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Acta Cryst. (2007). E63, m2568    [ doi:10.1107/S1600536807044753 ]

Bis(5,8-diazoniadispiro[4.2.4.2]tetradecane) hexakis(thiocyanato-[kappa]N)manganate(II)

Y.-X. Li, X.-L. Guo, Z. Wang and Y. Niu

Abstract top

The asymmetric unit of the title compound, (C12H24N2)2[Mn(NCS)6], comprises one cation and one half of the anion. The central Mn atom of the anion is situated on an inversion centre and shows the expected octahedral coordination with only minor deviations from the ideal geometry. Intermolecular C-H...S hydrogen-bonding interactions link all components into a three-dimensional network.

Comment top

Organic-inorganic compounds containing the [hexakis(isothiocyanato)manganese(II)] anion, [Mn(NCS)6]4−, have been the subject of several investigations, but reported crystal structures containing this building unit are relatively scarce (Böhland et al. (1997); Bose et al. (2006); Burla et al. (1995); Shen et al. (2002); Shi et al. (2005). In this communication we report the crystal structure of a new [hexakis(isothiocyanato)manganese(II)] salt containing the 5,8-diazoniadispiro[4.2.4.2]tetradecane counter cation.

The structure of the title compound (Fig. 1) comprises discrete (C12H24N2)2+ cations and [Mn(NCS)6]4− anions. The anion, which lies on an inversion center, displays the expected homoleptic N6-octahedral coordination with only minor deviations from the ideal geometry. In the cation, the six-membered ring displays a chair conformation, while the five-membered rings adopt a twist conformation. In the crystal structure, all building units are linked into a three-dimensional extended network via intermolecular C—H···S hydrogen bonding interactions (Table, Fig. 2).

Related literature top

For structures containing the complex [Ni(NCS)6]4− anion, see, for example,: Böhland et al. (1997); Bose et al. (2006); Burla et al. (1995); Shen et al. (2002); Shi et al. (2005).

Experimental top

All chemicals were used as purchased from Jinan Henghua Sci. & Tec. Co., Ltd. The title salt was synthesized from the reaction of 5,8-diazoniadispiro[4.2.4.2]tetradecane dibromide (0.034 g, 0.1 mmol) in methanol (5 ml) and a mixture of MnCl2 (0.012 g, 0.1 mmol) and K(NCS) (0.074 g, 0.4 mmol) in DMF (10 ml). The resulting mixture was set aside for the formation of colourless crystals in approximately 34% yield after several d. Anal. Calc. for C30H48MnN10S6: C 45.26, H 6.07, N 17.59%; Found: C 45.21, H 6.08, N 17.52%.

Refinement top

All H atoms bonded to C atoms were generated geometrically and refined as riding atoms with C—H= 0.97Å and Uiso(H)= 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. A view of the structure of the title compound, showing displacement ellipsoids at the 30% probability level. [Symmetry operator: (i) −x + 2,-y + 2,-z + 1.]
[Figure 2] Fig. 2. C—H···π interactions in the title compound.
Bis(5,8-diazoniadispiro[4.2.4.2]tetradecane) hexakis(thiocyanato-κN)- manganate(II) top
Crystal data top
(C12H24N2)2·[Mn(NCS)6]F000 = 838
Mr = 796.08Dx = 1.349 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2869 reflections
a = 9.8816 (15) Åθ = 2.3–23.4º
b = 13.382 (2) ŵ = 0.69 mm−1
c = 15.173 (2) ÅT = 273 (2) K
β = 102.431 (3)ºFragment, colorless
V = 1959.4 (5) Å30.53 × 0.15 × 0.12 mm
Z = 2
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3589 independent reflections
Radiation source: fine-focus sealed tube2679 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 273(2) Kθmax = 25.5º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −10→11
Tmin = 0.710, Tmax = 0.922k = −16→16
10582 measured reflectionsl = −18→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.141  w = 1/[σ2(Fo2) + (0.0826P)2 + 0.6082P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
3589 reflectionsΔρmax = 0.51 e Å−3
214 parametersΔρmin = −0.41 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C12H24N2)2·[Mn(NCS)6]V = 1959.4 (5) Å3
Mr = 796.08Z = 2
Monoclinic, P21/nMo Kα
a = 9.8816 (15) ŵ = 0.69 mm−1
b = 13.382 (2) ÅT = 273 (2) K
c = 15.173 (2) Å0.53 × 0.15 × 0.12 mm
β = 102.431 (3)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3589 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2679 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.922Rint = 0.024
10582 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046214 parameters
wR(F2) = 0.141H-atom parameters constrained
S = 1.00Δρmax = 0.51 e Å−3
3589 reflectionsΔρmin = −0.41 e Å−3
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
xyzUiso*/Ueq
Mn10.50000.50000.00000.0522 (2)
S10.39777 (8)0.43111 (6)0.30277 (5)0.0629 (2)
S20.96283 (13)0.64089 (10)0.14596 (8)0.1117 (5)
S30.69183 (9)0.15133 (6)0.01699 (7)0.0737 (3)
N10.4577 (3)0.4769 (2)0.1366 (2)0.0731 (8)
N20.7113 (3)0.5556 (2)0.06566 (19)0.0698 (7)
N30.5748 (3)0.3416 (2)−0.0022 (2)0.0718 (7)
N4−0.0605 (2)0.31563 (18)0.21676 (15)0.0522 (6)
N50.1560 (2)0.23697 (15)0.12676 (15)0.0454 (5)
C10.4340 (3)0.4584 (2)0.2058 (2)0.0535 (7)
C20.8136 (4)0.5917 (2)0.1000 (2)0.0588 (7)
C30.6225 (3)0.2633 (2)0.00443 (18)0.0518 (7)
C4−0.2133 (3)0.3136 (4)0.2228 (3)0.0870 (12)
H4A−0.27010.34840.17190.104*
H4B−0.24610.24540.22350.104*
C5−0.2180 (5)0.3621 (7)0.3035 (4)0.0778 (9)
H5A−0.21620.31270.35060.208*
H5B−0.30420.39900.29620.208*
C6−0.1051 (4)0.4288 (3)0.3302 (3)0.0796 (11)
H6A−0.07370.42860.39530.095*
H6B−0.13240.49620.31080.095*
C70.0067 (3)0.3931 (3)0.2866 (2)0.0624 (8)
H7A0.08110.36310.33090.075*
H7B0.04410.44810.25770.075*
C80.0024 (3)0.2135 (2)0.2360 (2)0.0582 (7)
H8A0.00330.19590.29820.070*
H8B−0.05510.16510.19750.070*
C90.1473 (3)0.2074 (2)0.22088 (19)0.0544 (7)
H9A0.18110.13960.23220.065*
H9B0.20680.25090.26360.065*
C10−0.0488 (3)0.3443 (2)0.12343 (19)0.0520 (7)
H10A−0.08410.41160.11070.062*
H10B−0.10550.29960.08040.062*
C110.0972 (3)0.33998 (19)0.11145 (18)0.0483 (6)
H11A0.10000.36140.05080.058*
H11B0.15370.38570.15350.058*
C120.3072 (3)0.2362 (2)0.1172 (2)0.0666 (8)
H12A0.32180.28390.07200.080*
H12B0.36950.25180.17420.080*
C130.3285 (4)0.1318 (3)0.0886 (3)0.0802 (10)
H13A0.40340.12890.05650.096*
H13B0.35030.08770.14040.096*
C140.1949 (3)0.1030 (3)0.0284 (2)0.0731 (9)
H14A0.17820.03210.03390.088*
H14B0.19700.1173−0.03400.088*
C150.0839 (3)0.1620 (2)0.0562 (2)0.0565 (7)
H15A0.02370.11850.08170.068*
H15B0.02840.19660.00470.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0530 (4)0.0457 (3)0.0566 (4)0.0007 (3)0.0087 (3)0.0067 (3)
S10.0679 (5)0.0649 (5)0.0582 (5)0.0009 (4)0.0187 (4)−0.0070 (3)
S20.1121 (9)0.1153 (9)0.0864 (7)−0.0565 (7)−0.0255 (6)0.0210 (6)
S30.0617 (5)0.0549 (5)0.0956 (6)0.0095 (4)−0.0032 (4)−0.0172 (4)
N10.083 (2)0.0689 (18)0.0693 (19)−0.0124 (15)0.0204 (15)0.0036 (14)
N20.0604 (17)0.0664 (17)0.0783 (18)−0.0023 (14)0.0056 (14)0.0072 (14)
N30.0711 (18)0.0584 (16)0.0807 (19)0.0109 (14)0.0051 (14)0.0068 (13)
N40.0405 (12)0.0662 (15)0.0518 (13)−0.0041 (10)0.0139 (10)−0.0138 (11)
N50.0430 (12)0.0385 (11)0.0553 (13)0.0046 (9)0.0114 (9)−0.0018 (9)
C10.0552 (17)0.0427 (14)0.0621 (19)−0.0016 (12)0.0113 (13)−0.0049 (13)
C20.074 (2)0.0470 (16)0.0533 (17)−0.0013 (15)0.0080 (15)0.0052 (13)
C30.0477 (15)0.0569 (18)0.0479 (15)−0.0028 (13)0.0039 (12)−0.0076 (12)
C40.0441 (17)0.132 (3)0.090 (3)−0.0091 (19)0.0240 (16)−0.042 (2)
C50.0744 (19)0.0477 (15)0.088 (2)0.0017 (14)0.0370 (16)−0.0168 (15)
C60.070 (2)0.095 (3)0.076 (2)0.0153 (19)0.0188 (17)−0.0264 (19)
C70.0552 (17)0.075 (2)0.0581 (17)−0.0022 (15)0.0149 (13)−0.0236 (15)
C80.0688 (19)0.0582 (17)0.0488 (16)−0.0111 (14)0.0153 (13)0.0041 (13)
C90.0574 (17)0.0454 (15)0.0568 (17)0.0082 (13)0.0048 (13)0.0071 (12)
C100.0508 (16)0.0533 (16)0.0502 (15)0.0141 (12)0.0073 (11)−0.0029 (12)
C110.0579 (16)0.0384 (13)0.0520 (15)0.0039 (11)0.0194 (12)0.0035 (11)
C120.0456 (16)0.067 (2)0.092 (2)0.0008 (14)0.0249 (15)−0.0129 (17)
C130.068 (2)0.077 (2)0.104 (3)0.0157 (18)0.034 (2)−0.014 (2)
C140.076 (2)0.082 (2)0.067 (2)0.0044 (18)0.0292 (17)−0.0226 (17)
C150.0619 (18)0.0507 (16)0.0554 (16)0.0044 (13)0.0097 (13)−0.0101 (13)
Geometric parameters (Å, °) top
Mn1—N12.223 (3)C6—C71.483 (4)
Mn1—N1i2.223 (3)C6—H6A0.9700
Mn1—N2i2.239 (3)C6—H6B0.9700
Mn1—N22.239 (3)C7—H7A0.9700
Mn1—N3i2.248 (3)C7—H7B0.9700
Mn1—N32.248 (3)C8—C91.500 (4)
S1—C11.629 (3)C8—H8A0.9700
S2—C21.628 (3)C8—H8B0.9700
S3—C31.641 (3)C9—H9A0.9700
N1—C11.150 (4)C9—H9B0.9700
N2—C21.140 (4)C10—C111.493 (4)
N3—C31.144 (4)C10—H10A0.9700
N4—C101.496 (4)C10—H10B0.9700
N4—C81.504 (4)C11—H11A0.9700
N4—C71.528 (4)C11—H11B0.9700
N4—C41.532 (4)C12—C131.492 (5)
N5—C111.494 (3)C12—H12A0.9700
N5—C91.502 (4)C12—H12B0.9700
N5—C151.527 (3)C13—C141.486 (5)
N5—C121.532 (3)C13—H13A0.9700
C4—C51.396 (5)C13—H13B0.9700
C4—H4A0.9700C14—C151.485 (4)
C4—H4B0.9700C14—H14A0.9700
C5—C61.417 (6)C14—H14B0.9700
C5—H5A0.9700C15—H15A0.9700
C5—H5B0.9700C15—H15B0.9700
N1—Mn1—N1i180.00 (15)N4—C7—H7A110.6
N1—Mn1—N2i91.38 (11)C6—C7—H7B110.6
N1i—Mn1—N2i88.62 (11)N4—C7—H7B110.6
N1—Mn1—N288.62 (11)H7A—C7—H7B108.7
N1i—Mn1—N291.38 (11)C9—C8—N4112.8 (2)
N2i—Mn1—N2180.0C9—C8—H8A109.0
N1—Mn1—N3i89.36 (11)N4—C8—H8A109.0
N1i—Mn1—N3i90.64 (11)C9—C8—H8B109.0
N2i—Mn1—N3i92.38 (10)N4—C8—H8B109.0
N2—Mn1—N3i87.62 (10)H8A—C8—H8B107.8
N1—Mn1—N390.64 (11)C8—C9—N5112.5 (2)
N1i—Mn1—N389.36 (11)C8—C9—H9A109.1
N2i—Mn1—N387.62 (10)N5—C9—H9A109.1
N2—Mn1—N392.38 (10)C8—C9—H9B109.1
N3i—Mn1—N3180.0N5—C9—H9B109.1
C1—N1—Mn1175.4 (3)H9A—C9—H9B107.8
C2—N2—Mn1174.0 (3)N4—C10—C11112.3 (2)
C3—N3—Mn1173.1 (3)N4—C10—H10A109.1
C10—N4—C8107.7 (2)C11—C10—H10A109.1
C10—N4—C7111.8 (2)N4—C10—H10B109.1
C8—N4—C7112.5 (2)C11—C10—H10B109.1
C10—N4—C4109.8 (2)H10A—C10—H10B107.9
C8—N4—C4110.1 (3)N5—C11—C10111.7 (2)
C7—N4—C4104.9 (2)N5—C11—H11A109.3
C11—N5—C9106.9 (2)C10—C11—H11A109.3
C11—N5—C15113.0 (2)N5—C11—H11B109.3
C9—N5—C15112.3 (2)C10—C11—H11B109.3
C11—N5—C12110.2 (2)H11A—C11—H11B107.9
C9—N5—C12110.2 (2)C13—C12—N5103.6 (2)
C15—N5—C12104.3 (2)C13—C12—H12A111.0
N1—C1—S1178.9 (3)N5—C12—H12A111.0
N2—C2—S2177.6 (3)C13—C12—H12B111.0
N3—C3—S3178.4 (3)N5—C12—H12B111.0
C5—C4—N4105.3 (3)H12A—C12—H12B109.0
C5—C4—H4A110.7C14—C13—C12105.0 (3)
N4—C4—H4A110.7C14—C13—H13A110.7
C5—C4—H4B110.7C12—C13—H13A110.7
N4—C4—H4B110.7C14—C13—H13B110.7
H4A—C4—H4B108.8C12—C13—H13B110.7
C4—C5—C6111.7 (4)H13A—C13—H13B108.8
C4—C5—H5A109.3C13—C14—C15107.5 (3)
C6—C5—H5A109.3C13—C14—H14A110.2
C4—C5—H5B109.3C15—C14—H14A110.2
C6—C5—H5B109.3C13—C14—H14B110.2
H5A—C5—H5B107.9C15—C14—H14B110.2
C5—C6—C7106.6 (3)H14A—C14—H14B108.5
C5—C6—H6A110.4C14—C15—N5106.7 (2)
C7—C6—H6A110.4C14—C15—H15A110.4
C5—C6—H6B110.4N5—C15—H15A110.4
C7—C6—H6B110.4C14—C15—H15B110.4
H6A—C6—H6B108.6N5—C15—H15B110.4
C6—C7—N4105.9 (2)H15A—C15—H15B108.6
C6—C7—H7A110.6
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···S3ii0.972.813.629 (3)143
C10—H10B···S3iii0.972.843.750 (3)157
Symmetry codes: (ii) x−1/2, −y+1/2, z+1/2; (iii) x−1, y, z.
Table 1
Selected geometric parameters (Å) top
Mn1—N12.223 (3)S3—C31.641 (3)
Mn1—N22.239 (3)N1—C11.150 (4)
Mn1—N32.248 (3)N2—C21.140 (4)
S1—C11.629 (3)N3—C31.144 (4)
S2—C21.628 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···S3i0.972.813.629 (3)143
C10—H10B···S3ii0.972.843.750 (3)157
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x−1, y, z.
Acknowledgements top

The authors thank the National Natural Science Foundation (grant No. 20671083), the Henan Province Excellent Youth Foundation (grant No. 0612002800) and Jinan Henghua Science and Technology Co. Ltd for supporting this work. We also thank Wuhan University for the diffraction measurements.

references
References top

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