Bis(2,6-diamino-pyridin-1-ium) hexa-aqua-cobalt(II) disulfate dihydrate.

In the title compound, (C(5)H(8)N(3))(2)[Co(H(2)O)(6)](SO(4))(2)·2H(2)O, the complete complex cation is generated by crystallographic inversion symmetry, such that the Co(II) cation is octa-hedrally coordinated by six water mol-ecules. The organic cation is essentially planar, with a maximum deviation of 0.013 (1) Å. In the crystal structure, the ions and mol-ecules are linked into a pseudo-layered three-dimensional supra-molecular network via O-H⋯O and N-H⋯O hydrogen bonds. Weak inter-molecular π-π inter-actions further stabilize the crystal structure [centroid-centroid distance = 3.5231 (4) Å].

Related literature

For general background to and applications of 1,6-diamino­pyridinium ions, see: Abu Zuhri & Cox (1989 ▶); Inuzuka & Fujimoto (1990 ▶); Ma & Huang (2003 ▶); Patani & LaVoie (1996 ▶). For closely related hexa­aqua­cobalt(II) structures, see: Li et al. (2004 ▶); Pan et al. (2003 ▶). For closely related pyridinium structures, see: Al-Dajani, Abdallah et al. (2009 ▶, 2010 ▶); Al-Dajani, Salhin et al. (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

(C5H8N3)2[Co(H2O)6](SO4)2·2H2O

M = 615.47

Orthorhombic,

a = 6.6219 (1) Å

b = 14.4347 (2) Å

c = 24.7590 (3) Å

V = 2366.59 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.99 mm−1

T = 100 K

0.35 × 0.31 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.725, T max = 0.821

86569 measured reflections

6333 independent reflections

5758 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.064

S = 1.08

6333 reflections

224 parameters

All H-atom parameters refined

Δρmax = 0.60 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026693/hb5536sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026693/hb5536Isup2.hkl

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

(C5H8N3)2[Co(H2O)6](SO4)2·2H2O	F(000) = 1284
Mr = 615.47	Dx = 1.727 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9901 reflections
a = 6.6219 (1) Å	θ = 3.5–37.6°
b = 14.4347 (2) Å	µ = 0.99 mm−1
c = 24.7590 (3) Å	T = 100 K
V = 2366.59 (6) Å3	Block, red
Z = 4	0.35 × 0.31 × 0.21 mm

Bruker SMART APEXII CCD diffractometer	6333 independent reflections
Radiation source: fine-focus sealed tube	5758 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 37.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.725, Tmax = 0.821	k = −24→24
86569 measured reflections	l = −42→42

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	All H-atom parameters refined
S = 1.08	w = 1/[σ2(Fo2) + (0.0322P)2 + 0.6554P] where P = (Fo2 + 2Fc2)/3
6333 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Co1	0.5000	0.5000	0.5000	0.00813 (3)
O1W	0.60030 (8)	0.62537 (4)	0.46843 (2)	0.01288 (8)
O2W	0.37213 (8)	0.57254 (4)	0.56500 (2)	0.01253 (8)
O3W	0.23481 (8)	0.51148 (4)	0.45350 (2)	0.01281 (9)
O4W	0.50958 (8)	0.83091 (4)	0.53640 (2)	0.01281 (9)
S1	0.86829 (2)	0.696844 (10)	0.616698 (6)	0.00760 (3)
O1	0.93408 (8)	0.79469 (3)	0.62001 (2)	0.01200 (8)
O2	0.64851 (8)	0.69401 (4)	0.60506 (2)	0.01254 (8)
O3	0.97898 (8)	0.64929 (4)	0.57237 (2)	0.01158 (8)
O4	0.90760 (9)	0.65018 (4)	0.66828 (2)	0.01417 (9)
N1	0.89603 (9)	0.85415 (4)	0.72893 (2)	0.00943 (8)
N2	0.97396 (10)	0.72061 (4)	0.77643 (3)	0.01420 (10)
N3	0.82794 (10)	0.97979 (4)	0.67371 (2)	0.01328 (10)
C1	0.91746 (10)	0.81030 (4)	0.77745 (2)	0.00979 (9)
C2	0.88017 (10)	0.86024 (5)	0.82461 (3)	0.01229 (10)
C3	0.82632 (11)	0.95288 (5)	0.82032 (3)	0.01297 (10)
C4	0.80547 (11)	0.99626 (5)	0.77070 (3)	0.01179 (10)
C5	0.84005 (9)	0.94478 (4)	0.72390 (2)	0.00965 (9)
H1W1	0.542 (2)	0.6492 (10)	0.4413 (6)	0.030 (4)*
H2W1	0.724 (2)	0.6368 (10)	0.4648 (6)	0.028 (3)*
H1W2	0.451 (2)	0.6080 (10)	0.5781 (6)	0.025 (3)*
H2W2	0.264 (2)	0.5990 (10)	0.5680 (6)	0.030 (4)*
H1W3	0.160 (2)	0.5580 (11)	0.4558 (6)	0.029 (4)*
H2W3	0.165 (2)	0.4675 (11)	0.4463 (6)	0.028 (3)*
H1W4	0.559 (3)	0.7850 (12)	0.5544 (6)	0.036 (4)*
H2W4	0.514 (2)	0.8192 (13)	0.5055 (6)	0.032 (4)*
H1N1	0.923 (2)	0.8224 (9)	0.6993 (5)	0.021 (3)*
H2N2	1.014 (2)	0.6963 (10)	0.8039 (6)	0.023 (3)*
H1N3	0.836 (2)	0.9442 (9)	0.6464 (5)	0.021 (3)*
H1N2	0.983 (2)	0.6940 (10)	0.7493 (6)	0.023 (3)*
H2N3	0.769 (2)	1.0311 (10)	0.6695 (5)	0.022 (3)*
H2	0.888 (2)	0.8281 (9)	0.8575 (5)	0.024 (3)*
H3	0.794 (2)	0.9854 (9)	0.8525 (5)	0.017 (3)*
H4	0.768 (2)	1.0617 (9)	0.7676 (5)	0.021 (3)*

	U11	U22	U33	U12	U13	U23
Co1	0.00772 (5)	0.00786 (5)	0.00880 (5)	−0.00035 (4)	−0.00063 (4)	0.00026 (3)
O1W	0.01163 (19)	0.0125 (2)	0.0145 (2)	−0.00216 (16)	−0.00227 (17)	0.00427 (15)
O2W	0.01003 (19)	0.0139 (2)	0.01366 (19)	−0.00017 (16)	−0.00004 (16)	−0.00345 (16)
O3W	0.01056 (19)	0.01071 (19)	0.0172 (2)	0.00053 (16)	−0.00386 (17)	−0.00187 (15)
O4W	0.0138 (2)	0.0137 (2)	0.01087 (19)	0.00064 (16)	−0.00068 (16)	−0.00023 (16)
S1	0.00845 (6)	0.00744 (6)	0.00691 (5)	−0.00042 (4)	0.00023 (4)	−0.00030 (4)
O1	0.0154 (2)	0.00811 (18)	0.01252 (19)	−0.00296 (16)	0.00154 (17)	−0.00110 (14)
O2	0.00834 (18)	0.0135 (2)	0.0158 (2)	−0.00022 (15)	−0.00093 (16)	−0.00211 (16)
O3	0.01201 (19)	0.01219 (19)	0.01052 (18)	0.00079 (15)	0.00229 (15)	−0.00298 (15)
O4	0.0201 (2)	0.0137 (2)	0.00873 (17)	−0.00068 (18)	−0.00182 (17)	0.00294 (15)
N1	0.0103 (2)	0.0097 (2)	0.00826 (19)	0.00011 (16)	−0.00031 (16)	−0.00037 (15)
N2	0.0180 (3)	0.0110 (2)	0.0136 (2)	0.00237 (19)	−0.0038 (2)	0.00052 (18)
N3	0.0147 (2)	0.0138 (2)	0.0113 (2)	0.00146 (19)	−0.00063 (19)	0.00307 (17)
C1	0.0089 (2)	0.0109 (2)	0.0096 (2)	−0.00068 (18)	−0.00122 (18)	0.00055 (17)
C2	0.0127 (2)	0.0153 (3)	0.0089 (2)	0.0001 (2)	−0.00031 (19)	−0.00021 (18)
C3	0.0119 (2)	0.0157 (3)	0.0113 (2)	0.0000 (2)	0.0004 (2)	−0.00380 (19)
C4	0.0112 (2)	0.0108 (2)	0.0134 (2)	0.00028 (19)	0.0003 (2)	−0.00217 (18)
C5	0.0080 (2)	0.0101 (2)	0.0109 (2)	−0.00041 (18)	−0.00031 (18)	0.00074 (17)

Co1—O1Wi	2.0801 (5)	S1—O3	1.4875 (5)
Co1—O1W	2.0801 (5)	N1—C1	1.3652 (8)
Co1—O2Wi	2.0985 (5)	N1—C5	1.3654 (8)
Co1—O2W	2.0985 (5)	N1—H1N1	0.884 (13)
Co1—O3Wi	2.1064 (5)	N2—C1	1.3478 (9)
Co1—O3W	2.1064 (5)	N2—H2N2	0.810 (14)
O1W—H1W1	0.848 (16)	N2—H1N2	0.776 (15)
O1W—H2W1	0.841 (16)	N3—C5	1.3438 (8)
O2W—H1W2	0.799 (15)	N3—H1N3	0.851 (14)
O2W—H2W2	0.817 (16)	N3—H2N3	0.843 (15)
O3W—H1W3	0.836 (16)	C1—C2	1.3942 (9)
O3W—H2W3	0.806 (16)	C2—C3	1.3881 (10)
O4W—H1W4	0.863 (17)	C2—H2	0.938 (13)
O4W—H2W4	0.784 (16)	C3—C4	1.3859 (10)
S1—O4	1.4672 (5)	C3—H3	0.949 (13)
S1—O1	1.4803 (5)	C4—C5	1.3953 (9)
S1—O2	1.4842 (5)	C4—H4	0.980 (13)
O1Wi—Co1—O1W	180.0	O4—S1—O3	110.06 (3)
O1Wi—Co1—O2Wi	89.02 (2)	O1—S1—O3	109.64 (3)
O1W—Co1—O2Wi	90.98 (2)	O2—S1—O3	109.10 (3)
O1Wi—Co1—O2W	90.98 (2)	C1—N1—C5	123.55 (5)
O1W—Co1—O2W	89.02 (2)	C1—N1—H1N1	117.9 (9)
O2Wi—Co1—O2W	180.0	C5—N1—H1N1	118.5 (9)
O1Wi—Co1—O3Wi	89.56 (2)	C1—N2—H2N2	119.5 (10)
O1W—Co1—O3Wi	90.44 (2)	C1—N2—H1N2	120.9 (11)
O2Wi—Co1—O3Wi	92.50 (2)	H2N2—N2—H1N2	119.0 (15)
O2W—Co1—O3Wi	87.50 (2)	C5—N3—H1N3	120.2 (9)
O1Wi—Co1—O3W	90.44 (2)	C5—N3—H2N3	118.2 (9)
O1W—Co1—O3W	89.56 (2)	H1N3—N3—H2N3	117.5 (13)
O2Wi—Co1—O3W	87.50 (2)	N2—C1—N1	117.24 (6)
O2W—Co1—O3W	92.50 (2)	N2—C1—C2	124.16 (6)
O3Wi—Co1—O3W	180.0	N1—C1—C2	118.60 (6)
Co1—O1W—H1W1	120.3 (10)	C3—C2—C1	118.66 (6)
Co1—O1W—H2W1	121.4 (10)	C3—C2—H2	123.9 (8)
H1W1—O1W—H2W1	106.3 (14)	C1—C2—H2	117.4 (8)
Co1—O2W—H1W2	111.5 (11)	C4—C3—C2	121.91 (6)
Co1—O2W—H2W2	131.1 (10)	C4—C3—H3	120.0 (8)
H1W2—O2W—H2W2	103.8 (14)	C2—C3—H3	118.0 (8)
Co1—O3W—H1W3	121.3 (10)	C3—C4—C5	118.63 (6)
Co1—O3W—H2W3	122.5 (11)	C3—C4—H4	122.0 (8)
H1W3—O3W—H2W3	108.0 (16)	C5—C4—H4	119.4 (8)
H1W4—O4W—H2W4	109.0 (17)	N3—C5—N1	117.44 (6)
O4—S1—O1	109.73 (3)	N3—C5—C4	123.90 (6)
O4—S1—O2	109.29 (3)	N1—C5—C4	118.63 (6)
O1—S1—O2	109.01 (3)
C5—N1—C1—N2	−179.89 (6)	C2—C3—C4—C5	−0.05 (11)
C5—N1—C1—C2	0.09 (10)	C1—N1—C5—N3	178.90 (6)
N2—C1—C2—C3	178.85 (7)	C1—N1—C5—C4	0.99 (10)
N1—C1—C2—C3	−1.13 (10)	C3—C4—C5—N3	−178.76 (7)
C1—C2—C3—C4	1.12 (11)	C3—C4—C5—N1	−0.99 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1ii	0.848 (14)	1.863 (15)	2.7088 (7)	175.4 (13)
O1W—H2W1···O4Wiii	0.840 (13)	1.948 (13)	2.7853 (8)	174.2 (13)
O2W—H1W2···O2	0.800 (14)	1.923 (14)	2.7217 (8)	176.3 (14)
O2W—H2W2···O3iv	0.815 (14)	2.025 (13)	2.8352 (8)	172.7 (15)
O3W—H1W3···O4Wii	0.836 (15)	1.898 (15)	2.7318 (8)	175.1 (13)
O3W—H2W3···O3i	0.805 (15)	1.991 (15)	2.7928 (8)	173.6 (14)
O4W—H1W4···O2	0.863 (17)	1.910 (17)	2.7643 (8)	169.9 (16)
O4W—H2W4···O3ii	0.784 (15)	1.994 (15)	2.7157 (7)	152.8 (18)
N1—H1N1···O1	0.883 (13)	2.005 (12)	2.8412 (7)	157.6 (12)
N2—H2N2···O2v	0.810 (15)	2.424 (15)	3.1769 (9)	155.1 (13)
N3—H1N3···O1	0.851 (13)	2.347 (13)	3.0660 (7)	142.6 (11)
N2—H1N2···O4	0.776 (15)	2.162 (15)	2.8977 (9)	158.5 (14)
N3—H2N3···O4vi	0.844 (14)	2.079 (14)	2.9155 (8)	171.0 (12)

Table 1

Selected bond lengths (Å)

Co1—O1W	2.0801 (5)
Co1—O2W	2.0985 (5)
Co1—O3W	2.1064 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1i	0.848 (14)	1.863 (15)	2.7088 (7)	175.4 (13)
O1W—H2W1⋯O4Wii	0.840 (13)	1.948 (13)	2.7853 (8)	174.2 (13)
O2W—H1W2⋯O2	0.800 (14)	1.923 (14)	2.7217 (8)	176.3 (14)
O2W—H2W2⋯O3iii	0.815 (14)	2.025 (13)	2.8352 (8)	172.7 (15)
O3W—H1W3⋯O4Wi	0.836 (15)	1.898 (15)	2.7318 (8)	175.1 (13)
O3W—H2W3⋯O3iv	0.805 (15)	1.991 (15)	2.7928 (8)	173.6 (14)
O4W—H1W4⋯O2	0.863 (17)	1.910 (17)	2.7643 (8)	169.9 (16)
O4W—H2W4⋯O3i	0.784 (15)	1.994 (15)	2.7157 (7)	152.8 (18)
N1—H1N1⋯O1	0.883 (13)	2.005 (12)	2.8412 (7)	157.6 (12)
N2—H2N2⋯O2v	0.810 (15)	2.424 (15)	3.1769 (9)	155.1 (13)
N3—H1N3⋯O1	0.851 (13)	2.347 (13)	3.0660 (7)	142.6 (11)
N2—H1N2⋯O4	0.776 (15)	2.162 (15)	2.8977 (9)	158.5 (14)
N3—H2N3⋯O4vi	0.844 (14)	2.079 (14)	2.9155 (8)	171.0 (12)

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