share
share
Issue contentsclose
Statistics
close
Download citation
closeDownload citation
Format BIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Text
Plain Text
Download PDF of article
Download PDF of articleclose
Acta Cryst. (2007). C63, o65-o67
https://doi.org/10.1107/S0108270106051201
Download PDF of article
Download PDF of articleclose
Download citation
closeDownload citation
Format BIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Text
Plain Text
Statistics
close
Issue contentsclose
share
link to html

Cyano-stabilized triphenyl­phospho­nium ylids

F. Castañeda, C. A. Bunton, R. Baggio and M. T. Garland
Crystalline cyano-stabilized triphenyl­phospho­nium ylids with keto or ester groups give rise to an extended electronic delocalization. In methyl 2-cyano-2-(trimethyl­phospho­nio)­ethenoate, Ph3P=C(CN)CO2CH3 or C22H18NO2P, (I), and 1-cyano-1-(trimethyl­phospho­nio)prop-1-en-2-olate, Ph3P=C(CN)CO-CH3 or C22H18NOP, (II), the carbonyl groups are oriented toward the cationoid P atom. Bond lengths and angles, torsion angles and P...O contact distances are consistent with a dominant coplanar conformation where the mol­ecular structures are the result of a balance between intra- and inter­molecular inter­actions. The main inter­actions presented by cyano-ester (I) and cyano-keto (II) are intra­molecular inter­actions between the carbonyl O and the P atoms. In addition, both compounds show other less important intra­molecular inter­actions between the carbonyl O and phenyl H atoms, which could contribute to form a preferred conformation in the crystal structure.
Read articleSimilar articles

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106051201/sq3045sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106051201/sq3045Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106051201/sq3045IIsup3.hkl
Contains datablock II

CCDC references: 634907; 634908

Comment top

Electronic delocalization involving acyl keto and ester groups stabilizes phosphonium ylids, and is maximized by their taking up planar conformations with favorable interactions between anionoid O atoms and cationoid phosphorus (Castañeda et al., 2001; Castañeda, Recabarren et al., 2003; Castañeda, Terraza et al., 2003). However, in crystalline diethyl ester derivatives, interference involving the trigonal ester groups leads to a conformation where the acyl O atoms are anti to phosphorus, and the acyl groups are twisted out of the ylidic plane (Castañeda et al., 2005, 2006). The linear cyano group is strongly electron withdrawing and should facilitate electronic delocalization in a planar ylidic unit (Scheme 1).

We therefore expected that the cyano group would favor cyano-keto or -ester compounds taking up conformations that allow extensive electronic delocalization and interactions between phosphorus and an acyl O atom. The conformations should be similar in the solid and in solution, and here we discuss the geometries of the following ylids in the crystal structure. Complete evidence on geometries in solution will be given elsewhere. Crystalline (methoxycarbonylcyanomethylene)triphenylphosphorane, (I), and (acetylcyanomethylene)triphenylphosphorane, (II), have the molecular structures and selected geometric parameters shown in Figs. 1 and 2 and Tables 1 and 2, respectively. In both ylids, the configurations about the P atom are approximately tetrahedral, with phenyl groups forming a propeller-like arrangement. For (I) and (II), the bond angles C31(phenyl)—P1—C11(phenyl), C21(phenyl)—P1—C11 (phenyl) and C31(phenyl)—P1—C21(phenyl) are 107.42 (12), 107.44 (12) and 106.35 (12)°, and 108.17 (9), 105.79 (10) and 106.81 (9)°, respectively. The sums of the angles about the ylidic C1 atom for (I) and (II) are 359.9 and 360° respectively, consistent with sp2-hybridization in an almost trigonal–planar geometry. It is well known that stabilized ylids have a longer P═C bond as a result of the electronic delocalization caused by the stabilizing groups (Bachrach & Nitsche, 1994; Howells et al. 1973). In cyano-ester ylid (1) and cyano-keto ylid (2), the P1—C1 bond lengths are 1.730 (3) and 1.744 (2) Å, respectively. These values are between those reported for a P—C single bond (1.80–1.83 Å; Howells et al., 1973) and P═C double bond (1.63–1.73 Å) (Howells et al., 1973) and they are considerably longer than the P═C bond in methylenetriphenylphosphorane, Ph3P=CH2 [1.661 (8) Å; Bart, 1969], where there is no opportunity for conjugation with other groups. Electronic delocalization toward the carbonyl groups shortens the C1—C3 and lengthens the C═O carbonyl bonds. In comparison with the normal value of 1.21 Å, the keto carbonyl bond is longer [1.239 (3) Å] than the ester carbonyl bond [1.212 (4) Å] as was reported by Castañeda et al. (2001, 2005) for keto-esters, diesters and diketo ylides. However, delocalization of the P═C bond toward the cyano group is small. Comparison of C≡N bond lengths for (I) [1.145 (4) Å] and (II) [1.150 (3) Å] with a normal value of 1.140 Å (Smith & March, 2001) could indicate that the CN group is mainly acting by inductive instead of resonance effects. Coplanarity between the ylidic, carbonyl and cyano units is established by their torsion angles (Tables 1 and 3). Ylids (I) and (II) present nearly coplanar systems with the carbonyl O atoms oriented syn to the P atoms showing O1···P1 contact distances of 3.022 (2) and 2.928 (2) Å, respectively. These attractive intramolecular interactions between the acyl O atoms and the cationoid P atoms lead to syn-preferred conformations where the alkoxy or alkyl groups adopt an anti conformation to avoid repulsive steric interactions with the phenyl groups. There is no evidence of a CH interaction involving alkoxy and phenyl groups (Castañeda, Terraza et al., 2003). The structures (I) and (II) have as a second intramolecular interaction C—H···O hydrogen bonds between phenyl donors and carbonyl acceptors (Tables 2 and 4). These types of non-classical interactions, despite being weak, could make a significant contribution to stabilizing conformations in the solid state. Several intermolecular interactions with phenyl groups acting as donors and acceptors are shown in Figs. 1 and 2. These interactions could affect favorably the observed molecular geometry and the packing conformations. The IR carbonyl stretching frequencies in KBr for (I) (1650 cm-1) and (II) (1584 cm-1) correlate with the crystallographic results, giving account of an extensive electronic delocalization for the carbonyl groups.

Experimental top

(Cyanomethylene)triphenylphosphorane was prepared by the literature method (Trippet & Walker, 1959). Ylids (I) and (II) have been reported previously (Horner & Oediger, 1958; Kobayashi et al., 2000). In this work, both (I) and (2) were synthesized by reaction of (cyanomethylene)triphenylphosphorane with methylchloroformate or acetyl chloride under transylidation conditions. A general synthetic procedure was as follows: A solution of alkyl chloroformate (9.1 mmol) or acetyl chloride (9.1 mmol) in dry benzene (5 ml) was added slowly to (cyanomethylene)triphenylphosphorane (18.2 mmol) dissolved in dry benzene (50 ml) under an inert atmosphere. The stirred solution was maintained at room temperature for 6 h to allow a white solid to separate. After filtration of (cyanomethyl)triphenylphosphonium chloride, the solvent was evaporated under reduced pressure to give the products which were crystallized from ethanol. For (I): yield 75%, m.p. 485–486 K; 1H NMR (CDCl3): δ 3.64 (s, 3H), 7.5–7.8 (m, 15 H); IR (KBr): 2179 (–CN), 1650 (CO) cm-1. For (2): yield 65%, m.p. 478 K; 1H NMR (CDCl3): δ 2.38 (s, 3 H), 7.5–7.7 (m, 15 H); IR (KBr): 2172 (–CN), 1584 (CO) cm-1.

Refinement top

H atoms were placed at idealized positions [C—H = 0.93 (CHarom) and 0.96 Å (CH3)] and allowed to ride on the corresponding host with Uiso(H) values of xUeq(C) [x = 1.2 (CHarom) and 1.5 (CH3)].

Structure description top

Electronic delocalization involving acyl keto and ester groups stabilizes phosphonium ylids, and is maximized by their taking up planar conformations with favorable interactions between anionoid O atoms and cationoid phosphorus (Castañeda et al., 2001; Castañeda, Recabarren et al., 2003; Castañeda, Terraza et al., 2003). However, in crystalline diethyl ester derivatives, interference involving the trigonal ester groups leads to a conformation where the acyl O atoms are anti to phosphorus, and the acyl groups are twisted out of the ylidic plane (Castañeda et al., 2005, 2006). The linear cyano group is strongly electron withdrawing and should facilitate electronic delocalization in a planar ylidic unit (Scheme 1).

We therefore expected that the cyano group would favor cyano-keto or -ester compounds taking up conformations that allow extensive electronic delocalization and interactions between phosphorus and an acyl O atom. The conformations should be similar in the solid and in solution, and here we discuss the geometries of the following ylids in the crystal structure. Complete evidence on geometries in solution will be given elsewhere. Crystalline (methoxycarbonylcyanomethylene)triphenylphosphorane, (I), and (acetylcyanomethylene)triphenylphosphorane, (II), have the molecular structures and selected geometric parameters shown in Figs. 1 and 2 and Tables 1 and 2, respectively. In both ylids, the configurations about the P atom are approximately tetrahedral, with phenyl groups forming a propeller-like arrangement. For (I) and (II), the bond angles C31(phenyl)—P1—C11(phenyl), C21(phenyl)—P1—C11 (phenyl) and C31(phenyl)—P1—C21(phenyl) are 107.42 (12), 107.44 (12) and 106.35 (12)°, and 108.17 (9), 105.79 (10) and 106.81 (9)°, respectively. The sums of the angles about the ylidic C1 atom for (I) and (II) are 359.9 and 360° respectively, consistent with sp2-hybridization in an almost trigonal–planar geometry. It is well known that stabilized ylids have a longer P═C bond as a result of the electronic delocalization caused by the stabilizing groups (Bachrach & Nitsche, 1994; Howells et al. 1973). In cyano-ester ylid (1) and cyano-keto ylid (2), the P1—C1 bond lengths are 1.730 (3) and 1.744 (2) Å, respectively. These values are between those reported for a P—C single bond (1.80–1.83 Å; Howells et al., 1973) and P═C double bond (1.63–1.73 Å) (Howells et al., 1973) and they are considerably longer than the P═C bond in methylenetriphenylphosphorane, Ph3P=CH2 [1.661 (8) Å; Bart, 1969], where there is no opportunity for conjugation with other groups. Electronic delocalization toward the carbonyl groups shortens the C1—C3 and lengthens the C═O carbonyl bonds. In comparison with the normal value of 1.21 Å, the keto carbonyl bond is longer [1.239 (3) Å] than the ester carbonyl bond [1.212 (4) Å] as was reported by Castañeda et al. (2001, 2005) for keto-esters, diesters and diketo ylides. However, delocalization of the P═C bond toward the cyano group is small. Comparison of C≡N bond lengths for (I) [1.145 (4) Å] and (II) [1.150 (3) Å] with a normal value of 1.140 Å (Smith & March, 2001) could indicate that the CN group is mainly acting by inductive instead of resonance effects. Coplanarity between the ylidic, carbonyl and cyano units is established by their torsion angles (Tables 1 and 3). Ylids (I) and (II) present nearly coplanar systems with the carbonyl O atoms oriented syn to the P atoms showing O1···P1 contact distances of 3.022 (2) and 2.928 (2) Å, respectively. These attractive intramolecular interactions between the acyl O atoms and the cationoid P atoms lead to syn-preferred conformations where the alkoxy or alkyl groups adopt an anti conformation to avoid repulsive steric interactions with the phenyl groups. There is no evidence of a CH interaction involving alkoxy and phenyl groups (Castañeda, Terraza et al., 2003). The structures (I) and (II) have as a second intramolecular interaction C—H···O hydrogen bonds between phenyl donors and carbonyl acceptors (Tables 2 and 4). These types of non-classical interactions, despite being weak, could make a significant contribution to stabilizing conformations in the solid state. Several intermolecular interactions with phenyl groups acting as donors and acceptors are shown in Figs. 1 and 2. These interactions could affect favorably the observed molecular geometry and the packing conformations. The IR carbonyl stretching frequencies in KBr for (I) (1650 cm-1) and (II) (1584 cm-1) correlate with the crystallographic results, giving account of an extensive electronic delocalization for the carbonyl groups.

Computing details top

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2001); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2001); software used to prepare material for publication: SHELXTL-NT and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. : The molecular structure of (I), showing the numbering scheme used. The intramolecular hydrogen bond is shown as a double-dashed line; the intermolecular C—H—π contacts as simple dashed lines. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes are as in Table 2.
[Figure 2] Fig. 2. : The molecular structure of (II), showing the numbering scheme used. The intramolecular hydrogen bond is shown as a double dashed line; the intermolecular C—H—π contacts as simple dashed lines. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes are as in Table 4.
(I) methyl 2-cyano-2-(trimethylphosphonio)ethenoate top
Crystal data top
C22H18NO2PF(000) = 752
Mr = 359.34Dx = 1.284 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6588 reflections
a = 9.9601 (14) Åθ = 2.2–25.1°
b = 9.0436 (13) ŵ = 0.16 mm−1
c = 20.708 (3) ÅT = 297 K
β = 94.659 (3)°Plate, colorless
V = 1859.1 (5) Å30.30 × 0.24 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2645 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.052
Graphite monochromatorθmax = 26.0°, θmin = 2.0°
φ and ω scansh = −12→12
14118 measured reflectionsk = −11→11
3659 independent reflectionsl = −25→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0653P)2 + 0.3502P]
where P = (Fo2 + 2Fc2)/3
3659 reflections(Δ/σ)max = 0.005
236 parametersΔρmax = 0.36 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C22H18NO2PV = 1859.1 (5) Å3
Mr = 359.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.9601 (14) ŵ = 0.16 mm−1
b = 9.0436 (13) ÅT = 297 K
c = 20.708 (3) Å0.30 × 0.24 × 0.10 mm
β = 94.659 (3)°
Data collection top
Bruker SMART CCD
diffractometer		2645 reflections with I > 2σ(I)
14118 measured reflectionsRint = 0.052
3659 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.07Δρmax = 0.36 e Å−3
3659 reflectionsΔρmin = −0.23 e Å−3
236 parameters
Special details top

Experimental. Melting points reported were uncorrected. 1HNMR spectra were obtained on Bruker DRX 300 or Varian Inova 500 spectrometers and referenced to TMS. IR spectra were recorded on a Bruker IFS56 FT spectrometer using a KBr disk.

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 (Å2) top
xyzUiso*/Ueq
P10.25113 (7)0.60562 (8)0.08637 (3)0.0373 (2)
O2−0.0287 (2)0.6458 (3)0.20689 (10)0.0714 (7)
C210.2269 (2)0.6440 (3)0.00079 (13)0.0368 (6)
C110.2800 (3)0.4106 (3)0.09544 (12)0.0386 (6)
C20.0170 (3)0.7590 (3)0.09282 (15)0.0476 (7)
C220.2062 (3)0.7879 (3)−0.02160 (14)0.0452 (7)
H220.20100.86500.00780.054*
C260.2355 (3)0.5320 (3)−0.04385 (13)0.0445 (7)
H260.25000.4354−0.02960.053*
C360.4987 (3)0.7421 (3)0.07415 (15)0.0502 (8)
H360.48310.72370.03000.060*
C310.4046 (3)0.6988 (3)0.11556 (13)0.0408 (7)
C160.1715 (3)0.3150 (3)0.08499 (14)0.0488 (7)
H160.08510.35240.07600.059*
C10.1097 (3)0.6592 (3)0.12367 (13)0.0430 (7)
O10.1706 (2)0.5283 (3)0.21984 (11)0.0771 (8)
C230.1933 (3)0.8167 (3)−0.08685 (15)0.0507 (8)
H230.17850.9129−0.10160.061*
C30.0915 (3)0.6044 (4)0.18696 (15)0.0559 (8)
C240.2024 (3)0.7035 (4)−0.13040 (15)0.0556 (8)
H240.19430.7233−0.17460.067*
C130.4266 (3)0.2031 (4)0.11173 (17)0.0627 (9)
H130.51260.16470.12100.075*
C250.2231 (3)0.5617 (4)−0.10896 (14)0.0540 (8)
H250.22880.4852−0.13860.065*
C120.4080 (3)0.3540 (3)0.10840 (15)0.0505 (8)
H120.48140.41730.11490.061*
C140.3194 (4)0.1097 (3)0.10153 (16)0.0607 (9)
H140.33290.00800.10390.073*
N1−0.0581 (3)0.8414 (3)0.06833 (15)0.0730 (9)
C350.6158 (3)0.8121 (3)0.09726 (17)0.0586 (9)
H350.67830.84130.06870.070*
C150.1921 (3)0.1643 (3)0.08787 (15)0.0555 (8)
H150.11970.09990.08060.067*
C340.6397 (4)0.8383 (4)0.16125 (19)0.0687 (10)
H340.71820.88670.17680.082*
C320.4302 (4)0.7254 (4)0.18100 (16)0.0691 (10)
H320.36820.69750.20990.083*
C330.5495 (4)0.7944 (5)0.20315 (18)0.0836 (12)
H330.56800.81080.24730.100*
C4−0.0640 (4)0.5878 (6)0.26756 (17)0.1051 (16)
H4A−0.01100.50130.27840.158*
H4B−0.15780.56200.26420.158*
H4C−0.04700.66100.30080.158*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0349 (4)0.0360 (4)0.0409 (4)0.0011 (3)0.0032 (3)−0.0017 (3)
O20.0517 (13)0.112 (2)0.0530 (14)−0.0027 (13)0.0190 (11)−0.0147 (13)
C210.0313 (14)0.0361 (15)0.0431 (15)0.0000 (11)0.0023 (11)−0.0017 (12)
C110.0422 (16)0.0348 (15)0.0392 (15)−0.0012 (12)0.0055 (12)0.0022 (12)
C20.0410 (17)0.0429 (17)0.0602 (19)−0.0037 (14)0.0130 (14)−0.0079 (15)
C220.0433 (16)0.0399 (17)0.0526 (18)−0.0016 (13)0.0055 (13)−0.0031 (14)
C260.0472 (17)0.0387 (16)0.0474 (17)0.0023 (13)0.0029 (13)−0.0019 (13)
C360.0430 (17)0.0518 (18)0.0558 (19)−0.0019 (14)0.0052 (14)−0.0082 (15)
C310.0414 (16)0.0329 (15)0.0470 (17)0.0006 (12)−0.0018 (13)−0.0010 (13)
C160.0446 (17)0.0427 (17)0.0596 (19)−0.0011 (14)0.0065 (14)0.0051 (14)
C10.0391 (15)0.0462 (17)0.0438 (16)0.0040 (13)0.0050 (12)−0.0031 (14)
O10.0668 (16)0.110 (2)0.0547 (14)0.0114 (14)0.0067 (12)0.0218 (14)
C230.0477 (18)0.0486 (19)0.055 (2)0.0011 (14)0.0005 (14)0.0091 (16)
C30.0495 (19)0.071 (2)0.0469 (19)−0.0035 (17)0.0049 (15)−0.0121 (17)
C240.0550 (19)0.070 (2)0.0409 (17)−0.0006 (17)−0.0004 (14)0.0071 (17)
C130.055 (2)0.050 (2)0.084 (2)0.0160 (16)0.0030 (17)0.0005 (17)
C250.059 (2)0.057 (2)0.0460 (18)0.0048 (16)0.0005 (14)−0.0072 (15)
C120.0436 (17)0.0453 (18)0.063 (2)0.0011 (14)0.0044 (14)0.0017 (15)
C140.077 (2)0.0367 (17)0.068 (2)0.0087 (18)0.0085 (18)−0.0002 (16)
N10.0537 (18)0.071 (2)0.096 (2)0.0233 (16)0.0162 (16)0.0108 (17)
C350.0447 (18)0.054 (2)0.077 (2)−0.0077 (15)0.0096 (16)−0.0074 (18)
C150.066 (2)0.0397 (18)0.061 (2)−0.0111 (16)0.0116 (16)−0.0029 (15)
C340.057 (2)0.064 (2)0.081 (3)−0.0206 (18)−0.0142 (19)0.000 (2)
C320.069 (2)0.086 (3)0.051 (2)−0.025 (2)−0.0010 (17)−0.0006 (18)
C330.088 (3)0.107 (3)0.052 (2)−0.029 (2)−0.019 (2)−0.002 (2)
C40.078 (3)0.193 (5)0.047 (2)−0.040 (3)0.0204 (19)−0.017 (3)
Geometric parameters (Å, º) top
P1—C11.730 (3)O1—C31.212 (4)
P1—C111.794 (3)C23—C241.372 (4)
P1—C211.803 (3)C23—H230.9300
P1—C311.806 (3)C24—C251.367 (4)
O2—C31.350 (4)C24—H240.9300
O2—C41.432 (4)C13—C141.364 (4)
C21—C261.378 (4)C13—C121.378 (4)
C21—C221.391 (4)C13—H130.9300
C11—C121.380 (4)C25—H250.9300
C11—C161.387 (4)C12—H120.9300
C2—N11.145 (4)C14—C151.368 (4)
C2—C11.407 (4)C14—H140.9300
C22—C231.372 (4)C35—C341.348 (4)
C22—H220.9300C35—H350.9300
C26—C251.371 (4)C15—H150.9300
C26—H260.9300C34—C331.358 (5)
C36—C311.378 (4)C34—H340.9300
C36—C351.378 (4)C32—C331.387 (5)
C36—H360.9300C32—H320.9300
C31—C321.380 (4)C33—H330.9300
C16—C151.379 (4)C4—H4A0.9600
C16—H160.9300C4—H4B0.9600
C1—C31.427 (4)C4—H4C0.9600
C1—P1—C11110.97 (13)O2—C3—C1111.5 (3)
C1—P1—C21109.64 (13)C25—C24—C23120.2 (3)
C11—P1—C21107.44 (12)C25—C24—H24119.9
C1—P1—C31114.68 (13)C23—C24—H24119.9
C11—P1—C31107.42 (12)C14—C13—C12120.3 (3)
C21—P1—C31106.35 (12)C14—C13—H13119.8
C3—O2—C4117.0 (3)C12—C13—H13119.8
C26—C21—C22118.6 (3)C24—C25—C26120.2 (3)
C26—C21—P1120.5 (2)C24—C25—H25119.9
C22—C21—P1120.8 (2)C26—C25—H25119.9
C12—C11—C16119.6 (3)C13—C12—C11119.7 (3)
C12—C11—P1121.5 (2)C13—C12—H12120.2
C16—C11—P1118.7 (2)C11—C12—H12120.2
N1—C2—C1179.2 (3)C13—C14—C15120.6 (3)
C23—C22—C21120.3 (3)C13—C14—H14119.7
C23—C22—H22119.8C15—C14—H14119.7
C21—C22—H22119.8C34—C35—C36119.9 (3)
C25—C26—C21120.7 (3)C34—C35—H35120.0
C25—C26—H26119.7C36—C35—H35120.0
C21—C26—H26119.7C14—C15—C16119.9 (3)
C31—C36—C35120.9 (3)C14—C15—H15120.1
C31—C36—H36119.5C16—C15—H15120.1
C35—C36—H36119.5C35—C34—C33120.2 (3)
C36—C31—C32118.7 (3)C35—C34—H34119.9
C36—C31—P1121.6 (2)C33—C34—H34119.9
C32—C31—P1119.6 (2)C31—C32—C33119.2 (3)
C15—C16—C11119.9 (3)C31—C32—H32120.4
C15—C16—H16120.1C33—C32—H32120.4
C11—C16—H16120.1C34—C33—C32120.9 (3)
C2—C1—C3120.8 (3)C34—C33—H33119.5
C2—C1—P1120.3 (2)C32—C33—H33119.5
C3—C1—P1118.8 (2)O2—C4—H4A109.5
C24—C23—C22120.0 (3)O2—C4—H4B109.5
C24—C23—H23120.0H4A—C4—H4B109.5
C22—C23—H23120.0O2—C4—H4C109.5
O1—C3—O2122.5 (3)H4A—C4—H4C109.5
O1—C3—C1126.0 (3)H4B—C4—H4C109.5
C1—P1—C21—C26−122.2 (2)C21—P1—C1—C2−18.6 (3)
C11—P1—C21—C26−1.5 (3)C31—P1—C1—C2100.9 (2)
C31—P1—C21—C26113.3 (2)C11—P1—C1—C345.0 (3)
C1—P1—C21—C2261.2 (2)C21—P1—C1—C3163.5 (2)
C11—P1—C21—C22−178.1 (2)C31—P1—C1—C3−77.0 (3)
C31—P1—C21—C22−63.3 (2)C21—C22—C23—C24−0.7 (4)
C1—P1—C11—C12−139.2 (2)C4—O2—C3—O1−4.1 (5)
C21—P1—C11—C12100.9 (2)C4—O2—C3—C1175.0 (3)
C31—P1—C11—C12−13.2 (3)C2—C1—C3—O1−173.5 (3)
C1—P1—C11—C1644.9 (3)P1—C1—C3—O14.4 (5)
C21—P1—C11—C16−74.9 (2)C2—C1—C3—O27.5 (4)
C31—P1—C11—C16171.0 (2)P1—C1—C3—O2−174.6 (2)
C26—C21—C22—C230.7 (4)C22—C23—C24—C250.5 (4)
P1—C21—C22—C23177.3 (2)C23—C24—C25—C26−0.3 (5)
C22—C21—C26—C25−0.4 (4)C21—C26—C25—C240.2 (4)
P1—C21—C26—C25−177.1 (2)C14—C13—C12—C110.8 (5)
C35—C36—C31—C32−0.7 (5)C16—C11—C12—C13−0.9 (4)
C35—C36—C31—P1−179.5 (2)P1—C11—C12—C13−176.7 (2)
C1—P1—C31—C36−140.8 (2)C12—C13—C14—C150.0 (5)
C11—P1—C31—C3695.4 (2)C31—C36—C35—C340.4 (5)
C21—P1—C31—C36−19.4 (3)C13—C14—C15—C16−0.6 (5)
C1—P1—C31—C3240.4 (3)C11—C16—C15—C140.5 (5)
C11—P1—C31—C32−83.5 (3)C36—C35—C34—C330.8 (5)
C21—P1—C31—C32161.7 (3)C36—C31—C32—C33−0.1 (5)
C12—C11—C16—C150.3 (4)P1—C31—C32—C33178.7 (3)
P1—C11—C16—C15176.2 (2)C35—C34—C33—C32−1.6 (6)
C11—P1—C1—C2−137.2 (2)C31—C32—C33—C341.3 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H32···O10.932.513.294 (4)142
C14—H14···Cg3i0.932.933.738 (3)146
C16—H16···Cg2ii0.932.990.835 (3)153
P1···O1??3.022 (2)?
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z+1/2.
(II) 1-cyano-1-(trimethylphosphonio)prop-1-en-2-olate top
Crystal data top
C22H18NOPF(000) = 720
Mr = 343.34Dx = 1.256 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5886 reflections
a = 10.1144 (11) Åθ = 2.8–24.9°
b = 8.9938 (10) ŵ = 0.16 mm−1
c = 19.968 (2) ÅT = 298 K
β = 91.744 (2)°Plate, colorless
V = 1815.6 (3) Å30.42 × 0.32 × 0.14 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2789 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Graphite monochromatorθmax = 26.0°, θmin = 2.0°
φ and ω scansh = −12→12
13496 measured reflectionsk = −11→11
3569 independent reflectionsl = −24→24
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0819P)2 + 0.1374P]
where P = (Fo2 + 2Fc2)/3
3569 reflections(Δ/σ)max = 0.009
227 parametersΔρmax = 0.45 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C22H18NOPV = 1815.6 (3) Å3
Mr = 343.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.1144 (11) ŵ = 0.16 mm−1
b = 8.9938 (10) ÅT = 298 K
c = 19.968 (2) Å0.42 × 0.32 × 0.14 mm
β = 91.744 (2)°
Data collection top
Bruker SMART CCD
diffractometer		2789 reflections with I > 2σ(I)
13496 measured reflectionsRint = 0.038
3569 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.03Δρmax = 0.45 e Å−3
3569 reflectionsΔρmin = −0.27 e Å−3
227 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
P10.74409 (5)0.89202 (6)0.09042 (3)0.03548 (19)
O10.67740 (17)0.9515 (2)0.22952 (8)0.0629 (5)
N10.4306 (2)0.6685 (3)0.07260 (13)0.0729 (7)
C10.6043 (2)0.8329 (3)0.13196 (11)0.0432 (5)
C20.5086 (2)0.7436 (3)0.09859 (13)0.0501 (6)
C30.5906 (2)0.8781 (3)0.19949 (12)0.0515 (6)
C40.4662 (3)0.8361 (4)0.23534 (14)0.0781 (9)
H4A0.46140.89240.27600.117*
H4B0.46820.73190.24570.117*
H4C0.39020.85740.20700.117*
C110.8953 (2)0.7985 (2)0.11691 (11)0.0394 (5)
C120.9842 (2)0.7496 (3)0.07029 (12)0.0490 (6)
H120.96690.76630.02490.059*
C131.0985 (2)0.6760 (3)0.09074 (14)0.0555 (6)
H131.15740.64340.05900.067*
C141.1253 (3)0.6510 (3)0.15691 (15)0.0615 (7)
H141.20150.60020.17050.074*
C151.0399 (3)0.7010 (4)0.20281 (15)0.0780 (9)
H151.05870.68510.24810.094*
C160.9254 (3)0.7750 (3)0.18354 (13)0.0661 (8)
H160.86850.80910.21590.079*
C210.72447 (19)0.8569 (2)0.00183 (11)0.0373 (5)
C220.7441 (2)0.9706 (3)−0.04357 (11)0.0453 (5)
H220.75921.0669−0.02820.054*
C230.7412 (2)0.9417 (3)−0.11121 (12)0.0574 (6)
H230.75641.0181−0.14140.069*
C240.7160 (2)0.8003 (3)−0.13441 (13)0.0589 (7)
H240.71430.7810−0.18020.071*
C250.6934 (2)0.6877 (3)−0.08995 (13)0.0554 (6)
H250.67430.5927−0.10590.066*
C260.6985 (2)0.7137 (3)−0.02227 (12)0.0471 (6)
H260.68470.63620.00750.057*
C310.7690 (2)1.0888 (2)0.10008 (10)0.0371 (5)
C320.6610 (2)1.1824 (3)0.09472 (12)0.0497 (6)
H320.57631.14340.08860.060*
C330.6796 (3)1.3339 (3)0.09850 (13)0.0587 (7)
H330.60731.39750.09450.070*
C340.8037 (3)1.3909 (3)0.10816 (14)0.0635 (7)
H340.81521.49320.11160.076*
C350.9117 (3)1.2988 (3)0.11285 (14)0.0631 (7)
H350.99601.33890.11890.076*
C360.8954 (2)1.1470 (3)0.10861 (12)0.0472 (6)
H360.96831.08420.11140.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0350 (3)0.0332 (3)0.0382 (3)−0.0015 (2)0.0009 (2)0.0022 (2)
O10.0608 (11)0.0810 (13)0.0468 (10)−0.0052 (10)0.0014 (8)−0.0015 (9)
N10.0532 (13)0.0770 (16)0.0888 (18)−0.0214 (12)0.0075 (12)−0.0084 (14)
C10.0362 (11)0.0466 (13)0.0467 (13)−0.0027 (10)0.0028 (9)0.0060 (10)
C20.0394 (12)0.0467 (14)0.0644 (16)−0.0011 (11)0.0062 (11)0.0073 (11)
C30.0429 (13)0.0628 (16)0.0492 (14)0.0045 (11)0.0053 (11)0.0145 (11)
C40.0555 (16)0.122 (3)0.0570 (17)−0.0013 (17)0.0128 (13)0.0247 (17)
C110.0395 (11)0.0345 (11)0.0442 (12)−0.0027 (9)−0.0011 (9)0.0018 (9)
C120.0415 (12)0.0540 (15)0.0515 (14)0.0028 (10)0.0012 (10)0.0070 (11)
C130.0392 (12)0.0552 (15)0.0721 (18)0.0062 (11)0.0046 (11)0.0027 (13)
C140.0519 (14)0.0544 (15)0.077 (2)0.0095 (12)−0.0127 (14)−0.0023 (14)
C150.083 (2)0.099 (2)0.0507 (16)0.0320 (18)−0.0182 (15)0.0030 (16)
C160.0700 (17)0.0825 (19)0.0459 (15)0.0275 (14)0.0003 (13)−0.0030 (13)
C210.0326 (10)0.0353 (11)0.0439 (12)0.0009 (8)0.0005 (9)0.0006 (9)
C220.0486 (13)0.0457 (13)0.0414 (13)−0.0037 (10)−0.0036 (10)0.0004 (10)
C230.0620 (16)0.0684 (17)0.0413 (14)−0.0029 (13)−0.0041 (11)0.0059 (12)
C240.0504 (14)0.0835 (19)0.0427 (14)0.0016 (13)−0.0025 (11)−0.0141 (13)
C250.0463 (13)0.0543 (15)0.0654 (17)0.0005 (11)−0.0024 (11)−0.0205 (13)
C260.0426 (12)0.0405 (12)0.0581 (15)0.0007 (10)−0.0009 (10)−0.0032 (10)
C310.0434 (11)0.0329 (11)0.0351 (11)−0.0007 (9)0.0043 (9)−0.0010 (8)
C320.0454 (13)0.0447 (13)0.0592 (15)0.0014 (10)0.0055 (11)0.0017 (11)
C330.0671 (16)0.0408 (13)0.0685 (17)0.0120 (12)0.0086 (13)0.0025 (12)
C340.088 (2)0.0345 (13)0.0676 (18)−0.0064 (13)0.0011 (15)0.0014 (11)
C350.0665 (17)0.0491 (15)0.0734 (19)−0.0196 (13)−0.0041 (14)0.0019 (13)
C360.0442 (12)0.0439 (13)0.0535 (14)−0.0072 (10)−0.0008 (10)−0.0007 (10)
Geometric parameters (Å, º) top
P1—C11.744 (2)C21—C221.385 (3)
P1—C311.797 (2)C21—C261.397 (3)
P1—C211.802 (2)C22—C231.375 (3)
P1—C111.810 (2)C22—H220.9300
O1—C31.239 (3)C23—C241.375 (4)
N1—C21.150 (3)C23—H230.9300
C1—C21.410 (3)C24—C251.370 (4)
C1—C31.419 (3)C24—H240.9300
C3—C41.514 (3)C25—C261.371 (3)
C4—H4A0.9600C25—H250.9300
C4—H4B0.9600C26—H260.9300
C4—H4C0.9600C31—C321.380 (3)
C11—C161.372 (3)C31—C361.387 (3)
C11—C121.386 (3)C32—C331.377 (3)
C12—C131.382 (3)C32—H320.9300
C12—H120.9300C33—C341.364 (4)
C13—C141.360 (4)C33—H330.9300
C13—H130.9300C34—C351.372 (4)
C14—C151.355 (4)C34—H340.9300
C14—H140.9300C35—C361.377 (3)
C15—C161.380 (4)C35—H350.9300
C15—H150.9300C36—H360.9300
C16—H160.9300
C1—P1—C31111.24 (10)C22—C21—C26119.0 (2)
C1—P1—C21110.29 (10)C22—C21—P1119.95 (16)
C31—P1—C21106.81 (9)C26—C21—P1120.93 (17)
C1—P1—C11114.15 (10)C23—C22—C21120.3 (2)
C31—P1—C11108.17 (9)C23—C22—H22119.9
C21—P1—C11105.79 (10)C21—C22—H22119.9
C2—C1—C3121.8 (2)C24—C23—C22120.3 (2)
C2—C1—P1120.27 (17)C24—C23—H23119.9
C3—C1—P1117.95 (17)C22—C23—H23119.9
N1—C2—C1178.4 (3)C23—C24—C25119.9 (2)
O1—C3—C1121.6 (2)C23—C24—H24120.1
O1—C3—C4119.4 (2)C25—C24—H24120.1
C1—C3—C4119.0 (2)C26—C25—C24120.7 (2)
C3—C4—H4A109.5C26—C25—H25119.7
C3—C4—H4B109.5C24—C25—H25119.7
H4A—C4—H4B109.5C25—C26—C21119.9 (2)
C3—C4—H4C109.5C25—C26—H26120.1
H4A—C4—H4C109.5C21—C26—H26120.1
H4B—C4—H4C109.5C32—C31—C36120.2 (2)
C16—C11—C12118.2 (2)C32—C31—P1118.96 (16)
C16—C11—P1121.04 (18)C36—C31—P1120.70 (16)
C12—C11—P1120.72 (16)C33—C32—C31119.5 (2)
C13—C12—C11120.5 (2)C33—C32—H32120.2
C13—C12—H12119.8C31—C32—H32120.2
C11—C12—H12119.8C34—C33—C32120.2 (2)
C14—C13—C12120.4 (2)C34—C33—H33119.9
C14—C13—H13119.8C32—C33—H33119.9
C12—C13—H13119.8C33—C34—C35120.7 (2)
C15—C14—C13119.3 (2)C33—C34—H34119.7
C15—C14—H14120.3C35—C34—H34119.7
C13—C14—H14120.3C36—C35—C34120.0 (2)
C14—C15—C16121.2 (3)C36—C35—H35120.0
C14—C15—H15119.4C34—C35—H35120.0
C16—C15—H15119.4C35—C36—C31119.3 (2)
C11—C16—C15120.3 (2)C35—C36—H36120.3
C11—C16—H16119.9C31—C36—H36120.3
C15—C16—H16119.9
C31—P1—C1—C2130.35 (18)C11—P1—C21—C22−108.32 (18)
C21—P1—C1—C212.0 (2)C1—P1—C21—C26−56.7 (2)
C11—P1—C1—C2−106.89 (19)C31—P1—C21—C26−177.67 (16)
C31—P1—C1—C3−49.3 (2)C11—P1—C21—C2667.24 (19)
C21—P1—C1—C3−167.64 (17)C26—C21—C22—C23−1.6 (3)
C11—P1—C1—C373.4 (2)P1—C21—C22—C23174.04 (17)
C2—C1—C3—O1177.0 (2)C21—C22—C23—C241.4 (4)
P1—C1—C3—O1−3.3 (3)C22—C23—C24—C250.1 (4)
C2—C1—C3—C4−3.3 (4)C23—C24—C25—C26−1.5 (4)
P1—C1—C3—C4176.34 (19)C24—C25—C26—C211.3 (3)
C1—P1—C11—C16−44.3 (2)C22—C21—C26—C250.3 (3)
C31—P1—C11—C1680.1 (2)P1—C21—C26—C25−175.33 (17)
C21—P1—C11—C16−165.7 (2)C1—P1—C31—C32−42.3 (2)
C1—P1—C11—C12136.17 (18)C21—P1—C31—C3278.12 (19)
C31—P1—C11—C12−99.42 (19)C11—P1—C31—C32−168.40 (18)
C21—P1—C11—C1214.7 (2)C1—P1—C31—C36141.73 (18)
C16—C11—C12—C131.5 (3)C21—P1—C31—C36−97.88 (19)
P1—C11—C12—C13−178.92 (17)C11—P1—C31—C3615.6 (2)
C11—C12—C13—C14−0.2 (4)C36—C31—C32—C33−0.6 (3)
C12—C13—C14—C15−1.0 (4)P1—C31—C32—C33−176.60 (18)
C13—C14—C15—C160.9 (5)C31—C32—C33—C34−0.6 (4)
C12—C11—C16—C15−1.7 (4)C32—C33—C34—C351.3 (4)
P1—C11—C16—C15178.8 (2)C33—C34—C35—C36−0.8 (4)
C14—C15—C16—C110.5 (5)C34—C35—C36—C31−0.5 (4)
C1—P1—C21—C22127.77 (18)C32—C31—C36—C351.1 (3)
C31—P1—C21—C226.8 (2)P1—C31—C36—C35177.08 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···O10.932.343.130 (3)142
C34—H34···Cg1i0.932.913.703 (3)144
P1···O1??2.928 (2)?
Symmetry code: (i) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC22H18NO2PC22H18NOP
Mr359.34343.34
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)297298
a, b, c (Å)9.9601 (14), 9.0436 (13), 20.708 (3)10.1144 (11), 8.9938 (10), 19.968 (2)
β (°) 94.659 (3) 91.744 (2)
V (Å3)1859.1 (5)1815.6 (3)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)0.160.16
Crystal size (mm)0.30 × 0.24 × 0.100.42 × 0.32 × 0.14
Data collection
DiffractometerBruker SMART CCDBruker SMART CCD
Absorption correction––
No. of measured, independent and
observed [I > 2σ(I)] reflections		14118, 3659, 2645 13496, 3569, 2789
Rint0.0520.038
(sin θ/λ)max (Å−1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.150, 1.07 0.054, 0.143, 1.03
No. of reflections36593569
No. of parameters236227
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.36, −0.230.45, −0.27

Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 2001), SAINT-NT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Bruker, 2001), SHELXTL-NT and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (I) top
P1—C11.730 (3)C2—C11.407 (4)
O2—C31.350 (4)C1—C31.427 (4)
O2—C41.432 (4)O1—C31.212 (4)
C2—N11.145 (4)
C3—O2—C4117.0 (3)C3—C1—P1118.8 (2)
N1—C2—C1179.2 (3)O1—C3—O2122.5 (3)
C2—C1—C3120.8 (3)O1—C3—C1126.0 (3)
C2—C1—P1120.3 (2)O2—C3—C1111.5 (3)
C4—O2—C3—O1−4.1 (5)P1—C1—C3—O14.4 (5)
C4—O2—C3—C1175.0 (3)C2—C1—C3—O27.5 (4)
C2—C1—C3—O1−173.5 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C32—H32···O10.932.513.294 (4)142
C14—H14···Cg3i0.932.933.738 (3)146
C16—H16···Cg2ii0.932.99.835 (3)153
P1···O1??3.022 (2)?
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z+1/2.
Selected geometric parameters (Å, º) for (II) top
P1—C11.744 (2)C1—C21.410 (3)
O1—C31.239 (3)C1—C31.419 (3)
N1—C21.150 (3)C3—C41.514 (3)
C2—C1—C3121.8 (2)O1—C3—C1121.6 (2)
C2—C1—P1120.27 (17)O1—C3—C4119.4 (2)
C3—C1—P1117.95 (17)C1—C3—C4119.0 (2)
N1—C2—C1178.4 (3)
C2—C1—C3—O1177.0 (2)C2—C1—C3—C4−3.3 (4)
P1—C1—C3—O1−3.3 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C16—H16···O10.932.343.130 (3)142
C34—H34···Cg1i0.932.913.703 (3)144
P1···O1??2.928 (2)?
Symmetry code: (i) x, y+1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS