Tetra-aqua-diazido-cobalt(II) 3,3'-dicarb-oxy-l-ato-1,1'-ethyl-enedipyridinium.

The asymmetric unit of the title compound, [Co(N(3))(2)(H(2)O)(4)]·C(14)H(12)N(2)O(4), comprises half of the cobalt(II) complex mol-ecule and a half of the 3,3'-dicarboxyl-ato-1,1'-ethyl-enedipyridinium mol-ecule. The Co(II) atom is located on an inversion centre and hence the complex mol-ecule adopts a centrosymmetric trans-octa-hedral geometry. The zwitterionic organic mol-ecule is also centrosymmetric with the centre of the C-C bond of the ethyl-ene moiety coinciding with an inversion centre. The adduct of metal complex and organic mol-ecule is associated into a three-dimenional network through O-H⋯O hydrogen bonds.

Related literature

For background to hydrogen bonds, see: Braga & Grepioni (2000 ▶); Fabbiani et al. (2010 ▶); Salitros et al. (2010 ▶); Schultheis et al. (2010 ▶). For the synthesis of the ligand, see: Loeb et al. (2006 ▶). For n class="Chemical">hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

[Co(N3)2(H2O)4]·C14n class="Species">H12N2O4

M = 487.31

Triclinic,

a = 7.4309 (6) Å

b = 7.7507 (7) Å

c = 8.5582 (7) Å

α = 95.463 (2)°

β = 90.586 (2)°

γ = 95.011 (2)°

V = 488.71 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.94 mm−1

T = 296 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.799, T max = 0.872

6091 measured reflections

1907 independent reflections

1889 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.074

S = 1.12

1907 reflections

154 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046143/kp2284sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046143/kp2284Isup2.hkl

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

[Co(N3)2(H2O)4]·C14H12N2O4	Z = 1
Mr = 487.31	F(000) = 251
Triclinic, P1	Dx = 1.656 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4309 (6) Å	Cell parameters from 15377 reflections
b = 7.7507 (7) Å	θ = 3.4–27.5°
c = 8.5582 (7) Å	µ = 0.94 mm−1
α = 95.463 (2)°	T = 296 K
β = 90.586 (2)°	Block, red
γ = 95.011 (2)°	0.25 × 0.20 × 0.15 mm
V = 488.71 (7) Å3

Bruker APEXII CCD area-detector diffractometer	1907 independent reflections
Radiation source: fine-focus sealed tube	1889 reflections with I > 2σ(I)
graphite	Rint = 0.015
phi and ω scans	θmax = 26.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.799, Tmax = 0.872	k = −9→8
6091 measured reflections	l = −10→10

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0411P)2 + 0.2239P] where P = (Fo2 + 2Fc2)/3
1907 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.28 e Å−3
9 restraints	Δρmin = −0.28 e Å−3

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 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 > σ(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	0.0000	0.0000	0.5000	0.02282 (12)
C1	0.3729 (2)	0.5896 (2)	0.3420 (2)	0.0283 (3)
C2	0.5025 (2)	0.4708 (2)	0.26023 (19)	0.0258 (3)
C3	0.6822 (2)	0.5278 (2)	0.2423 (2)	0.0335 (4)
H3A	0.7234	0.6424	0.2751	0.040*
C4	0.4437 (2)	0.3011 (2)	0.20731 (19)	0.0255 (3)
H4A	0.3228	0.2613	0.2153	0.031*
C5	0.8009 (2)	0.4148 (3)	0.1756 (3)	0.0392 (4)
H5A	0.9215	0.4530	0.1625	0.047*
C6	0.7382 (2)	0.2466 (2)	0.1293 (2)	0.0339 (4)
H6A	0.8173	0.1685	0.0875	0.041*
C7	0.5003 (2)	0.0111 (2)	0.08913 (19)	0.0286 (3)
H7A	0.3795	−0.0177	0.1265	0.034*
H7B	0.5803	−0.0667	0.1303	0.034*
N1	0.56206 (18)	0.19334 (17)	0.14405 (16)	0.0257 (3)
N2	0.0817 (2)	−0.0222 (2)	0.26583 (18)	0.0399 (4)
N3	−0.0146 (2)	−0.1006 (2)	0.16704 (17)	0.0320 (3)
N4	−0.1073 (3)	−0.1740 (2)	0.0672 (2)	0.0461 (4)
O1	0.43867 (18)	0.73681 (16)	0.39597 (19)	0.0435 (4)
O2	0.21281 (17)	0.52889 (16)	0.35044 (18)	0.0405 (3)
O3	0.27781 (16)	−0.00456 (16)	0.56790 (15)	0.0319 (3)
H3B	0.347 (3)	0.086 (2)	0.569 (3)	0.048*
H3C	0.321 (3)	−0.082 (2)	0.508 (3)	0.048*
O4	0.02796 (18)	0.26995 (16)	0.50991 (18)	0.0379 (3)
H4B	0.090 (3)	0.323 (3)	0.449 (3)	0.057*
H4C	−0.053 (3)	0.334 (3)	0.547 (3)	0.057*

	U11	U22	U33	U12	U13	U23
Co1	0.02008 (17)	0.02004 (17)	0.02747 (17)	−0.00003 (11)	0.00302 (11)	−0.00082 (11)
C1	0.0273 (8)	0.0202 (7)	0.0363 (8)	0.0007 (6)	0.0062 (7)	−0.0031 (6)
C2	0.0247 (8)	0.0210 (7)	0.0305 (8)	0.0009 (6)	0.0035 (6)	−0.0024 (6)
C3	0.0282 (9)	0.0247 (8)	0.0445 (10)	−0.0047 (7)	0.0040 (7)	−0.0067 (7)
C4	0.0220 (7)	0.0230 (8)	0.0301 (8)	0.0002 (6)	0.0040 (6)	−0.0026 (6)
C5	0.0231 (8)	0.0348 (9)	0.0565 (12)	−0.0035 (7)	0.0081 (8)	−0.0077 (8)
C6	0.0247 (8)	0.0311 (9)	0.0447 (10)	0.0045 (7)	0.0068 (7)	−0.0056 (7)
C7	0.0331 (8)	0.0179 (7)	0.0336 (9)	0.0000 (6)	0.0054 (7)	−0.0030 (6)
N1	0.0256 (7)	0.0203 (6)	0.0297 (7)	0.0006 (5)	0.0035 (5)	−0.0043 (5)
N2	0.0335 (8)	0.0555 (10)	0.0297 (8)	−0.0006 (7)	0.0064 (6)	0.0028 (7)
N3	0.0314 (8)	0.0343 (8)	0.0318 (8)	0.0069 (6)	0.0117 (7)	0.0059 (6)
N4	0.0475 (10)	0.0485 (10)	0.0398 (9)	−0.0053 (8)	0.0032 (8)	−0.0011 (8)
O1	0.0330 (7)	0.0226 (6)	0.0701 (10)	−0.0026 (5)	0.0105 (6)	−0.0159 (6)
O2	0.0282 (6)	0.0241 (6)	0.0665 (9)	−0.0017 (5)	0.0160 (6)	−0.0082 (6)
O3	0.0230 (6)	0.0274 (6)	0.0434 (7)	0.0016 (5)	0.0014 (5)	−0.0067 (5)
O4	0.0356 (7)	0.0210 (6)	0.0575 (8)	0.0026 (5)	0.0178 (6)	0.0028 (5)

Co1—O4	2.0780 (12)	C5—C6	1.366 (3)
Co1—O4i	2.0780 (12)	C5—H5A	0.9300
Co1—N2	2.0958 (15)	C6—N1	1.349 (2)
Co1—N2i	2.0958 (15)	C6—H6A	0.9300
Co1—O3i	2.1431 (12)	C7—N1	1.478 (2)
Co1—O3	2.1431 (12)	C7—C7ii	1.519 (3)
C1—O1	1.245 (2)	C7—H7A	0.9700
C1—O2	1.246 (2)	C7—H7B	0.9700
C1—C2	1.521 (2)	N2—N3	1.188 (2)
C2—C4	1.381 (2)	N3—N4	1.164 (2)
C2—C3	1.384 (2)	O3—H3B	0.836 (15)
C3—C5	1.386 (3)	O3—H3C	0.839 (15)
C3—H3A	0.9300	O4—H4B	0.813 (16)
C4—N1	1.348 (2)	O4—H4C	0.856 (16)
C4—H4A	0.9300
O4—Co1—O4i	180.0	N1—C4—H4A	120.1
O4—Co1—N2	91.41 (6)	C2—C4—H4A	120.1
O4i—Co1—N2	88.59 (6)	C6—C5—C3	119.02 (16)
O4—Co1—N2i	88.59 (6)	C6—C5—H5A	120.5
O4i—Co1—N2i	91.41 (6)	C3—C5—H5A	120.5
N2—Co1—N2i	180.0	N1—C6—C5	120.23 (16)
O4—Co1—O3i	88.83 (5)	N1—C6—H6A	119.9
O4i—Co1—O3i	91.17 (5)	C5—C6—H6A	119.9
N2—Co1—O3i	92.17 (6)	N1—C7—C7ii	109.09 (16)
N2i—Co1—O3i	87.83 (6)	N1—C7—H7A	109.9
O4—Co1—O3	91.17 (5)	C7ii—C7—H7A	109.9
O4i—Co1—O3	88.83 (5)	N1—C7—H7B	109.9
N2—Co1—O3	87.83 (6)	C7ii—C7—H7B	109.9
N2i—Co1—O3	92.17 (6)	H7A—C7—H7B	108.3
O3i—Co1—O3	180.0	C4—N1—C6	121.82 (14)
O1—C1—O2	126.73 (15)	C4—N1—C7	120.05 (13)
O1—C1—C2	116.50 (14)	C6—N1—C7	118.13 (14)
O2—C1—C2	116.75 (14)	N3—N2—Co1	120.05 (12)
C4—C2—C3	118.77 (14)	N4—N3—N2	178.01 (19)
C4—C2—C1	120.22 (14)	Co1—O3—H3B	119.4 (17)
C3—C2—C1	120.97 (14)	Co1—O3—H3C	107.1 (17)
C2—C3—C5	120.26 (16)	H3B—O3—H3C	108.0 (19)
C2—C3—H3A	119.9	Co1—O4—H4B	122.9 (18)
C5—C3—H3A	119.9	Co1—O4—H4C	123.1 (17)
N1—C4—C2	119.85 (14)	H4B—O4—H4C	109 (2)
O1—C1—C2—C4	175.22 (17)	C2—C4—N1—C6	−0.5 (3)
O2—C1—C2—C4	−3.6 (2)	C2—C4—N1—C7	179.21 (14)
O1—C1—C2—C3	−2.5 (3)	C5—C6—N1—C4	−1.6 (3)
O2—C1—C2—C3	178.67 (17)	C5—C6—N1—C7	178.70 (17)
C4—C2—C3—C5	−1.5 (3)	C7ii—C7—N1—C4	108.4 (2)
C1—C2—C3—C5	176.28 (18)	C7ii—C7—N1—C6	−71.9 (2)
C3—C2—C4—N1	2.0 (2)	O4—Co1—N2—N3	−122.40 (16)
C1—C2—C4—N1	−175.75 (15)	O4i—Co1—N2—N3	57.60 (16)
C2—C3—C5—C6	−0.6 (3)	O3i—Co1—N2—N3	−33.51 (16)
C3—C5—C6—N1	2.1 (3)	O3—Co1—N2—N3	146.49 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1iii	0.84 (2)	2.01 (2)	2.8180 (18)	163 (2)
O3—H3C···O1iv	0.84 (2)	1.91 (2)	2.7395 (17)	172 (2)
O4—H4C···O2v	0.86 (2)	1.84 (2)	2.6901 (18)	173 (3)
O4—H4B···O2	0.81 (2)	2.03 (2)	2.8028 (18)	159 (2)

Table 1

Selected bond lengths (Å)

Co1—O4	2.0780 (12)
Co1—N2	2.0958 (15)
Co1—O3	2.1431 (12)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1i	0.84 (2)	2.01 (2)	2.8180 (18)	163 (2)
O3—H3C⋯O1ii	0.84 (2)	1.91 (2)	2.7395 (17)	172 (2)
O4—H4C⋯O2iii	0.86 (2)	1.84 (2)	2.6901 (18)	173 (3)
O4—H4B⋯O2	0.81 (2)	2.03 (2)	2.8028 (18)	159 (2)

Symmetry codes: (i) ; (ii) ; (iii) .