catena-Poly[[[bis­(methanol-κO)bis­(seleno­cyanato-κN)manganese(II)]-μ-1,2-bis­(pyridin-4-yl)eth­ene-κ2N:N′] 1,2-bis­(pyridin-4-yl)eth­ene mono­solvate]

Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S1600536813012609

metal-organic compounds

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Volume 69| Part 6| June 2013| Page m319

doi:10.1107/S1600536813012609

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catena-Poly[[[bis(methanol-κO)bis(selenocyanato-κN)manganese(II)]-μ-1,2-bis(pyridin-4-yl)ethene-κ²N:N′] 1,2-bis(pyridin-4-yl)ethene monosolvate]

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: swoehlert@ac.uni-kiel.de

(Received 6 May 2013; accepted 8 May 2013; online 15 May 2013)

In the crystal structure of the title compound, {[Mn(NCSe)₂(C₁₂H₁₀N₂)(CH₃OH)₂]·C₁₂H₁₀N₂}_n, the Mn^II cation is coordinated by two terminal N-bonded selenocyanate anions, two methanol molecules and two 1,2-bis(pyridin-4-yl)ethene (bpe) ligands within a slightly distorted octahedral geometry. The Mn^II cations are linked into chains along the c-axis direction by the bpe ligands, which are further connected by intermolecular O—H⋯N hydrogen bonding between the methanol H atoms and additional bpe molecules that are not coordinated to the metal atoms. The Mn^II cation and both crystallographically independent bpe ligands are located on centers of inversion, whereas the selenocyanate and methanol ligands occupy general positions.

Related literature

For background to this work see: Boeckmann & Näther (2010 , 2012 ); Wöhlert et al. (2012 ).

Experimental

Crystal data

[Mn(NCSe)₂(C₁₂H₁₀N₂)(CH₄O)₂]·C₁₂H₁₀N₂
M_r = 693.42
Monoclinic, P 2₁ /c
a = 7.3580 (6) Å
b = 17.2445 (11) Å
c = 12.1219 (9) Å
β = 92.630 (9)°
V = 1536.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.83 mm⁻¹
T = 220 K
0.13 × 0.08 × 0.05 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.754, T_max = 0.862
14170 measured reflections
2633 independent reflections
2072 reflections with I > 2σ(I)
R_int = 0.091

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.112
S = 0.99
2633 reflections
179 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N1	2.185 (3)
Mn1—O1	2.188 (2)
Mn1—N10	2.281 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N30	0.83	1.85	2.675 (4)	173

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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: XCIF in SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813012609/zl2549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012609/zl2549Isup2.hkl

checkCIF report

Comment top

Recently, we have reported on the synthesis, thermal and magnetic properties of new coordination polymers based on paramagnetic transition metal thiocyanates with different neutral co-ligands like e. g. pyridine, 1,2-bis(pyridin-4-yl)ethene (Boeckmann & Näther, 2010, 2012; Wöhlert et al., 2012). In the course of these investigations we have reacted manganese(II) chloride dihydrate with potassium selenocyanate and 1,2-bis(pyridin-4-yl)ethene in methanol, which leads to the formation of crystals of the title compound that were identified by single-crystal structure analysis.

In the crystal structure of the title compound each manganese(II) cation is coordinated by two terminally N-bonded selenocyanate anions, two methanol molecules and two 1,2-bis(pyridin-4-yl)ethene (bpe) ligands within slightly distorted octahedra (Fig. 1). The Mn—O and Mn—N distances range from 2.187 (3) Å to 2.279 (3) Å with angles arround the manganese(II) cation between 86.82 (11) ° and 93.18 (11) ° and 180 ° (Tab. 1). The Mn(II) cations are linked by the bpe ligands into chains, which elongate in the direction of the crystallographic c-axis (Fig. 2). These chains are further linked into layers by intermolecular O—H···N hydrogen bonding to the non-coordinated bpe ligands (Fig. 2, Tab. 2).

Related literature top

For background to this work see: Boeckmann & Näther (2010, 2012); Wöhlert et al. (2012).

Experimental top

MnCl₂×2H₂O, KNCSe and 1,2-bis(pyridin-4-yl)ethene were obtained from Alfa Aesar. All chemicals were used without further purification. 0.15 mmol (24 mg) MnCl₂×2H₂O and 0.2 mmol (28 mg) KNCSe were reacted with 0.3 mmol (54 mg) 1,2-bis(pyridin-4-yl)ethene in 1 ml methanol.

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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x+2, -y+1, -z+1; ii = -x+1, -y+1, -z; iii = -x+2, -y, -z+1.
	Fig. 2. : Crystal structure of the title compound with view along the a-axis (black = manganese, blue = nitrogen, orange = selenium, red = oxygen, grey = carbon, white = hydrogen). Intermolecular hydrogen bonding is shown as dashed lines.

catena-Poly[[[bis(methanol-κO)bis(selenocyanato-κN)manganese(II)]-µ-1,2-bis(pyridin-4-yl)ethene-κ²N:N'] 1,2-bis(pyridin-4-yl)ethene monosolvate] top

Crystal data top

[Mn(NCSe)₂(C₁₂H₁₀N₂)(CH₄O)₂]·C₁₂H₁₀N₂	F(000) = 694
M_r = 693.42	D_x = 1.499 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14170 reflections
a = 7.3580 (6) Å	θ = 2.8–25.0°
b = 17.2445 (11) Å	µ = 2.83 mm⁻¹
c = 12.1219 (9) Å	T = 220 K
β = 92.630 (9)°	Block, yellow
V = 1536.5 (2) Å³	0.13 × 0.08 × 0.05 mm
Z = 2

Data collection top

Stoe IPDS-1 diffractometer	2633 independent reflections
Radiation source: fine-focus sealed tube	2072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
phi scan	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −8→8
T_min = 0.754, T_max = 0.862	k = −20→20
14170 measured reflections	l = −13→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.077P)²] where P = (F_o² + 2F_c²)/3
2633 reflections	(Δ/σ)_max < 0.001
179 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Mn(NCSe)₂(C₁₂H₁₀N₂)(CH₄O)₂]·C₁₂H₁₀N₂	V = 1536.5 (2) Å³
M_r = 693.42	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3580 (6) Å	µ = 2.83 mm⁻¹
b = 17.2445 (11) Å	T = 220 K
c = 12.1219 (9) Å	0.13 × 0.08 × 0.05 mm
β = 92.630 (9)°

Data collection top

Stoe IPDS-1 diffractometer	2633 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	2072 reflections with I > 2σ(I)
T_min = 0.754, T_max = 0.862	R_int = 0.091
14170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 0.99	Δρ_max = 0.38 e Å⁻³
2633 reflections	Δρ_min = −0.78 e Å⁻³
179 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	1.0000	0.5000	0.5000	0.02859 (18)
N1	0.8412 (3)	0.59745 (16)	0.5588 (2)	0.0411 (6)
C1	0.7531 (4)	0.65174 (18)	0.5703 (3)	0.0383 (7)
Se1	0.61619 (5)	0.73559 (2)	0.58880 (5)	0.0748 (2)
N10	0.8026 (3)	0.49379 (14)	0.3495 (2)	0.0317 (5)
C10	0.7810 (4)	0.55472 (17)	0.2815 (3)	0.0337 (7)
H10	0.8352	0.6020	0.3032	0.040*
C11	0.6839 (4)	0.55203 (17)	0.1814 (3)	0.0329 (6)
H11	0.6737	0.5964	0.1366	0.039*
C12	0.6011 (3)	0.48261 (16)	0.1474 (2)	0.0281 (6)
C13	0.6159 (4)	0.42049 (17)	0.2201 (3)	0.0342 (7)
H13	0.5574	0.3733	0.2025	0.041*
C14	0.7172 (4)	0.42818 (17)	0.3185 (3)	0.0358 (7)
H14	0.7264	0.3852	0.3661	0.043*
C15	0.5041 (4)	0.47366 (18)	0.0402 (3)	0.0312 (6)
H15	0.4423	0.4267	0.0268	0.037*
N30	0.9261 (4)	0.26379 (17)	0.5841 (4)	0.0604 (9)
C30	1.0231 (6)	0.2228 (2)	0.6583 (4)	0.0605 (10)
H30	1.0691	0.2483	0.7222	0.073*
C31	1.0604 (5)	0.1445 (2)	0.6469 (4)	0.0528 (9)
H31	1.1297	0.1182	0.7021	0.063*
C32	0.9951 (4)	0.10541 (19)	0.5537 (3)	0.0413 (8)
C33	0.8968 (5)	0.1487 (2)	0.4737 (4)	0.0576 (10)
H33	0.8518	0.1252	0.4081	0.069*
C34	0.8666 (5)	0.2261 (2)	0.4925 (5)	0.0663 (12)
H34	0.8004	0.2544	0.4379	0.080*
C35	1.0281 (4)	0.02177 (19)	0.5422 (3)	0.0403 (7)
H35	1.0950	−0.0029	0.6001	0.048*
O1	0.8375 (3)	0.41425 (12)	0.58486 (19)	0.0386 (5)
H1O1	0.8741	0.3687	0.5840	0.058*
C2	0.6647 (5)	0.4215 (2)	0.6300 (4)	0.0636 (11)
H2A	0.6565	0.4712	0.6671	0.095*
H2B	0.6480	0.3800	0.6827	0.095*
H2C	0.5709	0.4183	0.5713	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0300 (3)	0.0289 (3)	0.0260 (3)	0.0065 (2)	−0.0084 (2)	−0.0038 (2)
N1	0.0433 (14)	0.0367 (14)	0.0427 (17)	0.0107 (12)	−0.0045 (12)	−0.0074 (12)
C1	0.0337 (14)	0.0325 (16)	0.048 (2)	−0.0011 (13)	−0.0026 (13)	−0.0061 (13)
Se1	0.0493 (3)	0.0317 (3)	0.1452 (5)	0.01097 (15)	0.0249 (3)	−0.0019 (2)
N10	0.0335 (12)	0.0324 (13)	0.0282 (13)	0.0039 (10)	−0.0084 (10)	−0.0004 (10)
C10	0.0348 (14)	0.0307 (15)	0.0344 (17)	0.0000 (11)	−0.0100 (12)	−0.0011 (12)
C11	0.0376 (14)	0.0320 (15)	0.0282 (17)	0.0010 (11)	−0.0072 (12)	0.0040 (11)
C12	0.0232 (12)	0.0339 (15)	0.0268 (15)	0.0029 (10)	−0.0045 (10)	0.0019 (11)
C13	0.0350 (14)	0.0332 (16)	0.0337 (17)	−0.0035 (11)	−0.0062 (12)	−0.0011 (12)
C14	0.0410 (16)	0.0329 (16)	0.0324 (17)	0.0011 (12)	−0.0091 (13)	0.0031 (12)
C15	0.0263 (13)	0.0369 (15)	0.0297 (16)	0.0013 (11)	−0.0065 (11)	−0.0009 (12)
N30	0.0468 (17)	0.0362 (17)	0.099 (3)	0.0034 (13)	0.0122 (17)	0.0041 (17)
C30	0.059 (2)	0.046 (2)	0.078 (3)	0.0011 (17)	0.010 (2)	−0.001 (2)
C31	0.0517 (19)	0.045 (2)	0.062 (3)	0.0026 (15)	0.0041 (17)	0.0050 (17)
C32	0.0278 (14)	0.0377 (17)	0.059 (2)	0.0014 (12)	0.0099 (13)	0.0125 (15)
C33	0.0503 (19)	0.0381 (19)	0.083 (3)	0.0021 (15)	−0.0075 (19)	0.0109 (19)
C34	0.050 (2)	0.042 (2)	0.106 (4)	0.0091 (16)	−0.007 (2)	0.020 (2)
C35	0.0299 (14)	0.0361 (17)	0.055 (2)	0.0042 (12)	0.0062 (13)	0.0136 (14)
O1	0.0332 (10)	0.0350 (12)	0.0476 (14)	0.0057 (8)	0.0001 (9)	0.0008 (9)
C2	0.052 (2)	0.055 (2)	0.085 (3)	0.0040 (17)	0.023 (2)	−0.007 (2)

Geometric parameters (Å, º) top

Mn1—N1	2.185 (3)	C15—H15	0.9400
Mn1—N1ⁱ	2.185 (3)	N30—C30	1.327 (6)
Mn1—O1	2.188 (2)	N30—C34	1.343 (6)
Mn1—O1ⁱ	2.188 (2)	C30—C31	1.386 (6)
Mn1—N10ⁱ	2.281 (2)	C30—H30	0.9400
Mn1—N10	2.281 (2)	C31—C32	1.383 (6)
N1—C1	1.151 (4)	C31—H31	0.9400
C1—Se1	1.782 (3)	C32—C33	1.399 (5)
N10—C14	1.340 (4)	C32—C35	1.470 (5)
N10—C10	1.341 (4)	C33—C34	1.374 (6)
C10—C11	1.381 (4)	C33—H33	0.9400
C10—H10	0.9400	C34—H34	0.9400
C11—C12	1.397 (4)	C35—C35ⁱⁱⁱ	1.321 (7)
C11—H11	0.9400	C35—H35	0.9400
C12—C13	1.388 (4)	O1—C2	1.413 (4)
C12—C15	1.462 (4)	O1—H1O1	0.8300
C13—C14	1.384 (4)	C2—H2A	0.9700
C13—H13	0.9400	C2—H2B	0.9700
C14—H14	0.9400	C2—H2C	0.9700
C15—C15ⁱⁱ	1.331 (6)

N1—Mn1—N1ⁱ	180.00 (14)	N10—C14—H14	118.3
N1—Mn1—O1	93.12 (10)	C13—C14—H14	118.3
N1ⁱ—Mn1—O1	86.88 (10)	C15ⁱⁱ—C15—C12	125.6 (4)
N1—Mn1—O1ⁱ	86.88 (10)	C15ⁱⁱ—C15—H15	117.2
N1ⁱ—Mn1—O1ⁱ	93.12 (10)	C12—C15—H15	117.2
O1—Mn1—O1ⁱ	180.00 (8)	C30—N30—C34	116.6 (3)
N1—Mn1—N10ⁱ	91.91 (9)	N30—C30—C31	123.6 (4)
N1ⁱ—Mn1—N10ⁱ	88.09 (9)	N30—C30—H30	118.2
O1—Mn1—N10ⁱ	89.85 (9)	C31—C30—H30	118.2
O1ⁱ—Mn1—N10ⁱ	90.15 (9)	C32—C31—C30	119.6 (4)
N1—Mn1—N10	88.09 (9)	C32—C31—H31	120.2
N1ⁱ—Mn1—N10	91.91 (9)	C30—C31—H31	120.2
O1—Mn1—N10	90.15 (9)	C31—C32—C33	117.0 (3)
O1ⁱ—Mn1—N10	89.85 (8)	C31—C32—C35	120.2 (3)
N10ⁱ—Mn1—N10	180.000 (1)	C33—C32—C35	122.8 (4)
C1—N1—Mn1	167.9 (3)	C34—C33—C32	119.1 (4)
N1—C1—Se1	179.6 (3)	C34—C33—H33	120.4
C14—N10—C10	116.6 (2)	C32—C33—H33	120.4
C14—N10—Mn1	122.50 (19)	N30—C34—C33	123.9 (4)
C10—N10—Mn1	120.54 (19)	N30—C34—H34	118.0
N10—C10—C11	123.8 (3)	C33—C34—H34	118.0
N10—C10—H10	118.1	C35ⁱⁱⁱ—C35—C32	125.7 (4)
C11—C10—H10	118.1	C35ⁱⁱⁱ—C35—H35	117.2
C10—C11—C12	119.3 (3)	C32—C35—H35	117.2
C10—C11—H11	120.3	C2—O1—Mn1	130.0 (2)
C12—C11—H11	120.3	C2—O1—H1O1	112.7
C13—C12—C11	117.0 (3)	Mn1—O1—H1O1	116.7
C13—C12—C15	120.3 (3)	O1—C2—H2A	109.5
C11—C12—C15	122.8 (3)	O1—C2—H2B	109.5
C14—C13—C12	119.8 (3)	H2A—C2—H2B	109.5
C14—C13—H13	120.1	O1—C2—H2C	109.5
C12—C13—H13	120.1	H2A—C2—H2C	109.5
N10—C14—C13	123.4 (3)	H2B—C2—H2C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N30	0.83	1.85	2.675 (4)	173

Experimental details

Crystal data
Chemical formula	[Mn(NCSe)₂(C₁₂H₁₀N₂)(CH₄O)₂]·C₁₂H₁₀N₂
M_r	693.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	220
a, b, c (Å)	7.3580 (6), 17.2445 (11), 12.1219 (9)
β (°)	92.630 (9)
V (Å³)	1536.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.83
Crystal size (mm)	0.13 × 0.08 × 0.05

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.754, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	14170, 2633, 2072
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 0.99
No. of reflections	2633
No. of parameters	179
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.78

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), XCIF in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Mn1—N1	2.185 (3)	Mn1—N10	2.281 (2)
Mn1—O1	2.188 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N30	0.83	1.85	2.675 (4)	172.9

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facility.

References

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