Crystal structure of tri­aqua­(2,6-di­methyl­pyrazine-κN4)bis­(thio­cyanato-κN)manganese(II) 2,5-di­methyl­pyrazine disolvate

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

doi:10.1107/S2056989015020769

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m223-m224

https://doi.org/10.1107/S2056989015020769

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Crystal structure of triaqua(2,6-dimethylpyrazine-κN⁴)bis(thiocyanato-κN)manganese(II) 2,5-dimethylpyrazine disolvate

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 E. R. T. Tiekink, University of Malaya, Malaysia (Received 27 October 2015; accepted 2 November 2015; online 18 November 2015)

In the crystal structure of the title complex, [Mn(NCS)₂(C₆H₈N₂)(H₂O)₃]·2C₆H₈N₂, the Mn^II cation is coordinated by two terminally N-bonded thiocyanate anions, three water molecules and one 2,6-dimethylpyrazine ligand within a slightly distorted N₃O₃ octahedral geometry; the entire complex molecule is generated by the application of a twofold rotation axis. The asymmetric unit also contains an uncoordinating 2,5-dimethylpyrazine ligand in a general position. Obviously, the coordination to the 2,6-dimethylpyrazine ligand is preferred because coordination to the 2,5-dimethylpyrazine is hindered due to the bulky methyl group proximate to the N atom. The discrete complexes are linked by water-O—H⋯N(2,6-dimethylpyzazine/2,5-dimethylpyzazine) hydrogen bonding, forming a three-dimensional network. In the crystal, molecules are arranged in a way that cavities are formed in which unspecified, disordered solvent molecules reside. These were modelled employing the SQUEEZE routine in PLATON [Spek (2015 ). Acta Cryst. C71, 9–18]. The composition of the unit cell does not take into account the presence of the unspecified solvent.

Keywords: crystal structure; coordination complex; manganese(II); hydrogen bonding.

CCDC reference: 1434562

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

[Mn(NCS)₂(C₆H₈N₂)(H₂O)₃]·2C₆H₈N₂
M_r = 549.58
Monoclinic, C 2/c
a = 15.365 (1) Å
b = 27.9630 (14) Å
c = 7.0816 (5) Å
β = 93.59 (3)°
V = 3036.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 200 K
0.30 × 0.23 × 0.13 mm

2.2. Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008 ) T_min = 0.839, T_max = 0.921
12096 measured reflections
3674 independent reflections
2928 reflections with I > 2σ(I)
R_int = 0.034

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.137
S = 1.07
3674 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N20ⁱ	0.82	1.97	2.790 (2)	177
O2—H1O2⋯N21	0.82	1.95	2.769 (2)	179
O2—H2O2⋯N11ⁱⁱ	0.82	2.33	3.138 (3)	170
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe, 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: 1434562

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015020769/tk5403sup1.cif

checkCIF report

Synthesis and crystallization top

MnSO₄.H₂O was purchased from Merck and 2,5-dimethylpyrazine (97%) and Ba(NCS)₂.3H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂.3H₂O and 9.88 g (58.44 mmol) MnSO₄.H₂O in H₂O (300 mL) at RT for 3 h. The white residue of BaSO₄ was filtered off and the solvent removed with a rotary evaporator. The title compound was prepared by the reaction of Mn(NCS)₂. H₂O (60.1 mg, 0.25 mmol) and 2,5-dimethylpyrazine (108.0 µL, 1.00 mmol) in water (1.0 mL) at RT. After few days, yellow blocks of the title compound were obtained, that contains 2,6-dimethylpyrazine in addition anothe rmaterial. Later, it was found that the commercially available 2,5-dimethylpyrazine contains about 3% of 2,6-dimethylpyrazine as a contamination.

Refinement top

The C—H H atoms were positioned with idealized geometry and were refined isotropically with U_eq(H) = 1.2 U_eq(C) using a riding model with C—H = 0.95 Å for aromatic H atoms and U_eq(H) = 1.5 U_eq(C) and C—H = 0.98 Å for methyl H atoms. The methyl H atoms were allowed to rotate but not to tip. After refinement there is some residual electron density indicating a disordered N-donor ligand that is located on a center of inversion. As no reasonabe model was found and the identity of this moelcule is unknown the data were modelled for disordered solvent using the SQUEEZE routine in PLATON (Spek, 2015).

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, 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

	Fig. 1. The molecule structures of the complex molecule (located on a 2-fold axis) and solvent molecule (full weight) in the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) = -x + 1, y, -z + 3/2].
	Fig. 2. Part of the crystal structure of the title compound viewed along the c axis. Hydrogen bonding is shown as dashed lines.

Triaqua(2,6-dimethylpyrazine-κN⁴)bis(thiocyanato-κN)manganese(II) 2,5-dimethylpyrazine disolvate top

Crystal data top

[Mn(NCS)₂(C₆H₈N₂)(H₂O)₃]·2C₆H₈N₂	F(000) = 1148
M_r = 549.58	D_x = 1.202 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.365 (1) Å	Cell parameters from 12096 reflections
b = 27.9630 (14) Å	θ = 2.9–28.1°
c = 7.0816 (5) Å	µ = 0.60 mm⁻¹
β = 93.59 (3)°	T = 200 K
V = 3036.6 (3) Å³	Block, yellow
Z = 4	0.30 × 0.23 × 0.13 mm

Data collection top

Stoe IPDS-1 diffractometer	2928 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
phi–scans	θ_max = 28.1°, θ_min = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	h = −20→20
T_min = 0.839, T_max = 0.921	k = −36→33
12096 measured reflections	l = −9→9
3674 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0893P)² + 0.7561P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.56 e Å⁻³
3674 reflections	Δρ_min = −0.45 e Å⁻³
160 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0112 (14)

Crystal data top

[Mn(NCS)₂(C₆H₈N₂)(H₂O)₃]·2C₆H₈N₂	V = 3036.6 (3) Å³
M_r = 549.58	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.365 (1) Å	µ = 0.60 mm⁻¹
b = 27.9630 (14) Å	T = 200 K
c = 7.0816 (5) Å	0.30 × 0.23 × 0.13 mm
β = 93.59 (3)°

Data collection top

Stoe IPDS-1 diffractometer	3674 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	2928 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.921	R_int = 0.034
12096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.07	Δρ_max = 0.56 e Å⁻³
3674 reflections	Δρ_min = −0.45 e Å⁻³
160 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
Mn1	0.5000	0.35637 (2)	0.7500	0.02817 (16)
N1	0.63645 (12)	0.35855 (7)	0.8519 (3)	0.0392 (4)
C1	0.70974 (14)	0.36619 (7)	0.8897 (3)	0.0320 (4)
S1	0.81250 (4)	0.37677 (3)	0.94387 (10)	0.0516 (2)
N10	0.5000	0.44106 (9)	0.7500	0.0384 (6)
C10	0.57337 (19)	0.46610 (9)	0.7441 (4)	0.0466 (6)
H10	0.6271	0.4495	0.7390	0.056*
C11	0.5741 (3)	0.51597 (10)	0.7453 (5)	0.0701 (11)
N11	0.5000	0.54050 (11)	0.7500	0.0908 (18)
C14	0.6575 (3)	0.54330 (13)	0.7435 (7)	0.1057 (18)
H14A	0.6836	0.5460	0.8729	0.159*
H14B	0.6458	0.5753	0.6918	0.159*
H14C	0.6979	0.5265	0.6647	0.159*
N20	0.85869 (11)	0.27900 (7)	0.3202 (3)	0.0333 (4)
C20	0.85722 (13)	0.32096 (8)	0.4089 (3)	0.0328 (4)
C21	0.77715 (14)	0.34317 (8)	0.4339 (3)	0.0340 (4)
H21	0.7770	0.3729	0.4986	0.041*
C22	0.70304 (13)	0.28263 (7)	0.2784 (3)	0.0293 (4)
C23	0.78238 (13)	0.26022 (7)	0.2550 (3)	0.0317 (4)
H23	0.7825	0.2304	0.1905	0.038*
C24	0.94162 (15)	0.34348 (10)	0.4817 (4)	0.0481 (6)
H24A	0.9518	0.3727	0.4099	0.072*
H24B	0.9896	0.3210	0.4668	0.072*
H24C	0.9385	0.3514	0.6159	0.072*
C25	0.61833 (14)	0.26149 (9)	0.2047 (3)	0.0397 (5)
H25A	0.5932	0.2812	0.1006	0.060*
H25B	0.5780	0.2604	0.3064	0.060*
H25C	0.6282	0.2290	0.1588	0.060*
N21	0.70130 (11)	0.32445 (6)	0.3712 (3)	0.0327 (4)
O1	0.5000	0.27960 (7)	0.7500	0.0436 (6)
H1O1	0.5402	0.2616	0.7278	0.065*
O2	0.54166 (10)	0.36203 (6)	0.4560 (3)	0.0431 (4)
H1O2	0.5890	0.3508	0.4324	0.065*
H2O2	0.5375	0.3883	0.4048	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0211 (2)	0.0233 (2)	0.0402 (3)	0.000	0.00231 (16)	0.000
N1	0.0256 (8)	0.0395 (10)	0.0520 (12)	−0.0022 (7)	0.0000 (7)	−0.0025 (9)
C1	0.0309 (10)	0.0287 (9)	0.0366 (11)	0.0015 (7)	0.0034 (8)	0.0018 (8)
S1	0.0252 (3)	0.0799 (5)	0.0492 (4)	−0.0089 (3)	−0.0008 (2)	−0.0037 (3)
N10	0.0544 (16)	0.0242 (11)	0.0377 (14)	0.000	0.0107 (12)	0.000
C10	0.0690 (17)	0.0307 (11)	0.0419 (13)	−0.0106 (10)	0.0184 (12)	−0.0035 (9)
C11	0.120 (3)	0.0331 (13)	0.0631 (19)	−0.0243 (15)	0.053 (2)	−0.0122 (12)
N11	0.157 (4)	0.0227 (14)	0.103 (3)	0.000	0.095 (3)	0.000
C14	0.154 (4)	0.0514 (19)	0.121 (4)	−0.052 (2)	0.081 (3)	−0.029 (2)
N20	0.0268 (8)	0.0384 (9)	0.0348 (9)	0.0069 (7)	0.0023 (7)	0.0026 (7)
C20	0.0293 (9)	0.0389 (11)	0.0301 (10)	0.0024 (8)	0.0012 (7)	0.0045 (8)
C21	0.0346 (10)	0.0353 (10)	0.0322 (10)	0.0052 (8)	0.0030 (8)	−0.0023 (8)
C22	0.0280 (9)	0.0341 (10)	0.0260 (9)	0.0029 (7)	0.0036 (7)	0.0044 (8)
C23	0.0306 (9)	0.0320 (10)	0.0328 (10)	0.0051 (7)	0.0032 (7)	0.0004 (8)
C24	0.0314 (11)	0.0581 (15)	0.0543 (15)	−0.0061 (10)	−0.0010 (10)	−0.0051 (12)
C25	0.0289 (10)	0.0502 (13)	0.0396 (12)	−0.0025 (9)	−0.0009 (8)	0.0023 (10)
N21	0.0299 (8)	0.0384 (9)	0.0302 (9)	0.0072 (7)	0.0043 (6)	0.0019 (7)
O1	0.0194 (9)	0.0231 (10)	0.0887 (19)	0.000	0.0056 (10)	0.000
O2	0.0298 (8)	0.0495 (10)	0.0508 (10)	0.0038 (6)	0.0098 (7)	−0.0048 (8)

Geometric parameters (Å, º) top

Mn1—O1	2.147 (2)	C11—N11	1.331 (4)
Mn1—N1ⁱ	2.175 (2)	C11—C14	1.493 (5)
Mn1—N1	2.175 (2)	N11—C11ⁱ	1.331 (4)
Mn1—O2ⁱ	2.2216 (18)	N20—C20	1.332 (3)
Mn1—O2	2.2216 (18)	N20—C23	1.340 (3)
Mn1—N10	2.368 (2)	C20—C21	1.399 (3)
N1—C1	1.161 (3)	C20—C24	1.504 (3)
C1—S1	1.628 (2)	C21—N21	1.328 (3)
N10—C10	1.330 (3)	C22—N21	1.343 (3)
N10—C10ⁱ	1.330 (3)	C22—C23	1.390 (3)
C10—C11	1.395 (4)	C22—C25	1.493 (3)

O1—Mn1—N1ⁱ	91.61 (5)	C10—N10—Mn1	121.76 (15)
O1—Mn1—N1	91.61 (5)	C10ⁱ—N10—Mn1	121.77 (15)
N1ⁱ—Mn1—N1	176.79 (10)	N10—C10—C11	122.2 (3)
O1—Mn1—O2ⁱ	94.09 (5)	N11—C11—C10	120.6 (3)
N1ⁱ—Mn1—O2ⁱ	88.89 (8)	N11—C11—C14	118.2 (3)
N1—Mn1—O2ⁱ	90.88 (8)	C10—C11—C14	121.2 (4)
O1—Mn1—O2	94.09 (5)	C11—N11—C11ⁱ	118.0 (3)
N1ⁱ—Mn1—O2	90.88 (8)	C20—N20—C23	117.86 (17)
N1—Mn1—O2	88.89 (8)	N20—C20—C21	119.46 (19)
O2ⁱ—Mn1—O2	171.82 (9)	N20—C20—C24	119.41 (19)
O1—Mn1—N10	180.0	C21—C20—C24	121.1 (2)
N1ⁱ—Mn1—N10	88.39 (5)	N21—C21—C20	122.9 (2)
N1—Mn1—N10	88.39 (5)	N21—C22—C23	119.70 (19)
O2ⁱ—Mn1—N10	85.91 (5)	N21—C22—C25	118.18 (18)
O2—Mn1—N10	85.91 (5)	C23—C22—C25	122.12 (19)
C1—N1—Mn1	169.32 (19)	N20—C23—C22	122.52 (19)
N1—C1—S1	179.7 (2)	C21—N21—C22	117.57 (17)
C10—N10—C10ⁱ	116.5 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N20ⁱⁱ	0.82	1.97	2.790 (2)	177
O2—H1O2···N21	0.82	1.95	2.769 (2)	179
O2—H2O2···N11ⁱⁱⁱ	0.82	2.33	3.138 (3)	170

Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1; (iii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N20ⁱ	0.82	1.97	2.790 (2)	177
O2—H1O2···N21	0.82	1.95	2.769 (2)	179
O2—H2O2···N11ⁱⁱ	0.82	2.33	3.138 (3)	170

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+1, −y+1, −z+1.

Acknowledgements

We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

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
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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m223-m224

https://doi.org/10.1107/S2056989015020769

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