Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002143/bt6101sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002143/bt6101Isup2.hkl |
CCDC reference: 182599
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.122
- Data-to-parameter ratio = 16.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor P(1) - H(1P) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was synthesized according to previously published procedures and its physical and spectral properties were in full agreement with the literature data (Maffei & Buono, 1988; Emmick & Letsinger, 1968). Crystals were obtained by crystallization from benzene.
All H atoms, except that bonded to the P atom, were set in calculated positions and treated as riding on the adjacent C atom. The H atom bonded to the P atom was located in a difference Fourier syntheses and refined isotropically. The methyl group was allowed to rotate about its local threefold axis.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).
C13H13O2P | F(000) = 488 |
Mr = 232.20 | Dx = 1.287 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 8.576 (3) Å | Cell parameters from 99 reflections |
b = 8.804 (4) Å | θ = 18.7–28.9° |
c = 15.921 (6) Å | µ = 1.89 mm−1 |
β = 94.69 (3)° | T = 293 K |
V = 1198.1 (8) Å3 | Prism, colourless |
Z = 4 | 0.55 × 0.23 × 0.12 mm |
Enraf-Nonius CAD-4 diffractometer | 2175 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 75.1°, θmin = 5.2° |
ω–2θ scans | h = 0→10 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | k = −11→11 |
Tmin = 0.421, Tmax = 0.809 | l = −19→19 |
5076 measured reflections | 3 standard reflections every 60 min |
2465 independent reflections | intensity decay: 0.5% |
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)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.2516P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2465 reflections | Δρmax = 0.18 e Å−3 |
151 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0052 (7) |
C13H13O2P | V = 1198.1 (8) Å3 |
Mr = 232.20 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 8.576 (3) Å | µ = 1.89 mm−1 |
b = 8.804 (4) Å | T = 293 K |
c = 15.921 (6) Å | 0.55 × 0.23 × 0.12 mm |
β = 94.69 (3)° |
Enraf-Nonius CAD-4 diffractometer | 2175 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | Rint = 0.029 |
Tmin = 0.421, Tmax = 0.809 | 3 standard reflections every 60 min |
5076 measured reflections | intensity decay: 0.5% |
2465 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.18 e Å−3 |
2465 reflections | Δρmin = −0.22 e Å−3 |
151 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 | ||
P1 | 0.28987 (5) | 0.21983 (6) | 0.35898 (3) | 0.0632 (2) | |
O1 | 0.38235 (17) | 0.08178 (19) | 0.34478 (11) | 0.0935 (5) | |
O2 | 0.18333 (16) | 0.50916 (15) | 0.42498 (8) | 0.0696 (4) | |
C1 | 0.33299 (18) | 0.29594 (19) | 0.46244 (12) | 0.0572 (4) | |
C2 | 0.27410 (19) | 0.4357 (2) | 0.48634 (11) | 0.0573 (4) | |
C3 | 0.3075 (2) | 0.4893 (3) | 0.56705 (13) | 0.0759 (5) | |
H3 | 0.2693 | 0.5831 | 0.5827 | 0.091* | |
C4 | 0.3976 (3) | 0.4032 (3) | 0.62427 (14) | 0.0903 (7) | |
H4 | 0.4189 | 0.4392 | 0.6789 | 0.108* | |
C5 | 0.4566 (3) | 0.2661 (3) | 0.60271 (17) | 0.0926 (8) | |
H5 | 0.5171 | 0.2091 | 0.6423 | 0.111* | |
C6 | 0.4255 (2) | 0.2130 (2) | 0.52162 (16) | 0.0780 (6) | |
H6 | 0.4669 | 0.1203 | 0.5064 | 0.094* | |
C7 | 0.1220 (3) | 0.6544 (2) | 0.44369 (17) | 0.0866 (7) | |
H7A | 0.0628 | 0.6467 | 0.4922 | 0.130* | |
H7B | 0.0553 | 0.6897 | 0.3964 | 0.130* | |
H7C | 0.2066 | 0.7248 | 0.4552 | 0.130* | |
C8 | 0.0832 (2) | 0.1890 (2) | 0.34440 (10) | 0.0573 (4) | |
C9 | 0.0199 (2) | 0.0681 (2) | 0.38569 (14) | 0.0739 (5) | |
H9 | 0.0839 | 0.0060 | 0.4210 | 0.089* | |
C10 | −0.1394 (3) | 0.0404 (3) | 0.37403 (18) | 0.0980 (8) | |
H10 | −0.1827 | −0.0402 | 0.4019 | 0.118* | |
C11 | −0.2339 (2) | 0.1313 (4) | 0.32146 (18) | 0.1032 (10) | |
H11 | −0.3406 | 0.1116 | 0.3132 | 0.124* | |
C12 | −0.1710 (3) | 0.2499 (4) | 0.28154 (17) | 0.1017 (9) | |
H12 | −0.2354 | 0.3114 | 0.2461 | 0.122* | |
C13 | −0.0137 (3) | 0.2803 (3) | 0.29269 (13) | 0.0798 (6) | |
H13 | 0.0276 | 0.3626 | 0.2654 | 0.096* | |
H1P | 0.3174 (19) | 0.337 (2) | 0.3094 (11) | 0.058 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0478 (3) | 0.0675 (3) | 0.0758 (3) | 0.00054 (18) | 0.0147 (2) | −0.0080 (2) |
O1 | 0.0636 (8) | 0.0927 (11) | 0.1257 (13) | 0.0169 (8) | 0.0169 (8) | −0.0313 (10) |
O2 | 0.0737 (8) | 0.0592 (7) | 0.0751 (8) | 0.0126 (6) | 0.0005 (6) | 0.0024 (6) |
C1 | 0.0413 (7) | 0.0557 (9) | 0.0747 (10) | −0.0054 (6) | 0.0043 (7) | 0.0045 (8) |
C2 | 0.0504 (8) | 0.0576 (9) | 0.0640 (9) | −0.0069 (7) | 0.0062 (7) | 0.0039 (7) |
C3 | 0.0784 (13) | 0.0769 (13) | 0.0727 (12) | −0.0154 (10) | 0.0082 (10) | −0.0083 (10) |
C4 | 0.0888 (15) | 0.1101 (19) | 0.0693 (12) | −0.0360 (14) | −0.0096 (11) | 0.0076 (12) |
C5 | 0.0736 (13) | 0.0992 (17) | 0.0992 (16) | −0.0261 (13) | −0.0284 (12) | 0.0327 (14) |
C6 | 0.0547 (10) | 0.0638 (11) | 0.1126 (16) | −0.0054 (8) | −0.0112 (10) | 0.0146 (11) |
C7 | 0.0813 (14) | 0.0626 (12) | 0.1175 (18) | 0.0157 (10) | 0.0180 (13) | 0.0039 (12) |
C8 | 0.0527 (8) | 0.0621 (9) | 0.0578 (9) | 0.0003 (7) | 0.0085 (7) | −0.0116 (7) |
C9 | 0.0669 (11) | 0.0677 (11) | 0.0877 (13) | −0.0092 (9) | 0.0098 (9) | −0.0076 (10) |
C10 | 0.0767 (14) | 0.1059 (18) | 0.1151 (18) | −0.0376 (14) | 0.0296 (14) | −0.0350 (16) |
C11 | 0.0481 (10) | 0.155 (3) | 0.1065 (18) | −0.0113 (14) | 0.0077 (11) | −0.0657 (19) |
C12 | 0.0623 (13) | 0.152 (3) | 0.0872 (15) | 0.0205 (15) | −0.0138 (12) | −0.0243 (16) |
C13 | 0.0677 (12) | 0.1017 (17) | 0.0689 (11) | 0.0064 (11) | −0.0007 (9) | 0.0043 (11) |
P1—O1 | 1.4787 (16) | C6—H6 | 0.9300 |
P1—C1 | 1.789 (2) | C7—H7A | 0.9600 |
P1—C8 | 1.7895 (18) | C7—H7B | 0.9600 |
P1—H1P | 1.330 (18) | C7—H7C | 0.9600 |
O2—C2 | 1.362 (2) | C8—C13 | 1.380 (3) |
O2—C7 | 1.424 (2) | C8—C9 | 1.385 (3) |
C1—C6 | 1.388 (3) | C9—C10 | 1.386 (3) |
C1—C2 | 1.394 (2) | C9—H9 | 0.9300 |
C2—C3 | 1.377 (3) | C10—C11 | 1.373 (4) |
C3—C4 | 1.374 (3) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—C12 | 1.357 (4) |
C4—C5 | 1.363 (4) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | C12—C13 | 1.373 (3) |
C5—C6 | 1.379 (4) | C12—H12 | 0.9300 |
C5—H5 | 0.9300 | C13—H13 | 0.9300 |
O1—P1—C1 | 112.06 (9) | O2—C7—H7A | 109.5 |
O1—P1—C8 | 113.17 (9) | O2—C7—H7B | 109.5 |
C1—P1—C8 | 107.72 (8) | H7A—C7—H7B | 109.5 |
O1—P1—H1P | 115.0 (7) | O2—C7—H7C | 109.5 |
C1—P1—H1P | 102.9 (8) | H7A—C7—H7C | 109.5 |
C8—P1—H1P | 105.2 (7) | H7B—C7—H7C | 109.5 |
C2—O2—C7 | 118.42 (16) | C13—C8—C9 | 119.43 (18) |
C6—C1—C2 | 118.58 (18) | C13—C8—P1 | 122.06 (16) |
C6—C1—P1 | 119.43 (16) | C9—C8—P1 | 118.51 (15) |
C2—C1—P1 | 121.97 (13) | C8—C9—C10 | 119.5 (2) |
O2—C2—C3 | 124.72 (18) | C8—C9—H9 | 120.3 |
O2—C2—C1 | 114.95 (15) | C10—C9—H9 | 120.3 |
C3—C2—C1 | 120.33 (18) | C11—C10—C9 | 120.3 (3) |
C4—C3—C2 | 119.5 (2) | C11—C10—H10 | 119.8 |
C4—C3—H3 | 120.3 | C9—C10—H10 | 119.8 |
C2—C3—H3 | 120.3 | C12—C11—C10 | 119.8 (2) |
C5—C4—C3 | 121.5 (2) | C12—C11—H11 | 120.1 |
C5—C4—H4 | 119.3 | C10—C11—H11 | 120.1 |
C3—C4—H4 | 119.3 | C11—C12—C13 | 120.9 (3) |
C4—C5—C6 | 119.3 (2) | C11—C12—H12 | 119.5 |
C4—C5—H5 | 120.4 | C13—C12—H12 | 119.5 |
C6—C5—H5 | 120.4 | C12—C13—C8 | 120.1 (2) |
C5—C6—C1 | 120.9 (2) | C12—C13—H13 | 120.0 |
C5—C6—H6 | 119.6 | C8—C13—H13 | 120.0 |
C1—C6—H6 | 119.6 | ||
C3—C2—O2—C7 | 2.3 (3) | C1—C2—O2—C7 | −178.40 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.48 | 3.371 (3) | 160 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C13H13O2P |
Mr | 232.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.576 (3), 8.804 (4), 15.921 (6) |
β (°) | 94.69 (3) |
V (Å3) | 1198.1 (8) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.89 |
Crystal size (mm) | 0.55 × 0.23 × 0.12 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.421, 0.809 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5076, 2465, 2175 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.122, 1.09 |
No. of reflections | 2465 |
No. of parameters | 151 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.22 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990a), XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).
P1—O1 | 1.4787 (16) | P1—C8 | 1.7895 (18) |
P1—C1 | 1.789 (2) | P1—H1P | 1.330 (18) |
O1—P1—C1 | 112.06 (9) | O1—P1—H1P | 115.0 (7) |
O1—P1—C8 | 113.17 (9) | C1—P1—H1P | 102.9 (8) |
C1—P1—C8 | 107.72 (8) | C8—P1—H1P | 105.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.48 | 3.371 (3) | 159.8 |
Symmetry code: (i) x−1, y, z. |
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Secondary phosphine oxides are important synthetic intermediates in organophosphorus chemistry and their high reactivity is typically connected with the presence of a relatively acidic hydrogen in their structure (Engel, 1988). They exist in two tautomeric forms: R2P(═O)H and R2POH, the former being predominant in the equilibrium (Bailey & Fox, 1963, 1964). There are, however, cases like in the transition metal complexes, where the latter form is seen exclusively (Parkins, 1996; Han et al., 1996). It was therefore deemed interesting to study the crystal structure of some model secondary phosphine oxides in order to reveal their tautomeric preferences in the solid state and to study the character of the expected hydrogen bonding implied by their acidic functionality. The selected models include one alkylarylphosphine oxide, i.e. benzylphenylphosphine oxide (Kruszynski et al., 2002), and one diarylphosphine oxide, i.e. (2-methoxyphenyl)phenylphosphine oxide, (I).
The perspective view of (I), together with the atom-numbering scheme, is shown in Fig. 1. A l l interatomic distances can be considered as normal and the phenyl rings are planar in the range of experimental error. The overall molecular geometry of (I) is similar to the (2-methoxyphenyl)(phenyl)vinylphosphine oxide, (II) (Wieczorek, 1995). The weighted r.m.s. deviation for all non-H atoms in (I) and respective atoms of (II) is 0.156 (4) Å. The superposition of the two molecules (I) and (II) is shown in Fig. 2. The phosphorous tetrahedron exhibits its usual deformation, with C—P—C and C—P—H angles smaller than tetrahedral and O—P—C and O—P—H angles greater than tetrahedral (Table 1). The P═O bond makes the angles of 7.6 (2) and 46.56 (2)° with phenyl rings indicated by C1 and C8 atoms, respectively. Analogous angles in (II) are 1.7 (1) and 52.0 (1)°. The (2-methoxyphenyl)phosphine part is almost planar with maximum deviation of 0.0181 (17) Å for C6 atom. The adjacent C atom deviates by -1.551 (2) Å from the above plane and the O atom deviates by 0.190 (2) Å. The dihedral angle between weighted least-squares planes of the phenyl rings is 82.53 (7)°. In the structure can be found one C—H···O short intermolecular interaction (Table 2), which can be considered as a weak intermolecular hydrogen bond (Taylor & Kennard, 1982; Desiraju & Steiner, 1999). In this way, the one-dimensional hydrogen-bond chain is created (Fig. 3). There are no unusual intermolecular short contacts except for the hydrogen bond described in Table 2.