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The title compound, C10H7OP(Se)(C6H5)2 or C22H17OPSe, is isomorphous and isostructural with its sulfur analog and shows a distorted tetra­hedral geometry about the P atom. The P=Se bond of 2.0890 (5) Å is shorter than that of 2.106 (1) Å found in Ph3P=Se because the replacement of one carbon on phospho­rus by oxygen increases the effective electronegativity of the P atom, thereby enhancing pπ–dπ back-donation from a lone-pair orbital of the chalcogen atom and shortens the P=Se bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056334/xu2359sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056334/xu2359Isup2.hkl
Contains datablock I

CCDC reference: 674084

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.033
  • wR factor = 0.091
  • Data-to-parameter ratio = 20.7

checkCIF/PLATON results

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No errors found in this datablock

Comment top

During the past few decades, charge transfer (CT) compounds have been the subject of extensive structural and theoretical investigations (Mague et al., 2007), and more recently, several groups have begun to investigate the role of phosphine chalcogenide CT compounds in the above areas (see, e.g. Cross et al. (1999) and Arca et al. (1999)). The present study is part of a structural investigation of phosphine chalcogenide ligands directed at obtaining a better understanding of the factors that influence bonding in these molecules which in turn may help predict the type of CT compounds they may form.

A perspective view of I is shown in Fig. 1. The distorted tetrahedral geometry about phosphorus is evidenced by the angles at phosphorus which range from 97.68 (8)° (O1—P1—C17) to 116.37 (5)° (O1—P1—Se1). The PSe bond of 2.0890 (5) Å (Table 1) is shorter than 2.106 (1) Å found in Ph3P=Se (Codding & Kerr, 1979) because the replacement of one carbon on phosphorus by oxygen increases the effective electronegativity of the phosphorus atom thereby enhancing pπ-dπ back donation from a lone pair orbital of the chalcogen atom and shortens the PSe bond. In the title compound the dihedral angles between the mean plane of the naphthyl group and mean planes of the phenyl rings built on C11 and C17 are, respectively, 80.97 (7) and 56.88 (7)° while that between the mean planes of the phenyl rings is 70.15 (8)°. The P1—O1—C1—C2 torsion angle is 173.8 (1)°.

Related literature top

For general background, see: Mague et al. (2007); Cross et al. (1999); Arca et al. (1999). For related structures, see: Mague et al. (2007); Codding & Kerr (1979).

Experimental top

A mixture of C10H7OPPh2 (1 g, 3.04 mmol) and elemental selenium (0.24 g, 3.04 mmol) in toluene (20 ml) was heated to reflux for 10 h and was then cooled to room temperature. It was then filtered and the solvent removed in vacuo to yield a pasty liquid which was dissolved in CH2Cl2 and layered with petroleum ether. Colorless crystals of the title compound were formed on standing overnight at 0 °C. Yield: 91% (1.12 g). Anal. Calcd. for C22H17OPSe: C, 64.87; H, 4.21%. Found: C, 64.63; H, 4.13%.

Refinement top

H atoms were placed in calculated positions with C—H = 0.95 Å and refined as riding contributions with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2 (Bruker, 2007); software used to prepare material for publication: APEX2 (Bruker, 2007).

Figures top
[Figure 1] Fig. 1. Perspective view of I. Displacement ellipsoids are drawn at the 50% probability level and H-atoms are represented by spheres of arbitrary radius.
O-2-Naphthyl diphenylselenophosphinate top
Crystal data top
C22H17OPSeF(000) = 824
Mr = 407.29Dx = 1.490 Mg m3
Monoclinic, P21/nMelting point = 391–393 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.9490 (8) ÅCell parameters from 9901 reflections
b = 19.044 (2) Åθ = 2.4–29.2°
c = 9.9552 (8) ŵ = 2.16 mm1
β = 105.672 (1)°T = 100 K
V = 1816.1 (3) Å3Block, colourless
Z = 40.26 × 0.24 × 0.15 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
4675 independent reflections
Radiation source: fine-focus sealed tube3896 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 28.8°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 1313
Tmin = 0.545, Tmax = 0.727k = 2525
30965 measured reflectionsl = 1313
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0534P)2 + 0.981P]
where P = (Fo2 + 2Fc2)/3
4675 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.95 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
C22H17OPSeV = 1816.1 (3) Å3
Mr = 407.29Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.9490 (8) ŵ = 2.16 mm1
b = 19.044 (2) ÅT = 100 K
c = 9.9552 (8) Å0.26 × 0.24 × 0.15 mm
β = 105.672 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
4675 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
3896 reflections with I > 2σ(I)
Tmin = 0.545, Tmax = 0.727Rint = 0.036
30965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.04Δρmax = 0.95 e Å3
4675 reflectionsΔρmin = 0.61 e Å3
226 parameters
Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 °. in omega, colllected at phi = 0.00, 90.00 and 180.00 °. and 2 sets of 800 frames, each of width 0.45 ° in phi, collected at omega = -30.00 and 210.00 °. The scan time was 10 sec/frame.

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) top
xyzUiso*/Ueq
Se10.49213 (2)0.142334 (11)0.58260 (2)0.02478 (8)
P10.36997 (5)0.18120 (3)0.39250 (5)0.01726 (11)
O10.22562 (14)0.21964 (7)0.39571 (14)0.0206 (3)
C10.21246 (19)0.27988 (10)0.4718 (2)0.0192 (4)
C20.0736 (2)0.30497 (12)0.4418 (2)0.0229 (4)
H20.00120.28160.37460.027*
C30.0441 (2)0.36264 (11)0.5095 (2)0.0258 (4)
H30.04890.37990.48790.031*
C40.1507 (2)0.39731 (11)0.6119 (2)0.0231 (4)
C50.1234 (2)0.45743 (12)0.6846 (3)0.0309 (5)
H50.03120.47560.66460.037*
C60.2283 (3)0.48944 (13)0.7830 (3)0.0352 (5)
H60.20850.52950.83130.042*
C70.3657 (3)0.46325 (12)0.8133 (2)0.0321 (5)
H70.43800.48590.88160.038*
C80.3961 (2)0.40536 (11)0.7450 (2)0.0252 (4)
H80.48910.38820.76670.030*
C90.2897 (2)0.37103 (11)0.6423 (2)0.0208 (4)
C100.3189 (2)0.31175 (10)0.5677 (2)0.0197 (4)
H100.41170.29460.58460.024*
C110.45437 (19)0.24513 (10)0.30831 (19)0.0185 (4)
C120.3740 (2)0.29457 (11)0.2174 (2)0.0219 (4)
H120.27600.29650.20510.026*
C130.4370 (2)0.34104 (12)0.1447 (2)0.0276 (4)
H130.38200.37400.08170.033*
C140.5804 (2)0.33876 (12)0.1649 (2)0.0293 (5)
H140.62360.37010.11510.035*
C150.6610 (2)0.29102 (12)0.2574 (2)0.0279 (5)
H150.75940.29070.27210.033*
C160.5994 (2)0.24347 (11)0.3291 (2)0.0228 (4)
H160.65500.21030.39130.027*
C170.29536 (19)0.11402 (10)0.26658 (19)0.0187 (4)
C180.3096 (2)0.04341 (11)0.3035 (2)0.0247 (4)
H180.36100.03020.39490.030*
C190.2487 (2)0.00782 (12)0.2068 (2)0.0289 (5)
H190.25760.05600.23230.035*
C200.1746 (2)0.01165 (12)0.0725 (2)0.0280 (5)
H200.13370.02340.00620.034*
C210.1601 (2)0.08144 (13)0.0353 (2)0.0280 (4)
H210.10890.09430.05650.034*
C220.2201 (2)0.13322 (11)0.1311 (2)0.0234 (4)
H220.21020.18130.10500.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Se10.02718 (12)0.02680 (13)0.01673 (11)0.00020 (8)0.00029 (8)0.00236 (8)
P10.0171 (2)0.0201 (2)0.0142 (2)0.00042 (17)0.00361 (17)0.00038 (18)
O10.0194 (6)0.0253 (7)0.0178 (6)0.0003 (5)0.0063 (5)0.0041 (5)
C10.0204 (9)0.0220 (10)0.0176 (9)0.0006 (7)0.0095 (7)0.0010 (7)
C20.0190 (9)0.0294 (11)0.0210 (9)0.0005 (7)0.0067 (7)0.0026 (8)
C30.0203 (9)0.0304 (11)0.0294 (11)0.0044 (8)0.0114 (8)0.0054 (9)
C40.0276 (10)0.0212 (10)0.0251 (10)0.0024 (8)0.0151 (8)0.0040 (8)
C50.0359 (11)0.0261 (11)0.0384 (12)0.0028 (9)0.0235 (10)0.0002 (9)
C60.0506 (14)0.0265 (12)0.0368 (12)0.0002 (10)0.0262 (11)0.0065 (10)
C70.0447 (13)0.0290 (12)0.0242 (10)0.0051 (10)0.0122 (10)0.0060 (9)
C80.0312 (10)0.0253 (11)0.0208 (9)0.0008 (8)0.0098 (8)0.0003 (8)
C90.0257 (9)0.0215 (10)0.0184 (9)0.0006 (7)0.0112 (8)0.0018 (7)
C100.0195 (8)0.0230 (10)0.0181 (9)0.0016 (7)0.0077 (7)0.0012 (7)
C110.0187 (8)0.0210 (9)0.0160 (8)0.0017 (7)0.0051 (7)0.0042 (7)
C120.0235 (9)0.0219 (10)0.0216 (9)0.0006 (7)0.0081 (8)0.0010 (8)
C130.0377 (12)0.0222 (10)0.0255 (10)0.0001 (8)0.0132 (9)0.0004 (8)
C140.0399 (12)0.0260 (11)0.0293 (11)0.0105 (9)0.0218 (10)0.0076 (9)
C150.0233 (9)0.0342 (12)0.0305 (11)0.0087 (8)0.0148 (9)0.0133 (9)
C160.0196 (9)0.0269 (10)0.0221 (9)0.0004 (7)0.0061 (7)0.0085 (8)
C170.0178 (8)0.0220 (10)0.0170 (8)0.0035 (7)0.0062 (7)0.0036 (7)
C180.0218 (9)0.0254 (11)0.0250 (10)0.0005 (8)0.0032 (8)0.0008 (8)
C190.0259 (10)0.0216 (10)0.0377 (12)0.0002 (8)0.0059 (9)0.0041 (9)
C200.0226 (9)0.0332 (12)0.0292 (11)0.0048 (8)0.0088 (8)0.0133 (9)
C210.0281 (10)0.0387 (13)0.0174 (9)0.0084 (9)0.0069 (8)0.0045 (9)
C220.0263 (10)0.0254 (11)0.0182 (9)0.0044 (8)0.0053 (8)0.0015 (8)
Geometric parameters (Å, º) top
Se1—P12.0890 (5)C11—C121.398 (3)
P1—O11.6200 (14)C11—C161.401 (3)
P1—C171.805 (2)C12—C131.395 (3)
P1—C111.808 (2)C12—H120.9500
O1—C11.400 (2)C13—C141.387 (3)
C1—C101.362 (3)C13—H130.9500
C1—C21.416 (3)C14—C151.385 (3)
C2—C31.361 (3)C14—H140.9500
C2—H20.9500C15—C161.393 (3)
C3—C41.420 (3)C15—H150.9500
C3—H30.9500C16—H160.9500
C4—C51.420 (3)C17—C181.391 (3)
C4—C91.424 (3)C17—C221.403 (3)
C5—C61.367 (4)C18—C191.390 (3)
C5—H50.9500C18—H180.9500
C6—C71.409 (3)C19—C201.391 (3)
C6—H60.9500C19—H190.9500
C7—C81.371 (3)C20—C211.377 (3)
C7—H70.9500C20—H200.9500
C8—C91.417 (3)C21—C221.390 (3)
C8—H80.9500C21—H210.9500
C9—C101.424 (3)C22—H220.9500
C10—H100.9500
O1—P1—C1797.68 (8)C12—C11—C16119.78 (18)
O1—P1—C11103.29 (8)C12—C11—P1119.85 (14)
C17—P1—C11108.10 (9)C16—C11—P1120.32 (15)
O1—P1—Se1116.37 (5)C13—C12—C11120.33 (19)
C17—P1—Se1114.05 (7)C13—C12—H12119.8
C11—P1—Se1115.41 (6)C11—C12—H12119.8
C1—O1—P1126.43 (12)C14—C13—C12119.6 (2)
C10—C1—O1125.14 (17)C14—C13—H13120.2
C10—C1—C2121.84 (18)C12—C13—H13120.2
O1—C1—C2113.00 (17)C15—C14—C13120.3 (2)
C3—C2—C1119.76 (19)C15—C14—H14119.8
C3—C2—H2120.1C13—C14—H14119.8
C1—C2—H2120.1C14—C15—C16120.77 (19)
C2—C3—C4120.74 (19)C14—C15—H15119.6
C2—C3—H3119.6C16—C15—H15119.6
C4—C3—H3119.6C15—C16—C11119.2 (2)
C5—C4—C3122.15 (19)C15—C16—H16120.4
C5—C4—C9118.9 (2)C11—C16—H16120.4
C3—C4—C9118.93 (18)C18—C17—C22119.71 (18)
C6—C5—C4120.7 (2)C18—C17—P1120.56 (15)
C6—C5—H5119.6C22—C17—P1119.72 (15)
C4—C5—H5119.6C19—C18—C17120.10 (19)
C5—C6—C7120.3 (2)C19—C18—H18120.0
C5—C6—H6119.9C17—C18—H18119.9
C7—C6—H6119.9C18—C19—C20119.8 (2)
C8—C7—C6120.7 (2)C18—C19—H19120.1
C8—C7—H7119.7C20—C19—H19120.1
C6—C7—H7119.7C21—C20—C19120.4 (2)
C7—C8—C9120.5 (2)C21—C20—H20119.8
C7—C8—H8119.8C19—C20—H20119.8
C9—C8—H8119.8C20—C21—C22120.4 (2)
C8—C9—C10121.63 (18)C20—C21—H21119.8
C8—C9—C4118.96 (19)C22—C21—H21119.8
C10—C9—C4119.40 (18)C21—C22—C17119.6 (2)
C1—C10—C9119.29 (18)C21—C22—H22120.2
C1—C10—H10120.4C17—C22—H22120.2
C9—C10—H10120.4

Experimental details

Crystal data
Chemical formulaC22H17OPSe
Mr407.29
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)9.9490 (8), 19.044 (2), 9.9552 (8)
β (°) 105.672 (1)
V3)1816.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.16
Crystal size (mm)0.26 × 0.24 × 0.15
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.545, 0.727
No. of measured, independent and
observed [I > 2σ(I)] reflections
30965, 4675, 3896
Rint0.036
(sin θ/λ)max1)0.677
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.091, 1.04
No. of reflections4675
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.95, 0.61

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
Se1—P12.0890 (5)
O1—P1—C1797.68 (8)C17—P1—Se1114.05 (7)
O1—P1—C11103.29 (8)C11—P1—Se1115.41 (6)
C17—P1—C11108.10 (9)C1—O1—P1126.43 (12)
O1—P1—Se1116.37 (5)
 

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