organic papers
Acta Cryst.(2004). E60, o1935±o1936 doi: 10.1107/S1600536804024390 Andreas Deckenet al. C24H16O3P2
o1935
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
Dibenzophospholanic acid anhydride
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: [email protected]
Key indicators
Single-crystal X-ray study
T= 173 K
Mean(C±C) = 0.005 AÊ
Rfactor = 0.051
wRfactor = 0.142
Data-to-parameter ratio = 10.8
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 [alternatively called 9,90 -oxydi(9-phos-pha¯uoren-9-one) or bis(5-hydroxy-5-oxodibenzo-5H -phos-phole) anhydride], C24H16O3P2, is the only example of a
crystallographically characterized phospholanic acid anhy-dride. The molecule is highly twisted as evident by its O P P O angle [72.9 (1)].
Comment
To date, there are no reports of crystallographically authen-ticated phospholanic acid anhydrides. The title compound, (I), is highly twisted, forcing atoms O1 and O2 out of the P1Ð O3ÐP2 plane. The resulting O1ÐP1 P2ÐO2 twist angle measures 72.9 (1). However, this angle is low in comparison to those in related phosphinic acid anhydrides,viz.77.9 (no s.u. available) in [(Me2PhC)(Ph)P(O)]2O (Wareet al., 2002)
and 84.9 (no s.u. available) in [Me
2P(O)]2O (Weisbarth &
Jansen, 2002). The dibenzophosphole units are further tilted and are almost orthogonal to one another [89.03 (5)].
The molecule adopts an unusual orientation, analogous to that observed in bis(9H-¯uorenyl)methane (Nakano & Yade, 2003), where a skewed orientation of the ¯uorenyl groups is preferred due to the small end groups (hydrogen). Bulkier end groups result in ± stacking, facilitated by a cofacial align-ment of the ¯uorene rings, as reported for substituted deri-vatives (Rathoreet al., 2003; Nakano & Yade, 2003), as well as oligomeric compounds with 3±6 ¯uorenyl groups. Mixed cofacial/skewed orientations have also been reported (Nakano & Yade, 2003). We denote the cofacial con®guration as compound (II) (see Experimental), based on NMR assign-ments of the ¯uorenyl analogues (Rathoreet al., 2003).
Experimental
H2O2 (30%, 0.4 ml, 3.5 mmol) was added to a slurry of bis(1,10
-dibenzophospholyl) (0.200 g, 0.55 mmol) in ethanol (12 ml). The mixture was heated to re¯ux for 3.5 h and the solvent removed under reduced pressure to yield 0.226 g (0.55 mmol) of a mixture of (I) and (II) (ratio 1:2). Single crystals of (I) were obtained by recrystalliza-tion from ethanol.
Characterization of (I):1H NMR (CD
3OD, 399.945 MHz):7.96
(dd,J= 4.0, 8.0 Hz, 2H), 7.77 (tdd,J= 0.8, 7.2, 10.8 Hz, 2H), 7.69 (tdd, J= 1.2, 7.2, 7.2 Hz, 2H), 7.51 (dddd, J= 0.8, 4.0, 8.0, 8.0 Hz, 2H).
31P{1H} NMR (CD
3OD, 121.356 MHz):44.9. MS (m/e, %,
assign-ment): 414 (5) [M]+, 215 (100) [C
12H8PO2]+, 199 (75) [C12H8PO]+,
183 (4) [C12H8P]+, 168 (38) [C12H8O]+, 152 (32) [C12H8]+, 140 (18)
[C6H5PO2]+.
Characterization of (II):1H NMR (CD
3OD, 399.945 MHz):7.92
(dd,J= 4.0, 8.0 Hz, 2H), 7.72 (tdd,J= 0.8, 7.2, 10.8 Hz, 2H), 7.62 (tdd, J= 1.2, 7.2, 7.2 Hz, 2H), 7.46 (dddd, J= 0.8, 4.0, 8.0, 8.0 Hz, 2H).
31P{1H} NMR (CD
3OD, 121.356 MHz):40.4. MS: as for compound
(I).
Crystal data
C24H16O3P2
Mr= 414.31
Orthorhombic,Pbca a= 11.0105 (7) AÊ b= 13.6596 (10) AÊ c= 26.8832 (18) AÊ V= 4043.2 (5) AÊ3
Z= 8
Dx= 1.361 Mg mÿ3
MoKradiation Cell parameters from 6595
re¯ections = 2.4±25.1 = 0.24 mmÿ1
T= 173 (2) K Plate, colourless 0.450.250.05 mm
Data collection
Bruker AXS SMART1000/P4 diffractometer
!and'scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.832,Tmax= 0.990
19599 measured re¯ections
3530 independent re¯ections 2286 re¯ections withI> 2(I) Rint= 0.041
max= 25.0
h=ÿ13!13 k=ÿ16!15 l=ÿ28!30
Refinement
Re®nement onF2
R[F2> 2(F2)] = 0.051
wR(F2) = 0.142
S= 1.08 3530 re¯ections 326 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0738P)2
+ 1.2419P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.33 e AÊÿ3
min=ÿ0.27 e AÊÿ3
H atoms were placed in calculated positions and re®ned as riding atoms, with CÐH distances ®xed at 0.95 AÊ and with Uiso(H) =
1.2Ueq(C).
Data collection: SMART (Bruker, 1997±1999); cell re®nement: SAINT (Bruker, 1997±1999); data reduction: SAINT; 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
Bruker (1997±1999). SMART(Version 5.059) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.
Nakano, T. & Yade, T. (2003).J. Am. Chem. Soc.125, 1574±1584.
Rathore, R., Abdelwahed, S. H. & Guzei, I. A. (2003).J. Am. Chem. Soc.125, 8712±8713.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of
GoÈttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL.Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Ware, R. W. Jr, Day, C. S. & King, S. B. (2002).J. Org. Chem.67, 6174±6180. Weisbarth, R. & Jansen, M. (2002).Z. Kristallogr. New Cryst. Struct.217, 94.
Figure 1
supporting information
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Acta Cryst. (2004). E60, o1935–o1936
supporting information
Acta Cryst. (2004). E60, o1935–o1936 [https://doi.org/10.1107/S1600536804024390]
Dibenzophospholanic acid anhydride
Andreas Decken, Erin D. Gill and Frank Bottomley
bis(5-hydroxy-5-oxodibenzo-5H-phosphole) anhydride or 9,9′-oxydi(9-phosphafluoren-9-one)
Crystal data
C24H16O3P2
Mr = 414.31
Orthorhombic, Pbca
Hall symbol: -P 2ac 2ab
a = 11.0105 (7) Å
b = 13.6596 (10) Å
c = 26.8832 (18) Å
V = 4043.2 (5) Å3
Z = 8
F(000) = 1712
Dx = 1.361 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6595 reflections
θ = 2.4–25.1°
µ = 0.24 mm−1
T = 173 K
Plate, colourless 0.45 × 0.25 × 0.05 mm
Data collection
Bruker AXS SMART1000/P4 diffractometer
Radiation source: fine-focus sealed tube, Bruker AXS SMART1000/P4
Graphite monochromator
ω and φ scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.832, Tmax = 0.990
19599 measured reflections 3530 independent reflections
2286 reflections with I > 2σ(I)
Rint = 0.041
θmax = 25.0°, θmin = 1.5°
h = −13→13
k = −16→15
l = −28→30
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.051
wR(F2) = 0.142
S = 1.08
3530 reflections 326 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
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0738P)2 + 1.2419P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.33 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.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
P1 0.18678 (7) 0.62362 (6) 0.32800 (3) 0.0441 (3)
P2 0.32346 (7) 0.56650 (6) 0.41339 (3) 0.0424 (3)
O1 0.1403 (2) 0.70798 (17) 0.35561 (9) 0.0608 (7)
O2 0.20961 (19) 0.53565 (18) 0.43735 (8) 0.0573 (6)
O3 0.30687 (17) 0.57853 (16) 0.35412 (7) 0.0462 (6)
C1A 0.2314 (3) 0.6392 (2) 0.26502 (11) 0.0423 (7)
C1 0.3179 (3) 0.7015 (2) 0.24531 (13) 0.0517 (8)
H1 0.3649 0.7424 0.2664 0.062*
C2 0.3346 (3) 0.7033 (3) 0.19483 (14) 0.0672 (11)
H2 0.3942 0.7452 0.1806 0.081*
C3 0.2646 (4) 0.6442 (3) 0.16467 (14) 0.0772 (12)
H3 0.2760 0.6467 0.1297 0.093*
C4 0.1787 (3) 0.5818 (3) 0.18396 (13) 0.0651 (10)
H4 0.1314 0.5418 0.1625 0.078*
C4A 0.1618 (3) 0.5777 (2) 0.23479 (11) 0.0456 (8)
C5A 0.0786 (3) 0.5130 (2) 0.26296 (11) 0.0455 (8)
C5 −0.0019 (3) 0.4440 (3) 0.24317 (14) 0.0589 (9)
H5 −0.0092 0.4363 0.2082 0.071*
C6 −0.0699 (3) 0.3878 (3) 0.27471 (17) 0.0709 (11)
H6 −0.1239 0.3403 0.2614 0.085*
C7 −0.0613 (3) 0.3990 (3) 0.32580 (16) 0.0721 (11)
H7 −0.1088 0.3589 0.3471 0.087*
C8 0.0159 (3) 0.4681 (3) 0.34595 (13) 0.0607 (10)
H8 0.0213 0.4764 0.3810 0.073*
C8A 0.0854 (3) 0.5249 (2) 0.31422 (11) 0.0450 (8)
C21A 0.4548 (3) 0.4909 (2) 0.41877 (10) 0.0438 (8)
C21 0.4687 (4) 0.3938 (2) 0.40540 (11) 0.0565 (9)
H21 0.4042 0.3587 0.3901 0.068*
C22 0.5784 (5) 0.3490 (3) 0.41475 (13) 0.0739 (12)
H22 0.5900 0.2823 0.4061 0.089*
C23 0.6709 (4) 0.4006 (3) 0.43649 (14) 0.0725 (12)
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Acta Cryst. (2004). E60, o1935–o1936
H24 0.7244 0.5316 0.4649 0.068*
C24A 0.5487 (3) 0.5445 (2) 0.44102 (10) 0.0418 (8)
C25A 0.5166 (3) 0.6466 (2) 0.45246 (10) 0.0401 (7)
C25 0.5872 (3) 0.7154 (3) 0.47677 (11) 0.0518 (9)
H25 0.6672 0.6992 0.4871 0.062*
C26 0.5412 (3) 0.8074 (3) 0.48588 (12) 0.0572 (9)
H26 0.5889 0.8534 0.5038 0.069*
C27 0.4273 (3) 0.8341 (3) 0.46954 (12) 0.0551 (9)
H27 0.3981 0.8986 0.4751 0.066*
C28 0.3551 (3) 0.7656 (2) 0.44469 (11) 0.0459 (8)
H28 0.2766 0.7833 0.4331 0.055*
C28A 0.3986 (3) 0.6725 (2) 0.43724 (10) 0.0398 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
P1 0.0399 (4) 0.0546 (6) 0.0377 (5) 0.0001 (4) −0.0025 (3) −0.0103 (4)
P2 0.0449 (5) 0.0530 (5) 0.0293 (4) −0.0060 (4) 0.0001 (3) −0.0044 (4)
O1 0.0536 (13) 0.0647 (16) 0.0640 (15) 0.0014 (12) −0.0006 (11) −0.0265 (12)
O2 0.0569 (14) 0.0735 (17) 0.0415 (13) −0.0166 (12) 0.0052 (10) −0.0094 (12)
O3 0.0396 (11) 0.0682 (15) 0.0308 (11) 0.0010 (10) −0.0021 (8) −0.0061 (10)
C1A 0.0416 (16) 0.0446 (18) 0.0408 (17) 0.0104 (15) −0.0077 (13) −0.0019 (14)
C1 0.0472 (19) 0.056 (2) 0.052 (2) −0.0006 (17) −0.0058 (15) 0.0033 (17)
C2 0.067 (2) 0.077 (3) 0.057 (2) −0.002 (2) 0.0021 (18) 0.015 (2)
C3 0.105 (3) 0.086 (3) 0.041 (2) −0.006 (3) 0.001 (2) 0.011 (2)
C4 0.084 (3) 0.072 (3) 0.0390 (19) −0.004 (2) −0.0152 (18) −0.0028 (18)
C4A 0.0482 (18) 0.0489 (19) 0.0396 (17) 0.0112 (15) −0.0127 (14) −0.0036 (15)
C5A 0.0422 (17) 0.0459 (19) 0.0483 (19) 0.0075 (15) −0.0083 (14) −0.0066 (15)
C5 0.061 (2) 0.056 (2) 0.059 (2) −0.0036 (18) −0.0174 (18) −0.0143 (18)
C6 0.052 (2) 0.060 (3) 0.100 (3) −0.0132 (19) −0.014 (2) −0.021 (2)
C7 0.055 (2) 0.071 (3) 0.091 (3) −0.015 (2) 0.008 (2) −0.004 (2)
C8 0.052 (2) 0.075 (3) 0.056 (2) −0.0112 (19) 0.0066 (16) −0.0087 (19)
C8A 0.0364 (16) 0.052 (2) 0.0468 (18) 0.0037 (15) −0.0017 (14) −0.0069 (15)
C21A 0.0604 (19) 0.0458 (19) 0.0253 (15) 0.0029 (16) 0.0060 (13) 0.0005 (14)
C21 0.091 (3) 0.046 (2) 0.0331 (18) −0.004 (2) 0.0126 (17) 0.0001 (15)
C22 0.122 (4) 0.059 (3) 0.040 (2) 0.030 (3) 0.022 (2) 0.0025 (18)
C23 0.094 (3) 0.081 (3) 0.042 (2) 0.045 (3) 0.007 (2) 0.007 (2)
C24 0.061 (2) 0.077 (3) 0.0311 (17) 0.021 (2) −0.0028 (14) 0.0025 (17)
C24A 0.0506 (18) 0.052 (2) 0.0226 (14) 0.0062 (15) 0.0004 (12) 0.0033 (13)
C25A 0.0422 (16) 0.053 (2) 0.0251 (14) −0.0025 (15) −0.0006 (12) 0.0013 (13)
C25 0.0415 (17) 0.069 (3) 0.0445 (19) −0.0049 (17) −0.0029 (14) −0.0064 (17)
C26 0.056 (2) 0.064 (2) 0.052 (2) −0.0146 (19) 0.0025 (16) −0.0127 (18)
C27 0.069 (2) 0.049 (2) 0.0477 (19) 0.0026 (18) 0.0062 (17) −0.0033 (16)
C28 0.0485 (17) 0.054 (2) 0.0354 (16) 0.0072 (16) 0.0007 (13) 0.0020 (15)
Geometric parameters (Å, º)
P1—O1 1.463 (2) C7—C8 1.380 (5)
P1—O3 1.619 (2) C7—H7 0.9500
P1—C1A 1.776 (3) C8—C8A 1.384 (5)
P1—C8A 1.789 (3) C8—H8 0.9500
P2—O2 1.471 (2) C21A—C21 1.383 (5)
P2—O3 1.612 (2) C21A—C24A 1.401 (4)
P2—C21A 1.783 (3) C21—C22 1.377 (5)
P2—C28A 1.787 (3) C21—H21 0.9500
C1A—C1 1.383 (4) C22—C23 1.368 (6)
C1A—C4A 1.397 (4) C22—H22 0.9500
C1—C2 1.370 (5) C23—C24 1.378 (5)
C1—H1 0.9500 C23—H23 0.9500
C2—C3 1.379 (5) C24—C24A 1.392 (4)
C2—H2 0.9500 C24—H24 0.9500
C3—C4 1.375 (5) C24A—C25A 1.471 (4)
C3—H3 0.9500 C25A—C25 1.384 (4)
C4—C4A 1.380 (5) C25A—C28A 1.407 (4)
C4—H4 0.9500 C25—C26 1.377 (5)
C4A—C5A 1.482 (4) C25—H25 0.9500
C5A—C8A 1.390 (4) C26—C27 1.377 (5)
C5A—C5 1.398 (4) C26—H26 0.9500
C5—C6 1.367 (5) C27—C28 1.397 (4)
C5—H5 0.9500 C27—H27 0.9500
C6—C7 1.385 (6) C28—C28A 1.375 (4)
C6—H6 0.9500 C28—H28 0.9500
O1—P1—O3 111.43 (12) C7—C8—C8A 118.8 (3)
O1—P1—C1A 119.07 (15) C7—C8—H8 120.6
O3—P1—C1A 103.49 (12) C8A—C8—H8 120.6
O1—P1—C8A 118.70 (14) C8—C8A—C5A 121.0 (3)
O3—P1—C8A 108.23 (13) C8—C8A—P1 129.8 (3)
C1A—P1—C8A 93.75 (14) C5A—C8A—P1 109.1 (2)
O2—P2—O3 111.44 (11) C21—C21A—C24A 122.0 (3)
O2—P2—C21A 119.30 (15) C21—C21A—P2 128.7 (3)
O3—P2—C21A 103.36 (12) C24A—C21A—P2 109.3 (2)
O2—P2—C28A 118.02 (13) C22—C21—C21A 118.4 (4)
O3—P2—C28A 108.95 (12) C22—C21—H21 120.8
C21A—P2—C28A 93.71 (14) C21A—C21—H21 120.8
P2—O3—P1 124.05 (12) C23—C22—C21 120.2 (4)
C1—C1A—C4A 121.6 (3) C23—C22—H22 119.9
C1—C1A—P1 129.0 (2) C21—C22—H22 119.9
C4A—C1A—P1 109.3 (2) C22—C23—C24 122.2 (4)
C2—C1—C1A 118.9 (3) C22—C23—H23 118.9
C2—C1—H1 120.6 C24—C23—H23 118.9
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Acta Cryst. (2004). E60, o1935–o1936
C1—C2—H2 120.1 C24A—C24—H24 120.6
C3—C2—H2 120.1 C24—C24A—C21A 118.3 (3)
C4—C3—C2 121.7 (3) C24—C24A—C25A 127.6 (3)
C4—C3—H3 119.1 C21A—C24A—C25A 114.0 (3)
C2—C3—H3 119.1 C25—C25A—C28A 119.0 (3)
C3—C4—C4A 119.4 (3) C25—C25A—C24A 127.4 (3)
C3—C4—H4 120.3 C28A—C25A—C24A 113.5 (3)
C4A—C4—H4 120.3 C26—C25—C25A 119.8 (3)
C4—C4A—C1A 118.5 (3) C26—C25—H25 120.1
C4—C4A—C5A 127.8 (3) C25A—C25—H25 120.1
C1A—C4A—C5A 113.6 (3) C25—C26—C27 121.3 (3)
C8A—C5A—C5 119.4 (3) C25—C26—H26 119.4
C8A—C5A—C4A 113.8 (3) C27—C26—H26 119.4
C5—C5A—C4A 126.8 (3) C26—C27—C28 119.6 (3)
C6—C5—C5A 119.3 (3) C26—C27—H27 120.2
C6—C5—H5 120.3 C28—C27—H27 120.2
C5A—C5—H5 120.3 C28A—C28—C27 119.4 (3)
C5—C6—C7 121.0 (3) C28A—C28—H28 120.3
C5—C6—H6 119.5 C27—C28—H28 120.3
C7—C6—H6 119.5 C28—C28A—C25A 120.8 (3)
C8—C7—C6 120.5 (4) C28—C28A—P2 129.8 (2)
C8—C7—H7 119.8 C25A—C28A—P2 109.2 (2)