Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112040000/sk3449sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112040000/sk3449Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112040000/sk3449IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112040000/sk3449Isup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112040000/sk3449IIsup5.cml | |
Chemdraw file https://doi.org/10.1107/S0108270112040000/sk3449Isup6.cdx | |
Chemdraw file https://doi.org/10.1107/S0108270112040000/sk3449IIsup7.cdx |
CCDC references: 914643; 914644
For related literature, see: Avtomonov et al. (1996, 1997); Bondi (1964); Camerman & Trotter (1963); Deck & Vahrenkamp (1991); Deck et al. (1987); Gross et al. (1997); Huttner & Evertz (1986); Ilyin et al. (2012); Jutzi & Kroos (1990); Konchenko et al. (1999); Matuska et al. (2010); Megges et al. (1996); Pushkarevsky et al. (2006); Song et al. (2001); Twamley et al. (1999); Winter et al. (1983).
For the syntheses of arsonic acids [p- or m-HOOCC6H4AsO(OH)2], the corresponding aminobenzoic acids were diazotated in dilute HCl. The diazo solution was added dropwise to a solution containing NaAsO2 in the presence of excess KOH (Bart reaction). The mixture was heated for 30 min with activated coal and filtered. The mother solution was acidified with HCl and cooled. A crystalline powder of p- or m-HOOCC6H4AsO(OH)2 precipitated at pH 3. To obtain the iodide derivatives, p- or m-HOOCC6H4AsO(OH)2 was treated with excess NaI and Na2SO3 in aqueous solution. [Please give quantities or mole ratios, preferably for all steps but at the very least for this final step] Yellow precipitates of p- or m-HOOCC6H4AsI2 were filtered off, dried and recrystallized from chloroform–diethyl ether mixtures [Solvent ratios?].
For both compounds, H atoms were located in difference Fourier maps and subsequently positioned geometrically, with C—H = 0.93 and O—H = 0.82 Å. They were refined as riding, with Uiso(H) = 1.2Ueq(C,O). [Please check added text]
For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[As(C7H5O2)I2] | Z = 2 |
Mr = 449.83 | F(000) = 404 |
Triclinic, P1 | Dx = 2.789 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8992 (2) Å | Cell parameters from 2330 reflections |
b = 8.4434 (5) Å | θ = 2.5–28.2° |
c = 13.6616 (9) Å | µ = 8.90 mm−1 |
α = 107.148 (2)° | T = 296 K |
β = 91.569 (2)° | Prism, orange |
γ = 96.376 (2)° | 0.35 × 0.20 × 0.18 mm |
V = 535.59 (5) Å3 |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 2144 independent reflections |
Radiation source: fine-focus sealed tube | 1859 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 25 pixels mm-1 | θmax = 26.4°, θmin = 2.5° |
ϕ scans | h = −4→6 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −10→10 |
Tmin = 0.147, Tmax = 0.297 | l = −17→17 |
3909 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0622P)2 + 0.9538P] where P = (Fo2 + 2Fc2)/3 |
2144 reflections | (Δ/σ)max < 0.001 |
110 parameters | Δρmax = 1.87 e Å−3 |
0 restraints | Δρmin = −1.67 e Å−3 |
[As(C7H5O2)I2] | γ = 96.376 (2)° |
Mr = 449.83 | V = 535.59 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.8992 (2) Å | Mo Kα radiation |
b = 8.4434 (5) Å | µ = 8.90 mm−1 |
c = 13.6616 (9) Å | T = 296 K |
α = 107.148 (2)° | 0.35 × 0.20 × 0.18 mm |
β = 91.569 (2)° |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 2144 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1859 reflections with I > 2σ(I) |
Tmin = 0.147, Tmax = 0.297 | Rint = 0.027 |
3909 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.87 e Å−3 |
2144 reflections | Δρmin = −1.67 e Å−3 |
110 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 | 1.02638 (11) | 0.14239 (5) | 0.22256 (4) | 0.06112 (19) | |
I2 | 0.69106 (11) | 0.27248 (7) | −0.00248 (3) | 0.0675 (2) | |
As1 | 1.02783 (11) | 0.39534 (7) | 0.15666 (4) | 0.03714 (18) | |
O1 | 0.1103 (9) | 0.7967 (6) | 0.4937 (3) | 0.0499 (10) | |
H1 | −0.0001 | 0.8608 | 0.5195 | 0.060* | |
O2 | 0.2277 (9) | 0.9884 (5) | 0.4150 (3) | 0.0467 (10) | |
C1 | 0.2460 (11) | 0.8530 (7) | 0.4280 (4) | 0.0351 (11) | |
C2 | 0.4299 (10) | 0.7365 (6) | 0.3660 (4) | 0.0324 (11) | |
C3 | 0.4613 (12) | 0.5840 (7) | 0.3834 (4) | 0.0400 (12) | |
H3 | 0.3686 | 0.5533 | 0.4347 | 0.048* | |
C4 | 0.6327 (12) | 0.4782 (7) | 0.3231 (4) | 0.0404 (12) | |
H4 | 0.6549 | 0.3770 | 0.3346 | 0.048* | |
C5 | 0.7686 (10) | 0.5235 (6) | 0.2469 (4) | 0.0313 (10) | |
C6 | 0.7396 (11) | 0.6757 (7) | 0.2302 (4) | 0.0389 (12) | |
H6 | 0.8350 | 0.7064 | 0.1794 | 0.047* | |
C7 | 0.5689 (11) | 0.7821 (7) | 0.2891 (4) | 0.0365 (11) | |
H7 | 0.5477 | 0.8831 | 0.2771 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0802 (4) | 0.0431 (3) | 0.0748 (3) | 0.0304 (2) | 0.0300 (3) | 0.0296 (2) |
I2 | 0.0762 (4) | 0.0785 (4) | 0.0383 (3) | 0.0263 (3) | 0.0056 (2) | −0.0031 (2) |
As1 | 0.0409 (3) | 0.0342 (3) | 0.0402 (3) | 0.0158 (2) | 0.0168 (2) | 0.0120 (2) |
O1 | 0.059 (3) | 0.048 (2) | 0.049 (2) | 0.025 (2) | 0.024 (2) | 0.016 (2) |
O2 | 0.056 (2) | 0.041 (2) | 0.046 (2) | 0.0245 (19) | 0.0165 (19) | 0.0098 (18) |
C1 | 0.037 (3) | 0.040 (3) | 0.026 (2) | 0.012 (2) | 0.004 (2) | 0.004 (2) |
C2 | 0.032 (2) | 0.034 (3) | 0.030 (2) | 0.012 (2) | 0.002 (2) | 0.004 (2) |
C3 | 0.050 (3) | 0.041 (3) | 0.035 (3) | 0.020 (2) | 0.018 (2) | 0.015 (2) |
C4 | 0.055 (3) | 0.037 (3) | 0.038 (3) | 0.020 (2) | 0.016 (2) | 0.017 (2) |
C5 | 0.030 (2) | 0.032 (2) | 0.031 (2) | 0.0114 (19) | 0.0079 (19) | 0.003 (2) |
C6 | 0.041 (3) | 0.038 (3) | 0.039 (3) | 0.012 (2) | 0.012 (2) | 0.012 (2) |
C7 | 0.041 (3) | 0.031 (3) | 0.041 (3) | 0.010 (2) | 0.010 (2) | 0.013 (2) |
I1—As1 | 2.5501 (7) | C3—C4 | 1.397 (7) |
I2—As1 | 2.5726 (8) | C3—H3 | 0.9300 |
As1—C5 | 1.977 (5) | C4—C5 | 1.375 (7) |
O1—C1 | 1.300 (7) | C4—H4 | 0.9300 |
O1—H1 | 0.8200 | C5—C6 | 1.391 (8) |
O2—C1 | 1.220 (7) | C6—C7 | 1.389 (7) |
C1—C2 | 1.498 (7) | C6—H6 | 0.9300 |
C2—C7 | 1.392 (8) | C7—H7 | 0.9300 |
C2—C3 | 1.400 (8) | ||
C5—As1—I1 | 101.11 (16) | C5—C4—C3 | 120.1 (5) |
C5—As1—I2 | 96.83 (15) | C5—C4—H4 | 120.0 |
I1—As1—I2 | 100.32 (3) | C3—C4—H4 | 120.0 |
C1—O1—H1 | 109.5 | C4—C5—C6 | 120.3 (5) |
O2—C1—O1 | 124.2 (5) | C4—C5—As1 | 126.3 (4) |
O2—C1—C2 | 121.1 (5) | C6—C5—As1 | 113.4 (4) |
O1—C1—C2 | 114.7 (5) | C7—C6—C5 | 120.4 (5) |
C7—C2—C3 | 120.0 (5) | C7—C6—H6 | 119.8 |
C7—C2—C1 | 118.5 (5) | C5—C6—H6 | 119.8 |
C3—C2—C1 | 121.5 (5) | C6—C7—C2 | 119.5 (5) |
C4—C3—C2 | 119.7 (5) | C6—C7—H7 | 120.2 |
C4—C3—H3 | 120.2 | C2—C7—H7 | 120.2 |
C2—C3—H3 | 120.2 | ||
O2—C1—C2—C7 | −3.4 (8) | I1—As1—C5—C4 | 0.0 (5) |
O1—C1—C2—C7 | 175.8 (5) | I2—As1—C5—C4 | 101.9 (5) |
O2—C1—C2—C3 | 177.2 (5) | I1—As1—C5—C6 | 177.2 (4) |
O1—C1—C2—C3 | −3.6 (7) | I2—As1—C5—C6 | −80.8 (4) |
C7—C2—C3—C4 | 0.0 (8) | C4—C5—C6—C7 | −1.2 (8) |
C1—C2—C3—C4 | 179.3 (5) | As1—C5—C6—C7 | −178.7 (4) |
C2—C3—C4—C5 | −0.3 (9) | C5—C6—C7—C2 | 0.9 (8) |
C3—C4—C5—C6 | 0.9 (9) | C3—C2—C7—C6 | −0.3 (8) |
C3—C4—C5—As1 | 178.0 (4) | C1—C2—C7—C6 | −179.7 (5) |
[As(C7H5O2)I2] | F(000) = 2424 |
Mr = 449.83 | Dx = 2.843 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9956 reflections |
a = 7.6751 (5) Å | θ = 2.8–27.5° |
b = 18.6142 (12) Å | µ = 9.07 mm−1 |
c = 22.0692 (12) Å | T = 296 K |
β = 90.206 (2)° | Plate, orange |
V = 3152.9 (3) Å3 | 0.18 × 0.15 × 0.06 mm |
Z = 12 |
Bruker Nonius X8 APEX CCD area-detector diffractometer | 5996 independent reflections |
Radiation source: fine-focus sealed tube | 5277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 25 pixels mm-1 | θmax = 25.7°, θmin = 2.4° |
ϕ scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −22→22 |
Tmin = 0.292, Tmax = 0.612 | l = −17→26 |
23397 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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.046 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0089P)2 + 4.041P] where P = (Fo2 + 2Fc2)/3 |
5996 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 0.88 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
[As(C7H5O2)I2] | V = 3152.9 (3) Å3 |
Mr = 449.83 | Z = 12 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6751 (5) Å | µ = 9.07 mm−1 |
b = 18.6142 (12) Å | T = 296 K |
c = 22.0692 (12) Å | 0.18 × 0.15 × 0.06 mm |
β = 90.206 (2)° |
Bruker Nonius X8 APEX CCD area-detector diffractometer | 5996 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5277 reflections with I > 2σ(I) |
Tmin = 0.292, Tmax = 0.612 | Rint = 0.033 |
23397 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.046 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.88 e Å−3 |
5996 reflections | Δρmin = −0.78 e Å−3 |
325 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 | Occ. (<1) | |
I11 | 0.33036 (3) | 0.344090 (14) | 0.404221 (11) | 0.04052 (7) | |
I12 | −0.16707 (3) | 0.355612 (15) | 0.343524 (11) | 0.04430 (7) | |
I21 | 0.65172 (3) | 0.077740 (15) | 0.095365 (11) | 0.04173 (7) | |
I22 | 0.16121 (3) | 0.062395 (16) | 0.035467 (11) | 0.04637 (7) | |
I31 | 0.49621 (3) | 0.226146 (15) | 0.243134 (11) | 0.04468 (7) | |
I32 | −0.00493 (3) | 0.220330 (17) | 0.183977 (12) | 0.05156 (8) | |
As1 | 0.01740 (5) | 0.371427 (19) | 0.441333 (16) | 0.03251 (8) | |
As2 | 0.33939 (4) | 0.118495 (19) | 0.123774 (15) | 0.03020 (8) | |
As3 | 0.18184 (5) | 0.25492 (2) | 0.278397 (17) | 0.03654 (9) | |
O11 | 0.3286 (3) | 0.15495 (16) | 0.57083 (12) | 0.0498 (7) | |
H11 | 0.3903 | 0.1301 | 0.5928 | 0.060* | 0.50 |
O12 | 0.1199 (4) | 0.09822 (16) | 0.62175 (13) | 0.0542 (8) | |
H11A | 0.2055 | 0.0799 | 0.6379 | 0.065* | 0.50 |
O21 | 0.6500 (3) | −0.03724 (17) | 0.30615 (12) | 0.0542 (8) | |
H21 | 0.7110 | −0.0547 | 0.3329 | 0.065* | 0.50 |
O22 | 0.4407 (4) | −0.08732 (17) | 0.36147 (13) | 0.0564 (8) | |
H21A | 0.5252 | −0.0992 | 0.3820 | 0.068* | 0.50 |
O31 | 0.4965 (4) | 0.06411 (16) | 0.43918 (13) | 0.0542 (8) | |
H31 | 0.5555 | 0.0414 | 0.4636 | 0.065* | 0.50 |
O32 | 0.2828 (4) | 0.00745 (16) | 0.48789 (13) | 0.0532 (7) | |
H31A | 0.3666 | −0.0088 | 0.5066 | 0.064* | 0.50 |
C11 | −0.0392 (4) | 0.27807 (19) | 0.47918 (14) | 0.0315 (7) | |
C12 | 0.0860 (4) | 0.24050 (18) | 0.51161 (14) | 0.0314 (7) | |
H12 | 0.2025 | 0.2541 | 0.5096 | 0.038* | |
C13 | 0.0364 (5) | 0.18234 (19) | 0.54720 (15) | 0.0327 (8) | |
C14 | −0.1379 (5) | 0.1618 (2) | 0.55058 (17) | 0.0435 (9) | |
H14 | −0.1709 | 0.1232 | 0.5748 | 0.052* | |
C15 | −0.2609 (5) | 0.1991 (2) | 0.51761 (18) | 0.0484 (10) | |
H15 | −0.3775 | 0.1857 | 0.5195 | 0.058* | |
C16 | −0.2119 (5) | 0.2567 (2) | 0.48159 (17) | 0.0413 (9) | |
H16 | −0.2954 | 0.2811 | 0.4589 | 0.050* | |
C17 | 0.1685 (5) | 0.1425 (2) | 0.58238 (15) | 0.0353 (8) | |
C21 | 0.2835 (4) | 0.04487 (19) | 0.18495 (14) | 0.0307 (7) | |
C22 | 0.4074 (4) | 0.02018 (18) | 0.22551 (15) | 0.0320 (7) | |
H22 | 0.5235 | 0.0335 | 0.2211 | 0.038* | |
C23 | 0.3585 (5) | −0.02474 (19) | 0.27318 (15) | 0.0333 (8) | |
C24 | 0.1853 (5) | −0.0447 (2) | 0.27951 (17) | 0.0416 (9) | |
H24 | 0.1524 | −0.0745 | 0.3113 | 0.050* | |
C25 | 0.0623 (5) | −0.0205 (2) | 0.23904 (18) | 0.0472 (10) | |
H25 | −0.0534 | −0.0345 | 0.2431 | 0.057* | |
C26 | 0.1103 (5) | 0.0245 (2) | 0.19234 (16) | 0.0396 (9) | |
H26 | 0.0260 | 0.0414 | 0.1655 | 0.048* | |
C27 | 0.4911 (5) | −0.0517 (2) | 0.31641 (16) | 0.0369 (8) | |
C31 | 0.1308 (5) | 0.1701 (2) | 0.32930 (16) | 0.0361 (8) | |
C32 | 0.2564 (5) | 0.13725 (19) | 0.36535 (15) | 0.0354 (8) | |
H32 | 0.3733 | 0.1493 | 0.3611 | 0.043* | |
C33 | 0.2059 (5) | 0.08604 (19) | 0.40811 (16) | 0.0357 (8) | |
C34 | 0.0297 (5) | 0.0680 (2) | 0.41381 (18) | 0.0449 (9) | |
H34 | −0.0046 | 0.0341 | 0.4423 | 0.054* | |
C35 | −0.0926 (5) | 0.1002 (2) | 0.37735 (19) | 0.0507 (10) | |
H35 | −0.2094 | 0.0875 | 0.3808 | 0.061* | |
C36 | −0.0430 (5) | 0.1514 (2) | 0.33554 (18) | 0.0443 (9) | |
H36 | −0.1268 | 0.1735 | 0.3114 | 0.053* | |
C37 | 0.3357 (5) | 0.0502 (2) | 0.44754 (17) | 0.0403 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I11 | 0.02972 (12) | 0.04592 (15) | 0.04591 (14) | −0.00576 (10) | 0.00118 (10) | 0.00079 (11) |
I12 | 0.03793 (14) | 0.05514 (17) | 0.03978 (13) | 0.00256 (11) | −0.00776 (11) | 0.00523 (12) |
I21 | 0.02828 (12) | 0.05637 (17) | 0.04055 (13) | 0.00474 (11) | 0.00394 (10) | 0.00832 (11) |
I22 | 0.04183 (14) | 0.06285 (18) | 0.03435 (13) | −0.01505 (12) | −0.00812 (11) | 0.00167 (11) |
I31 | 0.03035 (13) | 0.05791 (17) | 0.04580 (14) | −0.00640 (11) | 0.00149 (11) | −0.00333 (12) |
I32 | 0.03820 (15) | 0.0703 (2) | 0.04614 (15) | 0.01008 (13) | −0.00749 (12) | −0.00136 (13) |
As1 | 0.03224 (19) | 0.03094 (19) | 0.03433 (18) | 0.00017 (15) | −0.00066 (15) | 0.00144 (15) |
As2 | 0.02696 (17) | 0.03394 (19) | 0.02969 (17) | 0.00064 (14) | −0.00093 (14) | 0.00141 (15) |
As3 | 0.0348 (2) | 0.0358 (2) | 0.0390 (2) | −0.00053 (16) | 0.00310 (16) | −0.00025 (16) |
O11 | 0.0323 (14) | 0.0619 (19) | 0.0553 (17) | −0.0036 (13) | −0.0003 (12) | 0.0238 (14) |
O12 | 0.0418 (16) | 0.065 (2) | 0.0554 (17) | −0.0057 (14) | −0.0014 (13) | 0.0323 (15) |
O21 | 0.0363 (15) | 0.079 (2) | 0.0476 (16) | −0.0034 (14) | −0.0006 (12) | 0.0275 (15) |
O22 | 0.0438 (16) | 0.071 (2) | 0.0540 (17) | 0.0059 (15) | 0.0102 (13) | 0.0331 (16) |
O31 | 0.0388 (16) | 0.066 (2) | 0.0578 (17) | −0.0040 (14) | 0.0036 (13) | 0.0210 (15) |
O32 | 0.0490 (17) | 0.0582 (19) | 0.0524 (16) | −0.0056 (14) | 0.0061 (13) | 0.0208 (14) |
C11 | 0.0316 (18) | 0.0342 (19) | 0.0289 (17) | −0.0016 (15) | 0.0013 (14) | 0.0022 (14) |
C12 | 0.0281 (18) | 0.0329 (19) | 0.0331 (17) | −0.0043 (14) | 0.0024 (14) | 0.0015 (15) |
C13 | 0.0338 (19) | 0.0338 (19) | 0.0304 (17) | −0.0024 (15) | 0.0016 (14) | 0.0011 (15) |
C14 | 0.040 (2) | 0.047 (2) | 0.043 (2) | −0.0103 (18) | 0.0029 (17) | 0.0117 (18) |
C15 | 0.031 (2) | 0.061 (3) | 0.053 (2) | −0.0103 (19) | 0.0037 (18) | 0.010 (2) |
C16 | 0.0298 (19) | 0.050 (2) | 0.044 (2) | −0.0019 (17) | −0.0021 (16) | 0.0055 (18) |
C17 | 0.038 (2) | 0.037 (2) | 0.0304 (17) | −0.0025 (16) | 0.0024 (15) | 0.0036 (16) |
C21 | 0.0290 (17) | 0.0362 (19) | 0.0269 (16) | −0.0007 (14) | 0.0031 (14) | 0.0020 (14) |
C22 | 0.0300 (18) | 0.0319 (19) | 0.0339 (18) | −0.0017 (14) | 0.0038 (14) | 0.0033 (15) |
C23 | 0.0350 (19) | 0.0335 (19) | 0.0313 (18) | 0.0014 (15) | 0.0064 (15) | 0.0009 (15) |
C24 | 0.038 (2) | 0.047 (2) | 0.040 (2) | −0.0068 (17) | 0.0105 (17) | 0.0086 (18) |
C25 | 0.0277 (19) | 0.067 (3) | 0.047 (2) | −0.0111 (18) | 0.0078 (17) | 0.007 (2) |
C26 | 0.0302 (19) | 0.055 (2) | 0.0338 (19) | −0.0005 (17) | −0.0011 (15) | 0.0061 (17) |
C27 | 0.038 (2) | 0.037 (2) | 0.0354 (19) | 0.0022 (16) | 0.0053 (16) | 0.0063 (16) |
C31 | 0.0347 (19) | 0.035 (2) | 0.0387 (19) | −0.0021 (15) | 0.0036 (16) | −0.0005 (16) |
C32 | 0.0318 (19) | 0.037 (2) | 0.0374 (19) | −0.0057 (15) | 0.0059 (15) | −0.0042 (16) |
C33 | 0.037 (2) | 0.034 (2) | 0.0361 (19) | −0.0045 (16) | 0.0060 (15) | −0.0031 (15) |
C34 | 0.042 (2) | 0.046 (2) | 0.046 (2) | −0.0124 (18) | 0.0102 (18) | 0.0020 (18) |
C35 | 0.029 (2) | 0.063 (3) | 0.060 (3) | −0.0074 (19) | 0.0067 (19) | 0.004 (2) |
C36 | 0.034 (2) | 0.051 (2) | 0.048 (2) | −0.0041 (17) | −0.0012 (17) | 0.0028 (19) |
C37 | 0.045 (2) | 0.035 (2) | 0.041 (2) | −0.0069 (17) | 0.0068 (17) | 0.0002 (17) |
I11—As1 | 2.5911 (4) | C14—C15 | 1.378 (5) |
I12—As1 | 2.5939 (4) | C14—H14 | 0.9300 |
I21—As2 | 2.5934 (4) | C15—C16 | 1.387 (5) |
I22—As2 | 2.5960 (4) | C15—H15 | 0.9300 |
I31—As3 | 2.5938 (5) | C16—H16 | 0.9300 |
I32—As3 | 2.6058 (5) | C21—C22 | 1.383 (5) |
As1—C11 | 1.977 (3) | C21—C26 | 1.393 (5) |
As2—C21 | 1.972 (3) | C22—C23 | 1.396 (5) |
As3—C31 | 1.978 (4) | C22—H22 | 0.9300 |
O11—C17 | 1.277 (4) | C23—C24 | 1.388 (5) |
O11—H11 | 0.8200 | C23—C27 | 1.480 (5) |
O12—C17 | 1.255 (4) | C24—C25 | 1.373 (5) |
O12—H11A | 0.8200 | C24—H24 | 0.9300 |
O21—C27 | 1.271 (4) | C25—C26 | 1.379 (5) |
O21—H21 | 0.8200 | C25—H25 | 0.9300 |
O22—C27 | 1.257 (4) | C26—H26 | 0.9300 |
O22—H21A | 0.8200 | C31—C36 | 1.386 (5) |
O31—C37 | 1.275 (4) | C31—C32 | 1.389 (5) |
O31—H31 | 0.8200 | C32—C33 | 1.397 (5) |
O32—C37 | 1.262 (4) | C32—H32 | 0.9300 |
O32—H31A | 0.8200 | C33—C34 | 1.400 (5) |
C11—C16 | 1.385 (5) | C33—C37 | 1.479 (5) |
C11—C12 | 1.386 (5) | C34—C35 | 1.372 (6) |
C12—C13 | 1.391 (5) | C34—H34 | 0.9300 |
C12—H12 | 0.9300 | C35—C36 | 1.381 (6) |
C13—C14 | 1.394 (5) | C35—H35 | 0.9300 |
C13—C17 | 1.475 (5) | C36—H36 | 0.9300 |
C11—As1—I11 | 99.57 (10) | C21—C22—C23 | 120.0 (3) |
C11—As1—I12 | 97.57 (10) | C21—C22—H22 | 120.0 |
I11—As1—I12 | 102.621 (15) | C23—C22—H22 | 120.0 |
C21—As2—I21 | 99.54 (10) | C24—C23—C22 | 119.8 (3) |
C21—As2—I22 | 96.84 (10) | C24—C23—C27 | 120.1 (3) |
I21—As2—I22 | 100.703 (15) | C22—C23—C27 | 120.2 (3) |
C31—As3—I31 | 101.06 (11) | C25—C24—C23 | 120.2 (3) |
C31—As3—I32 | 98.48 (11) | C25—C24—H24 | 119.9 |
I31—As3—I32 | 102.632 (15) | C23—C24—H24 | 119.9 |
C17—O11—H11 | 109.5 | C24—C25—C26 | 120.0 (3) |
C17—O12—H11A | 109.5 | C24—C25—H25 | 120.0 |
C27—O21—H21 | 109.5 | C26—C25—H25 | 120.0 |
C27—O22—H21A | 109.5 | C25—C26—C21 | 120.7 (3) |
C37—O31—H31 | 109.5 | C25—C26—H26 | 119.7 |
C37—O32—H31A | 109.5 | C21—C26—H26 | 119.7 |
C16—C11—C12 | 119.8 (3) | O22—C27—O21 | 123.5 (3) |
C16—C11—As1 | 118.7 (3) | O22—C27—C23 | 118.4 (3) |
C12—C11—As1 | 120.6 (3) | O21—C27—C23 | 118.1 (3) |
C11—C12—C13 | 119.6 (3) | C36—C31—C32 | 119.9 (3) |
C11—C12—H12 | 120.2 | C36—C31—As3 | 116.7 (3) |
C13—C12—H12 | 120.2 | C32—C31—As3 | 122.6 (3) |
C12—C13—C14 | 120.6 (3) | C31—C32—C33 | 119.6 (3) |
C12—C13—C17 | 120.0 (3) | C31—C32—H32 | 120.2 |
C14—C13—C17 | 119.5 (3) | C33—C32—H32 | 120.2 |
C15—C14—C13 | 119.3 (3) | C32—C33—C34 | 119.7 (3) |
C15—C14—H14 | 120.4 | C32—C33—C37 | 121.1 (3) |
C13—C14—H14 | 120.4 | C34—C33—C37 | 119.2 (3) |
C14—C15—C16 | 120.4 (4) | C35—C34—C33 | 120.1 (4) |
C14—C15—H15 | 119.8 | C35—C34—H34 | 120.0 |
C16—C15—H15 | 119.8 | C33—C34—H34 | 120.0 |
C11—C16—C15 | 120.4 (4) | C34—C35—C36 | 120.3 (4) |
C11—C16—H16 | 119.8 | C34—C35—H35 | 119.9 |
C15—C16—H16 | 119.8 | C36—C35—H35 | 119.9 |
O12—C17—O11 | 123.1 (3) | C35—C36—C31 | 120.5 (4) |
O12—C17—C13 | 119.3 (3) | C35—C36—H36 | 119.7 |
O11—C17—C13 | 117.6 (3) | C31—C36—H36 | 119.7 |
C22—C21—C26 | 119.3 (3) | O32—C37—O31 | 122.9 (4) |
C22—C21—As2 | 121.6 (2) | O32—C37—C33 | 118.8 (3) |
C26—C21—As2 | 118.6 (3) | O31—C37—C33 | 118.3 (3) |
I11—As1—C11—C16 | −152.1 (3) | C27—C23—C24—C25 | −179.2 (4) |
I12—As1—C11—C16 | −47.9 (3) | C23—C24—C25—C26 | −0.8 (6) |
I11—As1—C11—C12 | 38.7 (3) | C24—C25—C26—C21 | 1.2 (6) |
I12—As1—C11—C12 | 142.9 (3) | C22—C21—C26—C25 | −0.8 (6) |
C16—C11—C12—C13 | −1.1 (5) | As2—C21—C26—C25 | −172.5 (3) |
As1—C11—C12—C13 | 168.0 (3) | C24—C23—C27—O22 | −6.3 (5) |
C11—C12—C13—C14 | −0.2 (5) | C22—C23—C27—O22 | 174.4 (3) |
C11—C12—C13—C17 | −179.4 (3) | C24—C23—C27—O21 | 174.2 (4) |
C12—C13—C14—C15 | 0.8 (6) | C22—C23—C27—O21 | −5.1 (5) |
C17—C13—C14—C15 | −180.0 (4) | I31—As3—C31—C36 | −154.1 (3) |
C13—C14—C15—C16 | −0.2 (6) | I32—As3—C31—C36 | −49.3 (3) |
C12—C11—C16—C15 | 1.8 (6) | I31—As3—C31—C32 | 36.3 (3) |
As1—C11—C16—C15 | −167.5 (3) | I32—As3—C31—C32 | 141.1 (3) |
C14—C15—C16—C11 | −1.1 (6) | C36—C31—C32—C33 | −0.6 (5) |
C12—C13—C17—O12 | 168.3 (3) | As3—C31—C32—C33 | 168.6 (3) |
C14—C13—C17—O12 | −10.9 (5) | C31—C32—C33—C34 | 0.5 (5) |
C12—C13—C17—O11 | −11.9 (5) | C31—C32—C33—C37 | −179.7 (3) |
C14—C13—C17—O11 | 168.9 (3) | C32—C33—C34—C35 | 0.3 (6) |
I21—As2—C21—C22 | 38.0 (3) | C37—C33—C34—C35 | −179.5 (4) |
I22—As2—C21—C22 | 140.1 (3) | C33—C34—C35—C36 | −1.0 (6) |
I21—As2—C21—C26 | −150.5 (3) | C34—C35—C36—C31 | 0.9 (6) |
I22—As2—C21—C26 | −48.3 (3) | C32—C31—C36—C35 | 0.0 (6) |
C26—C21—C22—C23 | 0.1 (5) | As3—C31—C36—C35 | −170.0 (3) |
As2—C21—C22—C23 | 171.6 (3) | C32—C33—C37—O32 | 175.9 (3) |
C21—C22—C23—C24 | 0.2 (5) | C34—C33—C37—O32 | −4.3 (5) |
C21—C22—C23—C27 | 179.5 (3) | C32—C33—C37—O31 | −4.0 (5) |
C22—C23—C24—C25 | 0.1 (6) | C34—C33—C37—O31 | 175.8 (4) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [As(C7H5O2)I2] | [As(C7H5O2)I2] |
Mr | 449.83 | 449.83 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 4.8992 (2), 8.4434 (5), 13.6616 (9) | 7.6751 (5), 18.6142 (12), 22.0692 (12) |
α, β, γ (°) | 107.148 (2), 91.569 (2), 96.376 (2) | 90, 90.206 (2), 90 |
V (Å3) | 535.59 (5) | 3152.9 (3) |
Z | 2 | 12 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 8.90 | 9.07 |
Crystal size (mm) | 0.35 × 0.20 × 0.18 | 0.18 × 0.15 × 0.06 |
Data collection | ||
Diffractometer | Bruker Nonius X8 APEXII CCD area-detector diffractometer | Bruker Nonius X8 APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.147, 0.297 | 0.292, 0.612 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3909, 2144, 1859 | 23397, 5996, 5277 |
Rint | 0.027 | 0.033 |
(sin θ/λ)max (Å−1) | 0.625 | 0.610 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.109, 1.07 | 0.021, 0.046, 1.04 |
No. of reflections | 2144 | 5996 |
No. of parameters | 110 | 325 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.87, −1.67 | 0.88, −0.78 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008), DIAMOND (Bergerhoff et al., 1996).
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Organoarsenic halogenides are easily accessible AsIII compounds of the type RnAsHal3-n (n = 1, 2) and are widely used for the preparation of various organoarsenic derivatives (Gross et al., 1997), including arsa-heterocycles (Matuska et al., 2010; Avtomonov et al., 1997), diarsenes (Twamley et al., 1999), organometallic complexes such as arsinidenes (Huttner & Evertz, 1986; Jutzi & Kroos, 1990) and cluster compounds (Song et al., 2001; Deck & Vahrenkamp, 1991; Deck et al., 1987). Iodine derivatives, with the I atoms as good leaving groups, have been shown to be particularly good reagents for introducing the RAs group into cluster complexes as a result of nucleophilic substitution reactions (Konchenko et al., 1999; Pushkarevsky et al., 2006; Winter et al., 1983; Ilyin et al., 2012). There are only three known structures of RAsI2 compounds, and in all three cases the As atom has additional contacts with the donor atoms of neighbouring groups or molecules. Thus, in the case of CH3AsI2, the As atom contacts the two I atoms of a neighbouring molecule, which determines the stacked arrangement of the molecules (Camerman & Trotter, 1963). In the other two structures, which have bulky substituents (R = pentamethyl or tetraisopropylcyclopentadienyl), the As atom has additional contacts with a double bond of the cyclopentadienyl (Cp) ring of the same molecule (Megges et al., 1996; Avtomonov et al., 1996). As a consequence, the As atom, hidden by the bulky substituent, has no additional contacts with the other molecules.
The structures of 4-(diiodoarsanyl)benzoic acid, (I) (Fig. 1), and 3-(diiodoarsanyl)benzoic acid, (II) (Fig. 2), have asymmetric units with one and three crystallographically independent molecules, respectively. The molecules of both compounds are dimerized by hydrogen bonding between the carboxylic acid groups. The acidic H atom in (II) is disordered over two positions with 0.5 occupancy. The dimer packings in (I) and (II) are different. The planar molecules in (I) are located parallel to each other to form infinite stacks (Fig. 3). Interestingly, the environment of the As atoms is completed by the arene ring of a neighbouring molecule [3.469 (5) Å], which resembles the known interactions in the molecules of Cp*-substituted (Cp* is pentamethylcyclopentadienyl) diiodoarsenides (Avtomonov et al., 1996). The aromatic rings are shifted apart, so there is no π–π stacking between them in (I). In contrast, the π systems of the aryl fragments in (II) are most probably bound by π–π interactions [the distances between the centres of the aryl rings are 3.967 (7) and 3.902 (7) Å, with the nearest rings almost fully overlapped]. Also in contrast with (I), each As atom is positioned close to the two I atoms of a neighbouring molecule, thus forming two contacts of 3.56 (9) Å (cf. 3.605 and 3.658 Å for CH3AsI2; Camerman & Trotter, 1963), noticeably shorter than the sum of the van der Waals radii of the elements (3.98 Å; Bondi, 1964; Fig. 4). Being sufficiently large, the I atoms make it impossible for the arene cycles to remain parallel, analogous to the structure of (I), so the rings are skewed with respect to the line of hydrogen bonding (Fig. 4). Such bending makes it possible for only three molecules to pack on top of each other, so infinite packing analogous to (I) is not possible. Consequently, the three dimeric units are translated to form bundles of three ribbons of different bending (Fig. 5). The bundles themselves form a parquet-like layered packing parallel to (101).
The different –AsI2 group position relative to neighbouring molecules causes the two packing modes. Consequently, the orientation of this group with respect to the arene ring is different: the I1—As1—C5—C4 torsion angle is 0.0 (5)° in (I), and the equivalent angles are 38.7 (3), 38.0 (3) and 36.3 (3)° in (II), while the I1—As1—I2 torsion angle for both compounds has nearly the same value [101.6 (11)°]. The average As—C bond lengths do not seem to depend on the position of the carboxylic acid group, viz. 1.977 (5) Å for (I) and 1.976 (5) Å for (II).
As a consequence of (II) having more evident interactions between the molecules in the crystal packing, namely π–π and As···I versus only As···C6 interactions in the packing of (I), the packing of isomer (II) is slightly denser than that of (I) (Dcalc = 2.843 and 2.789 Mg m-3, respectively).