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]

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.

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.112
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.970
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.2
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         79
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          9

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined Donor-H Atoms ........          1
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          60 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

All C—H atoms were positions with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropic with U_iso(H) = 1.2 U_eq(C) using a riding model with C—H = 0.94 and 0.97 Å. The O—H H atom was located in a difference map, its bond length was set to 0.83 Å, and finally it was refined isotropically with U_iso(H) = 1.5 U_eq(O) using a riding model.

Computing details

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

	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]

Crystal data

[Mn(NCSe)2(C12H10N2)(CH4O)2]·C12H10N2	F(000) = 694
Mr = 693.42	Dx = 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) Å^3	0.13 × 0.08 × 0.05 mm
Z = 2

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Mn1—N1	2.185 (3)	C15—H15	0.9400
Mn1—N1^i	2.185 (3)	N30—C30	1.327 (6)
Mn1—O1	2.188 (2)	N30—C34	1.343 (6)
Mn1—O1^i	2.188 (2)	C30—C31	1.386 (6)
Mn1—N10^i	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—C35^iii	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—C15^ii	1.331 (6)
N1—Mn1—N1^i	180.00 (14)	N10—C14—H14	118.3
N1—Mn1—O1	93.12 (10)	C13—C14—H14	118.3
N1^i—Mn1—O1	86.88 (10)	C15^ii—C15—C12	125.6 (4)
N1—Mn1—O1^i	86.88 (10)	C15^ii—C15—H15	117.2
N1^i—Mn1—O1^i	93.12 (10)	C12—C15—H15	117.2
O1—Mn1—O1^i	180.00 (8)	C30—N30—C34	116.6 (3)
N1—Mn1—N10^i	91.91 (9)	N30—C30—C31	123.6 (4)
N1^i—Mn1—N10^i	88.09 (9)	N30—C30—H30	118.2
O1—Mn1—N10^i	89.85 (9)	C31—C30—H30	118.2
O1^i—Mn1—N10^i	90.15 (9)	C32—C31—C30	119.6 (4)
N1—Mn1—N10	88.09 (9)	C32—C31—H31	120.2
N1^i—Mn1—N10	91.91 (9)	C30—C31—H31	120.2
O1—Mn1—N10	90.15 (9)	C31—C32—C33	117.0 (3)
O1^i—Mn1—N10	89.85 (8)	C31—C32—C35	120.2 (3)
N10^i—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	C35^iii—C35—C32	125.7 (4)
C11—C10—H10	118.1	C35^iii—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)

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