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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o4.
Published online 2007 December 6. doi:  10.1107/S1600536807062228
PMCID: PMC2914894

5-Benzyl­idene-2,3-diphenyl-1,2-selenaphosphole-2-selenide

Abstract

The title compound, C23H19PSe2, has a central five-membered twist C3PSe ring conformation. One phenyl ring substituent, attached to an sp 2 carbon, is approximately coplanar with the C3PSe ring whilst the other organic substituents, attached to an sp 3-carbon and a PV atom, lie on the same side of the ring.

Related literature

For related literature, see: Yoshifuji et al. (1998 [triangle]); Fitzmaurice et al. (1988 [triangle]); Gray, Bhattacharyya et al. (2005 [triangle]); Gray, Slawin et al. (2005 [triangle]); Hua & Woollins (2007 [triangle]) and literature cited therein; Hua et al. (2006 [triangle]); Mugesh et al. (2001 [triangle]); Shi et al. (2006 [triangle], 2007 [triangle]); Sommen et al. (2005 [triangle]).

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Object name is e-64-000o4-scheme1.jpg

Experimental

Crystal data

  • C23H19PSe2
  • M r = 484.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-000o4-efi1.jpg
  • a = 22.385 (2) Å
  • b = 14.4348 (14) Å
  • c = 12.4433 (12) Å
  • β = 94.847 (2)°
  • V = 4006.4 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.78 mm−1
  • T = 93 (2) K
  • 0.30 × 0.15 × 0.10 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku,2004 [triangle]) T min = 0.515, T max = 0.692
  • 11508 measured reflections
  • 3667 independent reflections
  • 3125 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.077
  • S = 1.04
  • 3667 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.95 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 2004 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: Bruker SHELXTL (Sheldrick, 2003 [triangle]); software used to prepare material for publication: Bruker SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062228/si2054sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062228/si2054Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful to the Engineering and Physical Science Research Council (EPSRC, UK) for financial support.

supplementary crystallographic information

Comment

Organoselenium chemistry is attracting increasing attention because of chemo-, regio-, and stereoselective reactions and useful biological activity(Mugesh et al., 2001). However, the synthesis of selenium-containing organic heterocycles can be problematic involving use of toxic selenium reagents which are often difficult to handle. 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide [PhP(Se)(µ-Se)]2, known as Woollins reagent (WR) excels in efficiency and broad utility, capable of preparing a wide range selenium-containing heterocycles and the related compounds (Gray, Bhattacharyya et al. (2005); Gray, Slawin et al. (2005); Shi et al., 2006, 2007). In our new five membered P—Se heterocycle the P = Se bond length (2.1044 (9) Å) and the P—Se distance (2.2523 (9) Å, Table 1) are consistent with the related selenides-containing PV= Se bonds (2.081 (2) - 2.123 (3) Å) and PV—Se single bonds (Fitzmaurice et al. 1988, Yoshifuji et al. 1998).

Experimental

A mixture of dibenzoylideneacetone (0.47 g, 2 mmol) and Woollins' reagent (0.54 g, 1 mmol) in 10 ml of dry toluene was refluxed for 20 hr. The red suspension disappeared and a red solution was formed along with a small amount of elemental selenium in the bottom of flask. Upon cooling to room temperature the mixture was purified by silica gel column chromatograhy (toluene as eluent) to give the title compound in 83% yield. Colorless crystal were grown from dichloromethane with slow diffusion of n-hexane. Anal. Calcd for C23H19PSe2: C, 57.04; H, 3.95. Found: C, 57.01; H, 3.99. 1H NMR (CDCl3): 7.63–7.47 (m, 2H, ArH), 7.37–7.30 (m, 3H, ArH), 7.21–7.12 (m, 4H, ArH), 7.11–7.04 (m, 4H, AeH), 6.96–6.93 (m, 2H, ArH), 7.05 (d, 1H, CH=CH), 6.95 (d, 1H, CH=CH), 6.66 (dd, 1H, CH=CH), 6.36 (dd, 1H, CH=CH). 31P NMR (CDCl3): 69.85 (s, J(P,Seendo) = 350 Hz, J(P,Seexo) = 782 Hz). 77Se NMR (CDCl3): 354.85 (J(P,Seendo) = 350 Hz), -169.99 (J(P,Seexo) = 780 Hz).

Refinement

All H atoms were included in calculated positions (C—H distances are 0.98 Å for methyl H atoms, 0.99 Å for methylene H atoms and 0.95 Å for aryl H atoms) and were refined as riding atoms with Uiso(H) = 1.2 Ueq (parent atom, methylene and aryl H atoms) or Uiso(H) = 1.5 Ueq (parent atom,methyl H atoms).

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C23H19PSe2F000 = 1920
Mr = 484.27Dx = 1.606 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8628 reflections
a = 22.385 (2) Åθ = 1.6–25.3º
b = 14.4348 (14) ŵ = 3.78 mm1
c = 12.4433 (12) ÅT = 93 (2) K
β = 94.847 (2)ºPrism, colorless
V = 4006.4 (7) Å30.30 × 0.15 × 0.10 mm
Z = 8

Data collection

Rigaku Mercury CCD diffractometer3667 independent reflections
Radiation source: rotating anode3125 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.043
T = 93(2) Kθmax = 25.5º
ω and [var phi] scansθmin = 2.3º
Absorption correction: multi-scan(CrystalClear; Rigaku,2004)h = −26→17
Tmin = 0.515, Tmax = 0.692k = −18→18
11508 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.032P)2 + 14.4806P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3667 reflectionsΔρmax = 0.95 e Å3
235 parametersΔρmin = −0.41 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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.
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)

xyzUiso*/Ueq
Se20.946290 (15)−0.03631 (2)0.57968 (3)0.02008 (10)
Se10.960236 (16)0.21801 (2)0.57205 (3)0.02484 (11)
P10.90715 (4)0.10413 (6)0.60975 (7)0.01702 (19)
C190.93533 (15)−0.4014 (2)0.5818 (3)0.0236 (8)
H190.9426−0.37430.51450.028*
C60.81730 (16)0.1775 (2)0.4664 (3)0.0237 (8)
H60.84390.22810.46000.028*
C100.85050 (14)0.1485 (2)0.7960 (2)0.0182 (7)
C20.79343 (16)0.0315 (2)0.5460 (3)0.0254 (8)
H20.8042−0.01880.59310.030*
C110.79206 (15)0.1186 (3)0.8016 (3)0.0240 (8)
H110.78130.05730.78000.029*
C50.76207 (17)0.1763 (3)0.4063 (3)0.0326 (9)
H50.75150.22530.35730.039*
C130.76399 (17)0.2669 (3)0.8696 (3)0.0286 (9)
H130.73460.30720.89450.034*
C10.83355 (14)0.1048 (2)0.5360 (3)0.0188 (7)
C150.86516 (16)0.2385 (2)0.8277 (3)0.0245 (8)
H150.90500.26020.82450.029*
C220.91438 (18)−0.4819 (3)0.7761 (3)0.0326 (9)
H220.9070−0.50960.84300.039*
C180.92438 (14)−0.3447 (2)0.6681 (3)0.0201 (7)
C30.73807 (17)0.0323 (3)0.4872 (3)0.0330 (9)
H30.7106−0.01690.49490.040*
C120.74889 (16)0.1772 (3)0.8384 (3)0.0294 (8)
H120.70900.15560.84220.035*
C40.72257 (18)0.1045 (3)0.4173 (3)0.0349 (9)
H40.68460.10460.37690.042*
C80.89178 (15)−0.0157 (2)0.7738 (2)0.0202 (7)
H80.8729−0.03570.83540.024*
C140.82195 (17)0.2971 (3)0.8641 (3)0.0299 (9)
H140.83250.35860.88540.036*
C210.92538 (16)−0.5374 (2)0.6896 (3)0.0294 (8)
H210.9258−0.60290.69710.035*
C160.90956 (15)−0.1790 (2)0.7240 (3)0.0216 (7)
H160.8966−0.20030.79040.026*
C70.89842 (15)0.0864 (2)0.7559 (3)0.0186 (7)
H70.93720.10520.79550.022*
C230.91395 (17)−0.3864 (3)0.7666 (3)0.0274 (8)
H230.9066−0.34900.82690.033*
C170.92483 (14)−0.2435 (2)0.6540 (3)0.0196 (7)
H170.9374−0.22140.58760.024*
C90.91106 (14)−0.0799 (2)0.7077 (3)0.0185 (7)
C200.93580 (16)−0.4975 (3)0.5923 (3)0.0292 (8)
H200.9433−0.53540.53250.035*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Se20.02552 (19)0.01480 (18)0.02139 (18)0.00227 (13)0.01059 (13)0.00242 (14)
Se10.0290 (2)0.01641 (18)0.0306 (2)−0.00455 (14)0.01166 (15)0.00100 (15)
P10.0214 (4)0.0136 (4)0.0169 (4)−0.0008 (3)0.0065 (3)0.0003 (3)
C190.0256 (19)0.0207 (18)0.0248 (19)−0.0015 (14)0.0034 (14)−0.0006 (15)
C60.0312 (19)0.0211 (18)0.0200 (18)0.0048 (15)0.0083 (14)0.0030 (15)
C100.0246 (18)0.0223 (18)0.0078 (15)0.0015 (14)0.0013 (12)0.0015 (14)
C20.032 (2)0.0220 (18)0.0214 (18)−0.0023 (15)−0.0003 (14)0.0039 (16)
C110.0277 (19)0.0263 (19)0.0190 (18)−0.0022 (15)0.0076 (14)−0.0020 (15)
C50.041 (2)0.036 (2)0.0207 (19)0.0131 (18)−0.0013 (16)0.0044 (17)
C130.036 (2)0.032 (2)0.0183 (18)0.0138 (17)0.0096 (15)0.0010 (16)
C10.0226 (17)0.0199 (17)0.0142 (16)0.0005 (14)0.0039 (13)−0.0046 (14)
C150.0289 (19)0.0238 (19)0.0208 (18)0.0001 (15)0.0018 (14)−0.0012 (15)
C220.048 (2)0.023 (2)0.026 (2)−0.0017 (17)−0.0025 (17)0.0092 (17)
C180.0152 (16)0.0176 (17)0.0272 (19)−0.0003 (13)−0.0010 (13)0.0009 (15)
C30.032 (2)0.039 (2)0.028 (2)−0.0071 (18)−0.0020 (16)−0.0057 (19)
C120.0220 (18)0.042 (2)0.0252 (19)−0.0006 (16)0.0071 (14)0.0067 (17)
C40.034 (2)0.046 (3)0.023 (2)0.0075 (19)−0.0058 (16)−0.0061 (19)
C80.0263 (18)0.0233 (19)0.0114 (16)0.0011 (14)0.0036 (13)0.0018 (14)
C140.042 (2)0.022 (2)0.026 (2)0.0046 (16)0.0036 (16)−0.0053 (17)
C210.031 (2)0.0151 (18)0.040 (2)−0.0019 (15)−0.0068 (16)0.0023 (17)
C160.0279 (19)0.0191 (17)0.0183 (17)0.0011 (14)0.0035 (14)0.0067 (14)
C70.0214 (17)0.0181 (17)0.0164 (17)−0.0001 (13)0.0029 (13)0.0022 (14)
C230.038 (2)0.0219 (19)0.0219 (19)−0.0003 (16)−0.0006 (15)0.0008 (16)
C170.0195 (17)0.0192 (17)0.0204 (17)−0.0013 (13)0.0031 (13)0.0034 (14)
C90.0205 (17)0.0190 (17)0.0159 (17)0.0007 (13)0.0013 (13)0.0029 (14)
C200.031 (2)0.0215 (19)0.036 (2)−0.0027 (15)0.0029 (16)−0.0058 (17)

Geometric parameters (Å, °)

Se2—C91.941 (3)C15—C141.389 (5)
Se2—P12.2523 (9)C15—H150.9500
Se1—P12.1044 (9)C22—C211.381 (5)
P1—C11.817 (3)C22—C231.383 (5)
P1—C71.862 (3)C22—H220.9500
C19—C181.389 (5)C18—C231.402 (5)
C19—C201.393 (5)C18—C171.472 (5)
C19—H190.9500C3—C41.383 (6)
C6—C51.390 (5)C3—H30.9500
C6—C11.390 (5)C12—H120.9500
C6—H60.9500C4—H40.9500
C10—C111.385 (5)C8—C91.334 (5)
C10—C151.389 (5)C8—C71.500 (5)
C10—C71.515 (4)C8—H80.9500
C2—C31.385 (5)C14—H140.9500
C2—C11.400 (5)C21—C201.378 (5)
C2—H20.9500C21—H210.9500
C11—C121.390 (5)C16—C171.339 (5)
C11—H110.9500C16—C91.446 (5)
C5—C41.377 (6)C16—H160.9500
C5—H50.9500C7—H71.0000
C13—C141.376 (5)C23—H230.9500
C13—C121.385 (5)C17—H170.9500
C13—H130.9500C20—H200.9500
C9—Se2—P187.97 (10)C4—C3—C2120.3 (4)
C1—P1—C7109.16 (15)C4—C3—H3119.8
C1—P1—Se1112.86 (11)C2—C3—H3119.8
C7—P1—Se1115.65 (11)C13—C12—C11120.0 (3)
C1—P1—Se2105.64 (11)C13—C12—H12120.0
C7—P1—Se296.47 (10)C11—C12—H12120.0
Se1—P1—Se2115.54 (4)C5—C4—C3120.1 (4)
C18—C19—C20120.9 (3)C5—C4—H4120.0
C18—C19—H19119.5C3—C4—H4120.0
C20—C19—H19119.5C9—C8—C7123.3 (3)
C5—C6—C1120.0 (3)C9—C8—H8118.4
C5—C6—H6120.0C7—C8—H8118.4
C1—C6—H6120.0C13—C14—C15120.6 (3)
C11—C10—C15118.6 (3)C13—C14—H14119.7
C11—C10—C7122.0 (3)C15—C14—H14119.7
C15—C10—C7119.4 (3)C20—C21—C22119.7 (3)
C3—C2—C1119.9 (3)C20—C21—H21120.1
C3—C2—H2120.1C22—C21—H21120.1
C1—C2—H2120.1C17—C16—C9125.9 (3)
C10—C11—C12120.9 (3)C17—C16—H16117.1
C10—C11—H11119.6C9—C16—H16117.1
C12—C11—H11119.6C8—C7—C10116.8 (3)
C4—C5—C6120.3 (4)C8—C7—P1107.5 (2)
C4—C5—H5119.8C10—C7—P1112.1 (2)
C6—C5—H5119.8C8—C7—H7106.6
C14—C13—C12119.4 (3)C10—C7—H7106.6
C14—C13—H13120.3P1—C7—H7106.6
C12—C13—H13120.3C22—C23—C18120.2 (3)
C6—C1—C2119.4 (3)C22—C23—H23119.9
C6—C1—P1119.8 (3)C18—C23—H23119.9
C2—C1—P1120.8 (3)C16—C17—C18127.4 (3)
C14—C15—C10120.5 (3)C16—C17—H17116.3
C14—C15—H15119.7C18—C17—H17116.3
C10—C15—H15119.7C8—C9—C16126.0 (3)
C21—C22—C23120.8 (3)C8—C9—Se2117.1 (2)
C21—C22—H22119.6C16—C9—Se2116.8 (2)
C23—C22—H22119.6C21—C20—C19119.9 (3)
C19—C18—C23118.4 (3)C21—C20—H20120.0
C19—C18—C17119.3 (3)C19—C20—H20120.0
C23—C18—C17122.3 (3)
C9—Se2—P1—C1−90.70 (14)C23—C22—C21—C20−0.3 (6)
C9—Se2—P1—C721.31 (14)C9—C8—C7—C10149.3 (3)
C9—Se2—P1—Se1143.79 (10)C9—C8—C7—P122.4 (4)
C15—C10—C11—C12−0.2 (5)C11—C10—C7—C8−29.5 (4)
C7—C10—C11—C12−179.8 (3)C15—C10—C7—C8150.9 (3)
C1—C6—C5—C41.7 (5)C11—C10—C7—P195.1 (3)
C5—C6—C1—C2−1.0 (5)C15—C10—C7—P1−84.5 (3)
C5—C6—C1—P1177.2 (3)C1—P1—C7—C882.6 (2)
C3—C2—C1—C6−0.3 (5)Se1—P1—C7—C8−148.82 (19)
C3—C2—C1—P1−178.5 (3)Se2—P1—C7—C8−26.4 (2)
C7—P1—C1—C6128.1 (3)C1—P1—C7—C10−47.0 (3)
Se1—P1—C1—C6−2.0 (3)Se1—P1—C7—C1081.5 (2)
Se2—P1—C1—C6−129.2 (2)Se2—P1—C7—C10−156.1 (2)
C7—P1—C1—C2−53.7 (3)C21—C22—C23—C180.4 (6)
Se1—P1—C1—C2176.2 (2)C19—C18—C23—C22−0.3 (5)
Se2—P1—C1—C249.1 (3)C17—C18—C23—C22−179.6 (3)
C11—C10—C15—C14−0.1 (5)C9—C16—C17—C18179.4 (3)
C7—C10—C15—C14179.6 (3)C19—C18—C17—C16172.9 (3)
C20—C19—C18—C230.2 (5)C23—C18—C17—C16−7.9 (5)
C20—C19—C18—C17179.4 (3)C7—C8—C9—C16175.7 (3)
C1—C2—C3—C41.0 (5)C7—C8—C9—Se2−2.5 (4)
C14—C13—C12—C11−0.3 (5)C17—C16—C9—C8174.8 (3)
C10—C11—C12—C130.3 (5)C17—C16—C9—Se2−6.9 (5)
C6—C5—C4—C3−1.0 (6)P1—Se2—C9—C8−14.4 (3)
C2—C3—C4—C5−0.4 (6)P1—Se2—C9—C16167.2 (3)
C12—C13—C14—C150.0 (5)C22—C21—C20—C190.2 (5)
C10—C15—C14—C130.2 (5)C18—C19—C20—C21−0.1 (5)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2054).

References

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