Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102005930/bm1492sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102005930/bm1492Isup2.hkl |
CCDC reference: 188612
A dichloromethane solution of dppmSe2 and diiodine in a 1:2 molar ratio was stirred at room temperature for 3 h. Orange single crystals of (I) were obtained after exposing a small portion of the reaction mixture in an NMR tube to moist air for one week at room temperature with slow evaporation of the solvent. The formulation of the product was satisfactorily established by 31P NMR spectra and by mass spectrometry (FAB, o-nitrobenzylamine matrix). 31P NMR (δ, p.p.m., CH2Cl2/C6D6 solution): 42.6; mass spectrometry: m/z (%) = 417 {30, [Ph2P(O)CH2P(OH)Ph2]+}, appeared when a partially hydrolysed sample from dppmSe2I4 (Boraei et al., 2000) was studied by FAB-MS.
All H atoms except H1 and H2 were refined using a riding model starting from calculated positions, with Uiso(H) = 1.2 Uiso(C) and effective C—H distances of 0.99 Å for methylene protons and 0.95 Å for aromatic H atoms. H atoms H1 and H2 were found and refined satisfactorily on special positions (inversion centres) with no indication of disorder, although X-ray methods alone cannot determine the H-atom positions with absolute certainty. The maximum residual electron density was 0.94 Å from I3 and may indicate a minor twinning component.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C25H22O2P2·H+·I3− | Z = 2 |
Mr = 798.07 | F(000) = 756 |
Triclinic, P1 | Dx = 1.914 Mg m−3 |
a = 10.1284 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.8155 (10) Å | Cell parameters from 10022 reflections |
c = 12.5299 (10) Å | θ = 3–30° |
α = 110.852 (2)° | µ = 3.52 mm−1 |
β = 93.855 (2)° | T = 143 K |
γ = 96.043 (2)° | Rectangular prism, orange |
V = 1384.61 (19) Å3 | 0.37 × 0.20 × 0.15 mm |
Bruker SMART1000 CCD area-detector diffractometer | 8330 independent reflections |
Radiation source: normal-focus sealed tube | 6921 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30.6°, θmin = 1.8° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −16→16 |
Tmin = 0.384, Tmax = 0.590 | l = −17→17 |
16933 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)] = 0.035 | Hydrogen site location: mixed |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.832P] where P = (Fo2 + 2Fc2)/3 |
8330 reflections | (Δ/σ)max = 0.001 |
294 parameters | Δρmax = 2.65 e Å−3 |
204 restraints | Δρmin = −1.07 e Å−3 |
C25H22O2P2·H+·I3− | γ = 96.043 (2)° |
Mr = 798.07 | V = 1384.61 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.1284 (8) Å | Mo Kα radiation |
b = 11.8155 (10) Å | µ = 3.52 mm−1 |
c = 12.5299 (10) Å | T = 143 K |
α = 110.852 (2)° | 0.37 × 0.20 × 0.15 mm |
β = 93.855 (2)° |
Bruker SMART1000 CCD area-detector diffractometer | 8330 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 6921 reflections with I > 2σ(I) |
Tmin = 0.384, Tmax = 0.590 | Rint = 0.033 |
16933 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 204 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 2.65 e Å−3 |
8330 reflections | Δρmin = −1.07 e Å−3 |
294 parameters |
Refinement. Residual electron density at positions arithmetically related to those of the I atoms may indicate a minor twinning component. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.0000 | 0.0000 | 0.5000 | 0.02830 (7) | |
I2 | 0.13856 (2) | 0.22713 (2) | 0.497385 (18) | 0.03487 (6) | |
I3 | 0.50336 (2) | 0.49212 (2) | 0.72927 (2) | 0.03748 (7) | |
I4 | 0.5000 | 0.5000 | 0.5000 | 0.03006 (7) | |
P1 | 0.40501 (8) | 0.07929 (7) | 0.18627 (6) | 0.02225 (14) | |
P2 | 0.15790 (7) | 0.17539 (6) | 0.11313 (6) | 0.02170 (13) | |
O1 | 0.0836 (2) | 0.04687 (19) | 0.08028 (19) | 0.0290 (4) | |
H1 | 0.0000 | 0.0000 | 0.0000 | 0.019 (11)* | |
O2 | 0.4617 (3) | 0.0778 (2) | 0.0767 (2) | 0.0370 (5) | |
H2 | 0.5000 | 0.0000 | 0.0000 | 0.025 (12)* | |
C1 | 0.2931 (3) | 0.1927 (2) | 0.2197 (2) | 0.0219 (5) | |
H1A | 0.2546 | 0.1944 | 0.2908 | 0.026* | |
H1B | 0.3466 | 0.2736 | 0.2373 | 0.026* | |
C2 | 0.5321 (3) | 0.1316 (3) | 0.3055 (3) | 0.0253 (5) | |
C3 | 0.5080 (3) | 0.1184 (3) | 0.4090 (3) | 0.0316 (6) | |
H3 | 0.4240 | 0.0794 | 0.4165 | 0.038* | |
C4 | 0.6079 (4) | 0.1627 (4) | 0.5013 (3) | 0.0414 (8) | |
H4 | 0.5917 | 0.1549 | 0.5724 | 0.050* | |
C5 | 0.7302 (4) | 0.2178 (3) | 0.4901 (4) | 0.0428 (8) | |
H5 | 0.7983 | 0.2474 | 0.5533 | 0.051* | |
C6 | 0.7544 (4) | 0.2303 (4) | 0.3871 (4) | 0.0455 (9) | |
H6 | 0.8394 | 0.2675 | 0.3796 | 0.055* | |
C7 | 0.6555 (3) | 0.1889 (3) | 0.2950 (3) | 0.0372 (7) | |
H7 | 0.6716 | 0.1993 | 0.2251 | 0.045* | |
C8 | 0.3230 (3) | −0.0671 (3) | 0.1764 (2) | 0.0234 (5) | |
C9 | 0.3870 (3) | −0.1687 (3) | 0.1230 (3) | 0.0294 (6) | |
H9 | 0.4667 | −0.1597 | 0.0891 | 0.035* | |
C10 | 0.3324 (4) | −0.2829 (3) | 0.1202 (3) | 0.0355 (7) | |
H10 | 0.3761 | −0.3520 | 0.0852 | 0.043* | |
C11 | 0.2160 (4) | −0.2972 (3) | 0.1673 (3) | 0.0367 (7) | |
H11 | 0.1792 | −0.3760 | 0.1638 | 0.044* | |
C12 | 0.1521 (4) | −0.1965 (3) | 0.2201 (3) | 0.0354 (7) | |
H12 | 0.0713 | −0.2065 | 0.2522 | 0.042* | |
C13 | 0.2067 (3) | −0.0813 (3) | 0.2259 (3) | 0.0294 (6) | |
H13 | 0.1645 | −0.0120 | 0.2637 | 0.035* | |
C14 | 0.2130 (3) | 0.1988 (3) | −0.0108 (2) | 0.0252 (5) | |
C15 | 0.2505 (4) | 0.3176 (3) | −0.0071 (3) | 0.0333 (7) | |
H15 | 0.2491 | 0.3858 | 0.0617 | 0.040* | |
C16 | 0.2899 (4) | 0.3352 (4) | −0.1050 (3) | 0.0409 (8) | |
H16 | 0.3166 | 0.4156 | −0.1027 | 0.049* | |
C17 | 0.2902 (4) | 0.2359 (4) | −0.2055 (3) | 0.0359 (7) | |
H17 | 0.3177 | 0.2484 | −0.2719 | 0.043* | |
C18 | 0.2510 (3) | 0.1185 (3) | −0.2101 (3) | 0.0328 (6) | |
H18 | 0.2493 | 0.0510 | −0.2800 | 0.039* | |
C19 | 0.2136 (3) | 0.0991 (3) | −0.1118 (3) | 0.0294 (6) | |
H19 | 0.1889 | 0.0184 | −0.1142 | 0.035* | |
C20 | 0.0561 (3) | 0.2913 (3) | 0.1765 (3) | 0.0244 (5) | |
C21 | 0.0986 (3) | 0.3900 (3) | 0.2791 (3) | 0.0291 (6) | |
H21 | 0.1839 | 0.3973 | 0.3193 | 0.035* | |
C22 | 0.0138 (3) | 0.4780 (3) | 0.3219 (3) | 0.0352 (7) | |
H22 | 0.0423 | 0.5465 | 0.3907 | 0.042* | |
C23 | −0.1110 (4) | 0.4657 (3) | 0.2644 (3) | 0.0379 (7) | |
H23 | −0.1687 | 0.5249 | 0.2947 | 0.045* | |
C24 | −0.1526 (4) | 0.3674 (3) | 0.1629 (3) | 0.0398 (8) | |
H24 | −0.2389 | 0.3595 | 0.1241 | 0.048* | |
C25 | −0.0697 (3) | 0.2811 (3) | 0.1177 (3) | 0.0331 (7) | |
H25 | −0.0978 | 0.2150 | 0.0470 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.03104 (14) | 0.03545 (14) | 0.02040 (12) | 0.01320 (11) | 0.00553 (9) | 0.00975 (10) |
I2 | 0.04303 (12) | 0.03533 (11) | 0.02737 (11) | 0.00909 (9) | 0.01168 (8) | 0.01046 (8) |
I3 | 0.03486 (12) | 0.03891 (12) | 0.04313 (13) | −0.00386 (9) | 0.00189 (9) | 0.02333 (10) |
I4 | 0.02682 (13) | 0.02807 (13) | 0.03957 (16) | 0.00299 (10) | 0.00316 (11) | 0.01786 (12) |
P1 | 0.0275 (3) | 0.0205 (3) | 0.0213 (3) | 0.0066 (3) | 0.0077 (3) | 0.0089 (3) |
P2 | 0.0248 (3) | 0.0201 (3) | 0.0202 (3) | 0.0023 (3) | 0.0020 (2) | 0.0076 (3) |
O1 | 0.0339 (11) | 0.0223 (9) | 0.0281 (11) | −0.0028 (8) | −0.0027 (8) | 0.0089 (8) |
O2 | 0.0551 (15) | 0.0314 (11) | 0.0303 (12) | 0.0133 (11) | 0.0221 (11) | 0.0132 (10) |
C1 | 0.0241 (12) | 0.0212 (12) | 0.0211 (12) | 0.0035 (10) | 0.0020 (10) | 0.0083 (10) |
C2 | 0.0235 (13) | 0.0229 (12) | 0.0320 (14) | 0.0076 (10) | 0.0062 (11) | 0.0111 (11) |
C3 | 0.0302 (15) | 0.0345 (15) | 0.0317 (16) | 0.0026 (12) | 0.0020 (12) | 0.0147 (13) |
C4 | 0.0444 (19) | 0.0406 (18) | 0.0402 (19) | 0.0016 (15) | −0.0092 (15) | 0.0197 (16) |
C5 | 0.0357 (17) | 0.0338 (16) | 0.056 (2) | 0.0005 (14) | −0.0148 (16) | 0.0173 (16) |
C6 | 0.0275 (16) | 0.0422 (19) | 0.068 (3) | −0.0019 (14) | −0.0042 (16) | 0.0255 (19) |
C7 | 0.0287 (15) | 0.0390 (17) | 0.050 (2) | 0.0045 (13) | 0.0086 (14) | 0.0234 (16) |
C8 | 0.0295 (13) | 0.0204 (12) | 0.0195 (12) | 0.0049 (10) | 0.0008 (10) | 0.0063 (10) |
C9 | 0.0305 (15) | 0.0249 (13) | 0.0317 (15) | 0.0080 (11) | −0.0001 (12) | 0.0084 (12) |
C10 | 0.0430 (18) | 0.0214 (13) | 0.0423 (18) | 0.0108 (13) | 0.0025 (14) | 0.0105 (13) |
C11 | 0.048 (2) | 0.0221 (13) | 0.0412 (18) | 0.0016 (13) | 0.0008 (15) | 0.0149 (13) |
C12 | 0.0446 (19) | 0.0297 (15) | 0.0357 (17) | 0.0035 (13) | 0.0117 (14) | 0.0157 (13) |
C13 | 0.0404 (16) | 0.0254 (13) | 0.0244 (14) | 0.0082 (12) | 0.0100 (12) | 0.0095 (11) |
C14 | 0.0287 (14) | 0.0268 (13) | 0.0218 (13) | 0.0047 (11) | 0.0021 (10) | 0.0109 (11) |
C15 | 0.0461 (19) | 0.0270 (14) | 0.0283 (15) | 0.0036 (13) | 0.0057 (13) | 0.0120 (12) |
C16 | 0.055 (2) | 0.0380 (17) | 0.0372 (18) | 0.0037 (16) | 0.0101 (16) | 0.0220 (15) |
C17 | 0.0398 (17) | 0.052 (2) | 0.0253 (14) | 0.0088 (15) | 0.0058 (12) | 0.0239 (14) |
C18 | 0.0296 (15) | 0.0453 (18) | 0.0221 (13) | 0.0092 (13) | 0.0034 (11) | 0.0096 (13) |
C19 | 0.0297 (14) | 0.0303 (14) | 0.0279 (14) | 0.0030 (12) | 0.0038 (11) | 0.0105 (12) |
C20 | 0.0250 (13) | 0.0245 (12) | 0.0261 (13) | 0.0053 (10) | 0.0047 (10) | 0.0112 (11) |
C21 | 0.0274 (14) | 0.0273 (14) | 0.0307 (15) | 0.0046 (11) | 0.0013 (11) | 0.0084 (12) |
C22 | 0.0332 (16) | 0.0291 (15) | 0.0385 (17) | 0.0076 (13) | 0.0053 (13) | 0.0054 (13) |
C23 | 0.0344 (17) | 0.0340 (16) | 0.0433 (19) | 0.0144 (14) | 0.0054 (14) | 0.0090 (14) |
C24 | 0.0337 (17) | 0.0421 (19) | 0.0385 (18) | 0.0099 (14) | −0.0047 (14) | 0.0087 (15) |
C25 | 0.0324 (15) | 0.0370 (16) | 0.0283 (15) | 0.0088 (13) | −0.0009 (12) | 0.0096 (13) |
I1—I2 | 2.9066 (3) | C10—C11 | 1.375 (5) |
I3—I4 | 2.9052 (3) | C10—H10 | 0.9500 |
P1—O2 | 1.518 (2) | C11—C12 | 1.390 (5) |
P1—C2 | 1.785 (3) | C11—H11 | 0.9500 |
P1—C8 | 1.797 (3) | C12—C13 | 1.390 (4) |
P1—C1 | 1.801 (3) | C12—H12 | 0.9500 |
P2—O1 | 1.521 (2) | C13—H13 | 0.9500 |
P2—C14 | 1.786 (3) | C14—C19 | 1.390 (4) |
P2—C1 | 1.789 (3) | C14—C15 | 1.399 (4) |
P2—C20 | 1.789 (3) | C15—C16 | 1.391 (5) |
O1—H1 | 1.194 (2) | C15—H15 | 0.9500 |
O2—H2 | 1.190 (2) | C16—C17 | 1.383 (5) |
C1—H1A | 0.9900 | C16—H16 | 0.9500 |
C1—H1B | 0.9900 | C17—C18 | 1.381 (5) |
C2—C3 | 1.395 (4) | C17—H17 | 0.9500 |
C2—C7 | 1.395 (4) | C18—C19 | 1.399 (4) |
C3—C4 | 1.391 (5) | C18—H18 | 0.9500 |
C3—H3 | 0.9500 | C19—H19 | 0.9500 |
C4—C5 | 1.378 (6) | C20—C21 | 1.396 (4) |
C4—H4 | 0.9500 | C20—C25 | 1.400 (4) |
C5—C6 | 1.385 (6) | C21—C22 | 1.400 (4) |
C5—H5 | 0.9500 | C21—H21 | 0.9500 |
C6—C7 | 1.383 (6) | C22—C23 | 1.378 (5) |
C6—H6 | 0.9500 | C22—H22 | 0.9500 |
C7—H7 | 0.9500 | C23—C24 | 1.385 (5) |
C8—C13 | 1.389 (4) | C23—H23 | 0.9500 |
C8—C9 | 1.399 (4) | C24—C25 | 1.378 (5) |
C9—C10 | 1.391 (4) | C24—H24 | 0.9500 |
C9—H9 | 0.9500 | C25—H25 | 0.9500 |
I2i—I1—I2 | 180 | C11—C10—H10 | 119.5 |
I3ii—I4—I3 | 180 | C9—C10—H10 | 119.5 |
O2—P1—C2 | 111.33 (15) | C10—C11—C12 | 120.1 (3) |
O2—P1—C8 | 113.60 (14) | C10—C11—H11 | 120.0 |
C2—P1—C8 | 108.01 (13) | C12—C11—H11 | 120.0 |
O2—P1—C1 | 106.93 (13) | C11—C12—C13 | 119.8 (3) |
C2—P1—C1 | 105.14 (13) | C11—C12—H12 | 120.1 |
C8—P1—C1 | 111.53 (13) | C13—C12—H12 | 120.1 |
O1—P2—C14 | 110.52 (13) | C8—C13—C12 | 120.1 (3) |
O1—P2—C1 | 107.08 (13) | C8—C13—H13 | 119.9 |
C14—P2—C1 | 112.64 (13) | C12—C13—H13 | 119.9 |
O1—P2—C20 | 112.58 (14) | C19—C14—C15 | 120.2 (3) |
C14—P2—C20 | 107.07 (14) | C19—C14—P2 | 119.8 (2) |
C1—P2—C20 | 106.98 (13) | C15—C14—P2 | 119.9 (2) |
P2—O1—H1 | 123.93 (17) | C16—C15—C14 | 119.5 (3) |
P1—O2—H2 | 133.03 (19) | C16—C15—H15 | 120.2 |
P2—C1—P1 | 117.57 (15) | C14—C15—H15 | 120.2 |
P2—C1—H1A | 107.9 | C17—C16—C15 | 120.1 (3) |
P1—C1—H1A | 107.9 | C17—C16—H16 | 119.9 |
P2—C1—H1B | 107.9 | C15—C16—H16 | 119.9 |
P1—C1—H1B | 107.9 | C18—C17—C16 | 120.5 (3) |
H1A—C1—H1B | 107.2 | C18—C17—H17 | 119.7 |
C3—C2—C7 | 120.0 (3) | C16—C17—H17 | 119.7 |
C3—C2—P1 | 120.8 (2) | C17—C18—C19 | 120.0 (3) |
C7—C2—P1 | 119.1 (3) | C17—C18—H18 | 120.0 |
C4—C3—C2 | 119.5 (3) | C19—C18—H18 | 120.0 |
C4—C3—H3 | 120.3 | C14—C19—C18 | 119.5 (3) |
C2—C3—H3 | 120.3 | C14—C19—H19 | 120.2 |
C5—C4—C3 | 120.3 (4) | C18—C19—H19 | 120.2 |
C5—C4—H4 | 119.9 | C21—C20—C25 | 120.2 (3) |
C3—C4—H4 | 119.9 | C21—C20—P2 | 122.7 (2) |
C4—C5—C6 | 120.3 (3) | C25—C20—P2 | 117.2 (2) |
C4—C5—H5 | 119.9 | C20—C21—C22 | 119.1 (3) |
C6—C5—H5 | 119.9 | C20—C21—H21 | 120.4 |
C7—C6—C5 | 120.3 (3) | C22—C21—H21 | 120.4 |
C7—C6—H6 | 119.8 | C23—C22—C21 | 120.2 (3) |
C5—C6—H6 | 119.8 | C23—C22—H22 | 119.9 |
C6—C7—C2 | 119.6 (4) | C21—C22—H22 | 119.9 |
C6—C7—H7 | 120.2 | C22—C23—C24 | 120.4 (3) |
C2—C7—H7 | 120.2 | C22—C23—H23 | 119.8 |
C13—C8—C9 | 120.0 (3) | C24—C23—H23 | 119.8 |
C13—C8—P1 | 123.0 (2) | C25—C24—C23 | 120.5 (3) |
C9—C8—P1 | 116.8 (2) | C25—C24—H24 | 119.8 |
C10—C9—C8 | 119.1 (3) | C23—C24—H24 | 119.8 |
C10—C9—H9 | 120.5 | C24—C25—C20 | 119.6 (3) |
C8—C9—H9 | 120.5 | C24—C25—H25 | 120.2 |
C11—C10—C9 | 120.9 (3) | C20—C25—H25 | 120.2 |
O1—P2—C1—P1 | 53.25 (19) | C9—C8—C13—C12 | −1.5 (5) |
C14—P2—C1—P1 | −68.5 (2) | P1—C8—C13—C12 | −176.7 (3) |
C20—P2—C1—P1 | 174.17 (16) | C11—C12—C13—C8 | 1.6 (5) |
O2—P1—C1—P2 | 57.3 (2) | O1—P2—C14—C19 | −14.9 (3) |
C2—P1—C1—P2 | 175.76 (16) | C1—P2—C14—C19 | 104.9 (3) |
C8—P1—C1—P2 | −67.43 (19) | C20—P2—C14—C19 | −137.8 (3) |
O2—P1—C2—C3 | −167.7 (2) | O1—P2—C14—C15 | 162.7 (3) |
C8—P1—C2—C3 | −42.3 (3) | C1—P2—C14—C15 | −77.6 (3) |
C1—P1—C2—C3 | 76.9 (3) | C20—P2—C14—C15 | 39.7 (3) |
O2—P1—C2—C7 | 13.8 (3) | C19—C14—C15—C16 | −0.7 (5) |
C8—P1—C2—C7 | 139.2 (3) | P2—C14—C15—C16 | −178.3 (3) |
C1—P1—C2—C7 | −101.6 (3) | C14—C15—C16—C17 | 0.8 (6) |
C7—C2—C3—C4 | 0.0 (5) | C15—C16—C17—C18 | 0.3 (6) |
P1—C2—C3—C4 | −178.5 (3) | C16—C17—C18—C19 | −1.6 (5) |
C2—C3—C4—C5 | −0.8 (6) | C15—C14—C19—C18 | −0.5 (5) |
C3—C4—C5—C6 | 0.4 (6) | P2—C14—C19—C18 | 177.0 (2) |
C4—C5—C6—C7 | 0.8 (6) | C17—C18—C19—C14 | 1.7 (5) |
C5—C6—C7—C2 | −1.6 (6) | O1—P2—C20—C21 | 130.8 (3) |
C3—C2—C7—C6 | 1.2 (5) | C14—P2—C20—C21 | −107.5 (3) |
P1—C2—C7—C6 | 179.7 (3) | C1—P2—C20—C21 | 13.4 (3) |
O2—P1—C8—C13 | −141.4 (3) | O1—P2—C20—C25 | −50.3 (3) |
C2—P1—C8—C13 | 94.6 (3) | C14—P2—C20—C25 | 71.4 (3) |
C1—P1—C8—C13 | −20.5 (3) | C1—P2—C20—C25 | −167.6 (2) |
O2—P1—C8—C9 | 43.2 (3) | C25—C20—C21—C22 | 0.0 (5) |
C2—P1—C8—C9 | −80.8 (3) | P2—C20—C21—C22 | 178.9 (3) |
C1—P1—C8—C9 | 164.2 (2) | C20—C21—C22—C23 | 1.3 (5) |
C13—C8—C9—C10 | 0.1 (5) | C21—C22—C23—C24 | −1.2 (6) |
P1—C8—C9—C10 | 175.7 (3) | C22—C23—C24—C25 | −0.3 (6) |
C8—C9—C10—C11 | 1.0 (5) | C23—C24—C25—C20 | 1.6 (6) |
C9—C10—C11—C12 | −0.9 (6) | C21—C20—C25—C24 | −1.4 (5) |
C10—C11—C12—C13 | −0.5 (6) | P2—C20—C25—C24 | 179.6 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2iii | 1.19 | 1.19 | 2.380 (4) | 180 |
O1—H1···O1iv | 1.19 | 1.19 | 2.388 (4) | 180 |
C1—H1A···I2 | 0.99 | 2.83 | 3.818 (3) | 173 |
C1—H1B···I3ii | 0.99 | 2.89 | 3.878 (3) | 176 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C25H22O2P2·H+·I3− |
Mr | 798.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 143 |
a, b, c (Å) | 10.1284 (8), 11.8155 (10), 12.5299 (10) |
α, β, γ (°) | 110.852 (2), 93.855 (2), 96.043 (2) |
V (Å3) | 1384.61 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.52 |
Crystal size (mm) | 0.37 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.384, 0.590 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16933, 8330, 6921 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.03 |
No. of reflections | 8330 |
No. of parameters | 294 |
No. of restraints | 204 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 2.65, −1.07 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
I1—I2 | 2.9066 (3) | P1—C1 | 1.801 (3) |
I3—I4 | 2.9052 (3) | P2—O1 | 1.521 (2) |
P1—O2 | 1.518 (2) | P2—C14 | 1.786 (3) |
P1—C2 | 1.785 (3) | P2—C1 | 1.789 (3) |
P1—C8 | 1.797 (3) | P2—C20 | 1.789 (3) |
O2—P1—C2 | 111.33 (15) | C14—P2—C1 | 112.64 (13) |
O2—P1—C8 | 113.60 (14) | O1—P2—C20 | 112.58 (14) |
C2—P1—C8 | 108.01 (13) | C14—P2—C20 | 107.07 (14) |
O2—P1—C1 | 106.93 (13) | C1—P2—C20 | 106.98 (13) |
C2—P1—C1 | 105.14 (13) | P2—O1—H1 | 123.93 (17) |
C8—P1—C1 | 111.53 (13) | P1—O2—H2 | 133.03 (19) |
O1—P2—C14 | 110.52 (13) | P2—C1—P1 | 117.57 (15) |
O1—P2—C1 | 107.08 (13) | ||
O1—P2—C1—P1 | 53.25 (19) | O2—P1—C1—P2 | 57.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2i | 1.19 | 1.19 | 2.380 (4) | 180 |
O1—H1···O1ii | 1.19 | 1.19 | 2.388 (4) | 180 |
C1—H1A···I2 | 0.99 | 2.83 | 3.818 (3) | 173 |
C1—H1B···I3iii | 0.99 | 2.89 | 3.878 (3) | 176 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z; (iii) −x+1, −y+1, −z+1. |
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Extending our study of supramolecular structures of (iodoseleno)phosphonium salts (Seppälä et al., 1999; du Mont et al., 2001a,b) to bidentate ligands, we reacted [(C6H5)2P(═Se)]2CH2 (dppmSe2) with two equivalents of diiodine in dichloromethane (Boraei & du Mont, 2000). Attempted crystallization of the iodine adduct was accompanied by hydrolytic reactions, due to the access of moist air to the mother liquor, affording a small fraction of the title new compound, (I). \sch
The salt-like compound (I) consists of helical polymeric cations, (dppmO2H+)x, made up from ···H···OP(C6H5)2-CH2-(C6H5)2PO··· moieties and triidiode anions, which interconnect these chains through C—H···I—I—I interactions (CH···I 2.89 and 2.83 Å) with the H atoms of the (dppmO2H+)x methylene groups. These rather short non-classical hydrogen-bond contacts are in the range of those observed in 2,5-bis[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3,4,6-tetrathiapentalene triiodide (CH···I 2.832 Å; Mori et al., 1994) and in 1-azoniapropellane triiodide (CH···I 2.897 Å; Bakshi et al., 1996).
The P═O bond lengthening arising from coordination with bridging H+ is, at 0.07 Å, less than in true hydroxyphosphonium cations, R3POH+ (Ruthe et al., 2000), but is similar to that in the bis-AlCl3 complex [dppmO2(AlCl3)2] (Sangokoya et al., 1989).
The P═O···H···O═P bridges and I—I—I groups in (I) are centrosymmetric, with the central H and I atoms lying on centres of inversion. The P═O···H···O═P bonding within the polymeric cation, (dppmO2H+)x, is closely related to that of known molecular centrosymmetric bis(phosphineoxide)hydrogen(I) cations in [(Me3PO)2H]+·AuI2- (Godfrey et al., 1996) and in [(iPr3PO)2H]+·I3- (Ruthe et al., 2000). As in the latter triiodide salt, O···O distances in (I) (2.384(?)Å) are slightly shorter than in the comparable noncentrosymmetric compound [TPO3H]I3 (2.432(?)Å), where H+ is chelated by two R2R'P═O donor functions derived from the tridentate chelate ligand bis(o-diphenylphosphinophenyl)(phenyl)phosphane (Bigoli et al., 1992).
The packing of solid (I) can be described as corrugated layers of helical (dppmO2H+)x cations, whose methylene groups are centres of further bifurcating hydrogen-bond systems (–H···I—I—I···H—C—H···I—I—I···H–) cross-linking these cationic layers, leading to a complex three-dimensional network. The conformation of the helical (dppmO2H+)x cations is apparently determined by the geometric requirements of, firstly, linear O—H—O bridges [different from the chelate (dppmO2)3Na+; Hewertson et al. (1979)], secondly, wide P—O—H angles, and thirdly, preferred torsion angles, like those of the ligands dppm [by considering the P electron lone pairs as pseudoligands (Schmidbaur et al., 1988)], dppmO2 (Antipin et al., 1980), dppmS2 (Carmalt et al., 1996) and dppmSe2 (Carroll & Titus, 1977; Ahrens & Jones, 1997).