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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807012317/wn2128sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807012317/wn2128Isup2.hkl
Contains datablock I

CCDC reference: 643663

Key indicators

  • Single-crystal X-ray study
  • T = 160 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.038
  • wR factor = 0.090
  • Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 5.29 Ratio
Author Response: Together with some residual electron density peaks, this indicates probable minor disorder in one of the cations, but the disorder could not be resolved satisfactorily as discrete atom sites. The geometry of the current ordered structural model is entirely satisfactory, including hydrogen bonding involving freely refined NH groups.

Alert level B PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg.
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.34 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.03 Ratio
Author Response: Together with some residual electron density peaks, this indicates probable minor disorder in one of the cations, but the disorder could not be resolved satisfactorily as discrete atom sites. The geometry of the current ordered structural model is entirely satisfactory, including hydrogen bonding involving freely refined NH groups.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Mn
PLAT245_ALERT_2_C U(iso) H2      Smaller than U(eq) N2      by ...       0.01 AngSq
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.08

1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Structure description 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.

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.

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 m3
Mr = 401.14Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 24268 reflections
a = 12.0533 (5) Åθ = 2.2–28.4°
b = 13.0595 (6) ŵ = 1.16 mm1
c = 26.0147 (11) ÅT = 160 K
V = 4095.0 (3) Å3Tablet, colourless
Z = 80.40 × 0.24 × 0.10 mm
F(000) = 1688
Data collection top
Bruker SMART 1K CCD
diffractometer
3602 independent reflections
Radiation source: sealed tube3293 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 8.192 pixels mm-1θmax = 25.0°, θmin = 1.6°
Thin–slice ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 1515
Tmin = 0.650, Tmax = 0.900l = 3030
27106 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: mixed
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0267P)2 + 7.4604P]
where P = (Fo2 + 2Fc2)/3
3602 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 1.21 e Å3
0 restraintsΔρmin = 0.52 e Å3
Crystal data top
(C6H16N)[MnCl4]V = 4095.0 (3) Å3
Mr = 401.14Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.0533 (5) ŵ = 1.16 mm1
b = 13.0595 (6) ÅT = 160 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)] = 0.0380 restraints
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 1.21 e Å3
3602 reflectionsΔρmin = 0.52 e Å3
186 parameters
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, º) 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—C8165.6 (3)
C5—N1—C1—C264.8 (3)C11—N2—C7—C871.6 (4)
C1—N1—C3—C456.3 (4)C7—N2—C9—C1068.1 (4)
C5—N1—C3—C4175.1 (3)C11—N2—C9—C10171.0 (3)
C1—N1—C5—C665.9 (3)C7—N2—C11—C12170.1 (3)
C3—N1—C5—C6165.5 (2)C9—N2—C11—C1266.6 (4)
Hydrogen-bond geometry (Å, º) 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)

Experimental details

Crystal data
Chemical formula(C6H16N)[MnCl4]
Mr401.14
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)160
a, b, c (Å)12.0533 (5), 13.0595 (6), 26.0147 (11)
V3)4095.0 (3)
Z8
Radiation typeMo Kα
µ (mm1)1.16
Crystal size (mm)0.40 × 0.24 × 0.10
Data collection
DiffractometerBruker SMART 1K CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.650, 0.900
No. of measured, independent and
observed [I > 2σ(I)] reflections
27106, 3602, 3293
Rint0.028
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.090, 1.10
No. of reflections3602
No. of parameters186
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.21, 0.52

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.

Selected geometric parameters (Å, º) 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, º) 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)
 

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