Crystal structure of poly[[(2,2′-bi­pyridine)manganese(II)]-di-μ-thio­cyanato]

In the crystal structure of the polymeric title compound, [Mn(NCS)₂(C₁₀H₈N₂)]_n, the Mn^II cations are coordinated by one chelating 2,2′-bi­pyridine ligand and four thio­cyanate anions (two N- and two S-coordinating), forming a distorted [MnN₄S₂] octa­hedron. The asymmetric unit consists of one manganese cation located on a twofold rotation axis and half of a 2,2′-bi­pyridine ligand, the other half being generated by the same twofold rotation axis, as well as one thio­cyanate anion in a general position. The Mn^II cations are linked by two pairs of μ_1,3-bridging thio­cyanate ligands into chains along the c axis; because the N atoms of the 2,2′-bi­pyridine ligands, as well as the N and the S atoms of the thio­cyanate anions, are each cis-coordinating, these chains show a zigzag arrangement.

1. Related literature

For the magnetic properties of the title compound, see: Dockum et al. (1983). For general background to this work, see: Näther et al. (2013).

2. Experimental

2.1. Crystal data

• [Mn(NCS)₂(C₁₀H₈N₂)]

• M_r = 327.28

• Monoclinic, C 2/c

• a = 7.6158 (5) Å

• b = 16.2007 (14) Å

• c = 10.6784 (7) Å

• β = 90.129 (8)°

• V = 1317.51 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 1.31 mm⁻¹

• T = 180 K

• 0.24 × 0.18 × 0.11 mm

2.2. Data collection

• STOE IPDS-1 diffractometer

• Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) T_min = 0.714, T_max = 0.825

• 5163 measured reflections

• 1424 independent reflections

• 1208 reflections with I > 2σ(I)

• R_int = 0.029

2.3. Refinement

• R[F² > 2σ(F²)] = 0.026

• wR(F²) = 0.065

• S = 1.10

• 1424 reflections

• 87 parameters

• H-atom parameters constrained

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N1^i	2.1318 (13)
Mn1—N10	2.2433 (12)
Mn1—S1	2.8138 (5)
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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Supporting information

S1. Synthesis and crystallization

MnSO₄·H₂O was purchased from Merck and 2,2'-bi­pyridine and Ba(NCS)₂·3 H₂O 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 300 ml water at RT for three hours. The white precipitate of BaSO₄ was filtered off and the solvent removed with a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of (0.4 mmol) 70.0 mg Mn(NCS)₂ and (0.05 mmol) 7.0 mg 2,2'-bi­pyridine in 1.0 ml aceto­nitrile at RT. After few days, yellow block-shaped crystals of the title compound were obtained.

S2. Refinement

The H atoms were positioned with idealized geometry and were refined with C—H = 0.93 Å and U_eq(H) = 1.2U_eq(C) using a riding model.

Related literature

For the magnetic properties of the title compound, see: Dockum et al. (1983). For general background to this work, see: Näther et al. (2013).

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, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

The coordination of the Mn^II atom in the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: i) x,-y+1,z-1/2; ii) -x,-y+1,-z+1; iii) -x,y,-z+1/2.]

The polymeric arrangement of the chains in the crystal structure of the title compound in a view along the a axis. Colour code: Mn orange; N blue; S yellow; C black; H white.

Poly[[(2,2'-bipyridine)manganese(II)]-di-µ-thiocyanato]

Crystal data

[Mn(NCS)2(C10H8N2)]	F(000) = 660
Mr = 327.28	Dx = 1.650 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5163 reflections
a = 7.6158 (5) Å	θ = 3.2–27.0°
b = 16.2007 (14) Å	µ = 1.31 mm^−1
c = 10.6784 (7) Å	T = 180 K
β = 90.129 (8)°	Block, yellow
V = 1317.51 (17) Å^3	0.24 × 0.18 × 0.11 mm
Z = 4

Data collection

STOE IPDS-1 diffractometer	1424 independent reflections
Radiation source: fine-focus sealed tube	1208 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
phi scans	θmax = 27.0°, θmin = 3.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −9→9
Tmin = 0.714, Tmax = 0.825	k = −20→20
5163 measured reflections	l = −13→13

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 0.0505P] where P = (Fo^2 + 2Fc^2)/3
1424 reflections	(Δ/σ)max = 0.001
87 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

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 > 2sigma(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	0.0000	0.589163 (17)	0.2500	0.01511 (12)
S1	0.26426 (6)	0.59114 (3)	0.43456 (4)	0.02879 (14)
C1	0.1959 (2)	0.53098 (9)	0.54809 (13)	0.0157 (3)
N1	0.14566 (19)	0.48959 (8)	0.62863 (13)	0.0191 (3)
N10	0.15848 (17)	0.70040 (7)	0.19663 (11)	0.0150 (3)
C10	0.3171 (2)	0.69584 (10)	0.14411 (14)	0.0205 (3)
H10	0.3650	0.6440	0.1287	0.025*
C11	0.4133 (2)	0.76537 (11)	0.11149 (15)	0.0246 (4)
H11	0.5240	0.7605	0.0756	0.029*
C12	0.3400 (2)	0.84198 (11)	0.13384 (16)	0.0277 (4)
H12	0.4008	0.8897	0.1122	0.033*
C13	0.1770 (3)	0.84748 (9)	0.18819 (16)	0.0256 (4)
H13	0.1267	0.8988	0.2037	0.031*
C14	0.0878 (2)	0.77516 (9)	0.21990 (13)	0.0175 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0203 (2)	0.00785 (16)	0.01723 (18)	0.000	0.00916 (12)	0.000
S1	0.0261 (3)	0.0358 (3)	0.0244 (2)	−0.01473 (18)	0.00026 (18)	0.01435 (16)
C1	0.0150 (8)	0.0134 (6)	0.0186 (7)	−0.0014 (6)	0.0007 (5)	−0.0002 (5)
N1	0.0218 (7)	0.0167 (6)	0.0187 (6)	−0.0016 (5)	0.0031 (5)	0.0031 (5)
N10	0.0193 (7)	0.0116 (5)	0.0141 (6)	−0.0013 (5)	0.0024 (5)	0.0023 (4)
C10	0.0215 (9)	0.0203 (7)	0.0195 (7)	−0.0010 (6)	0.0016 (6)	0.0026 (6)
C11	0.0196 (9)	0.0319 (8)	0.0222 (8)	−0.0067 (7)	−0.0002 (6)	0.0060 (7)
C12	0.0319 (11)	0.0242 (8)	0.0269 (9)	−0.0145 (7)	−0.0025 (7)	0.0075 (6)
C13	0.0352 (11)	0.0140 (7)	0.0275 (8)	−0.0055 (7)	−0.0005 (7)	0.0002 (6)
C14	0.0254 (9)	0.0133 (7)	0.0137 (6)	−0.0011 (6)	−0.0009 (6)	0.0018 (5)

Geometric parameters (Å, º)

Mn1—N1^i	2.1318 (13)	N10—C14	1.3485 (18)
Mn1—N1^ii	2.1318 (13)	C10—C11	1.389 (2)
Mn1—N10^iii	2.2433 (12)	C10—H10	0.9300
Mn1—N10	2.2433 (12)	C11—C12	1.382 (3)
Mn1—S1^iii	2.8138 (5)	C11—H11	0.9300
Mn1—S1	2.8138 (5)	C12—C13	1.375 (3)
S1—C1	1.6411 (15)	C12—H12	0.9300
C1—N1	1.156 (2)	C13—C14	1.396 (2)
N1—Mn1^ii	2.1318 (13)	C13—H13	0.9300
N10—C10	1.335 (2)	C14—C14^iii	1.486 (3)
N1^i—Mn1—N1^ii	106.48 (7)	C10—N10—C14	119.27 (13)
N1^i—Mn1—N10^iii	156.38 (5)	C10—N10—Mn1	123.37 (11)
N1^ii—Mn1—N10^iii	92.60 (5)	C14—N10—Mn1	117.36 (10)
N1^i—Mn1—N10	92.60 (5)	N10—C10—C11	122.62 (16)
N1^ii—Mn1—N10	156.38 (5)	N10—C10—H10	118.7
N10^iii—Mn1—N10	73.10 (7)	C11—C10—H10	118.7
N1^i—Mn1—S1^iii	87.33 (4)	C12—C11—C10	118.14 (16)
N1^ii—Mn1—S1^iii	93.46 (4)	C12—C11—H11	120.9
N10^iii—Mn1—S1^iii	77.55 (3)	C10—C11—H11	120.9
N10—Mn1—S1^iii	101.38 (3)	C13—C12—C11	119.78 (15)
N1^i—Mn1—S1	93.46 (4)	C13—C12—H12	120.1
N1^ii—Mn1—S1	87.33 (4)	C11—C12—H12	120.1
N10^iii—Mn1—S1	101.38 (3)	C12—C13—C14	119.23 (15)
N10—Mn1—S1	77.55 (3)	C12—C13—H13	120.4
S1^iii—Mn1—S1	178.69 (2)	C14—C13—H13	120.4
C1—S1—Mn1	106.45 (6)	N10—C14—C13	120.96 (15)
N1—C1—S1	178.83 (15)	N10—C14—C14^iii	116.09 (8)
C1—N1—Mn1^ii	166.59 (14)	C13—C14—C14^iii	122.95 (10)

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