metal-organic compounds
κN)bis(thiocyanato-κN)cobalt(II) 2,5-dimethylpyrazine trisolvate
of diaquabis(2,6-dimethylpyrazine-aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: ssuckert@ac.uni-kiel.de
In the 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 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).
of the title compound, [Co(NCS)Keywords: crystal structure; coordination compound; octahedral coordination; cobalt(II); dimethylpyrazine.
CCDC reference: 1442780
1. Related literature
The et al., 2015b). For the structures of other metal thiocyanates with 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi & Morsali (2009); Suckert et al. (2015a).
of the 2,5-dimethylpyrazine monosolvate of the title compound was reported recently (Suckert2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: X-AREA (Stoe, 2008); cell X-AREA; data reduction: X-AREA; 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).
Supporting information
CCDC reference: 1442780
https://doi.org/10.1107/S2056989015024184/wm5255sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015024184/wm5255Isup2.hkl
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.
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.
The
of the 2,5-dimethylpyrazine monosolvate of the title compound was reported recently (Suckert et al., 2015b). For the structures of other metal with 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi et al. (2009); Suckert et al. (2015a).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.
detailsC-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.
Data collection: X-AREA (Stoe, 2008); cell
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).[Co(NCS)2(C6H8N2)2(H2O)2]·C6H8N2 | Z = 1 |
Mr = 751.84 | F(000) = 395 |
Triclinic, P1 | Dx = 1.288 Mg m−3 |
a = 9.3296 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.8407 (8) Å | Cell parameters from 8844 reflections |
c = 11.3906 (9) Å | θ = 2.6–22.0° |
α = 103.231 (9)° | µ = 0.60 mm−1 |
β = 111.888 (9)° | T = 200 K |
γ = 104.123 (9)° | Plate, purple |
V = 968.99 (15) Å3 | 0.17 × 0.13 × 0.06 mm |
Stoe IPDS-1 diffractometer | 3540 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.049 |
phi scans | θmax = 27.4°, θmin = 2.6° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008) | h = −11→11 |
Tmin = 0.909, Tmax = 0.963 | k = −13→13 |
8838 measured reflections | l = −14→14 |
4092 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H-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 reflections | Δρmax = 0.37 e Å−3 |
228 parameters | Δρmin = −0.79 e Å−3 |
[Co(NCS)2(C6H8N2)2(H2O)2]·C6H8N2 | γ = 104.123 (9)° |
Mr = 751.84 | V = 968.99 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.3296 (8) Å | Mo Kα radiation |
b = 10.8407 (8) Å | µ = 0.60 mm−1 |
c = 11.3906 (9) Å | T = 200 K |
α = 103.231 (9)° | 0.17 × 0.13 × 0.06 mm |
β = 111.888 (9)° |
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 = 0.963 | Rint = 0.049 |
8838 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.37 e Å−3 |
4092 reflections | Δρmin = −0.79 e Å−3 |
228 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.5000 | 0.5000 | 0.5000 | 0.02727 (14) | |
N1 | 0.4584 (2) | 0.32856 (19) | 0.34740 (18) | 0.0352 (4) | |
C1 | 0.4289 (3) | 0.2251 (2) | 0.2698 (2) | 0.0337 (4) | |
S1 | 0.38697 (12) | 0.08006 (6) | 0.15982 (8) | 0.0628 (2) | |
N10 | 0.2366 (2) | 0.47166 (18) | 0.40932 (18) | 0.0339 (4) | |
C10 | 0.1832 (3) | 0.5739 (2) | 0.4318 (2) | 0.0351 (4) | |
H10 | 0.2616 | 0.6618 | 0.4927 | 0.042* | |
C11 | 0.0166 (3) | 0.5558 (3) | 0.3691 (2) | 0.0397 (5) | |
C12 | −0.0429 (3) | 0.3307 (3) | 0.2646 (3) | 0.0492 (6) | |
C13 | 0.1238 (3) | 0.3506 (2) | 0.3258 (2) | 0.0416 (5) | |
H13 | 0.1579 | 0.2757 | 0.3073 | 0.050* | |
C14 | −0.0406 (3) | 0.6725 (3) | 0.3916 (3) | 0.0533 (6) | |
H14A | −0.0693 | 0.6993 | 0.3118 | 0.080* | |
H14B | 0.0483 | 0.7496 | 0.4710 | 0.080* | |
H14C | −0.1384 | 0.6451 | 0.4069 | 0.080* | |
C15 | −0.1686 (4) | 0.1922 (4) | 0.1715 (4) | 0.0830 (12) | |
H15A | −0.2500 | 0.1654 | 0.2047 | 0.125* | |
H15B | −0.1129 | 0.1265 | 0.1684 | 0.125* | |
H15C | −0.2252 | 0.1939 | 0.0804 | 0.125* | |
N11 | −0.0949 (2) | 0.4341 (2) | 0.2867 (2) | 0.0482 (5) | |
C20 | 0.8651 (3) | 0.4951 (3) | 0.9060 (3) | 0.0539 (7) | |
H20 | 0.7663 | 0.4936 | 0.8381 | 0.065* | |
N20 | 0.8981 (3) | 0.3820 (3) | 0.8896 (2) | 0.0532 (6) | |
C24 | 1.0768 (4) | 0.2597 (4) | 0.9700 (4) | 0.0691 (8) | |
H24A | 0.9786 | 0.1815 | 0.9460 | 0.104* | |
H24B | 1.1671 | 0.2702 | 1.0554 | 0.104* | |
H24C | 1.1115 | 0.2448 | 0.8982 | 0.104* | |
N30 | 0.5186 (3) | 0.87945 (19) | 0.4487 (2) | 0.0425 (4) | |
C30 | 0.3732 (3) | 0.8941 (2) | 0.4031 (2) | 0.0431 (5) | |
H30 | 0.2788 | 0.8192 | 0.3329 | 0.052* | |
C31 | 0.3532 (3) | 1.0149 (2) | 0.4541 (2) | 0.0423 (5) | |
C21 | 1.0360 (3) | 0.3855 (3) | 0.9857 (3) | 0.0515 (6) | |
C34 | 0.1905 (4) | 1.0312 (3) | 0.4020 (4) | 0.0596 (7) | |
H34A | 0.1321 | 1.0032 | 0.4529 | 0.089* | |
H34B | 0.1241 | 0.9743 | 0.3059 | 0.089* | |
H34C | 0.2076 | 1.1267 | 0.4126 | 0.089* | |
N40 | 0.4624 (3) | 0.4506 (2) | 0.86521 (18) | 0.0390 (4) | |
C40 | 0.4770 (3) | 0.5764 (2) | 0.9248 (2) | 0.0398 (5) | |
H40 | 0.4610 | 0.6333 | 0.8726 | 0.048* | |
C41 | 0.5148 (3) | 0.6284 (2) | 1.0603 (2) | 0.0369 (4) | |
C44 | 0.5314 (4) | 0.7707 (3) | 1.1266 (3) | 0.0566 (7) | |
H44A | 0.4322 | 0.7690 | 1.1384 | 0.085* | |
H44B | 0.5434 | 0.8240 | 1.0697 | 0.085* | |
H44C | 0.6294 | 0.8122 | 1.2152 | 0.085* | |
O1 | 0.5467 (2) | 0.62397 (14) | 0.39186 (14) | 0.0351 (3) | |
H1O1 | 0.5451 | 0.7009 | 0.4059 | 0.053* | |
H2O1 | 0.5481 | 0.5992 | 0.3192 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0321 (2) | 0.02219 (19) | 0.0215 (2) | 0.00973 (14) | 0.00805 (14) | 0.00454 (14) |
N1 | 0.0432 (9) | 0.0284 (8) | 0.0262 (8) | 0.0120 (7) | 0.0122 (7) | 0.0035 (7) |
C1 | 0.0383 (10) | 0.0302 (10) | 0.0301 (10) | 0.0121 (8) | 0.0140 (8) | 0.0094 (8) |
S1 | 0.0962 (6) | 0.0294 (3) | 0.0568 (4) | 0.0147 (3) | 0.0435 (4) | −0.0014 (3) |
N10 | 0.0333 (8) | 0.0325 (9) | 0.0306 (8) | 0.0121 (7) | 0.0091 (7) | 0.0114 (7) |
C10 | 0.0354 (10) | 0.0360 (10) | 0.0334 (10) | 0.0142 (8) | 0.0129 (8) | 0.0145 (9) |
C11 | 0.0358 (10) | 0.0493 (13) | 0.0389 (11) | 0.0175 (9) | 0.0186 (9) | 0.0196 (10) |
C12 | 0.0354 (11) | 0.0461 (13) | 0.0484 (14) | 0.0073 (10) | 0.0107 (10) | 0.0086 (11) |
C13 | 0.0364 (11) | 0.0353 (11) | 0.0411 (12) | 0.0093 (9) | 0.0104 (9) | 0.0094 (9) |
C14 | 0.0482 (13) | 0.0617 (16) | 0.0614 (16) | 0.0317 (12) | 0.0263 (12) | 0.0268 (14) |
C15 | 0.0432 (15) | 0.0558 (18) | 0.094 (3) | −0.0011 (13) | 0.0064 (16) | −0.0079 (18) |
N11 | 0.0344 (9) | 0.0547 (12) | 0.0478 (11) | 0.0135 (9) | 0.0140 (8) | 0.0158 (10) |
C20 | 0.0376 (12) | 0.0704 (18) | 0.0329 (12) | 0.0066 (12) | 0.0059 (9) | 0.0141 (12) |
N20 | 0.0433 (11) | 0.0593 (14) | 0.0330 (10) | 0.0024 (10) | 0.0077 (8) | 0.0089 (10) |
C24 | 0.0691 (19) | 0.072 (2) | 0.0572 (18) | 0.0237 (16) | 0.0231 (15) | 0.0190 (16) |
N30 | 0.0653 (12) | 0.0271 (8) | 0.0355 (10) | 0.0184 (9) | 0.0236 (9) | 0.0090 (8) |
C30 | 0.0606 (14) | 0.0251 (9) | 0.0374 (11) | 0.0145 (9) | 0.0182 (10) | 0.0084 (9) |
C31 | 0.0601 (14) | 0.0296 (10) | 0.0404 (12) | 0.0175 (10) | 0.0249 (11) | 0.0132 (9) |
C21 | 0.0431 (12) | 0.0624 (16) | 0.0350 (12) | 0.0073 (11) | 0.0122 (10) | 0.0154 (11) |
C34 | 0.0575 (15) | 0.0407 (13) | 0.078 (2) | 0.0197 (12) | 0.0283 (15) | 0.0200 (14) |
N40 | 0.0508 (10) | 0.0414 (10) | 0.0277 (8) | 0.0217 (8) | 0.0174 (8) | 0.0128 (8) |
C40 | 0.0538 (12) | 0.0402 (11) | 0.0320 (11) | 0.0226 (10) | 0.0205 (9) | 0.0164 (9) |
C41 | 0.0453 (11) | 0.0369 (11) | 0.0309 (10) | 0.0178 (9) | 0.0178 (9) | 0.0123 (9) |
C44 | 0.090 (2) | 0.0413 (13) | 0.0464 (14) | 0.0312 (14) | 0.0351 (14) | 0.0140 (12) |
O1 | 0.0549 (9) | 0.0257 (7) | 0.0277 (7) | 0.0181 (6) | 0.0194 (6) | 0.0101 (6) |
Co1—N1i | 2.0718 (18) | N20—C21 | 1.327 (4) |
Co1—N1 | 2.0718 (18) | C24—C21 | 1.494 (5) |
Co1—O1 | 2.0942 (15) | C24—H24A | 0.9800 |
Co1—O1i | 2.0942 (15) | C24—H24B | 0.9800 |
Co1—N10i | 2.1895 (18) | C24—H24C | 0.9800 |
Co1—N10 | 2.1895 (18) | N30—C31iii | 1.316 (3) |
N1—C1 | 1.153 (3) | N30—C30 | 1.324 (4) |
C1—S1 | 1.621 (2) | C30—C31 | 1.393 (3) |
N10—C13 | 1.320 (3) | C30—H30 | 0.9500 |
N10—C10 | 1.333 (3) | C31—N30iii | 1.316 (3) |
C10—C11 | 1.387 (3) | C31—C34 | 1.481 (4) |
C10—H10 | 0.9500 | C21—C20ii | 1.373 (4) |
C11—N11 | 1.320 (3) | C34—H34A | 0.9800 |
C11—C14 | 1.494 (4) | C34—H34B | 0.9800 |
C12—N11 | 1.335 (4) | C34—H34C | 0.9800 |
C12—C13 | 1.382 (3) | N40—C40 | 1.326 (3) |
C12—C15 | 1.497 (4) | N40—C41iv | 1.336 (3) |
C13—H13 | 0.9500 | C40—C41 | 1.386 (3) |
C14—H14A | 0.9800 | C40—H40 | 0.9500 |
C14—H14B | 0.9800 | C41—N40iv | 1.336 (3) |
C14—H14C | 0.9800 | C41—C44 | 1.495 (3) |
C15—H15A | 0.9800 | C44—H44A | 0.9800 |
C15—H15B | 0.9800 | C44—H44B | 0.9800 |
C15—H15C | 0.9800 | C44—H44C | 0.9800 |
C20—N20 | 1.325 (4) | O1—H1O1 | 0.8175 |
C20—C21ii | 1.373 (4) | O1—H2O1 | 0.8152 |
C20—H20 | 0.9500 | ||
N1i—Co1—N1 | 180.0 | C11—N11—C12 | 118.4 (2) |
N1i—Co1—O1 | 88.87 (7) | N20—C20—C21ii | 124.4 (3) |
N1—Co1—O1 | 91.13 (7) | N20—C20—H20 | 117.8 |
N1i—Co1—O1i | 91.13 (7) | C21ii—C20—H20 | 117.8 |
N1—Co1—O1i | 88.87 (7) | C20—N20—C21 | 117.1 (2) |
O1—Co1—O1i | 180.0 | C21—C24—H24A | 109.5 |
N1i—Co1—N10i | 91.60 (7) | C21—C24—H24B | 109.5 |
N1—Co1—N10i | 88.40 (7) | H24A—C24—H24B | 109.5 |
O1—Co1—N10i | 88.71 (7) | C21—C24—H24C | 109.5 |
O1i—Co1—N10i | 91.29 (7) | H24A—C24—H24C | 109.5 |
N1i—Co1—N10 | 88.40 (7) | H24B—C24—H24C | 109.5 |
N1—Co1—N10 | 91.60 (7) | C31iii—N30—C30 | 117.2 (2) |
O1—Co1—N10 | 91.29 (7) | N30—C30—C31 | 122.6 (2) |
O1i—Co1—N10 | 88.71 (7) | N30—C30—H30 | 118.7 |
N10i—Co1—N10 | 180.0 | C31—C30—H30 | 118.7 |
C1—N1—Co1 | 172.52 (19) | N30iii—C31—C30 | 120.3 (2) |
N1—C1—S1 | 179.6 (2) | N30iii—C31—C34 | 117.4 (2) |
C13—N10—C10 | 117.27 (19) | C30—C31—C34 | 122.4 (2) |
C13—N10—Co1 | 120.17 (16) | N20—C21—C20ii | 118.5 (3) |
C10—N10—Co1 | 122.53 (14) | N20—C21—C24 | 118.3 (3) |
N10—C10—C11 | 122.0 (2) | C20ii—C21—C24 | 123.2 (3) |
N10—C10—H10 | 119.0 | C31—C34—H34A | 109.5 |
C11—C10—H10 | 119.0 | C31—C34—H34B | 109.5 |
N11—C11—C10 | 120.1 (2) | H34A—C34—H34B | 109.5 |
N11—C11—C14 | 118.6 (2) | C31—C34—H34C | 109.5 |
C10—C11—C14 | 121.3 (2) | H34A—C34—H34C | 109.5 |
N11—C12—C13 | 121.0 (2) | H34B—C34—H34C | 109.5 |
N11—C12—C15 | 118.8 (2) | C40—N40—C41iv | 118.11 (19) |
C13—C12—C15 | 120.3 (3) | N40—C40—C41 | 122.6 (2) |
N10—C13—C12 | 121.3 (2) | N40—C40—H40 | 118.7 |
N10—C13—H13 | 119.3 | C41—C40—H40 | 118.7 |
C12—C13—H13 | 119.3 | N40iv—C41—C40 | 119.3 (2) |
C11—C14—H14A | 109.5 | N40iv—C41—C44 | 118.5 (2) |
C11—C14—H14B | 109.5 | C40—C41—C44 | 122.2 (2) |
H14A—C14—H14B | 109.5 | C41—C44—H44A | 109.5 |
C11—C14—H14C | 109.5 | C41—C44—H44B | 109.5 |
H14A—C14—H14C | 109.5 | H44A—C44—H44B | 109.5 |
H14B—C14—H14C | 109.5 | C41—C44—H44C | 109.5 |
C12—C15—H15A | 109.5 | H44A—C44—H44C | 109.5 |
C12—C15—H15B | 109.5 | H44B—C44—H44C | 109.5 |
H15A—C15—H15B | 109.5 | Co1—O1—H1O1 | 125.2 |
C12—C15—H15C | 109.5 | Co1—O1—H2O1 | 126.2 |
H15A—C15—H15C | 109.5 | H1O1—O1—H2O1 | 107.2 |
H15B—C15—H15C | 109.5 |
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. |
D—H···A | D—H | H···A | D···A | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···N30 | 0.82 | 1.98 | 2.796 (2) | 172.2 |
O1—H2O1···N40i | 0.82 | 2.00 | 2.816 (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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