Diaqua­bis­(propane-1,3-diamine)­copper(II) bis­[diamminetetra­kis­(thio­cyanato-κN)chromate(III)] dimethyl sulfoxide octa­solvate

Vitalina M Nikitina; Oksana V Nesterova; Roman I Zubatyuk; Oleg V Shishkin; Julia A Rusanova

doi:10.1107/S160053681102023X

. 2011 Jun 4;67(Pt 7):m849–m850. doi: 10.1107/S160053681102023X

Diaquabis(propane-1,3-diamine)copper(II) bis[diamminetetrakis(thiocyanato-κN)chromate(III)] dimethyl sulfoxide octasolvate

Vitalina M Nikitina ^a, Oksana V Nesterova ^a, Roman I Zubatyuk ^b, Oleg V Shishkin ^b, Julia A Rusanova ^a,^*

PMCID: PMC3152115 PMID: 21836852

Abstract

The ionic title complex, [Cu(C₃H₁₀N₂)₂(H₂O)₂][Cr(NCS)₄(NH₃)₂]·8C₂H₆OS, consists of complex [Cu(dipr)₂(H₂O)₂]²⁺ copper cations (dipr is propane-1,3-diamine), complex [Cr(NCS)₄(NH₃)₂]⁻ anions and uncoordinated solvent dimethyl sulfoxide (DMSO) molecules. All the metal atoms lie on crystallographic centers of symmetry. The cations are connected to the anions through N—H⋯O hydrogen bonds between the NH₃ molecules of the anion and the water molecules of the cation. The DMSO molecules are involved in hydrogen-bonded linkage of the [Cr(NCS)₄(NH₃)₂]⁻ anions into supramolecular chains through bridging O atoms. A network of hydrogen bonds as well as short S⋯S contacts [3.5159 (12) and 3.4880 (12) Å] between the NCS groups of the complex anions link the molecules into a three-dimensional supramolecular network.

Related literature

For background to direct synthesis see: Nesterov et al. (2004 ▶, 2006 ▶); Kovbasyuk et al. (1997 ▶, 1998 ▶); Vassilyeva et al. (1997 ▶). For the stuctures of related compexes, see: Zhang et al. (2001 ▶); Cucos et al. (2006 ▶); Cherkasova & Gorunova (2003 ▶); Kolotilov et al. (2010 ▶).

Experimental

Crystal data

[Cu(C₃H₁₀N₂)₂(H₂O)₂]·[Cr(NCS)₄(NH₃)₂]·8(C₂H₆OS)
M _r = 1509.63
Triclinic,
a = 12.2609 (11) Å
b = 12.2772 (12) Å
c = 13.8578 (12) Å
α = 72.466 (8)°
β = 89.664 (7)°
γ = 61.535 (10)°
V = 1724.9 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 100 K
0.6 × 0.4 × 0.3 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.58, T _max = 0.71
15229 measured reflections
8482 independent reflections
6966 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.08
8482 reflections
353 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102023X/br2167sup1.cif

e-67-0m849-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102023X/br2167Isup2.hkl

e-67-0m849-Isup2.hkl^{(414.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1E⋯O2ⁱ	0.87	1.88	2.732 (2)	165
O1—H1E⋯S5ⁱ	0.87	2.87	3.5905 (18)	142
O1—H1F⋯O4	0.87	1.98	2.786 (2)	153
N1—H1A⋯O2ⁱⁱ	0.92	2.10	2.995 (3)	163
N1—H1B⋯S4ⁱⁱⁱ	0.92	2.70	3.490 (2)	145
N2—H2A⋯O4	0.92	2.33	3.052 (2)	135
N2—H2B⋯O3	0.92	2.24	3.091 (3)	153
N5—H5A⋯O2	0.91	2.11	3.003 (2)	167
N5—H5B⋯O3^iv	0.91	2.21	3.079 (2)	161
N5—H5C⋯O5^v	0.91	2.09	2.966 (2)	160
N8—H8A⋯O1ⁱⁱⁱ	0.91	2.08	2.956 (2)	162
N8—H8B⋯O5^vi	0.91	2.19	3.054 (2)	159
N8—H8C⋯O3^vii	0.91	2.10	2.981 (2)	162

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

The authors gratefully acknowledge the Ukrainian State Fund for Fundamental Researchers (SFFR) for financial support of the Research Program (Chemistry).

supplementary crystallographic information

Comment

It has been shown that direct synthesis is an efficient method to obtained novel homo- and heterometallic complexes (Nesterov et al. (2004, 2006); Kovbasyuk et al. (1997, 1998); Vassilyeva et al. (1997)). Continuing our investigations in this paper we present a novel Cu/Cr heterometallic ionic complex which has been synthesized using zerovalent copper, Reinecke's salt and 1,3-propilenediamine as starting materials. As it shown on Fig. 1 Cu atoms in complex cations are in square bypiramidal coordination environment with four N atoms in equatorial position and two O atoms of the H₂O molecules in axial position. The Cr centers are coordinated to six N atoms - four NCS-groups in equatorial position and two NH₃ molecules in axial position. The bond distances and angles in the title molecule agree well with the corresponding bond distances and angles reported in closely related compounds (Zhang et al., 2001, Cucos et al., 2006; Cherkasova et al., 2003; Kolotilov et al., 2010). There are short interanionic S···S contacts between NCS-groups of the complex anions with the distances 3.5159 (12) and 3.4880 (12) Å whereas sum of standard Van-der-Vaals radius of the sulfur atom is 3.68 Å. The crystal packing of the title compound is presented on Fig 2.

Experimental

For the preparation of the title compound, copper powder 0.04 g (0.63 mmol), NH₄[Cr(NCS)₄(NH₃)₂]^.H₂O 0.45 g (1.26 mmol), 0.11 ml (1.26 mmol) 1,3-propilenediamine (dipr), 20 ml of DMSO, were heated to 323–333 K and stirred magnetically for 15 min, until total dissolution of the copper powder was observed. Addition of a few ml of the PrⁱOH to the cooled solution leads to precipitation within few days of the dark violet crystals suitable for X-ray analysis. They were collected by filter-suction, washed with dry PrⁱOH and finally dried in vacuo at room temperature (yield: 0.59 g, 69%).