Diaquadi-μ-formato-bis­{μ-2,2′-[propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenolato}cadmium(II)dinickel(II) dihydrate

Jian-Feng Zhang; Bo Wan; Wen Liu; Qian Shi

doi:10.1107/S1600536812029583

. 2012 Jul 28;68(Pt 8):m1122–m1123. doi: 10.1107/S1600536812029583

Diaquadi-μ-formato-bis{μ-2,2′-[propane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}cadmium(II)dinickel(II) dihydrate

Jian-Feng Zhang ^a, Bo Wan ^a, Wen Liu ^a, Qian Shi ^a,^*

PMCID: PMC3414165 PMID: 22904772

Abstract

In the centrosymmetric title compound, [CdNi₂(C₁₇H₁₆N₂O₂)₂(HCOO)₂(H₂O)₂]·2H₂O, The Ni^II cation is chelated by a 2,2′-[propane-1,3-diylbis(nitrilomethanylylidene)]diphenolate (salpn) anion, and further coordinated by a formate anion and a water molecule in a distorted NiN₂O₄ octahedral geometry. The Cd^II cation, located on an inversion center, is coordinated by four deprotonated hydroxy groups from two salpn anions and two carboxylate O atoms from formate anions in a distorted octahedral geometry. Both formate and salpn anions bridge the Cd and Ni cations, forming a trinuclear complex. Within the salpn anion, the benzene rings are twisted to each other at a dihedral angle of 61.46 (18)°. Intermolecular O—H⋯O hydrogen bonding is present in the crystal structure. The lattice water molecule is disorder over two positions with an occupancy ratio of 0.75:0.25.

Related literature

For background and applications of metal complexes with Schiff base ligands, see: Niederhoffer et al. (1984 ▶); Tisato et al. (1994 ▶); Yamada (1999 ▶). For the decomposition reaction of solvent DMF, see: Wang et al. (2004 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[CdNi₂(C₁₇H₁₆N₂O₂)₂(HCO₂)₂(H₂O)₂]·2H₂O
M _r = 952.56
Triclinic,
a = 9.6769 (9) Å
b = 10.6596 (10) Å
c = 10.7996 (10) Å
α = 72.851 (1)°
β = 63.551 (1)°
γ = 81.478 (1)°
V = 952.87 (15) Å³
Z = 1
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 298 K
0.26 × 0.20 × 0.19 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.681, T _max = 0.751
4842 measured reflections
3423 independent reflections
2910 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.074
S = 1.06
3423 reflections
259 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812029583/xu5190sup1.cif

e-68-m1122-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029583/xu5190Isup2.hkl

e-68-m1122-Isup2.hkl^{(167.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—O1	2.2809 (18)
Cd1—O2	2.2799 (18)
Cd1—O4	2.300 (2)
Ni1—O1	2.0098 (19)
Ni1—O2	2.0313 (19)
Ni1—O3	2.080 (2)
Ni1—O5	2.205 (2)
Ni1—N1	2.035 (2)
Ni1—N2	2.026 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6′ⁱ	0.85	2.04	2.662 (12)	130
O5—H5B⋯O6ⁱ	0.85	2.29	2.812 (4)	120
O6—H6B⋯O4ⁱⁱ	0.85	1.98	2.737 (4)	147
O6′—H6′B⋯O4ⁱⁱ	0.85	2.19	2.769 (12)	125

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors acknowledge financial support by the National Natural Science Foundation of China (grant No. 20971101).

supplementary crystallographic information

Comment

The molecular design and synthesis of Ni(II) complexes with the salen type Schiff-base ligands have attracted much attention in the past few years (Niederhoffer et al., 1984; Tisato et al., 1994; Yamada, 1999). Hererin we reported the structure of the title complex containing the Schiff base compound, N,N'-bis(salicylidene)-1,3-propanediaminato (salpn). In the compound, the formate anion may be generated from the decomposition of DMF solvents in solvothermal conditions, it has been reported by Wang et al. (2004) and by Zhang et al. (2007) previously.

In the title compound, the Cd(II) ion is situated on an inversion centre and two terminal Ni(II) ions are located on the symmetrical sides, forming a linear Ni—Cd—Ni trinuclear complex (Fig. 1). The Cd(II) ion has a distorted octahedral coordination environment, formed by four O atoms from two salpn ligands in the equatorial plane and two O atoms from two formate ligands at the axial positions. The coordination bond lengths and angles around the Cd(II) ion range between 2.2799 (18)–2.300 (2) Å, and 73.23 (7)–106.77 (7)°, respectively. The terminal Ni(II) ions have slightly distorted octahedral coordination environments formed by two O atoms and two N atoms from salpn ligands in the equatorial plane and two O atoms from formate ligand and auqa at the axial positions. In the Ni coordination sphere bond lengths and angles range between 2.0098 (2)–2.205 (2) Å, and 84.62 (8) - 177.57 (8)°, respectively. Each pair of metal ions is triply bridged via O atoms from salpn ligands and formate ligands. The crystal structure is stabilized by weak O—H···O hydrogen bonds.

Experimental

A mixture of Cd(NO₃)₂^.4H₂O (0.125 mmol, 0.0418 g), Ni(NO₃)₂^.6H₂O (0.125 mmol, 0.0347 g), 1,3-diaminopropane (0.125 mmol, 0.0102 g), salicyladehyde (0.300 mmol, 0.0366 g), DMF (5 ml), CH₃OH (5 ml) and ditilled water in a 30 ml Telfon-lined reactor was heated at 373 K for two days. After cooling to room temperature, green crystals are obtained for X-ray analysis.