Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112038176/yp3015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112038176/yp3015Isup2.hkl |
All compound and sample handling was carried out under standard Schlenk and argon glove-box techniques. Reaction took place in argon-filled and sealed glass ampoules that were dried at 573 K before use. The commercially available starting materials niobium(V) chloride (99.99%, ABCR) and tellurium powder (99.99%, ABCR) were dried in a vacuum for 24 h and used without further purification. Niobium(V) oxychloride was prepared according to a literature procedure (Brauer, 1981). The commercially available ionic liquid BMImCl (IoLiTec) was recrystallized and dried for 2 d in a vacuum prior to use.
In a typical reaction, tellurium (150 mg, 1.1 mmol), niobium(V) chloride (79.4 mg, 0.29 mmol) and niobium(V) oxychloride (62.4 mg, 0.29 mmol) were reacted in the ionic liquid BMImCl at 423 K for 14 d. Black crystals were obtained after cooling to room temperature at a rate of 1 K h-1. These crystals were separated from the ionic liquid by filtration through a glass filter, followed by washing (four times) with dried tetrahydrofuran (THF, 2ml). Finally, the product was dried in a vacuum overnight and obtained in a yield of about 30%.
EDX measurements were carried out using an AMETEC EDAX mounted on a Zeiss SEM Supra 35 VP scanning electron microscope. Powdered samples were pressed into pellets, which were then fixed with conductive carbon pads on aluminium sample holders.
Data collection: EXPOSE (Stoe & Cie, 2001); cell refinement: CELL and SELECT (Stoe & Cie, 2001); data reduction: INTEGRATE (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).
[Te8][NbOCl4]2 | Z = 2 |
Mr = 1522.22 | F(000) = 1300 |
Triclinic, P1 | Dx = 4.438 Mg m−3 |
a = 7.8670 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.049 (2) Å | Cell parameters from 1058 reflections |
c = 12.481 (3) Å | θ = 3.0–60.0° |
α = 80.85 (3)° | µ = 11.98 mm−1 |
β = 82.17 (3)° | T = 200 K |
γ = 78.84 (3)° | Needle, black |
V = 1139.1 (4) Å3 | 0.25 × 0.23 × 0.21 mm |
Stoe IPDS II diffractometer | 4371 independent reflections |
Radiation source: fine-focus sealed tube | 2699 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
image–plate diffraction system scans | θmax = 26.4°, θmin = 1.7° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2001) | h = −9→9 |
Tmin = 0.39, Tmax = 0.54 | k = −15→15 |
8557 measured reflections | l = −15→15 |
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)] = 0.047 | w = 1/[σ2(Fo2) + (0.0414P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.115 | (Δ/σ)max < 0.001 |
S = 0.91 | Δρmax = 1.87 e Å−3 |
4371 reflections | Δρmin = −1.53 e Å−3 |
182 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00159 (14) |
[Te8][NbOCl4]2 | γ = 78.84 (3)° |
Mr = 1522.22 | V = 1139.1 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8670 (16) Å | Mo Kα radiation |
b = 12.049 (2) Å | µ = 11.98 mm−1 |
c = 12.481 (3) Å | T = 200 K |
α = 80.85 (3)° | 0.25 × 0.23 × 0.21 mm |
β = 82.17 (3)° |
Stoe IPDS II diffractometer | 4371 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2001) | 2699 reflections with I > 2σ(I) |
Tmin = 0.39, Tmax = 0.54 | Rint = 0.070 |
8557 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 182 parameters |
wR(F2) = 0.115 | 0 restraints |
S = 0.91 | Δρmax = 1.87 e Å−3 |
4371 reflections | Δρmin = −1.53 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. For single-crystal structure analysis, suitable single crystals were chosen and adhered into glass capillaries with inert oil (KEL-F). Data collection was performed at 200 K on an IPDS II image-plate diffractometer (Stoe) using graphite-monochromated Mo Kα (0.71073 Å) radiation and a low-temperature device. Data reduction was performed using the program package X-AREA (Stoe & Cie, 2001); space-group determination was carried out via XPREP (Stoe & Cie, 2001). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008). Anisotropic refinement on 4σF was carried out for all atoms by full-matrix least-squares methods using SHELXL97 (Sheldrick, 2008). A numerical absorption correction was applied and H atoms were geometrically constructed. All crystallographic illustrations were created with DIAMOND (Brandenburg, 2012). publCIF (Westrip, 2010) has been used to prepare material for publication. More details concerning the crystallographic data can be requested from the Inorganic Crystal Structure Database (ICSD) at the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen (www.fiz-karlsruhe.de) with the deposition number CSD-424139. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Te3 | 0.43168 (16) | 0.42340 (10) | 0.28111 (10) | 0.0290 (3) | |
Te7 | 0.24771 (17) | 0.12246 (10) | 0.24102 (11) | 0.0327 (3) | |
Te4 | 0.75713 (17) | 0.34177 (11) | 0.35879 (11) | 0.0356 (3) | |
Te6 | 0.21770 (16) | 0.26864 (11) | 0.38746 (10) | 0.0313 (3) | |
Te1 | 0.76503 (17) | 0.15379 (10) | 0.12227 (10) | 0.0326 (3) | |
Te2 | 0.51624 (17) | 0.35157 (11) | 0.08236 (10) | 0.0341 (3) | |
Te5 | 0.72432 (18) | 0.12996 (10) | 0.34614 (11) | 0.0353 (3) | |
Te8 | 0.07161 (18) | 0.24869 (11) | 0.08088 (10) | 0.0344 (3) | |
Nb1 | 0.4428 (2) | 0.24104 (13) | 0.73156 (13) | 0.0230 (4) | |
Nb2 | 0.9443 (2) | 0.24170 (13) | 0.72627 (12) | 0.0218 (4) | |
Cl1 | 0.8496 (6) | 0.3614 (4) | 0.8686 (4) | 0.0317 (10) | |
Cl2 | 0.4310 (6) | 0.0993 (4) | 0.8827 (4) | 0.0382 (12) | |
Cl3 | 0.9092 (6) | 0.4073 (3) | 0.5978 (4) | 0.0289 (10) | |
Cl4 | 0.4908 (6) | 0.1030 (4) | 0.6088 (4) | 0.0332 (10) | |
Cl5 | 0.3830 (6) | 0.3893 (4) | 0.5838 (4) | 0.0318 (10) | |
Cl6 | 0.9606 (6) | 0.1270 (4) | 0.5871 (3) | 0.0300 (10) | |
Cl7 | 0.3216 (6) | 0.3822 (4) | 0.8482 (4) | 0.0313 (10) | |
Cl8 | 0.9176 (6) | 0.0814 (4) | 0.8615 (4) | 0.0311 (10) | |
O1 | 1.1645 (16) | 0.2310 (9) | 0.7293 (9) | 0.027 (3) | |
O2 | 0.6563 (15) | 0.2508 (10) | 0.7300 (9) | 0.028 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Te3 | 0.0276 (7) | 0.0274 (6) | 0.0315 (7) | −0.0031 (5) | −0.0024 (6) | −0.0056 (5) |
Te7 | 0.0333 (7) | 0.0315 (6) | 0.0353 (7) | −0.0066 (5) | −0.0091 (6) | −0.0052 (5) |
Te4 | 0.0349 (8) | 0.0406 (7) | 0.0341 (7) | −0.0005 (6) | −0.0115 (6) | −0.0139 (6) |
Te6 | 0.0294 (7) | 0.0405 (7) | 0.0262 (6) | −0.0094 (6) | −0.0030 (6) | −0.0068 (5) |
Te1 | 0.0332 (7) | 0.0370 (7) | 0.0293 (7) | −0.0041 (6) | −0.0035 (6) | −0.0121 (5) |
Te2 | 0.0367 (8) | 0.0410 (7) | 0.0232 (6) | −0.0059 (6) | −0.0048 (6) | −0.0001 (5) |
Te5 | 0.0383 (8) | 0.0319 (7) | 0.0317 (7) | −0.0003 (6) | −0.0036 (6) | 0.0005 (5) |
Te8 | 0.0349 (7) | 0.0414 (7) | 0.0263 (6) | −0.0087 (6) | −0.0022 (6) | −0.0020 (5) |
Nb1 | 0.0185 (8) | 0.0279 (8) | 0.0232 (8) | −0.0059 (6) | −0.0026 (7) | −0.0029 (6) |
Nb2 | 0.0180 (8) | 0.0270 (8) | 0.0208 (8) | −0.0048 (6) | −0.0024 (7) | −0.0032 (6) |
Cl1 | 0.034 (3) | 0.036 (2) | 0.026 (2) | −0.003 (2) | −0.004 (2) | −0.0102 (18) |
Cl2 | 0.034 (3) | 0.044 (3) | 0.033 (3) | −0.007 (2) | −0.004 (2) | 0.004 (2) |
Cl3 | 0.033 (3) | 0.026 (2) | 0.026 (2) | −0.0040 (18) | −0.002 (2) | 0.0000 (17) |
Cl4 | 0.032 (3) | 0.036 (2) | 0.033 (2) | −0.004 (2) | −0.004 (2) | −0.0093 (19) |
Cl5 | 0.036 (3) | 0.034 (2) | 0.025 (2) | −0.009 (2) | −0.003 (2) | −0.0016 (18) |
Cl6 | 0.032 (3) | 0.035 (2) | 0.024 (2) | −0.0042 (19) | −0.003 (2) | −0.0093 (18) |
Cl7 | 0.031 (2) | 0.040 (2) | 0.026 (2) | −0.010 (2) | −0.001 (2) | −0.0099 (19) |
Cl8 | 0.036 (3) | 0.032 (2) | 0.026 (2) | −0.008 (2) | −0.007 (2) | −0.0008 (18) |
O1 | 0.039 (7) | 0.023 (6) | 0.027 (6) | −0.022 (5) | −0.015 (6) | 0.002 (5) |
O2 | 0.020 (7) | 0.043 (7) | 0.021 (6) | −0.003 (6) | −0.002 (6) | −0.005 (5) |
Te3—Te2 | 2.7121 (19) | Nb1—Cl2 | 2.339 (5) |
Te3—Te4 | 2.8037 (18) | Nb1—Cl4 | 2.381 (5) |
Te3—Te6 | 2.809 (2) | Nb1—Cl5 | 2.382 (4) |
Te7—Te8 | 2.6832 (19) | Nb1—Cl7 | 2.388 (5) |
Te7—Te6 | 2.6915 (19) | Nb2—O1 | 1.718 (12) |
Te4—Te5 | 2.6455 (18) | Nb2—O2 | 2.241 (11) |
Te1—Te5 | 2.7439 (19) | Nb2—Cl3 | 2.349 (4) |
Te1—Te2 | 2.800 (2) | Nb2—Cl6 | 2.361 (4) |
Te1—Te8i | 2.8164 (19) | Nb2—Cl8 | 2.376 (4) |
Te8—Te1ii | 2.8164 (19) | Nb2—Cl1 | 2.415 (5) |
Nb1—O2 | 1.704 (11) | O1—Nb1i | 2.221 (11) |
Nb1—O1ii | 2.221 (11) | ||
Te2—Te3—Te4 | 97.02 (6) | O2—Nb1—Cl7 | 97.6 (4) |
Te2—Te3—Te6 | 101.47 (6) | O1ii—Nb1—Cl7 | 82.7 (3) |
Te4—Te3—Te6 | 105.06 (6) | Cl2—Nb1—Cl7 | 89.31 (18) |
Te8—Te7—Te6 | 102.70 (6) | Cl4—Nb1—Cl7 | 165.90 (16) |
Te5—Te4—Te3 | 90.18 (6) | Cl5—Nb1—Cl7 | 86.18 (16) |
Te7—Te6—Te3 | 102.08 (6) | O1—Nb2—O2 | 177.3 (5) |
Te5—Te1—Te2 | 98.46 (6) | O1—Nb2—Cl3 | 96.5 (4) |
Te5—Te1—Te8i | 99.51 (6) | O2—Nb2—Cl3 | 86.0 (3) |
Te2—Te1—Te8i | 100.02 (6) | O1—Nb2—Cl6 | 97.3 (4) |
Te3—Te2—Te1 | 103.32 (6) | O2—Nb2—Cl6 | 83.7 (3) |
Te4—Te5—Te1 | 95.31 (6) | Cl3—Nb2—Cl6 | 90.48 (16) |
Te7—Te8—Te1ii | 99.24 (6) | O1—Nb2—Cl8 | 94.8 (4) |
O2—Nb1—O1ii | 178.5 (5) | O2—Nb2—Cl8 | 82.7 (3) |
O2—Nb1—Cl2 | 96.9 (4) | Cl3—Nb2—Cl8 | 168.48 (17) |
O1ii—Nb1—Cl2 | 84.6 (3) | Cl6—Nb2—Cl8 | 90.41 (16) |
O2—Nb1—Cl4 | 96.2 (4) | O1—Nb2—Cl1 | 97.2 (4) |
O1ii—Nb1—Cl4 | 83.4 (3) | O2—Nb2—Cl1 | 81.8 (3) |
Cl2—Nb1—Cl4 | 91.51 (18) | Cl3—Nb2—Cl1 | 88.36 (16) |
O2—Nb1—Cl5 | 96.2 (4) | Cl6—Nb2—Cl1 | 165.53 (17) |
O1ii—Nb1—Cl5 | 82.4 (3) | Cl8—Nb2—Cl1 | 87.91 (16) |
Cl2—Nb1—Cl5 | 166.65 (18) | Nb2—O1—Nb1i | 172.7 (6) |
Cl4—Nb1—Cl5 | 89.86 (16) | Nb1—O2—Nb2 | 173.2 (7) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Te8][NbOCl4]2 |
Mr | 1522.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 7.8670 (16), 12.049 (2), 12.481 (3) |
α, β, γ (°) | 80.85 (3), 82.17 (3), 78.84 (3) |
V (Å3) | 1139.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.98 |
Crystal size (mm) | 0.25 × 0.23 × 0.21 |
Data collection | |
Diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 2001) |
Tmin, Tmax | 0.39, 0.54 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8557, 4371, 2699 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.115, 0.91 |
No. of reflections | 4371 |
No. of parameters | 182 |
Δρmax, Δρmin (e Å−3) | 1.87, −1.53 |
Computer programs: EXPOSE (Stoe & Cie, 2001), CELL and SELECT (Stoe & Cie, 2001), INTEGRATE (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2012), publCIF (Westrip, 2010).
Te3—Te2 | 2.7121 (19) | Te4—Te5 | 2.6455 (18) |
Te3—Te4 | 2.8037 (18) | Te1—Te5 | 2.7439 (19) |
Te3—Te6 | 2.809 (2) | Te1—Te2 | 2.800 (2) |
Te7—Te8 | 2.6832 (19) | Te1—Te8i | 2.8164 (19) |
Te7—Te6 | 2.6915 (19) |
Symmetry code: (i) x+1, y, z. |
Tellurium is well known for its chain-like structural arrangement. Such infinite chains are characteristic to the structure of the element (Straumanis, 1940) and are also found in compounds containing polycationic tellurium species such as Te8[Bi4Cl14] (Beck & Stankowski, 2001), Te8[U2Br10] (Beck & Fischer, 2002) and [Te8]2[Ta4O4Cl16] (Freudenmann & Feldmann, 2011a,b). Similar to these compounds, we could [were able to?] now obtain [Te8][NbOCl4]2 which also exhibits an infinite chain-like {[Te8]2+}n cation. While the other known catena-octatellurium(2+) cations in Te8[Bi4Cl14], Te8[U2Br10] and [Te8]2[Ta4O4Cl16] are composed of Te6 rings linked via Te2 units, the title compound [Te8][NbOCl4]2 shows an arrangement of Te5 rings that are linked via Te3 units. Te5 rings have been described for [Te6][HfCl6] which, however, exhibits a [Te5–Te–Te5] connectivity (Beck & Baumann, 2004). [Te8][NbOCl4]2 has been obtained as part of our studies concerning the use of ionic liquids in inorganic chemistry while aiming at novel polycationic (Freudenmann & Feldmann, 2011a,b) or polyanionic species (Wolff et al., 2011; Freudenmann et al., 2011).
The title compound, [Te8][NbOCl4]2, was prepared by reaction of tellurium, niobium(V) chloride and niobium(V) oxychloride in the ionic liquid BMImCl (BMImCl is 1-butyl-3-methylimidazolium chloride). The synthesis resulted in translucent, black, moisture-sensitive crystals. X-ray structure analysis based on single crystals revealed that the compound crystallizes with the triclinic space group P1. The title compound is constituted of infinite {[Te–Te–Te–(Te5)]2+}n chains and a chain-like arrangement of [NbOCl4]- counter-anions which are both directed along the crystallographic a axis (Fig. 1). The chemical composition of [Te8][NbOCl4]2 has been validated based on EDX [energy-dispersive X-ray diffraction?] analysis with values of 61.2 wt% Te, 12.2 wt% Nb and 17.0 wt% Cl resulting in a Te:Nb:Cl ratio of 3.6:1:4 (calculated data: 67.0 wt% Te, 12.2 wt% Nb and 18.6 wt% Cl; Te:Nb:Cl ratio: 4:1:4).
The most interesting aspect of [Te8][NbOCl4]2 is related to the infinite polycationic {[Te8]2+}n building unit. This cation is composed of Te5 rings that are interlinked by Te3 units via its 1,3-positions. As a result of this linkage, an infinite chain-like tellurium polycation according to the description [Te–Te–Te–(Te5)]n2+ is obtained. Although infinite Te chains are well known in principle, this concrete arrangement has not been found for tellurium yet. Five-membered chalcogen rings which are interconnected via Te atoms into chains are known for compounds such as [Te6][HfCl6], exhibiting a [Te5–Te–Te5] arrangement (Beck & Baumann, 2004). Moreover, triatomic chalcogen bridges are known for the mixed Te/Se compound [Se4.85Te3.15][WOCl4]2. Herein, the folding of the chalcogen chain is however different, and the precise position of Se and Te in [Se4.85Te3.15][WOCl4]2 remains partially unsolved (Beck & Schlörb, 1997).
For [Te8][NbOCl4]2, the Te—Te distances range from 2.645 (1) to 2.816 (1) Å (Fig. 2). These distances are in agreement with literature values, indicating a Te—Te single bond (i.e. 2.74 Å on average) (Brownridge et al., 2000; Beck & Bock, 1995; Lange et al., 2007). Thus, the bonding situation is very comparable to known polycationic tellurium species (Straumanis, 1940; Beck & Stankowski, 2001; Beck & Fischer, 2002; Freudenmann & Feldmann, 2011a,b). Discrete tellurium polycations containing [Te8]2+ species with different conformation have already been characterized in compounds such as [(Te6)(Te8)][WCl6]4 (Beck, 1997) and Te8[MCl6] (M = Hf, Re; Beck & Müller-Buschbaum, 1997). Bicyclic polycations such as in Te8[WCl6]2 have also been reported (Beck, 1990). Moreover, structural isomers of {[Te8]2+}n have been discovered in Te8[U2Br10] (Beck & Fischer, 2002), [Te8]2[Ta4O4Cl16] (Freudenmann & Feldmann, 2011a,b) and Te8[Bi4Cl14] (Beck & Schlörb, 1997). These compounds also contain infinite {[Te8]2+}n chains, but with six-membered tellurium rings connected via Te2 bridges (Fig. 3; from top to bottom: Freudenmann & Feldmann, 2011a,b; Beck & Stankowski, 2001; Beck & Schlörb, 1997). A connectivity of Te5 rings with Te3 bridges such as in [Te8][NbOCl4]2 is however firstly observed for the {[Te8]2+}n species.
The {[Te8]2+}n polycation is coordinated by two to four Cl atoms of [NbOCl4]- anions with Te—Cl distances ranging from 3.380 (2) to 4.291 (1) Å. This indicates only a weak Te—Cl interaction when compared to bulk Te3Cl2 (Te—Cl = 2.50–2.86 Å; Kniep et al., 1976). The pyramidal [NbOCl4]- anion is associated with infinite {[NbOCl4]-}n chains. Herein, the O atom of each [NbOCl4]- unit is in contact with a second [NbOCl4]- anion. The Nb—O distances are in the range 1.703 (1)–1.717 (1) Å within the anion and 2.221 (1)–2.241 (1) Å between different [NbOCl4]- anions. These data are in agreement with similar compounds, such as [Te7][NbOCl4]Cl, and can be attributed to an Nb—O double bond (1.70 Å on average) and an Nb—O coordinative bonding (around 2.25 Å; Beck & Bock, 1994). The Nb—O—Nb angles range from 172.7 to 173.3° and indicate a certain tilting of the anionic chain. Finally, the Nb—Cl bond lengths in [NbOCl4]- [2.339 (1)–2.414 (1) Å] also match literature values (2.32–2.40 Å; Collins et al., 1987).
Altogether, it is well known that the type of synthesis (e.g., liquid-phase synthesis, high-temperature gas-phase synthesis or chemical-transport reaction) and the concrete experimental conditions (e.g., type of solvent, type of starting material, temperature, concentration) have a strong impact on the composition and structure of polycationic tellurium–selenium compounds (Ahmed & Ruck, 2011). Thus, it is not a surprise that the mild conditions of the reaction (423 K) and the weakly coordinating properties of the ionic liquid result in a new polycationic species with a connectivity of the tellurium atoms different from that in already known compounds.