Hexa­kis­(dimethyl sulfoxide-κO)thallium(III) trinitrate

Ghadermazi, M.; Manteghi, F.

doi:10.1107/S1600536810022646

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m812

doi:10.1107/S1600536810022646

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Hexakis(dimethyl sulfoxide-κO)thallium(III) trinitrate

Mohammad Ghadermazi ^a ^* and Faranak Manteghi ^b

^aDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran, and ^bDepartment of Chemistry, Iran University of Science and Technology, Tehran, Iran
^*Correspondence e-mail: mghadermazi@yahoo.com

(Received 8 June 2010; accepted 13 June 2010; online 18 June 2010)

The title compound, [Tl(C₂H₆OS)₆](NO₃)₃, consists of six dimethyl sulfoxide (DMSO) molecules coordinated to a Tl^III atom, which lies on a $[\overline{3}]$ axis, and three nitrate anions (3. symmetry) to neutralize the charge. The coordination polyhedron around the Tl^III atom is octahedral, defined by six O atoms of the DMSO molecules. In the crystal structure, C—H⋯O hydrogen bonds are observed. One of the nitrate groups exhibits half-occupation.

Related literature

For general background to thallium(III) chemistry, see: Tóth & Gyõri (1994 ). For related structures, see: Aghabozorg, Ghadermazi et al. (2006 ); Aghabozorg, Ramezanipour et al. (2006 ); Ma et al. (2002 ); Notash et al. (2008 ).

Experimental

Crystal data

[Tl(C₂H₆OS)₆](NO₃)₃
M_r = 859.17
Trigonal, $[R \overline 3]$
a = 11.7207 (9) Å
c = 19.209 (3) Å
V = 2285.3 (4) Å³
Z = 3
Mo Kα radiation
μ = 5.78 mm⁻¹
T = 100 K
0.23 × 0.12 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.442, T_max = 0.786
9649 measured reflections
1480 independent reflections
1480 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.058
S = 0.99
1480 reflections
59 parameters
H-atom parameters constrained
Δρ_max = 1.97 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1	0.96	2.42	3.311 (4)	154
C1—H1C⋯O2ⁱ	0.96	2.54	3.448 (11)	158
C2—H2A⋯O1ⁱⁱ	0.96	2.55	3.380 (6)	145
C2—H2B⋯O2	0.96	1.99	2.915 (10)	161
C2—H2C⋯O1	0.96	2.55	3.423 (6)	152
Symmetry codes: (i) $[y-{\script{1\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ ; (ii) $[x-y+{\script{2\over 3}}, x+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810022646/hy2321sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022646/hy2321Isup2.hkl

checkCIF report

Comment top

There are some reports on coordination of dimethyl sulfoxide (DMSO) as a neutral ligand to Tl(III), such as a triiodo complex [TlI₃(DMSO)₂] (Ma et al., 2002) and [Tl(dm4bt)₂(NO₃)(DMSO)] (dm4bt = 2,2'-dimethyl-4,4'-bithiazole) (Notash et al., 2008). Thallium(III) can be classified as a medium-soft metal ion in contrast to the other trivalent ions of group 13, aluminium(III), gallium(III) and indium(III), which are regarded as hard from their coordination properties (Tóth & Gyõri, 1994). The title compound has a coordination number of six around the metal (Figs. 1 and 2). However, the coordination numbers 4 to 9 are observed in different thallium(III) complexes (Aghabozorg, Ramezanipour et al., 2006). Compared with [Tl(dm4bt)₂(NO₃)(DMSO)] and [TlI₃(DMSO)₂] mentioned above, in which the bond lengths of Tl(III) to O atoms of DMSO are 2.644 (7) and 2.468 (6) Å, the title compound has shorter Tl—O bonds [2.223 (2)–2.224 (2) Å]. This can be attributed to the less hindrance around the Tl centre. Also, compared with [Tl₂(pydcH)₃(pydc)(H₂O)₂] (pydcH₂ = pyridine-2,6-dicarboxylic acid) (Aghabozorg, Ramezanipour et al., 2006) and (pipzH₂)[Tl₂(pydc)₂Cl₄(H₂O)₂].4H₂O (pipz = piperazine) (Aghabozorg, Ghadermazi et al., 2006), whose Tl—O bond lengths vary in the range of 2.680 (4)–3.122 (4) and 2.436 (5)–2.508 (5) Å, respectively, again the Tl—O bond lengths in the title compound are obviously shorter. As shown in Table 1, only C—H···O hydrogen bonds can be seen in the lattice. The shortest C—H···O bond is C2—H2B···O2 with the best angle.

Related literature top

For general background to thallium(III) chemistry, see: Tóth & Gyõri (1994). For related structures, see: Aghabozorg, Ghadermazi et al. (2006); Aghabozorg, Ramezanipour et al. (2006); Ma et al. (2002); Notash et al. (2008).

Experimental top

To a DMSO solution of Tl(NO₃)₃.3H₂O (1 mmol, 443 mg) was added piperazinediium pyridine-2,6-dicarboxylate (3 mmol, 759 mg) prepared as literature (Aghabozorg, Ghadermazi et al., 2006). The total volume of solution was 40 ml. The colourless crystals suitable for crystallography were obtained after six months.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. [Symmetry codes: (i) 1/3+x-y, -1/3+x, 2/3-z; (ii) 1-y, x-y, z; (iii) 4/3-x, 2/3-y, 2/3-z; (iv) 1-x+y, 1-x, z; (v) 1/3+y, 2/3-x+y, 2/3-z.]
	Fig. 2. Coordination polyhedron around the metal centre.

Hexakis(dimethyl sulfoxide-κO)thallium(III) trinitrate top

Crystal data top

[Tl(C₂H₆OS)₆](NO₃)₃	D_x = 1.873 Mg m⁻³
M_r = 859.17	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1197 reflections
Hall symbol: -R 3	θ = 2.3–34.3°
a = 11.7207 (9) Å	µ = 5.78 mm⁻¹
c = 19.209 (3) Å	T = 100 K
V = 2285.3 (4) Å³	Plate, colourless
Z = 3	0.23 × 0.12 × 0.04 mm
F(000) = 1278

Data collection top

Bruker APEXII CCD diffractometer	1480 independent reflections
Radiation source: fine-focus sealed tube	1480 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.442, T_max = 0.786	k = −16→16
9649 measured reflections	l = −27→27

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.040P)² + 9.P] where P = (F_o² + 2F_c²)/3
1480 reflections	(Δ/σ)_max < 0.001
59 parameters	Δρ_max = 1.97 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

[Tl(C₂H₆OS)₆](NO₃)₃	Z = 3
M_r = 859.17	Mo Kα radiation
Trigonal, R3	µ = 5.78 mm⁻¹
a = 11.7207 (9) Å	T = 100 K
c = 19.209 (3) Å	0.23 × 0.12 × 0.04 mm
V = 2285.3 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	1480 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1480 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.786	R_int = 0.036
9649 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 0.99	Δρ_max = 1.97 e Å⁻³
1480 reflections	Δρ_min = −0.76 e Å⁻³
59 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Tl1	0.6667	0.3333	0.3333	0.01735 (8)
S1	0.47065 (6)	0.40706 (7)	0.24746 (4)	0.02613 (15)
N1	0.0000	0.0000	0.2520 (2)	0.0268 (8)
O3	0.48799 (19)	0.29141 (19)	0.27294 (11)	0.0235 (4)
O1	0.1049 (2)	0.1084 (2)	0.25261 (16)	0.0383 (5)
C1	0.3450 (3)	0.4021 (3)	0.30137 (19)	0.0333 (6)
H1A	0.3792	0.4312	0.3474	0.050*
H1B	0.2722	0.3136	0.3034	0.050*
H1C	0.3158	0.4589	0.2824	0.050*
C2	0.3806 (4)	0.3443 (5)	0.16924 (19)	0.0498 (11)
H2A	0.4345	0.3328	0.1355	0.075*
H2B	0.3554	0.4051	0.1515	0.075*
H2C	0.3031	0.2610	0.1783	0.075*
N2	0.3333	0.6667	0.1861 (4)	0.0280 (17)*	0.50
O2	0.3414 (8)	0.5668 (8)	0.1413 (4)	0.0609 (17)*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.01458 (8)	0.01458 (8)	0.02288 (12)	0.00729 (4)	0.000	0.000
S1	0.0176 (3)	0.0250 (3)	0.0332 (4)	0.0087 (2)	−0.0008 (2)	0.0090 (2)
N1	0.0221 (11)	0.0221 (11)	0.036 (2)	0.0110 (6)	0.000	0.000
O3	0.0209 (9)	0.0206 (8)	0.0287 (9)	0.0103 (7)	−0.0054 (7)	−0.0025 (7)
O1	0.0234 (10)	0.0229 (10)	0.0617 (16)	0.0063 (8)	−0.0014 (10)	−0.0006 (10)
C1	0.0278 (14)	0.0317 (15)	0.0436 (17)	0.0173 (12)	−0.0005 (12)	−0.0059 (12)
C2	0.0282 (16)	0.094 (3)	0.0273 (15)	0.0302 (19)	−0.0020 (12)	0.0109 (18)

Geometric parameters (Å, º) top

Tl1—O3ⁱ	2.2234 (19)	N1—O1^vii	1.250 (2)
Tl1—O3ⁱⁱ	2.2235 (19)	C1—H1A	0.9600
Tl1—O3ⁱⁱⁱ	2.2235 (19)	C1—H1B	0.9600
Tl1—O3^iv	2.2235 (19)	C1—H1C	0.9600
Tl1—O3	2.2235 (19)	C2—H2A	0.9600
Tl1—O3^v	2.2235 (19)	C2—H2B	0.9600
S1—O3	1.547 (2)	C2—H2C	0.9600
S1—C2	1.771 (4)	N2—O2^viii	1.226 (8)
S1—C1	1.777 (3)	N2—O2^ix	1.226 (8)
N1—O1	1.250 (2)	N2—O2^x	1.226 (8)
N1—O1^vi	1.250 (2)	O2—N2^x	1.226 (8)

O3ⁱ—Tl1—O3ⁱⁱ	95.26 (7)	O1—N1—O1^vii	119.993 (9)
O3ⁱ—Tl1—O3ⁱⁱⁱ	180.0	O1^vi—N1—O1^vii	119.993 (9)
O3ⁱⁱ—Tl1—O3ⁱⁱⁱ	84.74 (7)	S1—O3—Tl1	119.56 (11)
O3ⁱ—Tl1—O3^iv	84.74 (7)	S1—C1—H1A	109.5
O3ⁱⁱ—Tl1—O3^iv	180.0	S1—C1—H1B	109.5
O3ⁱⁱⁱ—Tl1—O3^iv	95.26 (7)	H1A—C1—H1B	109.5
O3ⁱ—Tl1—O3	84.74 (7)	S1—C1—H1C	109.5
O3ⁱⁱ—Tl1—O3	84.74 (7)	H1A—C1—H1C	109.5
O3ⁱⁱⁱ—Tl1—O3	95.26 (7)	H1B—C1—H1C	109.5
O3^iv—Tl1—O3	95.26 (7)	S1—C2—H2A	109.5
O3ⁱ—Tl1—O3^v	95.26 (7)	S1—C2—H2B	109.5
O3ⁱⁱ—Tl1—O3^v	95.26 (7)	H2A—C2—H2B	109.5
O3ⁱⁱⁱ—Tl1—O3^v	84.74 (7)	S1—C2—H2C	109.5
O3^iv—Tl1—O3^v	84.74 (7)	H2A—C2—H2C	109.5
O3—Tl1—O3^v	180.0	H2B—C2—H2C	109.5
O3—S1—C2	102.52 (19)	O2^viii—N2—O2^ix	119.14 (17)
O3—S1—C1	104.88 (14)	O2^viii—N2—O2^x	119.14 (17)
C2—S1—C1	99.72 (17)	O2^ix—N2—O2^x	119.13 (17)
O1—N1—O1^vi	119.993 (9)

C2—S1—O3—Tl1	148.95 (15)	O2^x—N2—O2—O2^viii	112.8 (4)
C1—S1—O3—Tl1	−107.29 (16)	O2^xi—N2—O2—O2^viii	157.9 (4)
O3ⁱ—Tl1—O3—S1	46.66 (9)	O2^xii—N2—O2—O2^viii	67.8 (6)
O3ⁱⁱ—Tl1—O3—S1	142.45 (17)	N2^x—N2—O2—O2^ix	−112.8 (4)
O3ⁱⁱⁱ—Tl1—O3—S1	−133.34 (9)	O2^viii—N2—O2—O2^ix	134.3 (9)
O3^iv—Tl1—O3—S1	−37.55 (17)	O2^x—N2—O2—O2^ix	−112.8 (4)
N2^x—N2—O2—O2^viii	112.8 (4)	O2^xi—N2—O2—O2^ix	−67.8 (6)
O2^ix—N2—O2—O2^viii	−134.3 (9)	O2^xii—N2—O2—O2^ix	−157.9 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1	0.96	2.42	3.311 (4)	154
C1—H1C···O2^ix	0.96	2.54	3.448 (11)	158
C2—H2A···O1^viii	0.96	2.55	3.380 (6)	145
C2—H2B···O2	0.96	1.99	2.915 (10)	161
C2—H2C···O1	0.96	2.55	3.423 (6)	152

Symmetry codes: (viii) x−y+2/3, x+1/3, −z+1/3; (ix) y−1/3, −x+y+1/3, −z+1/3.

Experimental details

Crystal data
Chemical formula	[Tl(C₂H₆OS)₆](NO₃)₃
M_r	859.17
Crystal system, space group	Trigonal, R3
Temperature (K)	100
a, c (Å)	11.7207 (9), 19.209 (3)
V (Å³)	2285.3 (4)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	5.78
Crystal size (mm)	0.23 × 0.12 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.442, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	9649, 1480, 1480
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.058, 0.99
No. of reflections	1480
No. of parameters	59
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.97, −0.76

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1	0.96	2.42	3.311 (4)	154
C1—H1C···O2ⁱ	0.96	2.54	3.448 (11)	158
C2—H2A···O1ⁱⁱ	0.96	2.55	3.380 (6)	145
C2—H2B···O2	0.96	1.99	2.915 (10)	161
C2—H2C···O1	0.96	2.55	3.423 (6)	152

Symmetry codes: (i) y−1/3, −x+y+1/3, −z+1/3; (ii) x−y+2/3, x+1/3, −z+1/3.

Acknowledgements

The authors gratefully acknowledge University of Kurdistan for financial support of this work.

References

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