Tetra­kis(2-amino­pyrazine-κN4)dichlorido­cobalt(II)

Kang, W.; Huo, L.-H.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809045309

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1502

doi:10.1107/S1600536809045309

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Tetrakis(2-aminopyrazine-κN⁴)dichloridocobalt(II)

Wei Kang,^a Li-Hua Huo,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 October 2009; accepted 29 October 2009; online 4 November 2009)

The Co^II atom in the title complex, [CoCl₂(C₄H₅N₃)₄], exists in an all-trans Cl₂N₄Co octahedral geometry. The Co^II atom lies on a special position of 2 site symmetry. Adjacent molecules are linked by N—H⋯N and N—H⋯Cl hydrogen bonds into a three-dimensional network.

Related literature

For the triclinic modification, see: Csöregh et al. (2000 ).

Experimental

Crystal data

[CoCl₂(C₄H₅N₃)₄]
M_r = 510.27
Orthorhombic, P c c n
a = 7.6347 (2) Å
b = 15.7341 (4) Å
c = 18.6074 (4) Å
V = 2235.22 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.746, T_max = 0.860
20053 measured reflections
2553 independent reflections
2234 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.074
S = 1.06
2553 reflections
157 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.2068 (11)
Co1—N4	2.1941 (11)
Co1—Cl1	2.4206 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯Cl1ⁱ	0.85 (1)	2.36 (1)	3.209 (2)	175 (2)
N3—H2⋯N5ⁱⁱ	0.86 (1)	2.43 (2)	3.134 (2)	140 (2)
N6—H3⋯Cl1ⁱⁱⁱ	0.85 (1)	2.42 (1)	3.265 (1)	171 (2)
N6—H4⋯N2^iv	0.86 (1)	2.33 (2)	3.045 (2)	142 (2)
Symmetry codes: (i) x-1, y, z; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045309/xu2656sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045309/xu2656Isup2.hkl

checkCIF report

Related literature top

For the triclinic modification, see: Csöregh et al. (2000).

Experimental top

Cobalt(II) chloride hexahydrate (0.48 g, 2 mmol) and 2-aminopyrazine (0.19 g, 2 mmol) were dissolved in a small volume of water. Red crystals of the adduct separated from the filtered solution after several days. CH&N elemental analysis. Calc. for C₁₆H₂₀Cl₂N₁₂Co: C 37.66, H 3.95, N 32.94%; found: C 37.63, H 3.89, N 32.97%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of CoCl₂(C₂H₅N₃)₄ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Tetrakis(2-aminopyrazine-κN⁴)dichloridocobalt(II) top

Crystal data top

[CoCl₂(C₄H₅N₃)₄]	F(000) = 1044
M_r = 510.27	D_x = 1.516 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 15790 reflections
a = 7.6347 (2) Å	θ = 2.3–27.5°
b = 15.7341 (4) Å	µ = 1.04 mm⁻¹
c = 18.6074 (4) Å	T = 293 K
V = 2235.22 (9) Å³	Block, red
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection top

Rigaku RAXIS-RAPID IP diffractometer	2553 independent reflections
Radiation source: fine-focus sealed tube	2234 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.746, T_max = 0.860	k = −20→20
20053 measured reflections	l = −24→24

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0439P)² + 0.4514P] where P = (F_o² + 2F_c²)/3
2553 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.29 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[CoCl₂(C₄H₅N₃)₄]	V = 2235.22 (9) Å³
M_r = 510.27	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.6347 (2) Å	µ = 1.04 mm⁻¹
b = 15.7341 (4) Å	T = 293 K
c = 18.6074 (4) Å	0.30 × 0.20 × 0.15 mm

Data collection top

Rigaku RAXIS-RAPID IP diffractometer	2553 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2234 reflections with I > 2σ(I)
T_min = 0.746, T_max = 0.860	R_int = 0.024
20053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	4 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.29 e Å⁻³
2553 reflections	Δρ_min = −0.25 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
Co1	0.7500	0.2500	0.103443 (12)	0.02794 (9)
Cl1	0.98632 (5)	0.14744 (2)	0.103952 (17)	0.03970 (11)
N1	0.61989 (16)	0.17473 (8)	0.01880 (6)	0.0348 (3)
N2	0.46194 (19)	0.08976 (11)	−0.09614 (7)	0.0553 (4)
N3	0.1968 (2)	0.09877 (14)	−0.03954 (8)	0.0686 (5)
N4	0.88907 (16)	0.31841 (7)	0.18890 (6)	0.0339 (3)
N5	1.03169 (17)	0.40550 (8)	0.30631 (6)	0.0387 (3)
N6	0.9535 (2)	0.53209 (8)	0.25231 (7)	0.0527 (4)
C1	0.45050 (19)	0.15892 (9)	0.01846 (7)	0.0357 (3)
H1A	0.3823	0.1771	0.0569	0.043*
C2	0.3693 (2)	0.11475 (10)	−0.03920 (7)	0.0413 (3)
C3	0.6338 (2)	0.10573 (14)	−0.09351 (9)	0.0625 (6)
H3A	0.7027	0.0878	−0.1318	0.075*
C4	0.7141 (2)	0.14683 (13)	−0.03790 (9)	0.0509 (4)
H4A	0.8345	0.1557	−0.0391	0.061*
C5	0.88843 (19)	0.40188 (8)	0.19189 (6)	0.0319 (3)
H5	0.8395	0.4324	0.1541	0.038*
C6	0.96002 (18)	0.44673 (8)	0.25094 (7)	0.0325 (3)
C7	1.0327 (2)	0.32043 (10)	0.30155 (8)	0.0453 (4)
H7	1.0823	0.2896	0.3390	0.054*
C8	0.9645 (2)	0.27664 (10)	0.24459 (8)	0.0452 (4)
H8	0.9700	0.2176	0.2440	0.054*
H1	0.136 (3)	0.1094 (14)	−0.0022 (8)	0.078 (7)*
H2	0.155 (3)	0.0704 (11)	−0.0753 (8)	0.063 (6)*
H3	0.978 (3)	0.5580 (12)	0.2913 (7)	0.060 (6)*
H4	0.909 (2)	0.5583 (11)	0.2164 (8)	0.061 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03367 (16)	0.02901 (14)	0.02114 (14)	−0.00229 (9)	0.000	0.000
Cl1	0.0462 (2)	0.0432 (2)	0.02968 (18)	0.01013 (15)	0.00662 (13)	0.00476 (12)
N1	0.0337 (6)	0.0435 (6)	0.0271 (5)	−0.0030 (5)	0.0015 (5)	−0.0079 (5)
N2	0.0407 (8)	0.0851 (11)	0.0401 (7)	−0.0055 (7)	0.0052 (6)	−0.0322 (7)
N3	0.0366 (8)	0.1287 (16)	0.0407 (8)	−0.0134 (9)	0.0027 (6)	−0.0368 (9)
N4	0.0428 (7)	0.0326 (5)	0.0262 (5)	−0.0011 (5)	−0.0058 (5)	0.0003 (4)
N5	0.0447 (7)	0.0433 (6)	0.0281 (5)	−0.0005 (5)	−0.0095 (5)	−0.0004 (5)
N6	0.0912 (12)	0.0339 (6)	0.0331 (6)	−0.0092 (7)	−0.0211 (7)	0.0002 (5)
C1	0.0359 (7)	0.0464 (7)	0.0248 (6)	0.0013 (6)	0.0028 (5)	−0.0084 (6)
C2	0.0352 (8)	0.0588 (9)	0.0300 (6)	−0.0012 (7)	0.0005 (6)	−0.0124 (6)
C3	0.0416 (9)	0.1031 (16)	0.0429 (9)	−0.0042 (10)	0.0106 (7)	−0.0368 (9)
C4	0.0340 (8)	0.0789 (12)	0.0398 (8)	−0.0060 (7)	0.0075 (6)	−0.0206 (8)
C5	0.0399 (7)	0.0323 (6)	0.0236 (6)	−0.0039 (5)	−0.0055 (5)	0.0036 (5)
C6	0.0376 (7)	0.0349 (6)	0.0251 (6)	−0.0057 (5)	−0.0034 (5)	0.0008 (5)
C7	0.0582 (10)	0.0450 (8)	0.0326 (7)	0.0103 (7)	−0.0151 (7)	0.0028 (6)
C8	0.0650 (11)	0.0335 (7)	0.0371 (7)	0.0090 (7)	−0.0136 (7)	0.0015 (6)

Geometric parameters (Å, º) top

Co1—N1ⁱ	2.2068 (11)	N5—C6	1.3348 (18)
Co1—N1	2.2068 (11)	N5—C7	1.341 (2)
Co1—N4	2.1941 (11)	N6—C6	1.3441 (18)
Co1—N4ⁱ	2.1941 (11)	N6—H3	0.852 (9)
Co1—Cl1ⁱ	2.4206 (4)	N6—H4	0.856 (9)
Co1—Cl1	2.4206 (4)	C1—C2	1.4207 (19)
N1—C1	1.3170 (19)	C1—H1A	0.9300
N1—C4	1.3501 (19)	C3—C4	1.366 (2)
N2—C2	1.3332 (19)	C3—H3A	0.9300
N2—C3	1.337 (2)	C4—H4A	0.9300
N3—C2	1.341 (2)	C5—C6	1.4157 (18)
N3—H1	0.853 (9)	C5—H5	0.9300
N3—H2	0.864 (9)	C7—C8	1.367 (2)
N4—C5	1.3145 (17)	C7—H7	0.9300
N4—C8	1.3556 (18)	C8—H8	0.9300

N4—Co1—N4ⁱ	87.12 (6)	C6—N6—H4	118.8 (14)
N4—Co1—N1ⁱ	92.07 (4)	H3—N6—H4	121 (2)
N4ⁱ—Co1—N1ⁱ	176.67 (4)	N1—C1—C2	121.63 (13)
N4—Co1—N1	176.67 (4)	N1—C1—H1A	119.2
N4ⁱ—Co1—N1	92.07 (4)	C2—C1—H1A	119.2
N1ⁱ—Co1—N1	88.93 (6)	N2—C2—N3	117.51 (14)
N4—Co1—Cl1ⁱ	91.77 (3)	N2—C2—C1	120.88 (15)
N4ⁱ—Co1—Cl1ⁱ	87.91 (3)	N3—C2—C1	121.59 (13)
N1ⁱ—Co1—Cl1ⁱ	88.89 (3)	N2—C3—C4	123.88 (15)
N1—Co1—Cl1ⁱ	91.43 (3)	N2—C3—H3A	118.1
N4—Co1—Cl1	87.91 (3)	C4—C3—H3A	118.1
N4ⁱ—Co1—Cl1	91.77 (3)	N1—C4—C3	120.47 (15)
N1ⁱ—Co1—Cl1	91.43 (3)	N1—C4—H4A	119.8
N1—Co1—Cl1	88.89 (3)	C3—C4—H4A	119.8
Cl1ⁱ—Co1—Cl1	179.552 (18)	N4—C5—C6	121.97 (12)
C1—N1—C4	117.25 (12)	N4—C5—H5	119.0
C1—N1—Co1	123.15 (9)	C6—C5—H5	119.0
C4—N1—Co1	119.50 (10)	N5—C6—N6	119.10 (12)
C2—N2—C3	115.85 (13)	N5—C6—C5	121.00 (12)
C2—N3—H1	119.6 (16)	N6—C6—C5	119.89 (12)
C2—N3—H2	117.9 (14)	N5—C7—C8	123.50 (13)
H1—N3—H2	122 (2)	N5—C7—H7	118.2
C5—N4—C8	116.97 (12)	C8—C7—H7	118.2
C5—N4—Co1	121.27 (9)	N4—C8—C7	120.67 (14)
C8—N4—Co1	121.45 (10)	N4—C8—H8	119.7
C6—N5—C7	115.87 (12)	C7—C8—H8	119.7
C6—N6—H3	119.0 (14)

N4ⁱ—Co1—N1—C1	45.73 (12)	C3—N2—C2—N3	−179.1 (2)
N1ⁱ—Co1—N1—C1	−131.09 (13)	C3—N2—C2—C1	2.7 (3)
Cl1ⁱ—Co1—N1—C1	−42.23 (11)	N1—C1—C2—N2	−1.9 (2)
Cl1—Co1—N1—C1	137.45 (11)	N1—C1—C2—N3	−179.93 (17)
N4ⁱ—Co1—N1—C4	−138.03 (13)	C2—N2—C3—C4	−1.6 (3)
N1ⁱ—Co1—N1—C4	45.15 (12)	C1—N1—C4—C3	1.4 (3)
Cl1ⁱ—Co1—N1—C4	134.01 (13)	Co1—N1—C4—C3	−175.03 (16)
Cl1—Co1—N1—C4	−46.30 (13)	N2—C3—C4—N1	−0.5 (4)
N4ⁱ—Co1—N4—C5	−124.52 (13)	C8—N4—C5—C6	−1.1 (2)
N1ⁱ—Co1—N4—C5	52.25 (11)	Co1—N4—C5—C6	172.58 (10)
Cl1ⁱ—Co1—N4—C5	−36.70 (11)	C7—N5—C6—N6	179.54 (15)
Cl1—Co1—N4—C5	143.61 (11)	C7—N5—C6—C5	0.7 (2)
N4ⁱ—Co1—N4—C8	48.91 (11)	N4—C5—C6—N5	0.1 (2)
N1ⁱ—Co1—N4—C8	−134.32 (13)	N4—C5—C6—N6	−178.74 (15)
Cl1ⁱ—Co1—N4—C8	136.73 (12)	C6—N5—C7—C8	−0.5 (3)
Cl1—Co1—N4—C8	−42.96 (12)	C5—N4—C8—C7	1.4 (2)
C4—N1—C1—C2	−0.3 (2)	Co1—N4—C8—C7	−172.29 (13)
Co1—N1—C1—C2	176.01 (11)	N5—C7—C8—N4	−0.6 (3)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱⁱ	0.85 (1)	2.36 (1)	3.209 (2)	175 (2)
N3—H2···N5ⁱⁱⁱ	0.86 (1)	2.43 (2)	3.134 (2)	140 (2)
N6—H3···Cl1^iv	0.85 (1)	2.42 (1)	3.265 (1)	171 (2)
N6—H4···N2^v	0.86 (1)	2.33 (2)	3.045 (2)	142 (2)

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

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₄H₅N₃)₄]
M_r	510.27
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	293
a, b, c (Å)	7.6347 (2), 15.7341 (4), 18.6074 (4)
V (Å³)	2235.22 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku RAXIS-RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.746, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	20053, 2553, 2234
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.074, 1.06
No. of reflections	2553
No. of parameters	157
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Co1—N1	2.2068 (11)	Co1—Cl1	2.4206 (4)
Co1—N4	2.1941 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱ	0.85 (1)	2.36 (1)	3.209 (2)	175 (2)
N3—H2···N5ⁱⁱ	0.86 (1)	2.43 (2)	3.134 (2)	140 (2)
N6—H3···Cl1ⁱⁱⁱ	0.85 (1)	2.42 (1)	3.265 (1)	171 (2)
N6—H4···N2^iv	0.86 (1)	2.33 (2)	3.045 (2)	142 (2)

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

Acknowledgements

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University, China, and the University of Malaya for supporting this study.

References

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