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

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Bis(3-acetyl­pyridine-κN)di­aqua­bis­­(seleno­cyanato-κN)cobalt(II)

aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: jwerner@ac.uni-kiel.de

(Received 23 April 2012; accepted 24 April 2012; online 28 April 2012)

In the crystal structure of the title compound, [Co(NCSe)2(C7H7NO)2(H2O)2], the Co2+ cation is coordinated by two seleno­cyanate anions, two 3-acetyl­pyridine ligands and two water mol­ecules within a slightly distorted CoN4O2 octa­hedron. The asymmetric unit consists of one Co2+ cation, which is located on a center of inversion, as well as one seleno­cyanate anion, one 3-acetyl­pyridine ligand and one water mol­ecule in general positions. Whereas one of the water H atoms makes a classical O—H⋯O hydrogen bond, the other shows a O—H⋯Se inter­action.

Related literature

For general background to this work, see: Näther & Greve (2003[Näther, C. & Greve, J. (2003). J. Solid State Chem. 176, 259-265.]). For the synthesis, structures and properties of the corresponding compounds with pyridine, see: Boeckmann & Näther (2010[Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019-11026.], 2011[Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104-7106.], 2012[Boeckmann, J. & Näther, C. (2012). Polyhedron, 31, 587-595.]).

[Scheme 1]

Experimental

Crystal data
  • [Co(NCSe)2(C7H7NO)2(H2O)2]

  • Mr = 547.19

  • Monoclinic, C 2/c

  • a = 19.1098 (6) Å

  • b = 9.0064 (4) Å

  • c = 14.9734 (5) Å

  • β = 128.203 (2)°

  • V = 2025.13 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 4.47 mm−1

  • T = 293 K

  • 0.35 × 0.27 × 0.19 mm

Data collection
  • Stoe IPDS-2 diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.240, Tmax = 0.423

  • 16689 measured reflections

  • 2409 independent reflections

  • 2260 reflections with I > 2σ(I)

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.066

  • S = 1.12

  • 2409 reflections

  • 125 parameters

  • H-atom parameters constrained

  • Δρmax = 0.50 e Å−3

  • Δρmin = −0.45 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O11i 0.82 1.97 2.780 (2) 169
O1—H2O⋯Se1ii 0.82 2.57 3.338 (2) 157
Symmetry codes: (i) x, y+1, z; (ii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: X-AREA (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2011[Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).; software used to prepare material for publication: publCIF (Westrip, 2010)[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.].

Supporting information


Comment top

Recently we have reported on the magnetic properties of 1D coordination polymers based on paramagnetic transition metal cations that are coordinated by pyridine as co-ligand and that are µ-1,3-bridged into chains by thio- or selenocyanato anions (Näther & Greve, 2003). Dependent on the nature of the metal cation, anti- or ferromagnetic ordering is observed and for the compounds with Co(II) as cation we have found a slow relaxation of the magnetization (Boeckmann & Näther 2010, 2011 and 2012). To investigate the influence of the co-ligand on the magnetic properties we tried to prepare similar compounds based on 3-acetylpyridine, which resulted in the formation of the title compound in which the anionic ligands are only terminal N-coordinated. Further investigations also show that this compound cannot be transformed into the corresponding 1D coordination polymers and therefore, it was characterized only by single crystal X-ray diffraction.

In the crystal structure the cobalt(II) cations are coordinated by four nitrogen atoms of two terminal N-bonded selenocyanato anions and two terminal bonded 3-acetylpyridine co-ligands as well as two water molecules into discrete complexes (Fig. 1). The coordination polyhedron of the Co cations can be described as a slightly distorted octahedron with the Co cation located on a centre of inversion. The discrete cobalt complexes are bridged by two pairs of intermolecular O—H···O hydrogen bonding into 16-membered rings that are located on centres of inversion (Fig. 2). These rings are further linked into hydrogen bonded chains that are parallel to the b axis (Fig. 2 and Table 1).

Related literature top

For general background to this work, see: Näther & Greve (2003). For the synthesis, structures and properties of the corresponding compounds with pyridine, see: Boeckmann & Näther (2010, 2011, 2012).

Experimental top

Potassium selenocyanate and 3-acetylpyridine were purchased from Alfa Aesar and the Co(NO3)2.6 H2O obtained from Merck. The title compound was prepared by the reaction of 72.8 mg Co(NO3)2.6 H2O (0.25 mmol), 64.8 mg KSeCN (0.45 mmol) and 54.6 µL 3-acetylpyridine (0.50 mmol) in 1.5 mL H2O at RT in a closed 3 ml snap cap vial. After three days pink blocks of the title compound were obtained.

Refinement top

The C-H H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropic with Uiso(H) = 1.2 Ueq(C) for aromatic H atoms (1.5 for methyl H atoms) using a riding model with C—H = 0.93 Å (aromatic) and with C—H = 0.96 Å (methyl). The O-H H atom were located in difference map, their bond lengths set to ideal values of 0.84 Å and afterwards they were refined using a riding model with Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011).; software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x+1,-y+1,-z.
[Figure 2] Fig. 2. : Crystal structure showing the discrete complexes that are linked by hydrogen bonding into chains that elongate in the direction of the crystallographic b axis. Hydrogen bonding is shown as dashed lines and for clarification only the O-H H atoms are shown.
Bis(3-acetylpyridine-κN)diaquabis(selenocyanato-κN)cobalt(II) top
Crystal data top
[Co(NCSe)2(C7H7NO)2(H2O)2]F(000) = 1076
Mr = 547.19Dx = 1.795 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 16689 reflections
a = 19.1098 (6) Åθ = 2.6–27.9°
b = 9.0064 (4) ŵ = 4.47 mm1
c = 14.9734 (5) ÅT = 293 K
β = 128.203 (2)°Block, pink
V = 2025.13 (13) Å30.35 × 0.27 × 0.19 mm
Z = 4
Data collection top
Stoe IPDS-2
diffractometer
2409 independent reflections
Radiation source: fine-focus sealed tube2260 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 27.9°, θmin = 2.6°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 2524
Tmin = 0.240, Tmax = 0.423k = 1111
16689 measured reflectionsl = 1919
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0275P)2 + 2.5784P]
where P = (Fo2 + 2Fc2)/3
2409 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Co(NCSe)2(C7H7NO)2(H2O)2]V = 2025.13 (13) Å3
Mr = 547.19Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.1098 (6) ŵ = 4.47 mm1
b = 9.0064 (4) ÅT = 293 K
c = 14.9734 (5) Å0.35 × 0.27 × 0.19 mm
β = 128.203 (2)°
Data collection top
Stoe IPDS-2
diffractometer
2409 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2260 reflections with I > 2σ(I)
Tmin = 0.240, Tmax = 0.423Rint = 0.028
16689 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.12Δρmax = 0.50 e Å3
2409 reflectionsΔρmin = 0.45 e Å3
125 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
Co10.50000.50000.00000.03364 (10)
Se10.725951 (16)0.09800 (3)0.20771 (2)0.05020 (9)
C10.65776 (13)0.2600 (2)0.13699 (18)0.0372 (4)
N10.61139 (12)0.3598 (2)0.09124 (17)0.0431 (4)
O10.55451 (11)0.64233 (17)0.14168 (13)0.0450 (4)
H1O0.52650.72000.12490.068*
H2O0.60800.65870.17920.068*
N110.43968 (12)0.36819 (19)0.05628 (16)0.0393 (4)
C110.44407 (14)0.2201 (2)0.06235 (18)0.0373 (4)
H110.47410.17090.04060.045*
C120.40582 (14)0.1366 (2)0.09965 (17)0.0370 (4)
C130.36145 (18)0.2091 (3)0.1322 (2)0.0499 (6)
H130.33390.15580.15600.060*
C140.3585 (2)0.3627 (3)0.1289 (3)0.0574 (7)
H140.33030.41460.15240.069*
C150.39775 (18)0.4364 (3)0.0905 (2)0.0497 (6)
H150.39520.53950.08800.060*
C160.41692 (16)0.0284 (2)0.10701 (19)0.0423 (5)
C170.3525 (2)0.1217 (3)0.1065 (3)0.0614 (7)
H17A0.29450.11290.03420.092*
H17B0.35000.08900.16550.092*
H17C0.37130.22360.11940.092*
O110.47857 (13)0.08133 (19)0.11398 (17)0.0558 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.03083 (19)0.02384 (18)0.0412 (2)0.00276 (13)0.01973 (16)0.00073 (14)
Se10.04556 (14)0.04665 (15)0.06007 (16)0.01964 (10)0.03351 (12)0.01574 (11)
C10.0309 (9)0.0380 (10)0.0403 (11)0.0027 (8)0.0208 (9)0.0010 (8)
N10.0335 (9)0.0369 (9)0.0504 (10)0.0059 (7)0.0217 (8)0.0035 (8)
O10.0406 (8)0.0337 (8)0.0491 (9)0.0013 (6)0.0218 (7)0.0061 (6)
N110.0400 (9)0.0303 (9)0.0499 (10)0.0021 (7)0.0289 (8)0.0011 (7)
C110.0387 (10)0.0302 (10)0.0435 (11)0.0021 (8)0.0258 (9)0.0007 (8)
C120.0389 (10)0.0306 (10)0.0382 (10)0.0001 (8)0.0222 (9)0.0004 (8)
C130.0598 (14)0.0450 (13)0.0603 (14)0.0013 (11)0.0449 (13)0.0002 (11)
C140.0723 (18)0.0462 (14)0.0800 (18)0.0040 (13)0.0603 (16)0.0056 (13)
C150.0586 (15)0.0316 (11)0.0690 (16)0.0030 (10)0.0445 (14)0.0046 (10)
C160.0500 (12)0.0330 (10)0.0390 (10)0.0001 (9)0.0250 (10)0.0013 (8)
C170.0768 (19)0.0403 (13)0.0705 (18)0.0095 (13)0.0473 (16)0.0032 (12)
O110.0598 (11)0.0342 (8)0.0701 (12)0.0088 (8)0.0386 (10)0.0034 (8)
Geometric parameters (Å, º) top
Co1—N1i2.0962 (18)C11—H110.9300
Co1—N12.0962 (18)C12—C131.376 (3)
Co1—O1i2.1202 (15)C12—C161.495 (3)
Co1—O12.1202 (15)C13—C141.384 (4)
Co1—N112.1562 (19)C13—H130.9300
Co1—N11i2.1562 (19)C14—C151.367 (4)
Se1—C11.800 (2)C14—H140.9300
C1—N11.146 (3)C15—H150.9300
O1—H1O0.8201C16—O111.214 (3)
O1—H2O0.8200C16—C171.487 (4)
N11—C111.336 (3)C17—H17A0.9600
N11—C151.338 (3)C17—H17B0.9600
C11—C121.384 (3)C17—H17C0.9600
N1i—Co1—N1180.00 (8)N11—C11—H11118.6
N1i—Co1—O1i92.26 (7)C12—C11—H11118.6
N1—Co1—O1i87.74 (7)C13—C12—C11118.7 (2)
N1i—Co1—O187.74 (7)C13—C12—C16122.4 (2)
N1—Co1—O192.26 (7)C11—C12—C16118.9 (2)
O1i—Co1—O1180.00 (9)C12—C13—C14118.9 (2)
N1i—Co1—N1190.77 (7)C12—C13—H13120.6
N1—Co1—N1189.23 (7)C14—C13—H13120.6
O1i—Co1—N1190.43 (7)C15—C14—C13118.6 (2)
O1—Co1—N1189.57 (7)C15—C14—H14120.7
N1i—Co1—N11i89.23 (7)C13—C14—H14120.7
N1—Co1—N11i90.77 (7)N11—C15—C14123.6 (2)
O1i—Co1—N11i89.57 (7)N11—C15—H15118.2
O1—Co1—N11i90.43 (7)C14—C15—H15118.2
N11—Co1—N11i180.00 (9)O11—C16—C17122.3 (2)
N1—C1—Se1177.1 (2)O11—C16—C12118.8 (2)
C1—N1—Co1163.86 (18)C17—C16—C12118.8 (2)
Co1—O1—H1O112.7C16—C17—H17A109.5
Co1—O1—H2O115.2C16—C17—H17B109.5
H1O—O1—H2O110.9H17A—C17—H17B109.5
C11—N11—C15117.4 (2)C16—C17—H17C109.5
C11—N11—Co1123.37 (15)H17A—C17—H17C109.5
C15—N11—Co1119.25 (15)H17B—C17—H17C109.5
N11—C11—C12122.9 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O11ii0.821.972.780 (2)169
O1—H2O···Se1iii0.822.573.338 (2)157
Symmetry codes: (ii) x, y+1, z; (iii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Co(NCSe)2(C7H7NO)2(H2O)2]
Mr547.19
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)19.1098 (6), 9.0064 (4), 14.9734 (5)
β (°) 128.203 (2)
V3)2025.13 (13)
Z4
Radiation typeMo Kα
µ (mm1)4.47
Crystal size (mm)0.35 × 0.27 × 0.19
Data collection
DiffractometerStoe IPDS2
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.240, 0.423
No. of measured, independent and
observed [I > 2σ(I)] reflections
16689, 2409, 2260
Rint0.028
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.066, 1.12
No. of reflections2409
No. of parameters125
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.45

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011)., publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O11i0.821.972.780 (2)169.1
O1—H2O···Se1ii0.82002.57003.338 (2)157.00
Symmetry codes: (i) x, y+1, z; (ii) x+3/2, y+1/2, z+1/2.
 

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

First citationBoeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationBoeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106.  Web of Science CSD CrossRef CAS Google Scholar
First citationBoeckmann, J. & Näther, C. (2012). Polyhedron, 31, 587–595.  Web of Science CSD CrossRef CAS Google Scholar
First citationBrandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationNäther, C. & Greve, J. (2003). J. Solid State Chem. 176, 259–265.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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