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

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 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

For the triclinic modification, see: Csöregh et al. (2000[Csöregh, I., Kennessey, G., Wadsten, T., Liptay, G. & Carson, B. R. (2000). Z. Kristallogr. 215, 547-552.]).

[Scheme 1]

Experimental

Crystal data
  • [CoCl2(C4H5N3)4]

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.746, Tmax = 0.860

  • 20053 measured reflections

  • 2553 independent reflections

  • 2234 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.29 e Å−3

  • Δρmin = −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 DA 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⋯N2iv 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[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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 m3
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 mm1
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)
Graphite monochromatorRint = 0.024
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 99
Tmin = 0.746, Tmax = 0.860k = 2020
20053 measured reflectionsl = 2424
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 = 0.29 e Å3
4 restraintsΔρmin = 0.25 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0254 restraints
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.29 e Å3
2553 reflectionsΔρmin = 0.25 e Å3
157 parameters
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)
H3A0.70270.08780.13180.075*
C40.7141 (2)0.14683 (13)0.03790 (9)0.0509 (4)
H4A0.83450.15570.03910.061*
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, º) 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—N3179.1 (2)
N1i—Co1—N1—C1131.09 (13)C3—N2—C2—C12.7 (3)
Cl1i—Co1—N1—C142.23 (11)N1—C1—C2—N21.9 (2)
Cl1—Co1—N1—C1137.45 (11)N1—C1—C2—N3179.93 (17)
N4i—Co1—N1—C4138.03 (13)C2—N2—C3—C41.6 (3)
N1i—Co1—N1—C445.15 (12)C1—N1—C4—C31.4 (3)
Cl1i—Co1—N1—C4134.01 (13)Co1—N1—C4—C3175.03 (16)
Cl1—Co1—N1—C446.30 (13)N2—C3—C4—N10.5 (4)
N4i—Co1—N4—C5124.52 (13)C8—N4—C5—C61.1 (2)
N1i—Co1—N4—C552.25 (11)Co1—N4—C5—C6172.58 (10)
Cl1i—Co1—N4—C536.70 (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—C8134.32 (13)N4—C5—C6—N6178.74 (15)
Cl1i—Co1—N4—C8136.73 (12)C6—N5—C7—C80.5 (3)
Cl1—Co1—N4—C842.96 (12)C5—N4—C8—C71.4 (2)
C4—N1—C1—C20.3 (2)Co1—N4—C8—C7172.29 (13)
Co1—N1—C1—C2176.01 (11)N5—C7—C8—N40.6 (3)
Symmetry code: (i) x+3/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) 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) x1, y, z; (iii) x1, y+1/2, z1/2; (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]
Mr510.27
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)293
a, b, c (Å)7.6347 (2), 15.7341 (4), 18.6074 (4)
V3)2235.22 (9)
Z4
Radiation typeMo Kα
µ (mm1)1.04
Crystal size (mm)0.30 × 0.20 × 0.15
Data collection
DiffractometerRigaku RAXIS-RAPID IP
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.746, 0.860
No. of measured, independent and
observed [I > 2σ(I)] reflections
20053, 2553, 2234
Rint0.024
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.074, 1.06
No. of reflections2553
No. of parameters157
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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—N12.2068 (11)Co1—Cl12.4206 (4)
Co1—N42.1941 (11)
Hydrogen-bond geometry (Å, º) 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) x1, y, z; (ii) x1, y+1/2, z1/2; (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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationCsöregh, I., Kennessey, G., Wadsten, T., Liptay, G. & Carson, B. R. (2000). Z. Kristallogr. 215, 547–552.  Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

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