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

Abstract

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 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,

• a = 11.7207 (9) Å

• c = 19.209 (3) Å

• V = 2285.3 (4) ų

• 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[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C). There is a high positive residual density of 1.97 e Å^-3 near the Tl1 atom (distance 0.76 Å) due to considerable absorption effects which could not be completely corrected.

Figures

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.

Crystal data

[Tl(C2H6OS)6](NO3)3	Dx = 1.873 Mg m−3
Mr = 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

Bruker APEXII CCD diffractometer	1480 independent reflections
Radiation source: fine-focus sealed tube	1480 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.442, Tmax = 0.786	k = −16→16
9649 measured reflections	l = −27→27

Refinement

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(Fo2) + (0.040P)2 + 9.P] where P = (Fo2 + 2Fc2)/3
1480 reflections	(Δ/σ)max < 0.001
59 parameters	Δρmax = 1.97 e Å−3
0 restraints	Δρmin = −0.76 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

Tl1—O3i	2.2234 (19)	N1—O1vii	1.250 (2)
Tl1—O3ii	2.2235 (19)	C1—H1A	0.9600
Tl1—O3iii	2.2235 (19)	C1—H1B	0.9600
Tl1—O3iv	2.2235 (19)	C1—H1C	0.9600
Tl1—O3	2.2235 (19)	C2—H2A	0.9600
Tl1—O3v	2.2235 (19)	C2—H2B	0.9600
S1—O3	1.547 (2)	C2—H2C	0.9600
S1—C2	1.771 (4)	N2—O2viii	1.226 (8)
S1—C1	1.777 (3)	N2—O2ix	1.226 (8)
N1—O1	1.250 (2)	N2—O2x	1.226 (8)
N1—O1vi	1.250 (2)	O2—N2x	1.226 (8)
O3i—Tl1—O3ii	95.26 (7)	O1—N1—O1vii	119.993 (9)
O3i—Tl1—O3iii	180.0	O1vi—N1—O1vii	119.993 (9)
O3ii—Tl1—O3iii	84.74 (7)	S1—O3—Tl1	119.56 (11)
O3i—Tl1—O3iv	84.74 (7)	S1—C1—H1A	109.5
O3ii—Tl1—O3iv	180.0	S1—C1—H1B	109.5
O3iii—Tl1—O3iv	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
O3iv—Tl1—O3	95.26 (7)	S1—C2—H2A	109.5
O3i—Tl1—O3v	95.26 (7)	S1—C2—H2B	109.5
O3ii—Tl1—O3v	95.26 (7)	H2A—C2—H2B	109.5
O3iii—Tl1—O3v	84.74 (7)	S1—C2—H2C	109.5
O3iv—Tl1—O3v	84.74 (7)	H2A—C2—H2C	109.5
O3—Tl1—O3v	180.0	H2B—C2—H2C	109.5
O3—S1—C2	102.52 (19)	O2viii—N2—O2ix	119.14 (17)
O3—S1—C1	104.88 (14)	O2viii—N2—O2x	119.14 (17)
C2—S1—C1	99.72 (17)	O2ix—N2—O2x	119.13 (17)
O1—N1—O1vi	119.993 (9)
C2—S1—O3—Tl1	148.95 (15)	O2x—N2—O2—O2viii	112.8 (4)
C1—S1—O3—Tl1	−107.29 (16)	O2xi—N2—O2—O2viii	157.9 (4)
O3i—Tl1—O3—S1	46.66 (9)	O2xii—N2—O2—O2viii	67.8 (6)
O3ii—Tl1—O3—S1	142.45 (17)	N2x—N2—O2—O2ix	−112.8 (4)
O3iii—Tl1—O3—S1	−133.34 (9)	O2viii—N2—O2—O2ix	134.3 (9)
O3iv—Tl1—O3—S1	−37.55 (17)	O2x—N2—O2—O2ix	−112.8 (4)
N2x—N2—O2—O2viii	112.8 (4)	O2xi—N2—O2—O2ix	−67.8 (6)
O2ix—N2—O2—O2viii	−134.3 (9)	O2xii—N2—O2—O2ix	−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, °)

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···O2ix	0.96	2.54	3.448 (11)	158
C2—H2A···O1xiii	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: (ix) y−1/3, −x+y+1/3, −z+1/3; (xiii) x−y+2/3, x+1/3, −z+1/3.