trans-Tetra­kis(pyridine-κN)bis­(thio­cyanato-κN)manganese(II)

In the title compound, [Mn(NCS)₂(C₅H₅N)₄], the Mn atom lies on an inversion centre and assumes a distorted octa­hedral geometry defined by four N atoms from four pyridine mol­ecules and two thio­cyanate anions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.090
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

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Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C1      ..       5.93 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1

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S1. Comment

A series of complexes of the type MP₄X₂ (Long & Clarke, 1978; Deng et al., 2006; Cheng et al., 2004)(where M is a divalent transition metal, P is a pyridine derivative and X is a halide or thiocyanate ion) have been synthesized. We have synthesized the title compound, (I), and characterized it by X-ray diffraction and elemental analysis which is reported in this paper.

In the structure of (I) (Fig. 1), the Mn atom lies on an inversion centre and assumes an octahedral coordination geometry from four N-bonded pyridy molecules and two N-bonded thiocyanate anions. The basal plane consisits of four pyridyl N atoms, with bond lengths in the rang 2.3188 (19)–2.3057 (19) Å. The apical positions are occupied by two thiocyanate N atoms, with equal bond distances. The complex exhibits a one dimensional chain structure via short intermolecular contact of the type C—H···S which are consistent with the similar contacts reported earlier (Ma et al., 2007).

The structural features of (I) are very similar to the early results reported for tetrakis(pyridine)metal (Ni, Fe, Co) chloride complexes (Long & Clarke, 1978).

Related literature

For the crystal structure of manganese complexes with related ligands, see: Long & Clarke (1978); Deng et al. (2006); Cheng et al. (2004).

For related literature, see: Ma et al. (2007).

S2. Experimental

A mixtutre of solutions of Mn(OAc)₂. 7 H₂O (0.0450 g, 0.2 mmol) in MeOH (10 ml) and NaSCN (0.0324 g, 0.4 mmol) in pyridine (10 ml) was stirred for four hours and brown single crystals were obtained after allowing the solution to stand at room temperature for three weeks.

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.93 Å (pylidyl) [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. A view of the title compound showing the atomic numbering and 30% probability displacement ellipsoids; symmetry code for atoms labelled with A: -x + 1/2, -y + 1/2, -z + 1.

trans-Tetrakis(pyridine-κN)bis(thiocyanato-κN)manganese

Crystal data

[Mn(NCS)2(C5H5N)4]	F(000) = 1004
Mr = 487.50	Dx = 1.355 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2791 reflections
a = 12.4982 (12) Å	θ = 2.3–26.7°
b = 13.1542 (14) Å	µ = 0.75 mm^−1
c = 15.236 (2) Å	T = 298 K
β = 107.413 (2)°	Block, brown
V = 2390.1 (5) Å^3	0.56 × 0.42 × 0.37 mm
Z = 4

Data collection

CCD area-detector diffractometer	2107 independent reflections
Radiation source: fine-focus sealed tube	1661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.680, Tmax = 0.769	k = −7→15
5844 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0386P)^2 + 2.2714P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2107 reflections	Δρmax = 0.28 e Å^−3
143 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0089 (6)

Special details

Experimental. Elemental analysis: calculated for C₂₂H₂₀MnN₆S₂: C 54.20, H 4.14, N 16.42%; found: C 54.21, H 4.13, N 16.40%.

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	0.2500	0.2500	0.5000	0.04435 (19)
N1	0.10819 (16)	0.16743 (16)	0.51970 (15)	0.0601 (6)
N2	0.21099 (15)	0.18519 (15)	0.35223 (13)	0.0498 (5)
N3	0.36836 (16)	0.11699 (15)	0.56271 (13)	0.0524 (5)
S1	−0.07605 (6)	0.14598 (6)	0.58350 (6)	0.0735 (3)
C1	0.03139 (19)	0.15820 (16)	0.54594 (15)	0.0453 (5)
C2	0.1569 (2)	0.0971 (2)	0.32889 (18)	0.0599 (7)
H2	0.1323	0.0633	0.3730	0.072*
C3	0.1355 (2)	0.0536 (2)	0.2437 (2)	0.0711 (8)
H3	0.0991	−0.0088	0.2311	0.085*
C4	0.1684 (2)	0.1034 (3)	0.1779 (2)	0.0797 (9)
H4	0.1541	0.0760	0.1192	0.096*
C5	0.2228 (3)	0.1940 (3)	0.1993 (2)	0.0806 (9)
H5	0.2457	0.2294	0.1553	0.097*
C6	0.2435 (2)	0.2326 (2)	0.28698 (18)	0.0626 (7)
H6	0.2816	0.2940	0.3012	0.075*
C7	0.3356 (2)	0.0206 (2)	0.5493 (2)	0.0664 (7)
H7	0.2613	0.0074	0.5165	0.080*
C8	0.4055 (3)	−0.0603 (2)	0.5813 (2)	0.0847 (10)
H8	0.3795	−0.1266	0.5691	0.102*
C9	0.5135 (3)	−0.0418 (3)	0.6309 (3)	0.0924 (11)
H9	0.5625	−0.0952	0.6541	0.111*
C10	0.5488 (3)	0.0562 (3)	0.6461 (2)	0.0907 (10)
H10	0.6225	0.0709	0.6796	0.109*
C11	0.4744 (2)	0.1328 (2)	0.6113 (2)	0.0701 (8)
H11	0.4994	0.1996	0.6222	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0405 (3)	0.0446 (3)	0.0497 (3)	−0.0004 (2)	0.0162 (2)	0.0014 (2)
N1	0.0493 (11)	0.0643 (13)	0.0705 (14)	−0.0099 (10)	0.0239 (11)	−0.0002 (11)
N2	0.0461 (10)	0.0537 (12)	0.0503 (11)	0.0016 (9)	0.0154 (9)	0.0013 (10)
N3	0.0487 (11)	0.0514 (12)	0.0582 (12)	0.0034 (9)	0.0178 (10)	0.0047 (10)
S1	0.0721 (5)	0.0691 (5)	0.0963 (6)	−0.0056 (4)	0.0509 (4)	0.0024 (4)
C1	0.0485 (12)	0.0377 (12)	0.0474 (13)	−0.0022 (10)	0.0109 (11)	0.0023 (10)
C2	0.0568 (15)	0.0658 (17)	0.0580 (16)	−0.0058 (13)	0.0188 (12)	−0.0054 (13)
C3	0.0616 (16)	0.082 (2)	0.0677 (18)	−0.0056 (14)	0.0169 (14)	−0.0206 (16)
C4	0.0650 (18)	0.116 (3)	0.0544 (17)	0.0082 (18)	0.0119 (14)	−0.0205 (18)
C5	0.079 (2)	0.115 (3)	0.0547 (17)	0.009 (2)	0.0302 (15)	0.0157 (18)
C6	0.0597 (15)	0.0704 (18)	0.0575 (16)	0.0016 (13)	0.0174 (13)	0.0095 (13)
C7	0.0664 (16)	0.0559 (16)	0.0783 (19)	0.0019 (13)	0.0236 (14)	0.0101 (14)
C8	0.110 (3)	0.0530 (17)	0.103 (2)	0.0173 (17)	0.050 (2)	0.0166 (16)
C9	0.093 (3)	0.089 (3)	0.103 (3)	0.046 (2)	0.041 (2)	0.035 (2)
C10	0.0607 (18)	0.099 (3)	0.103 (3)	0.0258 (18)	0.0096 (17)	0.021 (2)
C11	0.0565 (16)	0.0679 (18)	0.0804 (19)	0.0057 (14)	0.0120 (14)	0.0030 (15)

Geometric parameters (Å, º)

Mn1—N1^i	2.1747 (19)	C3—H3	0.9300
Mn1—N1	2.1747 (19)	C4—C5	1.362 (5)
Mn1—N3^i	2.3057 (19)	C4—H4	0.9300
Mn1—N3	2.3057 (19)	C5—C6	1.379 (4)
Mn1—N2^i	2.3188 (19)	C5—H5	0.9300
Mn1—N2	2.3188 (19)	C6—H6	0.9300
N1—C1	1.151 (3)	C7—C8	1.371 (4)
N2—C2	1.336 (3)	C7—H7	0.9300
N2—C6	1.336 (3)	C8—C9	1.356 (5)
N3—C11	1.327 (3)	C8—H8	0.9300
N3—C7	1.329 (3)	C9—C10	1.360 (5)
S1—C1	1.617 (2)	C9—H9	0.9300
C2—C3	1.369 (4)	C10—C11	1.366 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.360 (4)	C11—H11	0.9300
N1^i—Mn1—N1	180.00	C4—C3—H3	120.6
N1^i—Mn1—N3^i	90.69 (7)	C2—C3—H3	120.6
N1—Mn1—N3^i	89.31 (7)	C3—C4—C5	118.9 (3)
N1^i—Mn1—N3	89.31 (7)	C3—C4—H4	120.5
N1—Mn1—N3	90.69 (7)	C5—C4—H4	120.5
N3^i—Mn1—N3	180.00	C4—C5—C6	119.4 (3)
N1^i—Mn1—N2^i	90.41 (7)	C4—C5—H5	120.3
N1—Mn1—N2^i	89.59 (7)	C6—C5—H5	120.3
N3^i—Mn1—N2^i	92.62 (7)	N2—C6—C5	122.5 (3)
N3—Mn1—N2^i	87.38 (7)	N2—C6—H6	118.7
N1^i—Mn1—N2	89.59 (7)	C5—C6—H6	118.7
N1—Mn1—N2	90.41 (7)	N3—C7—C8	123.5 (3)
N3^i—Mn1—N2	87.38 (7)	N3—C7—H7	118.3
N3—Mn1—N2	92.62 (7)	C8—C7—H7	118.3
N2^i—Mn1—N2	180.0	C9—C8—C7	118.7 (3)
C1—N1—Mn1	154.0 (2)	C9—C8—H8	120.6
C2—N2—C6	116.7 (2)	C7—C8—H8	120.6
C2—N2—Mn1	121.34 (16)	C8—C9—C10	118.9 (3)
C6—N2—Mn1	121.90 (17)	C8—C9—H9	120.5
C11—N3—C7	116.5 (2)	C10—C9—H9	120.5
C11—N3—Mn1	121.45 (18)	C9—C10—C11	119.0 (3)
C7—N3—Mn1	122.01 (17)	C9—C10—H10	120.5
N1—C1—S1	179.5 (2)	C11—C10—H10	120.5
N2—C2—C3	123.7 (3)	N3—C11—C10	123.4 (3)
N2—C2—H2	118.2	N3—C11—H11	118.3
C3—C2—H2	118.2	C10—C11—H11	118.3
C4—C3—C2	118.8 (3)
N3^i—Mn1—N1—C1	−53.0 (4)	N2^i—Mn1—N3—C7	125.3 (2)
N3—Mn1—N1—C1	127.0 (4)	N2—Mn1—N3—C7	−54.7 (2)
N2^i—Mn1—N1—C1	39.6 (4)	C6—N2—C2—C3	1.1 (4)
N2—Mn1—N1—C1	−140.4 (4)	Mn1—N2—C2—C3	−177.5 (2)
N1^i—Mn1—N2—C2	154.24 (18)	N2—C2—C3—C4	−1.6 (4)
N1—Mn1—N2—C2	−25.76 (18)	C2—C3—C4—C5	0.9 (4)
N3^i—Mn1—N2—C2	−115.04 (18)	C3—C4—C5—C6	0.3 (4)
N3—Mn1—N2—C2	64.96 (18)	C2—N2—C6—C5	0.2 (4)
N1^i—Mn1—N2—C6	−24.21 (19)	Mn1—N2—C6—C5	178.7 (2)
N1—Mn1—N2—C6	155.79 (19)	C4—C5—C6—N2	−0.9 (4)
N3^i—Mn1—N2—C6	66.50 (19)	C11—N3—C7—C8	−1.2 (4)
N3—Mn1—N2—C6	−113.50 (19)	Mn1—N3—C7—C8	176.2 (2)
N1^i—Mn1—N3—C11	33.1 (2)	N3—C7—C8—C9	1.4 (5)
N1—Mn1—N3—C11	−146.9 (2)	C7—C8—C9—C10	−0.9 (5)
N2^i—Mn1—N3—C11	−57.3 (2)	C8—C9—C10—C11	0.3 (6)
N2—Mn1—N3—C11	122.7 (2)	C7—N3—C11—C10	0.6 (4)
N1^i—Mn1—N3—C7	−144.2 (2)	Mn1—N3—C11—C10	−176.9 (2)
N1—Mn1—N3—C7	35.8 (2)	C9—C10—C11—N3	−0.1 (5)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.