Bis(tetra­butyl­ammonium) tetra­chlorido­manganate(II) di­chloro­methane disolvate

Hay, M.T.; Yennawar, H.P.

doi:10.1107/S2414314623006107

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230610

https://doi.org/10.1107/S2414314623006107

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Bis(tetrabutylammonium) tetrachloridomanganate(II) dichloromethane disolvate

Michael T. Hay ^a ^* and Hemant P. Yennawar ^b

^aPenn State Beaver, 100 University Drive, Monaca, PA 15061, USA, and ^bThe Pennsylvania State University, Dept., Biochemistry and Molecular Biology, University Park, PA 16802, USA
^*Correspondence e-mail: mth7@psu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 May 2023; accepted 10 July 2023; online 14 July 2023)

The title compound, (C₁₆H₃₆N)₂[MnCl₄]·2CH₂Cl₂, is an ionic organic–inorganic hybride compound consisting of a tetrabutylammonium cation and a tetrachloridomanganate(II) anion in a 2:1 stoichiometric ratio. The cation contains a central nitrogen atom bonded to four n-butyl groups in a tetrahedral arrangement, while the anion contains a central Mn^II atom tetrahedrally coordinated by four chlorido ligands. It co-crystallized with two equivalents of dichloromethane solvent, CH₂Cl₂, to give the following empirical formula: [(C₄H₉)₄N]₂[MnCl₄]·(CH₂Cl₂)₂. The crystal structure is mainly stabilized by Coulombic interactions.

Keywords: crystal structure; organic–inorganic salt; manganese(II) complex; tetrabutylammonium salt; solvate.

CCDC reference: 2280618

Structure description

During our efforts to prepare novel manganese-containing coordination complexes, we synthesized the previously reported non-solvated compound bis(tetrabutylammonium) tetrachloridomanganate(II). In conducting our experiments, we inadvertently obtained the disolvated title compound and determined its crystal structure. After reviewing the literature, we realised that no crystallographic data had yet been reported on either the non-solvated or solvated forms of this substance. The only crystallographic data related to this system was the powder X-ray diffraction data for the non-solvated form at 900 K after it had already undergone thermal decomposition (Styczeń et al., 2009 ). Herein we present the results of the single-crystal structure analysis of the title compound.

The structural formula shows a ratio of 2:1 for the tetrabutylammonium cation and the tetrachloridomanganate(II) anion, combined with two solvent molecules of dichloromethane (Fig. 1). The above three molecular entities have internal symmetries allowing them to occupy different special positions in the lattice with point group symmetries $[\overline{4}]$ .. (multiplicity 4, Wyckoff letter a) for the anion, and .2. (8 d) both for the cation and the solvent molecule. The root-mean-square deviations from ideal T_d symmetry for the anion, S₄ symmetry for the cation and C_2v symmetry for the solvent molecule amount to 0.0123, 0.0501 and 0 Å, respectively, as calculated with PLATON (Spek, 2020 ), based on the SYMMOL program by Pilati & Forni (1998 , 2000 ). The tetrabutylammonium cation, (C₄H₉)₄N⁺, consists of a central nitrogen atom tetrahedrally surrounded by ordered butyl groups, with N—C bond lengths ranging from 1.505 (12) Å to 1.511 (11) Å and C—N—C bond angles in the range of 105.8 (5)–111.7 (11)°. The complex anion MnCl₄^2– is consistent with the structure previously published for the tetramethylammonium salt (Rodríguez-Lazcano et al., 2009 ) – the central Mn^II atom is bound with four chloride ligands tetrahedrally arranged. The Cl—Mn—Cl bond angles are 108.80 (12)-109.81 (12)°. The Mn—Cl bond lengths are all 2.364 (2) Å.

Figure 1
Molecular structures of the entities present in the title compound, with displacement ellipsoids drawn at the 50% probability level.

The crystal structure (Fig. 2) is stabilized primarily by Coulombic forces in the absence of classical hydrogen-bonding interactions.

Figure 2
Packing diagram of the crystal structure, which is stabilized primarily by Coulombic forces.

Synthesis and crystallization

A similar protocol was followed as previously reported in the literature (Styczeń et al., 2009). Pink MnCl₄·4H₂O (5.05 mmol, 1.00 g) was dissolved in warm absolute ethanol (10–15 ml). Separately, two equivalents of white (C₄H₉)₄NCl·H₂O (10.1 mmol, 2.81 g) were also dissolved in warm absolute ethanol (10–15 ml). The two ethanol solutions were then mixed, and the solution turned a light-green color. The ethanol was removed under reduced pressure with heating to produce a pale-green solid. The solid was recrystallized from dichloromethane/ether to give pale-green crystals. After drying the crystals under reduced pressure at 311 K, they were massed (3.07 g, 89.2% yield). They were analyzed by IR and elemental analysis. IR (cm⁻¹): 2962m, 2943m, 2875m, 1484s, 1468m, 1378m, 1151w, 1025w, 881m, 749m, 732m. Analysis calculated for (C₁₆H₃₆N)₂MnCl₄: C, 56.38; H, 10.65, N, 4.11. Found: C, 56.47; H, 11.47, N, 4.04. X-ray quality crystals were obtained from a mixture of dichloromethane/ether during a reaction involving the non-solvated form of the title compound as the starting material.

Refinement

Crystal data, data collection and structure refinement details for the reported structure is summarized in Table 1. The crystal diffracted poorly at high resolution. The average intensity drops below the 3σ level at 0.9933 Å. Consequently, the reliability factors are comparatively high. As a result of the special symmetry of the dichloromethane solvent molecule, the two H atoms (H9A and H9B) were refined with half-occupancy.

Table 1
Experimental details

Crystal data
Chemical formula	(C₁₆H₃₆N)₂[MnCl₄]·2CH₂Cl₂
M_r	851.50
Crystal system, space group	Tetragonal, I $[\overline{4}]$ 2d
Temperature (K)	173
a, c (Å)	14.0775 (3), 24.3492 (8)
V (Å³)	4825.4 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.46
Crystal size (mm)	0.38 × 0.28 × 0.13

Data collection
Diffractometer	ROD, Synergy Custom system, HyPix-Arc 150
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.060, 0.359
No. of measured, independent and observed [I > 2σ(I)] reflections	9265, 2334, 1567
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.222, 1.06
No. of reflections	2334
No. of parameters	108
No. of restraints	47
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.32
Absolute structure	Flack x determined using 458 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )
Absolute structure parameter	−0.018 (8)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL2018/3 (Sheldrick, 2015 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2280618

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006107/wm4191sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006107/wm4191Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Bis(tetrabutylammonium) tetrachloridomanganate(II) dichloromethane disolvate top

Crystal data top

(C₁₆H₃₆N)₂[MnCl₄]·2CH₂Cl₂	D_x = 1.172 Mg m⁻³
M_r = 851.50	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, I42d	Cell parameters from 3369 reflections
a = 14.0775 (3) Å	θ = 3.6–60.8°
c = 24.3492 (8) Å	µ = 6.46 mm⁻¹
V = 4825.4 (3) Å³	T = 173 K
Z = 4	Plate, clear yellow
F(000) = 1820	0.38 × 0.28 × 0.13 mm

Data collection top

ROD, Synergy Custom system, HyPix-Arc 150 diffractometer	2334 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	1567 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.038
Detector resolution: 10.0000 pixels mm^-1	θ_max = 74.1°, θ_min = 3.6°
ω scans	h = −17→16
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2021)	k = −16→17
T_min = 0.060, T_max = 0.359	l = −27→29
9265 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.075	w = 1/[σ²(F_o²) + (0.1133P)² + 4.1001P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.222	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.35 e Å⁻³
2334 reflections	Δρ_min = −0.32 e Å⁻³
108 parameters	Absolute structure: Flack x determined using 458 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
47 restraints	Absolute structure parameter: −0.018 (8)
Primary atom site location: iterative

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.500000	0.000000	0.750000	0.0722 (7)
Cl1	0.37996 (17)	−0.06513 (19)	0.69347 (9)	0.0925 (8)
Cl2	0.2523 (6)	0.1511 (5)	0.4325 (2)	0.248 (4)
C9	0.250000	0.2191 (18)	0.375000	0.152 (9)
H9	0.204 (11)	0.254 (12)	0.382 (8)	0.182*
N1	0.3681 (8)	0.250000	0.625000	0.090 (3)
C1	0.4291 (7)	0.2541 (7)	0.6760 (3)	0.094 (3)
H1A	0.466853	0.194827	0.677948	0.112*
H1B	0.386692	0.255178	0.708408	0.112*
C2	0.4966 (8)	0.3374 (6)	0.6802 (3)	0.100 (3)
H2A	0.540087	0.337104	0.648222	0.120*
H2B	0.459916	0.397367	0.679322	0.120*
C3	0.5535 (9)	0.3328 (8)	0.7322 (5)	0.125 (4)
H3A	0.587481	0.271263	0.733181	0.150*
H3B	0.509107	0.334000	0.763696	0.150*
C4	0.6252 (10)	0.4116 (9)	0.7396 (6)	0.142 (5)
H4A	0.664940	0.416247	0.706657	0.213*
H4B	0.665249	0.397709	0.771501	0.213*
H4C	0.591855	0.471854	0.745395	0.213*
C5	0.3081 (8)	0.1621 (7)	0.6308 (4)	0.101 (3)
H5A	0.270075	0.167990	0.664871	0.121*
H5B	0.350980	0.106950	0.635531	0.121*
C6	0.2413 (9)	0.1411 (9)	0.5839 (5)	0.127 (4)
H6A	0.278449	0.128709	0.550114	0.152*
H6B	0.200173	0.196905	0.577132	0.152*
C7	0.1799 (11)	0.0552 (10)	0.5969 (6)	0.155 (5)
H7A	0.221001	0.001495	0.608109	0.186*
H7B	0.137194	0.070402	0.627982	0.186*
C8	0.1215 (16)	0.026 (2)	0.5479 (8)	0.260 (13)
H8A	0.162622	0.022088	0.515483	0.390*
H8B	0.071993	0.074082	0.541378	0.390*
H8C	0.091990	−0.035380	0.554830	0.390*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0805 (10)	0.0805 (10)	0.0555 (13)	0.000	0.000	0.000
Cl1	0.0873 (14)	0.1130 (18)	0.0771 (12)	0.0069 (13)	−0.0096 (11)	−0.0207 (12)
Cl2	0.359 (8)	0.258 (7)	0.127 (3)	−0.111 (7)	−0.053 (5)	0.044 (4)
C9	0.17 (2)	0.137 (19)	0.145 (18)	0.000	0.050 (17)	0.000
N1	0.115 (8)	0.085 (7)	0.070 (6)	0.000	0.000	0.020 (5)
C1	0.122 (7)	0.096 (6)	0.063 (5)	−0.006 (6)	0.003 (5)	0.014 (4)
C2	0.130 (7)	0.093 (6)	0.077 (5)	0.000 (7)	0.003 (6)	0.009 (5)
C3	0.152 (10)	0.106 (8)	0.117 (9)	−0.022 (8)	−0.028 (8)	0.008 (6)
C4	0.146 (10)	0.140 (11)	0.139 (11)	−0.018 (9)	−0.018 (9)	0.005 (9)
C5	0.117 (8)	0.098 (7)	0.088 (6)	−0.007 (6)	0.000 (6)	0.008 (5)
C6	0.141 (10)	0.131 (10)	0.109 (8)	−0.030 (9)	−0.017 (8)	0.008 (7)
C7	0.166 (13)	0.163 (12)	0.136 (11)	−0.029 (11)	−0.028 (10)	−0.005 (10)
C8	0.22 (2)	0.32 (3)	0.24 (2)	−0.11 (2)	−0.07 (2)	0.06 (2)

Geometric parameters (Å, º) top

Mn1—Cl1ⁱ	2.364 (2)	C3—H3B	0.9900
Mn1—Cl1ⁱⁱ	2.364 (2)	C3—C4	1.510 (10)
Mn1—Cl1ⁱⁱⁱ	2.364 (2)	C4—H4A	0.9800
Mn1—Cl1	2.364 (2)	C4—H4B	0.9800
Cl2—C9	1.695 (15)	C4—H4C	0.9800
C9—H9	0.83 (15)	C5—H5A	0.9900
C9—H9^iv	0.83 (15)	C5—H5B	0.9900
N1—C1^v	1.511 (11)	C5—C6	1.510 (10)
N1—C1	1.511 (11)	C6—H6A	0.9900
N1—C5	1.505 (12)	C6—H6B	0.9900
N1—C5^v	1.505 (12)	C6—C7	1.519 (11)
C1—H1A	0.9900	C7—H7A	0.9900
C1—H1B	0.9900	C7—H7B	0.9900
C1—C2	1.513 (9)	C7—C8	1.505 (11)
C2—H2A	0.9900	C8—H8A	0.9800
C2—H2B	0.9900	C8—H8B	0.9800
C2—C3	1.500 (9)	C8—H8C	0.9800
C3—H3A	0.9900

Cl1ⁱ—Mn1—Cl1ⁱⁱ	109.81 (6)	H3A—C3—H3B	107.5
Cl1ⁱⁱ—Mn1—Cl1	108.80 (12)	C4—C3—H3A	108.5
Cl1ⁱ—Mn1—Cl1ⁱⁱⁱ	108.80 (12)	C4—C3—H3B	108.5
Cl1ⁱⁱⁱ—Mn1—Cl1	109.81 (6)	C3—C4—H4A	109.5
Cl1ⁱ—Mn1—Cl1	109.81 (6)	C3—C4—H4B	109.5
Cl1ⁱⁱ—Mn1—Cl1ⁱⁱⁱ	109.81 (6)	C3—C4—H4C	109.5
Cl2—C9—Cl2^iv	111.3 (14)	H4A—C4—H4B	109.5
Cl2^iv—C9—H9	120 (10)	H4A—C4—H4C	109.5
Cl2—C9—H9	100 (10)	H4B—C4—H4C	109.5
Cl2^iv—C9—H9^iv	100 (10)	N1—C5—H5A	108.3
Cl2—C9—H9^iv	120 (10)	N1—C5—H5B	108.3
H9—C9—H9^iv	107 (10)	N1—C5—C6	116.1 (8)
C1—N1—C1^v	110.7 (10)	H5A—C5—H5B	107.4
C5^v—N1—C1^v	105.8 (5)	C6—C5—H5A	108.3
C5—N1—C1	105.8 (5)	C6—C5—H5B	108.3
C5—N1—C1^v	111.4 (6)	C5—C6—H6A	109.5
C5^v—N1—C1	111.4 (6)	C5—C6—H6B	109.5
C5—N1—C5^v	111.7 (11)	C5—C6—C7	110.6 (9)
N1—C1—H1A	108.2	H6A—C6—H6B	108.1
N1—C1—H1B	108.2	C7—C6—H6A	109.5
N1—C1—C2	116.2 (7)	C7—C6—H6B	109.5
H1A—C1—H1B	107.4	C6—C7—H7A	109.4
C2—C1—H1A	108.2	C6—C7—H7B	109.4
C2—C1—H1B	108.2	H7A—C7—H7B	108.0
C1—C2—H2A	109.4	C8—C7—C6	111.0 (12)
C1—C2—H2B	109.4	C8—C7—H7A	109.4
H2A—C2—H2B	108.0	C8—C7—H7B	109.4
C3—C2—C1	111.0 (7)	C7—C8—H8A	109.5
C3—C2—H2A	109.4	C7—C8—H8B	109.5
C3—C2—H2B	109.4	C7—C8—H8C	109.5
C2—C3—H3A	108.5	H8A—C8—H8B	109.5
C2—C3—H3B	108.5	H8A—C8—H8C	109.5
C2—C3—C4	115.2 (9)	H8B—C8—H8C	109.5

N1—C1—C2—C3	−179.5 (10)	C1—C2—C3—C4	178.4 (11)
N1—C5—C6—C7	−175.7 (11)	C5^v—N1—C1—C2	−58.2 (12)
C1^v—N1—C1—C2	59.3 (7)	C5—N1—C1—C2	−179.8 (9)
C1^v—N1—C5—C6	−58.6 (12)	C5^v—N1—C5—C6	59.6 (8)
C1—N1—C5—C6	−179.0 (10)	C5—C6—C7—C8	−173.2 (16)

Symmetry codes: (i) y+1/2, −x+1/2, −z+3/2; (ii) −x+1, −y, z; (iii) −y+1/2, x−1/2, −z+3/2; (iv) −x+1/2, y, −z+3/4; (v) x, −y+1/2, −z+5/4.

Acknowledgements

Authors contributions are as follows. Conceptualization, MTH; validation, MTH and HPY; formal analysis, HPY; investigation, MTH (synthesis and characterization) and HPY (XRD); resources, MTH and HPY; writing (original draft), MTH and HPY; writing (review and editing of the manuscript), MTH and HPY; visualization, MTH and HPY; funding acquisition, MTH and HPY.

Funding information

NIH funding for the X-ray instrumentation – award Nos. 1S10OD028589–01 and 1S10RR023439–01 to Dr Neela Yennawar – is acknowledged.

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