Literature DB >> 22412475

Bis{μ-2-[bis-(pyridin-2-yl)methyl-idene]hydrazinecarbothio-amidato}bis-[bromido-copper(II)] methanol disolvate.

Roji J Kunnath, M Sithambaresan, M R Prathapachandra Kurup, Aiswarya Natarajan, A Ambili Aravindakshan.   

Abstract

In the centrosymmetric binuclear title compound, [Cu(2)Br(2)(C(12)H(10)N(5)S)(2)]·2CH(3)OH, the Cu(II) ion adopts a slightly dis-torted square-pyramidal coordination geometry. The hydrazine carbothio-amide moiety and one of the pyridyl rings together adopt an almost planar arrangement, with a maximum deviation of 0.052 (4) Å for the C atom of the thio-urea moiety. There are two mol-ecules of methanol solvent per complex in the asymmetric unit. The nonconventional intra-molecular C-H⋯Br hydrogen bonds make the mol-ecule more rigid, whereas the conventional N-H⋯N and O-H⋯Br inter-molecular hydrogen-bonding inter-actions, supported with N-H⋯π inter-actions, establish a supra-molecular linkage among the mol-ecules in the crystal. An intermolecular C-H⋯O inter-action is also present.

Entities:  

Year:  2012        PMID： 22412475      PMCID： PMC3297285          DOI： 10.1107/S1600536812005934

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the biological applications of multinuclear copper complexes of hydrazinecarbothio­amide, see: Moubaraki et al. (1998 ▶); Khan et al. (1985 ▶). For the synthesis of the title compound, see: Philip et al. (2006 ▶). For related structures of dimeric copper complexes of hydrazinecarbothio­amide, see: Ainscough et al. (1991 ▶); Philip et al. (2005 ▶). For related literature, see: Duan et al. (1996 ▶).

Experimental

Crystal data

[Cu2Br2(C12H10N5S)2]·2CH4O M = 863.62 Triclinic, a = 8.3052 (7) Å b = 9.2120 (7) Å c = 11.0500 (9) Å α = 68.341 (2)° β = 79.127 (3)° γ = 84.913 (2)° V = 771.45 (11) Å3 Z = 1 Mo Kα radiation μ = 4.15 mm−1 T = 296 K 0.30 × 0.25 × 0.25 mm

Data collection

Bruker AXS Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.300, T max = 0.354 11266 measured reflections 2688 independent reflections 2374 reflections with I > 2σ(I) R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.034 wR(F 2) = 0.094 S = 1.08 2688 reflections 209 parameters 2 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.46 e Å−3 Δρmin = −0.48 e Å−3 Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2/SAINT (Bruker, 2004 ▶); data reduction: SAINT/XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶). Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005934/fj2511sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005934/fj2511Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Cu2Br2(C12H10N5S)2]·2CH4OZ = 1
Mr = 863.62F(000) = 430.0
Triclinic, P1Dx = 1.859 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3052 (7) ÅCell parameters from 7050 reflections
b = 9.2120 (7) Åθ = 2.4–28.3°
c = 11.0500 (9) ŵ = 4.15 mm−1
α = 68.341 (2)°T = 296 K
β = 79.127 (3)°Block, black
γ = 84.913 (2)°0.30 × 0.25 × 0.25 mm
V = 771.45 (11) Å3
Bruker AXS Kappa APEXII CCD diffractometer2688 independent reflections
Radiation source: fine-focus sealed tube2374 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Detector resolution: 8.33 pixels mm-1θmax = 25.0°, θmin = 2.4°
ω and φ scanh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)k = −9→10
Tmin = 0.300, Tmax = 0.354l = −13→13
11266 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0351P)2 + 0.9038P] where P = (Fo2 + 2Fc2)/3
2688 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.46 e Å−3
2 restraintsΔρmin = −0.48 e Å−3
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.
xyzUiso*/Ueq
Br10.58511 (5)−0.08863 (4)0.69095 (4)0.04060 (15)
Cu10.47922 (5)0.17346 (5)0.59664 (4)0.03332 (15)
S10.22214 (12)0.12075 (11)0.70508 (10)0.0434 (3)
O10.7785 (5)0.7271 (5)0.9538 (4)0.0823 (12)
H1A0.73080.77350.89120.123*
N10.6759 (3)0.2576 (3)0.4581 (3)0.0299 (6)
N20.4272 (3)0.7176 (3)0.2495 (3)0.0302 (6)
N30.3754 (3)0.3618 (3)0.4794 (3)0.0238 (6)
N40.2129 (3)0.3997 (3)0.5030 (3)0.0294 (6)
N5−0.0218 (4)0.3210 (4)0.6483 (3)0.0417 (8)
C10.8282 (4)0.2004 (5)0.4516 (4)0.0379 (9)
H10.85260.11020.51970.045*
C20.9519 (5)0.2690 (5)0.3480 (4)0.0465 (10)
H21.05790.22690.34700.056*
C30.9154 (5)0.3999 (5)0.2473 (4)0.0445 (10)
H30.99640.44750.17580.053*
C40.7571 (5)0.4617 (5)0.2518 (4)0.0360 (8)
H40.73050.55100.18380.043*
C50.6401 (4)0.3882 (4)0.3587 (3)0.0268 (7)
C60.4688 (4)0.4423 (4)0.3730 (3)0.0248 (7)
C70.4119 (4)0.5710 (4)0.2597 (3)0.0248 (7)
C80.3584 (5)0.5319 (4)0.1652 (4)0.0384 (9)
H80.34790.42760.17710.046*
C90.3207 (5)0.6484 (5)0.0535 (4)0.0433 (10)
H90.28550.6248−0.01220.052*
C100.3360 (5)0.7995 (4)0.0412 (4)0.0377 (9)
H100.31160.8812−0.03340.045*
C110.3880 (5)0.8296 (4)0.1402 (4)0.0372 (9)
H110.39650.93320.13100.045*
C120.1364 (4)0.2936 (4)0.6108 (3)0.0288 (7)
C130.8997 (8)0.8191 (8)0.9536 (7)0.0809 (17)
H13A0.86660.86001.02300.121*
H13B0.91860.90390.87000.121*
H13C0.99880.75780.96750.121*
H5A−0.074 (5)0.401 (4)0.608 (4)0.058 (14)*
H5B−0.078 (5)0.261 (4)0.718 (3)0.053 (14)*
U11U22U33U12U13U23
Br10.0512 (3)0.0267 (2)0.0425 (3)0.01050 (16)−0.01669 (19)−0.00917 (17)
Cu10.0283 (3)0.0284 (3)0.0318 (3)0.00663 (18)−0.00458 (19)0.00051 (19)
S10.0334 (5)0.0364 (5)0.0404 (6)0.0031 (4)−0.0012 (4)0.0062 (4)
O10.070 (3)0.089 (3)0.072 (3)−0.014 (2)−0.023 (2)−0.002 (2)
N10.0262 (15)0.0315 (16)0.0310 (16)0.0048 (12)−0.0072 (12)−0.0103 (13)
N20.0306 (16)0.0280 (16)0.0283 (16)0.0002 (12)−0.0047 (13)−0.0061 (12)
N30.0202 (14)0.0251 (14)0.0256 (14)0.0027 (11)−0.0054 (11)−0.0084 (11)
N40.0260 (15)0.0281 (15)0.0283 (15)0.0045 (12)−0.0048 (12)−0.0045 (12)
N50.0282 (17)0.042 (2)0.0375 (19)0.0030 (15)0.0036 (15)0.0003 (16)
C10.0269 (19)0.040 (2)0.042 (2)0.0102 (16)−0.0082 (17)−0.0107 (17)
C20.028 (2)0.052 (3)0.055 (3)0.0104 (18)−0.0033 (19)−0.018 (2)
C30.029 (2)0.053 (3)0.047 (2)−0.0023 (17)0.0049 (18)−0.018 (2)
C40.034 (2)0.037 (2)0.033 (2)−0.0006 (16)−0.0025 (16)−0.0095 (16)
C50.0275 (18)0.0287 (17)0.0272 (18)0.0022 (13)−0.0070 (14)−0.0128 (14)
C60.0267 (18)0.0222 (16)0.0251 (17)0.0011 (13)−0.0067 (14)−0.0074 (14)
C70.0202 (16)0.0259 (17)0.0229 (16)0.0010 (13)−0.0013 (13)−0.0042 (13)
C80.049 (2)0.0285 (19)0.040 (2)0.0026 (16)−0.0159 (18)−0.0121 (16)
C90.050 (2)0.049 (2)0.034 (2)0.0027 (19)−0.0166 (18)−0.0155 (18)
C100.042 (2)0.037 (2)0.0258 (19)0.0055 (16)−0.0116 (16)−0.0002 (15)
C110.047 (2)0.0259 (18)0.033 (2)0.0012 (16)−0.0087 (17)−0.0031 (15)
C120.0238 (17)0.0317 (18)0.0287 (18)0.0032 (14)−0.0054 (14)−0.0087 (15)
C130.077 (4)0.087 (4)0.092 (4)0.006 (3)−0.024 (3)−0.045 (4)
Br1—Cu12.4084 (5)C2—C31.363 (6)
Cu1—N31.982 (3)C2—H20.9300
Cu1—N12.005 (3)C3—C41.385 (5)
Cu1—S12.2404 (11)C3—H30.9300
S1—C121.727 (3)C4—C51.376 (5)
O1—C131.371 (7)C4—H40.9300
O1—H1A0.8200C5—C61.464 (5)
N1—C11.326 (4)C6—C71.492 (4)
N1—C51.351 (4)C7—C81.378 (5)
N2—C71.329 (4)C8—C91.372 (5)
N2—C111.341 (5)C8—H80.9300
N3—C61.284 (4)C9—C101.363 (6)
N3—N41.365 (4)C9—H90.9300
N4—C121.320 (4)C10—C111.373 (5)
N5—C121.333 (5)C10—H100.9300
N5—H5A0.837 (19)C11—H110.9300
N5—H5B0.843 (19)C13—H13A0.9600
C1—C21.379 (6)C13—H13B0.9600
C1—H10.9300C13—H13C0.9600
N3—Cu1—N181.17 (11)N1—C5—C4121.6 (3)
N3—Cu1—S183.78 (8)N1—C5—C6115.1 (3)
N1—Cu1—S1163.80 (9)C4—C5—C6123.3 (3)
N3—Cu1—Br1162.00 (8)N3—C6—C5115.6 (3)
N1—Cu1—Br197.02 (8)N3—C6—C7125.0 (3)
S1—Cu1—Br195.45 (3)C5—C6—C7118.9 (3)
C12—S1—Cu195.59 (12)N2—C7—C8123.3 (3)
C13—O1—H1A109.5N2—C7—C6118.5 (3)
C1—N1—C5118.6 (3)C8—C7—C6118.1 (3)
C1—N1—Cu1128.9 (3)C9—C8—C7119.3 (3)
C5—N1—Cu1112.5 (2)C9—C8—H8120.3
C7—N2—C11116.4 (3)C7—C8—H8120.3
C6—N3—N4121.0 (3)C10—C9—C8118.2 (4)
C6—N3—Cu1115.6 (2)C10—C9—H9120.9
N4—N3—Cu1123.3 (2)C8—C9—H9120.9
C12—N4—N3111.1 (3)C9—C10—C11119.2 (3)
C12—N5—H5A124 (3)C9—C10—H10120.4
C12—N5—H5B123 (3)C11—C10—H10120.4
H5A—N5—H5B113 (4)N2—C11—C10123.5 (4)
N1—C1—C2122.8 (4)N2—C11—H11118.2
N1—C1—H1118.6C10—C11—H11118.2
C2—C1—H1118.6N4—C12—N5117.0 (3)
C3—C2—C1118.6 (4)N4—C12—S1125.8 (3)
C3—C2—H2120.7N5—C12—S1117.2 (3)
C1—C2—H2120.7O1—C13—H13A109.5
C2—C3—C4119.7 (4)O1—C13—H13B109.5
C2—C3—H3120.2H13A—C13—H13B109.5
C4—C3—H3120.2O1—C13—H13C109.5
C5—C4—C3118.7 (4)H13A—C13—H13C109.5
C5—C4—H4120.7H13B—C13—H13C109.5
C3—C4—H4120.7
N3—Cu1—S1—C12−4.96 (14)C3—C4—C5—N1−0.5 (5)
N1—Cu1—S1—C12−26.6 (3)C3—C4—C5—C6−179.3 (3)
Br1—Cu1—S1—C12−166.89 (12)N4—N3—C6—C5−179.2 (3)
N3—Cu1—N1—C1179.6 (3)Cu1—N3—C6—C5−3.8 (4)
S1—Cu1—N1—C1−158.5 (3)N4—N3—C6—C7−6.7 (5)
Br1—Cu1—N1—C1−18.4 (3)Cu1—N3—C6—C7168.7 (2)
N3—Cu1—N1—C5−2.2 (2)N1—C5—C6—N31.9 (4)
S1—Cu1—N1—C519.7 (5)C4—C5—C6—N3−179.3 (3)
Br1—Cu1—N1—C5159.8 (2)N1—C5—C6—C7−171.0 (3)
N1—Cu1—N3—C63.3 (2)C4—C5—C6—C77.8 (5)
S1—Cu1—N3—C6−170.7 (2)C11—N2—C7—C8−0.3 (5)
Br1—Cu1—N3—C6−82.2 (3)C11—N2—C7—C6174.3 (3)
N1—Cu1—N3—N4178.6 (3)N3—C6—C7—N299.6 (4)
S1—Cu1—N3—N44.6 (2)C5—C6—C7—N2−88.2 (4)
Br1—Cu1—N3—N493.1 (3)N3—C6—C7—C8−85.5 (4)
C6—N3—N4—C12173.7 (3)C5—C6—C7—C886.7 (4)
Cu1—N3—N4—C12−1.3 (4)N2—C7—C8—C91.0 (6)
C5—N1—C1—C20.3 (6)C6—C7—C8—C9−173.6 (3)
Cu1—N1—C1—C2178.4 (3)C7—C8—C9—C10−0.8 (6)
N1—C1—C2—C3−1.0 (6)C8—C9—C10—C11−0.1 (6)
C1—C2—C3—C40.8 (6)C7—N2—C11—C10−0.7 (5)
C2—C3—C4—C5−0.1 (6)C9—C10—C11—N20.9 (6)
C1—N1—C5—C40.4 (5)N3—N4—C12—N5176.8 (3)
Cu1—N1—C5—C4−178.0 (3)N3—N4—C12—S1−4.8 (4)
C1—N1—C5—C6179.3 (3)Cu1—S1—C12—N47.2 (3)
Cu1—N1—C5—C60.9 (3)Cu1—S1—C12—N5−174.4 (3)
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br1i0.822.583.396 (4)178
N5—H5A···N4ii0.84 (2)2.17 (2)3.006 (4)177 (5)
C4—H4···O1iii0.932.443.281 (5)151
C11—H11···Br1iv0.932.863.573 (4)135
C1—H1···Br10.932.913.450 (4)119
N5—H5B···Cg4ii0.84 (2)2.71 (4)3.310 (4)129 (3)
Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the N2/C7–C11 ring.

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O1—H1A⋯Br1i0.822.583.396 (4)178
N5—H5A⋯N4ii0.84 (2)2.17 (2)3.006 (4)177 (5)
C4—H4⋯O1iii0.932.443.281 (5)151
C11—H11⋯Br1iv0.932.863.573 (4)135
C1—H1⋯Br10.932.913.450 (4)119
N5—H5B⋯Cg4ii0.84 (2)2.71 (4)3.310 (4)129 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

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