Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102011411/bj1039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011411/bj1039Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270102011411/bj1039sup3.pdf |
CCDC reference: 164378
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.
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?
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.
C18H18N4S4·2C3H7NO | Z = 1 |
Mr = 564.84 | F(000) = 298 |
Triclinic, P1 | Dx = 1.273 Mg m−3 |
a = 6.104 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.3202 (18) Å | Cell parameters from 1445 reflections |
c = 11.960 (2) Å | θ = 2.8–25.9° |
α = 94.863 (3)° | µ = 0.35 mm−1 |
β = 94.078 (3)° | T = 293 K |
γ = 99.867 (3)° | Prism, pale yellow |
V = 736.8 (2) Å3 | 0.25 × 0.22 × 0.17 mm |
Siemens SMART CCD area-detector diffractometer | 3156 independent reflections |
Radiation source: fine-focus sealed tube | 1900 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.9°, θmin = 1.7° |
ω scans | h = −7→8 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −13→11 |
Tmin = 0.913, Tmax = 0.942 | l = −15→12 |
4486 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H 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 parameters | Δρmax = 0.41 e Å−3 |
38 restraints | Δρmin = −0.28 e Å−3 |
C18H18N4S4·2C3H7NO | γ = 99.867 (3)° |
Mr = 564.84 | V = 736.8 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.104 (1) Å | Mo Kα radiation |
b = 10.3202 (18) Å | µ = 0.35 mm−1 |
c = 11.960 (2) Å | T = 293 K |
α = 94.863 (3)° | 0.25 × 0.22 × 0.17 mm |
β = 94.078 (3)° |
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 = 0.942 | Rint = 0.013 |
4486 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 38 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.41 e Å−3 |
3156 reflections | Δρmin = −0.28 e Å−3 |
168 parameters |
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 | ||
S1 | 0.06846 (11) | 0.48333 (7) | 0.73835 (6) | 0.0675 (3) | |
S2 | 0.29519 (12) | 0.76296 (7) | 0.71832 (7) | 0.0838 (3) | |
N1 | −0.0813 (3) | 0.64299 (19) | 0.61019 (18) | 0.0619 (6) | |
H1A | −0.0847 | 0.7140 | 0.5778 | 0.074* | |
N2 | −0.2509 (3) | 0.53704 (19) | 0.58523 (18) | 0.0567 (6) | |
N3 | 0.0951 (4) | 0.9085 (2) | 0.3510 (2) | 0.0713 (7) | |
O1 | −0.1690 (3) | 0.83568 (18) | 0.46605 (19) | 0.0757 (6) | |
C1 | 0.4482 (7) | 0.2978 (4) | 0.8648 (3) | 0.1134 (13) | |
H1B | 0.5463 | 0.3161 | 0.8098 | 0.136* | |
C2 | 0.4449 (8) | 0.1843 (4) | 0.9171 (4) | 0.1406 (17) | |
H2B | 0.5403 | 0.1267 | 0.8970 | 0.169* | |
C3 | 0.3044 (8) | 0.1555 (4) | 0.9974 (4) | 0.1126 (13) | |
H3A | 0.3022 | 0.0781 | 1.0323 | 0.135* | |
C4 | 0.1715 (7) | 0.2374 (4) | 1.0257 (3) | 0.1089 (12) | |
H4A | 0.0744 | 0.2189 | 1.0811 | 0.131* | |
C5 | 0.1766 (6) | 0.3509 (3) | 0.9729 (3) | 0.0969 (11) | |
H5A | 0.0817 | 0.4084 | 0.9943 | 0.116* | |
C6 | 0.3124 (5) | 0.3830 (3) | 0.8917 (2) | 0.0632 (7) | |
C7 | 0.3178 (5) | 0.5079 (3) | 0.8359 (3) | 0.0770 (9) | |
H7A | 0.4506 | 0.5257 | 0.7957 | 0.092* | |
H7B | 0.3184 | 0.5820 | 0.8915 | 0.092* | |
C8 | 0.0897 (4) | 0.6368 (2) | 0.6846 (2) | 0.0571 (7) | |
C9 | −0.4083 (4) | 0.5536 (2) | 0.5149 (2) | 0.0579 (7) | |
H9A | −0.4042 | 0.6333 | 0.4835 | 0.069* | |
C10 | 0.1541 (7) | 0.9937 (4) | 0.2642 (4) | 0.1284 (15) | |
H10A | 0.0258 | 1.0284 | 0.2379 | 0.193* | |
H10B | 0.2048 | 0.9441 | 0.2027 | 0.193* | |
H10C | 0.2710 | 1.0652 | 0.2943 | 0.193* | |
C11 | 0.2628 (5) | 0.8451 (4) | 0.4030 (3) | 0.0967 (11) | |
H11A | 0.1986 | 0.7915 | 0.4584 | 0.145* | |
H11B | 0.3833 | 0.9110 | 0.4387 | 0.145* | |
H11C | 0.3183 | 0.7903 | 0.3467 | 0.145* | |
C12 | −0.1032 (5) | 0.8977 (3) | 0.3898 (3) | 0.0715 (9) | |
H12 | −0.187 (5) | 0.946 (3) | 0.352 (2) | 0.076 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0620 (4) | 0.0629 (5) | 0.0737 (5) | 0.0001 (3) | −0.0164 (3) | 0.0251 (4) |
S2 | 0.0667 (5) | 0.0697 (5) | 0.1040 (7) | −0.0127 (4) | −0.0280 (4) | 0.0272 (4) |
N1 | 0.0522 (12) | 0.0534 (12) | 0.0758 (15) | −0.0025 (10) | −0.0143 (11) | 0.0237 (10) |
N2 | 0.0462 (11) | 0.0546 (12) | 0.0669 (14) | 0.0009 (10) | −0.0077 (10) | 0.0189 (10) |
N3 | 0.0601 (15) | 0.0716 (16) | 0.0831 (18) | 0.0076 (12) | 0.0130 (13) | 0.0151 (12) |
O1 | 0.0609 (11) | 0.0695 (12) | 0.1010 (15) | 0.0067 (9) | 0.0080 (10) | 0.0424 (11) |
C1 | 0.138 (3) | 0.118 (3) | 0.103 (3) | 0.056 (2) | 0.034 (2) | 0.036 (2) |
C2 | 0.164 (3) | 0.129 (3) | 0.153 (3) | 0.079 (2) | 0.032 (3) | 0.027 (2) |
C3 | 0.150 (3) | 0.094 (3) | 0.104 (3) | 0.040 (2) | 0.012 (2) | 0.033 (2) |
C4 | 0.123 (3) | 0.115 (3) | 0.101 (3) | 0.032 (2) | 0.027 (2) | 0.043 (2) |
C5 | 0.104 (2) | 0.094 (2) | 0.111 (3) | 0.0469 (19) | 0.031 (2) | 0.039 (2) |
C6 | 0.0631 (17) | 0.0722 (18) | 0.0554 (17) | 0.0174 (14) | −0.0079 (13) | 0.0132 (13) |
C7 | 0.0692 (18) | 0.082 (2) | 0.077 (2) | 0.0052 (15) | −0.0204 (15) | 0.0262 (15) |
C8 | 0.0511 (14) | 0.0589 (15) | 0.0606 (16) | 0.0068 (12) | −0.0033 (12) | 0.0151 (12) |
C9 | 0.0485 (14) | 0.0537 (15) | 0.0712 (18) | 0.0046 (11) | −0.0044 (12) | 0.0227 (13) |
C10 | 0.127 (3) | 0.141 (3) | 0.128 (3) | 0.018 (3) | 0.056 (2) | 0.051 (3) |
C11 | 0.0622 (19) | 0.123 (3) | 0.105 (3) | 0.021 (2) | 0.0022 (18) | 0.005 (2) |
C12 | 0.0624 (19) | 0.0604 (18) | 0.093 (2) | 0.0111 (15) | −0.0023 (17) | 0.0249 (16) |
S1—C8 | 1.746 (2) | C3—H3A | 0.9300 |
S1—C7 | 1.818 (3) | C4—C5 | 1.374 (5) |
S2—C8 | 1.647 (3) | C4—H4A | 0.9300 |
N1—C8 | 1.337 (3) | C5—C6 | 1.347 (4) |
N1—N2 | 1.367 (3) | C5—H5A | 0.9300 |
N1—H1A | 0.8600 | C6—C7 | 1.498 (4) |
N2—C9 | 1.275 (3) | C7—H7A | 0.9700 |
N3—C12 | 1.317 (4) | C7—H7B | 0.9700 |
N3—C11 | 1.439 (4) | C9—C9i | 1.434 (5) |
N3—C10 | 1.442 (4) | C9—H9A | 0.9300 |
O1—C12 | 1.211 (3) | C10—H10A | 0.9600 |
C1—C6 | 1.343 (3) | C10—H10B | 0.9600 |
C1—C2 | 1.371 (3) | C10—H10C | 0.9600 |
C1—H1B | 0.9300 | C11—H11A | 0.9600 |
C2—C3 | 1.351 (5) | C11—H11B | 0.9600 |
C2—H2B | 0.9300 | C11—H11C | 0.9600 |
C3—C4 | 1.309 (5) | C12—H12 | 0.89 (3) |
C8—S1—C7 | 101.86 (12) | C6—C7—H7A | 110.4 |
C8—N1—N2 | 120.34 (19) | S1—C7—H7A | 110.4 |
C8—N1—H1A | 119.8 | C6—C7—H7B | 110.4 |
N2—N1—H1A | 119.8 | S1—C7—H7B | 110.4 |
C9—N2—N1 | 115.60 (19) | H7A—C7—H7B | 108.6 |
C12—N3—C11 | 119.8 (3) | N1—C8—S2 | 121.78 (18) |
C12—N3—C10 | 120.8 (3) | N1—C8—S1 | 112.77 (18) |
C11—N3—C10 | 119.1 (3) | S2—C8—S1 | 125.44 (15) |
C6—C1—C2 | 121.2 (4) | N2—C9—C9i | 118.5 (3) |
C6—C1—H1B | 119.4 | N2—C9—H9A | 120.8 |
C2—C1—H1B | 119.4 | C9i—C9—H9A | 120.8 |
C3—C2—C1 | 120.6 (4) | N3—C10—H10A | 109.5 |
C3—C2—H2B | 119.7 | N3—C10—H10B | 109.5 |
C1—C2—H2B | 119.7 | H10A—C10—H10B | 109.5 |
C4—C3—C2 | 119.4 (4) | N3—C10—H10C | 109.5 |
C4—C3—H3A | 120.3 | H10A—C10—H10C | 109.5 |
C2—C3—H3A | 120.3 | H10B—C10—H10C | 109.5 |
C3—C4—C5 | 119.4 (4) | N3—C11—H11A | 109.5 |
C3—C4—H4A | 120.3 | N3—C11—H11B | 109.5 |
C5—C4—H4A | 120.3 | H11A—C11—H11B | 109.5 |
C6—C5—C4 | 123.2 (3) | N3—C11—H11C | 109.5 |
C6—C5—H5A | 118.4 | H11A—C11—H11C | 109.5 |
C4—C5—H5A | 118.4 | H11B—C11—H11C | 109.5 |
C1—C6—C5 | 116.2 (3) | O1—C12—N3 | 127.3 (3) |
C1—C6—C7 | 121.3 (3) | O1—C12—H12 | 122.6 (18) |
C5—C6—C7 | 122.5 (3) | N3—C12—H12 | 110.1 (18) |
C6—C7—S1 | 106.70 (19) |
Symmetry code: (i) −x−1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1 | 0.93 | 2.36 | 3.147 (3) | 143 |
N1—H1A···O1 | 0.86 | 2.01 | 2.833 (2) | 160 |
Experimental details
Crystal data | |
Chemical formula | C18H18N4S4·2C3H7NO |
Mr | 564.84 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 736.8 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.25 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.913, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4486, 3156, 1900 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.130, 1.00 |
No. of reflections | 3156 |
No. of parameters | 168 |
No. of restraints | 38 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.28 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.
S1—C8 | 1.746 (2) | O1—C12 | 1.211 (3) |
S1—C7 | 1.818 (3) | C1—C6 | 1.343 (3) |
S2—C8 | 1.647 (3) | C1—C2 | 1.371 (3) |
N1—C8 | 1.337 (3) | C2—C3 | 1.351 (5) |
N1—N2 | 1.367 (3) | C3—C4 | 1.309 (5) |
N2—C9 | 1.275 (3) | C4—C5 | 1.374 (5) |
N3—C12 | 1.317 (4) | C5—C6 | 1.347 (4) |
N3—C11 | 1.439 (4) | C6—C7 | 1.498 (4) |
N3—C10 | 1.442 (4) | C9—C9i | 1.434 (5) |
C8—S1—C7 | 101.86 (12) | C6—C5—C4 | 123.2 (3) |
C8—N1—N2 | 120.34 (19) | C1—C6—C5 | 116.2 (3) |
C9—N2—N1 | 115.60 (19) | C1—C6—C7 | 121.3 (3) |
C12—N3—C11 | 119.8 (3) | C5—C6—C7 | 122.5 (3) |
C12—N3—C10 | 120.8 (3) | C6—C7—S1 | 106.70 (19) |
C11—N3—C10 | 119.1 (3) | N1—C8—S2 | 121.78 (18) |
C6—C1—C2 | 121.2 (4) | N1—C8—S1 | 112.77 (18) |
C3—C2—C1 | 120.6 (4) | S2—C8—S1 | 125.44 (15) |
C4—C3—C2 | 119.4 (4) | N2—C9—C9i | 118.5 (3) |
C3—C4—C5 | 119.4 (4) | O1—C12—N3 | 127.3 (3) |
Symmetry code: (i) −x−1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1 | 0.930 | 2.357 | 3.147 (3) | 143 |
N1—H1A···O1 | 0.860 | 2.009 | 2.833 (2) | 160 |
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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 π–π stacking found in the crystal structure.