Tetra-aqua-diazido-cobalt(II) 4,4'-dicarboxyl-ato-1,1'-ethyl-enedi-pyridinium dihydrate.

In the title compound, [Co(N(3))(2)(H(2)O)(4)]·C(14)H(12)N(2)O(4)·2H(2)O, the metal complex mol-ecule is centrosymmetric, the Co(II) ion being six-coordinated by two azide N atoms and four aqua O atoms with a trans-octa-hedral geometry. The zwitterionic organic mol-ecule is also centrosymmetric. In the crystal, the components are associated into a two-dimensional network through O-H⋯O hydrogen bonds. Further O-H⋯O and O-H⋯N inter-actions give a three-dimensional structure. The free water molecule is disordered over two positions in a 0.787 (5):0.213 (5) ratio.

Related literature

For background information on hydrogen bonds in crystal engineering, see: Baures et al. (2006 ▶); Braga & Grepioni (2000 ▶); Maly et al. (2006 ▶). For the ligand synthesis, see: Loeb et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

[Co(N3)2(H2O)4]·C14H12N2O4·2H2O

M = 523.34

Triclinic,

a = 7.1951 (5) Å

b = 9.0354 (7) Å

c = 9.0915 (5) Å

α = 71.402 (3)°

β = 85.568 (2)°

γ = 69.752 (2)°

V = 525.20 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.89 mm−1

T = 296 K

0.08 × 0.08 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.932, T max = 0.982

6498 measured reflections

2029 independent reflections

2016 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.089

S = 1.18

2029 reflections

183 parameters

13 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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/S1600536809049848/bg2309sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049848/bg2309Isup2.hkl

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

[Co(N3)2(H2O)4]·C14H12N2O4·2H2O	Z = 1
Mr = 523.34	F(000) = 271
Triclinic, P1	Dx = 1.655 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1951 (5) Å	Cell parameters from 7436 reflections
b = 9.0354 (7) Å	θ = 2.5–27.6°
c = 9.0915 (5) Å	µ = 0.89 mm−1
α = 71.402 (3)°	T = 296 K
β = 85.568 (2)°	Sheet, orange
γ = 69.752 (2)°	0.08 × 0.08 × 0.02 mm
V = 525.20 (6) Å3

Bruker APEXII CCD area-detector diffractometer	2029 independent reflections
Radiation source: fine-focus sealed tube	2016 reflections with I > 2σ(I)
graphite	Rint = 0.020
phi and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→8
Tmin = 0.932, Tmax = 0.982	k = −11→11
6498 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089	w = 1/[σ2(Fo2) + (0.0517P)2 + 0.2305P] where P = (Fo2 + 2Fc2)/3
S = 1.18	(Δ/σ)max < 0.001
2029 reflections	Δρmax = 0.34 e Å−3
183 parameters	Δρmin = −0.35 e Å−3
13 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.072 (7)

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	Occ. (<1)
Co1	0.5000	0.5000	0.0000	0.02233 (16)
N1	−0.0182 (2)	0.06625 (19)	0.78289 (17)	0.0240 (3)
N2	0.5369 (3)	0.4349 (3)	0.2408 (2)	0.0458 (5)
N3	0.4823 (2)	0.3822 (2)	0.36258 (18)	0.0283 (4)
O3	0.4820 (2)	0.26543 (17)	0.02090 (16)	0.0300 (3)
H31	0.425 (4)	0.272 (3)	−0.058 (2)	0.045*
H32	0.420 (4)	0.229 (3)	0.099 (2)	0.045*
O4	0.18626 (19)	0.59340 (17)	0.00759 (16)	0.0298 (3)
H42	0.146 (4)	0.535 (3)	0.087 (2)	0.045*
H41	0.135 (4)	0.600 (3)	−0.072 (2)	0.045*
C1	0.1394 (3)	0.2551 (3)	0.3161 (2)	0.0316 (4)
C2	0.0846 (3)	0.1895 (2)	0.4838 (2)	0.0267 (4)
C3	0.1985 (3)	0.0345 (2)	0.5774 (2)	0.0284 (4)
H3A	0.3109	−0.0288	0.5392	0.034*
C4	0.1448 (3)	−0.0255 (2)	0.7271 (2)	0.0279 (4)
H4A	0.2211	−0.1298	0.7903	0.033*
C5	−0.1306 (3)	0.2167 (2)	0.6939 (2)	0.0322 (4)
H5A	−0.2426	0.2779	0.7342	0.039*
C6	−0.0818 (3)	0.2812 (3)	0.5435 (2)	0.0335 (4)
H6A	−0.1602	0.3859	0.4823	0.040*
C7	−0.0719 (3)	−0.0022 (2)	0.9445 (2)	0.0283 (4)
H7A	−0.0663	−0.1156	0.9636	0.034*
H7B	−0.2061	0.0631	0.9607	0.034*
N4	0.4358 (4)	0.3278 (3)	0.4876 (2)	0.0546 (6)
O1	0.2747 (3)	0.1567 (2)	0.26605 (18)	0.0470 (4)
O2	0.0391 (2)	0.4020 (2)	0.24191 (17)	0.0447 (4)
O5	0.2585 (3)	0.2801 (3)	0.7844 (2)	0.0415 (7)	0.787 (5)
H5	0.344 (3)	0.244 (3)	0.727 (3)	0.062*
H51	0.193 (5)	0.377 (3)	0.760 (4)	0.062*	0.787 (5)
O5'	0.4261 (18)	0.1544 (12)	0.7953 (9)	0.059 (3)	0.213 (5)
H52	0.506 (13)	0.097 (6)	0.744 (6)	0.089*	0.213 (5)

	U11	U22	U33	U12	U13	U23
Co1	0.0217 (2)	0.0262 (2)	0.0185 (2)	−0.00944 (14)	0.00190 (12)	−0.00503 (13)
N1	0.0264 (7)	0.0293 (8)	0.0161 (7)	−0.0115 (6)	0.0029 (5)	−0.0050 (6)
N2	0.0542 (12)	0.0691 (13)	0.0221 (9)	−0.0363 (11)	0.0023 (8)	−0.0080 (8)
N3	0.0273 (8)	0.0341 (8)	0.0252 (9)	−0.0110 (7)	−0.0001 (6)	−0.0105 (7)
O3	0.0309 (7)	0.0337 (7)	0.0279 (7)	−0.0147 (6)	0.0038 (5)	−0.0096 (6)
O4	0.0256 (6)	0.0341 (7)	0.0267 (7)	−0.0118 (5)	0.0019 (5)	−0.0041 (6)
C1	0.0371 (10)	0.0469 (11)	0.0172 (8)	−0.0266 (9)	−0.0001 (7)	−0.0048 (8)
C2	0.0309 (9)	0.0378 (10)	0.0169 (8)	−0.0208 (8)	−0.0002 (7)	−0.0058 (7)
C3	0.0308 (9)	0.0330 (9)	0.0230 (9)	−0.0120 (8)	0.0068 (7)	−0.0108 (7)
C4	0.0299 (9)	0.0262 (8)	0.0231 (8)	−0.0073 (7)	0.0028 (7)	−0.0048 (7)
C5	0.0291 (9)	0.0329 (10)	0.0260 (9)	−0.0043 (8)	0.0027 (7)	−0.0052 (8)
C6	0.0327 (10)	0.0333 (10)	0.0248 (9)	−0.0077 (8)	−0.0026 (7)	0.0008 (8)
C7	0.0322 (9)	0.0345 (10)	0.0163 (8)	−0.0142 (8)	0.0062 (7)	−0.0037 (7)
N4	0.0637 (14)	0.0823 (16)	0.0274 (10)	−0.0407 (13)	0.0125 (9)	−0.0150 (10)
O1	0.0690 (11)	0.0510 (9)	0.0277 (7)	−0.0306 (9)	0.0198 (7)	−0.0143 (7)
O2	0.0378 (8)	0.0585 (10)	0.0247 (7)	−0.0191 (7)	0.0001 (6)	0.0074 (7)
O5	0.0513 (14)	0.0524 (13)	0.0298 (10)	−0.0267 (11)	0.0064 (8)	−0.0162 (9)
O5'	0.107 (9)	0.048 (5)	0.029 (4)	−0.031 (5)	−0.014 (4)	−0.011 (3)

Co1—N2	2.0903 (18)	C1—C2	1.524 (2)
Co1—N2i	2.0903 (18)	C2—C3	1.382 (3)
Co1—O3i	2.1152 (14)	C2—C6	1.384 (3)
Co1—O3	2.1152 (14)	C3—C4	1.375 (3)
Co1—O4i	2.1230 (13)	C3—H3A	0.9300
Co1—O4	2.1230 (13)	C4—H4A	0.9300
N1—C5	1.340 (2)	C5—C6	1.376 (3)
N1—C4	1.350 (2)	C5—H5A	0.9300
N1—C7	1.479 (2)	C6—H6A	0.9300
N2—N3	1.154 (2)	C7—C7ii	1.519 (4)
N3—N4	1.159 (3)	C7—H7A	0.9700
O3—H31	0.826 (16)	C7—H7B	0.9700
O3—H32	0.847 (16)	O5—H5	0.824 (17)
O4—H42	0.846 (16)	O5—H51	0.802 (17)
O4—H41	0.812 (16)	O5'—H5	0.894 (17)
C1—O1	1.239 (3)	O5'—H52	0.85 (2)
C1—O2	1.256 (3)
N2—Co1—N2i	180.0	O1—C1—O2	126.83 (18)
N2—Co1—O3i	89.06 (7)	O1—C1—C2	116.63 (18)
N2i—Co1—O3i	90.94 (7)	O2—C1—C2	116.51 (18)
N2—Co1—O3	90.94 (7)	C3—C2—C6	118.98 (16)
N2i—Co1—O3	89.06 (7)	C3—C2—C1	120.08 (18)
O3i—Co1—O3	180.00 (8)	C6—C2—C1	120.92 (18)
N2—Co1—O4i	87.27 (7)	C4—C3—C2	119.67 (17)
N2i—Co1—O4i	92.73 (7)	C4—C3—H3A	120.2
O3i—Co1—O4i	88.65 (5)	C2—C3—H3A	120.2
O3—Co1—O4i	91.35 (5)	N1—C4—C3	120.32 (17)
N2—Co1—O4	92.73 (7)	N1—C4—H4A	119.8
N2i—Co1—O4	87.27 (7)	C3—C4—H4A	119.8
O3i—Co1—O4	91.35 (5)	N1—C5—C6	120.57 (18)
O3—Co1—O4	88.65 (5)	N1—C5—H5A	119.7
O4i—Co1—O4	180.00 (3)	C6—C5—H5A	119.7
C5—N1—C4	120.90 (15)	C5—C6—C2	119.56 (18)
C5—N1—C7	120.17 (15)	C5—C6—H6A	120.2
C4—N1—C7	118.94 (15)	C2—C6—H6A	120.2
N3—N2—Co1	148.27 (17)	N1—C7—C7ii	109.17 (18)
N2—N3—N4	177.0 (2)	N1—C7—H7A	109.8
Co1—O3—H31	109.2 (19)	C7ii—C7—H7A	109.8
Co1—O3—H32	113.4 (18)	N1—C7—H7B	109.8
H31—O3—H32	108 (2)	C7ii—C7—H7B	109.8
Co1—O4—H42	111.1 (18)	H7A—C7—H7B	108.3
Co1—O4—H41	110.5 (19)	H5—O5—H51	121 (3)
H42—O4—H41	112 (2)	H5—O5'—H52	107 (3)
O3i—Co1—N2—N3	129.7 (4)	C5—N1—C4—C3	0.1 (3)
O3—Co1—N2—N3	−50.3 (4)	C7—N1—C4—C3	179.88 (17)
O4i—Co1—N2—N3	−141.6 (4)	C2—C3—C4—N1	−0.1 (3)
O4—Co1—N2—N3	38.4 (4)	C4—N1—C5—C6	−0.2 (3)
O1—C1—C2—C3	7.4 (3)	C7—N1—C5—C6	−179.94 (18)
O2—C1—C2—C3	−174.40 (18)	N1—C5—C6—C2	0.2 (3)
O1—C1—C2—C6	−170.78 (19)	C3—C2—C6—C5	−0.1 (3)
O2—C1—C2—C6	7.4 (3)	C1—C2—C6—C5	178.15 (18)
C6—C2—C3—C4	0.0 (3)	C5—N1—C7—C7ii	−107.1 (2)
C1—C2—C3—C4	−178.22 (17)	C4—N1—C7—C7ii	73.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O5iii	0.83 (2)	1.91 (2)	2.727 (2)	170 (2)
O3—H31···O5'iii	0.83 (2)	1.96 (2)	2.664 (8)	143 (3)
O4—H41···O2iv	0.81 (2)	2.07 (2)	2.870 (2)	167 (3)
O5—H51···O2v	0.80 (2)	2.11 (2)	2.877 (3)	160 (4)
O3—H32···O1	0.85 (2)	1.85 (2)	2.694 (2)	178 (3)
O4—H42···O2	0.85 (2)	1.85 (2)	2.687 (2)	172 (2)
O5—H5···N4	0.82 (2)	2.19 (2)	2.864 (3)	139 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O5i	0.826 (16)	1.908 (18)	2.727 (2)	170 (2)
O3—H31⋯O5′i	0.826 (16)	1.96 (2)	2.664 (8)	143 (3)
O4—H41⋯O2ii	0.812 (16)	2.072 (18)	2.870 (2)	167 (3)
O5—H51⋯O2iii	0.802 (17)	2.110 (18)	2.877 (3)	160 (4)
O3—H32⋯O1	0.847 (16)	1.847 (17)	2.694 (2)	178 (3)
O4—H42⋯O2	0.846 (16)	1.847 (17)	2.687 (2)	172 (2)
O5—H5⋯N4	0.824 (17)	2.19 (2)	2.864 (3)	138.6 (19)

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