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Acta Cryst. (2007). E63, m1151    [ doi:10.1107/S1600536807012317 ]

Bis(triethylammonium) tetrachloridomanganate(II)

W. Clegg and N. C. Martin

Abstract top

The title compound, (Et3NH)2[MnCl4], was obtained unexpectedly in an attempt to prepare a carboxylate-bridged coordination network. It is the first reported structure of a tertiary ammonium salt of the tetrahedral [MnCl4]2- anion (Table 1). Each of the two crystallographically independent cations forms an N—H···Cl hydrogen bond to the anion (Table 2), generating discrete ion triples. The Mn—Cl bonds involving the hydrogen-bonded Cl atoms are longer than the others.

Comment top

The title compound is the first reported for a tertiary ammonium salt of the [MnCl4]2- anion. The Cambridge Structural Database (Version 5.27 plus three updates, August 2006; Allen, 2002) contains several entries for primary alkylammonium salts and for quaternary alkylammonium salts, but none for secondary or tertiary ammonium salts. The full list of CSD REFCODES is as follows: for primary ammonium salts, BUAMCM, BUAMCM01, EAMNCL02, EAMNCL03, EAMNCL04, MATCMN08, MATCMN13, NAMNCL, OAMNCL, ZZZBMM, ZZZBMM01, ZZZBMP, ZZZBMP01, ZZZBMS, ZZZBMS01; for quaternary ammonium salts (the tetramethylammonium salt in each case), KAUWAF and the series KAUWAF01–06.

Related literature top

The Cambridge Structural Database (Version 5.27 plus three updates, August 2006; Allen, 2002) contains several entries for primary and quaternary ammonium salts (a full list of REFCODES is given in the deposited Comment section), but there are no previously reported structures for secondary or tertiary ammonium salts.

Experimental top

The compound was obtained unexpectedly in an unsuccessful attempt to prepare a polymeric carboxylate-bridged manganese complex. Crystals were obtained by vapour diffusion of triethylamine into a solution of manganese(II) chloride and pyromellitic acid in n-propanol.

Refinement top

N-bound H atoms were located in a difference map and refined isotropically; bond lengths are given in Table 2. Other H atoms were positioned geometrically and refined with a riding model (including free rotation about C—C bonds), with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Residual electron density peaks associated with one of the cations, the largest of which lies 1.04 Å from H12C, indicate possible minor disorder of this cation, but it could not be satisfactorily resolved.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. . The asymmetric unit with atom labels and 50% probability ellipsoids for non-H atoms. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. . The packing, viewed along the c axis. Hydrogen bonds are shown as dashed lines, and H atoms not involved in hydrogen bonding have been omitted.
Bis(triethylammonium) tetrachloridomanganate(II) top
Crystal data top
(C6H16N)[MnCl4]Dx = 1.301 Mg m−3
Mr = 401.14Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 24268 reflections
a = 12.0533 (5) Åθ = 2.2–28.4º
b = 13.0595 (6) ŵ = 1.16 mm−1
c = 26.0147 (11) ÅT = 160 (2) K
V = 4095.0 (3) Å3Tablet, colourless
Z = 80.40 × 0.24 × 0.10 mm
F000 = 1688
Data collection top
Bruker SMART 1K CCD
diffractometer		3602 independent reflections
Radiation source: sealed tube3293 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
Detector resolution: 8.192 pixels mm-1θmax = 25.0º
T = 160(2) Kθmin = 1.6º
Thin–slice ω scansh = −14→14
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		k = −15→15
Tmin = 0.650, Tmax = 0.900l = −30→30
27106 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0267P)2 + 7.4604P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.038(Δ/σ)max = 0.001
wR(F2) = 0.090Δρmax = 1.21 e Å−3
S = 1.10Δρmin = −0.52 e Å−3
3602 reflectionsExtinction correction: none
186 parameters
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: mixed
Crystal data top
(C6H16N)[MnCl4]V = 4095.0 (3) Å3
Mr = 401.14Z = 8
Orthorhombic, PbcaMo Kα
a = 12.0533 (5) ŵ = 1.16 mm−1
b = 13.0595 (6) ÅT = 160 (2) K
c = 26.0147 (11) Å0.40 × 0.24 × 0.10 mm
Data collection top
Bruker SMART 1K CCD
diffractometer		3602 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		3293 reflections with I > 2σ(I)
Tmin = 0.650, Tmax = 0.900Rint = 0.028
27106 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038Δρmax = 1.21 e Å−3
wR(F2) = 0.090Δρmin = −0.52 e Å−3
S = 1.10Absolute structure: ?
3602 reflectionsFlack parameter: ?
186 parametersRogers parameter: ?
H atoms treated by a mixture of
independent and constrained refinement
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn0.94241 (3)0.20976 (3)0.373324 (15)0.02832 (12)
Cl10.77218 (6)0.16735 (6)0.41181 (3)0.04164 (19)
Cl20.90717 (6)0.25111 (7)0.28522 (3)0.0465 (2)
Cl31.01603 (8)0.35169 (6)0.41945 (4)0.0569 (3)
Cl41.07413 (6)0.07780 (6)0.37680 (3)0.03715 (18)
N10.88971 (18)0.30677 (17)0.52513 (9)0.0274 (5)
H10.916 (3)0.310 (2)0.4937 (12)0.033 (8)*
C10.9667 (3)0.3711 (2)0.55729 (13)0.0418 (7)
H1A1.04220.34160.55550.050*
H1B0.97000.44100.54260.050*
C20.9322 (4)0.3784 (3)0.61257 (14)0.0665 (12)
H2A0.85580.40370.61460.100*
H2B0.98170.42560.63070.100*
H2C0.93650.31050.62850.100*
C30.7737 (2)0.3483 (2)0.52237 (12)0.0361 (7)
H3A0.74010.34580.55710.043*
H3B0.72890.30400.49950.043*
C40.7694 (3)0.4567 (2)0.50269 (15)0.0512 (9)
H4A0.80500.50250.52760.077*
H4B0.69190.47730.49790.077*
H4C0.80860.46090.46970.077*
C50.8878 (2)0.1958 (2)0.54057 (11)0.0326 (6)
H5A0.82890.16020.52100.039*
H5B0.86900.19090.57750.039*
C60.9967 (3)0.1424 (2)0.53127 (12)0.0383 (7)
H6A1.01440.14460.49450.057*
H6B0.99110.07090.54250.057*
H6C1.05540.17690.55070.057*
N20.7331 (2)0.4321 (2)0.26021 (9)0.0347 (6)
H20.777 (2)0.392 (2)0.2724 (11)0.024 (8)*
C70.6735 (3)0.3934 (3)0.21350 (12)0.0540 (9)
H7A0.61790.34200.22440.065*
H7B0.63310.45100.19740.065*
C80.7483 (3)0.3460 (3)0.17435 (11)0.0472 (8)
H8A0.79840.39830.16050.071*
H8B0.70370.31720.14640.071*
H8C0.79190.29140.19050.071*
C90.6545 (3)0.4546 (2)0.30393 (12)0.0442 (8)
H9A0.69550.49070.33150.053*
H9B0.59550.50110.29150.053*
C100.6017 (3)0.3606 (2)0.32609 (12)0.0432 (8)
H10A0.55600.32730.29980.065*
H10B0.55500.37980.35540.065*
H10C0.65960.31310.33760.065*
C110.7970 (3)0.5261 (3)0.24499 (16)0.0634 (11)
H11A0.83930.51110.21320.076*
H11B0.74380.58160.23700.076*
C120.8728 (4)0.5618 (4)0.28370 (18)0.0848 (16)
H12A0.83090.58780.31320.127*
H12B0.91890.61680.26950.127*
H12C0.92040.50510.29480.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0306 (2)0.0269 (2)0.0275 (2)0.00058 (17)0.00401 (17)0.00198 (17)
Cl10.0328 (4)0.0557 (5)0.0364 (4)−0.0059 (3)0.0066 (3)0.0057 (3)
Cl20.0430 (4)0.0630 (5)0.0336 (4)0.0144 (4)0.0062 (3)0.0181 (4)
Cl30.0719 (6)0.0351 (4)0.0638 (5)−0.0251 (4)0.0385 (5)−0.0207 (4)
Cl40.0374 (4)0.0358 (4)0.0383 (4)0.0075 (3)−0.0082 (3)−0.0061 (3)
N10.0272 (12)0.0231 (11)0.0318 (12)−0.0021 (9)0.0061 (10)−0.0044 (9)
C10.0349 (16)0.0295 (15)0.061 (2)−0.0059 (13)−0.0072 (15)−0.0073 (14)
C20.102 (3)0.049 (2)0.049 (2)−0.008 (2)−0.021 (2)−0.0112 (17)
C30.0266 (15)0.0322 (16)0.0494 (17)0.0007 (12)0.0038 (13)−0.0078 (13)
C40.0386 (18)0.0327 (17)0.082 (3)0.0079 (14)−0.0009 (17)0.0014 (17)
C50.0387 (16)0.0242 (14)0.0350 (15)−0.0046 (12)0.0028 (12)−0.0008 (12)
C60.0468 (18)0.0312 (15)0.0368 (16)0.0064 (14)−0.0008 (14)0.0009 (13)
N20.0350 (14)0.0338 (14)0.0352 (13)−0.0004 (12)0.0113 (11)−0.0001 (11)
C70.0367 (17)0.093 (3)0.0328 (16)0.0095 (18)−0.0009 (14)0.0078 (17)
C80.0406 (17)0.071 (2)0.0305 (15)−0.0052 (17)−0.0033 (14)−0.0066 (16)
C90.0506 (19)0.0378 (17)0.0443 (18)0.0024 (15)0.0224 (15)−0.0041 (14)
C100.0459 (18)0.0438 (18)0.0401 (17)0.0030 (15)0.0152 (14)0.0055 (14)
C110.063 (2)0.058 (2)0.069 (3)−0.014 (2)0.022 (2)−0.001 (2)
C120.065 (3)0.102 (4)0.088 (3)−0.042 (3)0.030 (2)−0.047 (3)
Geometric parameters (Å, °) top
Mn—Cl12.3492 (8)C6—H6B0.980
Mn—Cl22.3927 (8)C6—H6C0.980
Mn—Cl32.3797 (9)N2—H20.82 (3)
Mn—Cl42.3449 (8)N2—C71.500 (4)
N1—H10.88 (3)N2—C91.510 (4)
N1—C11.506 (4)N2—C111.502 (4)
N1—C31.501 (3)C7—H7A0.990
N1—C51.504 (3)C7—H7B0.990
C1—H1A0.990C7—C81.494 (5)
C1—H1B0.990C8—H8A0.980
C1—C21.500 (5)C8—H8B0.980
C2—H2A0.980C8—H8C0.980
C2—H2B0.980C9—H9A0.990
C2—H2C0.980C9—H9B0.990
C3—H3A0.990C9—C101.499 (4)
C3—H3B0.990C10—H10A0.980
C3—C41.507 (4)C10—H10B0.980
C4—H4A0.980C10—H10C0.980
C4—H4B0.980C11—H11A0.990
C4—H4C0.980C11—H11B0.990
C5—H5A0.990C11—C121.438 (6)
C5—H5B0.990C12—H12A0.980
C5—C61.506 (4)C12—H12B0.980
C6—H6A0.980C12—H12C0.980
Cl1—Mn—Cl2107.84 (3)H6A—C6—H6B109.5
Cl1—Mn—Cl3107.12 (3)H6A—C6—H6C109.5
Cl1—Mn—Cl4113.68 (3)H6B—C6—H6C109.5
Cl2—Mn—Cl3111.93 (4)H2—N2—C7114 (2)
Cl2—Mn—Cl4108.84 (3)H2—N2—C9104 (2)
Cl3—Mn—Cl4107.49 (4)H2—N2—C11107 (2)
H1—N1—C1105 (2)C7—N2—C9112.0 (2)
H1—N1—C3106 (2)C7—N2—C11107.9 (3)
H1—N1—C5108 (2)C9—N2—C11111.2 (3)
C1—N1—C3113.5 (2)N2—C7—H7A108.8
C1—N1—C5113.5 (2)N2—C7—H7B108.8
C3—N1—C5110.3 (2)N2—C7—C8113.8 (3)
N1—C1—H1A108.9H7A—C7—H7B107.7
N1—C1—H1B108.9H7A—C7—C8108.8
N1—C1—C2113.4 (3)H7B—C7—C8108.8
H1A—C1—H1B107.7C7—C8—H8A109.5
H1A—C1—C2108.9C7—C8—H8B109.5
H1B—C1—C2108.9C7—C8—H8C109.5
C1—C2—H2A109.5H8A—C8—H8B109.5
C1—C2—H2B109.5H8A—C8—H8C109.5
C1—C2—H2C109.5H8B—C8—H8C109.5
H2A—C2—H2B109.5N2—C9—H9A108.9
H2A—C2—H2C109.5N2—C9—H9B108.9
H2B—C2—H2C109.5N2—C9—C10113.4 (3)
N1—C3—H3A109.0H9A—C9—H9B107.7
N1—C3—H3B109.0H9A—C9—C10108.9
N1—C3—C4112.8 (2)H9B—C9—C10108.9
H3A—C3—H3B107.8C9—C10—H10A109.5
H3A—C3—C4109.0C9—C10—H10B109.5
H3B—C3—C4109.0C9—C10—H10C109.5
C3—C4—H4A109.5H10A—C10—H10B109.5
C3—C4—H4B109.5H10A—C10—H10C109.5
C3—C4—H4C109.5H10B—C10—H10C109.5
H4A—C4—H4B109.5N2—C11—H11A108.8
H4A—C4—H4C109.5N2—C11—H11B108.8
H4B—C4—H4C109.5N2—C11—C12114.0 (4)
N1—C5—H5A109.0H11A—C11—H11B107.7
N1—C5—H5B109.0H11A—C11—C12108.8
N1—C5—C6113.0 (2)H11B—C11—C12108.8
H5A—C5—H5B107.8C11—C12—H12A109.5
H5A—C5—C6109.0C11—C12—H12B109.5
H5B—C5—C6109.0C11—C12—H12C109.5
C5—C6—H6A109.5H12A—C12—H12B109.5
C5—C6—H6B109.5H12A—C12—H12C109.5
C5—C6—H6C109.5H12B—C12—H12C109.5
C3—N1—C1—C262.1 (4)C9—N2—C7—C8−165.6 (3)
C5—N1—C1—C2−64.8 (3)C11—N2—C7—C871.6 (4)
C1—N1—C3—C456.3 (4)C7—N2—C9—C1068.1 (4)
C5—N1—C3—C4−175.1 (3)C11—N2—C9—C10−171.0 (3)
C1—N1—C5—C6−65.9 (3)C7—N2—C11—C12−170.1 (3)
C3—N1—C5—C6165.5 (2)C9—N2—C11—C1266.6 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.88 (3)2.34 (3)3.197 (2)166 (3)
N2—H2···Cl20.82 (3)2.43 (3)3.227 (3)164 (3)
Selected geometric parameters (Å, °) top
Mn—Cl12.3492 (8)Mn—Cl32.3797 (9)
Mn—Cl22.3927 (8)Mn—Cl42.3449 (8)
Cl1—Mn—Cl2107.84 (3)Cl2—Mn—Cl3111.93 (4)
Cl1—Mn—Cl3107.12 (3)Cl2—Mn—Cl4108.84 (3)
Cl1—Mn—Cl4113.68 (3)Cl3—Mn—Cl4107.49 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.88 (3)2.34 (3)3.197 (2)166 (3)
N2—H2···Cl20.82 (3)2.43 (3)3.227 (3)164 (3)
Acknowledgements top

We thank the EPSRC for financial support.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Bruker (2001). SMART and SAINT area-detector control and integration software. Bruker AXS Inc., Madison, WI, U.S.A.

Sheldrick, G. M. (2001). SHELXTL Version 5. Bruker AXS Inc., Madison, Wi., U.S.A.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.