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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](S-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.022
• wR factor = 0.058
• Data-to-parameter ratio = 25.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.59
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?

Alert level G
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       9.00
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C2      ..       2.91 Ang.
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      33.00 Perc.
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.33 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

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).

S2. 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.

S3. 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.

Computing details

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

	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

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) Å^3	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 monochromator	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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.058	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 9.P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Tl1—O3^i	2.2234 (19)	N1—O1^vii	1.250 (2)
Tl1—O3^ii	2.2235 (19)	C1—H1A	0.9600
Tl1—O3^iii	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)
O3^i—Tl1—O3^ii	95.26 (7)	O1—N1—O1^vii	119.993 (9)
O3^i—Tl1—O3^iii	180.0	O1^vi—N1—O1^vii	119.993 (9)
O3^ii—Tl1—O3^iii	84.74 (7)	S1—O3—Tl1	119.56 (11)
O3^i—Tl1—O3^iv	84.74 (7)	S1—C1—H1A	109.5
O3^ii—Tl1—O3^iv	180.0	S1—C1—H1B	109.5
O3^iii—Tl1—O3^iv	95.26 (7)	H1A—C1—H1B	109.5
O3^i—Tl1—O3	84.74 (7)	S1—C1—H1C	109.5
O3^ii—Tl1—O3	84.74 (7)	H1A—C1—H1C	109.5
O3^iii—Tl1—O3	95.26 (7)	H1B—C1—H1C	109.5
O3^iv—Tl1—O3	95.26 (7)	S1—C2—H2A	109.5
O3^i—Tl1—O3^v	95.26 (7)	S1—C2—H2B	109.5
O3^ii—Tl1—O3^v	95.26 (7)	H2A—C2—H2B	109.5
O3^iii—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)
O3^i—Tl1—O3—S1	46.66 (9)	O2^xii—N2—O2—O2^viii	67.8 (6)
O3^ii—Tl1—O3—S1	142.45 (17)	N2^x—N2—O2—O2^ix	−112.8 (4)
O3^iii—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)

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.