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Acta Cryst. (2009). E65, m1502    [ doi:10.1107/S1600536809045309 ]

Tetrakis(2-aminopyrazine-[kappa]N4)dichloridocobalt(II)

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

Abstract top

The CoII atom in the title complex, [CoCl2(C4H5N3)4], exists in an all-trans Cl2N4Co octahedral geometry. The CoII 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 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%.

Refinement top

Amino-H atoms were located in a difference Fourier map and refined isotropically with a distance restraint of N–H = 0.86±0.01 Å. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 Å) and were included in the refinement in the riding model approximation with Uiso(H) set to 1.2Ueq(C).

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
[Figure 1] 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
Mr = 510.27Dx = 1.516 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 15790 reflections
a = 7.6347 (2) Åθ = 2.3–27.5°
b = 15.7341 (4) ŵ = 1.04 mm−1
c = 18.6074 (4) ÅT = 293 K
V = 2235.22 (9) Å3Block, red
Z = 40.30 × 0.20 × 0.15 mm
Data collection top
Rigaku RAXIS-RAPID IP
diffractometer		2553 independent reflections
Radiation source: fine-focus sealed tube2234 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −9→9
Tmin = 0.746, Tmax = 0.860k = −20→20
20053 measured reflectionsl = −24→24
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0439P)2 + 0.4514P]
where P = (Fo2 + 2Fc2)/3
2553 reflections(Δ/σ)max = 0.001
157 parametersΔρmax = 0.28 e Å−3
4 restraintsΔρmin = −0.25 e Å−3
Crystal data top
[CoCl2(C4H5N3)4]V = 2235.22 (9) Å3
Mr = 510.27Z = 4
Orthorhombic, PccnMo Kα radiation
a = 7.6347 (2) ŵ = 1.04 mm−1
b = 15.7341 (4) ÅT = 293 K
c = 18.6074 (4) Å0.30 × 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)
Tmin = 0.746, Tmax = 0.860Rint = 0.024
20053 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074Δρmax = 0.28 e Å−3
S = 1.06Δρmin = −0.25 e Å−3
2553 reflectionsAbsolute structure: ?
157 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.75000.25000.103443 (12)0.02794 (9)
Cl10.98632 (5)0.14744 (2)0.103952 (17)0.03970 (11)
N10.61989 (16)0.17473 (8)0.01880 (6)0.0348 (3)
N20.46194 (19)0.08976 (11)−0.09614 (7)0.0553 (4)
N30.1968 (2)0.09877 (14)−0.03954 (8)0.0686 (5)
N40.88907 (16)0.31841 (7)0.18890 (6)0.0339 (3)
N51.03169 (17)0.40550 (8)0.30631 (6)0.0387 (3)
N60.9535 (2)0.53209 (8)0.25231 (7)0.0527 (4)
C10.45050 (19)0.15892 (9)0.01846 (7)0.0357 (3)
H1A0.38230.17710.05690.043*
C20.3693 (2)0.11475 (10)−0.03920 (7)0.0413 (3)
C30.6338 (2)0.10573 (14)−0.09351 (9)0.0625 (6)
H3A0.70270.0878−0.13180.075*
C40.7141 (2)0.14683 (13)−0.03790 (9)0.0509 (4)
H4A0.83450.1557−0.03910.061*
C50.88843 (19)0.40188 (8)0.19189 (6)0.0319 (3)
H50.83950.43240.15410.038*
C60.96002 (18)0.44673 (8)0.25094 (7)0.0325 (3)
C71.0327 (2)0.32043 (10)0.30155 (8)0.0453 (4)
H71.08230.28960.33900.054*
C80.9645 (2)0.27664 (10)0.24459 (8)0.0452 (4)
H80.97000.21760.24400.054*
H10.136 (3)0.1094 (14)−0.0022 (8)0.078 (7)*
H20.155 (3)0.0704 (11)−0.0753 (8)0.063 (6)*
H30.978 (3)0.5580 (12)0.2913 (7)0.060 (6)*
H40.909 (2)0.5583 (11)0.2164 (8)0.061 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.03367 (16)0.02901 (14)0.02114 (14)−0.00229 (9)0.0000.000
Cl10.0462 (2)0.0432 (2)0.02968 (18)0.01013 (15)0.00662 (13)0.00476 (12)
N10.0337 (6)0.0435 (6)0.0271 (5)−0.0030 (5)0.0015 (5)−0.0079 (5)
N20.0407 (8)0.0851 (11)0.0401 (7)−0.0055 (7)0.0052 (6)−0.0322 (7)
N30.0366 (8)0.1287 (16)0.0407 (8)−0.0134 (9)0.0027 (6)−0.0368 (9)
N40.0428 (7)0.0326 (5)0.0262 (5)−0.0011 (5)−0.0058 (5)0.0003 (4)
N50.0447 (7)0.0433 (6)0.0281 (5)−0.0005 (5)−0.0095 (5)−0.0004 (5)
N60.0912 (12)0.0339 (6)0.0331 (6)−0.0092 (7)−0.0211 (7)0.0002 (5)
C10.0359 (7)0.0464 (7)0.0248 (6)0.0013 (6)0.0028 (5)−0.0084 (6)
C20.0352 (8)0.0588 (9)0.0300 (6)−0.0012 (7)0.0005 (6)−0.0124 (6)
C30.0416 (9)0.1031 (16)0.0429 (9)−0.0042 (10)0.0106 (7)−0.0368 (9)
C40.0340 (8)0.0789 (12)0.0398 (8)−0.0060 (7)0.0075 (6)−0.0206 (8)
C50.0399 (7)0.0323 (6)0.0236 (6)−0.0039 (5)−0.0055 (5)0.0036 (5)
C60.0376 (7)0.0349 (6)0.0251 (6)−0.0057 (5)−0.0034 (5)0.0008 (5)
C70.0582 (10)0.0450 (8)0.0326 (7)0.0103 (7)−0.0151 (7)0.0028 (6)
C80.0650 (11)0.0335 (7)0.0371 (7)0.0090 (7)−0.0136 (7)0.0015 (6)
Geometric parameters (Å, °) top
Co1—N1i2.2068 (11)N5—C61.3348 (18)
Co1—N12.2068 (11)N5—C71.341 (2)
Co1—N42.1941 (11)N6—C61.3441 (18)
Co1—N4i2.1941 (11)N6—H30.852 (9)
Co1—Cl1i2.4206 (4)N6—H40.856 (9)
Co1—Cl12.4206 (4)C1—C21.4207 (19)
N1—C11.3170 (19)C1—H1A0.9300
N1—C41.3501 (19)C3—C41.366 (2)
N2—C21.3332 (19)C3—H3A0.9300
N2—C31.337 (2)C4—H4A0.9300
N3—C21.341 (2)C5—C61.4157 (18)
N3—H10.853 (9)C5—H50.9300
N3—H20.864 (9)C7—C81.367 (2)
N4—C51.3145 (17)C7—H70.9300
N4—C81.3556 (18)C8—H80.9300
N4—Co1—N4i87.12 (6)C6—N6—H4118.8 (14)
N4—Co1—N1i92.07 (4)H3—N6—H4121 (2)
N4i—Co1—N1i176.67 (4)N1—C1—C2121.63 (13)
N4—Co1—N1176.67 (4)N1—C1—H1A119.2
N4i—Co1—N192.07 (4)C2—C1—H1A119.2
N1i—Co1—N188.93 (6)N2—C2—N3117.51 (14)
N4—Co1—Cl1i91.77 (3)N2—C2—C1120.88 (15)
N4i—Co1—Cl1i87.91 (3)N3—C2—C1121.59 (13)
N1i—Co1—Cl1i88.89 (3)N2—C3—C4123.88 (15)
N1—Co1—Cl1i91.43 (3)N2—C3—H3A118.1
N4—Co1—Cl187.91 (3)C4—C3—H3A118.1
N4i—Co1—Cl191.77 (3)N1—C4—C3120.47 (15)
N1i—Co1—Cl191.43 (3)N1—C4—H4A119.8
N1—Co1—Cl188.89 (3)C3—C4—H4A119.8
Cl1i—Co1—Cl1179.552 (18)N4—C5—C6121.97 (12)
C1—N1—C4117.25 (12)N4—C5—H5119.0
C1—N1—Co1123.15 (9)C6—C5—H5119.0
C4—N1—Co1119.50 (10)N5—C6—N6119.10 (12)
C2—N2—C3115.85 (13)N5—C6—C5121.00 (12)
C2—N3—H1119.6 (16)N6—C6—C5119.89 (12)
C2—N3—H2117.9 (14)N5—C7—C8123.50 (13)
H1—N3—H2122 (2)N5—C7—H7118.2
C5—N4—C8116.97 (12)C8—C7—H7118.2
C5—N4—Co1121.27 (9)N4—C8—C7120.67 (14)
C8—N4—Co1121.45 (10)N4—C8—H8119.7
C6—N5—C7115.87 (12)C7—C8—H8119.7
C6—N6—H3119.0 (14)
N4i—Co1—N1—C145.73 (12)C3—N2—C2—N3−179.1 (2)
N1i—Co1—N1—C1−131.09 (13)C3—N2—C2—C12.7 (3)
Cl1i—Co1—N1—C1−42.23 (11)N1—C1—C2—N2−1.9 (2)
Cl1—Co1—N1—C1137.45 (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—C445.15 (12)C1—N1—C4—C31.4 (3)
Cl1i—Co1—N1—C4134.01 (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—C552.25 (11)Co1—N4—C5—C6172.58 (10)
Cl1i—Co1—N4—C5−36.70 (11)C7—N5—C6—N6179.54 (15)
Cl1—Co1—N4—C5143.61 (11)C7—N5—C6—C50.7 (2)
N4i—Co1—N4—C848.91 (11)N4—C5—C6—N50.1 (2)
N1i—Co1—N4—C8−134.32 (13)N4—C5—C6—N6−178.74 (15)
Cl1i—Co1—N4—C8136.73 (12)C6—N5—C7—C8−0.5 (3)
Cl1—Co1—N4—C8−42.96 (12)C5—N4—C8—C71.4 (2)
C4—N1—C1—C2−0.3 (2)Co1—N4—C8—C7−172.29 (13)
Co1—N1—C1—C2176.01 (11)N5—C7—C8—N4−0.6 (3)
Symmetry codes: (i) −x+3/2, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H1···Cl1ii0.85 (1)2.36 (1)3.209 (2)175 (2)
N3—H2···N5iii0.86 (1)2.43 (2)3.134 (2)140 (2)
N6—H3···Cl1iv0.85 (1)2.42 (1)3.265 (1)171 (2)
N6—H4···N2v0.86 (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.
Table 1
Selected geometric parameters (Å) top
Co1—N12.2068 (11)Co1—Cl12.4206 (4)
Co1—N42.1941 (11)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H1···Cl1i0.85 (1)2.36 (1)3.209 (2)175 (2)
N3—H2···N5ii0.86 (1)2.43 (2)3.134 (2)140 (2)
N6—H3···Cl1iii0.85 (1)2.42 (1)3.265 (1)171 (2)
N6—H4···N2iv0.86 (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 top

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

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Csöregh, I., Kennessey, G., Wadsten, T., Liptay, G. & Carson, B. R. (2000). Z. Kristallogr. 215, 547–552.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.