Crystal structure of hexa­kis­(dimethyl sulfoxide-κO)manganese(II) tetra­iodide

Haque, M.A.; Davaasuren, B.; Rothenberger, A.; Wu, T.

doi:10.1107/S2056989016017904

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 12| December 2016| Pages 1791-1793

https://doi.org/10.1107/S2056989016017904

Open

access

Crystal structure of hexakis(dimethyl sulfoxide-κO)manganese(II) tetraiodide

Md Azimul Haque,^a ^* Bambar Davaasuren,^a Alexander Rothenberger ^a and Tom Wu ^a ^*

^aPhysical Sciences and Engineering Division, King Abdullah University of Science and Technology, KAUST, Thuwal 23955-6900, Kingdom of Saudi Arabia
^*Correspondence e-mail: azimul.mohammed@kaust.edu.sa, tao.wu@kaust.edu.sa

Edited by M. Weil, Vienna University of Technology, Austria (Received 27 October 2016; accepted 8 November 2016; online 15 November 2016)

The title salt, [Mn(C₂H₆OS)₆]I₄, is made up from discrete [Mn(DMSO)₆]²⁺ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I₄²⁻ tetraiodide anions. The Mn^II ion in the cation, situated on a position with site symmetry -3., is octahedrally coordinated by O atoms of the DMSO molecule with an Mn—O distance of 2.1808 (12) Å. The I₄²⁻ anion contains a neutral I₂ molecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetraiodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues.

Keywords: crystal structure; tetraiodide; octahedral coordination; isotypism.

CCDC reference: 1515632

1. Chemical context

Inorganic–organic hybrid compounds have attracted significant attention owing to their fascinating structural, optical and electrical properties (Stranks & Snaith, 2015 ). In particular, CH₃NH₃PbX₃ hybrids obtained from PbX₂ and CH₃NH₃X (X = I, Br, Cl) are interesting due to their high absorption coefficient and applications in optoelectronics (Stoumpos & Kanatzidis, 2015 ). In general, this family of materials adopts the perovskite ABX₃ structure type, where A is an organic cation, which is surrounded by twelve nearest X halide anions, and B is a metal cation (Grätzel, 2014 ). There are continuous efforts on replacing Pb in these hybrids due to its toxicity (Wang et al., 2015 ). In the present work, one such attempt was made to produce a hybrid between CH₃NH₃I and MnI₂. However, we obtained instead the title salt [Mn(DMSO)₆]I₄ (DMSO is dimethyl sulfoxide), and report here its crystal structure.

2. Structural commentary

The title salt is the first compound with a [Mn(DMSO]²⁺ cation and a linear tetraiodide anion. The Mn²⁺ cation is bound to the O atoms of six DMSO molecules arranged in an octahedral configuration (Fig. 1). Owing to the $[\overline{3}]$ . site symmetry of the metal cation, the deviations of corresponding angles from ideal values are minute [range cis O—Mn—O angles 86.28 (4)–93.73 (4)°; all trans angles 180°]. The Mn—O bond length is 2.1808 (12) Å. The four I atoms are arranged in a linear fashion. The bond length between the two central I atoms is 2.8460 (5) Å; this inner I₂ moiety is rather weakly bonded to two terminal I⁻ anions with a bond lengths of 3.3251 (6) Å. This confirms the existence of a linear, centrosymmetric polyiodide ion I₄²⁻, consistent with previous reports (Long et al., 1999 ). Both inner and terminal bond lengths of the I₄²⁻ anion are comparable with values found in [Cu(NH₃)₄]I₄ (Dubler & Linowsky, 1975 ) or other [M(DMSO)₆]I₄ compounds (Long et al., 1999; Tkachev et al., 1994 ; Garzón-Tovar et al., 2013a ,b ).

Figure 1
The molecular components of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (′) $[{4\over 3}]$ − x, $[{2\over 3}]$ − y, $[{5\over 3}]$ − z.]

3. Supramolecular features

Fig. 2 shows the unit-cell projection along [001]. The hexagonal rod packing of isolated [Mn(DMSO)₆]²⁺ molecules can be seen along [211]. The tetraiodide counter-anions are located between the rows (Fig. 3). An extended three-dimensional supramolecular network is accomplished through non-classical hydrogen bonding between H atoms of the DMSO molecules and the linear I₄²⁻ polyiodide anions. Table 1 collates numerical details of these C—H⋯I interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯I2	0.98	3.10	3.954 (2)	147
C2—H2B⋯I1ⁱ	0.98	3.26	4.182 (2)	158
C2—H2C⋯I2ⁱⁱ	0.98	3.20	4.108 (2)	154
Symmetry codes: (i) $[-x+{\script{5\over 3}}, -y+{\script{4\over 3}}, -z+{\script{4\over 3}}]$ ; (ii) -x+1, -y+1, -z+1.

Figure 2
The unit cell of [Mn(DMSO)₆]I₄ in a view approximately along [001]. H atoms have been omitted for clarity.

Figure 3
Packing diagram of the title compound. Non-classical hydrogen bonds are shown as dashed lines.

4. Database survey

A number of transition metals have been reported to form complexes with DMSO (Meek et al., 1960 ). However, reports on Mn complexes of DMSO with halide anions are scarce, as revealed by a search in the Cambridge Structural Database (Groom et al. 2016 ). Recently Glatz et al. (2016 ) reported the crystal structure of [Mn(DMSO)₆]I₂. In particular, polyiodide salts are interesting compounds owing to their high conductivity and non-linear properties that are predominantly observed in sulfur-rich compounds (Long et al., 1999). The structure of the title compound is isotypic with the Co, Ni, Cu, and Zn analogues: [Co(DMSO)₆]I₄ (Tkachev et al., 1994), [Ni(DMSO)₆]I₄ (Long et al., 1999), [Cu(DMSO)₆]I₄ (Garzón-Tovar et al., 2013a), [Zn(DMSO)₆]I₄ (Garzón-Tovar et al., 2013b).

5. Synthesis and crystallization

The title manganese salt was formed in the course of the targeted synthesis of a hybrid compound between CH₃NH₃I and MnI₂. Anhydrous MnI₂ and dimethyl sulfoxide (DMSO) were purchased from Alfa–Aesar and Sigma–Aldrich, respectively. CH₃NH₃I was purchased from Dyesol. The precursors were used without further purification. The title manganese salt was synthesized by adding anhydrous MnI₂ (308.7 mg) and CH₃NH₃I (158.9 mg) in a glass vial. Then 2 ml DMSO was added to the vial (capped afterwards) and stirred at 353 K for 24 h inside a nitrogen glove box. A reddish-black solution was observed after 24 h which was cooled down to room temperature and left for 7 d undisturbed. Single crystals of the title compound were obtained as the only solid product after 7 d. The crystals were removed from the vial and dried under nitrogen flow.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The methyl H atoms were treated as riding and U_iso(H) values set at 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Mn(C₂H₆OS)₆]I₄
M_r	1031.31
Crystal system, space group	Trigonal, R $[\overline{3}]$
Temperature (K)	200
a, c (Å)	11.8702 (10), 19.3860 (18)
V (Å³)	2365.6 (5)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	4.75
Crystal size (mm)	0.16 × 0.12 × 0.05

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED32; Stoe & Cie, 2013 )
T_min, T_max	0.415, 0.615
No. of measured, independent and observed [I > 2σ(I)] reflections	7644, 1417, 1301
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.038, 1.06
No. of reflections	1417
No. of parameters	47
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.93
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1515632

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016017904/wm5337sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016017904/wm5337Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2013); cell refinement: X-AREA (Stoe & Cie, 2013); data reduction: X-RED32 (Stoe & Cie, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Hexakis(dimethyl sulfoxide-κO)manganese(II) tetraiodide top

Crystal data top

[Mn(C₂H₆OS)₆]I₄	D_x = 2.172 Mg m⁻³
M_r = 1031.31	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3:H	Cell parameters from 10442 reflections
a = 11.8702 (10) Å	θ = 2.2–29.5°
c = 19.3860 (18) Å	µ = 4.75 mm⁻¹
V = 2365.6 (5) Å³	T = 200 K
Z = 3	Block, brown
F(000) = 1467	0.16 × 0.12 × 0.05 mm

Data collection top

Stoe IPDS-2 diffractometer	1417 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1301 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.045
rotation method scans	θ_max = 29.2°, θ_min = 2.2°
Absorption correction: numerical (X-RED32; Stoe & Cie, 2013)	h = −16→16
T_min = 0.415, T_max = 0.615	k = −16→16
7644 measured reflections	l = −26→26

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.038	w = 1/[σ²(F_o²) + (0.0105P)² + 3.7009P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1417 reflections	Δρ_max = 0.34 e Å⁻³
47 parameters	Δρ_min = −0.93 e Å⁻³

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	0.3333	0.6667	0.6667	0.01931 (12)
I1	0.6667	0.3333	0.75993 (2)	0.03170 (6)
I2	0.6667	0.3333	0.58841 (2)	0.03067 (6)
S1	0.54925 (4)	0.62436 (4)	0.58993 (2)	0.02341 (9)
O1	0.50872 (12)	0.72442 (12)	0.60608 (6)	0.0247 (2)
C1	0.67639 (18)	0.65612 (19)	0.64912 (11)	0.0325 (4)
H1A	0.7149	0.6023	0.6373	0.049*
H1B	0.6410	0.6353	0.6960	0.049*
H1C	0.7433	0.7482	0.6466	0.049*
C2	0.64415 (19)	0.6821 (2)	0.51353 (10)	0.0343 (4)
H2A	0.6785	0.6249	0.5015	0.051*
H2B	0.7165	0.7706	0.5212	0.051*
H2C	0.5897	0.6829	0.4757	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01701 (16)	0.01701 (16)	0.0239 (3)	0.00851 (8)	0.000	0.000
I1	0.02446 (7)	0.02446 (7)	0.04619 (13)	0.01223 (4)	0.000	0.000
I2	0.03185 (8)	0.03185 (8)	0.02833 (10)	0.01592 (4)	0.000	0.000
S1	0.01918 (17)	0.02122 (18)	0.0279 (2)	0.00868 (15)	0.00044 (15)	−0.00439 (15)
O1	0.0219 (5)	0.0245 (6)	0.0294 (6)	0.0128 (5)	0.0038 (5)	0.0002 (5)
C1	0.0318 (9)	0.0368 (10)	0.0344 (9)	0.0212 (8)	−0.0054 (8)	−0.0033 (8)
C2	0.0298 (9)	0.0447 (11)	0.0283 (9)	0.0185 (9)	0.0040 (7)	−0.0047 (8)

Geometric parameters (Å, º) top

Mn1—O1ⁱ	2.1808 (12)	S1—C2	1.778 (2)
Mn1—O1ⁱⁱ	2.1808 (12)	S1—C1	1.7798 (19)
Mn1—O1ⁱⁱⁱ	2.1808 (12)	C1—H1A	0.9800
Mn1—O1^iv	2.1808 (12)	C1—H1B	0.9800
Mn1—O1^v	2.1809 (12)	C1—H1C	0.9800
Mn1—O1	2.1808 (12)	C2—H2A	0.9800
I1—I1^vi	2.8460 (5)	C2—H2B	0.9800
S1—O1	1.5204 (12)	C2—H2C	0.9800

O1ⁱ—Mn1—O1ⁱⁱ	180.00 (6)	O1—S1—C1	105.53 (9)
O1ⁱ—Mn1—O1ⁱⁱⁱ	86.27 (4)	C2—S1—C1	98.56 (10)
O1ⁱⁱ—Mn1—O1ⁱⁱⁱ	93.73 (4)	S1—O1—Mn1	119.38 (7)
O1ⁱ—Mn1—O1^iv	93.73 (4)	S1—C1—H1A	109.5
O1ⁱⁱ—Mn1—O1^iv	86.27 (4)	S1—C1—H1B	109.5
O1ⁱⁱⁱ—Mn1—O1^iv	180.00 (5)	H1A—C1—H1B	109.5
O1ⁱ—Mn1—O1^v	93.73 (4)	S1—C1—H1C	109.5
O1ⁱⁱ—Mn1—O1^v	86.27 (4)	H1A—C1—H1C	109.5
O1ⁱⁱⁱ—Mn1—O1^v	86.27 (5)	H1B—C1—H1C	109.5
O1^iv—Mn1—O1^v	93.72 (4)	S1—C2—H2A	109.5
O1ⁱ—Mn1—O1	86.28 (4)	S1—C2—H2B	109.5
O1ⁱⁱ—Mn1—O1	93.73 (4)	H2A—C2—H2B	109.5
O1ⁱⁱⁱ—Mn1—O1	93.73 (4)	S1—C2—H2C	109.5
O1^iv—Mn1—O1	86.27 (5)	H2A—C2—H2C	109.5
O1^v—Mn1—O1	180.0	H2B—C2—H2C	109.5
O1—S1—C2	104.90 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···I2	0.98	3.10	3.954 (2)	147
C2—H2B···I1^vii	0.98	3.26	4.182 (2)	158
C2—H2C···I2^viii	0.98	3.20	4.108 (2)	154

Symmetry codes: (vii) −x+5/3, −y+4/3, −z+4/3; (viii) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the King Abdullah University of Science and Technology (KAUST).

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Dubler, E. & Linowsky, L. (1975). Helv. Chim. Acta, 58, 2604–2609. CrossRef CAS Web of Science Google Scholar
Garzón-Tovar, L., Duarte-Ruiz, Á. & Fanwick, P. E. (2013b). Acta Cryst. E69, m618. CSD CrossRef IUCr Journals Google Scholar
Garzón-Tovar, L., Duarte-Ruiz, A. & Wurst, K. (2013a). Inorg. Chem. Commun. 32, 64–67. Google Scholar
Glatz, M., Schroffenegger, M., Weil, M. & Kirchner, K. (2016). Acta Cryst. E72, 904–906. Web of Science CSD CrossRef IUCr Journals Google Scholar
Grätzel, M. (2014). Nat. Mater. 13, 838–842. Web of Science PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Long, D.-L., Hu, H.-M., Chen, J.-T. & Huang, J.-S. (1999). Acta Cryst. C55, 339–341. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Meek, D. W., Straub, D. K. & Drago, R. S. (1960). J. Am. Chem. Soc. 82, 6013–6016. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2013). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar
Stoumpos, C. C. & Kanatzidis, M. G. (2015). Acc. Chem. Res. 48, 2791–2802. Web of Science CrossRef CAS Google Scholar
Stranks, S. D. & Snaith, H. J. (2015). Nature Nanotech, 10, 391–402. Web of Science CrossRef CAS Google Scholar
Tkachev, V. V., Lavrent'eva, E. A., Rosschupkina, O. S., Lavrent'ev, I. P. & Atovmyan, L. O. (1994). Koord. Khim. 20, 674–676. CAS Google Scholar
Wang, K., Liang, Z., Wang, X. & Cui, X. (2015). Adv. Electron. Mater. 1, 1500089. Web of Science CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.