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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o367.
Published online 2008 January 4. doi:  10.1107/S1600536807067414
PMCID: PMC2960326

Three-centre hydrogen bonds in triphenyl­phosphine oxide–hydro­quinone (1/1)

Abstract

The title cocrystal, C18H15OP·C6H6O2, belongs to a series of mol­ecular systems based on triphenyl­phosphine P-oxide. The O atom of the oxide group acts as an acceptor for hydrogen bonds from OH groups of two hydro­quinone mol­ecules which lie on inversion centres [O(...)O = 2.7451 (17) and 2.681 (2) Å]. The crystal structure is stabilized by weak C—H(...)O hydrogen bonds, forming a C 2 1(8) chain which runs parallel to the [100] direction.

Related literature

For related literature, see: Al-Farhan (1992 [triangle]); Etter (1990 [triangle]); Fuquen & Lechat (1992 [triangle]); Wallwork & Powell (1980 [triangle]).

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Object name is e-64-0o367-scheme1.jpg

Experimental

Crystal data

  • C18H15OP·C6H6O2
  • M r = 388.38
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o367-efi1.jpg
  • a = 8.927 (4) Å
  • b = 9.3576 (10) Å
  • c = 14.459 (4) Å
  • α = 71.157 (7)°
  • β = 73.826 (6)°
  • γ = 62.83 (2)°
  • V = 1004.6 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 150 (2) K
  • 0.20 × 0.20 × 0.10 mm

Data collection

  • Oxford Diffraction Gemini diffractometer
  • Absorption correction: multi-scan (SCALE3 ABSPACK; Oxford Diffraction, 2006 [triangle]) T min = 0.97, T max = 0.98
  • 10150 measured reflections
  • 3560 independent reflections
  • 2837 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.077
  • S = 1.11
  • 3560 reflections
  • 261 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: PARST95 (Nardelli, 1995 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067414/hg2360sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067414/hg2360Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We are grateful to the Instituto de Química Física Rocasolano, CSIC, Spain, for the use of a licence for the Cambridge Structural Database System (Allen, 2002 [triangle]). RMF and JVN also acknowledge the Universidad del Valle, Colombia for partial financial support.

supplementary crystallographic information

Comment

The title compound, C18H15OP.C6H6O2, belongs to a series of molecular systems based on triphenylphosphine P-oxide (TPPO) with diverse hydrogen-bond donors (Fuquen et al., 1992). In order to expand the crystallographic information of the TPPO complexes, to study the hydrogen bond character of the complex, and to analize its supramolecular arrangement, the structure determination of TPPO + hydroquinone (HQ), (I), system was undertaken. The free HQ molecule in the more stable form at room temperature (Wallwork & Powell, 1980) and the free TPPO molecule (Al-Farhan, 1992) can be taken as a reference systems to compare with the structural characteristics of (I). A displacement ellipsoid plot of the title hydrogen-bonded complex (I), showing the atomic numbering scheme is given in Fig. 1. The O1 atom of the P-oxide group of TPPO acts as an acceptor for hydrogen bonds from O—H groups of two hydroquinone molecules [O1···O2, 2.7451 (17), O1···O3, 2.681 (2) Å and O1···H25—O2, O1···H26—O3 angles of 175 (2) and 170 (2)° respectively, (Table 2)]. These two HQ molecules are each disposed about a centre of symmetry. The title molecule shows a H25—O1—H26 bond angle close to the right angle, seeking an orientation with the minor repulsion between the rings of the molecule. The presence of the three centre hydrogen bond at O1 induces the lengthening of P—O bond length from 1.479 (2) Å in free TPPO molecule (Al-Farhan, 1992) to 1.5016 (13) Å in (I). Other bond lengths and angles of TPPO and HQ remain similar in the complex. The title molecules of (I) are additionally linked by C—H···O hydrogen bonds. Indeed, atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to O3iv atom in the molecule at (x, 1 + y, z), so generating a C21(8) chain (Etter, 1990) which is running parallel to [100] direction (Fig. 2, Supp.material). Other significant intermolecular hydrogen bonds are not observed in the crystalline structure.

Experimental

Crystals of the title compound (I), were obtained by slow evaporation of equimolecular quantities of HQ (1.826 g, 0.017 mol) and TPPO (4.725 g) in 150 ml of dry acetonitrile. After three days, colourless plates of a good quality suitable for X-ray analysis were obtained. Its melting point is 425 (1) K.

Refinement

All non-hydrogen atoms were identified by direct methods and the positions of all the hydrogen atoms were obtained from the use of difference Fourier maps. In the final refinement, all hydrogen atoms were constrained to geometrically sensible positions with a riding model (SHELX97), C—H= 0.95 Å, and Uiso(H)= 1.5Ueq(C), apart from H25 and H26, which were allowed to refine freely.

Figures

Fig. 1.
An ORTEP-3 (Farrugia, 1997) plot of the title compound with the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Ring H-atoms were omitted for clarity. The dashed line indicates a hydrogen bond. [Symmetry code: ...
Fig. 2.
View of the crystal structure of (I), showing the O—H···O and C—H···O interactions along [100] direction. [Symmetry codes: (iv) x, 1 + y, z (v) 1 + x, 1 + y, z]

Crystal data

C18H15OP·C6H6O2Z = 2
Mr = 388.38F000 = 408
Triclinic, P1Dx = 1.284 Mg m3
Hall symbol: -P 1Melting point: 425(1) K
a = 8.927 (4) ÅMo Kα radiation λ = 0.71073 Å
b = 9.3576 (10) ÅCell parameters from 6084 reflections
c = 14.459 (4) Åθ = 2.5–28.6º
α = 71.157 (7)ºµ = 0.16 mm1
β = 73.826 (6)ºT = 150 (2) K
γ = 62.83 (2)ºPlate, colourless
V = 1004.6 (6) Å30.20 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Gemini diffractometer3560 independent reflections
Radiation source: fine-focus sealed tube2837 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
Detector resolution: 15.975 pixels mm-1θmax = 25.0º
T = 150(2) Kθmin = 2.5º
ω and π scansh = −10→10
Absorption correction: multi-scan[empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction, 2006)]k = −11→11
Tmin = 0.97, Tmax = 0.98l = −14→17
10150 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.0364P)2 + 0.182P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
3560 reflectionsΔρmax = 0.36 e Å3
261 parametersΔρmin = −0.32 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
P10.95138 (5)0.39823 (5)0.27946 (3)0.01905 (11)
O11.12889 (12)0.37744 (12)0.27829 (7)0.0236 (2)
O20.31558 (16)0.56334 (14)0.18170 (8)0.0330 (3)
O30.43737 (16)0.13741 (16)0.30698 (8)0.0390 (3)
C190.40534 (19)0.52905 (18)0.09190 (10)0.0225 (3)
C130.95218 (18)0.23915 (17)0.23485 (10)0.0198 (3)
C181.0897 (2)0.08595 (18)0.24493 (11)0.0265 (4)
H181.18110.06700.27500.040*
C240.3343 (2)0.09996 (18)0.48323 (11)0.0269 (4)
H240.22030.16850.47190.040*
C210.59840 (19)0.58783 (18)−0.05380 (11)0.0240 (3)
H210.66540.6487−0.09050.036*
C100.6658 (2)0.37566 (19)0.59682 (11)0.0277 (4)
H100.60910.37010.66320.042*
C140.81782 (19)0.26512 (19)0.19154 (11)0.0254 (3)
H140.72300.36880.18480.038*
C10.84087 (18)0.59192 (17)0.19937 (10)0.0195 (3)
C80.7437 (2)0.29020 (19)0.44432 (11)0.0274 (4)
H80.74010.22580.40650.041*
C70.83224 (18)0.39133 (17)0.40226 (10)0.0200 (3)
C60.9123 (2)0.61763 (18)0.09972 (11)0.0250 (3)
H61.01290.53280.07650.037*
C30.6205 (2)0.86657 (19)0.16682 (12)0.0303 (4)
H30.52070.95240.18970.046*
C200.50465 (19)0.61583 (18)0.03765 (11)0.0237 (3)
H200.50860.69530.06330.035*
C90.6605 (2)0.2829 (2)0.54123 (11)0.0310 (4)
H90.59980.21400.56950.047*
C160.9609 (2)−0.01175 (19)0.16781 (12)0.0306 (4)
H160.9642−0.09720.14430.046*
C50.8378 (2)0.76576 (19)0.03425 (11)0.0281 (4)
H50.88660.7821−0.03360.042*
C120.8361 (2)0.48507 (19)0.45913 (11)0.0273 (4)
H120.89580.55500.43120.041*
C150.8228 (2)0.1395 (2)0.15826 (12)0.0308 (4)
H150.73110.15720.12880.046*
C171.0939 (2)−0.03884 (19)0.21136 (12)0.0310 (4)
H171.1881−0.14300.21830.046*
C220.6308 (2)−0.02875 (18)0.42058 (11)0.0262 (4)
H220.7207−0.04890.36630.039*
C20.69447 (19)0.71779 (18)0.23265 (11)0.0247 (3)
H20.64500.70210.30040.037*
C230.4649 (2)0.07154 (18)0.40370 (11)0.0258 (4)
C110.7535 (2)0.4765 (2)0.55590 (11)0.0306 (4)
H110.75700.54010.59430.046*
C40.6920 (2)0.88961 (19)0.06822 (12)0.0284 (4)
H40.64070.99120.02340.043*
H250.251 (3)0.509 (3)0.2108 (15)0.059 (6)*
H260.332 (3)0.209 (3)0.3043 (14)0.055 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0199 (2)0.0200 (2)0.0180 (2)−0.00858 (16)−0.00232 (15)−0.00511 (15)
O10.0217 (6)0.0269 (6)0.0236 (6)−0.0118 (5)−0.0035 (4)−0.0044 (4)
O20.0419 (7)0.0360 (7)0.0268 (6)−0.0243 (6)0.0089 (5)−0.0137 (5)
O30.0303 (7)0.0430 (7)0.0287 (7)−0.0009 (6)−0.0079 (5)−0.0079 (5)
C190.0222 (8)0.0216 (7)0.0213 (8)−0.0071 (7)−0.0030 (6)−0.0050 (6)
C130.0221 (8)0.0213 (7)0.0157 (7)−0.0094 (6)−0.0019 (6)−0.0036 (6)
C180.0281 (9)0.0236 (8)0.0263 (8)−0.0063 (7)−0.0097 (7)−0.0056 (6)
C240.0214 (8)0.0224 (8)0.0357 (9)−0.0062 (7)−0.0060 (7)−0.0077 (7)
C210.0226 (8)0.0233 (8)0.0275 (9)−0.0122 (7)−0.0038 (7)−0.0035 (6)
C100.0300 (9)0.0298 (9)0.0183 (8)−0.0113 (7)0.0001 (7)−0.0036 (7)
C140.0242 (9)0.0232 (8)0.0288 (9)−0.0076 (7)−0.0063 (7)−0.0071 (6)
C10.0211 (8)0.0205 (7)0.0210 (8)−0.0111 (6)−0.0025 (6)−0.0064 (6)
C80.0330 (9)0.0284 (8)0.0258 (9)−0.0170 (7)0.0010 (7)−0.0103 (7)
C70.0203 (8)0.0191 (7)0.0199 (8)−0.0075 (6)−0.0044 (6)−0.0032 (6)
C60.0261 (9)0.0241 (8)0.0237 (8)−0.0086 (7)−0.0023 (7)−0.0077 (6)
C30.0247 (9)0.0232 (8)0.0414 (10)−0.0052 (7)−0.0054 (7)−0.0119 (7)
C200.0259 (8)0.0205 (7)0.0268 (8)−0.0099 (7)−0.0053 (7)−0.0062 (6)
C90.0366 (10)0.0299 (9)0.0288 (9)−0.0211 (8)0.0051 (7)−0.0066 (7)
C160.0424 (10)0.0259 (9)0.0303 (9)−0.0175 (8)−0.0048 (8)−0.0099 (7)
C50.0356 (10)0.0302 (9)0.0209 (8)−0.0169 (8)−0.0047 (7)−0.0032 (7)
C120.0335 (9)0.0325 (9)0.0238 (8)−0.0206 (8)−0.0017 (7)−0.0075 (7)
C150.0324 (9)0.0339 (9)0.0339 (9)−0.0162 (8)−0.0090 (7)−0.0099 (7)
C170.0349 (10)0.0202 (8)0.0325 (9)−0.0047 (7)−0.0080 (8)−0.0066 (7)
C220.0235 (8)0.0236 (8)0.0297 (9)−0.0089 (7)0.0003 (7)−0.0084 (7)
C20.0220 (8)0.0256 (8)0.0260 (8)−0.0095 (7)−0.0001 (7)−0.0086 (7)
C230.0281 (9)0.0205 (8)0.0288 (9)−0.0088 (7)−0.0064 (7)−0.0055 (6)
C110.0384 (10)0.0366 (9)0.0242 (9)−0.0194 (8)−0.0024 (7)−0.0118 (7)
C40.0323 (9)0.0207 (8)0.0350 (10)−0.0111 (7)−0.0154 (8)−0.0007 (7)

Geometric parameters (Å, °)

P1—O11.5016 (13)C8—C91.387 (2)
P1—C71.7957 (15)C8—C71.391 (2)
P1—C131.8000 (14)C8—H80.9500
P1—C11.8020 (15)C7—C121.399 (2)
O2—C191.3732 (18)C6—C51.386 (2)
O2—H250.87 (2)C6—H60.9500
O3—C231.3756 (19)C3—C41.381 (2)
O3—H260.87 (2)C3—C21.391 (2)
C19—C201.385 (2)C3—H30.9500
C19—C21i1.391 (2)C20—H200.9500
C13—C181.393 (2)C9—H90.9500
C13—C141.394 (2)C16—C171.382 (2)
C18—C171.384 (2)C16—C151.384 (2)
C18—H180.9500C16—H160.9500
C24—C231.386 (2)C5—C41.383 (2)
C24—C22ii1.389 (2)C5—H50.9500
C24—H240.9500C12—C111.384 (2)
C21—C201.387 (2)C12—H120.9500
C21—C19i1.391 (2)C15—H150.9500
C21—H210.9500C17—H170.9500
C10—C111.382 (2)C22—C231.384 (2)
C10—C91.382 (2)C22—C24ii1.389 (2)
C10—H100.9500C22—H220.9500
C14—C151.386 (2)C2—H20.9500
C14—H140.9500C11—H110.9500
C1—C21.392 (2)C4—H40.9500
C1—C61.395 (2)
O1—P1—C7111.26 (6)C1—C6—H6119.7
O1—P1—C13111.76 (7)C4—C3—C2120.06 (15)
C7—P1—C13107.64 (7)C4—C3—H3120.0
O1—P1—C1110.35 (7)C2—C3—H3120.0
C7—P1—C1109.06 (7)C19—C20—C21120.68 (14)
C13—P1—C1106.61 (7)C19—C20—H20119.7
C19—O2—H25113.3 (14)C21—C20—H20119.7
C23—O3—H26110.4 (13)C10—C9—C8120.17 (15)
O2—C19—C20117.57 (13)C10—C9—H9119.9
O2—C19—C21i123.33 (14)C8—C9—H9119.9
C20—C19—C21i119.10 (14)C17—C16—C15120.20 (14)
C18—C13—C14119.35 (14)C17—C16—H16119.9
C18—C13—P1119.06 (11)C15—C16—H16119.9
C14—C13—P1121.58 (11)C4—C5—C6119.69 (15)
C17—C18—C13120.39 (15)C4—C5—H5120.2
C17—C18—H18119.8C6—C5—H5120.2
C13—C18—H18119.8C11—C12—C7120.35 (14)
C23—C24—C22ii120.31 (15)C11—C12—H12119.8
C23—C24—H24119.8C7—C12—H12119.8
C22ii—C24—H24119.8C16—C15—C14120.20 (15)
C20—C21—C19i120.21 (14)C16—C15—H15119.9
C20—C21—H21119.9C14—C15—H15119.9
C19i—C21—H21119.9C16—C17—C18119.93 (15)
C11—C10—C9120.09 (14)C16—C17—H17120.0
C11—C10—H10120.0C18—C17—H17120.0
C9—C10—H10120.0C23—C22—C24ii120.06 (14)
C15—C14—C13119.93 (14)C23—C22—H22120.0
C15—C14—H14120.0C24ii—C22—H22120.0
C13—C14—H14120.0C3—C2—C1120.11 (14)
C2—C1—C6119.13 (14)C3—C2—H2119.9
C2—C1—P1123.52 (11)C1—C2—H2119.9
C6—C1—P1117.28 (11)O3—C23—C22117.62 (14)
C9—C8—C7120.29 (14)O3—C23—C24122.74 (14)
C9—C8—H8119.9C22—C23—C24119.63 (14)
C7—C8—H8119.9C10—C11—C12120.10 (14)
C8—C7—C12119.00 (14)C10—C11—H11120.0
C8—C7—P1122.40 (11)C12—C11—H11120.0
C12—C7—P1118.52 (11)C3—C4—C5120.41 (14)
C5—C6—C1120.60 (14)C3—C4—H4119.8
C5—C6—H6119.7C5—C4—H4119.8
O1—P1—C13—C1827.30 (14)P1—C1—C6—C5−177.79 (12)
C7—P1—C13—C18−95.15 (13)O2—C19—C20—C21−179.84 (13)
C1—P1—C13—C18147.95 (12)C21i—C19—C20—C210.5 (2)
O1—P1—C13—C14−153.41 (12)C19i—C21—C20—C19−0.5 (2)
C7—P1—C13—C1484.14 (13)C11—C10—C9—C80.2 (2)
C1—P1—C13—C14−32.76 (14)C7—C8—C9—C10−0.3 (2)
C14—C13—C18—C170.7 (2)C1—C6—C5—C40.5 (2)
P1—C13—C18—C17179.98 (12)C8—C7—C12—C110.3 (2)
C18—C13—C14—C15−0.6 (2)P1—C7—C12—C11−176.59 (12)
P1—C13—C14—C15−179.84 (12)C17—C16—C15—C140.6 (2)
O1—P1—C1—C2−117.60 (13)C13—C14—C15—C16−0.1 (2)
C7—P1—C1—C24.90 (15)C15—C16—C17—C18−0.5 (2)
C13—P1—C1—C2120.85 (13)C13—C18—C17—C16−0.2 (2)
O1—P1—C1—C659.36 (13)C4—C3—C2—C10.1 (2)
C7—P1—C1—C6−178.14 (11)C6—C1—C2—C30.4 (2)
C13—P1—C1—C6−62.18 (13)P1—C1—C2—C3177.30 (11)
C9—C8—C7—C120.0 (2)C24ii—C22—C23—O3−179.31 (14)
C9—C8—C7—P1176.74 (12)C24ii—C22—C23—C24−0.2 (2)
O1—P1—C7—C8−129.66 (13)C22ii—C24—C23—O3179.27 (14)
C13—P1—C7—C8−6.90 (15)C22ii—C24—C23—C220.2 (2)
C1—P1—C7—C8108.39 (13)C9—C10—C11—C120.0 (2)
O1—P1—C7—C1247.07 (13)C7—C12—C11—C10−0.3 (2)
C13—P1—C7—C12169.82 (12)C2—C3—C4—C5−0.4 (2)
C1—P1—C7—C12−74.88 (13)C6—C5—C4—C30.1 (2)
C2—C1—C6—C5−0.7 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H25···O1iii0.87 (2)1.87 (2)2.7451 (17)175 (2)
O3—H26···O1iii0.87 (2)1.82 (2)2.681 (2)170 (2)
C3—H3···O3iv0.952.543.300 (2)137

Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2360).

References

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