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

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 MnII 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[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). Acta Cryst. C71, 9–18]. The composition of the unit cell does not take into account the presence of the unspecified solvent.

1. Related literature

For structures with metal thio­cyanates and 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.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Mn(NCS)2(C6H8N2)(H2O)3]·2C6H8N2

  • Mr = 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[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.839, Tmax = 0.921

  • 12096 measured reflections

  • 3674 independent reflections

  • 2928 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.56 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—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[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. C71, 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

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 Ueq(H) = 1.2 Ueq(C) using a riding model with C—H = 0.95 Å for aromatic H atoms and Ueq(H) = 1.5 Ueq(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

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 details top

The C—H H atoms were positioned with idealized geometry and were refined isotropically with Ueq(H) = 1.2 Ueq(C) using a riding model with C—H = 0.95 Å for aromatic H atoms and Ueq(H) = 1.5 Ueq(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).

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 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].
[Figure 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]·2C6H8N2F(000) = 1148
Mr = 549.58Dx = 1.202 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 15.365 (1) ÅCell parameters from 12096 reflections
b = 27.9630 (14) Åθ = 2.9–28.1°
c = 7.0816 (5) ŵ = 0.60 mm1
β = 93.59 (3)°T = 200 K
V = 3036.6 (3) Å3Block, yellow
Z = 40.30 × 0.23 × 0.13 mm
Data collection top
Stoe IPDS-1
diffractometer
2928 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
phi–scansθmax = 28.1°, θmin = 2.9°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
h = 2020
Tmin = 0.839, Tmax = 0.921k = 3633
12096 measured reflectionsl = 99
3674 independent reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046 w = 1/[σ2(Fo2) + (0.0893P)2 + 0.7561P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.137(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.56 e Å3
3674 reflectionsΔρmin = 0.45 e Å3
160 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0112 (14)
Crystal data top
[Mn(NCS)2(C6H8N2)(H2O)3]·2C6H8N2V = 3036.6 (3) Å3
Mr = 549.58Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.365 (1) ŵ = 0.60 mm1
b = 27.9630 (14) ÅT = 200 K
c = 7.0816 (5) Å0.30 × 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)
Tmin = 0.839, Tmax = 0.921Rint = 0.034
12096 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.07Δρmax = 0.56 e Å3
3674 reflectionsΔρmin = 0.45 e Å3
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
xyzUiso*/Ueq
Mn10.50000.35637 (2)0.75000.02817 (16)
N10.63645 (12)0.35855 (7)0.8519 (3)0.0392 (4)
C10.70974 (14)0.36619 (7)0.8897 (3)0.0320 (4)
S10.81250 (4)0.37677 (3)0.94387 (10)0.0516 (2)
N100.50000.44106 (9)0.75000.0384 (6)
C100.57337 (19)0.46610 (9)0.7441 (4)0.0466 (6)
H100.62710.44950.73900.056*
C110.5741 (3)0.51597 (10)0.7453 (5)0.0701 (11)
N110.50000.54050 (11)0.75000.0908 (18)
C140.6575 (3)0.54330 (13)0.7435 (7)0.1057 (18)
H14A0.68360.54600.87290.159*
H14B0.64580.57530.69180.159*
H14C0.69790.52650.66470.159*
N200.85869 (11)0.27900 (7)0.3202 (3)0.0333 (4)
C200.85722 (13)0.32096 (8)0.4089 (3)0.0328 (4)
C210.77715 (14)0.34317 (8)0.4339 (3)0.0340 (4)
H210.77700.37290.49860.041*
C220.70304 (13)0.28263 (7)0.2784 (3)0.0293 (4)
C230.78238 (13)0.26022 (7)0.2550 (3)0.0317 (4)
H230.78250.23040.19050.038*
C240.94162 (15)0.34348 (10)0.4817 (4)0.0481 (6)
H24A0.95180.37270.40990.072*
H24B0.98960.32100.46680.072*
H24C0.93850.35140.61590.072*
C250.61833 (14)0.26149 (9)0.2047 (3)0.0397 (5)
H25A0.59320.28120.10060.060*
H25B0.57800.26040.30640.060*
H25C0.62820.22900.15880.060*
N210.70130 (11)0.32445 (6)0.3712 (3)0.0327 (4)
O10.50000.27960 (7)0.75000.0436 (6)
H1O10.54020.26160.72780.065*
O20.54166 (10)0.36203 (6)0.4560 (3)0.0431 (4)
H1O20.58900.35080.43240.065*
H2O20.53750.38830.40480.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0211 (2)0.0233 (2)0.0402 (3)0.0000.00231 (16)0.000
N10.0256 (8)0.0395 (10)0.0520 (12)0.0022 (7)0.0000 (7)0.0025 (9)
C10.0309 (10)0.0287 (9)0.0366 (11)0.0015 (7)0.0034 (8)0.0018 (8)
S10.0252 (3)0.0799 (5)0.0492 (4)0.0089 (3)0.0008 (2)0.0037 (3)
N100.0544 (16)0.0242 (11)0.0377 (14)0.0000.0107 (12)0.000
C100.0690 (17)0.0307 (11)0.0419 (13)0.0106 (10)0.0184 (12)0.0035 (9)
C110.120 (3)0.0331 (13)0.0631 (19)0.0243 (15)0.053 (2)0.0122 (12)
N110.157 (4)0.0227 (14)0.103 (3)0.0000.095 (3)0.000
C140.154 (4)0.0514 (19)0.121 (4)0.052 (2)0.081 (3)0.029 (2)
N200.0268 (8)0.0384 (9)0.0348 (9)0.0069 (7)0.0023 (7)0.0026 (7)
C200.0293 (9)0.0389 (11)0.0301 (10)0.0024 (8)0.0012 (7)0.0045 (8)
C210.0346 (10)0.0353 (10)0.0322 (10)0.0052 (8)0.0030 (8)0.0023 (8)
C220.0280 (9)0.0341 (10)0.0260 (9)0.0029 (7)0.0036 (7)0.0044 (8)
C230.0306 (9)0.0320 (10)0.0328 (10)0.0051 (7)0.0032 (7)0.0004 (8)
C240.0314 (11)0.0581 (15)0.0543 (15)0.0061 (10)0.0010 (10)0.0051 (12)
C250.0289 (10)0.0502 (13)0.0396 (12)0.0025 (9)0.0009 (8)0.0023 (10)
N210.0299 (8)0.0384 (9)0.0302 (9)0.0072 (7)0.0043 (6)0.0019 (7)
O10.0194 (9)0.0231 (10)0.0887 (19)0.0000.0056 (10)0.000
O20.0298 (8)0.0495 (10)0.0508 (10)0.0038 (6)0.0098 (7)0.0048 (8)
Geometric parameters (Å, º) top
Mn1—O12.147 (2)C11—N111.331 (4)
Mn1—N1i2.175 (2)C11—C141.493 (5)
Mn1—N12.175 (2)N11—C11i1.331 (4)
Mn1—O2i2.2216 (18)N20—C201.332 (3)
Mn1—O22.2216 (18)N20—C231.340 (3)
Mn1—N102.368 (2)C20—C211.399 (3)
N1—C11.161 (3)C20—C241.504 (3)
C1—S11.628 (2)C21—N211.328 (3)
N10—C101.330 (3)C22—N211.343 (3)
N10—C10i1.330 (3)C22—C231.390 (3)
C10—C111.395 (4)C22—C251.493 (3)
O1—Mn1—N1i91.61 (5)C10—N10—Mn1121.76 (15)
O1—Mn1—N191.61 (5)C10i—N10—Mn1121.77 (15)
N1i—Mn1—N1176.79 (10)N10—C10—C11122.2 (3)
O1—Mn1—O2i94.09 (5)N11—C11—C10120.6 (3)
N1i—Mn1—O2i88.89 (8)N11—C11—C14118.2 (3)
N1—Mn1—O2i90.88 (8)C10—C11—C14121.2 (4)
O1—Mn1—O294.09 (5)C11—N11—C11i118.0 (3)
N1i—Mn1—O290.88 (8)C20—N20—C23117.86 (17)
N1—Mn1—O288.89 (8)N20—C20—C21119.46 (19)
O2i—Mn1—O2171.82 (9)N20—C20—C24119.41 (19)
O1—Mn1—N10180.0C21—C20—C24121.1 (2)
N1i—Mn1—N1088.39 (5)N21—C21—C20122.9 (2)
N1—Mn1—N1088.39 (5)N21—C22—C23119.70 (19)
O2i—Mn1—N1085.91 (5)N21—C22—C25118.18 (18)
O2—Mn1—N1085.91 (5)C23—C22—C25122.12 (19)
C1—N1—Mn1169.32 (19)N20—C23—C22122.52 (19)
N1—C1—S1179.7 (2)C21—N21—C22117.57 (17)
C10—N10—C10i116.5 (3)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N20ii0.821.972.790 (2)177
O2—H1O2···N210.821.952.769 (2)179
O2—H2O2···N11iii0.822.333.138 (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···AD—HH···AD···AD—H···A
O1—H1O1···N20i0.821.972.790 (2)177
O2—H1O2···N210.821.952.769 (2)179
O2—H2O2···N11ii0.822.333.138 (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

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationMahmoudi, G. & Morsali, A. (2009). CrystEngComm, 11, 1868–1879.  Web of Science CSD CrossRef CAS Google Scholar
First citationOtieno, T., Blanton, J. R., Lanham, K. J. & Parkin, S. (2003). J. Chem. Crystallogr. 33, 335–339.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2015). Acta Cryst. C71, 9–18.  Web of Science CrossRef IUCr Journals Google Scholar
First citationStoe (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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