Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111006639/gg3254sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111006639/gg3254IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111006639/gg3254IIIsup3.hkl |
CCDC references: 824032; 824033
For the preparation of compound (II), the published procedure of Thomas, Pugh et al. (2010) was followed. A solution of the reaction product dissolved in hexane (20 ml) was cooled to 255 K. After ca eight weeks, orange crystals of (II) had formed. For the preparation of compound (III), a solution of AsPh3 (0.8 g, 2.6 mmol) in toluene (20 ml) was added to a solution of TiBr4 (0.49 g, 1.33 mmol) in toluene (10 ml). The resulting solution turned deep red immediately on addition of the AsPh3. The reaction was stirred for 1 h and then refluxed for 24 h. After this time, volatiles were removed in vacuo, affording a black–brown solid (yield 67%). Spectroscopic analysis: 1H NMR (C6D6, δ, p.p.m.): 7.40 (m, 12H, m-Ph), 7.03 (m, 18H, o-Ph and p-Ph).
H atoms bonded to As in (II) were located in a Fourier difference map ca 1.5 Å from the As centre. Initial attempts at running refinement cycles with unconstrained H atoms were unsuccessful, which necessitated the use of the DFIX and DANG commands (SHELXL97; Sheldrick, 2008) in order to restrain the H atoms to a sensible geometry at As. H atoms bonded to C atoms were placed in geometrically assigned positions, with C—H = 0.95 (CH) or 0.98 Å (CH3), and refined using a riding model, with Uiso(H) = 1.2Ueq(CH) or 1.5Ueq(CH3). The H atoms on atom C3 in (II) exhibited positional disorder; this was modelled by fixing the partial occupancy of each H atom at 0.50.
Data collection: SMART (Bruker, 2006) for (II); COLLECT (Nonius, 1998) for (III). Cell refinement: SAINT (Bruker, 2006) for (II); DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (III). Data reduction: SAINT (Bruker, 2006) for (II); DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (III). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
(C4H12As)[Ti2Cl9] | F(000) = 1064 |
Mr = 549.91 | Dx = 2.016 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2c 2b | Cell parameters from 2113 reflections |
a = 9.7061 (15) Å | θ = 3.0–25.1° |
b = 17.855 (3) Å | µ = 4.00 mm−1 |
c = 10.4555 (16) Å | T = 150 K |
V = 1812.0 (5) Å3 | Rod, orange |
Z = 4 | 0.25 × 0.10 × 0.01 mm |
Bruker SMART APEX diffractometer | 2329 independent reflections |
Radiation source: fine-focus sealed tube | 1767 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω rotation with narrow frames scans | θmax = 28.3°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −12→12 |
Tmin = 0.435, Tmax = 0.961 | k = −22→23 |
14917 measured reflections | l = −13→13 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0353P)2 + 0.1344P] where P = (Fo2 + 2Fc2)/3 |
2329 reflections | (Δ/σ)max = 0.012 |
94 parameters | Δρmax = 0.52 e Å−3 |
4 restraints | Δρmin = −0.52 e Å−3 |
(C4H12As)[Ti2Cl9] | V = 1812.0 (5) Å3 |
Mr = 549.91 | Z = 4 |
Orthorhombic, Pbcm | Mo Kα radiation |
a = 9.7061 (15) Å | µ = 4.00 mm−1 |
b = 17.855 (3) Å | T = 150 K |
c = 10.4555 (16) Å | 0.25 × 0.10 × 0.01 mm |
Bruker SMART APEX diffractometer | 2329 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 1767 reflections with I > 2σ(I) |
Tmin = 0.435, Tmax = 0.961 | Rint = 0.064 |
14917 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 4 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.52 e Å−3 |
2329 reflections | Δρmin = −0.52 e Å−3 |
94 parameters |
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. 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. The protons attached to As were located in the difference map, but it was necessary to use the DFIX and DANG commands to restrain the protons into chemically sensible positions. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1004 (5) | 0.1143 (3) | 0.2500 | 0.0278 (11) | |
C2 | 0.0412 (4) | 0.1500 (3) | 0.1313 (4) | 0.0536 (12) | |
H2A | −0.0584 | 0.1413 | 0.1285 | 0.080* | |
H2B | 0.0843 | 0.1279 | 0.0554 | 0.080* | |
H2C | 0.0594 | 0.2040 | 0.1329 | 0.080* | |
C3 | 0.0812 (6) | 0.0302 (3) | 0.2500 | 0.0512 (17) | |
H3A | −0.0161 | 0.0184 | 0.2652 | 0.077* | 0.50 |
H3B | 0.1376 | 0.0080 | 0.3178 | 0.077* | 0.50 |
H3C | 0.1095 | 0.0099 | 0.1670 | 0.077* | 0.50 |
Cl1 | 0.29795 (10) | 0.49756 (5) | 0.41050 (9) | 0.0401 (3) | |
Cl2 | 0.13884 (13) | 0.35901 (7) | 0.2500 | 0.0410 (3) | |
Cl3 | 0.58417 (12) | 0.45463 (6) | 0.2500 | 0.0297 (3) | |
Cl4 | 0.43757 (9) | 0.32605 (4) | 0.10035 (8) | 0.0271 (2) | |
Cl5 | 0.78392 (9) | 0.33445 (5) | 0.09132 (9) | 0.0383 (2) | |
Cl6 | 0.63106 (12) | 0.19435 (6) | 0.2500 | 0.0317 (3) | |
Ti1 | 0.33805 (8) | 0.42016 (4) | 0.2500 | 0.0223 (2) | |
Ti2 | 0.64048 (8) | 0.31853 (4) | 0.2500 | 0.0209 (2) | |
As1 | 0.29634 (5) | 0.13767 (3) | 0.2500 | 0.02911 (15) | |
H1A | 0.3440 (17) | 0.107 (2) | 0.124 (2) | 0.068 (14)* | |
H1B | 0.2952 (19) | 0.2227 (6) | 0.2500 | 0.15 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.018 (3) | 0.033 (3) | 0.032 (3) | 0.001 (2) | 0.000 | 0.000 |
C2 | 0.047 (3) | 0.071 (3) | 0.044 (3) | 0.012 (2) | −0.013 (2) | 0.006 (2) |
C3 | 0.025 (3) | 0.039 (3) | 0.089 (5) | −0.010 (3) | 0.000 | 0.000 |
Cl1 | 0.0527 (6) | 0.0344 (5) | 0.0332 (5) | 0.0135 (4) | 0.0022 (5) | −0.0099 (4) |
Cl2 | 0.0248 (7) | 0.0326 (7) | 0.0656 (10) | 0.0019 (6) | 0.000 | 0.000 |
Cl3 | 0.0292 (7) | 0.0184 (6) | 0.0414 (8) | −0.0038 (5) | 0.000 | 0.000 |
Cl4 | 0.0334 (5) | 0.0263 (4) | 0.0215 (4) | 0.0068 (3) | −0.0057 (4) | −0.0065 (3) |
Cl5 | 0.0359 (5) | 0.0394 (5) | 0.0395 (6) | 0.0029 (4) | 0.0156 (4) | 0.0043 (4) |
Cl6 | 0.0278 (6) | 0.0204 (6) | 0.0467 (8) | 0.0029 (5) | 0.000 | 0.000 |
Ti1 | 0.0263 (5) | 0.0180 (4) | 0.0225 (5) | 0.0028 (3) | 0.000 | 0.000 |
Ti2 | 0.0210 (4) | 0.0195 (4) | 0.0222 (5) | −0.0006 (3) | 0.000 | 0.000 |
As1 | 0.0258 (3) | 0.0222 (3) | 0.0394 (3) | −0.0041 (2) | 0.000 | 0.000 |
C1—C2 | 1.509 (5) | Cl3—Ti1 | 2.4668 (15) |
C1—C2i | 1.509 (5) | Cl3—Ti2 | 2.4908 (14) |
C1—C3 | 1.512 (7) | Cl4—Ti1 | 2.4909 (10) |
C1—As1 | 1.947 (5) | Cl4—Ti2 | 2.5189 (11) |
C2—H2A | 0.9800 | Cl5—Ti2 | 2.1844 (10) |
C2—H2B | 0.9800 | Cl6—Ti2 | 2.2192 (14) |
C2—H2C | 0.9800 | Ti1—Cl1i | 2.2085 (10) |
C3—H3A | 0.9800 | Ti1—Cl4i | 2.4909 (10) |
C3—H3B | 0.9800 | Ti2—Cl5i | 2.1844 (10) |
C3—H3C | 0.9800 | Ti2—Cl4i | 2.5189 (11) |
Cl1—Ti1 | 2.2085 (10) | As1—H1A | 1.504 (10) |
Cl2—Ti1 | 2.2206 (15) | As1—H1B | 1.518 (10) |
C2—C1—C2i | 110.7 (5) | Cl1—Ti1—Cl4 | 165.41 (5) |
C2—C1—C3 | 111.9 (3) | Cl2—Ti1—Cl4 | 90.34 (4) |
C2i—C1—C3 | 111.9 (3) | Cl3—Ti1—Cl4 | 78.04 (4) |
C2—C1—As1 | 106.3 (3) | Cl1i—Ti1—Cl4i | 165.41 (5) |
C2i—C1—As1 | 106.3 (3) | Cl1—Ti1—Cl4i | 90.75 (3) |
C3—C1—As1 | 109.5 (3) | Cl2—Ti1—Cl4i | 90.34 (4) |
C1—C2—H2A | 109.5 | Cl3—Ti1—Cl4i | 78.04 (4) |
C1—C2—H2B | 109.5 | Cl4—Ti1—Cl4i | 77.83 (5) |
H2A—C2—H2B | 109.5 | Cl5i—Ti2—Cl5 | 98.84 (6) |
C1—C2—H2C | 109.5 | Cl5i—Ti2—Cl6 | 98.99 (4) |
H2A—C2—H2C | 109.5 | Cl5—Ti2—Cl6 | 98.99 (4) |
H2B—C2—H2C | 109.5 | Cl5i—Ti2—Cl3 | 90.74 (4) |
C1—C3—H3A | 109.5 | Cl5—Ti2—Cl3 | 90.74 (4) |
C1—C3—H3B | 109.5 | Cl6—Ti2—Cl3 | 164.96 (6) |
H3A—C3—H3B | 109.5 | Cl5i—Ti2—Cl4 | 164.40 (5) |
C1—C3—H3C | 109.5 | Cl5—Ti2—Cl4 | 91.12 (4) |
H3A—C3—H3C | 109.5 | Cl6—Ti2—Cl4 | 91.21 (4) |
H3B—C3—H3C | 109.5 | Cl3—Ti2—Cl4 | 77.08 (4) |
Ti1—Cl3—Ti2 | 88.23 (4) | Cl5i—Ti2—Cl4i | 91.12 (4) |
Ti1—Cl4—Ti2 | 87.07 (3) | Cl5—Ti2—Cl4i | 164.40 (5) |
Cl1i—Ti1—Cl1 | 98.90 (6) | Cl6—Ti2—Cl4i | 91.21 (4) |
Cl1i—Ti1—Cl2 | 98.87 (4) | Cl3—Ti2—Cl4i | 77.08 (4) |
Cl1—Ti1—Cl2 | 98.87 (4) | Cl4—Ti2—Cl4i | 76.80 (5) |
Cl1i—Ti1—Cl3 | 90.83 (4) | C1—As1—H1A | 102.9 (7) |
Cl1—Ti1—Cl3 | 90.83 (4) | C1—As1—H1B | 102.0 (7) |
Cl2—Ti1—Cl3 | 165.00 (6) | H1A—As1—H1B | 111.4 (15) |
Cl1i—Ti1—Cl4 | 90.75 (3) | ||
Ti2—Cl3—Ti1—Cl1i | −130.54 (3) | Ti1—Cl3—Ti2—Cl5i | −130.57 (3) |
Ti2—Cl3—Ti1—Cl1 | 130.54 (3) | Ti1—Cl3—Ti2—Cl5 | 130.57 (3) |
Ti2—Cl3—Ti1—Cl2 | 0.0 | Ti1—Cl3—Ti2—Cl6 | 0.0 |
Ti2—Cl3—Ti1—Cl4 | −39.95 (2) | Ti1—Cl3—Ti2—Cl4 | 39.59 (2) |
Ti2—Cl3—Ti1—Cl4i | 39.95 (2) | Ti1—Cl3—Ti2—Cl4i | −39.59 (2) |
Ti2—Cl4—Ti1—Cl1i | 130.14 (4) | Ti1—Cl4—Ti2—Cl5i | 0.27 (18) |
Ti2—Cl4—Ti1—Cl1 | −1.55 (19) | Ti1—Cl4—Ti2—Cl5 | −129.67 (4) |
Ti2—Cl4—Ti1—Cl2 | −130.98 (4) | Ti1—Cl4—Ti2—Cl6 | 131.31 (3) |
Ti2—Cl4—Ti1—Cl3 | 39.45 (3) | Ti1—Cl4—Ti2—Cl3 | −39.17 (3) |
Ti2—Cl4—Ti1—Cl4i | −40.70 (4) | Ti1—Cl4—Ti2—Cl4i | 40.35 (4) |
Symmetry code: (i) x, y, −z+1/2. |
(C18H15AsBr)2[Ti2Br8O] | Z = 2 |
Mr = 1523.34 | F(000) = 1428 |
Triclinic, P1 | Dx = 2.271 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4991 (2) Å | Cell parameters from 40727 reflections |
b = 10.7921 (3) Å | θ = 2.9–27.5° |
c = 21.5971 (6) Å | µ = 10.83 mm−1 |
α = 81.210 (1)° | T = 120 K |
β = 83.017 (2)° | Lath, orange |
γ = 67.448 (1)° | 0.20 × 0.20 × 0.08 mm |
V = 2228.12 (10) Å3 |
Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer | 10149 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 7721 reflections with I > 2σ(I) |
10cm confocal mirrors monochromator | Rint = 0.053 |
Detector resolution: 4096x4096 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −14→13 |
Tmin = 0.221, Tmax = 0.478 | l = −27→28 |
33234 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.P)2 + 15.7068P] where P = (Fo2 + 2Fc2)/3 |
10149 reflections | (Δ/σ)max = 0.015 |
460 parameters | Δρmax = 1.06 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
(C18H15AsBr)2[Ti2Br8O] | γ = 67.448 (1)° |
Mr = 1523.34 | V = 2228.12 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.4991 (2) Å | Mo Kα radiation |
b = 10.7921 (3) Å | µ = 10.83 mm−1 |
c = 21.5971 (6) Å | T = 120 K |
α = 81.210 (1)° | 0.20 × 0.20 × 0.08 mm |
β = 83.017 (2)° |
Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer | 10149 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 7721 reflections with I > 2σ(I) |
Tmin = 0.221, Tmax = 0.478 | Rint = 0.053 |
33234 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.P)2 + 15.7068P] where P = (Fo2 + 2Fc2)/3 |
10149 reflections | Δρmax = 1.06 e Å−3 |
460 parameters | Δρmin = −1.07 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. 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 | ||
C1 | 1.2649 (7) | 0.9500 (8) | 0.0355 (3) | 0.0302 (17) | |
C2 | 1.3277 (8) | 1.0193 (10) | −0.0089 (4) | 0.040 (2) | |
H2 | 1.3096 | 1.1118 | −0.0066 | 0.048* | |
C3 | 1.4167 (9) | 0.9540 (10) | −0.0565 (4) | 0.047 (2) | |
H3 | 1.4594 | 1.0008 | −0.0876 | 0.056* | |
C4 | 1.4420 (8) | 0.8204 (11) | −0.0579 (4) | 0.051 (2) | |
H4 | 1.5051 | 0.7745 | −0.0899 | 0.061* | |
C5 | 1.3797 (9) | 0.7496 (10) | −0.0150 (5) | 0.054 (3) | |
H5 | 1.3974 | 0.6575 | −0.0181 | 0.065* | |
C6 | 1.2893 (8) | 0.8154 (9) | 0.0337 (4) | 0.041 (2) | |
H6 | 1.2462 | 0.7686 | 0.0645 | 0.049* | |
C7 | 1.0360 (7) | 0.9497 (6) | 0.1451 (3) | 0.0219 (14) | |
C8 | 0.8936 (7) | 1.0037 (7) | 0.1391 (3) | 0.0236 (15) | |
H8 | 0.8519 | 1.0876 | 0.1143 | 0.028* | |
C9 | 0.8143 (8) | 0.9339 (8) | 0.1696 (4) | 0.0336 (18) | |
H9 | 0.7172 | 0.9702 | 0.1662 | 0.040* | |
C10 | 0.8744 (8) | 0.8119 (8) | 0.2050 (4) | 0.0362 (19) | |
H10 | 0.8188 | 0.7637 | 0.2252 | 0.043* | |
C11 | 1.0171 (9) | 0.7584 (8) | 0.2115 (4) | 0.041 (2) | |
H11 | 1.0579 | 0.6741 | 0.2362 | 0.049* | |
C12 | 1.0986 (8) | 0.8271 (7) | 0.1824 (4) | 0.0346 (18) | |
H12 | 1.1951 | 0.7924 | 0.1874 | 0.041* | |
C13 | 1.0309 (7) | 1.2196 (7) | 0.0664 (3) | 0.0257 (15) | |
C14 | 0.9696 (7) | 1.3196 (7) | 0.1055 (4) | 0.0332 (18) | |
H14 | 0.9899 | 1.3026 | 0.1484 | 0.040* | |
C15 | 0.8781 (8) | 1.4454 (8) | 0.0819 (4) | 0.044 (2) | |
H15 | 0.8353 | 1.5149 | 0.1084 | 0.053* | |
C16 | 0.8497 (9) | 1.4684 (9) | 0.0188 (5) | 0.049 (2) | |
H16 | 0.7862 | 1.5535 | 0.0023 | 0.058* | |
C17 | 0.9138 (10) | 1.3679 (9) | −0.0198 (5) | 0.054 (3) | |
H17 | 0.8953 | 1.3859 | −0.0629 | 0.065* | |
C18 | 1.0043 (8) | 1.2415 (8) | 0.0027 (4) | 0.0375 (19) | |
H18 | 1.0469 | 1.1722 | −0.0240 | 0.045* | |
C19 | 1.0729 (6) | 0.7056 (6) | 0.4714 (3) | 0.0189 (13) | |
C20 | 1.0687 (7) | 0.7117 (6) | 0.5362 (3) | 0.0208 (14) | |
H20 | 0.9889 | 0.7704 | 0.5575 | 0.025* | |
C21 | 1.1835 (7) | 0.6302 (7) | 0.5682 (3) | 0.0257 (15) | |
H21 | 1.1830 | 0.6340 | 0.6119 | 0.031* | |
C22 | 1.2986 (7) | 0.5438 (7) | 0.5378 (4) | 0.0265 (16) | |
H22 | 1.3765 | 0.4889 | 0.5608 | 0.032* | |
C23 | 1.3023 (7) | 0.5358 (7) | 0.4733 (4) | 0.0275 (16) | |
H23 | 1.3813 | 0.4748 | 0.4526 | 0.033* | |
C24 | 1.1883 (7) | 0.6186 (7) | 0.4404 (3) | 0.0237 (15) | |
H24 | 1.1895 | 0.6157 | 0.3966 | 0.028* | |
C25 | 0.7694 (6) | 0.9151 (6) | 0.4822 (3) | 0.0174 (13) | |
C26 | 0.7256 (6) | 1.0539 (7) | 0.4803 (3) | 0.0211 (14) | |
H26 | 0.7649 | 1.1046 | 0.4497 | 0.025* | |
C27 | 0.6214 (7) | 1.1174 (7) | 0.5250 (4) | 0.0278 (16) | |
H27 | 0.5896 | 1.2125 | 0.5250 | 0.033* | |
C28 | 0.5647 (7) | 1.0421 (8) | 0.5689 (3) | 0.0269 (16) | |
H28 | 0.4945 | 1.0861 | 0.5991 | 0.032* | |
C29 | 0.6085 (7) | 0.9050 (7) | 0.5694 (3) | 0.0233 (15) | |
H29 | 0.5680 | 0.8547 | 0.5997 | 0.028* | |
C30 | 0.7112 (7) | 0.8392 (7) | 0.5261 (3) | 0.0218 (14) | |
H30 | 0.7417 | 0.7442 | 0.5262 | 0.026* | |
C31 | 0.9675 (6) | 0.9486 (6) | 0.3670 (3) | 0.0199 (14) | |
C32 | 0.8731 (7) | 1.0345 (6) | 0.3243 (3) | 0.0206 (14) | |
H32 | 0.7897 | 1.0220 | 0.3206 | 0.025* | |
C33 | 0.9024 (7) | 1.1377 (6) | 0.2874 (3) | 0.0221 (14) | |
H33 | 0.8384 | 1.1976 | 0.2585 | 0.027* | |
C34 | 1.0252 (7) | 1.1536 (6) | 0.2924 (3) | 0.0215 (14) | |
H34 | 1.0447 | 1.2254 | 0.2672 | 0.026* | |
C35 | 1.1198 (6) | 1.0664 (7) | 0.3337 (3) | 0.0202 (14) | |
H35 | 1.2039 | 1.0784 | 0.3364 | 0.024* | |
C36 | 1.0935 (6) | 0.9620 (7) | 0.3711 (3) | 0.0217 (14) | |
H36 | 1.1593 | 0.9007 | 0.3988 | 0.026* | |
Ti1 | 0.38099 (11) | 0.38273 (11) | 0.24776 (6) | 0.0191 (2) | |
Ti2 | 0.54158 (12) | 0.56884 (11) | 0.24577 (6) | 0.0207 (3) | |
As1 | 1.14537 (7) | 1.04330 (7) | 0.10065 (3) | 0.02218 (15) | |
As2 | 0.91853 (6) | 0.82276 (6) | 0.42600 (3) | 0.01701 (14) | |
Br1 | 1.27908 (7) | 1.06628 (7) | 0.16974 (3) | 0.02563 (16) | |
Br2 | 0.84449 (7) | 0.69685 (7) | 0.37439 (3) | 0.02562 (16) | |
Br3 | 0.25392 (7) | 0.41739 (7) | 0.15637 (4) | 0.03071 (17) | |
Br4 | 0.18687 (7) | 0.40060 (7) | 0.32395 (3) | 0.02539 (16) | |
Br5 | 0.47508 (6) | 0.12789 (6) | 0.25888 (3) | 0.02162 (14) | |
Br6 | 0.61458 (6) | 0.36150 (6) | 0.17685 (3) | 0.02037 (14) | |
Br7 | 0.54759 (6) | 0.36068 (6) | 0.33780 (3) | 0.02021 (14) | |
Br8 | 0.54079 (8) | 0.72092 (7) | 0.15139 (4) | 0.03399 (18) | |
Br9 | 0.46219 (8) | 0.73170 (7) | 0.32042 (4) | 0.03552 (19) | |
Br10 | 0.79291 (7) | 0.50372 (6) | 0.25995 (3) | 0.02369 (15) | |
O1 | 0.3752 (4) | 0.5545 (4) | 0.2419 (2) | 0.0228 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.023 (4) | 0.052 (5) | 0.018 (4) | −0.014 (3) | −0.001 (3) | −0.013 (3) |
C2 | 0.030 (4) | 0.067 (6) | 0.031 (5) | −0.022 (4) | 0.004 (3) | −0.018 (4) |
C3 | 0.039 (5) | 0.072 (7) | 0.036 (5) | −0.025 (5) | 0.014 (4) | −0.024 (5) |
C4 | 0.023 (4) | 0.083 (7) | 0.045 (6) | −0.015 (4) | 0.001 (4) | −0.021 (5) |
C5 | 0.048 (5) | 0.061 (6) | 0.063 (7) | −0.019 (5) | −0.004 (5) | −0.040 (5) |
C6 | 0.032 (4) | 0.049 (5) | 0.043 (5) | −0.012 (4) | 0.001 (4) | −0.023 (4) |
C7 | 0.026 (3) | 0.019 (3) | 0.019 (4) | −0.007 (3) | 0.004 (3) | −0.002 (3) |
C8 | 0.024 (3) | 0.027 (4) | 0.018 (4) | −0.009 (3) | −0.001 (3) | 0.002 (3) |
C9 | 0.028 (4) | 0.046 (5) | 0.034 (5) | −0.017 (4) | −0.006 (3) | −0.011 (4) |
C10 | 0.052 (5) | 0.038 (4) | 0.030 (5) | −0.033 (4) | 0.016 (4) | −0.011 (4) |
C11 | 0.059 (6) | 0.023 (4) | 0.034 (5) | −0.013 (4) | 0.001 (4) | 0.008 (3) |
C12 | 0.038 (4) | 0.024 (4) | 0.033 (5) | −0.004 (3) | −0.005 (3) | 0.002 (3) |
C13 | 0.022 (3) | 0.038 (4) | 0.020 (4) | −0.017 (3) | −0.001 (3) | 0.004 (3) |
C14 | 0.029 (4) | 0.033 (4) | 0.032 (4) | −0.012 (3) | 0.005 (3) | 0.009 (3) |
C15 | 0.029 (4) | 0.038 (5) | 0.057 (6) | −0.012 (4) | 0.005 (4) | 0.012 (4) |
C16 | 0.042 (5) | 0.034 (5) | 0.069 (7) | −0.017 (4) | −0.016 (5) | 0.016 (5) |
C17 | 0.063 (6) | 0.052 (6) | 0.054 (6) | −0.033 (5) | −0.038 (5) | 0.031 (5) |
C18 | 0.048 (5) | 0.044 (5) | 0.030 (5) | −0.029 (4) | −0.014 (4) | 0.008 (4) |
C19 | 0.015 (3) | 0.016 (3) | 0.023 (4) | −0.003 (2) | −0.003 (3) | −0.001 (3) |
C20 | 0.023 (3) | 0.021 (3) | 0.018 (4) | −0.007 (3) | 0.004 (3) | −0.004 (3) |
C21 | 0.021 (3) | 0.032 (4) | 0.026 (4) | −0.012 (3) | −0.007 (3) | 0.001 (3) |
C22 | 0.022 (3) | 0.019 (3) | 0.039 (5) | −0.007 (3) | −0.010 (3) | 0.000 (3) |
C23 | 0.020 (3) | 0.022 (4) | 0.036 (5) | −0.002 (3) | −0.002 (3) | −0.005 (3) |
C24 | 0.028 (4) | 0.027 (4) | 0.019 (4) | −0.013 (3) | 0.001 (3) | −0.008 (3) |
C25 | 0.012 (3) | 0.027 (3) | 0.014 (3) | −0.008 (3) | 0.002 (2) | −0.004 (3) |
C26 | 0.018 (3) | 0.027 (3) | 0.019 (4) | −0.007 (3) | −0.004 (3) | −0.006 (3) |
C27 | 0.021 (3) | 0.021 (3) | 0.040 (5) | 0.001 (3) | −0.009 (3) | −0.014 (3) |
C28 | 0.021 (3) | 0.046 (4) | 0.020 (4) | −0.015 (3) | 0.001 (3) | −0.017 (3) |
C29 | 0.025 (3) | 0.032 (4) | 0.014 (3) | −0.013 (3) | 0.001 (3) | 0.000 (3) |
C30 | 0.024 (3) | 0.025 (3) | 0.016 (3) | −0.010 (3) | 0.002 (3) | −0.002 (3) |
C31 | 0.022 (3) | 0.023 (3) | 0.014 (3) | −0.007 (3) | −0.003 (3) | −0.003 (3) |
C32 | 0.021 (3) | 0.026 (3) | 0.012 (3) | −0.006 (3) | 0.000 (3) | −0.002 (3) |
C33 | 0.028 (4) | 0.016 (3) | 0.020 (4) | −0.006 (3) | −0.008 (3) | 0.002 (3) |
C34 | 0.027 (3) | 0.020 (3) | 0.016 (3) | −0.010 (3) | 0.002 (3) | 0.002 (3) |
C35 | 0.016 (3) | 0.030 (4) | 0.016 (3) | −0.009 (3) | 0.002 (2) | −0.007 (3) |
C36 | 0.018 (3) | 0.023 (3) | 0.020 (4) | −0.004 (3) | −0.001 (3) | −0.001 (3) |
Ti1 | 0.0176 (6) | 0.0185 (6) | 0.0209 (6) | −0.0044 (5) | −0.0025 (5) | −0.0064 (5) |
Ti2 | 0.0214 (6) | 0.0172 (6) | 0.0236 (7) | −0.0059 (5) | −0.0043 (5) | −0.0037 (5) |
As1 | 0.0187 (3) | 0.0301 (4) | 0.0185 (4) | −0.0098 (3) | −0.0002 (3) | −0.0037 (3) |
As2 | 0.0175 (3) | 0.0176 (3) | 0.0162 (3) | −0.0069 (3) | −0.0013 (2) | −0.0016 (3) |
Br1 | 0.0202 (3) | 0.0357 (4) | 0.0218 (4) | −0.0089 (3) | −0.0004 (3) | −0.0106 (3) |
Br2 | 0.0284 (4) | 0.0263 (3) | 0.0273 (4) | −0.0146 (3) | −0.0017 (3) | −0.0069 (3) |
Br3 | 0.0300 (4) | 0.0305 (4) | 0.0298 (4) | −0.0041 (3) | −0.0141 (3) | −0.0073 (3) |
Br4 | 0.0194 (3) | 0.0264 (3) | 0.0307 (4) | −0.0079 (3) | 0.0020 (3) | −0.0088 (3) |
Br5 | 0.0224 (3) | 0.0192 (3) | 0.0238 (4) | −0.0067 (3) | −0.0029 (3) | −0.0056 (3) |
Br6 | 0.0202 (3) | 0.0217 (3) | 0.0186 (3) | −0.0063 (3) | −0.0010 (2) | −0.0049 (3) |
Br7 | 0.0204 (3) | 0.0235 (3) | 0.0186 (3) | −0.0092 (3) | −0.0033 (2) | −0.0034 (3) |
Br8 | 0.0369 (4) | 0.0229 (4) | 0.0344 (4) | −0.0051 (3) | −0.0051 (3) | 0.0059 (3) |
Br9 | 0.0395 (4) | 0.0292 (4) | 0.0406 (5) | −0.0115 (3) | 0.0021 (3) | −0.0193 (3) |
Br10 | 0.0226 (3) | 0.0211 (3) | 0.0290 (4) | −0.0103 (3) | −0.0057 (3) | 0.0010 (3) |
O1 | 0.024 (2) | 0.018 (2) | 0.024 (3) | −0.0054 (19) | −0.0042 (19) | 0.0000 (19) |
C1—C6 | 1.380 (11) | C22—H22 | 0.9500 |
C1—C2 | 1.385 (11) | C23—C24 | 1.389 (9) |
C1—As1 | 1.899 (7) | C23—H23 | 0.9500 |
C2—C3 | 1.382 (11) | C24—H24 | 0.9500 |
C2—H2 | 0.9500 | C25—C26 | 1.384 (9) |
C3—C4 | 1.367 (13) | C25—C30 | 1.396 (9) |
C3—H3 | 0.9500 | C25—As2 | 1.905 (6) |
C4—C5 | 1.375 (13) | C26—C27 | 1.403 (9) |
C4—H4 | 0.9500 | C26—H26 | 0.9500 |
C5—C6 | 1.407 (12) | C27—C28 | 1.383 (10) |
C5—H5 | 0.9500 | C27—H27 | 0.9500 |
C6—H6 | 0.9500 | C28—C29 | 1.370 (10) |
C7—C8 | 1.396 (9) | C28—H28 | 0.9500 |
C7—C12 | 1.402 (9) | C29—C30 | 1.383 (9) |
C7—As1 | 1.893 (7) | C29—H29 | 0.9500 |
C8—C9 | 1.375 (10) | C30—H30 | 0.9500 |
C8—H8 | 0.9500 | C31—C32 | 1.396 (9) |
C9—C10 | 1.374 (11) | C31—C36 | 1.398 (9) |
C9—H9 | 0.9500 | C31—As2 | 1.893 (7) |
C10—C11 | 1.400 (12) | C32—C33 | 1.378 (9) |
C10—H10 | 0.9500 | C32—H32 | 0.9500 |
C11—C12 | 1.375 (11) | C33—C34 | 1.384 (9) |
C11—H11 | 0.9500 | C33—H33 | 0.9500 |
C12—H12 | 0.9500 | C34—C35 | 1.382 (9) |
C13—C14 | 1.381 (11) | C34—H34 | 0.9500 |
C13—C18 | 1.403 (10) | C35—C36 | 1.380 (9) |
C13—As1 | 1.909 (7) | C35—H35 | 0.9500 |
C14—C15 | 1.391 (10) | C36—H36 | 0.9500 |
C14—H14 | 0.9500 | Ti1—O1 | 1.817 (5) |
C15—C16 | 1.395 (13) | Ti1—Br3 | 2.4182 (14) |
C15—H15 | 0.9500 | Ti1—Br4 | 2.4246 (13) |
C16—C17 | 1.380 (14) | Ti1—Br5 | 2.5237 (13) |
C16—H16 | 0.9500 | Ti1—Br6 | 2.6787 (13) |
C17—C18 | 1.384 (11) | Ti1—Br7 | 2.6952 (13) |
C17—H17 | 0.9500 | Ti1—Ti2 | 3.0713 (16) |
C18—H18 | 0.9500 | Ti2—O1 | 1.825 (5) |
C19—C24 | 1.385 (9) | Ti2—Br9 | 2.4079 (14) |
C19—C20 | 1.406 (9) | Ti2—Br8 | 2.4125 (14) |
C19—As2 | 1.904 (6) | Ti2—Br10 | 2.5017 (13) |
C20—C21 | 1.380 (9) | Ti2—Br6 | 2.6898 (13) |
C20—H20 | 0.9500 | Ti2—Br7 | 2.7493 (14) |
C21—C22 | 1.374 (10) | As1—Br1 | 2.2689 (10) |
C21—H21 | 0.9500 | As2—Br2 | 2.2753 (9) |
C22—C23 | 1.404 (10) | ||
C6—C1—C2 | 121.5 (7) | C27—C28—H28 | 119.6 |
C6—C1—As1 | 119.9 (6) | C28—C29—C30 | 120.4 (6) |
C2—C1—As1 | 118.6 (6) | C28—C29—H29 | 119.8 |
C3—C2—C1 | 120.1 (9) | C30—C29—H29 | 119.8 |
C3—C2—H2 | 120.0 | C29—C30—C25 | 118.8 (6) |
C1—C2—H2 | 120.0 | C29—C30—H30 | 120.6 |
C4—C3—C2 | 118.4 (9) | C25—C30—H30 | 120.6 |
C4—C3—H3 | 120.8 | C32—C31—C36 | 121.1 (6) |
C2—C3—H3 | 120.8 | C32—C31—As2 | 119.9 (5) |
C3—C4—C5 | 122.7 (9) | C36—C31—As2 | 118.7 (5) |
C3—C4—H4 | 118.6 | C33—C32—C31 | 119.3 (6) |
C5—C4—H4 | 118.6 | C33—C32—H32 | 120.4 |
C4—C5—C6 | 119.1 (9) | C31—C32—H32 | 120.4 |
C4—C5—H5 | 120.5 | C32—C33—C34 | 119.8 (6) |
C6—C5—H5 | 120.5 | C32—C33—H33 | 120.1 |
C1—C6—C5 | 118.2 (8) | C34—C33—H33 | 120.1 |
C1—C6—H6 | 120.9 | C35—C34—C33 | 120.7 (6) |
C5—C6—H6 | 120.9 | C35—C34—H34 | 119.7 |
C8—C7—C12 | 121.1 (6) | C33—C34—H34 | 119.7 |
C8—C7—As1 | 118.9 (5) | C36—C35—C34 | 120.8 (6) |
C12—C7—As1 | 120.0 (5) | C36—C35—H35 | 119.6 |
C9—C8—C7 | 119.0 (6) | C34—C35—H35 | 119.6 |
C9—C8—H8 | 120.5 | C35—C36—C31 | 118.3 (6) |
C7—C8—H8 | 120.5 | C35—C36—H36 | 120.9 |
C10—C9—C8 | 120.6 (7) | C31—C36—H36 | 120.9 |
C10—C9—H9 | 119.7 | O1—Ti1—Br3 | 96.07 (15) |
C8—C9—H9 | 119.7 | O1—Ti1—Br4 | 99.12 (15) |
C9—C10—C11 | 120.3 (7) | Br3—Ti1—Br4 | 95.77 (5) |
C9—C10—H10 | 119.9 | O1—Ti1—Br5 | 160.37 (15) |
C11—C10—H10 | 119.9 | Br3—Ti1—Br5 | 96.63 (5) |
C12—C11—C10 | 120.4 (7) | Br4—Ti1—Br5 | 94.42 (5) |
C12—C11—H11 | 119.8 | O1—Ti1—Br6 | 79.19 (15) |
C10—C11—H11 | 119.8 | Br3—Ti1—Br6 | 91.99 (5) |
C11—C12—C7 | 118.5 (7) | Br4—Ti1—Br6 | 172.20 (6) |
C11—C12—H12 | 120.7 | Br5—Ti1—Br6 | 85.47 (4) |
C7—C12—H12 | 120.7 | O1—Ti1—Br7 | 78.58 (15) |
C14—C13—C18 | 121.7 (7) | Br3—Ti1—Br7 | 171.18 (6) |
C14—C13—As1 | 119.4 (5) | Br4—Ti1—Br7 | 92.02 (4) |
C18—C13—As1 | 118.8 (6) | Br5—Ti1—Br7 | 86.86 (4) |
C13—C14—C15 | 119.7 (8) | Br6—Ti1—Br7 | 80.19 (4) |
C13—C14—H14 | 120.2 | O1—Ti1—Ti2 | 32.58 (14) |
C15—C14—H14 | 120.2 | Br3—Ti1—Ti2 | 115.57 (5) |
C14—C15—C16 | 119.3 (9) | Br4—Ti1—Ti2 | 119.91 (5) |
C14—C15—H15 | 120.4 | Br5—Ti1—Ti2 | 127.80 (5) |
C16—C15—H15 | 120.4 | Br6—Ti1—Ti2 | 55.27 (3) |
C17—C16—C15 | 120.1 (8) | Br7—Ti1—Ti2 | 56.50 (3) |
C17—C16—H16 | 119.9 | O1—Ti2—Br9 | 96.17 (15) |
C15—C16—H16 | 119.9 | O1—Ti2—Br8 | 99.25 (15) |
C16—C17—C18 | 121.7 (9) | Br9—Ti2—Br8 | 98.55 (5) |
C16—C17—H17 | 119.1 | O1—Ti2—Br10 | 160.49 (15) |
C18—C17—H17 | 119.1 | Br9—Ti2—Br10 | 95.17 (5) |
C17—C18—C13 | 117.4 (9) | Br8—Ti2—Br10 | 94.70 (5) |
C17—C18—H18 | 121.3 | O1—Ti2—Br6 | 78.76 (15) |
C13—C18—H18 | 121.3 | Br9—Ti2—Br6 | 170.56 (6) |
C24—C19—C20 | 121.0 (6) | Br8—Ti2—Br6 | 90.17 (5) |
C24—C19—As2 | 120.1 (5) | Br10—Ti2—Br6 | 87.66 (4) |
C20—C19—As2 | 118.8 (5) | O1—Ti2—Br7 | 76.97 (14) |
C21—C20—C19 | 118.3 (6) | Br9—Ti2—Br7 | 92.12 (5) |
C21—C20—H20 | 120.9 | Br8—Ti2—Br7 | 169.04 (6) |
C19—C20—H20 | 120.9 | Br10—Ti2—Br7 | 86.80 (4) |
C22—C21—C20 | 121.2 (7) | Br6—Ti2—Br7 | 79.03 (4) |
C22—C21—H21 | 119.4 | O1—Ti2—Ti1 | 32.43 (14) |
C20—C21—H21 | 119.4 | Br9—Ti2—Ti1 | 117.09 (5) |
C21—C22—C23 | 120.7 (6) | Br8—Ti2—Ti1 | 117.06 (5) |
C21—C22—H22 | 119.6 | Br10—Ti2—Ti1 | 128.19 (5) |
C23—C22—H22 | 119.6 | Br6—Ti2—Ti1 | 54.93 (3) |
C24—C23—C22 | 118.8 (6) | Br7—Ti2—Ti1 | 54.83 (3) |
C24—C23—H23 | 120.6 | C7—As1—C1 | 113.0 (3) |
C22—C23—H23 | 120.6 | C7—As1—C13 | 110.5 (3) |
C19—C24—C23 | 120.0 (7) | C1—As1—C13 | 109.4 (3) |
C19—C24—H24 | 120.0 | C7—As1—Br1 | 107.9 (2) |
C23—C24—H24 | 120.0 | C1—As1—Br1 | 107.7 (2) |
C26—C25—C30 | 121.8 (6) | C13—As1—Br1 | 108.1 (2) |
C26—C25—As2 | 119.5 (5) | C31—As2—C19 | 110.8 (3) |
C30—C25—As2 | 118.6 (5) | C31—As2—C25 | 110.1 (3) |
C25—C26—C27 | 117.9 (6) | C19—As2—C25 | 110.4 (3) |
C25—C26—H26 | 121.0 | C31—As2—Br2 | 109.2 (2) |
C27—C26—H26 | 121.0 | C19—As2—Br2 | 108.9 (2) |
C28—C27—C26 | 120.3 (6) | C25—As2—Br2 | 107.38 (19) |
C28—C27—H27 | 119.9 | Ti1—Br6—Ti2 | 69.79 (4) |
C26—C27—H27 | 119.9 | Ti1—Br7—Ti2 | 68.67 (4) |
C29—C28—C27 | 120.8 (6) | Ti1—O1—Ti2 | 115.0 (2) |
C29—C28—H28 | 119.6 | ||
C6—C1—C2—C3 | 0.2 (12) | Br3—Ti1—Ti2—Br6 | −73.45 (5) |
As1—C1—C2—C3 | 179.2 (6) | Br4—Ti1—Ti2—Br6 | 172.73 (6) |
C1—C2—C3—C4 | −0.9 (13) | Br5—Ti1—Ti2—Br6 | 48.76 (6) |
C2—C3—C4—C5 | 1.8 (14) | Br7—Ti1—Ti2—Br6 | 102.13 (4) |
C3—C4—C5—C6 | −2.0 (14) | O1—Ti1—Ti2—Br7 | 126.5 (3) |
C2—C1—C6—C5 | −0.4 (12) | Br3—Ti1—Ti2—Br7 | −175.58 (6) |
As1—C1—C6—C5 | −179.3 (6) | Br4—Ti1—Ti2—Br7 | 70.60 (5) |
C4—C5—C6—C1 | 1.2 (13) | Br5—Ti1—Ti2—Br7 | −53.37 (6) |
C12—C7—C8—C9 | −1.1 (11) | Br6—Ti1—Ti2—Br7 | −102.13 (4) |
As1—C7—C8—C9 | 177.9 (5) | C8—C7—As1—C1 | −111.8 (6) |
C7—C8—C9—C10 | −0.6 (11) | C12—C7—As1—C1 | 67.2 (7) |
C8—C9—C10—C11 | 1.3 (12) | C8—C7—As1—C13 | 11.2 (7) |
C9—C10—C11—C12 | −0.2 (12) | C12—C7—As1—C13 | −169.8 (6) |
C10—C11—C12—C7 | −1.5 (12) | C8—C7—As1—Br1 | 129.3 (5) |
C8—C7—C12—C11 | 2.2 (11) | C12—C7—As1—Br1 | −51.7 (6) |
As1—C7—C12—C11 | −176.8 (6) | C6—C1—As1—C7 | −14.9 (7) |
C18—C13—C14—C15 | 0.6 (11) | C2—C1—As1—C7 | 166.1 (6) |
As1—C13—C14—C15 | −175.3 (5) | C6—C1—As1—C13 | −138.5 (6) |
C13—C14—C15—C16 | −0.1 (11) | C2—C1—As1—C13 | 42.5 (7) |
C14—C15—C16—C17 | −1.0 (12) | C6—C1—As1—Br1 | 104.2 (6) |
C15—C16—C17—C18 | 1.7 (13) | C2—C1—As1—Br1 | −74.8 (6) |
C16—C17—C18—C13 | −1.1 (12) | C14—C13—As1—C7 | 76.0 (6) |
C14—C13—C18—C17 | −0.1 (11) | C18—C13—As1—C7 | −100.0 (6) |
As1—C13—C18—C17 | 175.9 (6) | C14—C13—As1—C1 | −158.9 (5) |
C24—C19—C20—C21 | 1.0 (10) | C18—C13—As1—C1 | 25.0 (6) |
As2—C19—C20—C21 | −177.4 (5) | C14—C13—As1—Br1 | −41.9 (6) |
C19—C20—C21—C22 | −0.9 (10) | C18—C13—As1—Br1 | 142.0 (5) |
C20—C21—C22—C23 | −0.2 (10) | C32—C31—As2—C19 | 173.2 (5) |
C21—C22—C23—C24 | 1.1 (10) | C36—C31—As2—C19 | −12.6 (6) |
C20—C19—C24—C23 | 0.0 (10) | C32—C31—As2—C25 | −64.4 (6) |
As2—C19—C24—C23 | 178.3 (5) | C36—C31—As2—C25 | 109.8 (5) |
C22—C23—C24—C19 | −1.0 (10) | C32—C31—As2—Br2 | 53.3 (6) |
C30—C25—C26—C27 | 1.1 (10) | C36—C31—As2—Br2 | −132.5 (5) |
As2—C25—C26—C27 | −176.1 (5) | C24—C19—As2—C31 | −64.0 (6) |
C25—C26—C27—C28 | −0.4 (10) | C20—C19—As2—C31 | 114.4 (5) |
C26—C27—C28—C29 | −0.3 (10) | C24—C19—As2—C25 | 173.7 (5) |
C27—C28—C29—C30 | 0.5 (10) | C20—C19—As2—C25 | −7.9 (6) |
C28—C29—C30—C25 | 0.2 (10) | C24—C19—As2—Br2 | 56.1 (5) |
C26—C25—C30—C29 | −1.0 (10) | C20—C19—As2—Br2 | −125.5 (5) |
As2—C25—C30—C29 | 176.2 (5) | C26—C25—As2—C31 | −7.8 (6) |
C36—C31—C32—C33 | −2.8 (10) | C30—C25—As2—C31 | 175.0 (5) |
As2—C31—C32—C33 | 171.3 (5) | C26—C25—As2—C19 | 114.9 (5) |
C31—C32—C33—C34 | 1.0 (10) | C30—C25—As2—C19 | −62.4 (6) |
C32—C33—C34—C35 | 0.6 (10) | C26—C25—As2—Br2 | −126.6 (5) |
C33—C34—C35—C36 | −0.4 (10) | C30—C25—As2—Br2 | 56.2 (5) |
C34—C35—C36—C31 | −1.3 (10) | O1—Ti1—Br6—Ti2 | 24.29 (15) |
C32—C31—C36—C35 | 3.0 (10) | Br3—Ti1—Br6—Ti2 | 120.09 (5) |
As2—C31—C36—C35 | −171.2 (5) | Br5—Ti1—Br6—Ti2 | −143.41 (5) |
Br3—Ti1—Ti2—O1 | 57.9 (3) | Br7—Ti1—Br6—Ti2 | −55.83 (4) |
Br4—Ti1—Ti2—O1 | −55.9 (3) | O1—Ti2—Br6—Ti1 | −24.22 (15) |
Br5—Ti1—Ti2—O1 | −179.9 (3) | Br8—Ti2—Br6—Ti1 | −123.62 (5) |
Br6—Ti1—Ti2—O1 | 131.4 (3) | Br10—Ti2—Br6—Ti1 | 141.68 (5) |
Br7—Ti1—Ti2—O1 | −126.5 (3) | Br7—Ti2—Br6—Ti1 | 54.50 (4) |
O1—Ti1—Ti2—Br9 | 54.5 (3) | O1—Ti1—Br7—Ti2 | −26.21 (15) |
Br3—Ti1—Ti2—Br9 | 112.45 (6) | Br4—Ti1—Br7—Ti2 | −125.11 (5) |
Br4—Ti1—Ti2—Br9 | −1.36 (8) | Br5—Ti1—Br7—Ti2 | 140.57 (5) |
Br5—Ti1—Ti2—Br9 | −125.33 (6) | Br6—Ti1—Br7—Ti2 | 54.63 (3) |
Br6—Ti1—Ti2—Br9 | −174.09 (6) | O1—Ti2—Br7—Ti1 | 26.26 (15) |
Br7—Ti1—Ti2—Br9 | −71.96 (5) | Br9—Ti2—Br7—Ti1 | 122.10 (5) |
O1—Ti1—Ti2—Br8 | −62.1 (3) | Br8—Ti2—Br7—Ti1 | −44.6 (3) |
Br3—Ti1—Ti2—Br8 | −4.21 (8) | Br10—Ti2—Br7—Ti1 | −142.84 (5) |
Br4—Ti1—Ti2—Br8 | −118.02 (6) | Br6—Ti2—Br7—Ti1 | −54.60 (3) |
Br5—Ti1—Ti2—Br8 | 118.01 (7) | Br3—Ti1—O1—Ti2 | −129.8 (2) |
Br6—Ti1—Ti2—Br8 | 69.25 (5) | Br4—Ti1—O1—Ti2 | 133.4 (2) |
Br7—Ti1—Ti2—Br8 | 171.38 (6) | Br5—Ti1—O1—Ti2 | 0.3 (7) |
O1—Ti1—Ti2—Br10 | 176.6 (3) | Br6—Ti1—O1—Ti2 | −38.9 (2) |
Br3—Ti1—Ti2—Br10 | −125.46 (7) | Br7—Ti1—O1—Ti2 | 43.1 (2) |
Br4—Ti1—Ti2—Br10 | 120.72 (7) | Br9—Ti2—O1—Ti1 | −133.2 (2) |
Br5—Ti1—Ti2—Br10 | −3.25 (10) | Br8—Ti2—O1—Ti1 | 127.1 (2) |
Br6—Ti1—Ti2—Br10 | −52.01 (6) | Br10—Ti2—O1—Ti1 | −8.0 (7) |
Br7—Ti1—Ti2—Br10 | 50.12 (6) | Br6—Ti2—O1—Ti1 | 38.8 (2) |
O1—Ti1—Ti2—Br6 | −131.4 (3) | Br7—Ti2—O1—Ti1 | −42.4 (2) |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | (C4H12As)[Ti2Cl9] | (C18H15AsBr)2[Ti2Br8O] |
Mr | 549.91 | 1523.34 |
Crystal system, space group | Orthorhombic, Pbcm | Triclinic, P1 |
Temperature (K) | 150 | 120 |
a, b, c (Å) | 9.7061 (15), 17.855 (3), 10.4555 (16) | 10.4991 (2), 10.7921 (3), 21.5971 (6) |
α, β, γ (°) | 90, 90, 90 | 81.210 (1), 83.017 (2), 67.448 (1) |
V (Å3) | 1812.0 (5) | 2228.12 (10) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 4.00 | 10.83 |
Crystal size (mm) | 0.25 × 0.10 × 0.01 | 0.20 × 0.20 × 0.08 |
Data collection | ||
Diffractometer | Bruker SMART APEX diffractometer | Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.435, 0.961 | 0.221, 0.478 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14917, 2329, 1767 | 33234, 10149, 7721 |
Rint | 0.064 | 0.053 |
(sin θ/λ)max (Å−1) | 0.667 | 0.652 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.081, 1.06 | 0.050, 0.101, 1.14 |
No. of reflections | 2329 | 10149 |
No. of parameters | 94 | 460 |
No. of restraints | 4 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0353P)2 + 0.1344P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.P)2 + 15.7068P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.52, −0.52 | 1.06, −1.07 |
Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
Cl1—Ti1 | 2.2085 (10) | Cl4—Ti2 | 2.5189 (11) |
Cl2—Ti1 | 2.2206 (15) | Cl5—Ti2 | 2.1844 (10) |
Cl3—Ti1 | 2.4668 (15) | Cl6—Ti2 | 2.2192 (14) |
Cl3—Ti2 | 2.4908 (14) | As1—H1A | 1.504 (10) |
Cl4—Ti1 | 2.4909 (10) | As1—H1B | 1.518 (10) |
Ti1—Cl3—Ti2 | 88.23 (4) | Ti1—Cl4—Ti2 | 87.07 (3) |
C1—As1 | 1.899 (7) | C25—As2 | 1.905 (6) |
C7—As1 | 1.893 (7) | C31—As2 | 1.893 (7) |
C13—As1 | 1.909 (7) | As1—Br1 | 2.2689 (10) |
C19—As2 | 1.904 (6) | As2—Br2 | 2.2753 (9) |
O1—Ti1—Br5 | 160.37 (15) | Ti1—Br7—Ti2 | 68.67 (4) |
O1—Ti2—Br10 | 160.49 (15) | Ti1—O1—Ti2 | 115.0 (2) |
Ti1—Br6—Ti2 | 69.79 (4) |
The deposition of transition metal pnictide thin films is a growing area of research, owing mainly to the useful properties of these films, e.g. TiN (Carmalt et al., 2002; Newport et al., 2002); ZrN (Potts et al., 2009); TiP (Blackman et al., 2004); TiAs (Thomas, Blackman et al., 2010); CoAs (Senzaki & Gladfelter, 1994; Klingan et al., 1995) and MnAs (Lane et al., 1994). These films are often grown by chemical vapour deposition (CVD). This process combines a volatile metal compound with a volatile pnictogen compound in a gas-phase reaction before deposition onto a substrate occurs, but these volatile starting materials can be toxic, flammable and hazardous to work with. To circumvent this problem, `single-source' precursors have been developed (Cowley & Jones, 1994; Carmalt & Basharat, 2007). These are molecules which contain a preformed M—Pn bond (Pn = pnictogen) and are, in general, far less toxic and hazardous to work with. In an attempt to obtain single-source precursors to thin films of TiAs, we recently reported a series of novel titanium arsane coordination compounds. These were mostly adducts of TiCl4 with simple tertiary arsanes, e.g. [TiCl4(AsPh3)n] (n = 1, 2), although the reaction of TiCl4 with tBuAsH2, compound (I), was also reported (Thomas, Pugh et al., 2010).
It was possible to determine that an adduct had formed by comparing the chemical shift of the coordinated tBuAsH2 ligand with free tBuAsH2 in the 1H NMR spectrum of (I), although the exact stoichiometry of the product could not be determined. Owing to the exceptionally high volatility of (I), at the time it was not possible to grow crystals of the product. However, upon standing for several weeks at 255 K, orange rods were deposited from a concentrated hexane solution. The resulting product was not the expected adduct; instead, an ion pair had formed to give compound (II), the structure of which is reported here (Fig. 1).
Compound (II) crystallizes in the orthorhombic space group Pbcm and consists of a tert-butylarsenium cation with a [Ti2(µ-Cl)3Cl6]- anion. It constitutes the first structurally characterized example of a primary arsenium cation. This type of primary alkyl cation is ubiquitous for nitrogen, the lightest member of group 15, but primary alkyl phosphonium cations are extremely rare: only six examples exist in the Cambridge Structural Database (CSD, update of August 2010; Allen, 2002).
As is expected upon descending group 15, the length of the Pn—H bonds increases: the N—H bonds in ammonium cations are significantly shorter than the P—H bonds in phosphonium cations, which range from 1.212 to 1.405 Å (Fluck et al., 1986; Karnop et al., 1997). In (II), the H atoms were located in a Fourier difference map ca 1.5 Å from the As centre, continuing the trend and consistent with the larger atomic radius of As compared with P and N. However, it was necessary to use the DFIX and DANG commands (SHELXL97; Sheldrick, 2008) during the refinement cycles to restrain the As—H bond lengths and angles into a sensible tetrahedral geometry at the As atom.
The [Ti2(µ-Cl)3Cl6]- anion of (II) consists of two octahedral TiIV centres with three bridging chloride anions and six terminal chloride anions. As is expected for anions which bridge between two metal centres, the range of bridging Ti—Cl distances is significantly wider than the range of Ti—Cl distances for the terminal chloride anions (Table 1). The angles around the bridging chloride anions are close to the expected value of 90° for an octahedral compound. There are 15 examples of this anion in the CSD and the molecular geometry in (II) is consistent with the structures reported previously (e.g. Hollman et al., 2005).
Compound (II) lies on a mirror plane within the unit cell and the asymmetric unit consists of one half of each of the arsenium cation and the [Ti2(µ-Cl)3Cl6]-, anion with an overall Z of 4. The intermolecular interactions are mostly limited to As—H···Cl interactions between the arsenium H atoms and neighbouring [Ti2(µ-Cl)3Cl6]- anions. Two of the symmetry-related arsenium H atoms are bonded to [At least?] two chloride anions: atom H1A bonds to both Cl1 and Cl4, whereas atom H1B is bonded to three chloride anions, namely Cl2, Cl4 and a symmetry-related atom Cl4 at (x, y, -z + 1/2?) (Fig. 2). Also present are two short contacts between the As centre and the anion, and with As···Cl3 = 3.468 (1)Å and As···Cl6 = 3.403 (1) Å they are significantly shorter than the sum of the van der Waals radii of the two atoms (Bondi, 1964). The direction of the As···Cl3 interaction is diametrically opposite to the direction of the As—H1B bond (Fig. 2), and the direction of the As···Cl6 interaction is diametrically opposite to the direction of the As—C bond.
As mentioned above, we have previously reported the synthesis of adducts of TiCl4 with simple tertiary arsanes such as AsPh3 (Thomas, Pugh et al., 2010). However, it was found that these adducts were unsuitable precursors because the weak Ti—As bond decomposed too readily and films of TiAs were not formed. In an attempt to synthesize compounds with stronger Ti—As bonds, AsPh3 was reacted with the softer and less Lewis acidic TiBr4. Upon crystallization of the product, instead of the expected 1:1 adduct, an ion pair was isolated, compound (III), which resulted from oxidation of the AsPh3 ligand by water (Fig. 3).
Compound (III) crystallizes in the triclinic space group P1 and consists of two bromotriphenylarsenium(V) cations with a [Ti2(µ-O)(µ-Br)2Br6]2- dianion. It is the first structurally characterized example of the dianion. Structurally, it is similar to the [Ti2(µ-Cl)3Cl6]- anion observed in (II), with two octahedrally coordinated TiIV centres, six terminal halide anions and [How many?] bridging halide anions, but in (III) a bridging oxo dianion is present instead of one of the bridging halide anions. The presence of an oxo dianion significantly affects the geometry at the Ti centre, with the deviation from ideal octahedral evidenced in the O—Ti—Br (trans) angles, a long way from the ideal value of 180° (Table 2). The Ti—O—Ti bond angle and the bridging Ti—Br—Ti angles also show evidence of significant deviation away from the ideal value of 90° as a result of the oxo dianion.
The bromotriphenylarsenium cation in (III) has only been structurally characterized once before (Chitsaz et al., 1999). This was isolated with a [TeBr6]2- counterion from the reaction of Ph3AsBr2 and TeBr4. Structurally, the two cations are almost identical, with the As—Br distances [2.276 (3) and 2.283 (3) Å] consistent with those found in (III) (Table 2). Similarly, the As—C distances of 1.89 (2)–1.90 (2) Å are also consistent with those found in (III).
The cations and dianion of (III) interact mainly through the Br atom attached to the arsenium centre (Fig. 4). Atom Br1 exhibits halogen···halogen interactions with both Br3 [3.664 (1) Å] and Br5 [3.284 (1) Å] of the dianion [both atoms Br3 and Br5 are located at the symmetry position (1 + x, 1 + y, z)], which are significantly shorter than the sum of the van der Waals radii for two Br atoms (Bondi, 1964). There is only one interaction involving atom Br2; the Br2···Br10 distance of 3.676 (1) Å is also shorter than the sum of the van der Waals radii for two Br atoms.