Bis[hexa­amminecobalt(III)] penta­chloride nitrate

Qihui Wu; Chunyu Du; Yang Lv; Guoliang Chen; Qinhe Pan

doi:10.1107/S1600536812021332

. 2012 May 16;68(Pt 6):i45–i46. doi: 10.1107/S1600536812021332

Bis[hexaamminecobalt(III)] pentachloride nitrate

Qihui Wu ^a, Chunyu Du ^a, Yang Lv ^a, Guoliang Chen ^a, Qinhe Pan ^a,^*

PMCID: PMC3379055 PMID: 22719276

Abstract

The title compound, [Co(NH₃)₆]₂Cl₅(NO₃), was obtained under hydrothermal conditions. The asymmetric unit contains three Co³⁺ ions, one lying on an inversion center and the other two located at 2/m positions. All Co³⁺ ions are six-coordinated by NH₃ molecules, forming [Co(NH₃)₆]³⁺ octahedra, with Co—N distances in the range 1.945 (4)–1.967 (3) Å. The nitrate N atom and one of the O atoms lie at a mirror plane. Among the Cl⁻ anions, one lies in a general position, one on a twofold axis and two on a mirror plane. N—H⋯O and N—H⋯Cl hydrogen bonds link the cations and anions into a three-dimensional network.

Related literature

For metal phosphates and germanates prepared using metal complexes as templates, see: Wang et al. (2003a ▶,b ▶); Pan et al. (2005 ▶, 2008 ▶). For our continued research interest focused on the synthesis of microporous open-framework metal-organic hybride materials by introducing transition metal complexes as templates, see: Pan et al. (2010a ▶,b ▶, 2011 ▶); Tong & Pan (2011 ▶); Liang et al. (2011 ▶). For a structure containing a [Co(NH₃)₆]³⁺ cation, see: Han et al. (2012 ▶).

Experimental

Crystal data

[Co(NH₃)₆]₂Cl₅(NO₃)
M _r = 561.53
Monoclinic,
a = 21.118 (4) Å
b = 14.985 (3) Å
c = 6.8491 (11) Å
β = 92.147 (3)°
V = 2165.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.18 mm⁻¹
T = 296 K
0.20 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.738, T _max = 0.770
7927 measured reflections
2813 independent reflections
1870 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.140
S = 1.02
2813 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812021332/yk2056sup1.cif

e-68-00i45-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021332/yk2056Isup2.hkl

e-68-00i45-Isup2.hkl^{(138.2KB, 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
N1—H1A⋯Cl1	0.89	2.89	3.427 (4)	120
N1—H1A⋯Cl3ⁱ	0.89	2.90	3.484 (4)	125
N1—H1B⋯Cl1ⁱⁱ	0.89	2.59	3.410 (4)	154
N1—H1C⋯Cl3ⁱⁱⁱ	0.89	2.63	3.431 (4)	150
N3—H3A⋯O2^iv	0.89	2.53	3.155 (6)	128
N4—H4A⋯Cl3^v	0.89	2.79	3.287 (4)	117
N4—H4B⋯Cl4	0.89	2.62	3.448 (5)	155
N4—H4C⋯Cl2^v	0.89	2.73	3.321 (4)	125
N5—H5A⋯Cl1^vi	0.89	2.77	3.375 (4)	127
N5—H5A⋯Cl4^vii	0.89	2.91	3.456 (4)	122
N5—H5B⋯O2^vii	0.89	2.17	3.048 (5)	168
N5—H5C⋯Cl3^vi	0.89	2.56	3.337 (4)	146
N6—H6A⋯Cl4^vii	0.89	2.76	3.339 (4)	124
N6—H6C⋯Cl3^viii	0.89	2.93	3.445 (4)	118
N7—H7A⋯Cl4^iv	0.89	2.78	3.368 (4)	125
N7—H7B⋯Cl3^viii	0.89	2.87	3.394 (4)	119

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

Acknowledgments

This work was supported by the Program for New Century Excellent Talents in Universities (NCET-11–0929), the National Natural Science Foundation of China (No. 21101047), the Natural Science Foundation of Hainan Province (No. 211010) and the Priming Scientific Research Foundation of Hainan University (No. kyqd1051).

supplementary crystallographic information

Comment

Rencently, more attention has been paid to transition metal complexes, because they can to be employed as templates in the synthesis of various open-framework materials, including metal phosphates (Wang et al., 2003a,b) and germanates (Pan et al., 2005,2008). Our continued interest has been focused on the synthesis of microporous open-framework metal-organic hybride materials by introducing transition metal complexes as templates (Pan et al., 2010a,b, 2011; Tong & Pan, 2011; Liang et al., 2011). Unexpectedly, the title compound, [Co(NH₃)₆]₂(NO₃)Cl₅, was obtained.

The title compound is composed of [Co(NH₃)₆]³⁺ cations and the counterions Cl^- and NO₃^-, as shown in Fig. 1. The asymmetric part of this crystal structure contains three Co³⁺ ions; one is located on an inversion center, and the other two are positioned on the twofold rotation axis with center of symmetry (2/m). All Co(III) ions are six coordinated by NH₃ molecules to form [Co(NH₃)₆]³⁺ cations, having a slightly distorted octahedral geometry, as in the structure of [Co(NH₃)₆]₃[Zn₈(HPO₄)₈(PO₄)₂](PO₄) (Han et al., 2012). The Co—N bond distances are in the range from 1.945 (4) to 1.967 (3) Å. For the counterions, the N8 atom of NO₃^- anion is located on mirror plane and displays a trigonal geometry by bonded to three O atoms with the N—O distances of 1.234 (6)–1.253 (4) Å. The Cl^- anions are located in different positions: inversion center for Cl2, mirror plane for Cl1 and Cl4, and general position for Cl3. The [Co(NH₃)₆]³⁺ cations interact with the counterions Cl^- and NO₃^-via hydrogen bonds; the distances of N—H···O hydrogen bonds are in the range 3.048 (5)–3.155 (6) Å, and the distances of N—H···Cl hydrogen bonds lie in the range from 3.287 (4) to 3.484 (4) Å (Table 1), to form an extensive three-dimensional hydrogen-bonding network.

Experimental

In a typical synthesis, a mixture of Cd(NO₃)₂.4H₂O (0.231 g), pyromellitic acid (0.0254 g), [Co(NH₃)₆]Cl₃ (0.03 g), NaOH (0.016 g) and H₂O (10 ml) were added in a 20 ml Teflon-lined reactor under autogenous pressure at 100°C for 3 days. Yellow rod-like crystals were obtained.