Diaqua-bis-[N-(pyridin-4-yl)isonicotin-amide-κN]bis-(thio-cyanato-κN)cobalt(II).

In the title compound, [Co(NCS)₂(C₁₁H₉N₃O)₂(H₂O)₂], the octa-hedrally coordinated Co(II) ion lies on a crystallographic inversion center and is bound by two isothio-cyanate ligands, two aqua ligands and two N-(pyridin-4-yl)isonicotinamide (4-pina) ligands. The dihedral angle between the aromatic rings in the 4-pina ligand is 8.98 (11)°. In the crystal, the individual mol-ecular units are aggregated in three dimensions by O-H⋯N, O-H⋯S and N-H⋯S hydrogen-bonding pathways.

Related literature

For other cobalt isothio­cyanate coordination polymers containing dipyridyl ligands, see: Johnston et al. (2007 ▶); Martin et al. (2009 ▶). For other coordination polymers containing the 4-pina ligand, see: Uemura et al. (2008 ▶). For the synthesis of the 4-pina ligand, see: Gardner et al. (1954) ▶.

Experimental

Crystal data

[Co(NCS)2(C11H9N3O)2(H2O)2]

M = 609.55

Triclinic,

a = 7.0651 (4) Å

b = 9.3943 (5) Å

c = 10.5943 (6) Å

α = 81.433 (1)°

β = 76.343 (1)°

γ = 71.697 (1)°

V = 646.58 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.87 mm−1

T = 173 K

0.30 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.778, T max = 0.873

10537 measured reflections

2348 independent reflections

2224 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.06

2348 reflections

187 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.07 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536812024105/hb6817sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024105/hb6817Isup2.hkl

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

[Co(NCS)2(C11H9N3O)2(H2O)2]	Z = 1
Mr = 609.55	F(000) = 313
Triclinic, P1	Dx = 1.565 Mg m−3
a = 7.0651 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3943 (5) Å	Cell parameters from 7965 reflections
c = 10.5943 (6) Å	θ = 2.3–25.3°
α = 81.433 (1)°	µ = 0.87 mm−1
β = 76.343 (1)°	T = 173 K
γ = 71.697 (1)°	Prism, pink
V = 646.58 (6) Å3	0.30 × 0.19 × 0.16 mm

Bruker APEXII CCD diffractometer	2348 independent reflections
Radiation source: fine-focus sealed tube	2224 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 25.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.778, Tmax = 0.873	k = −11→11
10537 measured reflections	l = −12→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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0374P)2 + 0.6702P] where P = (Fo2 + 2Fc2)/3
2348 reflections	(Δ/σ)max < 0.001
187 parameters	Δρmax = 1.07 e Å−3
4 restraints	Δρmin = −0.33 e Å−3

Experimental. REM Highest difference peak 1.065, 1.00 Å from N2

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	0.5000	1.0000	0.5000	0.01560 (12)
S1	0.01686 (8)	0.77868 (6)	0.79444 (5)	0.02645 (15)
O1	0.7779 (2)	0.86741 (18)	0.54694 (15)	0.0256 (3)
H1A	0.815 (4)	0.861 (3)	0.6164 (18)	0.031*
H1B	0.879 (3)	0.847 (3)	0.4857 (19)	0.031*
O2	0.5678 (2)	0.71752 (16)	−0.10588 (14)	0.0266 (3)
N1	0.5585 (3)	0.86061 (19)	0.34441 (16)	0.0198 (4)
N2	0.7178 (3)	0.5618 (2)	0.05144 (18)	0.0283 (4)
H2N	0.790 (4)	0.462 (2)	0.066 (2)	0.034*
N3	0.9194 (3)	0.2524 (2)	−0.34165 (17)	0.0246 (4)
N4	0.3440 (3)	0.8620 (2)	0.62833 (17)	0.0247 (4)
C1	0.5605 (3)	0.9145 (2)	0.2200 (2)	0.0246 (5)
H1	0.5281	1.0203	0.2002	0.030*
C2	0.6077 (4)	0.8233 (3)	0.1186 (2)	0.0301 (5)
H2	0.6058	0.8663	0.0317	0.036*
C3	0.6578 (3)	0.6679 (3)	0.1461 (2)	0.0263 (5)
C4	0.6567 (3)	0.6116 (3)	0.2740 (2)	0.0280 (5)
H4	0.6907	0.5062	0.2965	0.034*
C5	0.6054 (3)	0.7106 (2)	0.3685 (2)	0.0248 (5)
H5	0.6031	0.6702	0.4564	0.030*
C6	0.8466 (3)	0.3991 (3)	−0.3756 (2)	0.0273 (5)
H6	0.8510	0.4297	−0.4656	0.033*
C7	0.7661 (3)	0.5084 (3)	−0.2891 (2)	0.0273 (5)
H7	0.7144	0.6110	−0.3187	0.033*
C8	0.7621 (3)	0.4658 (2)	−0.1579 (2)	0.0243 (5)
C9	0.8341 (3)	0.3146 (3)	−0.1199 (2)	0.0270 (5)
H9	0.8317	0.2813	−0.0305	0.032*
C10	0.9102 (3)	0.2119 (2)	−0.2148 (2)	0.0261 (5)
H10	0.9578	0.1081	−0.1879	0.031*
C11	0.6720 (3)	0.5941 (3)	−0.0696 (2)	0.0274 (5)
C12	0.2111 (3)	0.8259 (2)	0.69719 (19)	0.0200 (4)

	U11	U22	U33	U12	U13	U23
Co1	0.0173 (2)	0.0152 (2)	0.0135 (2)	−0.00330 (15)	−0.00210 (14)	−0.00348 (14)
S1	0.0252 (3)	0.0293 (3)	0.0243 (3)	−0.0109 (2)	−0.0049 (2)	0.0058 (2)
O1	0.0213 (8)	0.0345 (9)	0.0165 (7)	0.0012 (7)	−0.0044 (6)	−0.0072 (6)
O2	0.0319 (8)	0.0210 (8)	0.0237 (8)	0.0009 (6)	−0.0110 (6)	−0.0021 (6)
N1	0.0195 (8)	0.0203 (8)	0.0191 (8)	−0.0032 (7)	−0.0039 (7)	−0.0055 (7)
N2	0.0317 (10)	0.0254 (10)	0.0266 (10)	−0.0055 (8)	−0.0058 (8)	−0.0045 (8)
N3	0.0220 (9)	0.0267 (9)	0.0241 (9)	−0.0042 (7)	−0.0014 (7)	−0.0105 (7)
N4	0.0288 (10)	0.0241 (9)	0.0212 (9)	−0.0094 (8)	−0.0028 (8)	−0.0019 (7)
C1	0.0270 (11)	0.0245 (11)	0.0223 (11)	−0.0054 (9)	−0.0064 (9)	−0.0043 (8)
C2	0.0321 (12)	0.0437 (14)	0.0167 (10)	−0.0123 (10)	−0.0050 (9)	−0.0057 (9)
C3	0.0195 (10)	0.0301 (12)	0.0317 (12)	−0.0087 (9)	0.0005 (9)	−0.0160 (9)
C4	0.0282 (11)	0.0225 (11)	0.0324 (12)	−0.0051 (9)	−0.0029 (9)	−0.0097 (9)
C5	0.0271 (11)	0.0224 (11)	0.0245 (11)	−0.0051 (9)	−0.0053 (9)	−0.0057 (9)
C6	0.0287 (12)	0.0295 (12)	0.0220 (11)	−0.0059 (9)	−0.0032 (9)	−0.0058 (9)
C7	0.0270 (11)	0.0232 (11)	0.0308 (12)	−0.0064 (9)	−0.0030 (9)	−0.0058 (9)
C8	0.0173 (10)	0.0274 (11)	0.0306 (11)	−0.0098 (9)	0.0010 (8)	−0.0122 (9)
C9	0.0264 (11)	0.0387 (13)	0.0179 (10)	−0.0121 (10)	−0.0025 (8)	−0.0059 (9)
C10	0.0261 (11)	0.0228 (11)	0.0279 (11)	−0.0039 (9)	−0.0051 (9)	−0.0048 (9)
C11	0.0247 (11)	0.0328 (13)	0.0265 (11)	−0.0130 (10)	−0.0024 (9)	−0.0027 (9)
C12	0.0246 (11)	0.0158 (9)	0.0195 (10)	−0.0030 (8)	−0.0081 (9)	−0.0016 (8)

Co1—O1	2.0964 (15)	C1—C2	1.388 (3)
Co1—O1i	2.0964 (15)	C1—H1	0.9500
Co1—N4i	2.0994 (18)	C2—C3	1.392 (3)
Co1—N4	2.0994 (18)	C2—H2	0.9500
Co1—N1i	2.1410 (16)	C3—C4	1.379 (3)
Co1—N1	2.1410 (16)	C4—C5	1.376 (3)
S1—C12	1.649 (2)	C4—H4	0.9500
O1—H1A	0.825 (16)	C5—H5	0.9500
O1—H1B	0.836 (16)	C6—C7	1.373 (3)
O2—C11	1.225 (3)	C6—H6	0.9500
N1—C1	1.338 (3)	C7—C8	1.384 (3)
N1—C5	1.342 (3)	C7—H7	0.9500
N2—C11	1.364 (3)	C8—C9	1.383 (3)
N2—C3	1.418 (3)	C8—C11	1.518 (3)
N2—H2N	0.927 (17)	C9—C10	1.392 (3)
N3—C10	1.332 (3)	C9—H9	0.9500
N3—C6	1.337 (3)	C10—H10	0.9500
N4—C12	1.154 (3)
O1—Co1—O1i	180.0	C1—C2—H2	120.5
O1—Co1—N4i	88.84 (7)	C3—C2—H2	120.5
O1i—Co1—N4i	91.16 (7)	C4—C3—C2	118.11 (19)
O1—Co1—N4	91.16 (7)	C4—C3—N2	117.0 (2)
O1i—Co1—N4	88.84 (7)	C2—C3—N2	124.9 (2)
N4i—Co1—N4	180.0	C5—C4—C3	118.9 (2)
O1—Co1—N1i	91.88 (6)	C5—C4—H4	120.6
O1i—Co1—N1i	88.12 (6)	C3—C4—H4	120.6
N4i—Co1—N1i	91.27 (7)	N1—C5—C4	124.2 (2)
N4—Co1—N1i	88.73 (7)	N1—C5—H5	117.9
O1—Co1—N1	88.12 (6)	C4—C5—H5	117.9
O1i—Co1—N1	91.88 (6)	N3—C6—C7	124.4 (2)
N4i—Co1—N1	88.73 (7)	N3—C6—H6	117.8
N4—Co1—N1	91.27 (7)	C7—C6—H6	117.8
N1i—Co1—N1	180.0	C6—C7—C8	118.5 (2)
Co1—O1—H1A	127.1 (18)	C6—C7—H7	120.8
Co1—O1—H1B	117.5 (17)	C8—C7—H7	120.8
H1A—O1—H1B	110 (2)	C9—C8—C7	118.34 (19)
C1—N1—C5	116.63 (18)	C9—C8—C11	126.7 (2)
C1—N1—Co1	123.33 (14)	C7—C8—C11	114.90 (19)
C5—N1—Co1	119.97 (14)	C8—C9—C10	118.9 (2)
C11—N2—C3	124.0 (2)	C8—C9—H9	120.6
C11—N2—H2N	112.7 (16)	C10—C9—H9	120.6
C3—N2—H2N	123.3 (16)	N3—C10—C9	123.2 (2)
C10—N3—C6	116.73 (18)	N3—C10—H10	118.4
C12—N4—Co1	159.23 (17)	C9—C10—H10	118.4
N1—C1—C2	123.2 (2)	O2—C11—N2	123.0 (2)
N1—C1—H1	118.4	O2—C11—C8	121.9 (2)
C2—C1—H1	118.4	N2—C11—C8	115.1 (2)
C1—C2—C3	119.0 (2)	N4—C12—S1	178.42 (19)
O1—Co1—N1—C1	−124.58 (17)	C11—N2—C3—C2	−22.5 (3)
O1i—Co1—N1—C1	55.42 (17)	C2—C3—C4—C5	0.3 (3)
N4i—Co1—N1—C1	−35.70 (17)	N2—C3—C4—C5	178.0 (2)
N4—Co1—N1—C1	144.30 (17)	C1—N1—C5—C4	0.8 (3)
N1i—Co1—N1—C1	27 (35)	Co1—N1—C5—C4	−176.15 (17)
O1—Co1—N1—C5	52.17 (16)	C3—C4—C5—N1	−1.0 (3)
O1i—Co1—N1—C5	−127.83 (16)	C10—N3—C6—C7	0.5 (3)
N4i—Co1—N1—C5	141.05 (16)	N3—C6—C7—C8	1.1 (3)
N4—Co1—N1—C5	−38.95 (16)	C6—C7—C8—C9	−1.8 (3)
N1i—Co1—N1—C5	−156 (35)	C6—C7—C8—C11	179.56 (19)
O1—Co1—N4—C12	156.5 (5)	C7—C8—C9—C10	0.9 (3)
O1i—Co1—N4—C12	−23.5 (5)	C11—C8—C9—C10	179.4 (2)
N4i—Co1—N4—C12	−129 (100)	C6—N3—C10—C9	−1.5 (3)
N1i—Co1—N4—C12	64.7 (5)	C8—C9—C10—N3	0.8 (3)
N1—Co1—N4—C12	−115.3 (5)	C3—N2—C11—O2	−2.7 (3)
C5—N1—C1—C2	0.1 (3)	C3—N2—C11—C8	176.58 (19)
Co1—N1—C1—C2	176.94 (16)	C9—C8—C11—O2	−161.6 (2)
N1—C1—C2—C3	−0.7 (3)	C7—C8—C11—O2	16.8 (3)
C1—C2—C3—C4	0.5 (3)	C9—C8—C11—N2	19.1 (3)
C1—C2—C3—N2	−177.0 (2)	C7—C8—C11—N2	−162.41 (19)
C11—N2—C3—C4	159.9 (2)	Co1—N4—C12—S1	7 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···S1ii	0.83 (2)	2.52 (2)	3.3129 (16)	162 (2)
O1—H1B···N3iii	0.84 (2)	1.95 (2)	2.755 (2)	162 (2)
N2—H2N···S1iv	0.93 (2)	2.68 (2)	3.540 (2)	155 (2)

Table 1

Selected bond lengths (Å)

Co1—O1	2.0964 (15)
Co1—N4	2.0994 (18)
Co1—N1	2.1410 (16)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯S1i	0.83 (2)	2.52 (2)	3.3129 (16)	162 (2)
O1—H1B⋯N3ii	0.84 (2)	1.95 (2)	2.755 (2)	162 (2)
N2—H2N⋯S1iii	0.93 (2)	2.68 (2)	3.540 (2)	155 (2)

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