Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012111/cf1314sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012111/cf1314Isup2.hkl |
CCDC reference: 142719
Triphenylarsine (1.98 g, 7.25 mmol) was added to diethyl ether (ca 75 ml) under dry argon and a saturated ether solution of IBr (1.5 g, 7.25 mmol) was then added (Godfrey, 1993). A yellow solid precipitated immediately and was recrystallized from diethyl ether to give orange crystals suitable for X-ray analysis.
Data collection: CAD-4 Software (Enraf-Nonius, 1994); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELX97 (Sheldrick, 1997); program(s) used to refine structure: SHELX97; molecular graphics: ORTEPIII (Farrugia, 1997; Burnett & Johnson, 1996); software used to prepare material for publication: SHELX97.
Fig. 1. ORTEPIII (Farrugia, 1997; Burnett and Johnson, 1996) drawing of the structure of (I), showing the atom-numbering scheme and with 50% probability displacement ellispoids. |
[As(BrI)(C6H5)3] | F(000) = 976 |
Mr = 513.03 | Dx = 1.927 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1198 (13) Å | Cell parameters from 25 reflections |
b = 9.960 (2) Å | θ = 13.3–16.4° |
c = 19.483 (3) Å | µ = 5.92 mm−1 |
β = 92.176 (12)° | T = 203 K |
V = 1768.4 (6) Å3 | Needle, orange |
Z = 4 | 0.25 × 0.15 × 0.11 mm |
Nonius MACH3 diffractometer | 2360 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
2θ/ω scans | h = 0→10 |
Absorption correction: ψ-scan (North et al., 1968) | k = 0→11 |
Tmin = 0.386, Tmax = 0.521 | l = −23→23 |
3270 measured reflections | 3 standard reflections every 150 reflections |
3065 independent reflections | intensity decay: 0.0% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.089 | Calculated w = 1/[σ2(Fo2) + (0.0503P)2 + 2.5099P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3065 reflections | Δρmax = 0.65 e Å−3 |
191 parameters | Δρmin = −0.99 e Å−3 |
0 restraints | Extinction correction: SHELX97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00015 (19) |
[As(BrI)(C6H5)3] | V = 1768.4 (6) Å3 |
Mr = 513.03 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1198 (13) Å | µ = 5.92 mm−1 |
b = 9.960 (2) Å | T = 203 K |
c = 19.483 (3) Å | 0.25 × 0.15 × 0.11 mm |
β = 92.176 (12)° |
Nonius MACH3 diffractometer | 2360 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.041 |
Tmin = 0.386, Tmax = 0.521 | 3 standard reflections every 150 reflections |
3270 measured reflections | intensity decay: 0.0% |
3065 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.65 e Å−3 |
3065 reflections | Δρmin = −0.99 e Å−3 |
191 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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.25473 (4) | 0.91923 (4) | 0.664462 (18) | 0.03120 (14) | |
Br1 | 0.09272 (6) | 1.09119 (6) | 0.75101 (3) | 0.03675 (18) | |
As1 | 0.38469 (6) | 0.74618 (6) | 0.58831 (3) | 0.02898 (17) | |
C1 | 0.2719 (5) | 0.7190 (6) | 0.5051 (3) | 0.0295 (13) | |
C2 | 0.2100 (6) | 0.5955 (6) | 0.4894 (3) | 0.0313 (13) | |
H2 | 0.2251 | 0.5227 | 0.5195 | 0.038* | |
C3 | 0.1261 (6) | 0.5788 (7) | 0.4295 (3) | 0.0411 (15) | |
H3 | 0.0847 | 0.4945 | 0.4189 | 0.049* | |
C4 | 0.1029 (6) | 0.6847 (7) | 0.3854 (3) | 0.0386 (15) | |
H4 | 0.0469 | 0.6726 | 0.3444 | 0.046* | |
C5 | 0.1619 (6) | 0.8089 (7) | 0.4013 (3) | 0.0400 (15) | |
H5 | 0.1447 | 0.8819 | 0.3715 | 0.048* | |
C6 | 0.2476 (6) | 0.8261 (6) | 0.4621 (3) | 0.0330 (13) | |
H6 | 0.2880 | 0.9106 | 0.4731 | 0.040* | |
C7 | 0.3923 (6) | 0.5783 (6) | 0.6358 (3) | 0.0287 (12) | |
C8 | 0.2692 (6) | 0.5341 (7) | 0.6681 (3) | 0.0394 (16) | |
H8 | 0.1856 | 0.5892 | 0.6693 | 0.047* | |
C9 | 0.2686 (6) | 0.4104 (7) | 0.6984 (3) | 0.0405 (15) | |
H9 | 0.1837 | 0.3800 | 0.7195 | 0.049* | |
C10 | 0.3924 (7) | 0.3293 (6) | 0.6982 (3) | 0.0360 (14) | |
H10 | 0.3916 | 0.2439 | 0.7188 | 0.043* | |
C11 | 0.5180 (7) | 0.3760 (7) | 0.6672 (3) | 0.0397 (15) | |
H11 | 0.6027 | 0.3222 | 0.6674 | 0.048* | |
C12 | 0.5186 (6) | 0.4999 (7) | 0.6365 (3) | 0.0366 (15) | |
H12 | 0.6038 | 0.5317 | 0.6162 | 0.044* | |
C13 | 0.5814 (5) | 0.7866 (6) | 0.5633 (3) | 0.0298 (13) | |
C14 | 0.6242 (6) | 0.7721 (6) | 0.4968 (3) | 0.0348 (14) | |
H14 | 0.5554 | 0.7487 | 0.4617 | 0.042* | |
C15 | 0.7699 (7) | 0.7923 (7) | 0.4825 (3) | 0.0411 (16) | |
H15 | 0.7999 | 0.7864 | 0.4369 | 0.049* | |
C16 | 0.8710 (6) | 0.8212 (7) | 0.5346 (4) | 0.0408 (16) | |
H16 | 0.9703 | 0.8323 | 0.5246 | 0.049* | |
C17 | 0.8283 (6) | 0.8338 (7) | 0.6006 (4) | 0.0442 (17) | |
H17 | 0.8979 | 0.8553 | 0.6358 | 0.053* | |
C18 | 0.6838 (6) | 0.8151 (7) | 0.6160 (3) | 0.0408 (16) | |
H18 | 0.6546 | 0.8215 | 0.6616 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0184 (2) | 0.0404 (2) | 0.0344 (2) | −0.00318 (16) | −0.00319 (14) | −0.00032 (17) |
Br1 | 0.0309 (3) | 0.0378 (4) | 0.0420 (3) | 0.0022 (3) | 0.0070 (2) | 0.0009 (3) |
As1 | 0.0137 (3) | 0.0406 (4) | 0.0325 (3) | −0.0029 (2) | −0.0011 (2) | −0.0015 (3) |
C1 | 0.012 (3) | 0.037 (4) | 0.038 (3) | 0.004 (2) | −0.004 (2) | 0.001 (3) |
C2 | 0.022 (3) | 0.035 (3) | 0.037 (3) | −0.001 (3) | 0.002 (2) | −0.007 (3) |
C3 | 0.024 (3) | 0.050 (4) | 0.049 (4) | −0.012 (3) | −0.005 (3) | −0.012 (3) |
C4 | 0.019 (3) | 0.058 (4) | 0.039 (3) | 0.001 (3) | −0.006 (2) | −0.011 (3) |
C5 | 0.025 (3) | 0.054 (4) | 0.040 (3) | 0.009 (3) | −0.007 (3) | −0.001 (3) |
C6 | 0.021 (3) | 0.033 (3) | 0.045 (3) | 0.001 (2) | −0.001 (3) | −0.005 (3) |
C7 | 0.022 (3) | 0.031 (3) | 0.033 (3) | −0.002 (2) | −0.003 (2) | 0.002 (3) |
C8 | 0.014 (3) | 0.060 (4) | 0.044 (4) | −0.001 (3) | 0.000 (2) | 0.011 (3) |
C9 | 0.024 (3) | 0.053 (4) | 0.043 (3) | −0.011 (3) | −0.004 (2) | 0.007 (3) |
C10 | 0.039 (4) | 0.035 (4) | 0.034 (3) | −0.003 (3) | −0.006 (3) | 0.000 (3) |
C11 | 0.034 (3) | 0.049 (4) | 0.035 (3) | 0.009 (3) | −0.002 (3) | −0.005 (3) |
C12 | 0.020 (3) | 0.052 (4) | 0.037 (3) | 0.001 (3) | 0.004 (2) | −0.003 (3) |
C13 | 0.010 (2) | 0.034 (3) | 0.045 (3) | −0.007 (2) | −0.002 (2) | 0.004 (3) |
C14 | 0.020 (3) | 0.043 (4) | 0.041 (3) | −0.008 (3) | 0.002 (2) | −0.007 (3) |
C15 | 0.031 (3) | 0.053 (4) | 0.040 (4) | 0.007 (3) | 0.010 (3) | 0.003 (3) |
C16 | 0.017 (3) | 0.038 (4) | 0.067 (5) | 0.004 (3) | 0.000 (3) | 0.012 (3) |
C17 | 0.016 (3) | 0.055 (4) | 0.061 (4) | −0.005 (3) | −0.012 (3) | 0.018 (4) |
C18 | 0.030 (3) | 0.057 (4) | 0.035 (3) | −0.007 (3) | −0.006 (3) | 0.008 (3) |
I1—As1 | 2.5904 (8) | C7—C12 | 1.391 (8) |
I1—Br1 | 2.8546 (8) | C8—C9 | 1.366 (9) |
As1—C1 | 1.906 (5) | C9—C10 | 1.388 (9) |
As1—C7 | 1.911 (6) | C10—C11 | 1.395 (9) |
As1—C13 | 1.920 (5) | C11—C12 | 1.372 (9) |
C1—C6 | 1.370 (8) | C13—C14 | 1.374 (8) |
C1—C2 | 1.383 (8) | C13—C18 | 1.390 (8) |
C2—C3 | 1.381 (8) | C14—C15 | 1.383 (8) |
C3—C4 | 1.371 (9) | C15—C16 | 1.376 (9) |
C4—C5 | 1.380 (9) | C16—C17 | 1.364 (9) |
C5—C6 | 1.404 (8) | C17—C18 | 1.375 (8) |
C7—C8 | 1.381 (8) | ||
As1—I1—Br1 | 174.78 (2) | C8—C7—As1 | 119.0 (4) |
C1—As1—C7 | 107.2 (2) | C12—C7—As1 | 120.7 (4) |
C1—As1—C13 | 107.1 (2) | C9—C8—C7 | 120.1 (6) |
C7—As1—C13 | 106.8 (2) | C8—C9—C10 | 120.5 (6) |
C1—As1—I1 | 109.76 (17) | C9—C10—C11 | 119.2 (6) |
C7—As1—I1 | 108.30 (17) | C12—C11—C10 | 120.4 (6) |
C13—As1—I1 | 117.26 (18) | C11—C12—C7 | 119.5 (6) |
C6—C1—C2 | 120.1 (5) | C14—C13—C18 | 120.7 (5) |
C6—C1—As1 | 118.7 (4) | C14—C13—As1 | 121.2 (4) |
C2—C1—As1 | 121.2 (4) | C18—C13—As1 | 117.6 (4) |
C3—C2—C1 | 120.2 (6) | C13—C14—C15 | 119.0 (6) |
C4—C3—C2 | 120.3 (6) | C16—C15—C14 | 120.2 (6) |
C3—C4—C5 | 119.9 (6) | C17—C16—C15 | 120.5 (6) |
C4—C5—C6 | 119.9 (6) | C16—C17—C18 | 120.2 (6) |
C1—C6—C5 | 119.5 (6) | C17—C18—C13 | 119.3 (6) |
C8—C7—C12 | 120.3 (6) |
Experimental details
Crystal data | |
Chemical formula | [As(BrI)(C6H5)3] |
Mr | 513.03 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 203 |
a, b, c (Å) | 9.1198 (13), 9.960 (2), 19.483 (3) |
β (°) | 92.176 (12) |
V (Å3) | 1768.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.92 |
Crystal size (mm) | 0.25 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Nonius MACH3 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.386, 0.521 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3270, 3065, 2360 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.089, 1.02 |
No. of reflections | 3065 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.99 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1994), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELX97 (Sheldrick, 1997), SHELX97, ORTEPIII (Farrugia, 1997; Burnett & Johnson, 1996).
I1—As1 | 2.5904 (8) | As1—C7 | 1.911 (6) |
I1—Br1 | 2.8546 (8) | As1—C13 | 1.920 (5) |
As1—C1 | 1.906 (5) | ||
As1—I1—Br1 | 174.78 (2) | C1—As1—I1 | 109.76 (17) |
C1—As1—C7 | 107.2 (2) | C7—As1—I1 | 108.30 (17) |
C1—As1—C13 | 107.1 (2) | C13—As1—I1 | 117.26 (18) |
C7—As1—C13 | 106.8 (2) |
This work is a continuation of our investigation into adducts formed between group VA donors and the heavier halogens. Both Ph3PI2 [Godfrey et al., 1991; I—P—C—C 38 (1), 45 (1), 57 (1)°] and Ph3PBr2 [Bricklebank et al., 1992; Br—P—C—C 43.0 (9), 49.1 (9), 57.7 (8)°] have similar shapes to the title molecule, (I). However, at 2.5904 (8) Å, the As—I bond in (I) is shorter than any of the analogous bonds in the various polymorphs of Ph3AsI2 (Abbas et al., 1994; Beagley et al., 1988), which range from 2.613 (2) to 2.653 (2) Å. Interestingly, if a Lewis acid competes for the terminal iodine in Ph3AsI2, the As—I bond is shortened below the Ph3AsIBr value, e.g. 2.485 (1) Å when GaI3 is used as the Lewis acid (Baker et al., 1994). This suggests that the As—I bond is short in (I) because the Br—I bonding is weaker than the corresponding I—I interaction. In contrast to the disordered Ph3PI1.29Br0.71 structure (Bricklebank et al., 1993), where P is attached to Br in 14 (2)% of the molecules, the structure of (I) contains no As—Br bonds.