Bis(diethyl­enetriamine)­cobalt(III) hexa­chloridoindate(III)

Wu, Q.; Chen, S.; Zhang, C.; Zhi, X.; Chen, Z.

doi:10.1107/S1600536811016758

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m731

doi:10.1107/S1600536811016758

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Bis(diethylenetriamine)cobalt(III) hexachloridoindate(III)

Qihui Wu,^a Shangwen Chen,^a Cailing Zhang,^a Xia Zhi ^a and Zelin Chen ^a ^*

^aDepartment of Materials and Chemical Engineering, Ministry of Education Key Laboratory of Application Technology of Hainan, Superior Resources Chemical Materials, Hainan University, Haikou 570228, Hainan Province, People's Republic of China
^*Correspondence e-mail: czl69995@163.com

(Received 26 April 2011; accepted 3 May 2011; online 7 May 2011)

The title compound, [Co(C₄H₁₃N₃)₂][InCl₆], was synthesized under hydrothermal conditions. In the cation, the Co—N bond lengths lie in the range 1.967 (2)–1.9684 (15) Å. In the anion, the In^III atom is coordinated by six Cl atoms resulting in a slightly distorted octahedral geometry. Both metal atoms are located on special positions of site symmetry 2/m. Furthermore, one Cl atom and one N atom are located on a mirror plane. N—H⋯Cl hydrogen bonds between cations and anions consolidate the crystal packing.

Related literature

For the use of chiral metal complexes as templates in the synthesis of open-framework metal phosphates and germanates, see: Stalder & Wilkinson (1997 ); Wang et al. (2003a ,b ); Pan et al. (2005 , 2008 ). For the introduction of chiral metal complexes into coordination polymers, see: Pan et al. (2010a ,b , 2011 ); Tong & Pan (2011 ). For In—Cl bond lengths in other hexachloridoindium compounds, see: Rothammel et al. (1998 ).

Experimental

Crystal data

[Co(C₄H₁₃N₃)₂][InCl₆]
M_r = 592.80
Orthorhombic, C c c m
a = 10.8925 (5) Å
b = 14.7291 (7) Å
c = 12.2205 (6) Å
V = 1960.62 (16) Å³
Z = 4
Mo Kα radiation
μ = 2.84 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.572, T_max = 0.653
6910 measured reflections
1282 independent reflections
1139 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.046
S = 1.06
1282 reflections
57 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90	2.62	3.4915 (17)	164
N1—H1B⋯Cl2ⁱⁱ	0.90	2.61	3.3823 (18)	144
N1—H1B⋯Cl1ⁱⁱⁱ	0.90	2.72	3.3957 (17)	133
N2—H2⋯Cl1^iv	0.91	2.79	3.5407 (19)	141
N2—H2⋯Cl1^v	0.91	2.79	3.5407 (19)	141
Symmetry codes: (i) $[x, -y, -z+{\script{1\over 2}}]$ ; (ii) -x-1, -y, -z; (iii) -x-1, -y, z; (iv) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016758/vm2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016758/vm2092Isup2.hkl

checkCIF report

Comment top

Chiral metal complexes are interesting templates for the synthesis of novel materials, because they are versatile and can be made with a wide of shapes, charges and particularly chirality. As templates, they have been used in the synthesis of open-framework metal phosphates and germanates, (for example: Stalder & Wilkinson, 1997; Wang et al., 2003a; Pan et al., 2005, 2008) and a new concept of chirality transfer of the chiral metal complex into the inorganic framework has been demonstrated (Wang et al., 2003b). Recently, Pan et al. introduced the chiral metal complexes into coordination polymers (Pan et al., 2010a, 2010b, 2011; Tong & Pan, 2011).

In this paper, we present a new hexachloro-indium templated by the metal complex [Co(dien)₂]³⁺. As shown in Fig. 1, the crystal structure consists of discrete [InCl₆]^3- anions and [Co(dien)₂]³⁺ cations. In [InCl₆]^3-, the indium center is coorinated by six Cl atoms, resulting in a slightly distorted octahedral geometry. The In—Cl bond distances are in the range of 2.5024 (5)–2.5114 (7) Å, which is consistent with other hexachloro-indium compounds (Rothammel et al., 1998). In [Co(dien)₂]³⁺, the cobalt center also displays a slightly distorted octahedral geometry and is bonded to six N atoms of two diethylenetriamines with the Co—N distances of 1.967 (2)–1.9684 (15) Å.

Related literature top

For the use of chiral metal complexes as templates in the synthesis of open-framework metal phosphates and germanates, see: Stalder & Wilkinson (1997); Wang et al. (2003a,b); Pan et al. (2005, 2008). For the introduction of chiral metal complexes into coordination polymers, see: Pan et al. (2010a,b, 2011); Tong & Pan (2011). For In—Cl bond distances in other hexachloridoindium compounds, see: Rothammel et al. (1998).

Experimental top

In a typical synthesis, a mixture of InCl₃.4H₂O (1 mmol), H₃PO₄ (4 mmol) Co(dien)₂Cl₃ (0.25 mmol) and H₂O (10 ml) was added to a 20 ml Teflon-lined reactor under autogenous pressure at 100 °C for 3 days. Yellow block crystals were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the structure of complex. Ellipsoids are drawn at the 50% probability level.[Symmetry codes: (i) x,y,-z; (ii) -1/2 - x,-1/2 - y,z; (iii) -1/2 - x,-1/2 - y,-z.]

Bis(diethylenetriamine)cobalt(III) hexachloridoindate(III) top

Crystal data top

[Co(C₄H₁₃N₃)₂][InCl₆]	F(000) = 1176
M_r = 592.80	D_x = 2.008 Mg m⁻³
Orthorhombic, Cccm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2 2c	θ = 2.3–28.3°
a = 10.8925 (5) Å	µ = 2.84 mm⁻¹
b = 14.7291 (7) Å	T = 296 K
c = 12.2205 (6) Å	Block, yellow
V = 1960.62 (16) Å³	0.2 × 0.18 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1282 independent reflections
Radiation source: fine-focus sealed tube	1139 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 5.00cm pixels mm^-1	θ_max = 28.3°, θ_min = 2.3°
ϕ and ω scans	h = −14→11
Absorption correction: multi-scan (SADABS; Bruker, 2002)	k = −19→18
T_min = 0.572, T_max = 0.653	l = −12→16
6910 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0179P)² + 3.2797P] where P = (F_o² + 2F_c²)/3
1282 reflections	(Δ/σ)_max < 0.001
57 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Co(C₄H₁₃N₃)₂][InCl₆]	V = 1960.62 (16) Å³
M_r = 592.80	Z = 4
Orthorhombic, Cccm	Mo Kα radiation
a = 10.8925 (5) Å	µ = 2.84 mm⁻¹
b = 14.7291 (7) Å	T = 296 K
c = 12.2205 (6) Å	0.2 × 0.18 × 0.15 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1282 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1139 reflections with I > 2σ(I)
T_min = 0.572, T_max = 0.653	R_int = 0.021
6910 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.046	H-atom parameters constrained
S = 1.06	Δρ_max = 0.34 e Å⁻³
1282 reflections	Δρ_min = −0.37 e Å⁻³
57 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
In1	−0.2500	−0.2500	0.0000	0.02018 (8)
Co1	−0.2500	0.2500	0.0000	0.01769 (10)
Cl1	−0.38483 (5)	−0.31981 (4)	0.14285 (4)	0.03547 (12)
Cl2	−0.38713 (6)	−0.11293 (4)	0.0000	0.03569 (17)
N1	−0.35382 (15)	0.19629 (10)	0.11486 (13)	0.0265 (3)
H1A	−0.3447	0.2282	0.1772	0.080*
H1B	−0.4331	0.1999	0.0945	0.080*
N2	−0.1606 (2)	0.13392 (14)	0.0000	0.0228 (4)
H2	−0.0789	0.1466	0.0000	0.080*
C1	−0.18921 (19)	0.08352 (13)	0.10310 (16)	0.0289 (4)
H1C	−0.1353	0.1041	0.1612	0.080*
H1D	−0.1753	0.0191	0.0921	0.080*
C2	−0.32142 (19)	0.09943 (13)	0.13544 (17)	0.0295 (4)
H2A	−0.3748	0.0601	0.0931	0.080*
H2B	−0.3326	0.0853	0.2123	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
In1	0.01848 (12)	0.02348 (13)	0.01860 (12)	0.00027 (9)	0.000	0.000
Co1	0.0176 (2)	0.0165 (2)	0.0190 (2)	−0.00096 (17)	0.000	0.000
Cl1	0.0303 (2)	0.0454 (3)	0.0307 (2)	−0.0003 (2)	0.0080 (2)	0.0119 (2)
Cl2	0.0245 (3)	0.0231 (3)	0.0595 (5)	0.0016 (2)	0.000	0.000
N1	0.0266 (8)	0.0242 (7)	0.0286 (8)	−0.0011 (6)	0.0058 (6)	0.0023 (6)
N2	0.0220 (10)	0.0210 (10)	0.0255 (11)	0.0000 (8)	0.000	0.000
C1	0.0342 (10)	0.0247 (9)	0.0277 (9)	0.0031 (8)	−0.0027 (8)	0.0049 (7)
C2	0.0352 (11)	0.0234 (9)	0.0298 (10)	−0.0029 (8)	0.0031 (8)	0.0056 (7)

Geometric parameters (Å, º) top

In1—Cl1ⁱ	2.5024 (5)	N1—C2	1.491 (2)
In1—Cl1ⁱⁱ	2.5024 (5)	N1—H1A	0.9000
In1—Cl1	2.5024 (5)	N1—H1B	0.9000
In1—Cl1ⁱⁱⁱ	2.5024 (5)	N2—C1ⁱ	1.495 (2)
In1—Cl2ⁱⁱⁱ	2.5114 (7)	N2—C1	1.495 (2)
In1—Cl2	2.5114 (7)	N2—H2	0.9100
Co1—N2	1.967 (2)	C1—C2	1.512 (3)
Co1—N2^iv	1.967 (2)	C1—H1C	0.9700
Co1—N1ⁱ	1.9684 (15)	C1—H1D	0.9700
Co1—N1^v	1.9684 (15)	C2—H2A	0.9700
Co1—N1^iv	1.9684 (15)	C2—H2B	0.9700
Co1—N1	1.9684 (15)

Cl1ⁱ—In1—Cl1ⁱⁱ	180.0	N1ⁱ—Co1—N1	90.97 (10)
Cl1ⁱ—In1—Cl1	88.48 (3)	N1^v—Co1—N1	89.03 (10)
Cl1ⁱⁱ—In1—Cl1	91.52 (3)	N1^iv—Co1—N1	180.00 (8)
Cl1ⁱ—In1—Cl1ⁱⁱⁱ	91.52 (3)	C2—N1—Co1	111.65 (12)
Cl1ⁱⁱ—In1—Cl1ⁱⁱⁱ	88.48 (3)	C2—N1—H1A	109.3
Cl1—In1—Cl1ⁱⁱⁱ	180.0	Co1—N1—H1A	109.3
Cl1ⁱ—In1—Cl2ⁱⁱⁱ	91.076 (16)	C2—N1—H1B	109.3
Cl1ⁱⁱ—In1—Cl2ⁱⁱⁱ	88.924 (17)	Co1—N1—H1B	109.3
Cl1—In1—Cl2ⁱⁱⁱ	91.076 (16)	H1A—N1—H1B	108.0
Cl1ⁱⁱⁱ—In1—Cl2ⁱⁱⁱ	88.924 (17)	C1ⁱ—N2—C1	114.8 (2)
Cl1ⁱ—In1—Cl2	88.924 (17)	C1ⁱ—N2—Co1	109.18 (12)
Cl1ⁱⁱ—In1—Cl2	91.076 (16)	C1—N2—Co1	109.18 (12)
Cl1—In1—Cl2	88.924 (17)	C1ⁱ—N2—H2	107.8
Cl1ⁱⁱⁱ—In1—Cl2	91.076 (16)	C1—N2—H2	107.8
Cl2ⁱⁱⁱ—In1—Cl2	180.0	Co1—N2—H2	107.8
N2—Co1—N2^iv	180.0	N2—C1—C2	109.98 (16)
N2—Co1—N1ⁱ	86.27 (6)	N2—C1—H1C	109.7
N2^iv—Co1—N1ⁱ	93.73 (6)	C2—C1—H1C	109.7
N2—Co1—N1^v	93.73 (6)	N2—C1—H1D	109.7
N2^iv—Co1—N1^v	86.27 (6)	C2—C1—H1D	109.7
N1ⁱ—Co1—N1^v	180.00 (10)	H1C—C1—H1D	108.2
N2—Co1—N1^iv	93.73 (6)	N1—C2—C1	109.24 (15)
N2^iv—Co1—N1^iv	86.27 (6)	N1—C2—H2A	109.8
N1ⁱ—Co1—N1^iv	89.03 (10)	C1—C2—H2A	109.8
N1^v—Co1—N1^iv	90.97 (10)	N1—C2—H2B	109.8
N2—Co1—N1	86.27 (6)	C1—C2—H2B	109.8
N2^iv—Co1—N1	93.73 (6)	H2A—C2—H2B	108.3

Symmetry codes: (i) x, y, −z; (ii) −x−1/2, −y−1/2, z; (iii) −x−1/2, −y−1/2, −z; (iv) −x−1/2, −y+1/2, −z; (v) −x−1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^vi	0.90	2.62	3.4915 (17)	164
N1—H1B···Cl2^vii	0.90	2.61	3.3823 (18)	144
N1—H1B···Cl1^viii	0.90	2.72	3.3957 (17)	133
N2—H2···Cl1^ix	0.91	2.79	3.5407 (19)	141
N2—H2···Cl1^x	0.91	2.79	3.5407 (19)	141

Symmetry codes: (vi) x, −y, −z+1/2; (vii) −x−1, −y, −z; (viii) −x−1, −y, z; (ix) x+1/2, y+1/2, z; (x) x+1/2, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[Co(C₄H₁₃N₃)₂][InCl₆]
M_r	592.80
Crystal system, space group	Orthorhombic, Cccm
Temperature (K)	296
a, b, c (Å)	10.8925 (5), 14.7291 (7), 12.2205 (6)
V (Å³)	1960.62 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.84
Crystal size (mm)	0.2 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.572, 0.653
No. of measured, independent and observed [I > 2σ(I)] reflections	6910, 1282, 1139
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.046, 1.06
No. of reflections	1282
No. of parameters	57
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.37

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.62	3.4915 (17)	164
N1—H1B···Cl2ⁱⁱ	0.90	2.61	3.3823 (18)	144
N1—H1B···Cl1ⁱⁱⁱ	0.90	2.72	3.3957 (17)	133
N2—H2···Cl1^iv	0.91	2.79	3.5407 (19)	141
N2—H2···Cl1^v	0.91	2.79	3.5407 (19)	141

Symmetry codes: (i) x, −y, −z+1/2; (ii) −x−1, −y, −z; (iii) −x−1, −y, z; (iv) x+1/2, y+1/2, z; (v) x+1/2, y+1/2, −z.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m731

doi:10.1107/S1600536811016758

Open

access