Dichlorido(dimethyl­formamide-κO)[1,4,7-tris­(2-cyano­ethyl)-1,4,7-triaza­cyclo­nonane-κ3 N 1,N 4,N 7]cobalt(II)

Zhong Zhang; Zhi-Rong Geng; Qun Zhao; Zhi-Lin Wang

doi:10.1107/S160053680802179X

. 2008 Jul 19;64(Pt 8):m1041–m1042. doi: 10.1107/S160053680802179X

Dichlorido(dimethylformamide-κO)[1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane-κ³ N ¹,N ⁴,N ⁷]cobalt(II)

Zhong Zhang ^a, Zhi-Rong Geng ^a, Qun Zhao ^a, Zhi-Lin Wang ^a,^*

PMCID: PMC2961961 PMID: 21203031

Abstract

The title compound, [CoCl₂(C₁₅H₂₄N₆)(C₃H₇NO)], crystallizes as a monomeric complex. The coordination environment around the Co^II center could be described as a distorted octahedron consisting of three N donors from the facially coordinating triaza macrocyclic ligand, one O donor from dimethylformamide and two Cl⁻ ions. Neutral complex molecules are associated via intermolecular C—H⋯Cl hydrogen bonds to form two-dimensional layers. C—H⋯O hydrogen bonds are also present.

Related literature

For related literature, see: Scarpellini et al. (2005 ▶); Tei et al. (1998 ▶, 2003 ▶).

Experimental

Crystal data

[CoCl₂(C₁₅H₂₄N₆)(C₃H₇NO)]
M _r = 491.33
Monoclinic,
a = 9.787 (2) Å
b = 19.710 (5) Å
c = 12.370 (3) Å
β = 97.936 (4)°
V = 2363.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 298 (2) K
0.32 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.746, T _max = 0.800
12542 measured reflections
4630 independent reflections
3320 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.154
S = 1.07
4630 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802179X/ww2123sup1.cif

e-64-m1041-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802179X/ww2123Isup2.hkl

e-64-m1041-Isup2.hkl^{(226.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cl1—Co1	2.4382 (14)
Cl2—Co1	2.4096 (13)
Co1—O1	2.114 (3)
Co1—N2	2.194 (4)
Co1—N3	2.200 (4)
Co1—N1	2.232 (4)

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O1—Co1—N2	87.78 (12)
O1—Co1—N3	168.01 (13)
N2—Co1—N3	80.93 (13)
O1—Co1—N1	93.00 (13)
N2—Co1—N1	81.07 (14)
N3—Co1—N1	81.30 (13)
O1—Co1—Cl2	90.45 (9)
N2—Co1—Cl2	173.80 (10)
N3—Co1—Cl2	100.34 (10)
N1—Co1—Cl2	93.09 (10)
O1—Co1—Cl1	91.12 (9)
N2—Co1—Cl1	93.38 (10)
N3—Co1—Cl1	93.58 (10)
N1—Co1—Cl1	172.94 (10)
Cl2—Co1—Cl1	92.60 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl2ⁱ	0.97	2.75	3.658 (4)	157
C2—H2A⋯O1	0.97	2.58	3.120 (5)	116
C3—H3A⋯Cl2ⁱ	0.97	2.81	3.774 (4)	170
C7—H7A⋯Cl2	0.97	2.65	3.419 (4)	136
C10—H10A⋯O1	0.97	2.47	3.149 (6)	127
C10—H10B⋯Cl1	0.97	2.73	3.218 (4)	111
C11—H11A⋯Cl1ⁱ	0.97	2.62	3.525 (5)	156
C11—H11B⋯Cl2ⁱⁱ	0.97	2.65	3.502 (5)	147
C13—H13A⋯Cl1	0.97	2.72	3.460 (5)	133
C16—H16⋯Cl2	0.93	2.80	3.325 (5)	117
C17—H17A⋯O1	0.96	2.34	2.741 (7)	105

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

Acknowledgments

This project was supported by the Natural Science Foundation of China (grant No. 20475026).

supplementary crystallographic information

Comment

Structural investigations on metal complexes with nitrile pendant arm derivatives of 1,4,7-triazacyclononane ([9]aneN₃) reveal that these triazamacrocyclic ligands can either be used as building-blocks to assemble multi-dimensional polymeric networks (Tei et al., 1998) or only act as tridentate ligands in the formation of mononuclear complexes with the pendant nitrile groups not involved in metal coordination (Tei et al., 2003). In this paper, we report the crystal structure of the title compound, (I), which is a monomeric Co^II complex of a [9]aneN₃ derivative containing three pendant 2-cyanoethyl arms.

The molecular structure of (I) (Fig. 1) shows the Co^II ion is six-coordinated with three tertiary N donors from the nitrile-functionalized [9]aneN₃, one O donor from dimethylformamide ligand and two Cl^- ions completing an octahedral geometry. All bond distances and angles around the octahedral Co^II ion (Table 1) are generally within the normal ranges (Scarpellini et al., 2005). Three pendant 2-cyanoethyl arms attached to the triazamacrocycle adopt different conformations relative to the macrocycle framework and none of them participates in the coordination to the Co^II ion.

The crystal packing of (I) is dominated by intermolecular C—H···Cl hydrogen bonds (Table 2), which link the complex molecules to form two-dimensional hydrogen-bonded layers parallel to (010) plane (Fig. 2).

Experimental

The triazamacrocyclic ligand 1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane was prepared following a literature procedure (Tei et al., 1998). A mixture of the triazamacrocyclic ligand (29 mg, 0.1 mmol) and CoCl₂.6H₂O (24 mg, 0.1 mmol) in MeOH (10 ml) was stirred under reflux for 2 h. The precipitated pink solid was filtered off and subsequently redissolved in dimethylformamide. Purple single crystals of (I) suitable for X-ray diffraction analysis were obtained by slow diffusion of diethyl ether into the dimethylformamide solution. (yield 23 mg, 46.8%) Elemental analysis found: C 44.13; H 6.41; N 19.81%; calculated for C₁₈H₃₁Cl₂CoN₇O: C 44.00; H 6.36; N 19.96%.