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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 6| June 2014| Page m236
doi:10.1107/S1600536814011453

Di­aqua­bis­­(nicotinamide-κN1)bis­­(thio­cyanato-κS)cobalt(II)

Deepanjali Pandey,a* Shahid S. Narvia and Siddhartha Chaudhurib

aDepartment of Chemistry, Motilal Nehru National Institute of Technology, Allahabad 211 004, India, and bBose Institute, Kolkata 700 009, West Bengal, India
*Correspondence e-mail: deepanjalipandey.1@gmail.com

(Received 5 May 2014; accepted 18 May 2014; online 31 May 2014)

In the title compound, [Co(NCS)2(C6H6N2O)2(H2O)2], the CoII cation is located on an inversion centre and is coordinated by two thio­cyanate anions, two nicotinamide mol­ecules and two water mol­ecules in a distorted N2O2S2 octa­hedral geometry. The amide group is twisted by 31.30 (16)° with respect to the pyridine ring. In the crystal, mol­ecules are linked by O—H⋯O, O—H⋯S and N—H⋯S hydrogen bonds into a three-dimensional supra­molecular network. Weak π–π stacking is observed between parallel pyridine rings of adjacent mol­ecules, the centroid–centroid distance being 3.8270 (19) Å.

CCDC reference: 850080

Related literature

For general background and applications of transition-metal complexes with biochemically active ligands, see: Antolini et al. (1982[Antolini, L., Battaglia, L. P., Corradi, A. B., Marcotrigiano, G., Menabue, L., Pellacani, G. C. & Saladini, M. (1982). Inorg. Chem. 21, 1391-1395.]); Krishnamachari (1974[Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108-111.]). For related structures, see: Hökelek et al. (2009a[Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009a). Acta Cryst. E65, m481-m482.],b[Hökelek, T., Yılmaz, F., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009b). Acta Cryst. E65, m768-m769.]); Özbek et al. (2009[Özbek, F. E., Tercan, B., Şahin, E., Necefoğlu, H. & Hökelek, T. (2009). Acta Cryst. E65, m341-m342.]).

[Scheme 1]

Experimental

Crystal data

  • [Co(NCS)2(C6H6N2O)2(H2O)2]

  • Mr = 455.38

  • Triclinic, [P \overline 1]

  • a = 7.5475 (19) Å

  • b = 8.054 (2) Å

  • c = 8.932 (2) Å

  • α = 73.347 (4)°

  • β = 70.067 (4)°

  • γ = 66.559 (4)°

  • V = 461.07 (19) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 1.19 mm−1

  • T = 100 K

  • 0.35 × 0.33 × 0.31 mm
Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]) Tmin = 0.68, Tmax = 0.71

  • 2450 measured reflections

  • 1626 independent reflections

  • 1469 reflections with I > 2σ(I)

  • Rint = 0.017
Refinement

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.097

  • S = 1.07

  • 1626 reflections

  • 130 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.60 e Å−3

  • Δρmin = −0.39 e Å−3

Table 1
Selected bond lengths (Å)

Co—N1 2.050 (2)
Co—N2 2.119 (2)
Co—O2 2.0724 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2A⋯O1i 0.83 (2) 1.89 (2) 2.690 (2) 161 (4)
O2—H2B⋯S1ii 0.82 (4) 2.41 (3) 3.204 (3) 163 (3)
N3—H3A⋯S1iii 0.86 2.66 3.425 (3) 149
N3—H3B⋯S1iv 0.86 2.63 3.422 (3) 153
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) x-1, y, z.

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 850080

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814011453/xu5790sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011453/xu5790Isup2.hkl

checkCIF report


Comment top

The structural unit of hydrogen bonded framework of cobalt is depicted in Figure 1. Co(II) is at a slightly distorted octahedral coordination environment. The equatorial positions are occupied by two nitrogen atoms from two nicotinamide ligands, the Co N(nicotinamide) bond length is 2.117 (3) angstrom, and two oxygen atoms from two water molecules, the Co O(water) bond length is 2.075 (2)angstrom and two nitrogen atoms from NCS groups occupy the axial positions with bond length of 2.049 (3)angstrom for Co N(thiocyanate). The O(water) Co O(water), N(thiocyanate) Co N(thiocyanate), and N(nicotinamide) Co N(nicotinamide) angles are constrained by symmetry to 180. The N(thiocyanate) Co N(nicotinamide), O(water) Co N(thiocyanate), and O(water) Co N(nicotinamide) angles are 87.48, 91.9, and 90.50 respectively, indicating a slightly distorted octahedral coordination for the Co ion. Both ligands generally acts as bidentate, however in this polymer plays as unidentate. The thiocynate SCN presents multiform coordination modes connecting the metal ions with terminal and or bridging fashions. According to the concept of hard soft acid base the SCN ion prefers to bind to Cd(II) centre in both N and S bonded fashion, whereas in the only N terminal mode to Co(II) ion·As expected, the SCN anion is almost linear angle: 178 and coordinates in a little bent fashion to Co, exhibiting a Co—N—C angle of 159.56. These structural features have already been observed in other thiocyanato-containing metal complexes. As a result of the trans orientation of two terminal N-bonded thiocyanate groups around the Co(II) atom, the bond angle N(1) Co(1) N(1) is 180. The S C and C N distances of 1.638 (2) angtrom and 1.158 (2)angstrom in the SCN– moiety show the normal structure of the thiocyanate in the complex which is also observed in other thiocyanate complexes·The nicotinamides molecules are trans to each other with angle N(2) Co N(2) is 180. The nicotinamide ligand generally acts as a bidentate chelating ligand, coordinating to the metal ion through the carbonyl O and pyridine N atoms, but in this structure it acts as a unidentate ligand in which the pyridine N is coordinated to the Co ion while the carbonyl O is involved in hydrogen bonding with another water molecule·Water used as solvent whereas it involved in coordination with metal ions and act as ligand. The coordination of nitrogen atoms of each thiocynate molecules and nicotinamide molecules results in the formation of two symmetrical axis N1–Co–N1, N2–Co–N2 respectively. The oxygen atoms of water molecules describe the third axis O(1) W A–Co—O(1)WB. The Co Co distance spaced by the thiocynate ligand is 7.548 Å. The discrete units are connected by bifurcated hydrogen bonds between the coordinated water molecules and terminal thiocynate sulfur atoms forms O(2)—H(2) W A—-S(1) interlayer hydrogen bonding gives one-dimensional chain and forming ladder like structure. Further Oxygen atom of amide group from nicotinamide molecule makes hydrogen bonding with hydrogen atom of water molecule C(7)- - O(1)—H(2)WB to afford a 2-D layered architecture. As can be seen from the packing diagram, the Co atoms are located at the centre of the axis of the unit cell and the molecules of polymer are linked by intermolecular hydrogen bond O–H—O, O–H—-S and N–H—-S hydrogen bonds, forming a supramolecular structure. Dipole dipole and van der Waals interactions are also effective in the molecular packing. Remarkably, each sulfur atom of thiocynate molecule plays a trifurcated role to be involved in the hydrogen bonding with one hydrogen atom from water molecules and two hydrogen atoms from nicotinamide molecules thus formation of three S(1)—H2WA, S(1)—H3A andS(1)—H3B interlayer respectively. With the aid of these contacts polymer affords three-dimensional structure.

Related literature top

For general background and applications of transition-metal complexes with biochemically active ligands, see: Antolini et al. (1982); Krishnamachari (1974). For related structures, see: Hökelek et al. (2009a,b); Özbek et al. (2009).

Experimental top

An aqueous solution (10 ml) of Cobalt nitrate (0.2460 g, 1 mmol) and Potassium thiocyanate (0.196 g, 2 mmol) was slowly added drop wise to hot aqueous solution (10 ml) of Nicotinamide (0.241 g, 2 mmol) with stirring. Greenish blue colour solution was obtained. After filtration the final clear solution left undisturbed at room temperature for slow evaporation. Next day, needle shaped greenish blue crystals were collected and dried in vacuo over silica gel. Crystals suitable for single crystals X-ray diffraction was manually selected and immersed in silicon oil.

Refinement top

Water H atoms were located in a different Fourier map and refined in riding mode with distance constraint of O—H = 0.82 (2) Å, Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(N,C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP view of complex[Co(nicotinamide)2(thiocynate)2(H2O)2] with atom labelling.
[Figure 2] Fig. 2. Packing diagram of the Complex. Hydrogen bonds are shown as dashed lines.
Diaquabis(nicotinamide-κN1)bis(thiocyanato-κS)cobalt(II) top
Crystal data top
[Co(NCS)2(C6H6N2O)2(H2O)2]Z = 1
Mr = 455.38F(000) = 233
Triclinic, P1Dx = 1.640 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5475 (19) ÅCell parameters from 1626 reflections
b = 8.054 (2) Åθ = 2.5–25.2°
c = 8.932 (2) ŵ = 1.19 mm−1
α = 73.347 (4)°T = 100 K
β = 70.067 (4)°Prism, pink
γ = 66.559 (4)°0.35 × 0.33 × 0.31 mm
V = 461.07 (19) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		1626 independent reflections
Radiation source: fine-focus sealed tube1469 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
phi and ω scansθmax = 25.2°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −9→8
Tmin = 0.68, Tmax = 0.71k = −8→9
2450 measured reflectionsl = −6→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1481P]
where P = (Fo2 + 2Fc2)/3
1626 reflections(Δ/σ)max = 0.001
130 parametersΔρmax = 0.60 e Å−3
2 restraintsΔρmin = −0.39 e Å−3
Crystal data top
[Co(NCS)2(C6H6N2O)2(H2O)2]γ = 66.559 (4)°
Mr = 455.38V = 461.07 (19) Å3
Triclinic, P1Z = 1
a = 7.5475 (19) ÅMo Kα radiation
b = 8.054 (2) ŵ = 1.19 mm−1
c = 8.932 (2) ÅT = 100 K
α = 73.347 (4)°0.35 × 0.33 × 0.31 mm
β = 70.067 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1626 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1469 reflections with I > 2σ(I)
Tmin = 0.68, Tmax = 0.71Rint = 0.017
2450 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0362 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.60 e Å−3
1626 reflectionsΔρmin = −0.39 e Å−3
130 parameters
Special details top

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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.50000.50000.50000.01075 (18)
S11.10774 (10)0.10828 (9)0.64395 (8)0.0188 (2)
N10.7855 (3)0.3745 (3)0.5269 (3)0.0190 (5)
N20.5800 (3)0.3846 (3)0.2911 (3)0.0156 (5)
N30.2309 (3)0.1182 (3)0.2363 (3)0.0183 (5)
H3A0.14080.08390.22800.022*
H3B0.24470.10990.33010.022*
O10.3341 (3)0.1985 (3)−0.0328 (2)0.0219 (4)
O20.5635 (3)0.7330 (3)0.3582 (2)0.0187 (4)
C10.9198 (4)0.2665 (4)0.5745 (3)0.0163 (6)
C20.4546 (4)0.3214 (3)0.2666 (3)0.0156 (5)
H20.33420.32690.34430.019*
C30.4961 (4)0.2479 (4)0.1301 (3)0.0162 (6)
C40.6758 (4)0.2414 (4)0.0138 (3)0.0178 (6)
H40.70670.1965−0.08020.021*
C50.8072 (4)0.3027 (4)0.0404 (3)0.0188 (6)
H50.92960.2971−0.03440.023*
C60.7542 (4)0.3726 (4)0.1800 (3)0.0171 (6)
H60.84380.41320.19730.021*
C70.3480 (4)0.1838 (3)0.1049 (3)0.0156 (6)
H2A0.572 (5)0.748 (4)0.260 (2)0.023*
H2B0.662 (4)0.750 (4)0.363 (4)0.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0119 (3)0.0132 (3)0.0084 (3)−0.0052 (2)−0.00355 (19)−0.00102 (18)
S10.0173 (4)0.0203 (4)0.0188 (4)−0.0074 (3)−0.0069 (3)0.0011 (3)
N10.0212 (13)0.0203 (12)0.0166 (12)−0.0074 (10)−0.0059 (10)−0.0032 (9)
N20.0170 (12)0.0159 (12)0.0140 (11)−0.0062 (9)−0.0046 (9)−0.0009 (9)
N30.0205 (12)0.0254 (13)0.0140 (11)−0.0128 (10)−0.0051 (9)−0.0025 (9)
O10.0280 (11)0.0270 (11)0.0156 (10)−0.0134 (9)−0.0079 (8)−0.0021 (8)
O20.0217 (10)0.0247 (11)0.0143 (9)−0.0135 (9)−0.0058 (8)−0.0005 (8)
C10.0184 (14)0.0207 (14)0.0120 (13)−0.0101 (12)0.0003 (11)−0.0060 (11)
C20.0159 (13)0.0147 (13)0.0140 (12)−0.0044 (11)−0.0040 (10)−0.0001 (10)
C30.0185 (14)0.0147 (13)0.0141 (13)−0.0053 (11)−0.0052 (11)0.0003 (10)
C40.0215 (14)0.0182 (14)0.0126 (13)−0.0062 (11)−0.0041 (11)−0.0021 (10)
C50.0158 (14)0.0215 (15)0.0163 (13)−0.0065 (11)−0.0019 (11)−0.0016 (11)
C60.0171 (14)0.0175 (14)0.0175 (14)−0.0068 (11)−0.0065 (11)−0.0003 (11)
C70.0179 (14)0.0140 (13)0.0151 (13)−0.0034 (11)−0.0061 (11)−0.0032 (10)
Geometric parameters (Å, º) top
Co—N12.050 (2)O1—C71.237 (3)
Co—N1i2.050 (2)O2—H2A0.838 (18)
Co—N22.119 (2)O2—H2B0.825 (18)
Co—N2i2.119 (2)C2—C31.394 (4)
Co—O22.0724 (18)C2—H20.9300
Co—O2i2.0724 (18)C3—C41.391 (4)
S1—C11.652 (3)C3—C71.505 (4)
N1—C11.160 (4)C4—C51.378 (4)
N2—C61.337 (3)C4—H40.9300
N2—C21.338 (3)C5—C61.384 (4)
N3—C71.321 (3)C5—H50.9300
N3—H3A0.8600C6—H60.9300
N3—H3B0.8600
N1—Co—N1i180.0Co—O2—H2A116 (2)
N1—Co—O291.98 (8)Co—O2—H2B118 (2)
N1i—Co—O288.02 (8)H2A—O2—H2B106 (3)
N1—Co—O2i88.02 (8)N1—C1—S1178.4 (2)
N1i—Co—O2i91.98 (8)N2—C2—C3123.0 (2)
O2—Co—O2i180.000 (1)N2—C2—H2118.5
N1—Co—N291.21 (9)C3—C2—H2118.5
N1i—Co—N288.79 (9)C4—C3—C2118.2 (2)
O2—Co—N290.66 (8)C4—C3—C7120.5 (2)
O2i—Co—N289.34 (8)C2—C3—C7121.3 (2)
N1—Co—N2i88.79 (9)C5—C4—C3118.9 (2)
N1i—Co—N2i91.21 (9)C5—C4—H4120.5
O2—Co—N2i89.34 (8)C3—C4—H4120.5
O2i—Co—N2i90.66 (8)C4—C5—C6119.0 (2)
N2—Co—N2i180.0C4—C5—H5120.5
C1—N1—Co159.3 (2)C6—C5—H5120.5
C6—N2—C2117.8 (2)N2—C6—C5123.0 (2)
C6—N2—Co122.02 (17)N2—C6—H6118.5
C2—N2—Co120.17 (17)C5—C6—H6118.5
C7—N3—H3A120.0O1—C7—N3122.5 (2)
C7—N3—H3B120.0O1—C7—C3120.7 (2)
H3A—N3—H3B120.0N3—C7—C3116.7 (2)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1ii0.83 (2)1.89 (2)2.690 (2)161 (4)
O2—H2B···S1iii0.82 (4)2.41 (3)3.204 (3)163 (3)
N3—H3A···S1iv0.862.663.425 (3)149
N3—H3B···S1v0.862.633.422 (3)153
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) x−1, y, z.
Selected bond lengths (Å) top
Co—N12.050 (2)Co—O22.0724 (18)
Co—N22.119 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.834 (18)1.889 (17)2.690 (2)161 (4)
O2—H2B···S1ii0.82 (4)2.41 (3)3.204 (3)163 (3)
N3—H3A···S1iii0.862.663.425 (3)149
N3—H3B···S1iv0.862.633.422 (3)153
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1, y, z.
 

Acknowledgements

The authors wish to extend their gratitude to Professor P. Chakrabarti, Director, MNNIT, Allahabad, for providing the Institute Research fellowship to DP.

References

First citationAntolini, L., Battaglia, L. P., Corradi, A. B., Marcotrigiano, G., Menabue, L., Pellacani, G. C. & Saladini, M. (1982). Inorg. Chem. 21, 1391-1395.  CSD CrossRef CAS Web of Science Google Scholar
 First citationBruker (2002). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2007). SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
 First citationHökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009a). Acta Cryst. E65, m481–m482.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationHökelek, T., Yılmaz, F., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009b). Acta Cryst. E65, m768–m769.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationKrishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108-111.  CAS PubMed Web of Science Google Scholar
 First citationÖzbek, F. E., Tercan, B., Şahin, E., Necefoğlu, H. & Hökelek, T. (2009). Acta Cryst. E65, m341–m342.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 6| June 2014| Page m236
doi:10.1107/S1600536814011453
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