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Crystal structure of di­aqua­bis­­(2,6-di­methyl­pyrazine-κN)bis­­(thio­cyanato-κN)cobalt(II) 2,5-di­methyl­pyrazine tris­­olvate

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

Edited by M. Weil, Vienna University of Technology, Austria (Received 10 December 2015; accepted 16 December 2015; online 24 December 2015)

In the crystal structure of the title compound, [Co(NCS)2(C6H8N2)2(H2O)2]·3C6H8N2, the CoII cation is coordinated by two terminally N-bound thio­cyanate anions, two water mol­ecules and two 2,6-di­methyl­pyrazine ligands, forming a discrete complex with a slightly distorted octa­hedral N4O2 coordination environment. The asymmetric unit contains one CoII cation and three halves of 2,5-di­methyl­pyrazine solvate mol­ecules, all entities being completed by inversion symmetry, as well as one thio­cyanate anion, an aqua ligand and a 2,6-di­methyl­pyrazine ligand, all in general positions. In the crystal, discrete complexes are arranged in a way that cavities are formed where the noncoordinating 2,5-di­methyl­pyrazine mol­ecules are located. The coordination of the latter to the metal is prevented due to the bulky methyl groups in vicinal positions to the N atoms, leading to a preferential coordination through the 2,6-di­methyl­pyrazine ligands. The complex mol­ecules are linked by O—H⋯N hydrogen bonds between the water H atoms and the N atoms of 2,5-di­methyl­pyrazine solvent mol­ecules, leading to a layered structure extending parallel to (100).

1. Related literature

The crystal structure of the 2,5-di­methyl­pyrazine monosolvate of the title compound was reported recently (Suckert et al., 2015b[Suckert, S., Wöhlert, S., Jess, I. & Näther, C. (2015b). Acta Cryst. E71, m242-m243.]). For the structures of other metal thio­cyanates with 2,5-di­methyl­pyrazine or 2,6-di­methyl­pyrazine, see: Otieno et al. (2003[Otieno, T., Blanton, J. R., Lanham, K. J. & Parkin, S. (2003). J. Chem. Crystallogr. 33, 335-339.]); Mahmoudi & Morsali (2009[Mahmoudi, G. & Morsali, A. (2009). CrystEngComm, 11, 1868-1879.]); Suckert et al. (2015a[Suckert, S., Wöhlert, S., Jess, I. & Näther, C. (2015a). Acta Cryst. E71, m223-m224.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Co(NCS)2(C6H8N2)2(H2O)2]·C6H8N2

  • Mr = 751.84

  • Triclinic, [P \overline 1]

  • a = 9.3296 (8) Å

  • b = 10.8407 (8) Å

  • c = 11.3906 (9) Å

  • α = 103.231 (9)°

  • β = 111.888 (9)°

  • γ = 104.123 (9)°

  • V = 968.99 (15) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.60 mm−1

  • T = 200 K

  • 0.17 × 0.13 × 0.06 mm

2.2. Data collection

  • Stoe IPDS-1 diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.909, Tmax = 0.963

  • 8838 measured reflections

  • 4092 independent reflections

  • 3540 reflections with I > 2σ(I)

  • Rint = 0.049

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.130

  • S = 1.05

  • 4092 reflections

  • 228 parameters

  • H-atom parameters constrained

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.79 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O1⋯N30 0.82 1.98 2.796 (2) 172
O1—H2O1⋯N40i 0.82 2.00 2.816 (2) 174
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe, 2008[Stoe (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: SHELXL2013 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. A71, 3-8.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). 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


Synthesis and crystallization top

Co(SCN)2 and 2,5-di­methyl­pyrazine (97%) were purchased from Alfa Aesar. The title compound was prepared by the reaction of 28.9 mg (0.15 mmol) Co(NCS)2·H2O in 195.0 µl (1.8 mmol) 2,5-di­methyl­pyrazine at room temperature. After a few days, plate-like crystals of the title compound were obtained that contained 2,6-di­methyl­pyrazine in addition. Later it was found that the commercially available 2,5-di­methyl­pyrazine contains about 3%wt of 2,6-di­methyl­pyrazine as a contamination.

Refinement top

C-bound hydrogen atoms were positioned with idealized geometry (methyl H atoms were allowed to rotate but not to tip) and were refined with Ueq(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic H atoms and C—H = 0.98 Å for methyl H atoms. The O-bound hydrogen atoms were located in a difference map. The O—H bond length was constrained to 0.84 Å and H atoms were refined with Uiso(H) = 1.5Ueq(O) using a riding model.

Related literature top

The crystal structure of the 2,5-dimethylpyrazine monosolvate of the title compound was reported recently (Suckert et al., 2015b). For the structures of other metal thiocyanates with 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi et al. (2009); Suckert et al. (2015a).

Structure description top

The crystal structure of the 2,5-dimethylpyrazine monosolvate of the title compound was reported recently (Suckert et al., 2015b). For the structures of other metal thiocyanates with 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi et al. (2009); Suckert et al. (2015a).

Synthesis and crystallization top

Co(SCN)2 and 2,5-di­methyl­pyrazine (97%) were purchased from Alfa Aesar. The title compound was prepared by the reaction of 28.9 mg (0.15 mmol) Co(NCS)2·H2O in 195.0 µl (1.8 mmol) 2,5-di­methyl­pyrazine at room temperature. After a few days, plate-like crystals of the title compound were obtained that contained 2,6-di­methyl­pyrazine in addition. Later it was found that the commercially available 2,5-di­methyl­pyrazine contains about 3%wt of 2,6-di­methyl­pyrazine as a contamination.

Refinement details top

C-bound hydrogen atoms were positioned with idealized geometry (methyl H atoms were allowed to rotate but not to tip) and were refined with Ueq(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic H atoms and C—H = 0.98 Å for methyl H atoms. The O-bound hydrogen atoms were located in a difference map. The O—H bond length was constrained to 0.84 Å and H atoms were refined with Uiso(H) = 1.5Ueq(O) using a riding model.

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The structures of the molecular entities of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x + 1, y + 1, -z + 1; (ii) -x + 1, -y + 1, -z; (iii) -x + 1, -y + 2, -z + 1; (iv) -x + 1, -y + 1, -z + 2.]
[Figure 2] Fig. 2. The crystal packing of the title compound in a view along [100]. Hydrogen bonding is shown as dashed lines.
Diaquabis(2,6-dimethylpyrazine-κN)bis(thiocyanato-κN)cobalt(II) 2,5-dimethylpyrazine trisolvate top
Crystal data top
[Co(NCS)2(C6H8N2)2(H2O)2]·C6H8N2Z = 1
Mr = 751.84F(000) = 395
Triclinic, P1Dx = 1.288 Mg m3
a = 9.3296 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.8407 (8) ÅCell parameters from 8844 reflections
c = 11.3906 (9) Åθ = 2.6–22.0°
α = 103.231 (9)°µ = 0.60 mm1
β = 111.888 (9)°T = 200 K
γ = 104.123 (9)°Plate, purple
V = 968.99 (15) Å30.17 × 0.13 × 0.06 mm
Data collection top
Stoe IPDS-1
diffractometer
3540 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.049
phi scansθmax = 27.4°, θmin = 2.6°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
h = 1111
Tmin = 0.909, Tmax = 0.963k = 1313
8838 measured reflectionsl = 1414
4092 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.130 w = 1/[σ2(Fo2) + (0.0772P)2 + 0.2726P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.032
4092 reflectionsΔρmax = 0.37 e Å3
228 parametersΔρmin = 0.79 e Å3
Crystal data top
[Co(NCS)2(C6H8N2)2(H2O)2]·C6H8N2γ = 104.123 (9)°
Mr = 751.84V = 968.99 (15) Å3
Triclinic, P1Z = 1
a = 9.3296 (8) ÅMo Kα radiation
b = 10.8407 (8) ŵ = 0.60 mm1
c = 11.3906 (9) ÅT = 200 K
α = 103.231 (9)°0.17 × 0.13 × 0.06 mm
β = 111.888 (9)°
Data collection top
Stoe IPDS-1
diffractometer
4092 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
3540 reflections with I > 2σ(I)
Tmin = 0.909, Tmax = 0.963Rint = 0.049
8838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 1.05Δρmax = 0.37 e Å3
4092 reflectionsΔρmin = 0.79 e Å3
228 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.50000.50000.50000.02727 (14)
N10.4584 (2)0.32856 (19)0.34740 (18)0.0352 (4)
C10.4289 (3)0.2251 (2)0.2698 (2)0.0337 (4)
S10.38697 (12)0.08006 (6)0.15982 (8)0.0628 (2)
N100.2366 (2)0.47166 (18)0.40932 (18)0.0339 (4)
C100.1832 (3)0.5739 (2)0.4318 (2)0.0351 (4)
H100.26160.66180.49270.042*
C110.0166 (3)0.5558 (3)0.3691 (2)0.0397 (5)
C120.0429 (3)0.3307 (3)0.2646 (3)0.0492 (6)
C130.1238 (3)0.3506 (2)0.3258 (2)0.0416 (5)
H130.15790.27570.30730.050*
C140.0406 (3)0.6725 (3)0.3916 (3)0.0533 (6)
H14A0.06930.69930.31180.080*
H14B0.04830.74960.47100.080*
H14C0.13840.64510.40690.080*
C150.1686 (4)0.1922 (4)0.1715 (4)0.0830 (12)
H15A0.25000.16540.20470.125*
H15B0.11290.12650.16840.125*
H15C0.22520.19390.08040.125*
N110.0949 (2)0.4341 (2)0.2867 (2)0.0482 (5)
C200.8651 (3)0.4951 (3)0.9060 (3)0.0539 (7)
H200.76630.49360.83810.065*
N200.8981 (3)0.3820 (3)0.8896 (2)0.0532 (6)
C241.0768 (4)0.2597 (4)0.9700 (4)0.0691 (8)
H24A0.97860.18150.94600.104*
H24B1.16710.27021.05540.104*
H24C1.11150.24480.89820.104*
N300.5186 (3)0.87945 (19)0.4487 (2)0.0425 (4)
C300.3732 (3)0.8941 (2)0.4031 (2)0.0431 (5)
H300.27880.81920.33290.052*
C310.3532 (3)1.0149 (2)0.4541 (2)0.0423 (5)
C211.0360 (3)0.3855 (3)0.9857 (3)0.0515 (6)
C340.1905 (4)1.0312 (3)0.4020 (4)0.0596 (7)
H34A0.13211.00320.45290.089*
H34B0.12410.97430.30590.089*
H34C0.20761.12670.41260.089*
N400.4624 (3)0.4506 (2)0.86521 (18)0.0390 (4)
C400.4770 (3)0.5764 (2)0.9248 (2)0.0398 (5)
H400.46100.63330.87260.048*
C410.5148 (3)0.6284 (2)1.0603 (2)0.0369 (4)
C440.5314 (4)0.7707 (3)1.1266 (3)0.0566 (7)
H44A0.43220.76901.13840.085*
H44B0.54340.82401.06970.085*
H44C0.62940.81221.21520.085*
O10.5467 (2)0.62397 (14)0.39186 (14)0.0351 (3)
H1O10.54510.70090.40590.053*
H2O10.54810.59920.31920.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0321 (2)0.02219 (19)0.0215 (2)0.00973 (14)0.00805 (14)0.00454 (14)
N10.0432 (9)0.0284 (8)0.0262 (8)0.0120 (7)0.0122 (7)0.0035 (7)
C10.0383 (10)0.0302 (10)0.0301 (10)0.0121 (8)0.0140 (8)0.0094 (8)
S10.0962 (6)0.0294 (3)0.0568 (4)0.0147 (3)0.0435 (4)0.0014 (3)
N100.0333 (8)0.0325 (9)0.0306 (8)0.0121 (7)0.0091 (7)0.0114 (7)
C100.0354 (10)0.0360 (10)0.0334 (10)0.0142 (8)0.0129 (8)0.0145 (9)
C110.0358 (10)0.0493 (13)0.0389 (11)0.0175 (9)0.0186 (9)0.0196 (10)
C120.0354 (11)0.0461 (13)0.0484 (14)0.0073 (10)0.0107 (10)0.0086 (11)
C130.0364 (11)0.0353 (11)0.0411 (12)0.0093 (9)0.0104 (9)0.0094 (9)
C140.0482 (13)0.0617 (16)0.0614 (16)0.0317 (12)0.0263 (12)0.0268 (14)
C150.0432 (15)0.0558 (18)0.094 (3)0.0011 (13)0.0064 (16)0.0079 (18)
N110.0344 (9)0.0547 (12)0.0478 (11)0.0135 (9)0.0140 (8)0.0158 (10)
C200.0376 (12)0.0704 (18)0.0329 (12)0.0066 (12)0.0059 (9)0.0141 (12)
N200.0433 (11)0.0593 (14)0.0330 (10)0.0024 (10)0.0077 (8)0.0089 (10)
C240.0691 (19)0.072 (2)0.0572 (18)0.0237 (16)0.0231 (15)0.0190 (16)
N300.0653 (12)0.0271 (8)0.0355 (10)0.0184 (9)0.0236 (9)0.0090 (8)
C300.0606 (14)0.0251 (9)0.0374 (11)0.0145 (9)0.0182 (10)0.0084 (9)
C310.0601 (14)0.0296 (10)0.0404 (12)0.0175 (10)0.0249 (11)0.0132 (9)
C210.0431 (12)0.0624 (16)0.0350 (12)0.0073 (11)0.0122 (10)0.0154 (11)
C340.0575 (15)0.0407 (13)0.078 (2)0.0197 (12)0.0283 (15)0.0200 (14)
N400.0508 (10)0.0414 (10)0.0277 (8)0.0217 (8)0.0174 (8)0.0128 (8)
C400.0538 (12)0.0402 (11)0.0320 (11)0.0226 (10)0.0205 (9)0.0164 (9)
C410.0453 (11)0.0369 (11)0.0309 (10)0.0178 (9)0.0178 (9)0.0123 (9)
C440.090 (2)0.0413 (13)0.0464 (14)0.0312 (14)0.0351 (14)0.0140 (12)
O10.0549 (9)0.0257 (7)0.0277 (7)0.0181 (6)0.0194 (6)0.0101 (6)
Geometric parameters (Å, º) top
Co1—N1i2.0718 (18)N20—C211.327 (4)
Co1—N12.0718 (18)C24—C211.494 (5)
Co1—O12.0942 (15)C24—H24A0.9800
Co1—O1i2.0942 (15)C24—H24B0.9800
Co1—N10i2.1895 (18)C24—H24C0.9800
Co1—N102.1895 (18)N30—C31iii1.316 (3)
N1—C11.153 (3)N30—C301.324 (4)
C1—S11.621 (2)C30—C311.393 (3)
N10—C131.320 (3)C30—H300.9500
N10—C101.333 (3)C31—N30iii1.316 (3)
C10—C111.387 (3)C31—C341.481 (4)
C10—H100.9500C21—C20ii1.373 (4)
C11—N111.320 (3)C34—H34A0.9800
C11—C141.494 (4)C34—H34B0.9800
C12—N111.335 (4)C34—H34C0.9800
C12—C131.382 (3)N40—C401.326 (3)
C12—C151.497 (4)N40—C41iv1.336 (3)
C13—H130.9500C40—C411.386 (3)
C14—H14A0.9800C40—H400.9500
C14—H14B0.9800C41—N40iv1.336 (3)
C14—H14C0.9800C41—C441.495 (3)
C15—H15A0.9800C44—H44A0.9800
C15—H15B0.9800C44—H44B0.9800
C15—H15C0.9800C44—H44C0.9800
C20—N201.325 (4)O1—H1O10.8175
C20—C21ii1.373 (4)O1—H2O10.8152
C20—H200.9500
N1i—Co1—N1180.0C11—N11—C12118.4 (2)
N1i—Co1—O188.87 (7)N20—C20—C21ii124.4 (3)
N1—Co1—O191.13 (7)N20—C20—H20117.8
N1i—Co1—O1i91.13 (7)C21ii—C20—H20117.8
N1—Co1—O1i88.87 (7)C20—N20—C21117.1 (2)
O1—Co1—O1i180.0C21—C24—H24A109.5
N1i—Co1—N10i91.60 (7)C21—C24—H24B109.5
N1—Co1—N10i88.40 (7)H24A—C24—H24B109.5
O1—Co1—N10i88.71 (7)C21—C24—H24C109.5
O1i—Co1—N10i91.29 (7)H24A—C24—H24C109.5
N1i—Co1—N1088.40 (7)H24B—C24—H24C109.5
N1—Co1—N1091.60 (7)C31iii—N30—C30117.2 (2)
O1—Co1—N1091.29 (7)N30—C30—C31122.6 (2)
O1i—Co1—N1088.71 (7)N30—C30—H30118.7
N10i—Co1—N10180.0C31—C30—H30118.7
C1—N1—Co1172.52 (19)N30iii—C31—C30120.3 (2)
N1—C1—S1179.6 (2)N30iii—C31—C34117.4 (2)
C13—N10—C10117.27 (19)C30—C31—C34122.4 (2)
C13—N10—Co1120.17 (16)N20—C21—C20ii118.5 (3)
C10—N10—Co1122.53 (14)N20—C21—C24118.3 (3)
N10—C10—C11122.0 (2)C20ii—C21—C24123.2 (3)
N10—C10—H10119.0C31—C34—H34A109.5
C11—C10—H10119.0C31—C34—H34B109.5
N11—C11—C10120.1 (2)H34A—C34—H34B109.5
N11—C11—C14118.6 (2)C31—C34—H34C109.5
C10—C11—C14121.3 (2)H34A—C34—H34C109.5
N11—C12—C13121.0 (2)H34B—C34—H34C109.5
N11—C12—C15118.8 (2)C40—N40—C41iv118.11 (19)
C13—C12—C15120.3 (3)N40—C40—C41122.6 (2)
N10—C13—C12121.3 (2)N40—C40—H40118.7
N10—C13—H13119.3C41—C40—H40118.7
C12—C13—H13119.3N40iv—C41—C40119.3 (2)
C11—C14—H14A109.5N40iv—C41—C44118.5 (2)
C11—C14—H14B109.5C40—C41—C44122.2 (2)
H14A—C14—H14B109.5C41—C44—H44A109.5
C11—C14—H14C109.5C41—C44—H44B109.5
H14A—C14—H14C109.5H44A—C44—H44B109.5
H14B—C14—H14C109.5C41—C44—H44C109.5
C12—C15—H15A109.5H44A—C44—H44C109.5
C12—C15—H15B109.5H44B—C44—H44C109.5
H15A—C15—H15B109.5Co1—O1—H1O1125.2
C12—C15—H15C109.5Co1—O1—H2O1126.2
H15A—C15—H15C109.5H1O1—O1—H2O1107.2
H15B—C15—H15C109.5
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+2; (iii) x+1, y+2, z+1; (iv) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N300.821.982.796 (2)172
O1—H2O1···N40i0.822.002.816 (2)174
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N300.821.982.796 (2)172.2
O1—H2O1···N40i0.822.002.816 (2)174.2
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

This project was supported by the Deutsche Forschungsgemeinschaft (project No. Na 720/5-1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

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