Tris(ethyl-enedi-amine)-cobalt(II) dichloride.

The title compound, [Co(II)(C2H8N2)3]Cl2, was obtained unexpectedly as the product of an attempted solvothermal synthesis of cobalt selenide from the elements in the presence of NH4Cl in ethyl-enedi-amine solvent. The three chelate rings of the distorted octa-hedral [Co(C2H8N2)3](2+) complex cation adopt twisted conformations about their C-C bonds. The spread of cis-N-Co-N bond angles [80.17 (6)-98.10 (6)°] in the title compound is considerably greater than the equivalent data for [Co(III)(C2H8N2)3]Cl3 [Takamizawa et al. (2008 ▶). Angew. Chem. Int. Ed. 47, 1689-1692]. In the crystal, the components are linked by numerous N-H⋯Cl hydrogen bonds, generating a three-dimensional network in which the cationic complexes are stacked in columns along [010] and separated by columns of chloride anions.

Related literature

The corresponding CoIII–tris-ethyl­enedi­amine complex with chloride counter-anions has been reported by Takamizawa et al. (2008 ▶).

Experimental

Crystal data

[Co(C2n class="Species">H8N2)3]Cl2

M = 310.14

Orthorhombic,

a = 8.1590 (8) Å

b = 17.047 (3) Å

c = 20.3974 (14) Å

V = 2837.0 (6) Å3

Z = 8

Cu Kα radiation

μ = 12.81 mm−1

T = 90 K

0.31 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.109, T max = 0.243

17930 measured reflections

2700 independn class="Chemical">ent reflections

2437 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.059

S = 1.06

2700 reflections

232 parameters

All H-atom parameters refined

Δρmax = 0.26 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); cell refinemn class="Chemical">ent: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013135/hb7079sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013135/hb7079Isup2.hkl

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

[Co(C2H8N2)3]Cl2	Dx = 1.451 Mg m−3
Mr = 310.14	Melting point: not measured K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
a = 8.1590 (8) Å	Cell parameters from 6618 reflections
b = 17.047 (3) Å	θ = 4.3–71.0°
c = 20.3974 (14) Å	µ = 12.81 mm−1
V = 2837.0 (6) Å3	T = 90 K
Z = 8	Irregular, yellow
F(000) = 1304	0.31 × 0.17 × 0.15 mm

Bruker APEXII CCD diffractometer	2700 independent reflections
Radiation source: fine-focus sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
φ and ω scans	θmax = 72.0°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.109, Tmax = 0.243	k = −19→20
17930 measured reflections	l = −24→18

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0273P)2 + 1.3198P] where P = (Fo2 + 2Fc2)/3
2700 reflections	(Δ/σ)max = 0.001
232 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co	0.22206 (3)	0.636475 (16)	0.101937 (14)	0.01130 (9)
Cl1	0.22916 (5)	0.38557 (2)	0.02211 (2)	0.01517 (10)
Cl2	0.19514 (5)	0.63342 (2)	0.32464 (2)	0.01878 (11)
N1	0.31525 (19)	0.56644 (9)	0.18154 (8)	0.0144 (3)
H1A	0.419 (3)	0.5613 (12)	0.1780 (10)	0.021 (6)*
H1B	0.297 (3)	0.5888 (15)	0.2164 (12)	0.023 (6)*
N2	0.04364 (19)	0.54264 (9)	0.09943 (8)	0.0155 (3)
H2A	−0.051 (3)	0.5597 (13)	0.0934 (10)	0.019 (6)*
H2B	0.068 (3)	0.5088 (13)	0.0683 (11)	0.023 (6)*
C1	0.2324 (2)	0.48967 (10)	0.18119 (9)	0.0169 (4)
H1C	0.238 (2)	0.4648 (12)	0.2236 (10)	0.014 (5)*
H1D	0.285 (2)	0.4581 (12)	0.1472 (10)	0.016 (5)*
C2	0.0533 (2)	0.50142 (11)	0.16281 (9)	0.0167 (4)
H2C	0.003 (2)	0.5343 (12)	0.1971 (10)	0.020 (5)*
H2D	0.001 (2)	0.4511 (12)	0.1614 (10)	0.018 (5)*
N6	0.37572 (19)	0.57543 (9)	0.03100 (8)	0.0156 (3)
H5B	0.044 (3)	0.6765 (13)	0.0010 (10)	0.023 (6)*
H5A	0.135 (3)	0.7409 (15)	0.0172 (10)	0.024 (6)*
N5	0.14074 (19)	0.69328 (9)	0.01218 (8)	0.0152 (3)
H6A	0.474 (3)	0.5868 (13)	0.0328 (10)	0.020 (5)*
H6B	0.372 (3)	0.5247 (15)	0.0387 (11)	0.029 (6)*
C5	0.2573 (2)	0.67473 (11)	−0.04124 (9)	0.0179 (4)
H5D	0.351 (2)	0.7073 (12)	−0.0344 (9)	0.016 (5)*
H5C	0.211 (2)	0.6829 (13)	−0.0850 (11)	0.021 (5)*
C6	0.3113 (2)	0.59006 (11)	−0.03548 (9)	0.0182 (4)
H6D	0.217 (2)	0.5559 (11)	−0.0402 (9)	0.008 (4)*
H6C	0.391 (3)	0.5790 (12)	−0.0690 (10)	0.019 (5)*
N3	0.38406 (18)	0.73377 (9)	0.12091 (8)	0.0146 (3)
H3A	0.385 (2)	0.7681 (13)	0.0886 (10)	0.016 (5)*
H3B	0.478 (3)	0.7190 (13)	0.1278 (11)	0.023 (6)*
N4	0.07178 (18)	0.70245 (9)	0.17074 (8)	0.0155 (3)
H4B	−0.032 (3)	0.7045 (13)	0.1610 (10)	0.027 (6)*
H4A	0.079 (3)	0.6796 (14)	0.2080 (11)	0.026 (6)*
C3	0.3253 (2)	0.77480 (11)	0.17991 (9)	0.0175 (4)
H3D	0.353 (2)	0.7452 (12)	0.2186 (9)	0.011 (5)*
H3C	0.374 (2)	0.8260 (12)	0.1837 (9)	0.016 (5)*
C4	0.1402 (2)	0.78212 (10)	0.17682 (10)	0.0178 (4)
H4C	0.109 (2)	0.8107 (12)	0.1386 (10)	0.018 (5)*
H4D	0.097 (3)	0.8110 (12)	0.2159 (10)	0.020 (5)*

	U11	U22	U33	U12	U13	U23
Co	0.00953 (15)	0.00972 (15)	0.01465 (16)	−0.00031 (10)	−0.00038 (10)	0.00023 (10)
Cl1	0.0154 (2)	0.0123 (2)	0.0178 (2)	−0.00106 (14)	−0.00053 (15)	0.00024 (15)
Cl2	0.0122 (2)	0.0245 (2)	0.0197 (2)	0.00031 (15)	0.00082 (16)	−0.00254 (17)
N1	0.0125 (8)	0.0140 (7)	0.0166 (8)	0.0004 (6)	−0.0007 (6)	−0.0010 (6)
N2	0.0127 (8)	0.0134 (8)	0.0204 (9)	0.0004 (6)	−0.0011 (6)	−0.0001 (6)
C1	0.0196 (9)	0.0125 (9)	0.0186 (9)	−0.0005 (7)	−0.0005 (7)	0.0022 (7)
C2	0.0176 (9)	0.0119 (8)	0.0207 (10)	−0.0024 (7)	0.0022 (7)	0.0013 (7)
N6	0.0120 (8)	0.0138 (8)	0.0211 (8)	0.0009 (6)	0.0007 (6)	0.0007 (6)
N5	0.0133 (7)	0.0118 (8)	0.0204 (8)	0.0009 (6)	−0.0020 (6)	−0.0005 (6)
C5	0.0184 (9)	0.0175 (9)	0.0177 (10)	−0.0011 (7)	−0.0012 (7)	0.0010 (7)
C6	0.0189 (9)	0.0177 (9)	0.0181 (10)	0.0006 (7)	0.0022 (8)	−0.0030 (7)
N3	0.0114 (7)	0.0136 (7)	0.0189 (8)	−0.0005 (6)	−0.0006 (6)	0.0020 (6)
N4	0.0132 (8)	0.0129 (7)	0.0205 (9)	−0.0011 (6)	0.0019 (6)	0.0000 (6)
C3	0.0201 (9)	0.0125 (9)	0.0198 (10)	−0.0034 (7)	−0.0015 (7)	0.0003 (7)
C4	0.0210 (9)	0.0106 (8)	0.0217 (10)	0.0001 (7)	0.0023 (8)	−0.0001 (7)

Co—N1	2.1540 (15)	N5—C5	1.480 (2)
Co—N3	2.1558 (15)	N5—H5B	0.87 (2)
Co—N2	2.1635 (15)	N5—H5A	0.82 (2)
Co—N5	2.1748 (15)	C5—C6	1.514 (3)
Co—N4	2.1767 (15)	C5—H5D	0.95 (2)
Co—N6	2.1791 (16)	C5—H5C	0.98 (2)
N1—C1	1.473 (2)	C6—H6D	0.967 (19)
N1—H1A	0.86 (2)	C6—H6C	0.96 (2)
N1—H1B	0.82 (2)	N3—C3	1.472 (2)
N2—C2	1.473 (2)	N3—H3A	0.88 (2)
N2—H2A	0.83 (2)	N3—H3B	0.82 (2)
N2—H2B	0.88 (2)	N4—C4	1.474 (2)
C1—C2	1.522 (2)	N4—H4B	0.87 (2)
C1—H1C	0.96 (2)	N4—H4A	0.85 (2)
C1—H1D	0.98 (2)	C3—C4	1.517 (2)
C2—H2C	0.99 (2)	C3—H3D	0.963 (19)
C2—H2D	0.96 (2)	C3—H3C	0.96 (2)
N6—C6	1.475 (2)	C4—H4C	0.95 (2)
N6—H6A	0.83 (2)	C4—H4D	1.00 (2)
N6—H6B	0.88 (3)
N1—Co—N3	94.28 (6)	H6A—N6—H6B	105 (2)
N1—Co—N2	81.11 (6)	C5—N5—Co	109.18 (11)
N3—Co—N2	170.27 (6)	C5—N5—H5B	108.7 (14)
N1—Co—N5	171.51 (6)	Co—N5—H5B	110.5 (14)
N3—Co—N5	89.75 (6)	C5—N5—H5A	109.8 (15)
N2—Co—N5	95.97 (6)	Co—N5—H5A	110.6 (15)
N1—Co—N4	89.95 (6)	H5B—N5—H5A	108 (2)
N3—Co—N4	80.33 (6)	N5—C5—C6	109.49 (15)
N2—Co—N4	91.05 (6)	N5—C5—H5D	106.3 (12)
N5—Co—N4	98.10 (6)	C6—C5—H5D	108.2 (12)
N1—Co—N6	91.88 (6)	N5—C5—H5C	113.1 (12)
N3—Co—N6	97.69 (6)	C6—C5—H5C	108.5 (13)
N2—Co—N6	91.05 (6)	H5D—C5—H5C	111.1 (17)
N5—Co—N6	80.17 (6)	N6—C6—C5	109.64 (15)
N4—Co—N6	177.41 (6)	N6—C6—H6D	105.8 (11)
C1—N1—Co	109.07 (11)	C5—C6—H6D	109.6 (11)
C1—N1—H1A	111.3 (14)	N6—C6—H6C	112.2 (12)
Co—N1—H1A	110.0 (14)	C5—C6—H6C	109.1 (13)
C1—N1—H1B	109.6 (16)	H6D—C6—H6C	110.4 (16)
Co—N1—H1B	109.5 (16)	C3—N3—Co	108.21 (11)
H1A—N1—H1B	107 (2)	C3—N3—H3A	107.4 (13)
C2—N2—Co	107.21 (11)	Co—N3—H3A	112.6 (13)
C2—N2—H2A	110.2 (14)	C3—N3—H3B	108.1 (16)
Co—N2—H2A	111.6 (15)	Co—N3—H3B	111.7 (15)
C2—N2—H2B	108.0 (14)	H3A—N3—H3B	109 (2)
Co—N2—H2B	110.4 (14)	C4—N4—Co	108.49 (11)
H2A—N2—H2B	109 (2)	C4—N4—H4B	110.5 (15)
N1—C1—C2	108.96 (14)	Co—N4—H4B	114.9 (15)
N1—C1—H1C	111.3 (12)	C4—N4—H4A	108.7 (16)
C2—C1—H1C	109.1 (12)	Co—N4—H4A	107.5 (15)
N1—C1—H1D	106.9 (12)	H4B—N4—H4A	107 (2)
C2—C1—H1D	108.7 (11)	N3—C3—C4	109.24 (15)
H1C—C1—H1D	111.9 (16)	N3—C3—H3D	110.2 (11)
N2—C2—C1	109.29 (15)	C4—C3—H3D	108.0 (11)
N2—C2—H2C	109.2 (12)	N3—C3—H3C	111.2 (12)
C1—C2—H2C	107.6 (12)	C4—C3—H3C	110.0 (12)
N2—C2—H2D	112.1 (12)	H3D—C3—H3C	108.2 (16)
C1—C2—H2D	108.4 (12)	N4—C4—C3	107.74 (14)
H2C—C2—H2D	110.2 (17)	N4—C4—H4C	107.6 (12)
C6—N6—Co	108.95 (11)	C3—C4—H4C	109.8 (12)
C6—N6—H6A	110.3 (15)	N4—C4—H4D	112.8 (12)
Co—N6—H6A	114.7 (15)	C3—C4—H4D	110.8 (12)
C6—N6—H6B	108.5 (14)	H4C—C4—H4D	108.0 (16)
Co—N6—H6B	109.3 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2	0.82 (2)	2.48 (3)	3.2839 (17)	167 (2)
N1—H1A···Cl2i	0.86 (2)	2.57 (2)	3.3056 (16)	145.4 (18)
N2—H2A···Cl1ii	0.83 (2)	2.92 (2)	3.5494 (16)	133.6 (17)
N2—H2A···Cl2iii	0.83 (2)	2.94 (2)	3.5887 (17)	135.8 (17)
N2—H2B···Cl1	0.88 (2)	2.65 (2)	3.4566 (17)	152.5 (18)
N5—H5B···Cl1ii	0.87 (2)	2.51 (2)	3.3770 (16)	173.1 (19)
N5—H5A···Cl1iv	0.82 (2)	2.70 (2)	3.4514 (18)	152.4 (19)
N6—H6B···Cl1	0.88 (3)	2.66 (3)	3.4552 (18)	150.3 (19)
N6—H6A···Cl1v	0.83 (2)	2.71 (2)	3.4653 (16)	152.9 (19)
N3—H3A···Cl1iv	0.88 (2)	2.59 (2)	3.4075 (17)	154.2 (17)
N3—H3B···Cl2i	0.82 (2)	2.49 (2)	3.2560 (16)	156 (2)
N4—H4A···Cl2	0.85 (2)	2.68 (2)	3.5003 (17)	161 (2)
N4—H4B···Cl2iii	0.87 (2)	2.55 (2)	3.2919 (16)	143.5 (19)

Table 1

Selected bond lengths (Å)

Co—N1	2.1540 (15)
Co—N3	2.1558 (15)
Co—N2	2.1635 (15)
Co—N5	2.1748 (15)
Co—N4	2.1767 (15)
Co—N6	2.1791 (16)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl2	0.82 (2)	2.48 (3)	3.2839 (17)	167 (2)
N1—H1A⋯Cl2i	0.86 (2)	2.57 (2)	3.3056 (16)	145.4 (18)
N2—H2A⋯Cl1ii	0.83 (2)	2.92 (2)	3.5494 (16)	133.6 (17)
N2—H2A⋯Cl2iii	0.83 (2)	2.94 (2)	3.5887 (17)	135.8 (17)
N2—H2B⋯Cl1	0.88 (2)	2.65 (2)	3.4566 (17)	152.5 (18)
N5—H5B⋯Cl1ii	0.87 (2)	2.51 (2)	3.3770 (16)	173.1 (19)
N5—H5A⋯Cl1iv	0.82 (2)	2.70 (2)	3.4514 (18)	152.4 (19)
N6—H6B⋯Cl1	0.88 (3)	2.66 (3)	3.4552 (18)	150.3 (19)
N6—H6A⋯Cl1v	0.83 (2)	2.71 (2)	3.4653 (16)	152.9 (19)
N3—H3A⋯Cl1iv	0.88 (2)	2.59 (2)	3.4075 (17)	154.2 (17)
N3—H3B⋯Cl2i	0.82 (2)	2.49 (2)	3.2560 (16)	156 (2)
N4—H4A⋯Cl2	0.85 (2)	2.68 (2)	3.5003 (17)	161 (2)
N4—H4B⋯Cl2iii	0.87 (2)	2.55 (2)	3.2919 (16)	143.5 (19)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .