Crystal structure of di­aqua­bis­(2,6-di­methyl­pyrazine-κN4)bis­(thio­cyanato-κN)cobalt(II) 2,5-di­methyl­pyrazine monosolvate

Suckert, S.; Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S2056989015021829

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m242-m243

https://doi.org/10.1107/S2056989015021829

Open

access

Crystal structure of diaquabis(2,6-dimethylpyrazine-κN⁴)bis(thiocyanato-κN)cobalt(II) 2,5-dimethylpyrazine monosolvate

Stefan Suckert,^a ^* Susanne Wöhlert,^a Inke Jess ^a and Christian Näther ^a

^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 11 November 2015; accepted 16 November 2015; online 6 December 2015)

In the crystal structure of the title compound, [Co(NCS)₂(C₆H₈N₂)₂(H₂O)₂]·C₆H₈N₂, the Co^II cation is coordinated by the N atoms of two terminal thiocyanate anions, the O atoms of two water molecules and two N atoms of two 2,6-dimethylpyrazine ligands. The coordination sphere of the resulting discrete complex is that of a slightly distorted octahedron. The asymmetric unit comprises a Co^II cation and half of a 2,5-dimethylpyrazine ligand, both of which are located on centres of inversion, and a water ligand, a 2,6-dimethylpyrazine ligand and one thiocyanate anion in general positions. In the crystal, the discrete complexes are arranged in such a way that cavities are formed in which the 2,5-dimethylpyrazine solvent molecules are located. The coordination of the 2,5-dimethylpyrazine molecules to the metal is apparently hindered due to the bulky methyl groups in vicinal positions to the N atoms, leading to a preferential coordination of the 2,6-dimethylpyrazine ligands. The discrete complexes are linked by O—H⋯N hydrogen bonds between one water H atom and the non-coordinating N atom of the 2,6-dimethylpyrazine ligands. The remaining water H atom is hydrogen bonded to one N atom of the 2,5-dimethylpyrazine solvent molecule. This arrangement leads to the formation of a two-dimensional network extending parallel to (010).

Keywords: crystal structure; coordination polymer; octahedral coordination; cobalt(II).

CCDC reference: 1437251

1. Related literature

For structures with metal thiocyanates and 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003 ); Mahmoudi & Morsali (2009 ).

2. Experimental

2.1. Crystal data

[Co(NCS)₂(C₆H₈N₂)₂(H₂O)₂]·C₆H₈N₂
M_r = 535.55
Triclinic, $[P \overline 1]$
a = 8.3009 (4) Å
b = 9.0466 (5) Å
c = 10.4200 (6) Å
α = 96.640 (4)°
β = 105.820 (4)°
γ = 116.070 (4)°
V = 650.68 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 293 K
0.15 × 0.08 × 0.04 mm

2.2. Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.868, T_max = 0.959
10848 measured reflections
3447 independent reflections
3175 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.097
S = 1.05
3447 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2O1⋯N20	0.82	2.01	2.8193 (17)	172
O1—H1O1⋯N10ⁱ	0.82	2.01	2.8257 (15)	173
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: 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: 1437251

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015021829/wm5240sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015021829/wm5240Isup2.hkl

checkCIF report

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 57.9 mg (0.33 mmol) Co(SCN)₂ and 140.0 µl 2,5-dimethylpyrazine (1.28 mmol) in 1.0 ml water at 393 K. After few days block-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% of 2,6-dimethylpyrazine as a contamination.

Refinement top

The carbon-bound H atoms were positioned with idealized geometry (methyl H atoms were allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.93 Å for aromatic and C—H = 0.96 Å for methyl H atoms. The oxygen-bound H atoms were located in a difference map. The O—H bond length was constrained to 0.82 Å, with U_iso(H) = 1.5U_eq(O) using a riding model.

Related literature top

For structures with metal thiocyanates and 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi & Morsali (2009).

Structure description top

For structures with metal thiocyanates and 2,5-dimethylpyrazine or 2,6-dimethylpyrazine, see: Otieno et al. (2003); Mahmoudi & Morsali (2009).

Synthesis and crystallization top

Refinement details top

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: 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

	Fig. 1. The molecular components in the crystal structure 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.]
	Fig. 2. Crystal structure of the title compound in a view along [010]. O—H···N hydrogen bonding is shown as dashed lines.

Diaquabis(2,6-dimethylpyrazine-κN⁴)bis(thiocyanato-κN)cobalt(II) 2,5-dimethylpyrazine monosolvate top

Crystal data top

[Co(NCS)₂(C₆H₈N₂)₂(H₂O)₂]·C₆H₈N₂	Z = 1
M_r = 535.55	F(000) = 279
Triclinic, P1	D_x = 1.367 Mg m⁻³
a = 8.3009 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0466 (5) Å	Cell parameters from 10848 reflections
c = 10.4200 (6) Å	θ = 2.1–29.2°
α = 96.640 (4)°	µ = 0.85 mm⁻¹
β = 105.820 (4)°	T = 293 K
γ = 116.070 (4)°	Block, purple
V = 650.68 (7) Å³	0.15 × 0.08 × 0.04 mm

Data collection top

Stoe IPDS-2 diffractometer	3175 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
ω scans	θ_max = 29.2°, θ_min = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −11→11
T_min = 0.868, T_max = 0.959	k = −12→12
10848 measured reflections	l = −14→14
3447 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0528P)² + 0.1118P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3447 reflections	Δρ_max = 0.43 e Å⁻³
154 parameters	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Co(NCS)₂(C₆H₈N₂)₂(H₂O)₂]·C₆H₈N₂	γ = 116.070 (4)°
M_r = 535.55	V = 650.68 (7) Å³
Triclinic, P1	Z = 1
a = 8.3009 (4) Å	Mo Kα radiation
b = 9.0466 (5) Å	µ = 0.85 mm⁻¹
c = 10.4200 (6) Å	T = 293 K
α = 96.640 (4)°	0.15 × 0.08 × 0.04 mm
β = 105.820 (4)°

Data collection top

Stoe IPDS-2 diffractometer	3447 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	3175 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.959	R_int = 0.031
10848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.43 e Å⁻³
3447 reflections	Δρ_min = −0.39 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.5000	0.04299 (10)
N1	0.3328 (2)	0.26365 (19)	0.35238 (16)	0.0590 (3)
C1	0.2857 (2)	0.1399 (2)	0.27093 (18)	0.0558 (4)
S1	0.23050 (11)	−0.02995 (8)	0.15745 (7)	0.0943 (2)
N10	−0.05473 (17)	0.39022 (16)	0.65466 (14)	0.0467 (3)
C10	−0.0663 (2)	0.27462 (19)	0.55572 (16)	0.0476 (3)
C11	0.0930 (2)	0.30432 (19)	0.51972 (16)	0.0470 (3)
H11	0.0815	0.2212	0.4508	0.056*
C12	0.2717 (2)	0.5600 (2)	0.68289 (16)	0.0496 (3)
H12	0.3881	0.6602	0.7301	0.059*
C13	0.1150 (2)	0.5321 (2)	0.72101 (16)	0.0472 (3)
C14	−0.2559 (3)	0.1149 (2)	0.4835 (2)	0.0718 (5)
H14A	−0.3458	0.1151	0.5251	0.108*
H14B	−0.2400	0.0171	0.4918	0.108*
H14C	−0.3038	0.1098	0.3873	0.108*
C15	0.1285 (3)	0.6597 (3)	0.8350 (2)	0.0706 (5)
H15A	0.0349	0.6942	0.7993	0.106*
H15B	0.2551	0.7579	0.8702	0.106*
H15C	0.1043	0.6087	0.9083	0.106*
N11	0.26138 (16)	0.44839 (16)	0.58104 (13)	0.0451 (3)
N20	0.4442 (3)	0.5506 (2)	0.10190 (16)	0.0667 (4)
C20	0.5941 (3)	0.6633 (3)	0.07748 (19)	0.0653 (4)
C21	0.6487 (3)	0.6097 (3)	−0.0256 (2)	0.0676 (5)
H21	0.7542	0.6894	−0.0414	0.081*
C24	0.7003 (5)	0.8448 (3)	0.1628 (3)	0.1000 (9)
H24A	0.6111	0.8861	0.1601	0.150*
H24B	0.7935	0.9135	0.1263	0.150*
H24C	0.7647	0.8517	0.2569	0.150*
O1	0.40223 (16)	0.61584 (16)	0.35860 (12)	0.0560 (3)
H1O1	0.2978	0.6105	0.3470	0.084*
H2O1	0.4074	0.6011	0.2810	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03641 (14)	0.05128 (17)	0.04350 (15)	0.02088 (11)	0.02181 (10)	0.00580 (10)
N1	0.0497 (7)	0.0613 (8)	0.0578 (8)	0.0190 (6)	0.0283 (6)	0.0010 (6)
C1	0.0474 (7)	0.0589 (9)	0.0522 (8)	0.0181 (6)	0.0230 (6)	0.0064 (7)
S1	0.1115 (5)	0.0684 (3)	0.0760 (4)	0.0327 (3)	0.0290 (3)	−0.0124 (3)
N10	0.0437 (6)	0.0543 (7)	0.0542 (7)	0.0274 (5)	0.0288 (5)	0.0168 (5)
C10	0.0441 (6)	0.0505 (7)	0.0552 (8)	0.0230 (6)	0.0282 (6)	0.0152 (6)
C11	0.0457 (7)	0.0508 (7)	0.0521 (7)	0.0248 (6)	0.0279 (6)	0.0115 (6)
C12	0.0398 (6)	0.0572 (8)	0.0516 (7)	0.0225 (6)	0.0214 (6)	0.0083 (6)
C13	0.0462 (7)	0.0567 (8)	0.0486 (7)	0.0293 (6)	0.0250 (6)	0.0123 (6)
C14	0.0537 (9)	0.0600 (10)	0.0881 (14)	0.0129 (8)	0.0396 (9)	0.0031 (9)
C15	0.0662 (10)	0.0745 (12)	0.0702 (11)	0.0334 (9)	0.0348 (9)	−0.0027 (9)
N11	0.0396 (5)	0.0555 (7)	0.0479 (6)	0.0256 (5)	0.0235 (5)	0.0131 (5)
N20	0.0921 (11)	0.0828 (10)	0.0545 (8)	0.0558 (9)	0.0451 (8)	0.0220 (7)
C20	0.0919 (13)	0.0714 (11)	0.0511 (9)	0.0488 (10)	0.0364 (9)	0.0185 (8)
C21	0.0838 (12)	0.0782 (12)	0.0593 (10)	0.0441 (10)	0.0434 (9)	0.0228 (9)
C24	0.141 (2)	0.0768 (15)	0.0808 (16)	0.0478 (16)	0.0543 (17)	0.0092 (12)
O1	0.0550 (6)	0.0824 (8)	0.0515 (6)	0.0436 (6)	0.0317 (5)	0.0194 (5)

Geometric parameters (Å, º) top

Co1—N1ⁱ	2.0812 (15)	C14—H14A	0.9600
Co1—N1	2.0812 (15)	C14—H14B	0.9600
Co1—O1	2.0930 (12)	C14—H14C	0.9600
Co1—O1ⁱ	2.0930 (12)	C15—H15A	0.9600
Co1—N11	2.2460 (11)	C15—H15B	0.9600
Co1—N11ⁱ	2.2460 (11)	C15—H15C	0.9600
N1—C1	1.158 (2)	N20—C21ⁱⁱ	1.322 (3)
C1—S1	1.6232 (18)	N20—C20	1.330 (3)
N10—C10	1.3321 (19)	C20—C21	1.389 (2)
N10—C13	1.336 (2)	C20—C24	1.493 (3)
C10—C11	1.3935 (18)	C21—N20ⁱⁱ	1.322 (3)
C10—C14	1.495 (2)	C21—H21	0.9300
C11—N11	1.3343 (18)	C24—H24A	0.9600
C11—H11	0.9300	C24—H24B	0.9600
C12—N11	1.3342 (18)	C24—H24C	0.9600
C12—C13	1.3893 (18)	O1—H1O1	0.8201
C12—H12	0.9300	O1—H2O1	0.8200
C13—C15	1.501 (2)

N1ⁱ—Co1—N1	180.00 (9)	C10—C14—H14B	109.5
N1ⁱ—Co1—O1	89.38 (6)	H14A—C14—H14B	109.5
N1—Co1—O1	90.62 (6)	C10—C14—H14C	109.5
N1ⁱ—Co1—O1ⁱ	90.62 (6)	H14A—C14—H14C	109.5
N1—Co1—O1ⁱ	89.38 (6)	H14B—C14—H14C	109.5
O1—Co1—O1ⁱ	180.0	C13—C15—H15A	109.5
N1ⁱ—Co1—N11	88.99 (5)	C13—C15—H15B	109.5
N1—Co1—N11	91.01 (5)	H15A—C15—H15B	109.5
O1—Co1—N11	92.08 (4)	C13—C15—H15C	109.5
O1ⁱ—Co1—N11	87.92 (4)	H15A—C15—H15C	109.5
N1ⁱ—Co1—N11ⁱ	91.01 (5)	H15B—C15—H15C	109.5
N1—Co1—N11ⁱ	88.99 (5)	C12—N11—C11	116.38 (12)
O1—Co1—N11ⁱ	87.92 (4)	C12—N11—Co1	123.72 (10)
O1ⁱ—Co1—N11ⁱ	92.08 (4)	C11—N11—Co1	119.73 (9)
N11—Co1—N11ⁱ	180.0	C21ⁱⁱ—N20—C20	118.15 (15)
C1—N1—Co1	162.42 (13)	N20—C20—C21	119.60 (19)
N1—C1—S1	177.21 (15)	N20—C20—C24	118.75 (18)
C10—N10—C13	118.09 (12)	C21—C20—C24	121.6 (2)
N10—C10—C11	120.65 (14)	N20ⁱⁱ—C21—C20	122.25 (19)
N10—C10—C14	117.78 (13)	N20ⁱⁱ—C21—H21	118.9
C11—C10—C14	121.56 (15)	C20—C21—H21	118.9
N11—C11—C10	122.01 (13)	C20—C24—H24A	109.5
N11—C11—H11	119.0	C20—C24—H24B	109.5
C10—C11—H11	119.0	H24A—C24—H24B	109.5
N11—C12—C13	122.41 (14)	C20—C24—H24C	109.5
N11—C12—H12	118.8	H24A—C24—H24C	109.5
C13—C12—H12	118.8	H24B—C24—H24C	109.5
N10—C13—C12	120.37 (14)	Co1—O1—H1O1	119.4
N10—C13—C15	117.87 (13)	Co1—O1—H2O1	120.2
C12—C13—C15	121.76 (15)	H1O1—O1—H2O1	105.4
C10—C14—H14A	109.5

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O1···N20	0.82	2.01	2.8193 (17)	172
O1—H1O1···N10ⁱⁱⁱ	0.82	2.01	2.8257 (15)	173

Symmetry code: (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O1···N20	0.82	2.01	2.8193 (17)	171.7
O1—H1O1···N10ⁱ	0.82	2.01	2.8257 (15)	172.6

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

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

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Mahmoudi, G. & Morsali, A. (2009). CrystEngComm, 11, 1868–1879. Web of Science CSD CrossRef CAS Google Scholar
Otieno, T., Blanton, J. R., Lanham, K. J. & Parkin, S. (2003). J. Chem. Crystallogr. 33, 335–339. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m242-m243

https://doi.org/10.1107/S2056989015021829

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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