organic papers
o1456
Andreas Deckenet al. C14H9O2P DOI: 10.1107/S1600536804018616 Acta Cryst.(2004). E60, o1456±o1457 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
2-Phenylisophosphindoline-1,3-dione
Andreas Decken,* Erin D. Gill and Frank Bottomley
Department of Chemistry, University of New Brunswick, Fredericton, NB, PO Box 45222, Canada E3B 6E2
Correspondence e-mail: adecken@unb.ca
Key indicators Single-crystal X-ray study T= 173 K
Mean(C±C) = 0.003 AÊ Rfactor = 0.032 wRfactor = 0.091
Data-to-parameter ratio = 10.4
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C14H9O2P, displays a near-planar
iso-phosphindoline-1,3-dione skeleton with slightly displaced P and O atoms. Weak CÐH O hydrogen bonding in the crystal structure results in a three-dimensional network.
Comment
The title compound, (I), is a rare example of a crystal-lographically characterized dicarbonylphosphine. The only related compound whose crystal structure has been reported is bis(2,2-dimethylpropionyl)phenylphosphine, [tBuC(O)]
2P±Ph,
(II) (Beckeret al., 1985).
The isophosphindoline-1,3-dione skeleton in (I) is almost planar, in contrast to compound (II), where rotation around the PÐC bonds results in an almost orthogonal orientation of the two carbonyl groups with an OÐC CÐO angle of 73.49
[no standard uncertainty available (Becker et al., 1985)]. In compound (I), the P and O atoms deviate by ÿ0.388 (2), 0.209 (3) and 0.204 (2) AÊ from the C1/C3/C3A/C7A plane, most likely because of the steric demand of the phenyl group. In the absence of the phenyl group, as is the case in the isophosphindolyl-1,3-dione anion (Liotta et al., 1984), planarity of the same molecular fragment is observed. The geometry at the P atom is trigonal±pyramidal in compound (I), indicating a stereochemically active electron pair. This is in contrast to the nitrogen analogue of (I) (Magomedovaet al., 1981), where the N atom is in a trigonal±planar environment. In the crystal lattice, 2-phenylisophosphindoline-1,3-dione
Received 21 July 2004 Accepted 29 July 2004 Online 7 August 2004
Figure 1
employs both carbonyl O atoms for CÐH O hydrogen bonding (see Table 1), resulting in a three-dimensional network.
Experimental
The title compound was prepared according to a published procedure (Fenskeet al., 1976).
Crystal data
C14H9O2P
Mr= 240.18 Monoclinic,P21=n
a= 9.4273 (15) AÊ
b= 14.479 (2) AÊ
c= 9.4762 (15) AÊ
= 117.662 (2)
V= 1145.7 (3) AÊ3
Z= 4
Dx= 1.393 Mg mÿ3 MoKradiation Cell parameters from 3469
re¯ections
= 2.5±25.9
= 0.22 mmÿ1
T= 173 (2) K Plate, yellow
0.400.300.05 mm
Data collection
Bruker SMART 1000/P4 diffractometer
!and'scans
Absorption correction: none 5722 measured re¯ections 1970 independent re¯ections
1736 re¯ections withI> 2(I)
Rint= 0.021
max= 25.0
h=ÿ11!10
k=ÿ16!17
l=ÿ10!11
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.032
wR(F2) = 0.091
S= 1.07 1970 re¯ections 190 parameters
All H-atom parameters re®ned
w= 1/[2(F
o2) + (0.0543P)2 + 0.297P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.37 e AÊÿ3
min=ÿ0.16 e AÊÿ3
Table 1
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
C4ÐH4 O2i 0.96 (2) 2.59 (2) 3.517 (2) 163.5 (14)
C7ÐH7 O2ii 0.91 (2) 2.37 (2) 3.201 (2) 150.5 (17)
C10ÐH10 O1iii 0.90 (2) 2.53 (2) 3.368 (2) 155.5 (16)
Symmetry codes: (i) 1ÿx;ÿy;ÿz; (ii)3
2ÿx;12y;12ÿz; (iii)52ÿx;yÿ12;12ÿz.
H atoms were found in difference Fourier maps and re®ned with isotropic displacement parameters. The ®nal CÐH distances are in the range 0.91 (2)±0.96 (2) AÊ.
Data collection: SMART (Bruker, 1997±1999); cell re®nement:
SMART; data reduction: SAINT(Bruker, 1997±1999); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997a); molecular graphics:SHELXTL (Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.
This work was supported by the Natural Sciences and Engineering Research Council of Canada.
References
Becker, G., Becker, B., Birkhahn, M., Mundt, O. & Schmidt, R. E. (1985).Z. Anorg. Allg. Chem.529, 97±110.
Bruker (1997±1999).SMARTandSAINT.Versions 5.059. Bruker AXS Inc., Madison, Wisconsin, USA.
Fenske, D., Langer, E., Heymann, M. & Becher, H. J. (1976).Chem. Ber.109, 359±362.
Liotta, C. L., McLaughlin, M. L., VanDerveer, D. G. & O'Brian, B. A. (1984).
Tetrahedron Lett.25, 1665±1668.
Magomedova, N. S., Neigauz, M. G., Zavodnik, V. E. & Bel'skii, V. K. (1981).
Kristallogra®ya(Crystallogr. Rep.),26, 841±844.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
supporting information
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Acta Cryst. (2004). E60, o1456–o1457
supporting information
Acta Cryst. (2004). E60, o1456–o1457 [https://doi.org/10.1107/S1600536804018616]
2-Phenylisophosphindoline-1,3-dione
Andreas Decken, Erin D. Gill and Frank Bottomley
2H-2-Phenylisophosphindoline-1,3-dione
Crystal data
C14H9O2P Mr = 240.18
Monoclinic, P21/n Hall symbol: -P 2yn a = 9.4273 (15) Å b = 14.479 (2) Å c = 9.4762 (15) Å β = 117.662 (2)° V = 1145.7 (3) Å3 Z = 4
F(000) = 496 Dx = 1.393 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3469 reflections θ = 2.5–25.9°
µ = 0.22 mm−1 T = 173 K Plate, yellow
0.40 × 0.30 × 0.05 mm
Data collection
Bruker SMART1000/P4 diffractometer
Radiation source: fine-focus sealed tube, Bruker SMART1000/P4
Graphite monochromator ω and φ scans
5722 measured reflections
1970 independent reflections 1736 reflections with I > 2σ(I) Rint = 0.021
θmax = 25.0°, θmin = 2.5° h = −11→10
k = −16→17 l = −10→11
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.032 wR(F2) = 0.091 S = 1.07 1970 reflections 190 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined w = 1/[σ2(F
o2) + (0.0543P)2 + 0.297P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.37 e Å−3 Δρmin = −0.16 e Å−3
Special details
Experimental. Crystal decay was monitored by repeating the initial 50 frames at the end of the data collection and analyzing duplicate reflections.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
P 0.91945 (5) 0.15848 (3) 0.09908 (5) 0.03064 (16) C1 0.9097 (2) 0.25440 (10) 0.22354 (19) 0.0330 (4) O1 1.01436 (15) 0.30984 (8) 0.29308 (16) 0.0482 (3) C3 0.74442 (17) 0.10542 (10) 0.10761 (17) 0.0269 (3) O2 0.70197 (13) 0.02661 (7) 0.07410 (13) 0.0346 (3) C3A 0.66489 (18) 0.17416 (10) 0.16144 (17) 0.0272 (3) C4 0.5172 (2) 0.16283 (12) 0.1561 (2) 0.0357 (4) C5 0.4577 (2) 0.23381 (14) 0.2087 (2) 0.0450 (5) C6 0.5437 (2) 0.31423 (13) 0.2661 (2) 0.0444 (5) C7 0.6911 (2) 0.32518 (12) 0.2742 (2) 0.0386 (4) C7A 0.75202 (19) 0.25407 (10) 0.22099 (17) 0.0294 (4) C8 1.07845 (18) 0.08597 (11) 0.24142 (18) 0.0308 (4) C9 1.17345 (18) 0.03958 (11) 0.1895 (2) 0.0335 (4) C10 1.2884 (2) −0.02132 (12) 0.2878 (2) 0.0404 (4) C11 1.3100 (2) −0.03584 (13) 0.4392 (2) 0.0428 (4) C12 1.2184 (2) 0.01108 (14) 0.4935 (2) 0.0458 (5) C13 1.1030 (2) 0.07134 (13) 0.3954 (2) 0.0404 (4) H4 0.458 (2) 0.1072 (14) 0.114 (2) 0.048 (5)* H5 0.360 (3) 0.2253 (14) 0.206 (2) 0.055 (6)* H6 0.499 (2) 0.3591 (14) 0.300 (2) 0.050 (5)* H7 0.753 (2) 0.3770 (14) 0.311 (2) 0.051 (6)* H9 1.156 (2) 0.0487 (12) 0.085 (3) 0.040 (5)* H10 1.349 (2) −0.0514 (13) 0.252 (2) 0.042 (5)* H11 1.387 (2) −0.0788 (14) 0.507 (2) 0.047 (5)* H12 1.232 (3) 0.0016 (14) 0.598 (3) 0.060 (6)* H13 1.040 (2) 0.1021 (14) 0.432 (2) 0.048 (5)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
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Acta Cryst. (2004). E60, o1456–o1457
C7A 0.0365 (9) 0.0253 (7) 0.0242 (8) 0.0015 (6) 0.0124 (7) 0.0016 (6) C8 0.0270 (8) 0.0333 (8) 0.0316 (8) −0.0034 (6) 0.0131 (7) −0.0031 (6) C9 0.0280 (8) 0.0391 (9) 0.0333 (9) −0.0047 (7) 0.0142 (7) −0.0062 (7) C10 0.0301 (9) 0.0444 (10) 0.0449 (10) 0.0011 (7) 0.0160 (8) −0.0080 (8) C11 0.0308 (9) 0.0447 (10) 0.0421 (10) 0.0010 (8) 0.0077 (8) 0.0014 (8) C12 0.0421 (11) 0.0577 (11) 0.0331 (9) 0.0029 (9) 0.0138 (8) 0.0048 (8) C13 0.0378 (9) 0.0529 (11) 0.0329 (9) 0.0054 (8) 0.0184 (8) 0.0006 (8)
Geometric parameters (Å, º)
P—C8 1.8142 (16) C6—H6 0.91 (2) P—C1 1.8517 (16) C7—C7A 1.383 (2) P—C3 1.8556 (15) C7—H7 0.92 (2) C1—O1 1.2033 (19) C8—C9 1.380 (2) C1—C7A 1.476 (2) C8—C13 1.383 (2) C3—O2 1.2021 (18) C9—C10 1.372 (2) C3—C3A 1.473 (2) C9—H9 0.94 (2) C3A—C7A 1.379 (2) C10—C11 1.369 (3) C3A—C4 1.380 (2) C10—H10 0.90 (2) C4—C5 1.370 (2) C11—C12 1.373 (3) C4—H4 0.96 (2) C11—H11 0.95 (2) C5—C6 1.378 (3) C12—C13 1.368 (3) C5—H5 0.91 (2) C12—H12 0.94 (2) C6—C7 1.365 (3) C13—H13 0.928 (19)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C4—H4···O2i 0.96 (2) 2.59 (2) 3.517 (2) 163.5 (14) C7—H7···O2ii 0.91 (2) 2.37 (2) 3.201 (2) 150.5 (17) C10—H10···O1iii 0.90 (2) 2.53 (2) 3.368 (2) 155.5 (16)