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

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.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.141
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C5     -   C6      ..       8.34 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C2

Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.59 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mn1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C4     -   C5     ...       1.39 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C5     -   C6     ...       1.42 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.11

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

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

Computing details

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

	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.]
	Fig. 2. C—H···π interactions in the title compound.

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

Crystal data

(C12H24N2)2·[Mn(NCS)6]	F(000) = 838
Mr = 796.08	Dx = 1.349 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2869 reflections
a = 9.8816 (15) Å	θ = 2.3–23.4°
b = 13.382 (2) Å	µ = 0.69 mm^−1
c = 15.173 (2) Å	T = 273 K
β = 102.431 (3)°	Fragment, colorless
V = 1959.4 (5) Å^3	0.53 × 0.15 × 0.12 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	3589 independent reflections
Radiation source: fine-focus sealed tube	2679 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→11
Tmin = 0.710, Tmax = 0.922	k = −16→16
10582 measured reflections	l = −18→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0826P)^2 + 0.6082P] where P = (Fo^2 + 2Fc^2)/3
3589 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.41 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	0.5000	0.5000	0.0000	0.0522 (2)
S1	0.39777 (8)	0.43111 (6)	0.30277 (5)	0.0629 (2)
S2	0.96283 (13)	0.64089 (10)	0.14596 (8)	0.1117 (5)
S3	0.69183 (9)	0.15133 (6)	0.01699 (7)	0.0737 (3)
N1	0.4577 (3)	0.4769 (2)	0.1366 (2)	0.0731 (8)
N2	0.7113 (3)	0.5556 (2)	0.06566 (19)	0.0698 (7)
N3	0.5748 (3)	0.3416 (2)	−0.0022 (2)	0.0718 (7)
N4	−0.0605 (2)	0.31563 (18)	0.21676 (15)	0.0522 (6)
N5	0.1560 (2)	0.23697 (15)	0.12676 (15)	0.0454 (5)
C1	0.4340 (3)	0.4584 (2)	0.2058 (2)	0.0535 (7)
C2	0.8136 (4)	0.5917 (2)	0.1000 (2)	0.0588 (7)
C3	0.6225 (3)	0.2633 (2)	0.00443 (18)	0.0518 (7)
C4	−0.2133 (3)	0.3136 (4)	0.2228 (3)	0.0870 (12)
H4A	−0.2701	0.3484	0.1719	0.104*
H4B	−0.2461	0.2454	0.2235	0.104*
C5	−0.2180 (5)	0.3621 (7)	0.3035 (4)	0.0778 (9)
H5A	−0.2162	0.3127	0.3506	0.208*
H5B	−0.3042	0.3990	0.2962	0.208*
C6	−0.1051 (4)	0.4288 (3)	0.3302 (3)	0.0796 (11)
H6A	−0.0737	0.4286	0.3953	0.095*
H6B	−0.1324	0.4962	0.3108	0.095*
C7	0.0067 (3)	0.3931 (3)	0.2866 (2)	0.0624 (8)
H7A	0.0811	0.3631	0.3309	0.075*
H7B	0.0441	0.4481	0.2577	0.075*
C8	0.0024 (3)	0.2135 (2)	0.2360 (2)	0.0582 (7)
H8A	0.0033	0.1959	0.2982	0.070*
H8B	−0.0551	0.1651	0.1975	0.070*
C9	0.1473 (3)	0.2074 (2)	0.22088 (19)	0.0544 (7)
H9A	0.1811	0.1396	0.2322	0.065*
H9B	0.2068	0.2509	0.2636	0.065*
C10	−0.0488 (3)	0.3443 (2)	0.12343 (19)	0.0520 (7)
H10A	−0.0841	0.4116	0.1107	0.062*
H10B	−0.1055	0.2996	0.0804	0.062*
C11	0.0972 (3)	0.33998 (19)	0.11145 (18)	0.0483 (6)
H11A	0.1000	0.3614	0.0508	0.058*
H11B	0.1537	0.3857	0.1535	0.058*
C12	0.3072 (3)	0.2362 (2)	0.1172 (2)	0.0666 (8)
H12A	0.3218	0.2839	0.0720	0.080*
H12B	0.3695	0.2518	0.1742	0.080*
C13	0.3285 (4)	0.1318 (3)	0.0886 (3)	0.0802 (10)
H13A	0.4034	0.1289	0.0565	0.096*
H13B	0.3503	0.0877	0.1404	0.096*
C14	0.1949 (3)	0.1030 (3)	0.0284 (2)	0.0731 (9)
H14A	0.1782	0.0321	0.0339	0.088*
H14B	0.1970	0.1173	−0.0340	0.088*
C15	0.0839 (3)	0.1620 (2)	0.0562 (2)	0.0565 (7)
H15A	0.0237	0.1185	0.0817	0.068*
H15B	0.0284	0.1966	0.0047	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0530 (4)	0.0457 (3)	0.0566 (4)	0.0007 (3)	0.0087 (3)	0.0067 (3)
S1	0.0679 (5)	0.0649 (5)	0.0582 (5)	0.0009 (4)	0.0187 (4)	−0.0070 (3)
S2	0.1121 (9)	0.1153 (9)	0.0864 (7)	−0.0565 (7)	−0.0255 (6)	0.0210 (6)
S3	0.0617 (5)	0.0549 (5)	0.0956 (6)	0.0095 (4)	−0.0032 (4)	−0.0172 (4)
N1	0.083 (2)	0.0689 (18)	0.0693 (19)	−0.0124 (15)	0.0204 (15)	0.0036 (14)
N2	0.0604 (17)	0.0664 (17)	0.0783 (18)	−0.0023 (14)	0.0056 (14)	0.0072 (14)
N3	0.0711 (18)	0.0584 (16)	0.0807 (19)	0.0109 (14)	0.0051 (14)	0.0068 (13)
N4	0.0405 (12)	0.0662 (15)	0.0518 (13)	−0.0041 (10)	0.0139 (10)	−0.0138 (11)
N5	0.0430 (12)	0.0385 (11)	0.0553 (13)	0.0046 (9)	0.0114 (9)	−0.0018 (9)
C1	0.0552 (17)	0.0427 (14)	0.0621 (19)	−0.0016 (12)	0.0113 (13)	−0.0049 (13)
C2	0.074 (2)	0.0470 (16)	0.0533 (17)	−0.0013 (15)	0.0080 (15)	0.0052 (13)
C3	0.0477 (15)	0.0569 (18)	0.0479 (15)	−0.0028 (13)	0.0039 (12)	−0.0076 (12)
C4	0.0441 (17)	0.132 (3)	0.090 (3)	−0.0091 (19)	0.0240 (16)	−0.042 (2)
C5	0.0744 (19)	0.0477 (15)	0.088 (2)	0.0017 (14)	0.0370 (16)	−0.0168 (15)
C6	0.070 (2)	0.095 (3)	0.076 (2)	0.0153 (19)	0.0188 (17)	−0.0264 (19)
C7	0.0552 (17)	0.075 (2)	0.0581 (17)	−0.0022 (15)	0.0149 (13)	−0.0236 (15)
C8	0.0688 (19)	0.0582 (17)	0.0488 (16)	−0.0111 (14)	0.0153 (13)	0.0041 (13)
C9	0.0574 (17)	0.0454 (15)	0.0568 (17)	0.0082 (13)	0.0048 (13)	0.0071 (12)
C10	0.0508 (16)	0.0533 (16)	0.0502 (15)	0.0141 (12)	0.0073 (11)	−0.0029 (12)
C11	0.0579 (16)	0.0384 (13)	0.0520 (15)	0.0039 (11)	0.0194 (12)	0.0035 (11)
C12	0.0456 (16)	0.067 (2)	0.092 (2)	0.0008 (14)	0.0249 (15)	−0.0129 (17)
C13	0.068 (2)	0.077 (2)	0.104 (3)	0.0157 (18)	0.034 (2)	−0.014 (2)
C14	0.076 (2)	0.082 (2)	0.067 (2)	0.0044 (18)	0.0292 (17)	−0.0226 (17)
C15	0.0619 (18)	0.0507 (16)	0.0554 (16)	0.0044 (13)	0.0097 (13)	−0.0101 (13)

Geometric parameters (Å, º)

Mn1—N1	2.223 (3)	C6—C7	1.483 (4)
Mn1—N1^i	2.223 (3)	C6—H6A	0.9700
Mn1—N2^i	2.239 (3)	C6—H6B	0.9700
Mn1—N2	2.239 (3)	C7—H7A	0.9700
Mn1—N3^i	2.248 (3)	C7—H7B	0.9700
Mn1—N3	2.248 (3)	C8—C9	1.500 (4)
S1—C1	1.629 (3)	C8—H8A	0.9700
S2—C2	1.628 (3)	C8—H8B	0.9700
S3—C3	1.641 (3)	C9—H9A	0.9700
N1—C1	1.150 (4)	C9—H9B	0.9700
N2—C2	1.140 (4)	C10—C11	1.493 (4)
N3—C3	1.144 (4)	C10—H10A	0.9700
N4—C10	1.496 (4)	C10—H10B	0.9700
N4—C8	1.504 (4)	C11—H11A	0.9700
N4—C7	1.528 (4)	C11—H11B	0.9700
N4—C4	1.532 (4)	C12—C13	1.492 (5)
N5—C11	1.494 (3)	C12—H12A	0.9700
N5—C9	1.502 (4)	C12—H12B	0.9700
N5—C15	1.527 (3)	C13—C14	1.486 (5)
N5—C12	1.532 (3)	C13—H13A	0.9700
C4—C5	1.396 (5)	C13—H13B	0.9700
C4—H4A	0.9700	C14—C15	1.485 (4)
C4—H4B	0.9700	C14—H14A	0.9700
C5—C6	1.417 (6)	C14—H14B	0.9700
C5—H5A	0.9700	C15—H15A	0.9700
C5—H5B	0.9700	C15—H15B	0.9700
N1—Mn1—N1^i	180.00 (15)	N4—C7—H7A	110.6
N1—Mn1—N2^i	91.38 (11)	C6—C7—H7B	110.6
N1^i—Mn1—N2^i	88.62 (11)	N4—C7—H7B	110.6
N1—Mn1—N2	88.62 (11)	H7A—C7—H7B	108.7
N1^i—Mn1—N2	91.38 (11)	C9—C8—N4	112.8 (2)
N2^i—Mn1—N2	180.0	C9—C8—H8A	109.0
N1—Mn1—N3^i	89.36 (11)	N4—C8—H8A	109.0
N1^i—Mn1—N3^i	90.64 (11)	C9—C8—H8B	109.0
N2^i—Mn1—N3^i	92.38 (10)	N4—C8—H8B	109.0
N2—Mn1—N3^i	87.62 (10)	H8A—C8—H8B	107.8
N1—Mn1—N3	90.64 (11)	C8—C9—N5	112.5 (2)
N1^i—Mn1—N3	89.36 (11)	C8—C9—H9A	109.1
N2^i—Mn1—N3	87.62 (10)	N5—C9—H9A	109.1
N2—Mn1—N3	92.38 (10)	C8—C9—H9B	109.1
N3^i—Mn1—N3	180.0	N5—C9—H9B	109.1
C1—N1—Mn1	175.4 (3)	H9A—C9—H9B	107.8
C2—N2—Mn1	174.0 (3)	N4—C10—C11	112.3 (2)
C3—N3—Mn1	173.1 (3)	N4—C10—H10A	109.1
C10—N4—C8	107.7 (2)	C11—C10—H10A	109.1
C10—N4—C7	111.8 (2)	N4—C10—H10B	109.1
C8—N4—C7	112.5 (2)	C11—C10—H10B	109.1
C10—N4—C4	109.8 (2)	H10A—C10—H10B	107.9
C8—N4—C4	110.1 (3)	N5—C11—C10	111.7 (2)
C7—N4—C4	104.9 (2)	N5—C11—H11A	109.3
C11—N5—C9	106.9 (2)	C10—C11—H11A	109.3
C11—N5—C15	113.0 (2)	N5—C11—H11B	109.3
C9—N5—C15	112.3 (2)	C10—C11—H11B	109.3
C11—N5—C12	110.2 (2)	H11A—C11—H11B	107.9
C9—N5—C12	110.2 (2)	C13—C12—N5	103.6 (2)
C15—N5—C12	104.3 (2)	C13—C12—H12A	111.0
N1—C1—S1	178.9 (3)	N5—C12—H12A	111.0
N2—C2—S2	177.6 (3)	C13—C12—H12B	111.0
N3—C3—S3	178.4 (3)	N5—C12—H12B	111.0
C5—C4—N4	105.3 (3)	H12A—C12—H12B	109.0
C5—C4—H4A	110.7	C14—C13—C12	105.0 (3)
N4—C4—H4A	110.7	C14—C13—H13A	110.7
C5—C4—H4B	110.7	C12—C13—H13A	110.7
N4—C4—H4B	110.7	C14—C13—H13B	110.7
H4A—C4—H4B	108.8	C12—C13—H13B	110.7
C4—C5—C6	111.7 (4)	H13A—C13—H13B	108.8
C4—C5—H5A	109.3	C13—C14—C15	107.5 (3)
C6—C5—H5A	109.3	C13—C14—H14A	110.2
C4—C5—H5B	109.3	C15—C14—H14A	110.2
C6—C5—H5B	109.3	C13—C14—H14B	110.2
H5A—C5—H5B	107.9	C15—C14—H14B	110.2
C5—C6—C7	106.6 (3)	H14A—C14—H14B	108.5
C5—C6—H6A	110.4	C14—C15—N5	106.7 (2)
C7—C6—H6A	110.4	C14—C15—H15A	110.4
C5—C6—H6B	110.4	N5—C15—H15A	110.4
C7—C6—H6B	110.4	C14—C15—H15B	110.4
H6A—C6—H6B	108.6	N5—C15—H15B	110.4
C6—C7—N4	105.9 (2)	H15A—C15—H15B	108.6
C6—C7—H7A	110.6

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···S3^ii	0.97	2.81	3.629 (3)	143
C10—H10B···S3^iii	0.97	2.84	3.750 (3)	157

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