Bis(2-amino-6-methyl-pyridinium) trans-diaqua-bis-(pyrazine-2,3-dicarboxyl-ato)cobaltate(II) octa-hydrate.

The title compound, (C(6)H(9)N(2))(2)[Co(C(6)H(2)N(2)O(4))(2)(H(2)O)(2)]·8H(2)O, was obtained by the reaction of CoCl(2)·6H(2)O with 1,4-pyrazine-2,3-dicarb-oxy-lic acid and 2-amino-6-methyl-pyridine in aqueous solution (molar ratio 1:2:2). The Co(II) ion is situated on an inversion centre and is coordinated by two O and two N atoms of two symmetry-related 1,4-pyrazine-2,3-dicarboxyl-ate ligands and two water mol-ecules and has a disorted octa-hedral coordination environment. The asymmetric unit also contains four water mol-ecules. In the crystal, extensive inter-molecular classical N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.490 (1) Å] connect the various components, forming a three-dimensional network.

Related literature

For related structures based on 1,4-pyrazine-2,3-dicarboxylate ligands, see: Eshtiagh-Hosseini, Alfi et al. (2010 ▶). Eshtiagh-Hosseini, Gschwind et al. (2010 ▶). Eshtiagh-Hosseini, Necas et al. (2010 ▶).

Experimental

Crystal data

(C6H9N2)2[Co(C6H2N2O4)2(H2O)2]·8H2O

M = 789.58

Triclinic,

a = 6.8570 (4) Å

b = 10.2348 (5) Å

c = 13.6403 (10) Å

α = 109.604 (4)°

β = 90.424 (5)°

γ = 105.524 (4)°

V = 863.89 (9) Å3

Z = 1

Cu Kα radiation

μ = 4.68 mm−1

T = 150 K

0.20 × 0.18 × 0.14 mm

Data collection

Rigaku RAPID II diffractometer

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.280, T max = 0.508

19137 measured reflections

3152 independent reflections

3151 reflections with > 2.0σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.087

S = 1.04

3152 reflections

285 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.40 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and local programs.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001127/bt5444sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001127/bt5444Isup2.hkl

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

(C6H9N2)2[Co(C6H2N2O4)2(H2O)2]·8H2O	Z = 1
Mr = 789.58	F(000) = 413
Triclinic, P1	Dx = 1.518 Mg m−3
Hall symbol: -P 1	Cu - Kα radiation, λ = 1.54184 Å
a = 6.8570 (4) Å	Cell parameters from 3181 reflections
b = 10.2348 (5) Å	θ = 3–71°
c = 13.6403 (10) Å	µ = 4.68 mm−1
α = 109.604 (4)°	T = 150 K
β = 90.424 (5)°	Chunk, brown
γ = 105.524 (4)°	0.20 × 0.18 × 0.14 mm
V = 863.89 (9) Å3

Rigaku RAPID II diffractometer	3151 reflections with > 2.0σ(I)
confocal optics	Rint = 0.036
ω scans	θmax = 71.9°, θmin = 3.5°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = 0→8
Tmin = 0.280, Tmax = 0.508	k = −12→12
19137 measured reflections	l = −16→16
3152 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.057P)2 + 0.2735P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.23 e Å−3
3152 reflections	Δρmin = −0.40 e Å−3
285 parameters

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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R_factor_obs 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
Co1	1.0000	0.5000	0.0000	0.01861 (12)
O1W	0.78751 (19)	0.34893 (13)	−0.12293 (10)	0.0281 (3)
O21	0.79587 (17)	0.45953 (12)	0.10552 (10)	0.0244 (3)
O22	0.70494 (18)	0.32395 (14)	0.20508 (10)	0.0309 (3)
O2W	0.4756 (2)	0.56148 (13)	0.22356 (12)	0.0277 (3)
O31	0.97825 (17)	0.20966 (12)	0.31826 (9)	0.0257 (3)
O32	0.77764 (18)	0.02378 (12)	0.18707 (10)	0.0278 (3)
O3W	0.6610 (2)	0.37101 (15)	0.42401 (11)	0.0318 (3)
O4W	0.3166 (2)	0.44434 (16)	0.37295 (12)	0.0307 (3)
O5W	0.3645 (2)	0.92255 (14)	0.12233 (11)	0.0301 (3)
N1	1.08935 (19)	0.33770 (13)	0.03478 (10)	0.0185 (3)
N4	1.1850 (2)	0.14113 (14)	0.11111 (11)	0.0212 (3)
N11	0.82673 (19)	0.07875 (14)	0.46263 (11)	0.0201 (3)
N12	0.6818 (2)	−0.13230 (16)	0.32292 (12)	0.0243 (3)
C2	0.9819 (2)	0.29538 (15)	0.10633 (12)	0.0179 (3)
C3	1.0303 (2)	0.19613 (16)	0.14422 (13)	0.0188 (3)
C5	1.2920 (2)	0.18647 (17)	0.04140 (13)	0.0219 (3)
C6	1.2436 (2)	0.28428 (17)	0.00249 (13)	0.0213 (3)
C12	0.7163 (2)	−0.06269 (17)	0.42549 (13)	0.0200 (3)
C13	0.6442 (2)	−0.12847 (18)	0.49910 (14)	0.0240 (4)
C14	0.6901 (3)	−0.0497 (2)	0.60314 (15)	0.0286 (4)
C15	0.8071 (3)	0.0960 (2)	0.63821 (14)	0.0281 (4)
C16	0.8729 (2)	0.15970 (18)	0.56645 (14)	0.0239 (3)
C17	0.9948 (3)	0.31426 (18)	0.59367 (16)	0.0307 (4)
C21	0.8125 (2)	0.36383 (17)	0.14298 (13)	0.0215 (3)
C31	0.9158 (2)	0.13968 (17)	0.22335 (13)	0.0211 (3)
H5	1.4018	0.1516	0.0183	0.026*
H6	1.3200	0.3128	−0.0467	0.026*
H11	0.869 (3)	0.117 (2)	0.4202 (17)	0.023 (5)*
H13	0.5660	−0.2248	0.4768	0.029*
H14	0.6432	−0.0930	0.6518	0.034*
H15	0.8394	0.1485	0.7095	0.034*
H121	0.618 (3)	−0.223 (3)	0.3014 (17)	0.032 (5)*
H122	0.716 (3)	−0.086 (3)	0.2827 (19)	0.035 (6)*
H17A	1.1225	0.3185	0.5646	0.046*
H17B	1.0194	0.3600	0.6684	0.046*
H17C	0.9210	0.3636	0.5655	0.046*
H1W1	0.712 (4)	0.374 (3)	−0.150 (2)	0.044 (7)*
H1W2	0.729 (4)	0.263 (3)	−0.1249 (19)	0.045 (7)*
H2W1	0.561 (4)	0.520 (3)	0.191 (2)	0.052 (7)*
H2W2	0.431 (4)	0.528 (3)	0.260 (2)	0.037 (7)*
H3W1	0.728 (4)	0.345 (3)	0.378 (2)	0.046 (7)*
H3W2	0.564 (4)	0.389 (3)	0.399 (2)	0.050 (7)*
H4W1	0.300 (4)	0.493 (3)	0.430 (2)	0.039 (7)*
H4W2	0.219 (4)	0.375 (3)	0.356 (2)	0.051 (7)*
H5W1	0.478 (4)	0.970 (3)	0.145 (2)	0.049 (7)*
H5W2	0.304 (4)	0.977 (3)	0.125 (2)	0.042 (7)*

	U11	U22	U33	U12	U13	U23
Co1	0.02261 (19)	0.01812 (18)	0.0174 (2)	0.00806 (13)	0.00137 (13)	0.00745 (14)
O1W	0.0329 (6)	0.0208 (6)	0.0290 (8)	0.0054 (5)	−0.0089 (5)	0.0086 (5)
O21	0.0262 (6)	0.0268 (6)	0.0269 (7)	0.0142 (5)	0.0064 (5)	0.0126 (5)
O22	0.0295 (6)	0.0455 (7)	0.0302 (8)	0.0197 (5)	0.0137 (5)	0.0219 (6)
O2W	0.0279 (6)	0.0239 (6)	0.0322 (8)	0.0108 (5)	0.0006 (5)	0.0083 (6)
O31	0.0292 (6)	0.0268 (6)	0.0191 (7)	0.0024 (5)	−0.0001 (5)	0.0100 (5)
O32	0.0292 (6)	0.0258 (6)	0.0242 (7)	−0.0011 (5)	−0.0008 (5)	0.0105 (5)
O3W	0.0355 (7)	0.0367 (7)	0.0249 (8)	0.0124 (6)	0.0078 (6)	0.0113 (6)
O4W	0.0306 (7)	0.0281 (6)	0.0273 (9)	0.0037 (6)	0.0009 (5)	0.0058 (6)
O5W	0.0247 (6)	0.0248 (6)	0.0455 (9)	0.0092 (5)	0.0019 (5)	0.0166 (6)
N1	0.0216 (6)	0.0175 (6)	0.0158 (7)	0.0058 (5)	0.0009 (5)	0.0051 (5)
N4	0.0232 (6)	0.0203 (6)	0.0211 (8)	0.0084 (5)	0.0008 (5)	0.0069 (5)
N11	0.0193 (6)	0.0221 (6)	0.0213 (8)	0.0071 (5)	0.0034 (5)	0.0098 (6)
N12	0.0257 (7)	0.0217 (7)	0.0235 (9)	0.0014 (6)	0.0001 (6)	0.0098 (6)
C2	0.0194 (7)	0.0173 (7)	0.0152 (9)	0.0045 (5)	0.0001 (6)	0.0040 (6)
C3	0.0193 (7)	0.0178 (7)	0.0167 (9)	0.0035 (5)	−0.0015 (6)	0.0042 (6)
C5	0.0224 (7)	0.0232 (7)	0.0205 (9)	0.0101 (6)	0.0038 (6)	0.0053 (6)
C6	0.0233 (7)	0.0223 (7)	0.0192 (9)	0.0081 (6)	0.0061 (6)	0.0070 (6)
C12	0.0157 (7)	0.0239 (7)	0.0232 (10)	0.0081 (6)	0.0024 (6)	0.0099 (7)
C13	0.0206 (7)	0.0264 (8)	0.0288 (11)	0.0072 (6)	0.0056 (6)	0.0139 (7)
C14	0.0259 (8)	0.0404 (10)	0.0286 (11)	0.0145 (7)	0.0109 (7)	0.0194 (8)
C15	0.0276 (8)	0.0383 (9)	0.0201 (10)	0.0159 (7)	0.0057 (7)	0.0072 (8)
C16	0.0200 (7)	0.0268 (8)	0.0260 (10)	0.0123 (6)	0.0021 (6)	0.0062 (7)
C17	0.0326 (9)	0.0248 (8)	0.0312 (11)	0.0111 (7)	−0.0016 (7)	0.0031 (7)
C21	0.0211 (7)	0.0243 (8)	0.0196 (9)	0.0086 (6)	0.0009 (6)	0.0066 (7)
C31	0.0214 (7)	0.0220 (7)	0.0230 (10)	0.0079 (6)	0.0019 (6)	0.0104 (7)

Co1—O21i	2.0790 (12)	N11—C12	1.357 (2)
Co1—O21	2.0790 (11)	N11—C16	1.363 (2)
Co1—O1W	2.0841 (12)	N11—H11	0.82 (2)
Co1—O1Wi	2.0841 (12)	N12—C12	1.325 (2)
Co1—N1	2.1045 (12)	N12—H121	0.86 (2)
Co1—N1i	2.1045 (12)	N12—H122	0.84 (2)
O1W—H1W1	0.77 (3)	C2—C3	1.393 (2)
O1W—H1W2	0.86 (3)	C2—C21	1.516 (2)
O21—C21	1.2760 (19)	C3—C31	1.518 (2)
O22—C21	1.228 (2)	C5—C6	1.388 (2)
O2W—H2W1	0.85 (3)	C5—H5	0.9300
O2W—H2W2	0.72 (3)	C6—H6	0.9300
O31—C31	1.256 (2)	C12—C13	1.410 (2)
O32—C31	1.244 (2)	C13—C14	1.361 (3)
O3W—H3W1	0.80 (3)	C13—H13	0.9300
O3W—H3W2	0.84 (3)	C14—C15	1.404 (3)
O4W—H4W1	0.80 (3)	C14—H14	0.9300
O4W—H4W2	0.80 (3)	C15—C16	1.365 (3)
O5W—H5W1	0.79 (3)	C15—H15	0.9300
O5W—H5W2	0.77 (3)	C16—C17	1.494 (2)
N1—C6	1.329 (2)	C17—H17A	0.9600
N1—C2	1.344 (2)	C17—H17B	0.9600
N4—C5	1.335 (2)	C17—H17C	0.9600
N4—C3	1.342 (2)
O21i—Co1—O21	180.00 (7)	N4—C3—C2	121.24 (14)
O21i—Co1—O1W	90.50 (5)	N4—C3—C31	114.49 (13)
O21—Co1—O1W	89.50 (5)	C2—C3—C31	124.27 (14)
O21i—Co1—O1Wi	89.50 (5)	N4—C5—C6	121.69 (14)
O21—Co1—O1Wi	90.50 (5)	N4—C5—H5	119.20
O1W—Co1—O1Wi	180.00 (6)	C6—C5—H5	119.20
O21i—Co1—N1	100.88 (5)	N1—C6—C5	120.75 (14)
O21—Co1—N1	79.12 (5)	N1—C6—H6	119.60
O1W—Co1—N1	92.48 (5)	C5—C6—H6	119.60
O1Wi—Co1—N1	87.52 (5)	N12—C12—N11	119.07 (15)
O21i—Co1—N1i	79.12 (5)	N12—C12—C13	123.23 (15)
O21—Co1—N1i	100.88 (5)	N11—C12—C13	117.70 (15)
O1W—Co1—N1i	87.52 (5)	C14—C13—C12	119.36 (15)
O1Wi—Co1—N1i	92.48 (5)	C14—C13—H13	120.30
N1—Co1—N1i	180.00 (6)	C12—C13—H13	120.30
Co1—O1W—H1W1	119.7 (19)	C13—C14—C15	121.07 (16)
Co1—O1W—H1W2	122.8 (17)	C13—C14—H14	119.50
H1W1—O1W—H1W2	109 (2)	C15—C14—H14	119.50
C21—O21—Co1	116.29 (10)	C16—C15—C14	119.19 (17)
H2W1—O2W—H2W2	110 (3)	C16—C15—H15	120.40
H3W1—O3W—H3W2	108 (3)	C14—C15—H15	120.40
H4W1—O4W—H4W2	104 (3)	N11—C16—C15	118.88 (15)
H5W1—O5W—H5W2	106 (3)	N11—C16—C17	116.76 (16)
C6—N1—C2	118.50 (13)	C15—C16—C17	124.35 (17)
C6—N1—Co1	128.65 (11)	C16—C17—H17A	109.50
C2—N1—Co1	112.57 (10)	C16—C17—H17B	109.50
C5—N4—C3	117.44 (13)	H17A—C17—H17B	109.50
C12—N11—C16	123.77 (15)	C16—C17—H17C	109.50
C12—N11—H11	117.9 (15)	H17A—C17—H17C	109.50
C16—N11—H11	118.3 (15)	H17B—C17—H17C	109.50
C12—N12—H121	117.3 (15)	O22—C21—O21	125.85 (15)
C12—N12—H122	119.2 (16)	O22—C21—C2	118.38 (14)
H121—N12—H122	123 (2)	O21—C21—C2	115.77 (13)
N1—C2—C3	120.37 (14)	O32—C31—O31	126.69 (15)
N1—C2—C21	116.14 (13)	O32—C31—C3	116.34 (15)
C3—C2—C21	123.47 (14)	O31—C31—C3	116.80 (13)
O21i—Co1—O21—C21	113 (47)	C3—N4—C5—C6	−1.4 (2)
O1W—Co1—O21—C21	93.19 (12)	C2—N1—C6—C5	0.3 (2)
O1Wi—Co1—O21—C21	−86.81 (12)	Co1—N1—C6—C5	173.81 (11)
N1—Co1—O21—C21	0.57 (11)	N4—C5—C6—N1	0.9 (2)
N1i—Co1—O21—C21	−179.43 (11)	C16—N11—C12—N12	−179.22 (14)
O21i—Co1—N1—C6	3.94 (14)	C16—N11—C12—C13	0.6 (2)
O21—Co1—N1—C6	−176.06 (14)	N12—C12—C13—C14	178.72 (15)
O1W—Co1—N1—C6	94.93 (14)	N11—C12—C13—C14	−1.1 (2)
O1Wi—Co1—N1—C6	−85.07 (14)	C12—C13—C14—C15	0.3 (2)
N1i—Co1—N1—C6	85 (62)	C13—C14—C15—C16	1.0 (2)
O21i—Co1—N1—C2	177.76 (10)	C12—N11—C16—C15	0.7 (2)
O21—Co1—N1—C2	−2.24 (10)	C12—N11—C16—C17	−179.59 (14)
O1W—Co1—N1—C2	−91.26 (11)	C14—C15—C16—N11	−1.5 (2)
O1Wi—Co1—N1—C2	88.74 (11)	C14—C15—C16—C17	178.83 (15)
N1i—Co1—N1—C2	−102 (62)	Co1—O21—C21—O22	−179.10 (14)
C6—N1—C2—C3	−0.9 (2)	Co1—O21—C21—C2	1.06 (18)
Co1—N1—C2—C3	−175.43 (11)	N1—C2—C21—O22	177.04 (14)
C6—N1—C2—C21	177.95 (13)	C3—C2—C21—O22	−4.1 (2)
Co1—N1—C2—C21	3.44 (16)	N1—C2—C21—O21	−3.1 (2)
C5—N4—C3—C2	0.7 (2)	C3—C2—C21—O21	175.73 (14)
C5—N4—C3—C31	−179.98 (13)	N4—C3—C31—O32	−85.16 (17)
N1—C2—C3—N4	0.4 (2)	C2—C3—C31—O32	94.11 (19)
C21—C2—C3—N4	−178.37 (14)	N4—C3—C31—O31	90.54 (17)
N1—C2—C3—C31	−178.80 (14)	C2—C3—C31—O31	−90.20 (19)
C21—C2—C3—C31	2.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O31	0.82 (2)	1.98 (2)	2.794 (3)	179 (2)
N12—H121···O2Wii	0.86 (3)	2.05 (2)	2.900 (2)	170 (2)
N12—H122···O32	0.84 (3)	1.97 (3)	2.804 (3)	176 (2)
O1W—H1W1···O2Wiii	0.78 (3)	1.99 (3)	2.770 (3)	178 (3)
O1W—H1W2···O5Wiii	0.85 (3)	1.85 (3)	2.697 (2)	172 (3)
O2W—H2W1···O21	0.85 (3)	2.10 (3)	2.942 (3)	168 (3)
O2W—H2W2···O4W	0.72 (3)	2.07 (3)	2.784 (3)	176 (2)
O3W—H3W2···O4W	0.83 (3)	1.99 (3)	2.811 (3)	167 (3)
O4W—H4W1···O3Wiv	0.80 (3)	1.98 (2)	2.755 (2)	165 (3)
O4W—H4W2···O31v	0.80 (2)	1.94 (2)	2.738 (2)	178 (3)
O5W—H5W1···O32vi	0.79 (2)	2.00 (3)	2.767 (2)	161 (3)
O5W—H5W2···N4vii	0.77 (3)	2.11 (3)	2.871 (3)	167 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O31	0.82 (2)	1.98 (2)	2.794 (3)	179 (2)
N12—H121⋯O2Wi	0.86 (3)	2.05 (2)	2.900 (2)	170 (2)
N12—H122⋯O32	0.84 (3)	1.97 (3)	2.804 (3)	176 (2)
O1W—H1W1⋯O2Wii	0.78 (3)	1.99 (3)	2.770 (3)	178 (3)
O1W—H1W2⋯O5Wii	0.85 (3)	1.85 (3)	2.697 (2)	172 (3)
O2W—H2W1⋯O21	0.85 (3)	2.10 (3)	2.942 (3)	168 (3)
O2W—H2W2⋯O4W	0.72 (3)	2.07 (3)	2.784 (3)	176 (2)
O3W—H3W2⋯O4W	0.83 (3)	1.99 (3)	2.811 (3)	167 (3)
O4W—H4W1⋯O3Wiii	0.80 (3)	1.98 (2)	2.755 (2)	165 (3)
O4W—H4W2⋯O31iv	0.80 (2)	1.94 (2)	2.738 (2)	178 (3)
O5W—H5W1⋯O32v	0.79 (2)	2.00 (3)	2.767 (2)	161 (3)
O5W—H5W2⋯N4vi	0.77 (3)	2.11 (3)	2.871 (3)	167 (3)

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