Diazido-bis-(5,5'-dimethyl-2,2'-bipyridyl-κN,N')cobalt(II) monohydrate.

In the title compound, [Co(C(12)H(12)N(2))(2)(N(3))(2)]·H(2)O, the Co(II) ion is situated on a crystallographic twofold axis and adopts a distorted octa-hedral geometry with the two dmbpy (dmbpy = 5,5'-dimethyl-2,2'-bipyrid-yl) and the two azido ligands in a cis arrangement. The solvent water mol-ecule and one methyl group of the dmbpy ligand are disordered over two sets of sites in a 1:1 ratio. The crystal structure is stabilized by intra-molecular C-H⋯N(dmbpy) and inter-molecular O-H⋯N(azide) hydrogen bonds.

Related literature

For related structures with dmbpy ligands, see: Phatchimkun et al. (2009 ▶); van Albada et al. (2004 ▶, 2005 ▶); Catalan et al. (1995 ▶); Kooijman et al. (2002 ▶). For azido complexes, see: Ribas et al. (1999 ▶) and references therein. For Co—N bond lengths in azido-containing mononuclear Co(II) complexes, see: Cheng & Hu (2003 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Co(C12H12N2)2(N3)2]·H2O

M = 529.46

Orthorhombic,

a = 17.1030 (3) Å

b = 8.5544 (2) Å

c = 16.7062 (5) Å

V = 2444.22 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.74 mm−1

T = 298 K

0.30 × 0.25 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.801, T max = 0.957

13768 measured reflections

2606 independent reflections

2176 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.067

S = 1.03

2606 reflections

208 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.25 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: COLLECT and DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; 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/S1600536811011305/fj2407sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011305/fj2407Isup2.hkl

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

[Co(C12H12N2)2(N3)2]·H2O	F(000) = 1096
Mr = 529.46	Dx = 1.439 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 7908 reflections
a = 17.1030 (3) Å	θ = 0.5–0.6°
b = 8.5544 (2) Å	µ = 0.74 mm−1
c = 16.7062 (5) Å	T = 298 K
V = 2444.22 (10) Å3	Plate, red
Z = 4	0.30 × 0.25 × 0.06 mm

Nonius KappaCCD diffractometer	2606 independent reflections
Radiation source: fine-focus sealed tube	2176 reflections with I > 2σ(I)
graphite	Rint = 0.022
ω scans	θmax = 26.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
Tmin = 0.801, Tmax = 0.957	k = −9→10
13768 measured reflections	l = −18→21

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) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0369P)2 + 0.4953P] where P = (Fo2 + 2Fc2)/3
2606 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.24 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	Occ. (<1)
Co1	0.5000	0.74215 (2)	0.7500	0.02599 (9)
O1	0.4695 (2)	0.2010 (3)	0.7390 (2)	0.0867 (12)	0.50
N1	0.38268 (6)	0.73352 (12)	0.71511 (7)	0.0331 (2)
N2	0.45546 (6)	0.56878 (12)	0.82573 (6)	0.0324 (2)
N3	0.47390 (7)	0.91391 (14)	0.83657 (7)	0.0418 (3)
N4	0.41325 (7)	0.92089 (14)	0.87142 (7)	0.0386 (3)
N5	0.35504 (8)	0.9289 (2)	0.90686 (9)	0.0648 (4)
C1	0.35034 (8)	0.81583 (17)	0.65500 (8)	0.0376 (3)
C2	0.27051 (8)	0.81862 (18)	0.63952 (9)	0.0417 (3)
C3	0.22267 (9)	0.73661 (18)	0.69218 (10)	0.0473 (4)
C4	0.25489 (9)	0.65180 (19)	0.75451 (9)	0.0437 (3)
C5	0.33587 (7)	0.64967 (16)	0.76406 (7)	0.0338 (3)
C6	0.37688 (7)	0.55243 (15)	0.82431 (7)	0.0331 (3)
C7	0.33975 (9)	0.44448 (18)	0.87336 (9)	0.0443 (3)
C8	0.38418 (9)	0.34791 (18)	0.92141 (9)	0.0468 (4)
C9	0.46490 (9)	0.35865 (16)	0.92140 (8)	0.0394 (3)
C10	0.49719 (8)	0.47402 (16)	0.87300 (8)	0.0369 (3)
C11	0.51626 (11)	0.24943 (17)	0.96857 (11)	0.0527 (4)
C12	0.23851 (11)	0.9052 (2)	0.56797 (11)	0.0560 (4)
H1	0.3877 (9)	0.8771 (18)	0.6223 (9)	0.045 (4)*
H3	0.1649 (12)	0.7387 (19)	0.6823 (11)	0.064 (5)*
H4	0.2211 (9)	0.5925 (19)	0.7907 (9)	0.050 (4)*
H7	0.2847 (10)	0.434 (2)	0.8706 (10)	0.055 (5)*
H8	0.3590 (10)	0.2688 (19)	0.9545 (11)	0.057 (5)*
H10	0.5560 (9)	0.4903 (17)	0.8720 (8)	0.041 (4)*
H11A	0.4975	0.2431	1.0226	0.079*	0.50
H11B	0.5689	0.2881	0.9685	0.079*	0.50
H11C	0.5150	0.1474	0.9446	0.079*	0.50
H11D	0.4887	0.1705	0.9986	0.079*	0.50
H11E	0.5459	0.3090	1.0125	0.079*	0.50
H11F	0.5566	0.1983	0.9373	0.079*	0.50
H12A	0.2140 (13)	0.826 (3)	0.5282 (14)	0.093 (7)*
H12B	0.1962 (13)	0.974 (3)	0.5817 (13)	0.087 (7)*
H12C	0.2796 (13)	0.967 (3)	0.5389 (13)	0.086 (6)*
H1O	0.514 (3)	0.125 (6)	0.712 (3)	0.106 (16)*	0.50

	U11	U22	U33	U12	U13	U23
Co1	0.02194 (13)	0.02914 (14)	0.02690 (14)	0.000	0.00172 (8)	0.000
O1	0.135 (4)	0.0515 (13)	0.074 (2)	0.0214 (17)	0.026 (2)	0.0093 (15)
N1	0.0284 (5)	0.0368 (6)	0.0340 (6)	0.0012 (4)	0.0010 (4)	−0.0002 (4)
N2	0.0306 (6)	0.0345 (6)	0.0320 (5)	−0.0013 (4)	0.0014 (4)	−0.0006 (4)
N3	0.0409 (6)	0.0431 (7)	0.0414 (6)	−0.0021 (5)	0.0078 (5)	−0.0071 (5)
N4	0.0370 (6)	0.0434 (6)	0.0354 (6)	0.0076 (5)	−0.0039 (5)	−0.0028 (5)
N5	0.0394 (7)	0.0930 (12)	0.0621 (9)	0.0146 (7)	0.0087 (7)	−0.0108 (8)
C1	0.0353 (7)	0.0410 (7)	0.0364 (7)	0.0038 (6)	0.0008 (6)	0.0008 (6)
C2	0.0362 (7)	0.0451 (8)	0.0440 (8)	0.0079 (6)	−0.0047 (6)	−0.0027 (6)
C3	0.0291 (7)	0.0580 (10)	0.0548 (9)	0.0023 (6)	−0.0041 (6)	−0.0017 (7)
C4	0.0307 (7)	0.0520 (8)	0.0483 (8)	−0.0034 (6)	0.0019 (6)	0.0018 (7)
C5	0.0302 (6)	0.0368 (7)	0.0345 (6)	−0.0006 (5)	0.0017 (5)	−0.0041 (5)
C6	0.0297 (6)	0.0373 (7)	0.0323 (6)	−0.0021 (5)	0.0027 (5)	−0.0033 (5)
C7	0.0352 (7)	0.0524 (9)	0.0453 (8)	−0.0074 (6)	0.0037 (6)	0.0057 (7)
C8	0.0505 (9)	0.0481 (9)	0.0418 (8)	−0.0096 (7)	0.0055 (6)	0.0096 (7)
C9	0.0478 (8)	0.0387 (7)	0.0316 (7)	0.0000 (6)	−0.0007 (6)	0.0006 (6)
C10	0.0353 (7)	0.0390 (7)	0.0365 (7)	0.0003 (6)	−0.0009 (5)	0.0017 (6)
C11	0.0652 (11)	0.0488 (9)	0.0441 (9)	0.0043 (7)	−0.0062 (8)	0.0107 (7)
C12	0.0451 (9)	0.0679 (12)	0.0551 (10)	0.0106 (8)	−0.0099 (8)	0.0100 (9)

O1—O1i	1.108 (8)	C5—C4	1.3943 (19)
O1—H1O	1.10 (5)	C2—C3	1.391 (2)
Co1—N1i	2.0907 (11)	C2—C12	1.509 (2)
Co1—N1	2.0907 (11)	C8—C9	1.383 (2)
Co1—N2i	2.0929 (10)	C8—H8	0.974 (18)
Co1—N2	2.0929 (10)	C10—C9	1.3903 (19)
Co1—N3	2.1095 (11)	C10—H10	1.016 (16)
Co1—N3i	2.1095 (12)	C9—C11	1.505 (2)
N2—C10	1.3379 (17)	C4—C3	1.384 (2)
N2—C6	1.3515 (16)	C4—H4	0.978 (16)
N1—C1	1.3454 (17)	C11—H11A	0.9600
N1—C5	1.3505 (17)	C11—H11B	0.9600
N4—N5	1.1604 (17)	C11—H11C	0.9600
N4—N3	1.1909 (16)	C11—H11D	0.9650
C1—C2	1.3898 (19)	C11—H11E	1.0271
C1—H1	0.990 (15)	C11—H11F	0.9703
C6—C7	1.3884 (19)	C12—H12B	0.96 (2)
C6—C5	1.4822 (18)	C12—H12C	1.01 (2)
C7—C8	1.380 (2)	C12—H12A	1.04 (2)
C7—H7	0.946 (17)	C3—H3	1.00 (2)
O1i—O1—H1O	58 (3)	C9—C8—H8	119.1 (10)
N1i—Co1—N1	175.95 (6)	N2—C10—C9	124.16 (13)
N1i—Co1—N2i	78.13 (4)	N2—C10—H10	115.8 (8)
N1—Co1—N2i	98.96 (4)	C9—C10—H10	120.0 (8)
N1i—Co1—N2	98.96 (4)	C8—C9—C10	116.33 (13)
N1—Co1—N2	78.13 (4)	C8—C9—C11	122.76 (14)
N2i—Co1—N2	89.76 (6)	C10—C9—C11	120.88 (14)
N1i—Co1—N3	92.09 (5)	C3—C4—C5	119.25 (14)
N1—Co1—N3	90.72 (5)	C3—C4—H4	120.1 (9)
N2i—Co1—N3	170.08 (4)	C5—C4—H4	120.6 (9)
N2—Co1—N3	90.12 (4)	C9—C11—H11A	109.5
N1i—Co1—N3i	90.72 (5)	C9—C11—H11B	109.5
N1—Co1—N3i	92.09 (5)	H11A—C11—H11B	109.5
N2i—Co1—N3i	90.12 (4)	C9—C11—H11C	109.5
N2—Co1—N3i	170.08 (4)	H11A—C11—H11C	109.5
N3—Co1—N3i	91.70 (7)	H11B—C11—H11C	109.5
C10—N2—C6	118.56 (11)	C9—C11—H11D	114.9
C10—N2—Co1	126.30 (9)	H11A—C11—H11D	46.2
C6—N2—Co1	115.13 (8)	H11B—C11—H11D	134.5
C1—N1—C5	119.08 (11)	H11C—C11—H11D	64.5
C1—N1—Co1	125.75 (9)	C9—C11—H11E	110.7
C5—N1—Co1	114.76 (9)	H11A—C11—H11E	61.3
N5—N4—N3	178.48 (15)	H11B—C11—H11E	50.7
N1—C1—C2	123.49 (13)	H11C—C11—H11E	139.4
N1—C1—H1	115.0 (9)	H11D—C11—H11E	102.5
C2—C1—H1	121.5 (9)	C9—C11—H11F	114.4
N2—C6—C7	120.89 (12)	H11A—C11—H11F	136.0
N2—C6—C5	115.11 (11)	H11B—C11—H11F	59.1
C7—C6—C5	123.89 (12)	H11C—C11—H11F	51.8
C8—C7—C6	119.32 (13)	H11D—C11—H11F	108.3
C8—C7—H7	121.3 (10)	H11E—C11—H11F	104.9
C6—C7—H7	119.2 (10)	C2—C12—H12B	112.6 (13)
N4—N3—Co1	123.67 (10)	C2—C12—H12C	112.9 (13)
N1—C5—C4	120.84 (12)	H12B—C12—H12C	108.6 (18)
N1—C5—C6	115.39 (11)	C2—C12—H12A	109.6 (13)
C4—C5—C6	123.71 (12)	H12B—C12—H12A	104.3 (18)
C1—C2—C3	116.83 (13)	H12C—C12—H12A	108.5 (17)
C1—C2—C12	120.81 (14)	C4—C3—C2	120.40 (14)
C3—C2—C12	122.36 (14)	C4—C3—H3	121.7 (10)
C7—C8—C9	120.64 (13)	C2—C3—H3	117.8 (10)
C7—C8—H8	120.2 (11)
N1i—Co1—N2—C10	−7.07 (11)	N1—Co1—N3—N4	32.12 (12)
N1—Co1—N2—C10	170.07 (11)	N2—Co1—N3—N4	−46.01 (12)
N2i—Co1—N2—C10	70.87 (10)	N3i—Co1—N3—N4	124.24 (13)
N3—Co1—N2—C10	−99.21 (11)	C1—N1—C5—C4	−2.10 (19)
N1i—Co1—N2—C6	174.06 (9)	Co1—N1—C5—C4	170.99 (11)
N1—Co1—N2—C6	−8.79 (9)	C1—N1—C5—C6	175.16 (11)
N2i—Co1—N2—C6	−108.00 (9)	Co1—N1—C5—C6	−11.75 (14)
N3—Co1—N2—C6	81.92 (9)	N2—C6—C5—N1	4.27 (16)
N2i—Co1—N1—C1	−88.45 (11)	C7—C6—C5—N1	−172.02 (13)
N2—Co1—N1—C1	−176.30 (11)	N2—C6—C5—C4	−178.57 (13)
N3—Co1—N1—C1	93.73 (11)	C7—C6—C5—C4	5.1 (2)
N3i—Co1—N1—C1	2.00 (11)	N1—C1—C2—C3	3.0 (2)
N2i—Co1—N1—C5	98.99 (9)	N1—C1—C2—C12	−176.10 (14)
N2—Co1—N1—C5	11.14 (9)	C6—C7—C8—C9	0.4 (2)
N3—Co1—N1—C5	−78.82 (9)	C6—N2—C10—C9	−0.1 (2)
N3i—Co1—N1—C5	−170.56 (9)	Co1—N2—C10—C9	−178.91 (10)
C5—N1—C1—C2	−0.7 (2)	C7—C8—C9—C10	2.1 (2)
Co1—N1—C1—C2	−172.92 (10)	C7—C8—C9—C11	−175.95 (15)
C10—N2—C6—C7	2.80 (19)	N2—C10—C9—C8	−2.3 (2)
Co1—N2—C6—C7	−178.24 (10)	N2—C10—C9—C11	175.74 (13)
C10—N2—C6—C5	−173.61 (11)	N1—C5—C4—C3	2.4 (2)
Co1—N2—C6—C5	5.35 (14)	C6—C5—C4—C3	−174.66 (13)
N2—C6—C7—C8	−3.0 (2)	C5—C4—C3—C2	0.1 (2)
C5—C6—C7—C8	173.09 (13)	C1—C2—C3—C4	−2.7 (2)
N1i—Co1—N3—N4	−144.98 (12)	C12—C2—C3—C4	176.44 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N3ii	1.05 (5)	1.99 (5)	2.926 (3)	141 (4)
C3—H3···O1iii	1.00 (2)	2.51 (2)	3.392 (4)	147.1 (14)
C1—H1···N3i	0.991 (15)	2.485 (15)	3.1241 (18)	121.9 (11)

Table 1

Selected bond lengths (Å)

Co1—N1	2.0907 (11)
Co1—N2	2.0929 (10)
Co1—N3	2.1095 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N3i	1.05 (5)	1.99 (5)	2.926 (3)	141 (4)
C3—H3⋯O1ii	1.00 (2)	2.51 (2)	3.392 (4)	147.1 (14)
C1—H1⋯N3iii	0.991 (15)	2.485 (15)	3.1241 (18)	121.9 (11)

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