Bis(2,2'-bipyridyl dioxide-κN,N')bis-(tricyano-methanido)cobalt(II) dihydrate.

In the title compound, [Co(C(4)N(3))(2)(C(10)H(8)N(2)O(2))]·2H(2)O, a novel tricyano-methanide complex, the Co(II) atom is located on an inversion center and has a distorted octa-hedral coordination with two 2,2'-bipyridyl dioxide (dpdo) mol-ecules and two trans tricyano-methanide (tcm) anions. The equatorial plane is formed by the four O atoms of the two chelating dpdo ligands, with one N atom of each of the two tcm ligands occupying an apical position. There is a disordered solvent water mol-ecule in the asymmetric unit (occupancy ratio 0.63:0.37). These water mol-ecules result in the formation of O-H⋯O and O-H⋯N hydrogen bonds, building a layer parallel to (100). The layers are linked by C-H⋯N hydrogen-bonding inter-actions, leading to a three-dimensional network.

Related literature

For coordination polymers constructed with tricyano­methanide, see: Abrahams et al. (2003 ▶); Batten & Murray (2003 ▶); Batten et al. (1998 ▶, 1999 ▶, 2000 ▶); Feyerherm et al. (2003 ▶, 2004 ▶); Hoshino et al. (1999 ▶); Manson & Schlueter (2004 ▶); Manson et al. (1998 ▶, 2000 ▶); Miller & Manson (2001 ▶); Yuste et al. (2007 ▶, 2008 ▶). For complexes containing dpdo, see: Luo et al. (2009 ▶); Zhang et al. (2010 ▶); Su & Lan (2007 ▶).

Experimental

Crystal data

[Co(C4N3)2(C10H8N2O2)]·2n class="Chemical">H2O

M = 651.47

Monoclinic,

a = 9.575 (3) Å

b = 16.699 (6) Å

c = 9.442 (3) Å

β = 95.307 (4)°

V = 1503.3 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.63 mm−1

T = 293 K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.911, T max = 0.940

7102 measured reflections

3193 independent reflections

2511 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.084

S = 0.99

3193 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017435/dn2560sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017435/dn2560Isup2.hkl

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

[Co(C4N3)2(C10H8N2O2)]·2H2O	F(000) = 666
Mr = 651.47	Dx = 1.439 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 887 reflections
a = 9.575 (3) Å	θ = 2.5–26.6°
b = 16.699 (6) Å	µ = 0.63 mm−1
c = 9.442 (3) Å	T = 293 K
β = 95.307 (4)°	Block, orange
V = 1503.3 (9) Å3	0.15 × 0.12 × 0.10 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	3193 independent reflections
Radiation source: fine-focus sealed tube	2511 reflections with I > 2σ(I)
graphite	Rint = 0.026
phi and ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→7
Tmin = 0.911, Tmax = 0.940	k = −20→18
7102 measured reflections	l = −8→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0476P)2] where P = (Fo2 + 2Fc2)/3
3193 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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 > 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	0.5000	0.03207 (11)
O1	0.63648 (11)	0.55420 (6)	0.37193 (12)	0.0390 (3)
O2	0.60938 (11)	0.55988 (6)	0.66433 (12)	0.0390 (3)
N1	0.64813 (13)	0.63342 (7)	0.38754 (14)	0.0361 (3)
N2	0.74874 (13)	0.55615 (7)	0.67045 (14)	0.0371 (3)
N3	0.36144 (13)	0.59847 (8)	0.48907 (16)	0.0451 (4)
N4	0.3061 (2)	0.85771 (11)	0.5359 (3)	0.0933 (7)
N5	0.0012 (2)	0.71277 (15)	0.2587 (3)	0.1017 (8)
C1	0.57248 (18)	0.68142 (10)	0.29627 (19)	0.0447 (4)
H1	0.5131	0.6595	0.2229	0.054*
C2	0.5829 (2)	0.76308 (11)	0.3113 (2)	0.0519 (5)
H2	0.5295	0.7964	0.2487	0.062*
C3	0.6710 (2)	0.79551 (10)	0.4175 (2)	0.0524 (5)
H3	0.6780	0.8508	0.4283	0.063*
C4	0.74983 (19)	0.74506 (10)	0.5088 (2)	0.0476 (4)
H4	0.8123	0.7664	0.5802	0.057*
C5	0.73654 (16)	0.66330 (9)	0.49468 (18)	0.0374 (4)
C6	0.81807 (16)	0.60621 (9)	0.58911 (18)	0.0394 (4)
C7	0.96264 (18)	0.60478 (12)	0.6027 (2)	0.0591 (5)
H7	1.0118	0.6399	0.5493	0.071*
C8	1.0347 (2)	0.55240 (13)	0.6937 (3)	0.0707 (6)
H8	1.1323	0.5515	0.7019	0.085*
C9	0.9616 (2)	0.50173 (12)	0.7720 (3)	0.0643 (6)
H9	1.0092	0.4653	0.8333	0.077*
C10	0.8172 (2)	0.50427 (9)	0.7606 (2)	0.0494 (5)
H10	0.7673	0.4701	0.8153	0.059*
C11	0.29971 (16)	0.65579 (10)	0.45990 (19)	0.0400 (4)
C12	0.22334 (18)	0.72533 (10)	0.4249 (2)	0.0471 (4)
C13	0.2679 (2)	0.79855 (12)	0.4860 (3)	0.0598 (5)
C14	0.1018 (2)	0.71979 (11)	0.3308 (2)	0.0607 (5)
O3	0.6888 (5)	0.5258 (4)	0.0838 (8)	0.0781 (13)	0.63
H3A	0.6797	0.4749	0.0780	0.117*	0.63
H3B	0.6715	0.5385	0.1685	0.117*	0.63
O3B	0.6196 (10)	0.5240 (9)	0.0694 (16)	0.108 (4)	0.37
H3C	0.6343	0.4776	0.0362	0.162*	0.37
H3D	0.6149	0.5187	0.1591	0.162*	0.37

	U11	U22	U33	U12	U13	U23
Co1	0.03347 (17)	0.02267 (16)	0.03967 (19)	−0.00084 (11)	0.00116 (12)	−0.00023 (12)
O1	0.0486 (6)	0.0276 (5)	0.0414 (6)	−0.0048 (5)	0.0064 (5)	−0.0029 (5)
O2	0.0377 (6)	0.0376 (6)	0.0418 (6)	−0.0045 (5)	0.0037 (5)	−0.0035 (5)
N1	0.0404 (7)	0.0305 (7)	0.0378 (8)	−0.0036 (5)	0.0055 (6)	0.0028 (6)
N2	0.0399 (7)	0.0321 (7)	0.0380 (8)	−0.0036 (6)	−0.0035 (6)	−0.0019 (6)
N3	0.0413 (8)	0.0309 (7)	0.0620 (10)	0.0021 (6)	−0.0015 (7)	−0.0011 (7)
N4	0.1096 (17)	0.0452 (11)	0.1228 (19)	0.0050 (10)	−0.0019 (14)	−0.0175 (12)
N5	0.0858 (15)	0.0982 (16)	0.1116 (19)	0.0178 (12)	−0.0413 (15)	0.0107 (13)
C1	0.0485 (10)	0.0441 (10)	0.0410 (10)	−0.0025 (7)	0.0006 (8)	0.0083 (8)
C2	0.0592 (11)	0.0422 (10)	0.0548 (12)	0.0059 (8)	0.0086 (9)	0.0175 (9)
C3	0.0689 (12)	0.0290 (9)	0.0611 (13)	−0.0025 (8)	0.0147 (10)	0.0080 (8)
C4	0.0546 (11)	0.0361 (9)	0.0522 (11)	−0.0107 (8)	0.0053 (8)	−0.0011 (8)
C5	0.0375 (8)	0.0324 (8)	0.0421 (9)	−0.0057 (6)	0.0030 (7)	0.0019 (7)
C6	0.0389 (9)	0.0327 (8)	0.0457 (10)	−0.0061 (6)	−0.0015 (7)	0.0003 (7)
C7	0.0401 (10)	0.0592 (12)	0.0771 (15)	−0.0072 (9)	0.0000 (9)	0.0098 (11)
C8	0.0439 (11)	0.0753 (15)	0.0897 (17)	0.0017 (10)	−0.0113 (11)	0.0099 (13)
C9	0.0636 (14)	0.0550 (12)	0.0692 (15)	0.0087 (10)	−0.0214 (11)	0.0057 (10)
C10	0.0594 (11)	0.0387 (10)	0.0475 (11)	−0.0013 (8)	−0.0091 (9)	0.0075 (8)
C11	0.0370 (9)	0.0349 (9)	0.0481 (10)	−0.0006 (7)	0.0030 (7)	−0.0011 (7)
C12	0.0464 (10)	0.0353 (9)	0.0590 (12)	0.0099 (7)	0.0019 (9)	0.0029 (8)
C13	0.0659 (13)	0.0389 (11)	0.0748 (15)	0.0136 (9)	0.0073 (11)	−0.0003 (10)
C14	0.0626 (13)	0.0488 (11)	0.0688 (14)	0.0153 (9)	−0.0046 (11)	0.0099 (10)
O3	0.118 (4)	0.0587 (17)	0.058 (2)	0.012 (3)	0.015 (3)	−0.0030 (15)
O3B	0.164 (11)	0.086 (4)	0.075 (5)	0.034 (8)	0.018 (8)	−0.002 (4)

Co1—O2	2.0503 (11)	C4—H4	0.9300
Co1—O2i	2.0503 (11)	C5—C6	1.478 (2)
Co1—O1	2.0691 (11)	C6—C7	1.378 (2)
Co1—O1i	2.0691 (11)	C7—C8	1.367 (3)
Co1—N3i	2.1093 (14)	C7—H7	0.9300
Co1—N3	2.1093 (14)	C8—C9	1.359 (3)
O1—N1	1.3346 (16)	C8—H8	0.9300
O2—N2	1.3318 (16)	C9—C10	1.378 (3)
N1—C1	1.340 (2)	C9—H9	0.9300
N1—C5	1.353 (2)	C10—H10	0.9300
N2—C10	1.342 (2)	C11—C12	1.396 (2)
N2—C6	1.350 (2)	C12—C14	1.400 (3)
N3—C11	1.145 (2)	C12—C13	1.401 (3)
N4—C13	1.140 (3)	O3—H3A	0.8567
N5—C14	1.134 (3)	O3—H3B	0.8584
C1—C2	1.374 (3)	O3—H3C	1.0384
C1—H1	0.9300	O3—H3D	1.0555
C2—C3	1.362 (3)	O3B—H3A	1.0017
C2—H2	0.9300	O3B—H3B	1.0464
C3—C4	1.379 (3)	O3B—H3C	0.8522
C3—H3	0.9300	O3B—H3D	0.8564
C4—C5	1.376 (2)
O2—Co1—O2i	180.00 (5)	N1—C5—C4	118.94 (15)
O2—Co1—O1	85.58 (5)	N1—C5—C6	118.18 (13)
O2i—Co1—O1	94.42 (5)	C4—C5—C6	122.86 (15)
O2—Co1—O1i	94.42 (5)	N2—C6—C7	118.58 (16)
O2i—Co1—O1i	85.58 (5)	N2—C6—C5	118.84 (14)
O1—Co1—O1i	180.00 (5)	C7—C6—C5	122.49 (15)
O2—Co1—N3i	93.91 (5)	C8—C7—C6	120.92 (19)
O2i—Co1—N3i	86.09 (5)	C8—C7—H7	119.5
O1—Co1—N3i	86.63 (5)	C6—C7—H7	119.5
O1i—Co1—N3i	93.37 (5)	C9—C8—C7	118.97 (19)
O2—Co1—N3	86.09 (5)	C9—C8—H8	120.5
O2i—Co1—N3	93.91 (5)	C7—C8—H8	120.5
O1—Co1—N3	93.37 (5)	C8—C9—C10	120.15 (18)
O1i—Co1—N3	86.63 (5)	C8—C9—H9	119.9
N3i—Co1—N3	180.0	C10—C9—H9	119.9
N1—O1—Co1	114.83 (9)	N2—C10—C9	119.79 (17)
N2—O2—Co1	116.72 (9)	N2—C10—H10	120.1
O1—N1—C1	119.17 (13)	C9—C10—H10	120.1
O1—N1—C5	119.23 (12)	N3—C11—C12	179.43 (19)
C1—N1—C5	121.60 (14)	C11—C12—C14	118.80 (16)
O2—N2—C10	119.10 (14)	C11—C12—C13	119.73 (16)
O2—N2—C6	119.31 (12)	C14—C12—C13	121.46 (15)
C10—N2—C6	121.56 (15)	N4—C13—C12	179.0 (2)
C11—N3—Co1	166.34 (15)	N5—C14—C12	176.8 (3)
N1—C1—C2	119.85 (16)	H3A—O3—H3B	106.1
N1—C1—H1	120.1	H3A—O3—H3C	32.7
C2—C1—H1	120.1	H3B—O3—H3C	117.5
C3—C2—C1	120.34 (16)	H3A—O3—H3D	82.0
C3—C2—H2	119.8	H3B—O3—H3D	36.9
C1—C2—H2	119.8	H3C—O3—H3D	82.1
C2—C3—C4	118.89 (17)	H3A—O3B—H3B	84.0
C2—C3—H3	120.6	H3A—O3B—H3C	34.1
C4—C3—H3	120.6	H3B—O3B—H3C	117.3
C5—C4—C3	120.36 (17)	H3A—O3B—H3D	85.3
C5—C4—H4	119.8	H3B—O3B—H3D	37.3
C3—C4—H4	119.8	H3C—O3B—H3D	107.2

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1	0.86	2.00	2.851 (8)	173
O3B—H3D···O1	0.86	2.09	2.890 (15)	156
O3—H3A···N4ii	0.86	2.24	3.028 (8)	152
O3B—H3C···N4ii	0.85	2.21	3.056 (15)	174
C1—H1···N4iii	0.93	2.55	3.437 (3)	161
C4—H4···N5iv	0.93	2.38	3.287 (3)	165
C10—H10···N4v	0.93	2.48	3.390 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1	0.86	2.00	2.851 (8)	173
O3B—H3D⋯O1	0.86	2.09	2.890 (15)	156
O3—H3A⋯N4i	0.86	2.24	3.028 (8)	152
O3B—H3C⋯N4i	0.85	2.21	3.056 (15)	174
C1—H1⋯N4ii	0.93	2.55	3.437 (3)	161
C4—H4⋯N5iii	0.93	2.38	3.287 (3)	165
C10—H10⋯N4iv	0.93	2.48	3.390 (3)	164

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