.1 (18)
C6—C7—S1106.70 (19)
Symmetry code: (i) x1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O10.932.363.147 (3)143
N1—H1A···O10.862.012.833 (2)160

Experimental details

Crystal data
Chemical formulaC18H18N4S4·2C3H7NO
Mr564.84
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.104 (1), 10.3202 (18), 11.960 (2)
α, β, γ (°)94.863 (3), 94.078 (3), 99.867 (3)
V3)736.8 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.25 × 0.22 × 0.17
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.913, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
4486, 3156, 1900
Rint0.013
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.130, 1.00
No. of reflections3156
No. of parameters168
No. of restraints38
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.41, 0.28

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C81.746 (2)O1—C121.211 (3)
S1—C71.818 (3)C1—C61.343 (3)
S2—C81.647 (3)C1—C21.371 (3)
N1—C81.337 (3)C2—C31.351 (5)
N1—N21.367 (3)C3—C41.309 (5)
N2—C91.275 (3)C4—C51.374 (5)
N3—C121.317 (4)C5—C61.347 (4)
N3—C111.439 (4)C6—C71.498 (4)
N3—C101.442 (4)C9—C9i1.434 (5)
C8—S1—C7101.86 (12)C6—C5—C4123.2 (3)
C8—N1—N2120.34 (19)C1—C6—C5116.2 (3)
C9—N2—N1115.60 (19)C1—C6—C7121.3 (3)
C12—N3—C11119.8 (3)C5—C6—C7122.5 (3)
C12—N3—C10120.8 (3)C6—C7—S1106.70 (19)
C11—N3—C10119.1 (3)N1—C8—S2121.78 (18)
C6—C1—C2121.2 (4)N1—C8—S1112.77 (18)
C3—C2—C1120.6 (4)S2—C8—S1125.44 (15)
C4—C3—C2119.4 (4)N2—C9—C9i118.5 (3)
C3—C4—C5119.4 (4)O1—C12—N3127.3 (3)
Symmetry code: (i) x1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O10.9302.3573.147 (3)143
N1—H1A···O10.8602.0092.833 (2)160
 

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