Favoured conformations of methyl isopropyl, ethyl isopropyl, methyl tert-butyl, and ethyl tert-butyl 2-(tri­phenyl­phospho­ranylidene)malonate

The conformations of organic compounds determined in the solid state are important because they can be compared with those in solution and/or from theoretical calculations. In this work, the crystal and mol­ecular structures of four closely related diesters, namely methyl isopropyl 2-(triphenyl­phosphoranylidene)malonate, C₂₅H₂₅O₄P, ethyl isopropyl 2-(triphenyl­phosphoranylidene)malonate, C₂₆H₂₇O₄P, methyl tert-butyl 2-(triphenyl­phosphoranylidene)malonate, C₂₆H₂₇O₄P, and ethyl tert-butyl 2-(triphenyl­phosphoranylidene)­malonate, C₂₇H₂₉O₄P, have been analysed as a preliminary step for such comparative studies. As a result of extensive electronic delocalization, as well as intra- and inter­molecular inter­actions, a remarkably similar pattern of preferred conformations in the crystal structures results, viz. a syn-anti conformation of the acyl groups with respect to the P atom, with the bulkier alk­oxy groups oriented towards the P atom. The crystal structures are controlled by nonconventional hydrogen-bonding and intra­molecular inter­actions between cationoid P and acyl and alk­oxy O atoms in syn positions.

S1. Comment

The conformations of crystalline triphenylphosphonium ylides stabilized by electron-withdrawing groups such as ester, keto or cyano depend on the balance between electronic delocalization and intra- and intermolecular non-bonding interactions (Castañeda et al., 2003; Castañeda, Acuña et al., 2007). The bond between P and the ylidic C atom allows free rotation at ambient temperatures on the NMR time scale, indicating the inadequacy of a structure with a classical C═P double bond (Bachrach & Nitsche, 1994). In ylides stabilized by a single keto or ester group, there is a strong interaction between cationoid phosphorus and the syn acyl O atom (Wilson & Tebby, 1972; Zeliger et al., 1969), but syn–syn diesters have never been observed and are not shown, as in the first scheme for syn–anti and anti–anti mixtures. The crystal conformation is controlled by minor changes in the diester groups because the dimethyl ester is a 1:1 anti–anti:syn–anti mixture, in the methyl ethyl diester the acyl O atom of the methyl ester group is syn and that of the ethyl ester group is anti (Castañeda, Jullian et al., 2007), and in the diethyl ester both acyl O atoms are anti to the P atom (Castañeda et al., 2005). This limited evidence indicates that acyl groups can adopt either geometry, but the bulkier alkoxy group tends to be syn to P.

A series of diesters with methoxy, ethoxy, isopropoxy or tert-butoxy groups, methyl isopropyl-, ethyl isopropyl-, methyl tert-butyl- and ethyl tert-butyl 2-triphenylphosphoranylidene malonate diesters, Ph₃P═C(CO₂R)CO₂R' (where R = Me or Et and R' = ⁱPr or ^tBu), the title compounds (Ia)–(IIb), respectively, have been prepared and their structures analysed. Figs. 1, 3, 5 and 7 show the molecular structures of the compounds, while Figs. 2, 4, 6 and 8 present the corresponding packing views. Selected bond distances for (Ia), (Ib), (IIa) and (IIb) are given in Tables 1, 3, 5 and 7. Tables 2, 4, 6, 8 and 9 show the non-bonding interactions and short contacts relevant to the packing discussion.

In the crystals of these diesters, the bulkier alkoxy groups are oriented towards, and smaller alkoxy groups away from, the P atom. The ester groups have Z conformations, as is typical of carboxylic esters (Eliel & Wilen, 1994), and are approximately in the ylidic plane. The ¹H and ¹³C NMR spectra of these diesters indicate that the conformations are the same in solution and the solid state, as detailed elsewhere (Reference?). The geometries of the crystalline diesters are governed by the balance between ylidic resonance and intra- and intermolecular interactions. As is generally the case, the C≐P bond lengths are in between those characteristic of single and double bonds (Howells et al., 1973) and in solution the ¹H and ¹³C NMR signals indicate free rotation about this bond. However, in the crystal structure, the orientations of the phenyl groups are similar in the four ylides and are apparently insensitive to the bulkiness of the alkoxy ester groups.

To a first approximation, the bonds between the ylidic and acyl C atoms are in the same plane, consistent with important ylidic resonance. Some angles at these C atoms differ from the expected 120°, but the sum of the angles is approximately 360°. In earlier observations of ylidic diesters with methoxy or ethoxy substituents, we found that the bulkier alkoxy group was oriented towards the P atom (Castañeda, Jullian et al., 2007), and the present results fit this generalization. In the crystal structure, bulky alkoxy groups oriented away from the P atom would interfere both intra- and intermolecularly. Both isopropoxy and tert-butoxy groups are oriented towards the face of the phenyl group which is approximately orthogonal to the C≐P bond, as shown by the ¹H NMR signals in solution (CDCl₃). The bond lengths between ylidic and acyl C atoms are in between those typical of single and double bonds, as are those in the acyl groups (Howells et al., 1973).

Elsewhere, we show that computed interatomic distances and angles for isolated molecules are generally similar to those in the crystal structure (Reference?). Computations indicate that the conformations of isolated ylidic diesters have minor effects on their computed energies, indicating the role of intermolecular interactions in controlling conformation. Intramolecular interactions in the crystal structure, and probably also in solution, involve interactions between cationoid P and acyl and alkyl O atoms in the syn position, which slightly lengthens the acyl group syn to P relative to the anti acyl group, as shown by the relative lengths of O4—C3 and O2—C2. This generalization fails for the methyl tert-butyl diester, (IIa). There are also, in some diesters, intramolecular interactions between methyl H atoms and anti acyl O atoms. There are always intermolecular interactions between phenyl H atoms and the acyl O atoms of an adjacent molecule (Desiraju & Steiner, 1999). These interactions between phenyl H atoms and acyl O atoms are generally important and play key roles in determining the conformations of individual molecules and crystal structures (Castañeda, Jullian et al., 2007).

In the crystal structure of (Ib) (Fig. 4), one alkoxy group syn to P is directed towards the face of a phenyl group which is approximately orthogonal to the ylidic C—P bond. The consequent C—H—π interaction should be modestly stabilizing (Nishio et al., 1995, Nishio & Hirota, 1989) and is seen in a variety of diesters and keto esters. In the other ester residue, the syn-acyl group is oriented between two phenyl groups, and independent evidence indicates that for some diester ylides the geometries are similar for isolated molecules and in the crystal structure.

Due to the common skeleton, all four ylides exhibit analogous weak intramolecular interactions, viz. two short P···O contacts and one further C—H···π hydrogen bond between the terminal methyl H atom (C5—H5C) and the phenyl ring C31–C36 (Cg3) (entries 1–3 in Tables 2, 4, 6 and 8). There are, however, differences in the intermolecular interactions and the derived packing schemes. In (Ia) and (Ib), there is one non-conventional intermolecular C—H···O bond between the C21–C26 phenyl ring (Cg2) and atom O4, but it gives dissimilar packing schemes: in (Ia), hydrogen-bonded dimers are built up around a group of symmetry centres (Fig. 2), while for (Ib) it results in the formation of a chain around the screw axis running along the unique b axis (Fig. 4) In ylides (IIa) and (IIb), these interactions differ, viz. in (IIa), the preferred intermolecular contacts are non-conventional C—H···O bonds (Table 6,) while in (IIb) they are mainly C—H···π (Table 8) and π–π bonds (Table 9), and the crystal structures differ. In (IIa), the predominant C—H···O bonds are spread uniformly in four directions (Fig. 6), generating a homogeneously connected three-dimensional structure. In (IIb), dimeric structures are built up around a group of symmetry centres [at (0, 1/2, 0), Zone A in Fig. 8], connected into [111] chains by rather weak π–π bonds around the inversion centre at (1/2, 1, 1/2) (B in Fig. 8). Finally, weak hydrogen bonds with atom O2 as an acceptor link these chains, with their [100] translated homologues, into a two-dimensional structure parallel to the (011) plane.

Related literature

For related literature, see: Bachrach & Nitsche (1994); Castañeda, Acuña, Garland, Gillitt, Shirazi, Yunes & Bunton (2007); Castañeda, Aliaga, Bunton, Garland & Baggio (2005); Castañeda, Jullian, Bunton, Garland & Baggio (2007); Castañeda, Terraza, Bunton, Gillitt & Garland (2003); Cristau & Plénat (1994); Desiraju & Steiner (1999); Eliel & Wilen (1994); Howells et al. (1973); Nishio & Hirota (1989); Nishio et al. (1995); Wilson & Tebby (1972); Zeliger et al. (1969).

S2. Experimental

The isopropyl and tert-butyl diesters of triphenylphosphonium ylides, (Ia), (Ib), (IIa) and (IIb), were synthesized by transylidation (Cristau & Plénat, 1994). The general procedure was as follows. A solution of methyl or ethyl chloroformate (20 mmol) in dry benzene (8 ml) was added slowly to isopropyl or tert-butyl 2-triphenylphosphoranylidene acetate (Ph₃P═CH—CO₂R, R = ⁱPr or ^tBu; 40 mmol) in dry benzene (100 ml) under a dry atmosphere. The resulting solution was stirred for 4 h at room temperature and a white solid separated. The carboalkoxy methyltriphenylphosphonium chloride (Ph₃P⁺—CH₂—CO₂R Cl^-; R = ⁱPr or ^tBu) was removed by filtration and the solvent was evaporated, giving a solid or an oil. Recrystallization from ethyl acetate gave the title novel diester ylides, (Ia), (Ib), (IIa) or (IIb) (yields 65–80%).

For methyl isopropyl 2-triphenylphosphoranylidene malonate, (Ia): yield 82%; m.p. 393 K; analysis calculated for C₂₅H₂₅O₄P: C 71.42, H 5.99%; found: C 71.70, H 6.22%.

For ethyl isopropyl 2-triphenylphosphoranylidene malonate, (Ib): yield 78%; m.p. 397 K; analysis calculated for C₂₆H₂₇O₄P: C 71.88, H 6.26%; found: C 72.15, H 6.35%.

For methyl tert-butyl 2-triphenylphosphoranylidene malonate, (IIa): yield 70%; m.p. 460 K; analysis calculated for C₂₆H₂₇O₄P: C 71.88, H 6.26%; found: C 72.12, H 6.30%.

For ethyl tert-butyl 2-triphenylphosphoranylidene malonate, (IIb): yield 65%; m.p. 412 K; analysis calculated for C₂₇H₂₉O₄P: C 72.31, H 6.52%; found: C 72.45, H 6.80%.

¹H NMR spectra in solution were monitored on a Bruker DRX 300 spectrometer referenced to trimethyl siloxane. IR spectra were obtained with a KBr disk on a Bruker IFS 56 FT spectrometer. Elemental analyses were carried out with a Fison EA 1108 analyser. Spectroscopic data are available in the archived CIF.

S3. Refinement

H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 (aromatic), 0.97 (CH₂) or 0.96 Å (CH₃), and with U_iso(H) = 1.2U_eq(C) for aromatic H and CH₂, or 1.5U_eq(C) for CH₃.

Some terminal groups were disordered over two different orientations and accordingly were refined with a metrically restrained split model; these were the OMe group in (Ia) and the OEt groups in (Ib and IIb). The refinements converged to final occupancies of 0.66/0.34 (2), 0.616/384 (4) and 0.747 (4)/0.253 (4), using two, seven and three restraints, respectively.

Computing details

For all compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2001); data reduction: SAINT-NT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. A molecular diagram of (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Cg1, Cg2 and Cg3 denote ring centroids. Intramolecular interactions (P···P [P···O ?] contacts and C—H···π bonds) are shown as single dashed lines. The minor component of the disordered methyl group is shown by double dashed bonds and dashed ellipsoids.
	Fig. 2. A packing diagram for (Ia), showing the weakly connected dimeric structure. Intermolecular C—H···O and intramolecular C—H···π bonds are shown as dashed lines. Symmetry codes as in Table 2.
	Fig. 3. A molecular diagram of (Ib), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Cg1, Cg2 and Cg3 denote ring centroids. Intramolecular interactions (P···P [P···O ?] contacts and C—H···π bonds) are shown as single dashed lines. The minor component of the disordered ethyl group is shown by double dashed bonds and dashed ellipsoids.
	Fig. 4. A packing diagram for (Ib), showing the weakly connected chains running along the b axis. Intermolecular C—H···O and intramolecular C—H···π bonds are shown as dashed lines. Symmetry codes as in Table 4.
	Fig. 5. A molecular diagram of (IIa), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Cg1, Cg2 and Cg3 denote ring centroids. Intramolecular interactions (P···P [P···O ?] contacts and C—H···π bonds) are shown as dashed lines.
	Fig. 6. A packing diagram for (IIa), showing the three-dimensional structure. Intermolecular C—H···O bonds are shown as dashed lines. Intramolecular hydrogen bonds have been omitted for clarity. Symmetry codes as in Table 6.
	Fig. 7. A molecular diagram of (IIb), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Cg1, Cg2 and Cg3 denote ring centroids. Intramolecular interactions (P···P [P···O ?] contacts and C—H···π bonds) are shown as dashed lines. The minor component of the disordered ethyl group is shown by double dashed bonds and dashed ellipsoids.
	Fig. 8. A packing diagram for (IIb), showing the dimeric structures (at site A) conected into chains (at site B). Intermolecular C—H···π and π–π interactions are shown as dashed lines. Intramolecular interactions have been omitted for clarity. Symmetry codes as in Tables 8 and 9.

(Ia) methyl isopropyl 2-(triphenylphosphoranyliden)malonate

Crystal data

C25H25O4P	Z = 2
Mr = 420.42	F(000) = 444
Triclinic, P1	Dx = 1.277 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8033 (6) Å	Cell parameters from 1718 reflections
b = 10.4492 (7) Å	θ = 2.5–21.9°
c = 11.2169 (7) Å	µ = 0.15 mm^−1
α = 100.573 (2)°	T = 273 K
β = 94.878 (2)°	Block, colourless
γ = 102.446 (3)°	0.20 × 0.17 × 0.14 mm
V = 1093.64 (12) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3133 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 27.8°, θmin = 1.9°
ϕ and ω scans	h = −12→12
9176 measured reflections	k = −13→13
4675 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0646P)^2] where P = (Fo^2 + 2Fc^2)/3
4675 reflections	(Δ/σ)max < 0.001
282 parameters	Δρmax = 0.27 e Å^−3
2 restraints	Δρmin = −0.17 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.15100 (5)	0.32873 (5)	0.22639 (5)	0.04233 (17)
O1	0.37276 (15)	0.23368 (13)	0.12939 (14)	0.0538 (4)
O2	0.36216 (19)	0.04992 (16)	0.20754 (18)	0.0788 (6)
O3	0.2072 (16)	0.0425 (8)	0.3867 (10)	0.0620 (16)	0.66 (2)
C7	0.1996 (15)	0.0002 (13)	0.5010 (12)	0.067 (2)	0.66 (2)
H7A	0.2688	−0.0506	0.5119	0.101*	0.66 (2)
H7B	0.1074	−0.0545	0.5011	0.101*	0.66 (2)
H7C	0.2175	0.0774	0.5666	0.101*	0.66 (2)
O3'	0.221 (3)	0.0571 (15)	0.4171 (15)	0.0620 (16)	0.34 (2)
C7'	0.189 (3)	0.022 (3)	0.5312 (17)	0.067 (2)	0.34 (2)
H7'A	0.1025	0.0448	0.5505	0.101*	0.34 (2)
H7'B	0.2640	0.0703	0.5947	0.101*	0.34 (2)
H7'C	0.1793	−0.0725	0.5246	0.101*	0.34 (2)
O4	0.14402 (17)	0.23495 (16)	0.46638 (14)	0.0638 (4)
C1	0.2189 (2)	0.20166 (19)	0.27093 (19)	0.0444 (5)
C2	0.3203 (2)	0.1497 (2)	0.2025 (2)	0.0510 (5)
C3	0.1872 (2)	0.1672 (2)	0.3853 (2)	0.0490 (5)
C4	0.4666 (2)	0.1924 (2)	0.0455 (2)	0.0575 (6)
H4	0.5222	0.1391	0.0827	0.069*
C5	0.3833 (3)	0.1088 (3)	−0.0698 (3)	0.0808 (8)
H5A	0.3202	0.0327	−0.0520	0.121*
H5B	0.4458	0.0787	−0.1241	0.121*
H5C	0.3299	0.1608	−0.1078	0.121*
C6	0.5634 (3)	0.3176 (3)	0.0289 (3)	0.0889 (9)
H6A	0.5101	0.3695	−0.0096	0.133*
H6B	0.6325	0.2948	−0.0216	0.133*
H6C	0.6098	0.3691	0.1073	0.133*
C11	0.2649 (2)	0.49492 (19)	0.27479 (18)	0.0438 (5)
C12	0.3953 (2)	0.5102 (2)	0.3400 (2)	0.0540 (6)
H12	0.4224	0.4358	0.3598	0.065*
C13	0.4854 (3)	0.6352 (3)	0.3759 (2)	0.0692 (7)
H13	0.5739	0.6448	0.4184	0.083*
C14	0.4447 (3)	0.7456 (2)	0.3490 (3)	0.0728 (7)
H14	0.5053	0.8299	0.3745	0.087*
C15	0.3155 (3)	0.7322 (2)	0.2850 (2)	0.0666 (7)
H15	0.2883	0.8074	0.2677	0.080*
C16	0.2259 (2)	0.6077 (2)	0.2464 (2)	0.0534 (6)
H16	0.1391	0.5985	0.2012	0.064*
C21	−0.0163 (2)	0.3286 (2)	0.28335 (18)	0.0449 (5)
C22	−0.0486 (2)	0.4440 (2)	0.3444 (2)	0.0534 (6)
H22	0.0186	0.5248	0.3597	0.064*
C23	−0.1797 (3)	0.4405 (3)	0.3830 (2)	0.0640 (7)
H23	−0.1998	0.5183	0.4247	0.077*
C24	−0.2795 (3)	0.3221 (3)	0.3595 (2)	0.0654 (7)
H24	−0.3682	0.3202	0.3837	0.079*
C25	−0.2496 (2)	0.2072 (3)	0.3011 (2)	0.0623 (6)
H25	−0.3178	0.1271	0.2862	0.075*
C26	−0.1183 (2)	0.2088 (2)	0.2637 (2)	0.0552 (6)
H26	−0.0983	0.1295	0.2252	0.066*
C31	0.1138 (2)	0.29891 (19)	0.06101 (18)	0.0436 (5)
C32	0.0160 (2)	0.1853 (2)	−0.0032 (2)	0.0598 (6)
H32	−0.0332	0.1261	0.0395	0.072*
C33	−0.0098 (3)	0.1588 (3)	−0.1287 (2)	0.0678 (7)
H33	−0.0768	0.0827	−0.1698	0.081*
C34	0.0622 (3)	0.2432 (3)	−0.1932 (2)	0.0646 (7)
H34	0.0456	0.2244	−0.2782	0.078*
C35	0.1591 (3)	0.3557 (2)	−0.1321 (2)	0.0668 (7)
H35	0.2080	0.4140	−0.1757	0.080*
C36	0.1851 (2)	0.3833 (2)	−0.0061 (2)	0.0574 (6)
H36	0.2517	0.4601	0.0342	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0441 (3)	0.0381 (3)	0.0480 (3)	0.0128 (2)	0.0062 (2)	0.0135 (2)
O1	0.0579 (9)	0.0459 (8)	0.0698 (10)	0.0214 (7)	0.0239 (8)	0.0250 (7)
O2	0.0845 (12)	0.0628 (11)	0.1221 (16)	0.0449 (10)	0.0522 (11)	0.0531 (10)
O3	0.104 (3)	0.0550 (18)	0.039 (4)	0.032 (2)	0.013 (4)	0.023 (2)
C7	0.093 (3)	0.076 (5)	0.050 (5)	0.034 (2)	0.023 (3)	0.033 (4)
O3'	0.104 (3)	0.0550 (18)	0.039 (4)	0.032 (2)	0.013 (4)	0.023 (2)
C7'	0.093 (3)	0.076 (5)	0.050 (5)	0.034 (2)	0.023 (3)	0.033 (4)
O4	0.0813 (12)	0.0655 (10)	0.0530 (10)	0.0303 (9)	0.0134 (9)	0.0160 (8)
C1	0.0481 (12)	0.0404 (11)	0.0501 (12)	0.0149 (9)	0.0078 (10)	0.0166 (9)
C2	0.0488 (13)	0.0414 (12)	0.0683 (15)	0.0123 (10)	0.0114 (11)	0.0221 (11)
C3	0.0470 (12)	0.0441 (12)	0.0568 (14)	0.0109 (10)	0.0004 (11)	0.0153 (11)
C4	0.0513 (13)	0.0590 (14)	0.0721 (16)	0.0213 (11)	0.0205 (12)	0.0232 (12)
C5	0.0772 (19)	0.0745 (18)	0.090 (2)	0.0271 (15)	0.0163 (16)	0.0020 (15)
C6	0.086 (2)	0.0833 (19)	0.097 (2)	0.0016 (16)	0.0353 (17)	0.0286 (16)
C11	0.0461 (12)	0.0401 (11)	0.0463 (12)	0.0105 (9)	0.0065 (9)	0.0110 (9)
C12	0.0523 (14)	0.0525 (13)	0.0574 (14)	0.0134 (11)	0.0049 (11)	0.0118 (11)
C13	0.0506 (14)	0.0719 (17)	0.0754 (18)	0.0023 (13)	−0.0004 (12)	0.0092 (14)
C14	0.0714 (18)	0.0505 (15)	0.0839 (19)	−0.0067 (13)	0.0086 (15)	0.0072 (13)
C15	0.0790 (18)	0.0455 (14)	0.0791 (18)	0.0142 (13)	0.0183 (15)	0.0190 (12)
C16	0.0564 (13)	0.0433 (12)	0.0636 (15)	0.0148 (10)	0.0083 (11)	0.0154 (10)
C21	0.0460 (12)	0.0499 (12)	0.0441 (12)	0.0179 (10)	0.0052 (9)	0.0160 (9)
C22	0.0606 (14)	0.0533 (13)	0.0520 (13)	0.0210 (11)	0.0102 (11)	0.0153 (10)
C23	0.0693 (17)	0.0766 (18)	0.0588 (15)	0.0367 (14)	0.0185 (13)	0.0187 (13)
C24	0.0543 (15)	0.095 (2)	0.0581 (15)	0.0318 (15)	0.0145 (12)	0.0247 (14)
C25	0.0503 (14)	0.0775 (17)	0.0588 (15)	0.0070 (12)	0.0074 (11)	0.0225 (13)
C26	0.0522 (13)	0.0576 (14)	0.0563 (14)	0.0128 (11)	0.0103 (11)	0.0120 (11)
C31	0.0460 (12)	0.0405 (11)	0.0478 (12)	0.0155 (9)	0.0044 (9)	0.0121 (9)
C32	0.0647 (15)	0.0536 (14)	0.0567 (15)	0.0040 (12)	0.0069 (12)	0.0126 (11)
C33	0.0681 (16)	0.0639 (16)	0.0602 (16)	0.0062 (13)	−0.0029 (13)	0.0008 (13)
C34	0.0762 (17)	0.0722 (17)	0.0501 (14)	0.0322 (14)	−0.0015 (13)	0.0114 (13)
C35	0.0835 (18)	0.0638 (16)	0.0570 (15)	0.0135 (14)	0.0086 (13)	0.0268 (13)
C36	0.0656 (15)	0.0509 (13)	0.0546 (14)	0.0081 (11)	0.0023 (11)	0.0171 (11)

Geometric parameters (Å, º)

P1—C1	1.7388 (19)	C12—C13	1.377 (3)
P1—C11	1.809 (2)	C12—H12	0.9300
P1—C21	1.810 (2)	C13—C14	1.374 (3)
P1—C31	1.815 (2)	C13—H13	0.9300
O1—C2	1.360 (2)	C14—C15	1.368 (4)
O1—C4	1.445 (3)	C14—H14	0.9300
O2—C2	1.208 (2)	C15—C16	1.374 (3)
O3—C3	1.362 (4)	C15—H15	0.9300
O3—C7	1.434 (5)	C16—H16	0.9300
C7—H7A	0.9600	C21—C22	1.386 (3)
C7—H7B	0.9600	C21—C26	1.392 (3)
C7—H7C	0.9600	C22—C23	1.385 (3)
O3'—C3	1.361 (7)	C22—H22	0.9300
O3'—C7'	1.435 (8)	C23—C24	1.368 (3)
C7'—H7'A	0.9600	C23—H23	0.9300
C7'—H7'B	0.9600	C24—C25	1.361 (3)
C7'—H7'C	0.9600	C24—H24	0.9300
O4—C3	1.211 (2)	C25—C26	1.385 (3)
C1—C3	1.436 (3)	C25—H25	0.9300
C1—C2	1.443 (3)	C26—H26	0.9300
C4—C5	1.483 (3)	C31—C36	1.378 (3)
C4—C6	1.494 (3)	C31—C32	1.388 (3)
C4—H4	0.9800	C32—C33	1.374 (3)
C5—H5A	0.9600	C32—H32	0.9300
C5—H5B	0.9600	C33—C34	1.361 (3)
C5—H5C	0.9600	C33—H33	0.9300
C6—H6A	0.9600	C34—C35	1.366 (3)
C6—H6B	0.9600	C34—H34	0.9300
C6—H6C	0.9600	C35—C36	1.379 (3)
C11—C12	1.380 (3)	C35—H35	0.9300
C11—C16	1.395 (3)	C36—H36	0.9300
C1—P1—C11	114.92 (9)	C11—C12—H12	119.9
C1—P1—C21	109.49 (9)	C14—C13—C12	120.1 (2)
C11—P1—C21	108.93 (9)	C14—C13—H13	120.0
C1—P1—C31	110.74 (9)	C12—C13—H13	120.0
C11—P1—C31	106.43 (9)	C15—C14—C13	120.4 (2)
C21—P1—C31	105.91 (9)	C15—C14—H14	119.8
C2—O1—C4	118.34 (16)	C13—C14—H14	119.8
C3—O3—C7	116.3 (7)	C14—C15—C16	120.0 (2)
C3—O3'—C7'	120.6 (18)	C14—C15—H15	120.0
O3'—C7'—H7'A	109.5	C16—C15—H15	120.0
O3'—C7'—H7'B	109.5	C15—C16—C11	120.2 (2)
H7'A—C7'—H7'B	109.5	C15—C16—H16	119.9
O3'—C7'—H7'C	109.5	C11—C16—H16	119.9
H7'A—C7'—H7'C	109.5	C22—C21—C26	118.1 (2)
H7'B—C7'—H7'C	109.5	C22—C21—P1	122.64 (17)
C3—C1—C2	122.36 (18)	C26—C21—P1	119.22 (16)
C3—C1—P1	117.71 (15)	C23—C22—C21	120.9 (2)
C2—C1—P1	119.26 (15)	C23—C22—H22	119.5
O2—C2—O1	121.2 (2)	C21—C22—H22	119.5
O2—C2—C1	128.4 (2)	C24—C23—C22	119.8 (2)
O1—C2—C1	110.30 (17)	C24—C23—H23	120.1
O4—C3—O3'	113.3 (8)	C22—C23—H23	120.1
O4—C3—O3	124.7 (5)	C25—C24—C23	120.4 (2)
O4—C3—C1	126.00 (19)	C25—C24—H24	119.8
O3'—C3—C1	120.3 (9)	C23—C24—H24	119.8
O3—C3—C1	109.2 (5)	C24—C25—C26	120.5 (2)
O1—C4—C5	109.69 (18)	C24—C25—H25	119.8
O1—C4—C6	106.54 (19)	C26—C25—H25	119.8
C5—C4—C6	113.9 (2)	C25—C26—C21	120.3 (2)
O1—C4—H4	108.9	C25—C26—H26	119.9
C5—C4—H4	108.9	C21—C26—H26	119.9
C6—C4—H4	108.9	C36—C31—C32	117.4 (2)
C4—C5—H5A	109.5	C36—C31—P1	122.03 (16)
C4—C5—H5B	109.5	C32—C31—P1	120.52 (16)
H5A—C5—H5B	109.5	C33—C32—C31	121.3 (2)
C4—C5—H5C	109.5	C33—C32—H32	119.4
H5A—C5—H5C	109.5	C31—C32—H32	119.4
H5B—C5—H5C	109.5	C34—C33—C32	120.4 (2)
C4—C6—H6A	109.5	C34—C33—H33	119.8
C4—C6—H6B	109.5	C32—C33—H33	119.8
H6A—C6—H6B	109.5	C33—C34—C35	119.4 (2)
C4—C6—H6C	109.5	C33—C34—H34	120.3
H6A—C6—H6C	109.5	C35—C34—H34	120.3
H6B—C6—H6C	109.5	C34—C35—C36	120.5 (2)
C12—C11—C16	119.1 (2)	C34—C35—H35	119.7
C12—C11—P1	118.92 (16)	C36—C35—H35	119.7
C16—C11—P1	121.99 (16)	C31—C36—C35	121.0 (2)
C13—C12—C11	120.2 (2)	C31—C36—H36	119.5
C13—C12—H12	119.9	C35—C36—H36	119.5
C11—P1—C1—C3	91.24 (18)	C11—C12—C13—C14	1.3 (4)
C21—P1—C1—C3	−31.72 (19)	C12—C13—C14—C15	−0.9 (4)
C31—P1—C1—C3	−148.13 (16)	C13—C14—C15—C16	−0.5 (4)
C11—P1—C1—C2	−79.61 (19)	C14—C15—C16—C11	1.6 (4)
C21—P1—C1—C2	157.44 (16)	C12—C11—C16—C15	−1.2 (3)
C31—P1—C1—C2	41.02 (19)	P1—C11—C16—C15	179.91 (17)
C4—O1—C2—O2	8.0 (3)	C1—P1—C21—C22	131.52 (18)
C4—O1—C2—C1	−174.49 (17)	C11—P1—C21—C22	5.1 (2)
C3—C1—C2—O2	22.0 (4)	C31—P1—C21—C22	−109.04 (18)
P1—C1—C2—O2	−167.6 (2)	C1—P1—C21—C26	−49.68 (19)
C3—C1—C2—O1	−155.35 (19)	C11—P1—C21—C26	−176.12 (16)
P1—C1—C2—O1	15.0 (2)	C31—P1—C21—C26	69.76 (18)
C7'—O3'—C3—O4	7 (3)	C26—C21—C22—C23	−1.0 (3)
C7'—O3'—C3—O3	−136 (10)	P1—C21—C22—C23	177.79 (16)
C7'—O3'—C3—C1	−180 (2)	C21—C22—C23—C24	−0.7 (3)
C7—O3—C3—O4	−11.2 (16)	C22—C23—C24—C25	1.6 (4)
C7—O3—C3—O3'	30 (7)	C23—C24—C25—C26	−0.6 (4)
C7—O3—C3—C1	171.4 (10)	C24—C25—C26—C21	−1.2 (3)
C2—C1—C3—O4	153.5 (2)	C22—C21—C26—C25	2.0 (3)
P1—C1—C3—O4	−17.0 (3)	P1—C21—C26—C25	−176.85 (16)
C2—C1—C3—O3'	−18.5 (15)	C1—P1—C31—C36	−115.23 (18)
P1—C1—C3—O3'	171.0 (15)	C11—P1—C31—C36	10.3 (2)
C2—C1—C3—O3	−29.1 (8)	C21—P1—C31—C36	126.16 (18)
P1—C1—C3—O3	160.3 (7)	C1—P1—C31—C32	61.69 (19)
C2—O1—C4—C5	85.8 (2)	C11—P1—C31—C32	−172.75 (17)
C2—O1—C4—C6	−150.5 (2)	C21—P1—C31—C32	−56.92 (19)
C1—P1—C11—C12	1.1 (2)	C36—C31—C32—C33	−0.6 (3)
C21—P1—C11—C12	124.33 (17)	P1—C31—C32—C33	−177.64 (18)
C31—P1—C11—C12	−121.88 (17)	C31—C32—C33—C34	0.9 (4)
C1—P1—C11—C16	179.97 (17)	C32—C33—C34—C35	−0.9 (4)
C21—P1—C11—C16	−56.78 (19)	C33—C34—C35—C36	0.6 (4)
C31—P1—C11—C16	57.00 (19)	C32—C31—C36—C35	0.3 (3)
C16—C11—C12—C13	−0.2 (3)	P1—C31—C36—C35	177.29 (17)
P1—C11—C12—C13	178.70 (17)	C34—C35—C36—C31	−0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
P1···O1			2.799 (2)
P1···O4			3.030 (2)
C5—H5C···Cg3	0.96	2.89	3.657 (3)	138
C23—H23···O4^i	0.93	2.56	3.430 (3)	156

Symmetry code: (i) −x, −y+1, −z+1.

(Ib) ethyl isopropyl 2-(triphenylphosphoranyliden)malonate

Crystal data

C26H27O4P	F(000) = 920
Mr = 434.45	Dx = 1.245 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1773 reflections
a = 12.5175 (16) Å	θ = 2.4–18.8°
b = 9.1555 (12) Å	µ = 0.15 mm^−1
c = 20.351 (3) Å	T = 140 K
β = 96.342 (2)°	Block, colourless
V = 2318.0 (5) Å^3	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2713 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
Graphite monochromator	θmax = 28.1°, θmin = 2.0°
ϕ and ω scans	h = −16→16
19001 measured reflections	k = −12→11
5252 independent reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0649P)^2] where P = (Fo^2 + 2Fc^2)/3
5252 reflections	(Δ/σ)max < 0.001
300 parameters	Δρmax = 0.33 e Å^−3
7 restraints	Δρmin = −0.27 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.73850 (5)	0.02844 (7)	0.17875 (3)	0.0439 (2)
O1	0.62126 (16)	0.2614 (2)	0.10059 (10)	0.0973 (8)
O2	0.73010 (15)	0.2958 (2)	0.02568 (9)	0.0903 (7)
O3	0.9224 (3)	0.1642 (6)	0.0498 (2)	0.0647 (15)	0.616 (4)
O3'	0.9339 (5)	0.2182 (8)	0.0701 (4)	0.070 (3)	0.384 (4)
O4	0.95195 (13)	0.04885 (19)	0.14924 (9)	0.0686 (5)
C1	0.77891 (17)	0.1334 (2)	0.11455 (10)	0.0456 (6)
C2	0.71144 (19)	0.2344 (3)	0.07458 (12)	0.0510 (6)
C3	0.8908 (2)	0.1173 (3)	0.10908 (13)	0.0595 (7)
C4	0.5427 (2)	0.3578 (4)	0.06629 (17)	0.0883 (10)
H4	0.5727	0.4019	0.0285	0.106*
C5	0.4466 (3)	0.2731 (4)	0.04265 (18)	0.1286 (14)
H5A	0.4660	0.1958	0.0144	0.193*
H5B	0.3950	0.3358	0.0184	0.193*
H5C	0.4159	0.2321	0.0797	0.193*
C6	0.5222 (3)	0.4721 (4)	0.11353 (19)	0.1204 (13)
H6A	0.5880	0.5221	0.1279	0.181*
H6B	0.4940	0.4289	0.1510	0.181*
H6C	0.4710	0.5405	0.0927	0.181*
C7	1.0358 (3)	0.1456 (6)	0.0431 (3)	0.0897 (17)	0.616 (4)
H7A	1.0459	0.1293	−0.0029	0.108*	0.616 (4)
H7B	1.0637	0.0615	0.0685	0.108*	0.616 (4)
C7'	1.0485 (5)	0.2473 (9)	0.0793 (5)	0.0897 (17)	0.384 (4)
H7'A	1.0751	0.2396	0.1258	0.108*	0.384 (4)
H7'B	1.0626	0.3455	0.0645	0.108*	0.384 (4)
C8	1.0953 (6)	0.2825 (8)	0.0683 (4)	0.185 (4)	0.616 (4)
H8A	1.0629	0.3663	0.0457	0.278*	0.616 (4)
H8B	1.1692	0.2756	0.0601	0.278*	0.616 (4)
H8C	1.0914	0.2923	0.1149	0.278*	0.616 (4)
C8'	1.1053 (8)	0.1363 (14)	0.0393 (6)	0.185 (4)	0.384 (4)
H8'A	1.0862	0.1536	−0.0070	0.278*	0.384 (4)
H8'B	1.0837	0.0394	0.0502	0.278*	0.384 (4)
H8'C	1.1817	0.1460	0.0496	0.278*	0.384 (4)
C11	0.78585 (17)	−0.1571 (2)	0.17111 (12)	0.0472 (6)
C12	0.82857 (19)	−0.2374 (3)	0.22506 (12)	0.0571 (7)
H12	0.8358	−0.1957	0.2670	0.069*
C13	0.8607 (2)	−0.3802 (3)	0.21667 (16)	0.0739 (8)
H13	0.8901	−0.4339	0.2531	0.089*
C14	0.8498 (2)	−0.4429 (3)	0.15545 (18)	0.0774 (9)
H14	0.8701	−0.5396	0.1503	0.093*
C15	0.8090 (2)	−0.3634 (3)	0.10210 (15)	0.0775 (8)
H15	0.8021	−0.4059	0.0603	0.093*
C16	0.7780 (2)	−0.2208 (3)	0.10917 (13)	0.0622 (7)
H16	0.7515	−0.1669	0.0722	0.075*
C21	0.78327 (17)	0.0933 (2)	0.26071 (11)	0.0447 (6)
C22	0.74220 (18)	0.0353 (3)	0.31610 (11)	0.0544 (6)
H22	0.6935	−0.0416	0.3109	0.065*
C23	0.7725 (2)	0.0898 (3)	0.37771 (12)	0.0631 (7)
H23	0.7435	0.0505	0.4140	0.076*
C24	0.8454 (2)	0.2020 (3)	0.38665 (13)	0.0670 (8)
H24	0.8656	0.2390	0.4287	0.080*
C25	0.8880 (2)	0.2588 (3)	0.33310 (14)	0.0661 (7)
H25	0.9383	0.3337	0.3389	0.079*
C26	0.85643 (19)	0.2052 (3)	0.27018 (12)	0.0560 (7)
H26	0.8851	0.2455	0.2340	0.067*
C31	0.59357 (18)	0.0143 (3)	0.17709 (11)	0.0483 (6)
C32	0.5370 (2)	−0.0903 (3)	0.13930 (14)	0.0718 (8)
H32	0.5733	−0.1551	0.1144	0.086*
C33	0.4269 (2)	−0.1000 (4)	0.13799 (18)	0.0948 (11)
H33	0.3892	−0.1696	0.1114	0.114*
C34	0.3730 (2)	−0.0081 (4)	0.17536 (19)	0.0952 (11)
H34	0.2988	−0.0163	0.1750	0.114*
C35	0.4283 (2)	0.0969 (4)	0.21374 (15)	0.0805 (9)
H35	0.3919	0.1598	0.2394	0.097*
C36	0.5376 (2)	0.1081 (3)	0.21376 (12)	0.0627 (7)
H36	0.5747	0.1804	0.2390	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0432 (4)	0.0451 (4)	0.0433 (4)	0.0004 (3)	0.0037 (3)	0.0017 (3)
O1	0.0757 (13)	0.1258 (17)	0.0976 (15)	0.0543 (13)	0.0420 (12)	0.0682 (13)
O2	0.0849 (14)	0.1184 (17)	0.0729 (13)	0.0319 (12)	0.0317 (11)	0.0499 (13)
O3	0.046 (2)	0.087 (4)	0.064 (3)	0.003 (2)	0.0169 (18)	0.019 (3)
O3'	0.060 (4)	0.083 (5)	0.068 (5)	−0.025 (3)	0.017 (3)	0.003 (4)
O4	0.0474 (11)	0.0798 (13)	0.0781 (13)	0.0087 (9)	0.0050 (9)	0.0189 (11)
C1	0.0432 (14)	0.0486 (14)	0.0455 (14)	0.0017 (11)	0.0062 (11)	0.0044 (11)
C2	0.0501 (15)	0.0578 (16)	0.0455 (15)	0.0045 (12)	0.0074 (12)	0.0042 (13)
C3	0.0533 (17)	0.0624 (17)	0.0637 (18)	0.0032 (14)	0.0110 (14)	0.0111 (14)
C4	0.073 (2)	0.106 (3)	0.089 (2)	0.039 (2)	0.0226 (18)	0.049 (2)
C5	0.127 (3)	0.132 (3)	0.114 (3)	0.014 (3)	−0.042 (3)	0.027 (3)
C6	0.105 (3)	0.114 (3)	0.143 (3)	0.038 (2)	0.017 (3)	0.019 (3)
C7	0.065 (3)	0.115 (5)	0.096 (4)	−0.009 (3)	0.037 (3)	0.019 (3)
C7'	0.065 (3)	0.115 (5)	0.096 (4)	−0.009 (3)	0.037 (3)	0.019 (3)
C8	0.108 (5)	0.275 (11)	0.185 (7)	−0.092 (6)	0.070 (5)	−0.089 (7)
C8'	0.108 (5)	0.275 (11)	0.185 (7)	−0.092 (6)	0.070 (5)	−0.089 (7)
C11	0.0423 (13)	0.0456 (14)	0.0534 (15)	−0.0011 (11)	0.0035 (11)	0.0028 (12)
C12	0.0542 (16)	0.0559 (17)	0.0607 (17)	0.0005 (13)	0.0035 (13)	0.0091 (13)
C13	0.0708 (19)	0.0570 (18)	0.091 (2)	0.0082 (15)	−0.0022 (17)	0.0204 (17)
C14	0.074 (2)	0.0485 (18)	0.110 (3)	0.0069 (14)	0.0072 (19)	−0.0025 (19)
C15	0.087 (2)	0.064 (2)	0.080 (2)	0.0066 (17)	0.0030 (17)	−0.0158 (17)
C16	0.0716 (18)	0.0575 (17)	0.0557 (17)	0.0105 (14)	−0.0008 (13)	−0.0047 (13)
C21	0.0407 (13)	0.0452 (13)	0.0477 (14)	0.0006 (11)	0.0032 (11)	−0.0013 (11)
C22	0.0525 (15)	0.0623 (16)	0.0481 (15)	−0.0106 (13)	0.0047 (12)	−0.0009 (13)
C23	0.0606 (17)	0.083 (2)	0.0454 (16)	0.0006 (15)	0.0063 (13)	0.0012 (14)
C24	0.0610 (18)	0.083 (2)	0.0545 (17)	0.0064 (15)	−0.0067 (14)	−0.0168 (15)
C25	0.0597 (17)	0.0647 (18)	0.0721 (19)	−0.0076 (14)	−0.0006 (15)	−0.0161 (15)
C26	0.0563 (16)	0.0552 (16)	0.0566 (16)	−0.0027 (13)	0.0075 (13)	−0.0004 (13)
C31	0.0432 (13)	0.0504 (14)	0.0513 (14)	−0.0013 (12)	0.0056 (11)	0.0065 (12)
C32	0.0519 (17)	0.0607 (17)	0.102 (2)	−0.0052 (14)	0.0039 (15)	−0.0089 (16)
C33	0.057 (2)	0.077 (2)	0.147 (3)	−0.0189 (17)	−0.005 (2)	−0.006 (2)
C34	0.0464 (18)	0.111 (3)	0.129 (3)	−0.0029 (19)	0.015 (2)	0.030 (2)
C35	0.0547 (19)	0.109 (3)	0.080 (2)	0.0156 (18)	0.0176 (16)	0.0113 (19)
C36	0.0502 (16)	0.0799 (19)	0.0577 (17)	0.0052 (14)	0.0045 (13)	−0.0009 (15)

Geometric parameters (Å, º)

P1—C1	1.741 (2)	C8'—H8'C	0.9600
P1—C21	1.801 (2)	C11—C12	1.379 (3)
P1—C11	1.811 (2)	C11—C16	1.382 (3)
P1—C31	1.815 (2)	C12—C13	1.384 (3)
O1—C2	1.322 (3)	C12—H12	0.9300
O1—C4	1.442 (3)	C13—C14	1.365 (4)
O2—C2	1.188 (3)	C13—H13	0.9300
O3—C3	1.379 (4)	C14—C15	1.359 (4)
O3—C7	1.451 (3)	C14—H14	0.9300
O3'—C3	1.367 (7)	C15—C16	1.375 (3)
O3'—C7'	1.451 (3)	C15—H15	0.9300
O4—C3	1.228 (3)	C16—H16	0.9300
C1—C3	1.425 (3)	C21—C26	1.373 (3)
C1—C2	1.441 (3)	C21—C22	1.395 (3)
C4—C6	1.463 (4)	C22—C23	1.364 (3)
C4—C5	1.467 (4)	C22—H22	0.9300
C4—H4	0.9800	C23—C24	1.373 (3)
C5—H5A	0.9600	C23—H23	0.9300
C5—H5B	0.9600	C24—C25	1.368 (3)
C5—H5C	0.9600	C24—H24	0.9300
C6—H6A	0.9600	C25—C26	1.387 (3)
C6—H6B	0.9600	C25—H25	0.9300
C6—H6C	0.9600	C26—H26	0.9300
C7—C8	1.518 (3)	C31—C32	1.375 (3)
C7—H7A	0.9700	C31—C36	1.378 (3)
C7—H7B	0.9700	C32—C33	1.379 (4)
C7'—C8'	1.526 (3)	C32—H32	0.9300
C7'—H7'A	0.9700	C33—C34	1.362 (4)
C7'—H7'B	0.9700	C33—H33	0.9300
C8—H8A	0.9600	C34—C35	1.377 (4)
C8—H8B	0.9600	C34—H34	0.9300
C8—H8C	0.9600	C35—C36	1.372 (3)
C8'—H8'A	0.9600	C35—H35	0.9300
C8'—H8'B	0.9600	C36—H36	0.9300
C1—P1—C21	115.24 (11)	H8'B—C8'—H8'C	109.5
C1—P1—C11	109.17 (11)	C12—C11—C16	118.9 (2)
C21—P1—C11	108.51 (11)	C12—C11—P1	122.24 (19)
C1—P1—C31	113.44 (10)	C16—C11—P1	118.85 (18)
C21—P1—C31	104.40 (11)	C11—C12—C13	119.9 (2)
C11—P1—C31	105.51 (11)	C11—C12—H12	120.1
C2—O1—C4	119.2 (2)	C13—C12—H12	120.1
C3—O3—C7	115.1 (4)	C14—C13—C12	120.6 (3)
C3—O3'—C7'	119.8 (7)	C14—C13—H13	119.7
C3—C1—C2	122.8 (2)	C12—C13—H13	119.7
C3—C1—P1	111.77 (17)	C15—C14—C13	119.7 (3)
C2—C1—P1	125.22 (17)	C15—C14—H14	120.2
O2—C2—O1	120.1 (2)	C13—C14—H14	120.2
O2—C2—C1	128.2 (2)	C14—C15—C16	120.7 (3)
O1—C2—C1	111.5 (2)	C14—C15—H15	119.6
O4—C3—O3'	118.4 (4)	C16—C15—H15	119.6
O4—C3—O3	121.5 (3)	C15—C16—C11	120.2 (3)
O4—C3—C1	123.1 (2)	C15—C16—H16	119.9
O3'—C3—C1	115.4 (4)	C11—C16—H16	119.9
O3—C3—C1	114.6 (3)	C26—C21—C22	118.1 (2)
O1—C4—C6	106.2 (3)	C26—C21—P1	120.69 (18)
O1—C4—C5	109.0 (3)	C22—C21—P1	121.22 (18)
C6—C4—C5	113.3 (3)	C23—C22—C21	120.9 (2)
O1—C4—H4	109.4	C23—C22—H22	119.5
C6—C4—H4	109.4	C21—C22—H22	119.5
C5—C4—H4	109.4	C22—C23—C24	120.6 (2)
C4—C5—H5A	109.5	C22—C23—H23	119.7
C4—C5—H5B	109.5	C24—C23—H23	119.7
H5A—C5—H5B	109.5	C25—C24—C23	119.4 (2)
C4—C5—H5C	109.5	C25—C24—H24	120.3
H5A—C5—H5C	109.5	C23—C24—H24	120.3
H5B—C5—H5C	109.5	C24—C25—C26	120.3 (2)
C4—C6—H6A	109.5	C24—C25—H25	119.8
C4—C6—H6B	109.5	C26—C25—H25	119.8
H6A—C6—H6B	109.5	C21—C26—C25	120.7 (2)
C4—C6—H6C	109.5	C21—C26—H26	119.7
H6A—C6—H6C	109.5	C25—C26—H26	119.7
H6B—C6—H6C	109.5	C32—C31—C36	118.4 (2)
O3—C7—C8	108.7 (4)	C32—C31—P1	120.77 (19)
O3—C7—H7A	110.0	C36—C31—P1	120.80 (19)
C8—C7—H7A	110.0	C31—C32—C33	120.5 (3)
O3—C7—H7B	110.0	C31—C32—H32	119.8
C8—C7—H7B	110.0	C33—C32—H32	119.8
H7A—C7—H7B	108.3	C34—C33—C32	120.4 (3)
O3'—C7'—C8'	108.7 (6)	C34—C33—H33	119.8
O3'—C7'—H7'A	109.9	C32—C33—H33	119.8
C8'—C7'—H7'A	109.9	C33—C34—C35	119.9 (3)
O3'—C7'—H7'B	109.9	C33—C34—H34	120.0
C8'—C7'—H7'B	109.9	C35—C34—H34	120.0
H7'A—C7'—H7'B	108.3	C36—C35—C34	119.5 (3)
C7'—C8'—H8'A	109.5	C36—C35—H35	120.3
C7'—C8'—H8'B	109.5	C34—C35—H35	120.3
H8'A—C8'—H8'B	109.5	C35—C36—C31	121.3 (3)
C7'—C8'—H8'C	109.5	C35—C36—H36	119.4
H8'A—C8'—H8'C	109.5	C31—C36—H36	119.4
C21—P1—C1—C3	72.0 (2)	P1—C11—C12—C13	178.16 (19)
C11—P1—C1—C3	−50.4 (2)	C11—C12—C13—C14	−0.5 (4)
C31—P1—C1—C3	−167.72 (17)	C12—C13—C14—C15	1.4 (4)
C21—P1—C1—C2	−103.2 (2)	C13—C14—C15—C16	−0.5 (4)
C11—P1—C1—C2	134.5 (2)	C14—C15—C16—C11	−1.3 (4)
C31—P1—C1—C2	17.1 (2)	C12—C11—C16—C15	2.1 (4)
C4—O1—C2—O2	4.5 (4)	P1—C11—C16—C15	−177.3 (2)
C4—O1—C2—C1	−178.6 (2)	C1—P1—C21—C26	−8.9 (2)
C3—C1—C2—O2	15.0 (4)	C11—P1—C21—C26	113.87 (19)
P1—C1—C2—O2	−170.4 (2)	C31—P1—C21—C26	−133.97 (19)
C3—C1—C2—O1	−161.6 (2)	C1—P1—C21—C22	168.92 (18)
P1—C1—C2—O1	13.0 (3)	C11—P1—C21—C22	−68.4 (2)
C7'—O3'—C3—O4	−3.2 (8)	C31—P1—C21—C22	43.8 (2)
C7'—O3'—C3—O3	−107.7 (12)	C26—C21—C22—C23	1.1 (3)
C7'—O3'—C3—C1	157.5 (5)	P1—C21—C22—C23	−176.75 (18)
C7—O3—C3—O4	−8.6 (6)	C21—C22—C23—C24	−0.9 (4)
C7—O3—C3—O3'	82.9 (10)	C22—C23—C24—C25	−0.2 (4)
C7—O3—C3—C1	−178.8 (3)	C23—C24—C25—C26	1.1 (4)
C2—C1—C3—O4	168.6 (2)	C22—C21—C26—C25	−0.2 (3)
P1—C1—C3—O4	−6.7 (3)	P1—C21—C26—C25	177.64 (18)
C2—C1—C3—O3'	8.9 (5)	C24—C25—C26—C21	−0.9 (4)
P1—C1—C3—O3'	−166.4 (4)	C1—P1—C31—C32	85.3 (2)
C2—C1—C3—O3	−21.4 (4)	C21—P1—C31—C32	−148.4 (2)
P1—C1—C3—O3	163.3 (3)	C11—P1—C31—C32	−34.1 (2)
C2—O1—C4—C6	−125.0 (3)	C1—P1—C31—C36	−94.8 (2)
C2—O1—C4—C5	112.5 (3)	C21—P1—C31—C36	31.5 (2)
C3—O3—C7—C8	−90.3 (6)	C11—P1—C31—C36	145.8 (2)
C3—O3'—C7'—C8'	85.6 (10)	C36—C31—C32—C33	0.4 (4)
C1—P1—C11—C12	138.36 (19)	P1—C31—C32—C33	−179.7 (2)
C21—P1—C11—C12	12.0 (2)	C31—C32—C33—C34	−1.6 (5)
C31—P1—C11—C12	−99.4 (2)	C32—C33—C34—C35	1.2 (5)
C1—P1—C11—C16	−42.3 (2)	C33—C34—C35—C36	0.2 (5)
C21—P1—C11—C16	−168.59 (19)	C34—C35—C36—C31	−1.3 (4)
C31—P1—C11—C16	80.0 (2)	C32—C31—C36—C35	1.0 (4)
C16—C11—C12—C13	−1.2 (4)	P1—C31—C36—C35	−178.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
P1···O1			2.953 (2)
P1···O4			2.809 (2)
C5—H5C···Cg3	0.96	2.93	3.663 (4)	134
C25—H25···O4^i	0.93	2.40	3.323 (3)	172

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

(IIa) methyl tert-butyl 2-(triphenylphosphoranyliden)malonate

Crystal data

C26H27O4P	F(000) = 920
Mr = 434.45	Dx = 1.201 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7347 reflections
a = 9.8140 (7) Å	θ = 2.4–27.5°
b = 15.889 (2) Å	µ = 0.14 mm^−1
c = 15.404 (2) Å	T = 140 K
β = 90.413 (2)°	Block, colourless
V = 2402.0 (5) Å^3	0.16 × 0.16 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4501 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 27.8°, θmin = 1.8°
ϕ and ω scans	h = −11→12
19840 measured reflections	k = −20→20
5292 independent reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0764P)^2 + 0.8536P] where P = (Fo^2 + 2Fc^2)/3
5292 reflections	(Δ/σ)max = 0.008
284 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
P1	0.14127 (4)	0.18082 (3)	0.47388 (3)	0.03449 (14)
O1	−0.03175 (14)	0.28668 (8)	0.56513 (8)	0.0484 (3)
O2	−0.04149 (14)	0.22305 (9)	0.69524 (8)	0.0525 (3)
O3	0.11969 (15)	0.08631 (9)	0.70944 (8)	0.0583 (4)
O4	0.2686 (2)	0.06909 (18)	0.60761 (12)	0.1345 (12)
C1	0.09323 (16)	0.16494 (10)	0.58150 (10)	0.0365 (3)
C2	0.00120 (17)	0.22425 (10)	0.62166 (10)	0.0392 (4)
C3	0.16718 (18)	0.10306 (12)	0.63060 (11)	0.0464 (4)
C4	−0.1236 (3)	0.35562 (14)	0.58826 (14)	0.0665 (6)
C5	−0.1376 (4)	0.40236 (18)	0.50279 (19)	0.0982 (10)
H5A	−0.0491	0.4191	0.4831	0.147*
H5B	−0.1933	0.4514	0.5109	0.147*
H5C	−0.1795	0.3662	0.4604	0.147*
C6	−0.0546 (5)	0.40994 (18)	0.6566 (2)	0.1148 (13)
H6A	−0.0497	0.3796	0.7104	0.172*
H6B	−0.1063	0.4606	0.6646	0.172*
H6C	0.0357	0.4240	0.6380	0.172*
C7	−0.2604 (3)	0.3214 (2)	0.6159 (2)	0.1119 (13)
H7A	−0.2498	0.2907	0.6692	0.168*
H7B	−0.2955	0.2846	0.5717	0.168*
H7C	−0.3226	0.3672	0.6245	0.168*
C8	0.1943 (3)	0.02723 (16)	0.76090 (15)	0.0767 (7)
H8A	0.1602	0.0277	0.8192	0.115*
H8B	0.2890	0.0423	0.7615	0.115*
H8C	0.1839	−0.0281	0.7367	0.115*
C11	0.26076 (17)	0.26686 (10)	0.46337 (11)	0.0387 (4)
C12	0.3300 (2)	0.28250 (12)	0.38661 (11)	0.0477 (4)
H12A	0.3128	0.2493	0.3380	0.057*
C13	0.4241 (2)	0.34692 (14)	0.38185 (14)	0.0588 (5)
H13	0.4692	0.3575	0.3301	0.071*
C14	0.4506 (3)	0.39522 (15)	0.45370 (16)	0.0708 (7)
H14	0.5143	0.4384	0.4506	0.085*
C15	0.3836 (3)	0.38024 (15)	0.53036 (15)	0.0707 (7)
H15	0.4021	0.4134	0.5788	0.085*
C16	0.2890 (2)	0.31607 (12)	0.53573 (12)	0.0512 (5)
H16	0.2444	0.3059	0.5877	0.061*
C21	0.22434 (17)	0.09091 (10)	0.42527 (10)	0.0387 (4)
C22	0.1478 (2)	0.03033 (12)	0.38286 (13)	0.0517 (4)
H22	0.0537	0.0360	0.3789	0.062*
C23	0.2116 (3)	−0.03907 (13)	0.34610 (16)	0.0658 (6)
H23	0.1600	−0.0800	0.3178	0.079*
C24	0.3503 (3)	−0.04726 (14)	0.35148 (16)	0.0666 (6)
H24	0.3925	−0.0938	0.3268	0.080*
C25	0.4274 (2)	0.01279 (14)	0.39303 (14)	0.0602 (5)
H25	0.5216	0.0069	0.3962	0.072*
C26	0.36547 (19)	0.08184 (13)	0.43009 (13)	0.0500 (4)
H26	0.4179	0.1224	0.4583	0.060*
C31	−0.00707 (18)	0.20010 (11)	0.40597 (11)	0.0418 (4)
C32	−0.1290 (2)	0.16113 (13)	0.42658 (14)	0.0539 (5)
H32	−0.1345	0.1261	0.4748	0.065*
C33	−0.2431 (2)	0.17488 (16)	0.37440 (17)	0.0695 (6)
H33	−0.3251	0.1489	0.3882	0.083*
C34	−0.2367 (3)	0.22568 (18)	0.30367 (17)	0.0772 (7)
H34	−0.3143	0.2351	0.2700	0.093*
C35	−0.1165 (3)	0.26294 (19)	0.28190 (16)	0.0804 (8)
H35	−0.1117	0.2965	0.2326	0.096*
C36	−0.0010 (2)	0.25077 (15)	0.33332 (14)	0.0625 (5)
H36	0.0805	0.2769	0.3187	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0317 (2)	0.0407 (2)	0.0311 (2)	−0.00082 (15)	0.00176 (16)	0.00031 (15)
O1	0.0604 (8)	0.0452 (7)	0.0397 (6)	0.0135 (6)	0.0059 (6)	0.0031 (5)
O2	0.0598 (8)	0.0608 (8)	0.0369 (6)	0.0137 (6)	0.0121 (6)	0.0032 (6)
O3	0.0698 (9)	0.0637 (8)	0.0416 (7)	0.0220 (7)	0.0111 (6)	0.0158 (6)
O4	0.1237 (17)	0.218 (3)	0.0619 (11)	0.1255 (19)	0.0422 (11)	0.0563 (14)
C1	0.0329 (8)	0.0443 (8)	0.0324 (8)	−0.0009 (6)	0.0025 (6)	0.0019 (6)
C2	0.0375 (8)	0.0437 (9)	0.0365 (8)	−0.0004 (7)	0.0010 (7)	0.0003 (7)
C3	0.0423 (9)	0.0602 (11)	0.0367 (9)	0.0093 (8)	0.0055 (7)	0.0048 (8)
C4	0.0855 (16)	0.0594 (12)	0.0547 (12)	0.0324 (12)	0.0033 (11)	0.0003 (10)
C5	0.148 (3)	0.0711 (16)	0.0752 (17)	0.0497 (18)	−0.0028 (17)	0.0162 (13)
C6	0.189 (4)	0.0683 (17)	0.087 (2)	0.038 (2)	−0.022 (2)	−0.0282 (15)
C7	0.0759 (19)	0.144 (3)	0.116 (3)	0.055 (2)	0.0222 (18)	0.028 (2)
C8	0.107 (2)	0.0749 (15)	0.0482 (12)	0.0345 (14)	0.0042 (12)	0.0197 (11)
C11	0.0375 (8)	0.0423 (8)	0.0362 (8)	−0.0050 (6)	0.0034 (6)	−0.0004 (6)
C12	0.0543 (11)	0.0522 (10)	0.0367 (9)	−0.0108 (8)	0.0093 (8)	−0.0066 (7)
C13	0.0675 (13)	0.0599 (11)	0.0492 (11)	−0.0187 (10)	0.0215 (10)	−0.0041 (9)
C14	0.0799 (16)	0.0644 (13)	0.0686 (14)	−0.0346 (12)	0.0257 (12)	−0.0163 (11)
C15	0.0813 (16)	0.0729 (14)	0.0583 (13)	−0.0342 (12)	0.0195 (11)	−0.0266 (11)
C16	0.0537 (11)	0.0596 (11)	0.0405 (9)	−0.0142 (9)	0.0119 (8)	−0.0097 (8)
C21	0.0391 (8)	0.0423 (8)	0.0349 (8)	0.0013 (7)	0.0058 (6)	0.0005 (6)
C22	0.0480 (10)	0.0488 (10)	0.0584 (11)	−0.0050 (8)	0.0063 (9)	−0.0071 (8)
C23	0.0749 (15)	0.0492 (11)	0.0736 (15)	−0.0066 (10)	0.0117 (12)	−0.0171 (10)
C24	0.0785 (16)	0.0508 (11)	0.0707 (14)	0.0140 (10)	0.0229 (12)	−0.0059 (10)
C25	0.0510 (11)	0.0665 (13)	0.0631 (13)	0.0156 (10)	0.0121 (9)	0.0021 (10)
C26	0.0411 (10)	0.0579 (11)	0.0510 (10)	0.0033 (8)	0.0044 (8)	−0.0041 (8)
C31	0.0384 (9)	0.0502 (9)	0.0368 (8)	0.0050 (7)	−0.0040 (7)	−0.0031 (7)
C32	0.0430 (10)	0.0631 (11)	0.0556 (11)	−0.0014 (9)	−0.0047 (8)	−0.0016 (9)
C33	0.0419 (11)	0.0859 (16)	0.0804 (16)	−0.0019 (10)	−0.0139 (11)	−0.0127 (13)
C34	0.0609 (15)	0.1006 (19)	0.0696 (15)	0.0190 (13)	−0.0283 (12)	−0.0068 (14)
C35	0.0766 (17)	0.107 (2)	0.0575 (14)	0.0124 (15)	−0.0199 (12)	0.0199 (13)
C36	0.0559 (12)	0.0820 (15)	0.0494 (11)	0.0028 (10)	−0.0049 (9)	0.0153 (10)

Geometric parameters (Å, º)

P1—C1	1.7451 (16)	C12—H12A	0.9300
P1—C11	1.8092 (17)	C13—C14	1.370 (3)
P1—C21	1.8097 (17)	C13—H13	0.9300
P1—C31	1.8126 (17)	C14—C15	1.376 (3)
O1—C2	1.357 (2)	C14—H14	0.9300
O1—C4	1.464 (2)	C15—C16	1.382 (3)
O2—C2	1.211 (2)	C15—H15	0.9300
O3—C3	1.331 (2)	C16—H16	0.9300
O3—C8	1.427 (2)	C21—C22	1.382 (2)
O4—C3	1.188 (2)	C21—C26	1.394 (2)
C1—C3	1.434 (2)	C22—C23	1.390 (3)
C1—C2	1.447 (2)	C22—H22	0.9300
C4—C7	1.512 (4)	C23—C24	1.369 (3)
C4—C6	1.516 (4)	C23—H23	0.9300
C4—C5	1.517 (3)	C24—C25	1.373 (3)
C5—H5A	0.9600	C24—H24	0.9300
C5—H5B	0.9600	C25—C26	1.380 (3)
C5—H5C	0.9600	C25—H25	0.9300
C6—H6A	0.9600	C26—H26	0.9300
C6—H6B	0.9600	C31—C36	1.380 (3)
C6—H6C	0.9600	C31—C32	1.386 (3)
C7—H7A	0.9600	C32—C33	1.391 (3)
C7—H7B	0.9600	C32—H32	0.9300
C7—H7C	0.9600	C33—C34	1.358 (4)
C8—H8A	0.9600	C33—H33	0.9300
C8—H8B	0.9600	C34—C35	1.364 (4)
C8—H8C	0.9600	C34—H34	0.9300
C11—C16	1.388 (2)	C35—C36	1.392 (3)
C11—C12	1.390 (2)	C35—H35	0.9300
C12—C13	1.381 (3)	C36—H36	0.9300
C1—P1—C11	111.96 (8)	C13—C12—H12A	119.7
C1—P1—C21	113.86 (8)	C11—C12—H12A	119.7
C11—P1—C21	105.38 (8)	C14—C13—C12	119.70 (18)
C1—P1—C31	110.57 (8)	C14—C13—H13	120.1
C11—P1—C31	109.82 (8)	C12—C13—H13	120.1
C21—P1—C31	104.89 (8)	C13—C14—C15	120.47 (19)
C2—O1—C4	122.33 (14)	C13—C14—H14	119.8
C3—O3—C8	117.18 (16)	C15—C14—H14	119.8
C3—C1—C2	122.41 (15)	C14—C15—C16	120.27 (19)
C3—C1—P1	117.44 (12)	C14—C15—H15	119.9
C2—C1—P1	119.05 (12)	C16—C15—H15	119.9
O2—C2—O1	121.96 (15)	C15—C16—C11	119.88 (17)
O2—C2—C1	127.64 (15)	C15—C16—H16	120.1
O1—C2—C1	110.37 (14)	C11—C16—H16	120.1
O4—C3—O3	118.73 (17)	C22—C21—C26	119.29 (16)
O4—C3—C1	125.16 (17)	C22—C21—P1	120.04 (14)
O3—C3—C1	116.04 (15)	C26—C21—P1	120.66 (14)
O1—C4—C7	110.4 (2)	C21—C22—C23	120.03 (19)
O1—C4—C6	108.8 (2)	C21—C22—H22	120.0
C7—C4—C6	113.7 (3)	C23—C22—H22	120.0
O1—C4—C5	101.97 (18)	C24—C23—C22	120.1 (2)
C7—C4—C5	110.2 (2)	C24—C23—H23	120.0
C6—C4—C5	111.2 (2)	C22—C23—H23	120.0
C4—C5—H5A	109.5	C23—C24—C25	120.43 (19)
C4—C5—H5B	109.5	C23—C24—H24	119.8
H5A—C5—H5B	109.5	C25—C24—H24	119.8
C4—C5—H5C	109.5	C24—C25—C26	120.1 (2)
H5A—C5—H5C	109.5	C24—C25—H25	119.9
H5B—C5—H5C	109.5	C26—C25—H25	119.9
C4—C6—H6A	109.5	C25—C26—C21	120.04 (19)
C4—C6—H6B	109.5	C25—C26—H26	120.0
H6A—C6—H6B	109.5	C21—C26—H26	120.0
C4—C6—H6C	109.5	C36—C31—C32	119.25 (18)
H6A—C6—H6C	109.5	C36—C31—P1	121.82 (15)
H6B—C6—H6C	109.5	C32—C31—P1	118.91 (14)
C4—C7—H7A	109.5	C31—C32—C33	119.4 (2)
C4—C7—H7B	109.5	C31—C32—H32	120.3
H7A—C7—H7B	109.5	C33—C32—H32	120.3
C4—C7—H7C	109.5	C34—C33—C32	121.0 (2)
H7A—C7—H7C	109.5	C34—C33—H33	119.5
H7B—C7—H7C	109.5	C32—C33—H33	119.5
O3—C8—H8A	109.5	C33—C34—C35	120.1 (2)
O3—C8—H8B	109.5	C33—C34—H34	120.0
H8A—C8—H8B	109.5	C35—C34—H34	120.0
O3—C8—H8C	109.5	C34—C35—C36	120.1 (2)
H8A—C8—H8C	109.5	C34—C35—H35	119.9
H8B—C8—H8C	109.5	C36—C35—H35	119.9
C16—C11—C12	119.09 (16)	C31—C36—C35	120.2 (2)
C16—C11—P1	118.67 (13)	C31—C36—H36	119.9
C12—C11—P1	122.16 (13)	C35—C36—H36	119.9
C13—C12—C11	120.58 (17)
C11—P1—C1—C3	−94.67 (15)	C14—C15—C16—C11	−0.4 (4)
C21—P1—C1—C3	24.74 (16)	C12—C11—C16—C15	0.8 (3)
C31—P1—C1—C3	142.52 (14)	P1—C11—C16—C15	177.62 (19)
C11—P1—C1—C2	73.63 (15)	C1—P1—C21—C22	89.73 (16)
C21—P1—C1—C2	−166.96 (13)	C11—P1—C21—C22	−147.19 (15)
C31—P1—C1—C2	−49.18 (15)	C31—P1—C21—C22	−31.27 (17)
C4—O1—C2—O2	−1.5 (3)	C1—P1—C21—C26	−90.24 (16)
C4—O1—C2—C1	179.97 (17)	C11—P1—C21—C26	32.84 (16)
C3—C1—C2—O2	−11.8 (3)	C31—P1—C21—C26	148.75 (15)
P1—C1—C2—O2	−179.49 (15)	C26—C21—C22—C23	0.5 (3)
C3—C1—C2—O1	166.58 (16)	P1—C21—C22—C23	−179.50 (16)
P1—C1—C2—O1	−1.12 (19)	C21—C22—C23—C24	−0.3 (3)
C8—O3—C3—O4	−0.7 (3)	C22—C23—C24—C25	0.0 (4)
C8—O3—C3—C1	−177.8 (2)	C23—C24—C25—C26	0.3 (4)
C2—C1—C3—O4	−158.2 (3)	C24—C25—C26—C21	−0.1 (3)
P1—C1—C3—O4	9.6 (3)	C22—C21—C26—C25	−0.2 (3)
C2—C1—C3—O3	18.6 (3)	P1—C21—C26—C25	179.73 (15)
P1—C1—C3—O3	−173.51 (14)	C1—P1—C31—C36	149.13 (17)
C2—O1—C4—C7	−57.8 (3)	C11—P1—C31—C36	25.08 (19)
C2—O1—C4—C6	67.6 (3)	C21—P1—C31—C36	−87.72 (18)
C2—O1—C4—C5	−174.9 (2)	C1—P1—C31—C32	−32.46 (18)
C1—P1—C11—C16	−7.33 (18)	C11—P1—C31—C32	−156.51 (15)
C21—P1—C11—C16	−131.61 (15)	C21—P1—C31—C32	90.70 (16)
C31—P1—C11—C16	115.91 (16)	C36—C31—C32—C33	−0.9 (3)
C1—P1—C11—C12	169.37 (15)	P1—C31—C32—C33	−179.39 (16)
C21—P1—C11—C12	45.09 (17)	C31—C32—C33—C34	0.1 (3)
C31—P1—C11—C12	−67.39 (17)	C32—C33—C34—C35	1.2 (4)
C16—C11—C12—C13	−1.0 (3)	C33—C34—C35—C36	−1.7 (4)
P1—C11—C12—C13	−177.70 (17)	C32—C31—C36—C35	0.5 (3)
C11—C12—C13—C14	0.8 (4)	P1—C31—C36—C35	178.9 (2)
C12—C13—C14—C15	−0.3 (4)	C34—C35—C36—C31	0.8 (4)
C13—C14—C15—C16	0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
P1···O1			2.729 (2)
P1···O4			2.986 (2)
C5—H5C···Cg3	0.96	2.99	3.788 (3)	141
C23—H23···O2^i	0.93	2.56	3.424 (2)	154
C25—H25···O4^ii	0.93	2.39	3.255 (3)	155
C34—H34···O2^iii	0.93	2.59	3.511 (3)	171
C13—H13···O3^iv	0.93	2.54	3.455 (3)	166

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2.

(IIb) ethyl tert-butyl 2-(triphenylphosphoranyliden)malonate

Crystal data

C27H29O4P	Z = 2
Mr = 448.47	F(000) = 476
Triclinic, P1	Dx = 1.231 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9616 (7) Å	Cell parameters from 2361 reflections
b = 10.3589 (8) Å	θ = 2.3–23.8°
c = 14.5644 (11) Å	µ = 0.14 mm^−1
α = 97.388 (2)°	T = 140 K
β = 107.705 (3)°	Block, colourless
γ = 105.338 (2)°	0.20 × 0.18 × 0.14 mm
V = 1209.55 (16) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3919 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 27.9°, θmin = 2.1°
ϕ and ω scans	h = −11→11
10154 measured reflections	k = −13→13
5183 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.070P)^2 + 0.1417P] where P = (Fo^2 + 2Fc^2)/3
5183 reflections	(Δ/σ)max = 0.018
299 parameters	Δρmax = 0.36 e Å^−3
3 restraints	Δρmin = −0.16 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.42921 (4)	0.76990 (4)	0.21270 (3)	0.03683 (9)
O1	0.61257 (12)	0.58687 (10)	0.27373 (8)	0.0503 (3)
O2	0.84030 (12)	0.68548 (12)	0.24039 (9)	0.0627 (3)
O3	0.89536 (17)	0.95837 (9)	0.25831 (11)	0.0572 (4)	0.747 (4)
C8	0.9971 (3)	1.10238 (17)	0.29425 (10)	0.0817 (7)	0.747 (4)
H8A	1.0887	1.1173	0.2703	0.098*	0.747 (4)
H8B	0.9315	1.1587	0.2671	0.098*	0.747 (4)
C9	1.0620 (4)	1.1465 (4)	0.40136 (14)	0.0982 (11)	0.747 (4)
H9A	1.1305	1.2410	0.4207	0.147*	0.747 (4)
H9B	1.1265	1.0908	0.4289	0.147*	0.747 (4)
H9C	0.9720	1.1367	0.4254	0.147*	0.747 (4)
O3'	0.8921 (5)	0.97469 (16)	0.2822 (3)	0.0572 (4)	0.253 (4)
C8'	1.0056 (6)	1.1099 (3)	0.2922 (3)	0.0817 (7)	0.253 (4)
H8'A	1.1063	1.1042	0.2825	0.098*	0.253 (4)
H8'B	0.9546	1.1598	0.2469	0.098*	0.253 (4)
C9'	1.0355 (14)	1.1705 (14)	0.3943 (4)	0.0982 (11)	0.253 (4)
H9'A	1.1079	1.2637	0.4118	0.147*	0.253 (4)
H9'B	1.0860	1.1186	0.4368	0.147*	0.253 (4)
H9'C	0.9324	1.1695	0.4017	0.147*	0.253 (4)
O4	0.67961 (12)	1.03388 (11)	0.26410 (8)	0.0535 (3)
C1	0.63747 (16)	0.79704 (14)	0.23226 (10)	0.0389 (3)
C2	0.71058 (17)	0.68898 (15)	0.24759 (11)	0.0437 (4)
C3	0.73341 (17)	0.93876 (16)	0.25398 (11)	0.0434 (4)
C4	0.6506 (2)	0.45896 (17)	0.28767 (14)	0.0604 (5)
C5	0.5013 (3)	0.3781 (2)	0.30767 (18)	0.0906 (7)
H5A	0.4969	0.4265	0.3671	0.136*
H5B	0.5095	0.2894	0.3156	0.136*
H5C	0.4027	0.3670	0.2531	0.136*
C6	0.6591 (3)	0.3845 (2)	0.19436 (17)	0.0876 (7)
H6A	0.7545	0.4366	0.1825	0.131*
H6B	0.5610	0.3740	0.1395	0.131*
H6C	0.6671	0.2955	0.2016	0.131*
C7	0.8083 (3)	0.4914 (2)	0.37591 (19)	0.1079 (9)
H7A	0.7975	0.5395	0.4332	0.162*
H7B	0.8995	0.5478	0.3624	0.162*
H7C	0.8280	0.4074	0.3880	0.162*
C11	0.38572 (16)	0.79984 (15)	0.32493 (10)	0.0408 (4)
C12	0.23174 (17)	0.80506 (16)	0.32664 (12)	0.0484 (4)
H12	0.1475	0.7972	0.2679	0.058*
C13	0.2051 (2)	0.82173 (17)	0.41457 (12)	0.0557 (4)
H13	0.1027	0.8250	0.4152	0.067*
C14	0.3288 (2)	0.83371 (18)	0.50179 (13)	0.0601 (5)
H14	0.3101	0.8453	0.5613	0.072*
C15	0.4802 (2)	0.82852 (19)	0.50116 (12)	0.0600 (5)
H15	0.5637	0.8365	0.5603	0.072*
C16	0.50869 (18)	0.81148 (16)	0.41330 (11)	0.0479 (4)
H16	0.6113	0.8078	0.4134	0.058*
C21	0.35241 (16)	0.87693 (14)	0.13323 (10)	0.0387 (3)
C22	0.35132 (18)	0.85366 (16)	0.03733 (11)	0.0482 (4)
H22	0.3908	0.7853	0.0161	0.058*
C23	0.2925 (2)	0.93023 (17)	−0.02746 (12)	0.0541 (4)
H23	0.2928	0.9135	−0.0917	0.065*
C24	0.2337 (2)	1.03107 (17)	0.00327 (13)	0.0584 (5)
H24	0.1929	1.0823	−0.0403	0.070*
C25	0.2354 (2)	1.05596 (18)	0.09807 (14)	0.0659 (5)
H25	0.1954	1.1243	0.1187	0.079*
C26	0.2958 (2)	0.98094 (17)	0.16349 (12)	0.0549 (4)
H26	0.2984	1.0003	0.2282	0.066*
C31	0.30318 (16)	0.59683 (14)	0.14338 (11)	0.0408 (4)
C32	0.16589 (19)	0.52632 (17)	0.16322 (13)	0.0542 (4)
H32	0.1432	0.5649	0.2166	0.065*
C33	0.0628 (2)	0.39923 (18)	0.10418 (15)	0.0628 (5)
H33	−0.0288	0.3526	0.1182	0.075*
C34	0.0946 (2)	0.34161 (17)	0.02529 (14)	0.0603 (5)
H34	0.0238	0.2567	−0.0149	0.072*
C35	0.2306 (2)	0.40903 (17)	0.00554 (13)	0.0578 (5)
H35	0.2525	0.3693	−0.0478	0.069*
C36	0.33556 (19)	0.53558 (16)	0.06426 (11)	0.0491 (4)
H36	0.4285	0.5801	0.0508	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.03210 (16)	0.03876 (18)	0.03629 (18)	0.00930 (14)	0.00937 (14)	0.00832 (14)
O1	0.0479 (5)	0.0490 (5)	0.0612 (6)	0.0198 (4)	0.0214 (5)	0.0227 (5)
O2	0.0406 (5)	0.0616 (7)	0.0897 (8)	0.0200 (5)	0.0248 (5)	0.0179 (6)
O3	0.0395 (5)	0.0494 (7)	0.0758 (9)	0.0041 (5)	0.0276 (6)	−0.0050 (6)
C8	0.0526 (10)	0.0702 (13)	0.1054 (16)	−0.0009 (10)	0.0298 (10)	0.0010 (11)
C9	0.0669 (16)	0.102 (2)	0.1039 (19)	0.0286 (15)	0.0094 (14)	−0.0035 (16)
O3'	0.0395 (5)	0.0494 (7)	0.0758 (9)	0.0041 (5)	0.0276 (6)	−0.0050 (6)
C8'	0.0526 (10)	0.0702 (13)	0.1054 (16)	−0.0009 (10)	0.0298 (10)	0.0010 (11)
C9'	0.0669 (16)	0.102 (2)	0.1039 (19)	0.0286 (15)	0.0094 (14)	−0.0035 (16)
O4	0.0471 (5)	0.0440 (6)	0.0600 (7)	0.0109 (5)	0.0110 (5)	0.0072 (5)
C1	0.0329 (6)	0.0424 (7)	0.0394 (7)	0.0101 (6)	0.0116 (5)	0.0103 (6)
C2	0.0338 (7)	0.0491 (8)	0.0424 (8)	0.0101 (6)	0.0097 (6)	0.0070 (6)
C3	0.0370 (7)	0.0475 (8)	0.0402 (8)	0.0081 (6)	0.0112 (6)	0.0089 (6)
C4	0.0587 (9)	0.0517 (9)	0.0688 (11)	0.0229 (7)	0.0108 (8)	0.0250 (8)
C5	0.0988 (14)	0.0734 (12)	0.1100 (16)	0.0247 (11)	0.0420 (12)	0.0494 (11)
C6	0.1047 (14)	0.0654 (12)	0.1031 (16)	0.0413 (11)	0.0407 (12)	0.0157 (11)
C7	0.0982 (16)	0.0875 (14)	0.1065 (18)	0.0310 (13)	−0.0155 (14)	0.0405 (13)
C11	0.0376 (7)	0.0405 (7)	0.0401 (7)	0.0080 (6)	0.0124 (6)	0.0079 (6)
C12	0.0400 (7)	0.0541 (9)	0.0475 (8)	0.0128 (7)	0.0144 (6)	0.0073 (7)
C13	0.0502 (8)	0.0595 (10)	0.0609 (9)	0.0147 (7)	0.0283 (7)	0.0102 (8)
C14	0.0696 (9)	0.0676 (11)	0.0509 (9)	0.0199 (8)	0.0329 (8)	0.0158 (8)
C15	0.0606 (9)	0.0758 (11)	0.0419 (8)	0.0204 (8)	0.0150 (7)	0.0188 (8)
C16	0.0432 (7)	0.0581 (9)	0.0423 (8)	0.0162 (7)	0.0138 (6)	0.0137 (7)
C21	0.0306 (6)	0.0374 (7)	0.0412 (7)	0.0066 (5)	0.0071 (5)	0.0081 (6)
C22	0.0521 (8)	0.0468 (8)	0.0477 (8)	0.0169 (7)	0.0184 (7)	0.0132 (6)
C23	0.0605 (9)	0.0559 (9)	0.0459 (8)	0.0176 (7)	0.0161 (7)	0.0198 (7)
C24	0.0581 (9)	0.0533 (9)	0.0616 (10)	0.0205 (7)	0.0111 (8)	0.0242 (7)
C25	0.0835 (11)	0.0590 (9)	0.0676 (11)	0.0420 (8)	0.0254 (9)	0.0195 (8)
C26	0.0674 (9)	0.0540 (9)	0.0492 (9)	0.0301 (7)	0.0196 (7)	0.0120 (7)
C31	0.0358 (6)	0.0400 (7)	0.0426 (7)	0.0123 (6)	0.0076 (6)	0.0112 (6)
C32	0.0445 (8)	0.0483 (9)	0.0643 (10)	0.0079 (7)	0.0201 (7)	0.0070 (7)
C33	0.0455 (8)	0.0467 (9)	0.0871 (13)	0.0041 (7)	0.0226 (8)	0.0084 (9)
C34	0.0491 (9)	0.0414 (9)	0.0692 (11)	0.0098 (7)	0.0002 (8)	0.0018 (8)
C35	0.0642 (10)	0.0468 (9)	0.0529 (9)	0.0174 (8)	0.0122 (8)	0.0004 (7)
C36	0.0492 (8)	0.0458 (8)	0.0475 (8)	0.0109 (7)	0.0156 (7)	0.0078 (7)

Geometric parameters (Å, º)

P1—C1	1.7383 (14)	C7—H7B	0.9600
P1—C11	1.8004 (15)	C7—H7C	0.9600
P1—C31	1.8107 (14)	C11—C16	1.383 (2)
P1—C21	1.8142 (15)	C11—C12	1.403 (2)
O1—C2	1.3603 (18)	C12—C13	1.370 (2)
O1—C4	1.476 (2)	C12—H12	0.9300
O2—C2	1.2080 (18)	C13—C14	1.374 (2)
O3—C3	1.392 (2)	C13—H13	0.9300
O3—C8	1.4560 (17)	C14—C15	1.374 (2)
C8—C9	1.451 (2)	C14—H14	0.9300
C8—H8A	0.9700	C15—C16	1.378 (2)
C8—H8B	0.9700	C15—H15	0.9300
C9—H9A	0.9600	C16—H16	0.9300
C9—H9B	0.9600	C21—C22	1.383 (2)
C9—H9C	0.9600	C21—C26	1.384 (2)
O3'—C3	1.287 (4)	C22—C23	1.381 (2)
O3'—C8'	1.4560 (19)	C22—H22	0.9300
C8'—C9'	1.451 (2)	C23—C24	1.373 (2)
C8'—H8'A	0.9700	C23—H23	0.9300
C8'—H8'B	0.9700	C24—C25	1.366 (3)
C9'—H9'A	0.9600	C24—H24	0.9300
C9'—H9'B	0.9600	C25—C26	1.380 (2)
C9'—H9'C	0.9600	C25—H25	0.9300
O4—C3	1.2174 (19)	C26—H26	0.9300
C1—C3	1.429 (2)	C31—C32	1.388 (2)
C1—C2	1.448 (2)	C31—C36	1.388 (2)
C4—C6	1.507 (3)	C32—C33	1.381 (2)
C4—C5	1.511 (3)	C32—H32	0.9300
C4—C7	1.515 (3)	C33—C34	1.368 (3)
C5—H5A	0.9600	C33—H33	0.9300
C5—H5B	0.9600	C34—C35	1.368 (2)
C5—H5C	0.9600	C34—H34	0.9300
C6—H6A	0.9600	C35—C36	1.380 (2)
C6—H6B	0.9600	C35—H35	0.9300
C6—H6C	0.9600	C36—H36	0.9300
C7—H7A	0.9600
C1—P1—C11	113.80 (6)	H6B—C6—H6C	109.5
C1—P1—C31	111.58 (7)	C4—C7—H7A	109.5
C11—P1—C31	107.85 (7)	C4—C7—H7B	109.5
C1—P1—C21	110.05 (7)	H7A—C7—H7B	109.5
C11—P1—C21	109.51 (7)	C4—C7—H7C	109.5
C31—P1—C21	103.53 (6)	H7A—C7—H7C	109.5
C2—O1—C4	122.35 (13)	H7B—C7—H7C	109.5
C3—O3—C8	112.12 (16)	C16—C11—C12	118.70 (14)
C9—C8—O3	113.2 (2)	C16—C11—P1	117.81 (12)
C9—C8—H8A	108.9	C12—C11—P1	123.41 (11)
O3—C8—H8A	108.9	C13—C12—C11	120.20 (14)
C9—C8—H8B	108.9	C13—C12—H12	119.9
O3—C8—H8B	108.9	C11—C12—H12	119.9
H8A—C8—H8B	107.7	C12—C13—C14	120.39 (16)
C8—C9—H9A	109.5	C12—C13—H13	119.8
C8—C9—H9B	109.5	C14—C13—H13	119.8
H9A—C9—H9B	109.5	C13—C14—C15	120.02 (16)
C8—C9—H9C	109.5	C13—C14—H14	120.0
H9A—C9—H9C	109.5	C15—C14—H14	120.0
H9B—C9—H9C	109.5	C14—C15—C16	120.26 (15)
C3—O3'—C8'	127.1 (3)	C14—C15—H15	119.9
C9'—C8'—O3'	99.5 (6)	C16—C15—H15	119.9
C9'—C8'—H8'A	111.9	C15—C16—C11	120.44 (15)
O3'—C8'—H8'A	111.9	C15—C16—H16	119.8
C9'—C8'—H8'B	111.8	C11—C16—H16	119.8
O3'—C8'—H8'B	111.9	C22—C21—C26	118.28 (14)
H8'A—C8'—H8'B	109.6	C22—C21—P1	118.11 (12)
C8'—C9'—H9'A	109.5	C26—C21—P1	123.61 (12)
C8'—C9'—H9'B	109.5	C23—C22—C21	121.10 (16)
H9'A—C9'—H9'B	109.5	C23—C22—H22	119.4
C8'—C9'—H9'C	109.5	C21—C22—H22	119.5
H9'A—C9'—H9'C	109.5	C24—C23—C22	119.78 (16)
H9'B—C9'—H9'C	109.5	C24—C23—H23	120.1
C3—C1—C2	123.02 (12)	C22—C23—H23	120.1
C3—C1—P1	113.73 (11)	C25—C24—C23	119.73 (16)
C2—C1—P1	121.77 (10)	C25—C24—H24	120.1
O2—C2—O1	122.42 (15)	C23—C24—H24	120.1
O2—C2—C1	127.20 (15)	C24—C25—C26	120.77 (17)
O1—C2—C1	110.38 (12)	C24—C25—H25	119.6
O4—C3—O3'	114.29 (16)	C26—C25—H25	119.6
O4—C3—O3	122.50 (13)	C25—C26—C21	120.31 (16)
O4—C3—C1	124.35 (13)	C25—C26—H26	119.8
O3'—C3—C1	120.22 (15)	C21—C26—H26	119.8
O3—C3—C1	113.09 (13)	C32—C31—C36	118.47 (13)
O1—C4—C6	110.87 (15)	C32—C31—P1	121.13 (12)
O1—C4—C5	101.49 (15)	C36—C31—P1	120.25 (11)
C6—C4—C5	110.16 (16)	C33—C32—C31	120.42 (17)
O1—C4—C7	109.66 (14)	C33—C32—H32	119.8
C6—C4—C7	112.54 (19)	C31—C32—H32	119.8
C5—C4—C7	111.59 (18)	C34—C33—C32	120.36 (16)
C4—C5—H5A	109.5	C34—C33—H33	119.8
C4—C5—H5B	109.5	C32—C33—H33	119.8
H5A—C5—H5B	109.5	C33—C34—C35	119.91 (15)
C4—C5—H5C	109.5	C33—C34—H34	120.0
H5A—C5—H5C	109.5	C35—C34—H34	120.0
H5B—C5—H5C	109.5	C34—C35—C36	120.46 (17)
C4—C6—H6A	109.5	C34—C35—H35	119.8
C4—C6—H6B	109.5	C36—C35—H35	119.8
H6A—C6—H6B	109.5	C35—C36—C31	120.36 (15)
C4—C6—H6C	109.5	C35—C36—H36	119.8
H6A—C6—H6C	109.5	C31—C36—H36	119.8
C3—O3—C8—C9	82.8 (3)	P1—C11—C12—C13	176.87 (12)
C3—O3'—C8'—C9'	89.8 (7)	C11—C12—C13—C14	0.1 (2)
C11—P1—C1—C3	−78.64 (12)	C12—C13—C14—C15	−0.2 (3)
C31—P1—C1—C3	159.04 (11)	C13—C14—C15—C16	0.1 (3)
C21—P1—C1—C3	44.70 (13)	C14—C15—C16—C11	0.2 (3)
C11—P1—C1—C2	87.90 (13)	C12—C11—C16—C15	−0.3 (2)
C31—P1—C1—C2	−34.42 (14)	P1—C11—C16—C15	−177.20 (13)
C21—P1—C1—C2	−148.77 (12)	C1—P1—C21—C22	63.88 (12)
C4—O1—C2—O2	−4.9 (2)	C11—P1—C21—C22	−170.31 (10)
C4—O1—C2—C1	175.87 (12)	C31—P1—C21—C22	−55.49 (12)
C3—C1—C2—O2	−32.2 (2)	C1—P1—C21—C26	−115.75 (13)
P1—C1—C2—O2	162.53 (13)	C11—P1—C21—C26	10.05 (14)
C3—C1—C2—O1	146.98 (14)	C31—P1—C21—C26	124.87 (13)
P1—C1—C2—O1	−18.30 (17)	C26—C21—C22—C23	−1.2 (2)
C8'—O3'—C3—O4	−22.0 (5)	P1—C21—C22—C23	179.17 (11)
C8'—O3'—C3—O3	103.0 (5)	C21—C22—C23—C24	−0.1 (2)
C8'—O3'—C3—C1	169.7 (3)	C22—C23—C24—C25	0.7 (2)
C8—O3—C3—O4	10.9 (2)	C23—C24—C25—C26	0.1 (3)
C8—O3—C3—O3'	−51.4 (2)	C24—C25—C26—C21	−1.4 (3)
C8—O3—C3—C1	−171.79 (13)	C22—C21—C26—C25	1.9 (2)
C2—C1—C3—O4	−162.15 (15)	P1—C21—C26—C25	−178.43 (13)
P1—C1—C3—O4	4.2 (2)	C1—P1—C31—C32	143.80 (13)
C2—C1—C3—O3'	4.9 (3)	C11—P1—C31—C32	18.12 (15)
P1—C1—C3—O3'	171.3 (2)	C21—P1—C31—C32	−97.89 (14)
C2—C1—C3—O3	20.5 (2)	C1—P1—C31—C36	−40.81 (14)
P1—C1—C3—O3	−173.11 (11)	C11—P1—C31—C36	−166.49 (12)
C2—O1—C4—C6	−58.90 (18)	C21—P1—C31—C36	77.51 (13)
C2—O1—C4—C5	−175.89 (14)	C36—C31—C32—C33	−1.1 (2)
C2—O1—C4—C7	66.0 (2)	P1—C31—C32—C33	174.34 (14)
C1—P1—C11—C16	−13.50 (15)	C31—C32—C33—C34	−0.2 (3)
C31—P1—C11—C16	110.86 (12)	C32—C33—C34—C35	1.0 (3)
C21—P1—C11—C16	−137.12 (12)	C33—C34—C35—C36	−0.5 (3)
C1—P1—C11—C12	169.76 (12)	C34—C35—C36—C31	−0.8 (3)
C31—P1—C11—C12	−65.88 (14)	C32—C31—C36—C35	1.6 (2)
C21—P1—C11—C12	46.14 (14)	P1—C31—C36—C35	−173.87 (13)
C16—C11—C12—C13	0.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
P1···O1			2.877 (2)
P1···O4			2.877 (2)
C5—H5C···Cg3	0.96	3.07	3.944 (2)	152
C34—H34···Cg2^i	0.93	2.90	3.712 (2)	146
C12—H12···O2^ii	0.93	2.57	3.168 (2)	123

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