In the title compound, C
18H
15OP·C
7H
5ClO
2, the triphenylphosphine oxide molecule forms a single directed hydrogen bond with the 3-chlorobenzoic acid molecule, with an O
O=P distance of 2.607 (2) Å. The C-Cl and C=O bonds adopt a
cisoid conformation in the 3-chlorobenzoic acid molecule.
Supporting information
CCDC reference: 211737
The title compound was prepared by mixing equimolar amounts of TPPO and 3-chlorobenzoic acid in CCl4. Slow evaporation of the solvent afforded colourless crystals of (I) suitable for X-ray analysis.
H atoms were found in the difference Fourier map and were treated as riding atoms (C—H = 0.96 Å) with refinable isotropic displacement parameters, except for the H atom of the carboxylic acid group, which was allowed to refine freely.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97.
Triphenylphosphine oxide-3-chlorobenzoic acid (1/1)
top
Crystal data top
C18H15OP·C7H5ClO2 | F(000) = 904 |
Mr = 434.83 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/n | Melting point: 348 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 8.845 (1) Å | Cell parameters from 25 reflections |
b = 16.101 (1) Å | θ = 17.4–17.5° |
c = 16.029 (2) Å | µ = 0.27 mm−1 |
β = 103.97 (1)° | T = 296 K |
V = 2215.2 (4) Å3 | Plate, colourless |
Z = 4 | 0.3 × 0.3 × 0.1 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.021 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = −1→10 |
θ/2θ scans | k = −1→19 |
5044 measured reflections | l = −19→18 |
3868 independent reflections | 3 standard reflections every 200 reflections |
3343 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0533P)2 + 1.0553P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3868 reflections | Δρmax = 0.57 e Å−3 |
295 parameters | Δρmin = −0.57 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.041 (2) |
Crystal data top
C18H15OP·C7H5ClO2 | V = 2215.2 (4) Å3 |
Mr = 434.83 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.845 (1) Å | µ = 0.27 mm−1 |
b = 16.101 (1) Å | T = 296 K |
c = 16.029 (2) Å | 0.3 × 0.3 × 0.1 mm |
β = 103.97 (1)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.021 |
5044 measured reflections | 3 standard reflections every 200 reflections |
3868 independent reflections | intensity decay: none |
3343 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.57 e Å−3 |
3868 reflections | Δρmin = −0.57 e Å−3 |
295 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.34344 (6) | 0.87738 (3) | 0.65724 (3) | 0.04667 (18) | |
O1 | 0.3902 (2) | 0.84066 (10) | 0.58176 (10) | 0.0660 (4) | |
C1 | 0.4022 (2) | 0.81496 (12) | 0.75300 (13) | 0.0485 (5) | |
C2 | 0.3312 (3) | 0.82171 (14) | 0.82110 (14) | 0.0599 (6) | |
H2 | 0.2477 | 0.8606 | 0.8181 | 0.074 (7)* | |
C3 | 0.3805 (3) | 0.77250 (16) | 0.89325 (15) | 0.0703 (7) | |
H3 | 0.3311 | 0.7774 | 0.9402 | 0.095 (9)* | |
C4 | 0.4995 (3) | 0.71688 (16) | 0.89813 (16) | 0.0739 (7) | |
H4 | 0.5335 | 0.6829 | 0.9484 | 0.079 (8)* | |
C5 | 0.5700 (3) | 0.70997 (17) | 0.83070 (17) | 0.0790 (7) | |
H5 | 0.6531 | 0.6708 | 0.8341 | 0.106 (10)* | |
C6 | 0.5226 (3) | 0.75863 (15) | 0.75836 (15) | 0.0641 (6) | |
H6 | 0.5729 | 0.7535 | 0.7118 | 0.078 (7)* | |
C7 | 0.4264 (2) | 0.97959 (12) | 0.67925 (13) | 0.0477 (5) | |
C8 | 0.4705 (3) | 1.01389 (15) | 0.76057 (16) | 0.0722 (7) | |
H8 | 0.4614 | 0.9821 | 0.8098 | 0.091 (9)* | |
C9 | 0.5280 (4) | 1.09460 (17) | 0.77092 (19) | 0.0857 (8) | |
H9 | 0.5585 | 1.1184 | 0.8274 | 0.129 (13)* | |
C10 | 0.5414 (3) | 1.13999 (17) | 0.7013 (2) | 0.0802 (8) | |
H10 | 0.5803 | 1.1958 | 0.7089 | 0.095 (9)* | |
C11 | 0.4998 (4) | 1.10651 (17) | 0.6212 (2) | 0.0849 (8) | |
H11 | 0.5098 | 1.1387 | 0.5724 | 0.122 (12)* | |
C12 | 0.4430 (3) | 1.02613 (15) | 0.60986 (15) | 0.0662 (6) | |
H12 | 0.4149 | 1.0026 | 0.5532 | 0.088 (8)* | |
C13 | 0.1352 (2) | 0.88917 (12) | 0.63849 (12) | 0.0486 (5) | |
C14 | 0.0603 (2) | 0.96473 (14) | 0.61708 (14) | 0.0579 (5) | |
H14 | 0.1202 | 1.0143 | 0.6159 | 0.068 (7)* | |
C15 | −0.1013 (3) | 0.96867 (18) | 0.59736 (16) | 0.0725 (7) | |
H15 | −0.1532 | 1.0208 | 0.5815 | 0.094 (9)* | |
C16 | −0.1871 (3) | 0.8980 (2) | 0.60047 (16) | 0.0794 (8) | |
H16 | −0.2987 | 0.9010 | 0.5874 | 0.087 (8)* | |
C17 | −0.1143 (3) | 0.8238 (2) | 0.62194 (18) | 0.0812 (8) | |
H17 | −0.1751 | 0.7748 | 0.6241 | 0.115 (11)* | |
C18 | 0.0461 (3) | 0.81838 (16) | 0.64060 (16) | 0.0692 (6) | |
H18 | 0.0962 | 0.7656 | 0.6550 | 0.088 (9)* | |
Cl1 | 0.85659 (12) | 0.41131 (5) | 0.46171 (8) | 0.1153 (4) | |
O2 | 0.4212 (2) | 0.71509 (12) | 0.48453 (12) | 0.0732 (5) | |
H1 | 0.409 (3) | 0.752 (2) | 0.5202 (19) | 0.096 (10)* | |
O3 | 0.6357 (2) | 0.67806 (11) | 0.58134 (12) | 0.0778 (5) | |
C19 | 0.5432 (3) | 0.66793 (13) | 0.51304 (15) | 0.0560 (5) | |
C20 | 0.5578 (3) | 0.59818 (13) | 0.45394 (14) | 0.0563 (5) | |
C21 | 0.6842 (3) | 0.54555 (14) | 0.47894 (16) | 0.0627 (6) | |
H21 | 0.7605 | 0.5553 | 0.5318 | 0.077 (8)* | |
C22 | 0.7000 (3) | 0.47920 (15) | 0.42779 (19) | 0.0751 (7) | |
C23 | 0.5930 (4) | 0.46471 (19) | 0.3521 (2) | 0.0895 (9) | |
H23 | 0.6060 | 0.4185 | 0.3166 | 0.113 (11)* | |
C24 | 0.4670 (4) | 0.5164 (2) | 0.32714 (18) | 0.0913 (9) | |
H24 | 0.3914 | 0.5059 | 0.2742 | 0.124 (12)* | |
C25 | 0.4476 (3) | 0.58414 (17) | 0.37792 (15) | 0.0734 (7) | |
H25 | 0.3594 | 0.6203 | 0.3604 | 0.055 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0548 (3) | 0.0422 (3) | 0.0465 (3) | 0.0015 (2) | 0.0191 (2) | 0.0006 (2) |
O1 | 0.0907 (11) | 0.0575 (9) | 0.0592 (9) | 0.0057 (8) | 0.0366 (8) | −0.0024 (7) |
C1 | 0.0530 (11) | 0.0421 (10) | 0.0523 (11) | 0.0010 (8) | 0.0167 (9) | 0.0005 (8) |
C2 | 0.0692 (14) | 0.0574 (13) | 0.0586 (12) | 0.0160 (11) | 0.0263 (10) | 0.0085 (10) |
C3 | 0.0900 (17) | 0.0700 (15) | 0.0574 (13) | 0.0151 (13) | 0.0306 (12) | 0.0126 (11) |
C4 | 0.0927 (18) | 0.0682 (15) | 0.0588 (14) | 0.0174 (14) | 0.0146 (12) | 0.0156 (12) |
C5 | 0.0793 (17) | 0.0773 (17) | 0.0810 (17) | 0.0328 (14) | 0.0204 (13) | 0.0155 (14) |
C6 | 0.0651 (13) | 0.0653 (14) | 0.0669 (14) | 0.0145 (11) | 0.0256 (11) | 0.0057 (11) |
C7 | 0.0438 (10) | 0.0474 (11) | 0.0536 (11) | −0.0004 (8) | 0.0153 (8) | 0.0031 (9) |
C8 | 0.0995 (19) | 0.0598 (14) | 0.0580 (13) | −0.0171 (13) | 0.0205 (12) | 0.0006 (11) |
C9 | 0.112 (2) | 0.0657 (16) | 0.0769 (17) | −0.0263 (15) | 0.0186 (16) | −0.0121 (13) |
C10 | 0.0853 (18) | 0.0582 (14) | 0.099 (2) | −0.0243 (13) | 0.0266 (15) | −0.0006 (14) |
C11 | 0.103 (2) | 0.0699 (17) | 0.0860 (19) | −0.0249 (15) | 0.0304 (16) | 0.0172 (14) |
C12 | 0.0756 (15) | 0.0660 (14) | 0.0582 (13) | −0.0153 (12) | 0.0183 (11) | 0.0071 (11) |
C13 | 0.0537 (11) | 0.0506 (11) | 0.0412 (10) | −0.0058 (9) | 0.0106 (8) | −0.0009 (8) |
C14 | 0.0557 (12) | 0.0567 (12) | 0.0607 (12) | −0.0019 (10) | 0.0130 (10) | 0.0065 (10) |
C15 | 0.0561 (13) | 0.0851 (18) | 0.0731 (15) | 0.0078 (13) | 0.0092 (11) | 0.0094 (13) |
C16 | 0.0496 (13) | 0.122 (2) | 0.0629 (14) | −0.0138 (15) | 0.0058 (11) | 0.0049 (15) |
C17 | 0.0703 (16) | 0.089 (2) | 0.0784 (17) | −0.0343 (15) | 0.0066 (13) | 0.0040 (14) |
C18 | 0.0699 (15) | 0.0574 (14) | 0.0757 (15) | −0.0152 (12) | 0.0088 (12) | 0.0014 (11) |
Cl1 | 0.1304 (7) | 0.0692 (5) | 0.1693 (9) | 0.0125 (4) | 0.0811 (7) | −0.0007 (5) |
O2 | 0.0890 (12) | 0.0634 (10) | 0.0681 (11) | 0.0038 (9) | 0.0208 (9) | −0.0075 (9) |
O3 | 0.0728 (11) | 0.0720 (11) | 0.0843 (12) | −0.0093 (9) | 0.0109 (9) | −0.0298 (9) |
C19 | 0.0621 (13) | 0.0477 (11) | 0.0635 (13) | −0.0160 (10) | 0.0260 (11) | −0.0040 (10) |
C20 | 0.0718 (14) | 0.0496 (11) | 0.0557 (12) | −0.0197 (10) | 0.0311 (10) | −0.0038 (9) |
C21 | 0.0746 (15) | 0.0520 (12) | 0.0710 (14) | −0.0149 (11) | 0.0362 (12) | −0.0041 (11) |
C22 | 0.1019 (19) | 0.0517 (13) | 0.0901 (19) | −0.0135 (13) | 0.0587 (16) | −0.0067 (12) |
C23 | 0.134 (3) | 0.0656 (16) | 0.087 (2) | −0.0235 (18) | 0.062 (2) | −0.0206 (15) |
C24 | 0.125 (3) | 0.097 (2) | 0.0555 (15) | −0.034 (2) | 0.0284 (16) | −0.0196 (15) |
C25 | 0.0937 (19) | 0.0722 (16) | 0.0581 (14) | −0.0152 (14) | 0.0255 (13) | −0.0016 (12) |
Geometric parameters (Å, º) top
P1—O1 | 1.492 (2) | C13—C14 | 1.388 (3) |
P1—C1 | 1.803 (2) | C13—C18 | 1.391 (3) |
P1—C7 | 1.802 (2) | C14—C15 | 1.389 (3) |
P1—C13 | 1.803 (2) | C14—H14 | 0.9600 |
C1—C6 | 1.386 (3) | C15—C16 | 1.375 (4) |
C1—C2 | 1.389 (3) | C15—H15 | 0.9600 |
C2—C3 | 1.383 (3) | C16—C17 | 1.361 (4) |
C2—H2 | 0.9600 | C16—H16 | 0.9600 |
C3—C4 | 1.370 (3) | C17—C18 | 1.381 (4) |
C3—H3 | 0.9600 | C17—H17 | 0.9600 |
C4—C5 | 1.377 (4) | C18—H18 | 0.9600 |
C4—H4 | 0.9600 | Cl1—C22 | 1.745 (3) |
C5—C6 | 1.378 (3) | C19—C20 | 1.495 (3) |
C5—H5 | 0.9600 | O2—C19 | 1.308 (3) |
C6—H6 | 0.9600 | O2—H1 | 0.85 (3) |
C7—C12 | 1.378 (3) | O3—C19 | 1.209 (3) |
C7—C8 | 1.382 (3) | C20—C21 | 1.383 (3) |
C8—C9 | 1.391 (3) | C20—C25 | 1.383 (3) |
C8—H8 | 0.9600 | C21—C22 | 1.374 (3) |
C9—C10 | 1.363 (4) | C21—H21 | 0.9600 |
C9—H9 | 0.9600 | C22—C23 | 1.366 (4) |
C10—C11 | 1.358 (4) | C23—C24 | 1.371 (5) |
C10—H10 | 0.9600 | C23—H23 | 0.9600 |
C11—C12 | 1.384 (4) | C24—C25 | 1.396 (4) |
C11—H11 | 0.9600 | C24—H24 | 0.9600 |
C12—H12 | 0.9600 | C25—H25 | 0.9600 |
| | | |
O1—P1—C1 | 112.96 (9) | C11—C12—H12 | 119.7 |
O1—P1—C7 | 109.93 (9) | C14—C13—C18 | 119.0 (2) |
O1—P1—C13 | 112.25 (10) | C14—C13—P1 | 122.73 (16) |
C1—P1—C7 | 108.81 (9) | C18—C13—P1 | 118.14 (17) |
C1—P1—C13 | 105.88 (9) | C13—C14—C15 | 120.0 (2) |
C7—P1—C13 | 106.73 (9) | C13—C14—H14 | 120.0 |
C6—C1—C2 | 119.29 (19) | C15—C14—H14 | 120.0 |
C2—C1—P1 | 122.23 (15) | C16—C15—C14 | 120.0 (3) |
C6—C1—P1 | 118.48 (16) | C16—C15—H15 | 120.0 |
C3—C2—C1 | 120.1 (2) | C14—C15—H15 | 120.0 |
C3—C2—H2 | 120.0 | C17—C16—C15 | 120.3 (2) |
C1—C2—H2 | 120.0 | C17—C16—H16 | 119.9 |
C4—C3—C2 | 120.4 (2) | C15—C16—H16 | 119.9 |
C4—C3—H3 | 119.8 | C16—C17—C18 | 120.6 (2) |
C2—C3—H3 | 119.8 | C16—C17—H17 | 119.7 |
C3—C4—C5 | 119.7 (2) | C18—C17—H17 | 119.7 |
C3—C4—H4 | 120.2 | C17—C18—C13 | 120.1 (2) |
C5—C4—H4 | 120.2 | C17—C18—H18 | 120.0 |
C4—C5—C6 | 120.8 (2) | C13—C18—H18 | 120.0 |
C4—C5—H5 | 119.6 | C19—O2—H1 | 114 (2) |
C6—C5—H5 | 119.6 | O3—C19—O2 | 124.0 (2) |
C5—C6—C1 | 119.8 (2) | O3—C19—C20 | 122.1 (2) |
C5—C6—H6 | 120.1 | O2—C19—C20 | 113.9 (2) |
C1—C6—H6 | 120.1 | C21—C20—C25 | 120.2 (2) |
C12—C7—C8 | 118.9 (2) | C21—C20—C19 | 117.7 (2) |
C8—C7—P1 | 123.93 (16) | C25—C20—C19 | 122.0 (2) |
C12—C7—P1 | 117.15 (16) | C22—C21—C20 | 119.7 (3) |
C7—C8—C9 | 119.8 (2) | C22—C21—H21 | 120.2 |
C7—C8—H8 | 120.1 | C20—C21—H21 | 120.2 |
C9—C8—H8 | 120.1 | C23—C22—C21 | 120.9 (3) |
C10—C9—C8 | 120.3 (3) | C23—C22—Cl1 | 119.8 (2) |
C10—C9—H9 | 119.8 | C21—C22—Cl1 | 119.3 (2) |
C8—C9—H9 | 119.8 | C22—C23—C24 | 119.7 (3) |
C11—C10—C9 | 120.2 (2) | C22—C23—H23 | 120.1 |
C11—C10—H10 | 119.9 | C24—C23—H23 | 120.1 |
C9—C10—H10 | 119.9 | C23—C24—C25 | 120.6 (3) |
C10—C11—C12 | 120.2 (2) | C23—C24—H24 | 119.7 |
C10—C11—H11 | 119.9 | C25—C24—H24 | 119.7 |
C12—C11—H11 | 119.9 | C20—C25—C24 | 118.8 (3) |
C7—C12—C11 | 120.5 (2) | C20—C25—H25 | 120.6 |
C7—C12—H12 | 119.7 | C24—C25—H25 | 120.6 |
| | | |
O1—P1—C1—C6 | 21.2 (2) | O1—P1—C13—C14 | −101.20 (18) |
C7—P1—C1—C6 | −101.17 (19) | C7—P1—C13—C14 | 19.3 (2) |
C13—P1—C1—C6 | 144.43 (18) | C1—P1—C13—C14 | 135.12 (17) |
O1—P1—C1—C2 | −158.94 (18) | O1—P1—C13—C18 | 74.8 (2) |
C7—P1—C1—C2 | 78.7 (2) | C7—P1—C13—C18 | −164.68 (17) |
C13—P1—C1—C2 | −35.7 (2) | C1—P1—C13—C18 | −48.86 (19) |
C6—C1—C2—C3 | −0.1 (3) | C18—C13—C14—C15 | −0.6 (3) |
P1—C1—C2—C3 | −179.94 (19) | P1—C13—C14—C15 | 175.36 (17) |
C1—C2—C3—C4 | 0.0 (4) | C13—C14—C15—C16 | 1.1 (4) |
C2—C3—C4—C5 | −0.1 (4) | C14—C15—C16—C17 | −0.7 (4) |
C3—C4—C5—C6 | 0.2 (4) | C15—C16—C17—C18 | −0.2 (4) |
C4—C5—C6—C1 | −0.3 (4) | C16—C17—C18—C13 | 0.7 (4) |
C2—C1—C6—C5 | 0.2 (4) | C14—C13—C18—C17 | −0.3 (3) |
P1—C1—C6—C5 | −179.9 (2) | P1—C13—C18—C17 | −176.4 (2) |
O1—P1—C7—C12 | 33.3 (2) | O3—C19—C20—C21 | −1.4 (3) |
C1—P1—C7—C12 | 157.50 (17) | O2—C19—C20—C21 | 179.63 (18) |
C13—P1—C7—C12 | −88.66 (18) | O3—C19—C20—C25 | 176.6 (2) |
O1—P1—C7—C8 | −148.1 (2) | O2—C19—C20—C25 | −2.4 (3) |
C1—P1—C7—C8 | −23.9 (2) | C25—C20—C21—C22 | 0.1 (3) |
C13—P1—C7—C8 | 89.9 (2) | C19—C20—C21—C22 | 178.17 (19) |
C12—C7—C8—C9 | 1.0 (4) | C20—C21—C22—C23 | 0.4 (3) |
P1—C7—C8—C9 | −177.5 (2) | C20—C21—C22—Cl1 | −177.95 (16) |
C7—C8—C9—C10 | −0.1 (5) | C21—C22—C23—C24 | −0.7 (4) |
C8—C9—C10—C11 | −0.6 (5) | Cl1—C22—C23—C24 | 177.6 (2) |
C9—C10—C11—C12 | 0.3 (5) | C22—C23—C24—C25 | 0.5 (4) |
C8—C7—C12—C11 | −1.3 (4) | C21—C20—C25—C24 | −0.3 (3) |
P1—C7—C12—C11 | 177.3 (2) | C19—C20—C25—C24 | −178.3 (2) |
C10—C11—C12—C7 | 0.7 (4) | C23—C24—C25—C20 | 0.0 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.85 (3) | 1.76 (3) | 2.607 (2) | 171 (3) |
Experimental details
Crystal data |
Chemical formula | C18H15OP·C7H5ClO2 |
Mr | 434.83 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 8.845 (1), 16.101 (1), 16.029 (2) |
β (°) | 103.97 (1) |
V (Å3) | 2215.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.3 × 0.3 × 0.1 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5044, 3868, 3343 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.118, 1.02 |
No. of reflections | 3868 |
No. of parameters | 295 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.57 |
Selected geometric parameters (Å, º) topP1—O1 | 1.492 (2) | C19—C20 | 1.495 (3) |
P1—C1 | 1.803 (2) | O2—C19 | 1.308 (3) |
P1—C7 | 1.802 (2) | O2—H1 | 0.85 (3) |
P1—C13 | 1.803 (2) | O3—C19 | 1.209 (3) |
Cl1—C22 | 1.745 (3) | | |
| | | |
O1—P1—C1 | 112.96 (9) | C12—C7—P1 | 117.15 (16) |
O1—P1—C7 | 109.93 (9) | C14—C13—P1 | 122.73 (16) |
O1—P1—C13 | 112.25 (10) | C18—C13—P1 | 118.14 (17) |
C1—P1—C7 | 108.81 (9) | O3—C19—O2 | 124.0 (2) |
C1—P1—C13 | 105.88 (9) | O3—C19—C20 | 122.1 (2) |
C7—P1—C13 | 106.73 (9) | O2—C19—C20 | 113.9 (2) |
C2—C1—P1 | 122.23 (15) | C21—C20—C19 | 117.7 (2) |
C6—C1—P1 | 118.48 (16) | C25—C20—C19 | 122.0 (2) |
C8—C7—P1 | 123.93 (16) | | |
| | | |
O1—P1—C1—C6 | 21.2 (2) | O1—P1—C13—C18 | 74.8 (2) |
O1—P1—C7—C12 | 33.3 (2) | O3—C19—C20—C25 | 176.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.85 (3) | 1.76 (3) | 2.607 (2) | 171 (3) |
Triphenylphosphine oxide (TPPO) is a very useful molecule for hydrogen-bond model studies. Its bulky shape, its conformational flexibility via rotation of the phenyl rings about the P—C bonds and the electron-density concentration at the phosphoryl O atom make it ready to form strong, medium and weak hydrogen bonds of different types with various proton donors (Al-Farhan et al., 1990; Fuquen & Lechat, 1992; Baures, 1991). The hydrogen bond itself is of major interest in chemistry and biology. Because the hydrogen bond is sufficiently strong and directional, it is able to control and direct the structures of molecular assemblies. This control is both reliable and reproducible enough to be used in molecular recognition and crystal engineering (Desiraju & Steiner, 1999; Etter & Baures, 1988; Etter et al., 1986, 1990; Rebek et al., 1987, 1988). As part of our hydrogen-bond studies involving TPPO, the crystal structure determination of the title compound, (I), was undertaken and the results are presented here. \sch
Compound (I) is a 1:1 adduct between TPPO and 3-chlorobenzoic acid, linked by a single directed hydrogen bond [graph set D (Etter, 1990)]. A view of the adduct with the atom-numbering scheme is in Fig. 1 and selected geometric parameters are in Table 1.
The relevant distances and angles within the directed hydrogen-bond interaction are O2—H1 0.85 (3) and O1···O2 2.607 (2) Å, and O2—H1···O1 171 (3)°, C19—O2···O1 115.98 (15)° and P1—O1···O2 151.8 (1)°. As a result of the hydrogen bonding, the P1—O1 distance of 1.492 (2) Å is 0.013 Å longer than the P—O distance in free TPPO (Al-Farhan, 1992). The P1—O1 and O1···O2 values in (I) compare with the values of 1.492 (2) and 2.630 (4) Å (Fuquen & Lechat, 1992) and 1.496 (2) and 2.645 (2) Å (Gramstad et al., 1986) for the TPPO adducts with 4-nitrophenol and pentafluorophenol, respectively.
The dihedral angles between the TPPO phenyl rings, C1—C6/C7—C12, C1—C6/C13—C18 and C7—C12/C13—C18, are 70.3 (1), 66.2 (1) and 81.5 (1)°, respectively. The O—P—C—C torsion angles of the TPPO are 21.2 (2), 33.3 (2) and 74.8 (2)°, and these are distinctly different from the minimum-energy conformation (threefold symmetry and torsion angles of 40°) deduced from analysis of the observed conformations of a wide range of TPPO derivatives (Bye et al., 1982).
The significant structural change in 3-chlorobenzoic acid is that the C—Cl and C═O bonds have adopted a cisoid conformation in (I), whereas they are in a transoid conformation in the crystal structure of 3-chlorobenzoic acid (Gougoutas & Lessinger 1975). The dihedral angle between the plane of the benzene ring and that of the carboxylic acid group is 2.96 (35)°.
Examination of the structure with PLATON (Spek, 2003) showed that there were no solvent accessible voids in the crystal lattice of (I).