Bis[4-(dimethyl­amino)­pyridinium] bis­[4-(dimethyl­amino)­pyridine-κN1]tetra­kis­(thio­cyanato-κN)manganate(II)

Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S1600536812047678

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1528

doi:10.1107/S1600536812047678

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Bis[4-(dimethylamino)pyridinium] bis[4-(dimethylamino)pyridine-κN¹]tetrakis(thiocyanato-κN)manganate(II)

Susanne Wöhlert,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 15 November 2012; accepted 20 November 2012; online 24 November 2012)

In the crystal structure of the title compound, (C₇H₁₁N₂)₂[Mn(NCS)₄(C₇H₁₀N₂)₂], the manganese(II) cations are coordinated by four N-bonded thiocyanate anions and two N-bonded 4-(dimethylamino)pyridine ligands into discrete complex dianions. For charge balance, two 4-(dimethylamino)pyridine counter cations are present, which do not coordinate to the metal cation. The asymmetric unit consists of one manganese(II) cation, four thiocyanate anions and two 4-(dimethylamino)pyridine ligands, as well as two protonated 4-(dimethylamino)pyridinium cations. The discrete complex anions are connected to the non-coordinating pyridinium cations by weak N—H⋯S hydrogen-bonding interactions.

Related literature

For general background, see: Boeckmann & Näther (2011 , 2012 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[Mn(NCS)₄(C₇H₁₀N₂)₂]
M_r = 777.96
Triclinic, $[P \overline 1]$
a = 11.7307 (8) Å
b = 11.9010 (9) Å
c = 15.4224 (12) Å
α = 102.520 (9)°
β = 96.794 (9)°
γ = 107.400 (8)°
V = 1966.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 180 K
0.18 × 0.11 × 0.05 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.873, T_max = 0.968
24452 measured reflections
9338 independent reflections
6752 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.121
S = 1.02
9338 reflections
450 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N1	2.1928 (17)
Mn1—N2	2.2014 (19)
Mn1—N3	2.2468 (19)
Mn1—N4	2.2535 (18)
Mn1—N20	2.2561 (16)
Mn1—N10	2.2659 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N30—H30⋯S4	0.88	2.36	3.217 (2)	165
N40—H40A⋯S3ⁱ	0.88	2.35	3.213 (3)	166
Symmetry code: (i) x+1, 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, 2012 ); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047678/vm2182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047678/vm2182Isup2.hkl

checkCIF report

Comment top

The structure determination was performed during a project on the synthesis, thermal and magnetic properties of coordination compounds based on transition metal thiocyanates and neutral N-donor co-ligands (Boeckmann & Näther, 2011 & 2012). In order to investigate the influence of the co-ligand, N,N'-dimethylaminopyridine was reacted with manganese(II) thiocyanate which resulted in the formation of crystals of the title compound that were identified by single-crystal X-ray diffraction.

In the crystal structure of the title compound each manganese(II) cation is coordinated by four N-bonded thiocyanato anions and two N-bonded dimethylaminopyridine ligands (Fig. 1). The MnN₆ octahedra are slightly distorted with distances in the range of 2.1928 (19) Å to 2.2659 (16) Å (Table 1). The angles arround the manganese(II) cations are ranging from 87.73 (6)° to 92.86 (7) ° and 173.95 (6) ° to 178.78 (7) ° (Table 1). There are additional protonated dimethylaminopyridine ligands that does not coordinate to the metal cations, but which are linked to the complex cations by weak intermolecular N–H···S hydrogen bonding, which are ranging from 3.213 (3) Å (N40-H40A···S3[1 + x, 1 + y, 1 + z]) to 3.217 (2) Å (N30-H30···S4, see Fig. 2).

Related literature top

For general background, see: Boeckmann & Näther (2011, 2012).

Experimental top

MnSO₄xH₂O, Ba(NCS)₂x3H₂O and N,N'-dimethylaminopyridine were obtained from Sigma Aldrich. 0.15 mmol (26 mg) Mn(NCS)₂ and 0.3 mmol (58.3 mg) dimethylaminopyridine were reacted with 1 mL ethanol in a snap cap vial. After three days yellow colored block-shaped single crystals of the title compound were obtained.

Computing details top

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, 2012); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal structure of the title compound with view along the crystallographic b-axis. Intermolecular hydrogen bonding is shown as dashed lines.

Bis[4-(dimethylamino)pyridinium] bis[4-(dimethylamino)pyridine- κN¹]tetrakis(thiocyanato-κN)manganate(II) top

Crystal data top

(C₇H₁₁N₂)₂[Mn(NCS)₄(C₇H₁₀N₂)₂]	Z = 2
M_r = 777.96	F(000) = 814
Triclinic, P1	D_x = 1.314 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.7307 (8) Å	Cell parameters from 24452 reflections
b = 11.9010 (9) Å	θ = 2.6–28.0°
c = 15.4224 (12) Å	µ = 0.59 mm⁻¹
α = 102.520 (9)°	T = 180 K
β = 96.794 (9)°	Block, yellow
γ = 107.400 (8)°	0.18 × 0.11 × 0.05 mm
V = 1966.6 (3) Å³

Data collection top

Stoe IPDS-1 diffractometer	9338 independent reflections
Radiation source: fine-focus sealed tube	6752 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
phi scan	θ_max = 28.0°, θ_min = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −15→15
T_min = 0.873, T_max = 0.968	k = −15→15
24452 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0727P)² + 0.0822P] where P = (F_o² + 2F_c²)/3
9338 reflections	(Δ/σ)_max = 0.001
450 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[Mn(NCS)₄(C₇H₁₀N₂)₂]	γ = 107.400 (8)°
M_r = 777.96	V = 1966.6 (3) Å³
Triclinic, P1	Z = 2
a = 11.7307 (8) Å	Mo Kα radiation
b = 11.9010 (9) Å	µ = 0.59 mm⁻¹
c = 15.4224 (12) Å	T = 180 K
α = 102.520 (9)°	0.18 × 0.11 × 0.05 mm
β = 96.794 (9)°

Data collection top

Stoe IPDS-1 diffractometer	9338 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	6752 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.968	R_int = 0.041
24452 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.02	Δρ_max = 0.80 e Å⁻³
9338 reflections	Δρ_min = −0.72 e Å⁻³
450 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.68016 (2)	0.43208 (2)	0.733534 (19)	0.03223 (9)
N1	0.58727 (17)	0.35462 (17)	0.83317 (13)	0.0465 (4)
C1	0.5433 (2)	0.29723 (19)	0.87948 (16)	0.0449 (5)
S1	0.48122 (9)	0.21875 (8)	0.94635 (7)	0.0889 (3)
N2	0.81931 (17)	0.57958 (16)	0.84005 (13)	0.0479 (4)
C2	0.90686 (19)	0.65777 (17)	0.87884 (14)	0.0387 (4)
S2	1.03117 (6)	0.76864 (5)	0.93376 (6)	0.0679 (2)
N3	0.54216 (18)	0.28333 (16)	0.62122 (14)	0.0516 (5)
C3	0.45842 (18)	0.19649 (17)	0.59757 (13)	0.0363 (4)
S3	0.33917 (6)	0.07240 (6)	0.56332 (5)	0.0677 (2)
N4	0.77439 (18)	0.50766 (18)	0.62913 (14)	0.0507 (5)
C4	0.84494 (19)	0.58781 (17)	0.61404 (13)	0.0364 (4)
S4	0.94638 (7)	0.70095 (6)	0.59289 (5)	0.0673 (2)
N10	0.79695 (14)	0.31067 (13)	0.72983 (11)	0.0344 (3)
C10	0.81667 (19)	0.25345 (17)	0.65092 (14)	0.0392 (4)
H10	0.7793	0.2649	0.5969	0.047*
C11	0.8868 (2)	0.17989 (17)	0.64293 (15)	0.0429 (5)
H11	0.8969	0.1422	0.5847	0.052*
C12	0.94409 (18)	0.15981 (16)	0.72082 (16)	0.0416 (5)
C13	0.92381 (19)	0.21962 (18)	0.80340 (15)	0.0418 (5)
H13	0.9598	0.2103	0.8587	0.050*
C14	0.85175 (18)	0.29156 (17)	0.80394 (14)	0.0379 (4)
H14	0.8398	0.3307	0.8610	0.045*
N11	1.01300 (19)	0.08574 (18)	0.71490 (18)	0.0611 (6)
C15	1.0336 (3)	0.0294 (2)	0.6272 (3)	0.0813 (10)
H15A	0.9558	−0.0266	0.5891	0.122*
H15B	1.0894	−0.0161	0.6356	0.122*
H15C	1.0694	0.0930	0.5977	0.122*
C16	1.0718 (3)	0.0642 (3)	0.7951 (3)	0.0855 (11)
H16A	1.1449	0.1348	0.8250	0.128*
H16B	1.0949	−0.0089	0.7775	0.128*
H16C	1.0153	0.0522	0.8369	0.128*
N20	0.56112 (15)	0.54793 (14)	0.72115 (11)	0.0345 (3)
C20	0.51483 (18)	0.55514 (17)	0.63922 (13)	0.0369 (4)
H20	0.5362	0.5118	0.5879	0.044*
C21	0.43956 (19)	0.61995 (17)	0.62432 (13)	0.0365 (4)
H21	0.4107	0.6209	0.5644	0.044*
C22	0.40472 (17)	0.68564 (16)	0.69838 (13)	0.0346 (4)
C23	0.45337 (18)	0.67870 (16)	0.78447 (13)	0.0359 (4)
H23	0.4343	0.7210	0.8374	0.043*
C24	0.52809 (17)	0.61082 (16)	0.79141 (13)	0.0348 (4)
H24	0.5590	0.6079	0.8504	0.042*
N21	0.32914 (17)	0.74991 (16)	0.68615 (13)	0.0444 (4)
C25	0.2838 (2)	0.7546 (2)	0.59538 (18)	0.0538 (6)
H25A	0.3527	0.7902	0.5682	0.081*
H25B	0.2312	0.8051	0.5989	0.081*
H25C	0.2371	0.6718	0.5580	0.081*
C26	0.2942 (2)	0.8181 (2)	0.76234 (19)	0.0584 (6)
H26A	0.2535	0.7623	0.7962	0.088*
H26B	0.2384	0.8571	0.7401	0.088*
H26C	0.3670	0.8808	0.8022	0.088*
N30	0.84902 (18)	0.59839 (17)	0.37737 (13)	0.0502 (5)
H30	0.8663	0.6130	0.4367	0.060*
C30	0.9012 (2)	0.5296 (2)	0.32567 (17)	0.0483 (5)
H30A	0.9558	0.4972	0.3539	0.058*
C31	0.87713 (18)	0.50555 (17)	0.23413 (15)	0.0392 (4)
H31	0.9138	0.4557	0.1987	0.047*
C32	0.79728 (17)	0.55486 (15)	0.19124 (13)	0.0333 (4)
C33	0.74295 (19)	0.62532 (17)	0.24890 (15)	0.0405 (4)
H33	0.6869	0.6585	0.2236	0.049*
C34	0.7712 (2)	0.64492 (19)	0.33973 (16)	0.0474 (5)
H34	0.7351	0.6927	0.3776	0.057*
N31	0.77449 (17)	0.53660 (16)	0.10194 (12)	0.0436 (4)
C35	0.8320 (3)	0.4662 (2)	0.04314 (17)	0.0598 (6)
H35A	0.8009	0.3803	0.0438	0.090*
H35B	0.9205	0.4984	0.0650	0.090*
H35C	0.8133	0.4727	−0.0188	0.090*
C36	0.6889 (3)	0.5836 (2)	0.05802 (17)	0.0583 (6)
H36A	0.7067	0.6697	0.0892	0.087*
H36B	0.6056	0.5366	0.0606	0.087*
H36C	0.6966	0.5761	−0.0054	0.087*
N40	1.3442 (2)	1.0729 (2)	1.35554 (18)	0.0741 (7)
H40A	1.3569	1.0786	1.4140	0.089*
C40	1.3919 (2)	1.0029 (2)	1.3001 (2)	0.0652 (8)
H40	1.4394	0.9611	1.3249	0.078*
C41	1.37352 (19)	0.99125 (19)	1.21042 (19)	0.0495 (6)
H41	1.4083	0.9419	1.1726	0.059*
C42	1.30213 (17)	1.05255 (16)	1.17213 (17)	0.0414 (5)
C43	1.2558 (2)	1.12694 (19)	1.23391 (19)	0.0509 (6)
H43	1.2093	1.1717	1.2120	0.061*
C44	1.2772 (3)	1.1342 (2)	1.3222 (2)	0.0644 (7)
H44	1.2448	1.1834	1.3624	0.077*
N41	1.28055 (16)	1.04136 (15)	1.08378 (14)	0.0445 (4)
C45	1.3279 (2)	0.9643 (2)	1.02188 (19)	0.0555 (6)
H45A	1.4171	0.9935	1.0382	0.083*
H45B	1.3027	0.9675	0.9598	0.083*
H45C	1.2959	0.8799	1.0259	0.083*
C46	1.2060 (2)	1.1027 (2)	1.0441 (2)	0.0581 (6)
H46A	1.1233	1.0732	1.0556	0.087*
H46B	1.2030	1.0853	0.9786	0.087*
H46C	1.2416	1.1911	1.0714	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02959 (15)	0.02651 (13)	0.03901 (16)	0.00659 (10)	0.00554 (11)	0.01014 (11)
N1	0.0466 (10)	0.0481 (10)	0.0521 (11)	0.0159 (8)	0.0183 (9)	0.0232 (8)
C1	0.0484 (12)	0.0459 (11)	0.0602 (13)	0.0322 (10)	0.0241 (11)	0.0243 (10)
S1	0.1152 (7)	0.0995 (6)	0.1337 (7)	0.0841 (6)	0.0926 (6)	0.0925 (6)
N2	0.0442 (10)	0.0363 (9)	0.0529 (11)	0.0093 (8)	−0.0018 (9)	0.0028 (8)
C2	0.0388 (11)	0.0325 (9)	0.0478 (11)	0.0203 (8)	0.0054 (9)	0.0069 (8)
S2	0.0375 (3)	0.0424 (3)	0.1037 (6)	0.0146 (2)	−0.0138 (3)	−0.0082 (3)
N3	0.0442 (10)	0.0387 (9)	0.0582 (12)	0.0076 (8)	−0.0057 (9)	0.0025 (8)
C3	0.0367 (10)	0.0362 (9)	0.0368 (10)	0.0177 (8)	0.0022 (8)	0.0065 (8)
S3	0.0525 (4)	0.0541 (3)	0.0742 (4)	−0.0096 (3)	0.0026 (3)	0.0156 (3)
N4	0.0523 (11)	0.0505 (10)	0.0601 (12)	0.0184 (9)	0.0235 (10)	0.0282 (9)
C4	0.0417 (11)	0.0404 (10)	0.0347 (10)	0.0215 (8)	0.0103 (8)	0.0131 (8)
S4	0.0672 (4)	0.0586 (4)	0.0569 (4)	−0.0107 (3)	0.0068 (3)	0.0244 (3)
N10	0.0323 (8)	0.0317 (7)	0.0374 (8)	0.0098 (6)	0.0050 (7)	0.0079 (6)
C10	0.0426 (11)	0.0352 (9)	0.0369 (10)	0.0114 (8)	0.0050 (8)	0.0077 (8)
C11	0.0421 (11)	0.0331 (9)	0.0491 (12)	0.0098 (8)	0.0129 (9)	0.0036 (8)
C12	0.0291 (10)	0.0269 (8)	0.0661 (14)	0.0057 (7)	0.0088 (9)	0.0121 (9)
C13	0.0361 (11)	0.0368 (9)	0.0487 (12)	0.0086 (8)	0.0000 (9)	0.0135 (9)
C14	0.0369 (10)	0.0353 (9)	0.0369 (10)	0.0088 (8)	0.0042 (8)	0.0069 (8)
N11	0.0457 (11)	0.0421 (10)	0.1033 (18)	0.0220 (9)	0.0201 (12)	0.0215 (11)
C15	0.0727 (19)	0.0453 (13)	0.139 (3)	0.0292 (13)	0.054 (2)	0.0190 (16)
C16	0.0543 (17)	0.0700 (18)	0.142 (3)	0.0330 (14)	0.0018 (18)	0.041 (2)
N20	0.0338 (8)	0.0320 (7)	0.0382 (8)	0.0111 (6)	0.0060 (7)	0.0107 (6)
C20	0.0408 (11)	0.0368 (9)	0.0343 (9)	0.0159 (8)	0.0083 (8)	0.0070 (7)
C21	0.0402 (11)	0.0379 (9)	0.0340 (9)	0.0160 (8)	0.0068 (8)	0.0109 (8)
C22	0.0323 (10)	0.0278 (8)	0.0435 (10)	0.0082 (7)	0.0100 (8)	0.0103 (7)
C23	0.0382 (10)	0.0307 (8)	0.0371 (10)	0.0084 (7)	0.0127 (8)	0.0071 (7)
C24	0.0349 (10)	0.0330 (9)	0.0333 (9)	0.0064 (7)	0.0053 (8)	0.0103 (7)
N21	0.0481 (10)	0.0421 (9)	0.0509 (10)	0.0260 (8)	0.0120 (8)	0.0115 (8)
C25	0.0541 (14)	0.0552 (13)	0.0665 (15)	0.0310 (11)	0.0122 (12)	0.0274 (12)
C26	0.0582 (15)	0.0530 (13)	0.0718 (17)	0.0335 (12)	0.0189 (13)	0.0078 (12)
N30	0.0524 (11)	0.0491 (10)	0.0413 (10)	0.0029 (9)	0.0119 (9)	0.0147 (8)
C30	0.0394 (11)	0.0479 (11)	0.0606 (14)	0.0107 (9)	0.0073 (10)	0.0273 (11)
C31	0.0345 (10)	0.0361 (9)	0.0534 (12)	0.0169 (8)	0.0105 (9)	0.0169 (8)
C32	0.0302 (9)	0.0258 (8)	0.0453 (11)	0.0112 (7)	0.0079 (8)	0.0096 (7)
C33	0.0387 (11)	0.0315 (9)	0.0534 (12)	0.0157 (8)	0.0130 (9)	0.0080 (8)
C34	0.0473 (12)	0.0365 (10)	0.0551 (13)	0.0085 (9)	0.0217 (10)	0.0071 (9)
N31	0.0505 (11)	0.0422 (9)	0.0446 (10)	0.0286 (8)	0.0063 (8)	0.0079 (7)
C35	0.0777 (18)	0.0674 (15)	0.0462 (13)	0.0473 (14)	0.0131 (12)	0.0064 (11)
C36	0.0701 (17)	0.0613 (14)	0.0520 (13)	0.0410 (13)	−0.0021 (12)	0.0130 (11)
N40	0.0617 (15)	0.0691 (15)	0.0688 (15)	−0.0134 (12)	0.0079 (12)	0.0243 (13)
C40	0.0426 (13)	0.0569 (15)	0.090 (2)	0.0009 (11)	−0.0024 (13)	0.0387 (15)
C41	0.0324 (11)	0.0368 (10)	0.0816 (17)	0.0105 (8)	0.0084 (11)	0.0233 (11)
C42	0.0263 (9)	0.0272 (8)	0.0725 (15)	0.0081 (7)	0.0120 (9)	0.0171 (9)
C43	0.0392 (12)	0.0380 (10)	0.0768 (17)	0.0117 (9)	0.0205 (11)	0.0146 (10)
C44	0.0524 (15)	0.0523 (14)	0.0772 (19)	0.0009 (11)	0.0238 (14)	0.0119 (13)
N41	0.0376 (9)	0.0363 (8)	0.0659 (12)	0.0194 (7)	0.0112 (9)	0.0161 (8)
C45	0.0474 (13)	0.0452 (12)	0.0766 (17)	0.0202 (10)	0.0191 (12)	0.0115 (11)
C46	0.0525 (14)	0.0541 (13)	0.0782 (17)	0.0295 (11)	0.0067 (13)	0.0257 (12)

Geometric parameters (Å, º) top

Mn1—N1	2.1928 (17)	C25—H25A	0.9800
Mn1—N2	2.2014 (19)	C25—H25B	0.9800
Mn1—N3	2.2468 (19)	C25—H25C	0.9800
Mn1—N4	2.2535 (18)	C26—H26A	0.9800
Mn1—N20	2.2561 (16)	C26—H26B	0.9800
Mn1—N10	2.2659 (16)	C26—H26C	0.9800
N1—C1	1.153 (3)	N30—C34	1.339 (3)
C1—S1	1.629 (2)	N30—C30	1.346 (3)
N2—C2	1.149 (3)	N30—H30	0.8800
C2—S2	1.630 (2)	C30—C31	1.355 (3)
N3—C3	1.145 (3)	C30—H30A	0.9500
C3—S3	1.633 (2)	C31—C32	1.418 (3)
N4—C4	1.148 (3)	C31—H31	0.9500
C4—S4	1.631 (2)	C32—N31	1.328 (3)
N10—C14	1.341 (2)	C32—C33	1.425 (3)
N10—C10	1.342 (3)	C33—C34	1.352 (3)
C10—C11	1.366 (3)	C33—H33	0.9500
C10—H10	0.9500	C34—H34	0.9500
C11—C12	1.408 (3)	N31—C36	1.456 (3)
C11—H11	0.9500	N31—C35	1.461 (3)
C12—N11	1.359 (3)	C35—H35A	0.9800
C12—C13	1.402 (3)	C35—H35B	0.9800
C13—C14	1.371 (3)	C35—H35C	0.9800
C13—H13	0.9500	C36—H36A	0.9800
C14—H14	0.9500	C36—H36B	0.9800
N11—C16	1.454 (4)	C36—H36C	0.9800
N11—C15	1.456 (4)	N40—C40	1.349 (4)
C15—H15A	0.9800	N40—C44	1.350 (4)
C15—H15B	0.9800	N40—H40A	0.8800
C15—H15C	0.9800	C40—C41	1.345 (4)
C16—H16A	0.9800	C40—H40	0.9500
C16—H16B	0.9800	C41—C42	1.420 (3)
C16—H16C	0.9800	C41—H41	0.9500
N20—C24	1.344 (3)	C42—N41	1.326 (3)
N20—C20	1.346 (2)	C42—C43	1.425 (3)
C20—C21	1.365 (3)	C43—C44	1.335 (4)
C20—H20	0.9500	C43—H43	0.9500
C21—C22	1.413 (3)	C44—H44	0.9500
C21—H21	0.9500	N41—C45	1.453 (3)
C22—N21	1.355 (2)	N41—C46	1.457 (3)
C22—C23	1.411 (3)	C45—H45A	0.9800
C23—C24	1.368 (3)	C45—H45B	0.9800
C23—H23	0.9500	C45—H45C	0.9800
C24—H24	0.9500	C46—H46A	0.9800
N21—C26	1.452 (3)	C46—H46B	0.9800
N21—C25	1.457 (3)	C46—H46C	0.9800

N1—Mn1—N2	92.28 (7)	N21—C25—H25B	109.5
N1—Mn1—N3	89.70 (8)	H25A—C25—H25B	109.5
N2—Mn1—N3	177.98 (7)	N21—C25—H25C	109.5
N1—Mn1—N4	178.78 (7)	H25A—C25—H25C	109.5
N2—Mn1—N4	88.76 (8)	H25B—C25—H25C	109.5
N3—Mn1—N4	89.26 (8)	N21—C26—H26A	109.5
N1—Mn1—N20	92.86 (6)	N21—C26—H26B	109.5
N2—Mn1—N20	92.57 (7)	H26A—C26—H26B	109.5
N3—Mn1—N20	87.73 (7)	N21—C26—H26C	109.5
N4—Mn1—N20	87.73 (6)	H26A—C26—H26C	109.5
N1—Mn1—N10	91.48 (6)	H26B—C26—H26C	109.5
N2—Mn1—N10	91.46 (7)	C34—N30—C30	120.9 (2)
N3—Mn1—N10	88.08 (7)	C34—N30—H30	119.6
N4—Mn1—N10	87.86 (6)	C30—N30—H30	119.6
N20—Mn1—N10	173.95 (6)	N30—C30—C31	121.2 (2)
C1—N1—Mn1	168.73 (18)	N30—C30—H30A	119.4
N1—C1—S1	178.8 (2)	C31—C30—H30A	119.4
C2—N2—Mn1	163.48 (19)	C30—C31—C32	120.0 (2)
N2—C2—S2	179.9 (3)	C30—C31—H31	120.0
C3—N3—Mn1	150.20 (18)	C32—C31—H31	120.0
N3—C3—S3	179.7 (2)	N31—C32—C31	121.73 (18)
C4—N4—Mn1	147.24 (19)	N31—C32—C33	121.70 (18)
N4—C4—S4	179.3 (2)	C31—C32—C33	116.57 (19)
C14—N10—C10	115.37 (17)	C34—C33—C32	120.0 (2)
C14—N10—Mn1	123.78 (13)	C34—C33—H33	120.0
C10—N10—Mn1	120.85 (13)	C32—C33—H33	120.0
N10—C10—C11	124.47 (19)	N30—C34—C33	121.4 (2)
N10—C10—H10	117.8	N30—C34—H34	119.3
C11—C10—H10	117.8	C33—C34—H34	119.3
C10—C11—C12	120.1 (2)	C32—N31—C36	121.46 (18)
C10—C11—H11	120.0	C32—N31—C35	121.58 (17)
C12—C11—H11	120.0	C36—N31—C35	116.95 (19)
N11—C12—C13	123.0 (2)	N31—C35—H35A	109.5
N11—C12—C11	121.4 (2)	N31—C35—H35B	109.5
C13—C12—C11	115.61 (18)	H35A—C35—H35B	109.5
C14—C13—C12	119.70 (19)	N31—C35—H35C	109.5
C14—C13—H13	120.2	H35A—C35—H35C	109.5
C12—C13—H13	120.2	H35B—C35—H35C	109.5
N10—C14—C13	124.79 (19)	N31—C36—H36A	109.5
N10—C14—H14	117.6	N31—C36—H36B	109.5
C13—C14—H14	117.6	H36A—C36—H36B	109.5
C12—N11—C16	121.6 (3)	N31—C36—H36C	109.5
C12—N11—C15	120.2 (2)	H36A—C36—H36C	109.5
C16—N11—C15	118.2 (2)	H36B—C36—H36C	109.5
N11—C15—H15A	109.5	C40—N40—C44	120.7 (3)
N11—C15—H15B	109.5	C40—N40—H40A	119.7
H15A—C15—H15B	109.5	C44—N40—H40A	119.7
N11—C15—H15C	109.5	C41—C40—N40	121.3 (3)
H15A—C15—H15C	109.5	C41—C40—H40	119.4
H15B—C15—H15C	109.5	N40—C40—H40	119.4
N11—C16—H16A	109.5	C40—C41—C42	120.1 (2)
N11—C16—H16B	109.5	C40—C41—H41	120.0
H16A—C16—H16B	109.5	C42—C41—H41	120.0
N11—C16—H16C	109.5	N41—C42—C41	121.6 (2)
H16A—C16—H16C	109.5	N41—C42—C43	122.07 (19)
H16B—C16—H16C	109.5	C41—C42—C43	116.3 (2)
C24—N20—C20	115.08 (16)	C44—C43—C42	120.5 (2)
C24—N20—Mn1	124.47 (13)	C44—C43—H43	119.7
C20—N20—Mn1	120.43 (13)	C42—C43—H43	119.7
N20—C20—C21	124.96 (18)	C43—C44—N40	121.1 (3)
N20—C20—H20	117.5	C43—C44—H44	119.4
C21—C20—H20	117.5	N40—C44—H44	119.4
C20—C21—C22	119.79 (18)	C42—N41—C45	121.17 (18)
C20—C21—H21	120.1	C42—N41—C46	121.77 (19)
C22—C21—H21	120.1	C45—N41—C46	117.0 (2)
N21—C22—C23	123.08 (18)	N41—C45—H45A	109.5
N21—C22—C21	121.45 (18)	N41—C45—H45B	109.5
C23—C22—C21	115.47 (17)	H45A—C45—H45B	109.5
C24—C23—C22	119.75 (18)	N41—C45—H45C	109.5
C24—C23—H23	120.1	H45A—C45—H45C	109.5
C22—C23—H23	120.1	H45B—C45—H45C	109.5
N20—C24—C23	124.95 (18)	N41—C46—H46A	109.5
N20—C24—H24	117.5	N41—C46—H46B	109.5
C23—C24—H24	117.5	H46A—C46—H46B	109.5
C22—N21—C26	121.37 (19)	N41—C46—H46C	109.5
C22—N21—C25	120.15 (18)	H46A—C46—H46C	109.5
C26—N21—C25	118.46 (18)	H46B—C46—H46C	109.5
N21—C25—H25A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N30—H30···S4	0.88	2.36	3.217 (2)	165
N40—H40A···S3ⁱ	0.88	2.35	3.213 (3)	166

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

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[Mn(NCS)₄(C₇H₁₀N₂)₂]
M_r	777.96
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	11.7307 (8), 11.9010 (9), 15.4224 (12)
α, β, γ (°)	102.520 (9), 96.794 (9), 107.400 (8)
V (Å³)	1966.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.18 × 0.11 × 0.05

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.873, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	24452, 9338, 6752
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.121, 1.02
No. of reflections	9338
No. of parameters	450
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.72

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2012), XCIF in SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—N1	2.1928 (17)	Mn1—N4	2.2535 (18)
Mn1—N2	2.2014 (19)	Mn1—N20	2.2561 (16)
Mn1—N3	2.2468 (19)	Mn1—N10	2.2659 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N30—H30···S4	0.88	2.36	3.217 (2)	165
N40—H40A···S3ⁱ	0.88	2.35	3.213 (3)	166

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

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Project 720/3-1). We thank Professor Dr Wolfgang Bensch for access to his experimental facility.

References

Boeckmann, J. & Näther, C. (2011). Dalton Trans. 39, 11019–11026. Web of Science CSD CrossRef Google Scholar
Boeckmann, J. & Näther, C. (2012). Polyhedron, 31 587–595. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar

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