metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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[μ-N1,N2-Bis(pyridin-2-yl)hydrazine-1,2-dicarbo­thio­amidato]bis­­[chlorido­copper(II)]

aCollege of Chemistry and Material Science, South-Central University for Nationalities, Wuhan, Hubei 430074, People's Republic of China
*Correspondence e-mail: zhangbg68@yahoo.com

(Received 16 March 2012; accepted 27 November 2012; online 12 December 2012)

The binuclear title compound, [Cu2(C12H10N6S2)Cl2], possesses twofold rotational symmetry. The CuII atom occupies a four-coordinate pseudo-tetra­hedral environment bound to one S atom, one imine N atom and one pyridine N atom from the N1,N2-bis­(pyridin-2-yl)hydrazine-1,2-dicarbo­thio­amidate ligand, and one Cl anion. The metal atoms are connected via the bis-tridentate ligand into a binuclear structure. The mol­ecule is bow-shaped with the pyridine rings inclined to one another by 51.56 (14)°. In the crystal, N—H⋯Cl hydrogen bonds lead to the formation of ribbons propagating along [001]. These ribbons are connected via C—H⋯Cl, C—H⋯S and ππ inter­actions [centroid–centroid distance = 3.6146 (19) Å], leading to the formation of a three-dimensional structure.

Related literature

For the biological activity of thio­semicarbazides and their metal complexes, see: West et al. (1993[West, D. X., Liberta, A. E., Padhye, S. B., Chikate, R. C., Sonawane, P. B., Kumbhar, A. S. & Yerande, R. G. (1993). Coord. Chem. Rev. 123, 49-71.]). For related structures, see: Wang et al. (2011[Wang, H. Y., Zhao, P. S., Song, J. & Li, R. Q. (2011). J. Chem. Crystallogr. 41, 379-385.]); Yamin & Yusof (2003[Yamin, B. M. & Yusof, M. S. M. (2003). Acta Cryst. E59, o358-o359.]); Akinchan et al. (2002[Akinchan, N. T., Drozdzewski, P. M. & Battagli, L. P. (2002). J. Chem. Crystallogr. 32, 91-97.]). For the synthesis of the ligand, see: Szecsenyi et al. (2006[Szecsenyi, K. M., Leovac, V. M. & Evans, I. R. (2006). J. Coord. Chem. 59, 523-530.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu2(C12H10N6S2)Cl2]

  • Mr = 500.36

  • Monoclinic, C 2/c

  • a = 15.825 (3) Å

  • b = 7.6190 (13) Å

  • c = 15.082 (4) Å

  • β = 118.179 (2)°

  • V = 1602.9 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.26 mm−1

  • T = 293 K

  • 0.32 × 0.28 × 0.27 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.422, Tmax = 0.474

  • 4270 measured reflections

  • 1561 independent reflections

  • 1445 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.068

  • S = 1.07

  • 1561 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.73 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Selected bond lengths (Å)

Cu1—Cl1 2.2619 (10)
Cu1—S2 2.2295 (9)
Cu1—N1 1.986 (2)
Cu1—N3i 1.961 (3)
Symmetry code: (i) [-x, y, -z+{\script{1\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯Cl1ii 0.86 2.70 3.507 (2) 156
C2—H2⋯Cl1iii 0.93 2.77 3.482 (3) 134
C5—H5⋯S2iv 0.93 2.82 3.425 (3) 124
Symmetry codes: (ii) [x, -y+1, z+{\script{1\over 2}}]; (iii) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (iv) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2003[Bruker (2003). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2003[Bruker (2003). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Thiosemicarbazide and their metal complexes have attracked considerable interest due to their biological activities, such as antiviral, antibacterial, antimalarial, antifungal, and antitumoral activities (West et al., 1993). Thiosemicarbazide are versatile ligands that can coordinate as neutral ligands or in the deprotonated form. They can also be used as flexible spacers with potential multiple binding sites to construct coordination polymers with multiple dimensions and various topologies. In the present paper, the synthesis and crystal structure of the title thiosemicarbazide binuclear copper(II) compound is reported.

The title compound possesses twofold rotational symmetry (Fig.1). Each CuII center occupies a four-coordinated pseudotetrahedral environment bound to one sulfur atom, one imine nitrogen atom, and one pyridine nitrogen atom from one N,N'-di(pyridin-2-yl)hydrazine-1,2-bis(carbothioamide) ligand, and one chlorine anion. The metal centres are connected via the hexadentate ligand into a binuclear structure. The molecule is bow-shaped. The thiosemicarbazide moiety (S2/N2(N3/N6) is twisted by 20.14 (13)° from the pyridine ring to which it is attached. The two thiosemicarbazide moieties, (S2/N2/N3/N6) and (S2A/N2A/N3A/N6A), are inclined to one another by 23.36 (13) °, while the pyrdine rings make a dihedral angle of 51.56 (14)°.

The Cu—S distance is 2.2295 (9) Å, and the Cu—N distances vary between 1.961 (3)–1.986 (2) Å. The C—S bond distances of 1.711 (3) Å are within the normal range for a C—S single bond, indicating that the thiosemicarbazide moieties adopt the thiol tautomeric form, acting as a doubly charged negative ligand. The C6—N distances of 1.311 (3)–1.366 (3) Å and the N3—N3A distance of 1.399 (3) Å are intermediate between formal single and double bonds, pointing to extensive electron delocalization over the entire ligand skeleton. This agrees well with the same distances observed in related compounds (Wang et al., 2011; Yamin & Yusof, 2003; Akinchan et al., 2002).

In the crystal, there are N-H···Cl hydrogen bonds, leading to the formation of ribbons propagating along [001], and C-H···Cl and C-H···S interactions (Table 1). The latter link the ribbons and together with ππ interactions lead to the formation of a three-dimensional structure [Cg1···Cg1i 3.6146 (19) Å; perpendicular separation 3.5312 (11) Å; slippage 0.772 Å; Cg1 is the centroid of pyrdine ring N1/C1-C5; symmetry code: (i) -x, -y+2, -z].

Related literature top

For the biological activity of thiosemicarbazides and their metal complexes, see: West et al. (1993). For related structures, see: Wang et al. (2011); Yamin & Yusof (2003); Akinchan et al. (2002). For the synthesis of the ligand, see: Szecsenyi et al. (2006).

Experimental top

The ligand (L), N,N'-di(pyridin-2-yl)hydrazine-1,2-bis(carbothioamide,) was prepared by the literature method (Szecsenyi et al., 2006). L (0.05 mmol) was solved in DMF (5 ml) in a test tube, then an 8 ml solvent mixture of CH3OH and DMF (v/v = 1:1) was added as a buffer layer. A solution of CuCl2(0.10 mmol) in CH3OH (3 ml) was then carefully layered on top. The system was sealed and kept for a week, after which black block-like single crystals, suitable for X-ray analysis, were obtained. Anal. Calcd for C12H10Cl2Cu2N6S2: C 28.80, H 2.01, N16.80. Found: C 29.23; H, 2.40; N, 16.44.

Refinement top

The NH and C-bound H atoms were included in calculated positions and treated as riding atoms: N–H = 0.86 Å and C–H = 0.93 Å , with Uiso(H) = 1.2Ueq(N,C).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound, with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level [symmetry code: (a) - x, y, - z + 1/2].
[µ-N1,N2-Bis(pyridin-2-yl)hydrazine-1,2- dicarbothioamidato]bis[chloridocopper(II)] top
Crystal data top
[Cu2(C12H10N6S2)Cl2]F(000) = 992
Mr = 500.36Dx = 2.073 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 253 reflections
a = 15.825 (3) Åθ = 2.9–29.5°
b = 7.6190 (13) ŵ = 3.26 mm1
c = 15.082 (4) ÅT = 293 K
β = 118.179 (2)°Block, black
V = 1602.9 (6) Å30.32 × 0.28 × 0.27 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
1561 independent reflections
Radiation source: fine-focus sealed tube1445 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1918
Tmin = 0.422, Tmax = 0.474k = 97
4270 measured reflectionsl = 1817
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.068 w = 1/[σ2(Fo2) + (0.0374P)2 + 2.3083P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1561 reflectionsΔρmax = 0.73 e Å3
110 parametersΔρmin = 0.34 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0018 (3)
Crystal data top
[Cu2(C12H10N6S2)Cl2]V = 1602.9 (6) Å3
Mr = 500.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.825 (3) ŵ = 3.26 mm1
b = 7.6190 (13) ÅT = 293 K
c = 15.082 (4) Å0.32 × 0.28 × 0.27 mm
β = 118.179 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer
1561 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
1445 reflections with I > 2σ(I)
Tmin = 0.422, Tmax = 0.474Rint = 0.018
4270 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 1.07Δρmax = 0.73 e Å3
1561 reflectionsΔρmin = 0.34 e Å3
110 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Cu10.12780 (2)0.63445 (4)0.20890 (2)0.0266 (1)
Cl10.25399 (4)0.50248 (9)0.20491 (5)0.0355 (2)
S20.18501 (4)0.59737 (10)0.37400 (5)0.0336 (2)
N10.07304 (14)0.7259 (3)0.06931 (14)0.0267 (6)
N20.08612 (15)0.6577 (3)0.46876 (15)0.0297 (6)
N30.00303 (14)0.6631 (3)0.29480 (15)0.0258 (6)
C10.02056 (17)0.7259 (3)0.00390 (18)0.0265 (7)
C20.05668 (19)0.7912 (4)0.09283 (19)0.0356 (8)
C30.0058 (2)0.8611 (4)0.1223 (2)0.0452 (10)
C40.1031 (2)0.8622 (4)0.0559 (2)0.0434 (10)
C50.13323 (19)0.7951 (4)0.03822 (19)0.0340 (8)
C60.07986 (17)0.6433 (3)0.37555 (18)0.0248 (7)
H20.122100.787700.136900.0430*
H2A0.138400.618700.517600.0360*
H30.016900.907400.186600.0540*
H40.146700.907500.074900.0520*
H50.198500.797100.083200.0410*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0178 (2)0.0406 (2)0.0238 (2)0.0017 (1)0.0118 (1)0.0002 (1)
Cl10.0250 (3)0.0472 (4)0.0381 (3)0.0039 (3)0.0181 (3)0.0055 (3)
S20.0188 (3)0.0567 (4)0.0270 (3)0.0091 (3)0.0123 (3)0.0067 (3)
N10.0221 (10)0.0354 (12)0.0249 (10)0.0031 (8)0.0131 (8)0.0023 (9)
N20.0190 (10)0.0477 (13)0.0217 (10)0.0072 (9)0.0090 (9)0.0026 (9)
N30.0191 (10)0.0392 (12)0.0213 (9)0.0001 (8)0.0113 (8)0.0005 (8)
C10.0251 (12)0.0323 (13)0.0260 (11)0.0019 (10)0.0152 (10)0.0031 (10)
C20.0294 (13)0.0508 (17)0.0245 (12)0.0022 (12)0.0109 (11)0.0020 (11)
C30.0462 (18)0.064 (2)0.0302 (14)0.0015 (14)0.0221 (14)0.0078 (13)
C40.0428 (17)0.0564 (19)0.0422 (16)0.0074 (13)0.0294 (15)0.0031 (13)
C50.0268 (13)0.0445 (15)0.0354 (13)0.0062 (11)0.0186 (12)0.0029 (12)
C60.0204 (12)0.0304 (13)0.0252 (11)0.0001 (9)0.0121 (10)0.0007 (9)
Geometric parameters (Å, º) top
Cu1—Cl12.2619 (10)N3—N3i1.399 (3)
Cu1—S22.2295 (9)N2—H2A0.8600
Cu1—N11.986 (2)C1—C21.384 (4)
Cu1—N3i1.961 (3)C2—C31.369 (5)
S2—C61.711 (3)C3—C41.385 (4)
N1—C11.337 (4)C4—C51.366 (4)
N1—C51.352 (4)C2—H20.9300
N2—C61.366 (3)C3—H30.9300
N2—C1i1.386 (4)C4—H40.9300
N3—C61.311 (3)C5—H50.9300
Cl1—Cu1—S294.32 (3)N1—C1—C2122.7 (3)
Cl1—Cu1—N194.39 (7)N1—C1—N2i120.3 (2)
Cl1—Cu1—N3i159.80 (7)C1—C2—C3118.7 (3)
S2—Cu1—N1166.41 (7)C2—C3—C4119.6 (3)
S2—Cu1—N3i85.31 (6)C3—C4—C5118.2 (3)
N1—Cu1—N3i90.08 (9)N1—C5—C4123.3 (3)
Cu1—S2—C696.01 (9)N2—C6—N3120.1 (3)
Cu1—N1—C1123.98 (19)S2—C6—N2115.6 (2)
Cu1—N1—C5118.58 (18)S2—C6—N3124.3 (2)
C1—N1—C5117.4 (2)C1—C2—H2121.00
C1i—N2—C6129.5 (2)C3—C2—H2121.00
Cu1i—N3—C6124.48 (19)C2—C3—H3120.00
N3i—N3—C6113.7 (2)C4—C3—H3120.00
Cu1i—N3—N3i119.99 (16)C3—C4—H4121.00
C6—N2—H2A115.00C5—C4—H4121.00
C1i—N2—H2A115.00N1—C5—H5118.00
N2i—C1—C2117.0 (3)C4—C5—H5118.00
Cl1—Cu1—S2—C6165.43 (8)C5—N1—C1—N2i179.7 (2)
N3i—Cu1—S2—C65.68 (11)Cu1—N1—C5—C4179.7 (2)
Cl1—Cu1—N1—C1138.8 (2)C1i—N2—C6—S2166.0 (2)
Cl1—Cu1—N1—C542.3 (2)C6i—N2i—C1—N126.4 (4)
N3i—Cu1—N1—C121.5 (2)C6i—N2i—C1—C2154.0 (3)
N3i—Cu1—N1—C5157.5 (2)C1i—N2—C6—N314.5 (4)
Cl1—Cu1—N3i—N394.0 (2)N3i—N3—C6—N2173.7 (2)
Cl1—Cu1—N3i—C6i69.8 (3)Cu1i—N3—C6—S2157.76 (14)
S2—Cu1—N3i—N34.18 (18)Cu1i—N3—C6—N221.7 (3)
S2—Cu1—N3i—C6i159.6 (2)C6—N3—N3i—Cu10.2 (3)
N1—Cu1—N3i—N3163.03 (19)C6—N3—N3i—C6i165.6 (2)
N1—Cu1—N3i—C6i33.2 (2)Cu1i—N3—N3i—Cu1165.23 (11)
Cu1—S2—C6—N2171.77 (17)N3i—N3—C6—S26.9 (3)
Cu1—S2—C6—N38.8 (2)N1—C1—C2—C31.0 (4)
C1—N1—C5—C40.7 (4)N2i—C1—C2—C3179.4 (3)
Cu1—N1—C1—C2179.7 (2)C1—C2—C3—C41.1 (4)
C5—N1—C1—C20.8 (4)C2—C3—C4—C51.0 (5)
Cu1—N1—C1—N2i0.7 (3)C3—C4—C5—N10.8 (5)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl1ii0.862.703.507 (2)156
C2—H2···Cl1iii0.932.773.482 (3)134
C5—H5···S2iv0.932.823.425 (3)124
Symmetry codes: (ii) x, y+1, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu2(C12H10N6S2)Cl2]
Mr500.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)15.825 (3), 7.6190 (13), 15.082 (4)
β (°) 118.179 (2)
V3)1602.9 (6)
Z4
Radiation typeMo Kα
µ (mm1)3.26
Crystal size (mm)0.32 × 0.28 × 0.27
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.422, 0.474
No. of measured, independent and
observed [I > 2σ(I)] reflections
4270, 1561, 1445
Rint0.018
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.068, 1.07
No. of reflections1561
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.73, 0.34

Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Cu1—Cl12.2619 (10)Cu1—N11.986 (2)
Cu1—S22.2295 (9)Cu1—N3i1.961 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl1ii0.862.703.507 (2)156
C2—H2···Cl1iii0.932.773.482 (3)134
C5—H5···S2iv0.932.823.425 (3)124
Symmetry codes: (ii) x, y+1, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x+1/2, y+1/2, z+1/2.
 

Acknowledgements

This work was sponsored by the National Natural Science Foundation of China (No. 20977115).

References

First citationAkinchan, N. T., Drozdzewski, P. M. & Battagli, L. P. (2002). J. Chem. Crystallogr. 32, 91–97.  Web of Science CSD CrossRef CAS
First citationBruker (2003). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSzecsenyi, K. M., Leovac, V. M. & Evans, I. R. (2006). J. Coord. Chem. 59, 523–530.  CAS
First citationWang, H. Y., Zhao, P. S., Song, J. & Li, R. Q. (2011). J. Chem. Crystallogr. 41, 379–385.  Web of Science CSD CrossRef CAS
First citationWest, D. X., Liberta, A. E., Padhye, S. B., Chikate, R. C., Sonawane, P. B., Kumbhar, A. S. & Yerande, R. G. (1993). Coord. Chem. Rev. 123, 49–71.  CrossRef CAS Web of Science
First citationYamin, B. M. & Yusof, M. S. M. (2003). Acta Cryst. E59, o358–o359.  Web of Science CSD CrossRef IUCr Journals

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