Poly[[bis-(μ-4,4'-bipyridyl-κN:N')bis-(thio-cyanato-κN)manganese(II)] diethyl ether disolvate].

In the title compound, {[Mn(NCS)(2)(C(10)H(8)N(2))(2)]·2C(4)H(10)O}(n), the Mn(II) ion is coordinated by four N-bonded 4,4'-bipyridine (bipy) ligands and two N-bonded thio-cyanate anions in a distorted octa-hedral coordination geometry. The asymmetric unit consists of one Mn(II) ion and two bipy ligands each located on a twofold rotation axis, as well as one thio-cyanate anion and one diethyl ether mol-ecule in general positions. In the crystal structure, the metal centers with terminally bonded thicyanate anions are bridged by the bipy ligands into layers parallel to (001). The diethyl ether solvent mol-ecules occupy the voids of the structure.

Related literature

For general background to thermal decomposition reactions as an alternative tool for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a ▶,b ▶); Wriedt et al. (2009a ▶,b ▶). For the isotypic cobalt(II) structure, see: Lu et al. (1997 ▶).

Experimental

Crystal data

[Mn(NCS)2(C10H8N2)2]·2C4H10O

M = 631.71

Monoclinic,

a = 11.702 (2) Å

b = 11.6391 (18) Å

c = 13.424 (2) Å

β = 106.75 (2)°

V = 1750.8 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.53 mm−1

T = 230 K

0.22 × 0.14 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002 ▶) T min = 0.912, T max = 0.968

11086 measured reflections

2954 independent reflections

2446 reflections with I > 2σ(I)

R int = 0.134

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.206

S = 1.07

2954 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.72 e Å−3

Δρmin = −1.37 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021665/hy2314sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021665/hy2314Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(NCS)2(C10H8N2)2]·2C4H10O	F(000) = 662
Mr = 631.71	Dx = 1.198 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 11086 reflections
a = 11.702 (2) Å	θ = 2.4–25.0°
b = 11.6391 (18) Å	µ = 0.53 mm−1
c = 13.424 (2) Å	T = 230 K
β = 106.75 (2)°	Block, colourless
V = 1750.8 (5) Å3	0.22 × 0.14 × 0.07 mm
Z = 2

Stoe IPDS-1 diffractometer	2954 independent reflections
Radiation source: fine-focus sealed tube	2446 reflections with I > 2σ(I)
graphite	Rint = 0.134
ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	h = −13→13
Tmin = 0.912, Tmax = 0.968	k = −13→13
11086 measured reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073	H-atom parameters constrained
wR(F2) = 0.206	w = 1/[σ2(Fo2) + (0.1115P)2 + 1.3719P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2954 reflections	Δρmax = 0.72 e Å−3
191 parameters	Δρmin = −1.37 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (7)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.71119 (6)	0.7500	0.0284 (3)
N1	0.3018 (2)	0.7070 (3)	0.7479 (3)	0.0385 (8)
C1	0.2710 (3)	0.6632 (5)	0.8264 (4)	0.0557 (13)
H1	0.3317	0.6340	0.8829	0.067*
C2	0.1544 (4)	0.6575 (5)	0.8310 (4)	0.0617 (15)
H2	0.1373	0.6249	0.8892	0.074*
C3	0.0633 (3)	0.7003 (4)	0.7491 (4)	0.0408 (10)
C4	0.0940 (3)	0.7447 (5)	0.6646 (4)	0.0577 (13)
H4	0.0352	0.7725	0.6061	0.069*
C5	0.2141 (3)	0.7470 (5)	0.6684 (4)	0.0559 (13)
H5	0.2346	0.7788	0.6115	0.067*
N11	0.5000	0.9088 (4)	0.7500	0.0367 (11)
N12	0.5000	1.5156 (3)	0.7500	0.0354 (11)
C11	0.4781 (4)	0.9689 (3)	0.8272 (4)	0.0448 (10)
H11	0.4624	0.9285	0.8824	0.054*
C12	0.4775 (4)	1.0865 (4)	0.8300 (4)	0.0498 (11)
H12	0.4619	1.1249	0.8862	0.060*
C13	0.5000	1.1484 (4)	0.7500	0.0384 (13)
C16	0.4344 (4)	1.4556 (4)	0.6684 (4)	0.0488 (11)
H16	0.3880	1.4963	0.6104	0.059*
C15	0.4314 (4)	1.3368 (4)	0.6652 (4)	0.0509 (11)
H17	0.3837	1.2982	0.6063	0.061*
C14	0.5000	1.2758 (4)	0.7500	0.0390 (13)
N21	0.5534 (3)	0.7169 (3)	0.9196 (3)	0.0386 (8)
C21	0.6253 (3)	0.6927 (3)	0.9963 (4)	0.0412 (10)
S21	0.72754 (14)	0.65840 (19)	1.10210 (13)	0.0900 (6)
C31	0.0822 (10)	0.3656 (13)	0.6206 (10)	0.170 (6)
H31A	0.1479	0.4018	0.6020	0.255*
H31B	0.0756	0.3981	0.6853	0.255*
H31C	0.0086	0.3787	0.5659	0.255*
C32	0.1059 (12)	0.2324 (15)	0.6347 (9)	0.172 (6)
H32A	0.1679	0.2177	0.7002	0.206*
H32B	0.0329	0.1930	0.6375	0.206*
O31	0.1431 (5)	0.1896 (8)	0.5502 (5)	0.138 (3)
C33	0.1686 (9)	0.0670 (10)	0.5534 (11)	0.146 (5)
H33A	0.0974	0.0238	0.5554	0.175*
H33B	0.2328	0.0489	0.6166	0.175*
C34	0.2049 (11)	0.0329 (12)	0.4606 (12)	0.167 (5)
H34A	0.1368	0.0383	0.3991	0.251*
H34B	0.2341	−0.0456	0.4688	0.251*
H34C	0.2676	0.0837	0.4530	0.251*

	U11	U22	U33	U12	U13	U23
Mn1	0.0147 (4)	0.0265 (5)	0.0448 (6)	0.000	0.0100 (3)	0.000
N1	0.0135 (13)	0.0482 (19)	0.057 (2)	0.0019 (12)	0.0146 (14)	0.0072 (15)
C1	0.0196 (17)	0.087 (3)	0.060 (3)	0.0062 (19)	0.0109 (18)	0.025 (3)
C2	0.0233 (18)	0.101 (4)	0.064 (3)	0.005 (2)	0.0176 (19)	0.032 (3)
C3	0.0130 (17)	0.060 (2)	0.051 (3)	0.0018 (15)	0.0119 (15)	0.0015 (19)
C4	0.0209 (17)	0.103 (4)	0.050 (3)	0.012 (2)	0.0110 (17)	0.011 (3)
C5	0.0220 (18)	0.095 (4)	0.054 (3)	0.011 (2)	0.0174 (18)	0.019 (3)
N11	0.034 (2)	0.026 (2)	0.054 (3)	0.000	0.018 (2)	0.000
N12	0.0246 (19)	0.025 (2)	0.055 (3)	0.000	0.0101 (19)	0.000
C11	0.057 (2)	0.032 (2)	0.055 (3)	0.0032 (18)	0.030 (2)	0.0031 (18)
C12	0.065 (3)	0.036 (2)	0.058 (3)	0.004 (2)	0.032 (2)	−0.0027 (19)
C13	0.034 (2)	0.028 (3)	0.054 (4)	0.000	0.013 (2)	0.000
C16	0.050 (2)	0.032 (2)	0.055 (3)	−0.0014 (18)	0.0004 (19)	0.0048 (18)
C15	0.056 (2)	0.034 (2)	0.054 (3)	−0.0069 (19)	0.002 (2)	−0.0031 (19)
C14	0.036 (3)	0.028 (3)	0.056 (4)	0.000	0.018 (3)	0.000
N21	0.0276 (15)	0.0389 (18)	0.049 (2)	0.0025 (12)	0.0111 (15)	0.0026 (14)
C21	0.034 (2)	0.044 (2)	0.049 (3)	0.0014 (16)	0.0167 (19)	−0.0025 (18)
S21	0.0624 (9)	0.1362 (16)	0.0578 (12)	0.0265 (9)	−0.0047 (7)	0.0143 (9)
C31	0.111 (8)	0.246 (16)	0.144 (11)	0.028 (9)	0.022 (7)	−0.056 (11)
C32	0.136 (9)	0.308 (19)	0.079 (8)	−0.067 (11)	0.041 (7)	−0.028 (10)
O31	0.078 (3)	0.235 (9)	0.093 (5)	−0.005 (4)	0.010 (3)	0.028 (5)
C33	0.089 (6)	0.131 (8)	0.204 (14)	0.015 (6)	0.020 (7)	0.061 (8)
C34	0.134 (9)	0.179 (11)	0.198 (13)	0.057 (8)	0.062 (9)	0.020 (10)

Mn1—N21	2.181 (4)	C13—C12iii	1.380 (5)
Mn1—N12i	2.277 (4)	C13—C14	1.483 (7)
Mn1—N11	2.300 (4)	C16—C15	1.383 (6)
Mn1—N1	2.312 (3)	C16—H16	0.9400
N1—C1	1.311 (6)	C15—C14	1.385 (5)
N1—C5	1.333 (6)	C15—H17	0.9400
C1—C2	1.385 (5)	C14—C15iii	1.385 (5)
C1—H1	0.9400	N21—C21	1.161 (6)
C2—C3	1.386 (6)	C21—S21	1.621 (5)
C2—H2	0.9400	C31—C32	1.577 (18)
C3—C4	1.384 (7)	C31—H31A	0.9700
C3—C3ii	1.488 (6)	C31—H31B	0.9700
C4—C5	1.392 (5)	C31—H31C	0.9700
C4—H4	0.9400	C32—O31	1.418 (13)
C5—H5	0.9400	C32—H32A	0.9800
N11—C11	1.334 (5)	C32—H32B	0.9800
N11—C11iii	1.334 (5)	O31—C33	1.455 (12)
N12—C16	1.338 (5)	C33—C34	1.482 (16)
N12—C16iii	1.338 (5)	C33—H33A	0.9800
N12—Mn1iv	2.277 (4)	C33—H33B	0.9800
C11—C12	1.370 (6)	C34—H34A	0.9700
C11—H11	0.9400	C34—H34B	0.9700
C12—C13	1.380 (5)	C34—H34C	0.9700
C12—H12	0.9400
N21—Mn1—N21iii	176.54 (16)	C11—C12—C13	119.8 (4)
N21—Mn1—N12i	91.73 (8)	C11—C12—H12	120.1
N21iii—Mn1—N12i	91.73 (8)	C13—C12—H12	120.1
N21—Mn1—N11	88.27 (8)	C12—C13—C12iii	117.0 (5)
N21iii—Mn1—N11	88.27 (8)	C12—C13—C14	121.5 (3)
N12i—Mn1—N11	180.0	C12iii—C13—C14	121.5 (3)
N21—Mn1—N1	89.88 (12)	N12—C16—C15	123.4 (4)
N21iii—Mn1—N1	90.19 (12)	N12—C16—H16	118.3
N12i—Mn1—N1	88.79 (8)	C15—C16—H16	118.3
N11—Mn1—N1	91.21 (8)	C16—C15—C14	118.9 (4)
N21—Mn1—N1iii	90.19 (12)	C16—C15—H17	120.6
N21iii—Mn1—N1iii	89.88 (12)	C14—C15—H17	120.6
N12i—Mn1—N1iii	88.79 (8)	C15iii—C14—C15	118.3 (5)
N11—Mn1—N1iii	91.21 (8)	C15iii—C14—C13	120.8 (3)
N1—Mn1—N1iii	177.58 (16)	C15—C14—C13	120.8 (3)
C1—N1—C5	116.9 (3)	C21—N21—Mn1	146.6 (3)
C1—N1—Mn1	120.3 (3)	N21—C21—S21	178.9 (4)
C5—N1—Mn1	122.7 (3)	C32—C31—H31A	109.5
N1—C1—C2	123.8 (4)	C32—C31—H31B	109.5
N1—C1—H1	118.1	H31A—C31—H31B	109.5
C2—C1—H1	118.1	C32—C31—H31C	109.5
C1—C2—C3	119.4 (4)	H31A—C31—H31C	109.5
C1—C2—H2	120.3	H31B—C31—H31C	109.5
C3—C2—H2	120.3	O31—C32—C31	109.5 (10)
C4—C3—C2	117.5 (3)	O31—C32—H32A	109.8
C4—C3—C3ii	120.5 (4)	C31—C32—H32A	109.8
C2—C3—C3ii	122.0 (5)	O31—C32—H32B	109.8
C3—C4—C5	118.4 (4)	C31—C32—H32B	109.8
C3—C4—H4	120.8	H32A—C32—H32B	108.2
C5—C4—H4	120.8	C32—O31—C33	115.3 (10)
N1—C5—C4	124.0 (4)	O31—C33—C34	110.1 (10)
N1—C5—H5	118.0	O31—C33—H33A	109.6
C4—C5—H5	118.0	C34—C33—H33A	109.6
C11—N11—C11iii	116.8 (5)	O31—C33—H33B	109.6
C11—N11—Mn1	121.6 (2)	C34—C33—H33B	109.6
C11iii—N11—Mn1	121.6 (2)	H33A—C33—H33B	108.2
C16—N12—C16iii	117.1 (5)	C33—C34—H34A	109.5
C16—N12—Mn1iv	121.4 (2)	C33—C34—H34B	109.5
C16iii—N12—Mn1iv	121.4 (2)	H34A—C34—H34B	109.5
N11—C11—C12	123.3 (4)	C33—C34—H34C	109.5
N11—C11—H11	118.4	H34A—C34—H34C	109.5
C12—C11—H11	118.4	H34B—C34—H34C	109.5

Table 1

Selected bond lengths (Å)

Mn1—N21	2.181 (4)
Mn1—N12i	2.277 (4)
Mn1—N11	2.300 (4)
Mn1—N1	2.312 (3)

Symmetry code: (i) .