Benzyltriphenylphosphonium gluta­conaldehyde

The title compound, C₂₅H₂₂P⁺·C₅H₅O₂⁻, crystallizes in space group P2₁/c. The phospho­nium cations form zigzag chains with P...P distances of 6.475 (1) and 8.287 (2) Å, and are related by inversion centres. Two types of attractive edge-to-face phenyl interactions exist, resulting in a dominant supramolecular motif. The glutaconaldehyde anions occupy the interchain spacing and hold adjacent chains together via multiple C—­H...O hydrogen bonds. The bond-length alternation, a parameter which reveals the non-linear optical efficiency at the molecular level, is optimized in the chromophore anion.

S1. Comment

Conjugated polyenes are nonlinear optical chromophores displaying large molecular hyperpolarizabilities. Crystals built up from such chromophores are very rare. We describe here the crystal structure of the title compound, (I), containing a conjugated polyene, the glutaconaldehydate anion, with optimized bond length alternation. This situation is due to the associated cation, the benzyltriphenylphosphonium. Semiempirical calculations performed on push-pull polyenes have shown that the static quadratic hyperpolarizability can be correlated with the ground state polarization and concomitantly with a structural parameter, the bond length alternation (BLA) (Marder et al., 1994; Meyers et al., 1994). The BLA describes the ground state geometry of the molecule and is defined as the average difference in the lengths between adjacent C—C bonds in the polyenic chain. Calculations indicate that the molecular hyperpolarizability (β) is a maximum when the BLA is ± 0.05 (1) Å (Blanchard-Desce et al., 1997). \sch

The glutaconaldehydate anion is not stable in solution at room temperature and at acidic pH and undergoes polymerization. However it is known to be stable in solution at low temperatures and basic pH, and in the solid state only with bulky counterions. In solution, it exists in two similar resonance forms with equal contribution and hence BLA = 0. Computational studies have shown that by modifying the parameters that govern the relative weights of these two resonance forms, it should be possible to optimize the molecular structure so as to maximize the optical nonlinearity in the solid state (Barzoukas et al., 1996). The balance between the two limiting resonance forms of a polyene can be modified by altering the donor-acceptor strengths at the terminals or the nature of the conjugated path with external perturbation. We have attempted to perturb the contribution of the two resonance forms of the glutaconaldehydate anion by external charged centres [metal cations such as sodium (Muthuraman et al., 1999) or bulky organic cations], to optimize the BLA. However, these salts crystallize in centrosymmetric space groups, excluding possible optical nonlinearity at the macroscopic level.

The unit cell of (I) contains four cation-anion entities. In the crystal lattice, the phosphonium cations form a zigzag chain with P···P distances of 8.287 (2) Å (-x, −y, 1 − z) and 6.475 (1) Å (1 − x, −y, 1 − z), running parallel with the a direction. The cations in the chain are held together by two types of edge-to-face (ef) phenyl interactions (Fig. 2). One type involves four phenyl rings (two per phosphonium cation), resulting in two ef interactions leading to a P···P distance of 8.287 (2) Å, related by an inversion centre. The other type involves two phenyl rings and two benzyl groups (one phenyl and one benzyl per phosphonium cation), having two ef interactions leading to a P···P distance of 6.475 (1) Å, also related by inversion centre. The phenylphosphonium cations are known to form supramolecular synthons, the so-called phenyl embraces, through phenyl-phenyl interactions, and Dance et al. (Dance & Sudder, 1996; Sudder & Dance, 1998; Hasselgren et al., 1998) have extensively analysed various kinds of multiple attractive phenyl interactions leading to chains and networks, as shown in Fig. 2.

The anions in (I) occupy the space between the chains and hold the chains together through multiple C—H···O hydrogen bonds (Desiraju, 1996; Steiner & Desiraju, 1998; Table 1). Atom O2(1 − x, 1 − y, 1 − z) of the glutaconaldehydate anion is closer [4.161 (2) Å] to the P than O1(x, 1/2 − y, 1/2 + z) [4.967 (2) Å] and the values of the C—O distances [C26—O1 = 1.230 (3) and C30—O2 = 1.249 (3) Å] suggest that O2 carries more negative charge and C26—O1 has more double bond character than C30—O2. Such an anion dissymetry due to the counterbalance of charges gives an optimal value for the BLA. There are two C—C single bonds and two C=C double bonds in the anion and a BLA of 0.021 (6) Å is calculated [(1.386 + 1.383)/2 - (1.363 + 1.364)/2].

The crystal structure of (I), as well as that of sodium glutaconaldehyde dihydrate (Muthuraman et al., 1999), establishes that the BLA of polyene entities can reach, in the solid state, the ideal values observed at molecular level with polyenes onto which electron donor and acceptor groups are grafted. Thus the hyperpolarizability of anion polyenes can be manipulated by the choice of the associated cations in crystalline materials.

S2. Experimental

Compound (I) was prepared by the cation exchange reaction of potassium glutaconaldehyde with benzyltriphenylphosphonium chloride. Benzyltriphenylphosphonium chloride (0.001 mol) was dissolved in water (25 ml) and the pH was adjusted to 12 by adding 0.01 N aqueous NaOH. This solution was cooled to 263 K and solid potassium glutaconaldehyde (0.001 mol; Becher, 1988) was added with stirring. After 15 min of stirring, the cooling bath was removed. The solution was extracted immediately with CH₂Cl₂, dried over K₂CO₃ and evaporated to obtain a brown solid. Recrystallization was carried out by dissolution in ethyl acetate and treatment with activated carbon, followed by filtration and slow evaporation to obtain X-ray quality dark-brown needle crystals of (I).

S3. Refinement

All H atoms were found by difference Fourier analyses and not refined. Since their refinement introduced an excess of parameters with respect to the number of reflections we preserved their positions, taking into account the remarkable C—H distances between 0.85 and 1.1 Å and the C—C—H angles close to their ideal value. An average displacement factor U_iso = 0.082 Ų was attributed to each H atom.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: KappaCCD Server Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare et al. 1993); program(s) used to refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.

Figures

	Fig. 1. The molecular structure of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are plotted at the 50% probability level.
	Fig. 2. The chain of benzyltriphenylphosphonium cations in (I) formed by ef phenyl-phenylinteractions.

(I)

Crystal data

C25H22P^+·C5H5O2^−	F(000) = 952.00
Mr = 450.52	Dx = 1.189 Mg m^−3
Monoclinic, P21/c	Ag Kα radiation, λ = 0.5608 Å
a = 12.983 (1) Å	Cell parameters from 5616 reflections
b = 11.435 (1) Å	θ = 2.1–21.0°
c = 17.028 (2) Å	µ = 0.08 mm^−1
β = 95.35 (2)°	T = 296 K
V = 2517.0 (4) Å^3	Needle, dark brown
Z = 4	0.29 × 0.16 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	3489 reflections with I > 2.6σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 21.0°, θmin = 2.1°
Data from ϕ = 1°, ϕ scans	h = 0→16
10920 measured reflections	k = −14→14
5616 independent reflections	l = −21→21

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters not refined
wR(F^2) = 0.051	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.00006|Fo|^2]
S = 2.00	(Δ/σ)max < 0.001
3489 reflections	Δρmax = 0.35 e Å^−3
298 parameters	Δρmin = −0.37 e Å^−3

Special details

Experimental. scan mode: 180 exposures, ϕ = 1°

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

	x	y	z	Uiso*/Ueq
P	0.30174 (3)	0.04186 (3)	0.59864 (2)	0.04091 (13)
O1	0.07113 (9)	0.46135 (11)	0.31557 (8)	0.0913 (5)
O2	0.49757 (9)	0.76097 (11)	0.52492 (7)	0.0836 (5)
C1	0.22084 (11)	−0.08083 (12)	0.61374 (9)	0.0446 (5)
C2	0.12640 (13)	−0.0934 (2)	0.56941 (10)	0.0619 (6)
C3	0.0663 (1)	−0.1907 (2)	0.5808 (1)	0.0865 (8)
C4	0.0988 (2)	−0.2737 (2)	0.6341 (2)	0.1066 (10)
C5	0.1924 (2)	−0.2634 (2)	0.6769 (2)	0.1028 (9)
C6	0.25390 (13)	−0.1670 (2)	0.66799 (11)	0.0701 (6)
C7	0.40634 (11)	0.04830 (13)	0.67518 (9)	0.0450 (5)
C8	0.49173 (13)	−0.0239 (1)	0.67337 (10)	0.0623 (6)
C9	0.56947 (13)	−0.0207 (2)	0.73501 (12)	0.0796 (7)
C10	0.5625 (2)	0.0533 (2)	0.79709 (12)	0.0809 (8)
C11	0.4786 (2)	0.1250 (2)	0.79922 (10)	0.0771 (7)
C12	0.40121 (13)	0.1240 (1)	0.73853 (10)	0.0617 (6)
C13	0.22857 (10)	0.17393 (12)	0.60053 (8)	0.0428 (5)
C14	0.13318 (12)	0.17741 (13)	0.63094 (10)	0.0555 (5)
C15	0.07921 (12)	0.2822 (2)	0.63044 (11)	0.0707 (7)
C16	0.1203 (2)	0.3812 (2)	0.60068 (12)	0.0748 (7)
C17	0.2156 (2)	0.3793 (2)	0.57299 (10)	0.0675 (6)
C18	0.27031 (11)	0.2761 (1)	0.57284 (9)	0.0549 (5)
C19	0.35432 (10)	0.02719 (12)	0.50449 (8)	0.0468 (5)
C20	0.27452 (11)	0.0351 (1)	0.43454 (8)	0.0445 (5)
C21	0.24971 (12)	0.1425 (1)	0.39924 (10)	0.0577 (6)
C22	0.1732 (1)	0.1512 (2)	0.33705 (10)	0.0723 (7)
C23	0.1207 (1)	0.0538 (2)	0.30937 (10)	0.0773 (7)
C24	0.1447 (1)	−0.0523 (2)	0.34194 (11)	0.0719 (7)
C25	0.22360 (13)	−0.0629 (1)	0.40448 (10)	0.0620 (6)
C26	0.1587 (1)	0.4976 (2)	0.33616 (12)	0.0718 (7)
C27	0.19424 (12)	0.5644 (2)	0.40103 (11)	0.0650 (6)
C28	0.29515 (13)	0.5969 (2)	0.41590 (10)	0.0609 (6)
C29	0.34425 (13)	0.6636 (1)	0.47599 (10)	0.0638 (6)
C30	0.4459 (1)	0.6945 (2)	0.47825 (11)	0.0738 (7)
H1	0.1001	−0.0341	0.5307	0.082*
H2	−0.0008	−0.1923	0.5467	0.082*
H3	0.0561	−0.3355	0.6425	0.082*
H4	0.2167	−0.3166	0.7197	0.082*
H5	0.3143	−0.1546	0.6995	0.082*
H6	0.4930	−0.0759	0.6341	0.082*
H7	0.6232	−0.0729	0.7316	0.082*
H8	0.6130	0.0537	0.8395	0.082*
H9	0.4781	0.1804	0.8405	0.082*
H10	0.3409	0.1764	0.7358	0.082*
H11	0.1047	0.1077	0.6510	0.082*
H12	0.0094	0.2809	0.6533	0.082*
H13	0.0882	0.4457	0.6041	0.082*
H14	0.2548	0.4434	0.5549	0.082*
H15	0.3328	0.2737	0.5543	0.082*
H16	0.3909	−0.0471	0.5097	0.082*
H17	0.3977	0.0878	0.5047	0.082*
H18	0.2848	0.2123	0.4186	0.082*
H19	0.1524	0.2300	0.3126	0.082*
H20	0.0636	0.0595	0.2652	0.082*
H21	0.1131	−0.1195	0.3251	0.082*
H22	0.2397	−0.1346	0.4245	0.082*
H23	0.2218	0.4675	0.3021	0.082*
H24	0.1373	0.5903	0.4355	0.082*
H25	0.3322	0.5704	0.3724	0.082*
H26	0.3052	0.6934	0.5199	0.082*
H27	0.4831	0.6551	0.4289	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0387 (2)	0.0417 (3)	0.0425 (3)	−0.0018 (2)	0.0048 (2)	0.0025 (2)
O1	0.0594 (8)	0.0936 (10)	0.1169 (12)	−0.0150 (7)	−0.0131 (8)	0.0037 (8)
O2	0.0926 (9)	0.0786 (9)	0.0770 (9)	−0.0366 (8)	−0.0059 (7)	0.0006 (7)
C1	0.0461 (9)	0.0394 (10)	0.0500 (10)	−0.0032 (7)	0.0135 (8)	−0.0016 (8)
C2	0.0589 (11)	0.0598 (12)	0.0696 (12)	−0.0173 (9)	0.0191 (9)	−0.0163 (9)
C3	0.0708 (13)	0.079 (2)	0.115 (2)	−0.0348 (12)	0.0335 (13)	−0.038 (1)
C4	0.100 (2)	0.051 (1)	0.181 (3)	−0.031 (1)	0.080 (2)	−0.023 (2)
C5	0.116 (2)	0.060 (2)	0.143 (2)	0.007 (1)	0.071 (2)	0.037 (1)
C6	0.0736 (12)	0.0591 (12)	0.081 (1)	−0.0040 (10)	0.0259 (10)	0.0169 (10)
C7	0.0449 (9)	0.0474 (10)	0.0427 (10)	−0.0012 (8)	0.0038 (7)	0.0021 (8)
C8	0.0583 (11)	0.0733 (12)	0.0540 (11)	0.0098 (9)	−0.0013 (9)	−0.0036 (9)
C9	0.0603 (12)	0.106 (2)	0.070 (1)	0.0199 (11)	−0.0078 (11)	0.0020 (12)
C10	0.0700 (13)	0.103 (2)	0.064 (1)	−0.0045 (12)	−0.0219 (11)	0.0038 (12)
C11	0.090 (1)	0.078 (1)	0.0593 (13)	−0.0024 (12)	−0.0166 (11)	−0.0156 (10)
C12	0.0669 (11)	0.0607 (12)	0.0555 (12)	−0.0008 (9)	−0.0038 (9)	−0.0059 (10)
C13	0.0442 (9)	0.0427 (10)	0.0411 (9)	−0.0026 (7)	0.0016 (7)	0.0002 (7)
C14	0.0515 (10)	0.0498 (11)	0.0657 (12)	0.0037 (8)	0.0079 (9)	−0.0031 (9)
C15	0.0616 (11)	0.0613 (13)	0.090 (2)	0.0065 (10)	0.0116 (10)	−0.0119 (11)
C16	0.081 (1)	0.0515 (13)	0.088 (2)	0.0207 (11)	−0.0102 (12)	−0.0121 (11)
C17	0.089 (1)	0.0440 (12)	0.0691 (13)	−0.0062 (10)	0.0025 (11)	0.0035 (9)
C18	0.0581 (10)	0.0479 (11)	0.0589 (11)	−0.0025 (9)	0.0057 (8)	0.0041 (9)
C19	0.0443 (9)	0.0502 (10)	0.0463 (10)	−0.0008 (7)	0.0064 (7)	0.0039 (8)
C20	0.0433 (9)	0.0522 (11)	0.0392 (10)	−0.0030 (8)	0.0098 (7)	−0.0017 (8)
C21	0.0650 (11)	0.0596 (12)	0.0475 (11)	0.0018 (9)	0.0002 (9)	0.0024 (9)
C22	0.0782 (13)	0.082 (2)	0.0545 (12)	0.0065 (11)	−0.0051 (10)	0.0062 (11)
C23	0.0602 (12)	0.119 (2)	0.0520 (12)	−0.0048 (12)	0.0011 (9)	−0.0015 (13)
C24	0.0731 (13)	0.087 (2)	0.0560 (13)	−0.0281 (11)	0.0097 (10)	−0.0194 (11)
C25	0.0761 (12)	0.0589 (12)	0.0523 (12)	−0.0062 (10)	0.0140 (10)	−0.0066 (9)
C26	0.0533 (12)	0.0709 (13)	0.090 (2)	−0.0102 (10)	0.0017 (10)	0.0018 (11)
C27	0.0512 (11)	0.0699 (13)	0.0730 (13)	−0.0016 (9)	0.0020 (9)	0.0087 (10)
C28	0.0559 (11)	0.0595 (12)	0.0678 (12)	−0.0040 (9)	0.0087 (9)	0.0024 (10)
C29	0.0641 (12)	0.0595 (12)	0.0672 (13)	−0.0057 (9)	0.0029 (10)	0.0015 (10)
C30	0.0722 (13)	0.0738 (13)	0.076 (1)	−0.0205 (11)	0.0071 (10)	−0.0057 (11)

Geometric parameters (Å, º)

P—C1	1.786 (2)	C14—C15	1.388 (3)
P—C13	1.786 (2)	C15—H12	1.02
P—C7	1.794 (2)	C15—C16	1.368 (3)
P—C19	1.808 (2)	C16—H13	0.85
O1—C26	1.230 (3)	C16—C17	1.366 (3)
O2—C30	1.249 (3)	C17—H14	0.96
C1—C2	1.386 (3)	C17—C18	1.377 (3)
C1—C6	1.391 (3)	C18—H15	0.90
C2—H1	0.98	C19—H17	0.89
C2—C3	1.383 (3)	C19—H16	0.97
C3—H2	1.00	C19—C20	1.507 (3)
C3—C4	1.353 (4)	C20—C25	1.376 (3)
C4—H3	0.92	C20—C21	1.391 (3)
C4—C5	1.363 (4)	C21—H18	0.96
C5—H4	0.98	C21—C22	1.386 (3)
C5—C6	1.378 (4)	C22—H19	1.02
C6—H5	0.92	C22—C23	1.366 (3)
C7—C8	1.385 (3)	C23—H20	1.01
C7—C12	1.390 (3)	C23—C24	1.358 (3)
C8—H6	0.90	C24—H21	0.90
C8—C9	1.387 (3)	C24—C25	1.412 (3)
C9—H7	0.92	C25—H22	0.91
C9—C10	1.364 (4)	C26—H23	1.10
C10—H8	0.93	C26—C27	1.386 (3)
C10—C11	1.366 (3)	C27—H24	1.03
C11—H9	0.95	C27—C28	1.363 (3)
C11—C12	1.372 (3)	C28—H25	0.97
C12—H10	0.98	C28—C29	1.383 (3)
C13—C14	1.387 (3)	C29—H26	1.00
C13—C18	1.389 (3)	C29—C30	1.364 (3)
C14—H11	0.96	C30—H27	1.10
O1···H3^i	2.3518	C16···H20^xi	3.0385
O1···H20^ii	2.4001	C16···C23^xi	3.630 (4)
O1···H13^iii	2.7935	C17···C27	3.603 (3)
O1···H19	2.8504	C21···H7^x	3.0004
O1···H11^iv	2.9823	C22···H7^x	3.1193
O1···C4^i	3.250 (3)	C24···H4^xii	2.7956
O1···C23^ii	3.296 (3)	C25···C29^ix	3.655 (3)
O1···C16^iii	3.480 (3)	C26···H19	3.0864
O1···C14^iv	3.677 (3)	C27···H14	3.0027
O1···C15^iii	3.686 (3)	C28···H14	3.0319
O1···C24^ii	3.697 (3)	C29···H22^vii	2.7770
O2···H17^v	2.2850	C29···H14	3.1284
O2···H9^vi	2.4632	C30···H15^v	2.9980
O2···H16^vii	2.5948	C30···H16^vii	3.0981
O2···H6^vii	2.6381	H3···H13^ix	2.6288
O2···H15^v	2.7167	H4···H21^viii	2.4522
O2···H18^v	2.9147	H8···H14^xiii	2.6820
O2···C19^v	3.162 (3)	H10···H23^xi	2.5888
O2···C11^vi	3.363 (3)	H12···H21^i	2.4864
O2···C8^vii	3.533 (3)	H12···H20^xi	2.6843
O2···C19^vii	3.568 (3)	H12···H24^iii	2.7472
O2···C21^v	3.586 (3)	H15···H27^v	2.5162
O2···C18^v	3.601 (3)	H22···H26^ix	2.6404
C3···C22^i	3.556 (4)	H3···O1^i	2.3518
C3···C23^i	3.563 (4)	H6···O2^ix	2.6381
C5···H21^viii	3.1152	H9···O2^xiii	2.4632
C5···C24^viii	3.612 (4)	H15···O2^v	2.7167
C6···H26^ix	3.1087	H16···O2^ix	2.5948
C8···C20^x	3.694 (3)	H17···O2^v	2.2850
C9···C20^x	3.682 (4)	H20···O1^xiv	2.4001
C9···C21^x	3.698 (4)	H23···O1	1.9914
C12···H23^xi	2.8578	H24···O1	2.5996
C15···H20^xi	2.9440	H26···O2	2.6078
C15···C23^xi	3.575 (4)	H27···O2	2.0293
C15···C22^xi	3.694 (4)
C1—P—C13	109.93 (10)	C16—C15—C14	120.2 (2)
C1—P—C7	110.07 (10)	H13—C16—C17	120.1
C1—P—C19	109.31 (9)	H13—C16—C15	118.8
C13—P—C7	108.67 (10)	C17—C16—C15	120.8 (2)
C13—P—C19	109.87 (10)	H14—C17—C16	128.6
C7—P—C19	108.98 (9)	H14—C17—C18	111.4
C2—C1—C6	119.4 (2)	C16—C17—C18	119.9 (2)
C2—C1—P	120.4 (2)	H15—C18—C17	120.7
C6—C1—P	120.2 (2)	H15—C18—C13	119.1
H1—C2—C3	118.9	C17—C18—C13	120.2 (2)
H1—C2—C1	121.8	H17—C19—H16	112.0
C3—C2—C1	119.3 (3)	H17—C19—C20	110.1
H2—C3—C4	125.2	H17—C19—P	102.4
H2—C3—C2	113.9	H16—C19—C20	114.7
C4—C3—C2	120.9 (3)	H16—C19—P	102.8
H3—C4—C3	119.3	C20—C19—P	114.00 (13)
H3—C4—C5	120.3	C25—C20—C21	118.3 (2)
C3—C4—C5	120.3 (3)	C25—C20—C19	121.1 (2)
H4—C5—C4	123.7	C21—C20—C19	120.6 (2)
H4—C5—C6	115.4	H18—C21—C22	119.0
C4—C5—C6	120.5 (3)	H18—C21—C20	120.1
H5—C6—C5	122.1	C22—C21—C20	120.9 (2)
H5—C6—C1	118.1	H19—C22—C23	118.4
C5—C6—C1	119.6 (2)	H19—C22—C21	121.3
C8—C7—C12	119.0 (2)	C23—C22—C21	120.2 (2)
C8—C7—P	120.8 (2)	H20—C23—C24	119.1
C12—C7—P	120.1 (2)	H20—C23—C22	120.9
H6—C8—C7	118.9	C24—C23—C22	120.0 (2)
H6—C8—C9	121.3	H21—C24—C23	123.3
C7—C8—C9	119.6 (2)	H21—C24—C25	116.2
H7—C9—C10	123.7	C23—C24—C25	120.5 (2)
H7—C9—C8	115.8	H22—C25—C20	120.8
C10—C9—C8	120.5 (2)	H22—C25—C24	119.2
H8—C10—C9	120.8	C20—C25—C24	120.0 (2)
H8—C10—C11	118.9	H23—C26—O1	117.2
C9—C10—C11	120.2 (2)	H23—C26—C27	112.5
H9—C11—C10	118.8	O1—C26—C27	130.1 (3)
H9—C11—C12	120.6	H24—C27—C28	123.0
C10—C11—C12	120.3 (2)	H24—C27—C26	114.2
H10—C12—C11	123.6	C28—C27—C26	122.8 (2)
H10—C12—C7	116.0	H25—C28—C27	108.0
C11—C12—C7	120.3 (2)	H25—C28—C29	120.7
C14—C13—C18	119.5 (2)	C27—C28—C29	131.1 (2)
C14—C13—P	121.7 (2)	H26—C29—C30	116.5
C18—C13—P	118.7 (2)	H26—C29—C28	120.6
H11—C14—C13	119.9	C30—C29—C28	122.8 (2)
H11—C14—C15	120.7	H27—C30—O2	119.1
C13—C14—C15	119.4 (2)	H27—C30—C29	111.3
H12—C15—C16	123.0	O2—C30—C29	129.5 (3)
H12—C15—C14	116.8

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) x, −y+1/2, z−1/2; (v) −x+1, −y+1, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) x, y+1, z; (viii) x, −y−1/2, z+1/2; (ix) x, y−1, z; (x) −x+1, −y, −z+1; (xi) x, −y+1/2, z+1/2; (xii) x, −y−1/2, z−1/2; (xiii) −x+1, y−1/2, −z+3/2; (xiv) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4^i—H3^i···O1	0.92	2.35	3.250 (3)	166
C8^vii—H6^vii···O2	0.90	2.64	3.533 (3)	177
C11^vi—H9^vi···O2	0.95	2.46	3.363 (3)	159
C16^iii—H13^iii···O1	0.85	2.79	3.480 (3)	139
C18^v—H15^v···O2	0.90	2.72	3.601 (3)	168
C19^vii—H16^vii···O2	0.97	2.60	3.568 (3)	177
C19^v—H17^v···O2	0.89	2.29	3.162 (2)	167
C23^ii—H20^ii···O1	1.01	2.40	3.296 (3)	148

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) x, y+1, z.