2-Isobutyl-2-phosphabicyclo-[3.3.1]nonane 2-selenide.

The title compound, C(12)H(23)PSe, represents the first structure of a phosphine containing the bicyclic 2-phospha-bicyclo-[3.3.1]nonane (VCH) unit. It contains two chiral centres per mol-ecule which can be either R,R- or S,S and crystallizes as a centrosymmetric, racemic micture of the enanti-omers. The P-Se bond distance of 2.1360 (16) Å is typical for these compounds. The Tolman cone angle (2.28 Å from P) was calculated as 163°, and the effective cone angle (using the crystallographically determined P-Se bond distance) is 168°.

Related literature

For the synthesis of phosphine selenides, see: Otto et al. (2005 ▶). For the evaluation of ligand electronic properties, see: Allen & Taylor (1982 ▶); Bungu & Otto (2007b ▶); Muller et al. (2008 ▶); Otto & Roodt (2004 ▶); Roodt & Steyn (2000 ▶). For the application of bicyclic ligands in catalysis, see: Bungu & Otto (2007a ▶); Crause et al. (2003 ▶); Dwyer et al. (2004 ▶); Steynberg et al. (2003 ▶); Van Winkle et al. (1969 ▶). For information on cone angles, see: Tolman (1977 ▶); Otto (2001 ▶).

Experimental

Crystal data

C12H23PSe

M = 277.23

Monoclinic,

a = 10.763 (2) Å

b = 7.2540 (15) Å

c = 17.530 (4) Å

β = 97.93 (3)°

V = 1355.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.85 mm−1

T = 293 K

0.14 × 0.12 × 0.08 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.691, T max = 0.804

9132 measured reflections

3366 independent reflections

1658 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.181

S = 1.02

3366 reflections

129 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005492/hb2909sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005492/hb2909Isup2.hkl

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

C12H23PSe	F(000) = 576
Mr = 277.23	Dx = 1.358 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.763 (2) Å	Cell parameters from 1002 reflections
b = 7.2540 (15) Å	θ = 2.8–25.7°
c = 17.530 (4) Å	µ = 2.85 mm−1
β = 97.93 (3)°	T = 293 K
V = 1355.6 (5) Å3	Block, colourless
Z = 4	0.14 × 0.12 × 0.08 mm

Bruker X8 APEXII 4K KappaCCD diffractometer	3366 independent reflections
Radiation source: fine-focus sealed tube	1658 reflections with I > 2σ(I)
graphite	Rint = 0.062
Detector resolution: 512 pixels mm-1	θmax = 28.3°, θmin = 1.9°
φ and ω scans	h = −11→14
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −8→9
Tmin = 0.691, Tmax = 0.804	l = −23→23
9132 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0816P)2 + 0.9034P] where P = (Fo2 + 2Fc2)/3
3366 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.58 e Å−3

Experimental. The intensity data were collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 40 s/frame with a frame width of 0.3°; a total of 1315 frames were collected.The crystals were of poor quality and were, as a precautionary measure, covered with Canada balsam. Consequently some intensity in the reflextions were sacrificed and the completeness is somewhat low at high angles.

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.

	x	y	z	Uiso*/Ueq
P	0.21847 (13)	−0.0934 (2)	−0.03355 (8)	0.0418 (4)
Se	0.23308 (6)	0.16679 (9)	0.02405 (4)	0.0633 (3)
C11	0.1179 (6)	−0.0851 (9)	−0.1269 (3)	0.0588 (16)
H11A	0.0957	−0.2100	−0.1433	0.071*
H11B	0.0410	−0.0206	−0.1207	0.071*
C12	0.1797 (6)	0.0105 (11)	−0.1899 (4)	0.0712 (19)
H12A	0.1870	0.1411	−0.1780	0.085*
H12B	0.1251	−0.0022	−0.2384	0.085*
C13	0.3099 (7)	−0.0640 (12)	−0.1997 (4)	0.078 (2)
H13	0.3411	0.0092	−0.2401	0.094*
C14	0.3999 (6)	−0.0340 (10)	−0.1255 (4)	0.0699 (19)
H14A	0.3940	0.0930	−0.1090	0.084*
H14B	0.4852	−0.0554	−0.1353	0.084*
C15	0.3697 (5)	−0.1675 (8)	−0.0582 (4)	0.0528 (15)
H15	0.4336	−0.1494	−0.0133	0.063*
C16	0.3785 (6)	−0.3676 (8)	−0.0870 (4)	0.0610 (17)
H16A	0.4652	−0.3938	−0.0924	0.073*
H16B	0.3544	−0.4505	−0.0481	0.073*
C17	0.2984 (7)	−0.4081 (11)	−0.1622 (4)	0.082 (2)
H17A	0.2112	−0.4131	−0.1538	0.099*
H17B	0.3208	−0.5285	−0.1802	0.099*
C18	0.3119 (8)	−0.2667 (14)	−0.2240 (5)	0.091 (2)
H18A	0.2446	−0.2859	−0.2661	0.110*
H18B	0.3903	−0.2900	−0.2438	0.110*
C21	0.1449 (5)	−0.2707 (7)	0.0190 (3)	0.0452 (13)
H21A	0.0547	−0.2558	0.0076	0.054*
H21B	0.1655	−0.3899	−0.0010	0.054*
C22	0.1795 (5)	−0.2755 (8)	0.1068 (3)	0.0490 (14)
H22	0.1706	−0.1505	0.1266	0.059*
C23	0.0893 (6)	−0.4026 (10)	0.1427 (4)	0.0680 (18)
H23A	0.0046	−0.3618	0.1277	0.102*
H23B	0.1087	−0.3991	0.1978	0.102*
H23C	0.0981	−0.5265	0.1250	0.102*
C24	0.3154 (6)	−0.3372 (10)	0.1303 (4)	0.0708 (19)
H24A	0.3258	−0.4603	0.1121	0.106*
H24B	0.3350	−0.3345	0.1854	0.106*
H24C	0.3707	−0.2554	0.1080	0.106*

	U11	U22	U33	U12	U13	U23
P	0.0394 (8)	0.0373 (7)	0.0482 (8)	−0.0002 (6)	0.0044 (6)	−0.0054 (6)
Se	0.0709 (5)	0.0383 (4)	0.0804 (5)	−0.0015 (3)	0.0100 (3)	−0.0152 (3)
C11	0.056 (4)	0.061 (4)	0.057 (4)	0.000 (3)	0.002 (3)	0.007 (3)
C12	0.062 (4)	0.085 (5)	0.063 (4)	−0.003 (4)	−0.001 (3)	0.022 (4)
C13	0.067 (5)	0.105 (7)	0.060 (4)	−0.018 (4)	0.001 (3)	0.017 (4)
C14	0.062 (4)	0.074 (5)	0.077 (5)	−0.013 (3)	0.020 (4)	−0.006 (4)
C15	0.039 (3)	0.054 (4)	0.065 (4)	−0.005 (3)	0.006 (3)	−0.014 (3)
C16	0.055 (4)	0.047 (4)	0.083 (5)	0.008 (3)	0.018 (3)	−0.010 (3)
C17	0.091 (6)	0.080 (5)	0.078 (5)	−0.010 (4)	0.019 (4)	−0.032 (4)
C18	0.093 (6)	0.108 (7)	0.075 (5)	−0.014 (5)	0.020 (4)	−0.018 (5)
C21	0.047 (3)	0.036 (3)	0.052 (3)	0.001 (2)	0.008 (3)	−0.003 (2)
C22	0.056 (4)	0.042 (3)	0.049 (3)	0.000 (3)	0.009 (3)	−0.004 (3)
C23	0.073 (5)	0.063 (4)	0.073 (4)	−0.001 (4)	0.027 (4)	0.010 (3)
C24	0.068 (4)	0.078 (5)	0.062 (4)	−0.008 (4)	−0.009 (3)	0.013 (4)

P—C15	1.822 (6)	C16—H16A	0.9700
P—C21	1.825 (6)	C16—H16B	0.9700
P—C11	1.835 (6)	C17—C18	1.514 (12)
P—Se	2.1360 (16)	C17—H17A	0.9700
C11—C12	1.531 (9)	C17—H17B	0.9700
C11—H11A	0.9700	C18—H18A	0.9700
C11—H11B	0.9700	C18—H18B	0.9700
C12—C13	1.534 (10)	C21—C22	1.533 (8)
C12—H12A	0.9700	C21—H21A	0.9700
C12—H12B	0.9700	C21—H21B	0.9700
C13—C14	1.527 (9)	C22—C24	1.530 (9)
C13—C18	1.532 (12)	C22—C23	1.536 (8)
C13—H13	0.9800	C22—H22	0.9800
C14—C15	1.594 (9)	C23—H23A	0.9600
C14—H14A	0.9700	C23—H23B	0.9600
C14—H14B	0.9700	C23—H23C	0.9600
C15—C16	1.544 (8)	C24—H24A	0.9600
C15—H15	0.9800	C24—H24B	0.9600
C16—C17	1.501 (9)	C24—H24C	0.9600
C15—P—C21	112.0 (3)	C17—C16—H16B	108.6
C15—P—C11	103.6 (3)	C15—C16—H16B	108.6
C21—P—C11	103.3 (3)	H16A—C16—H16B	107.6
C15—P—Se	111.27 (19)	C16—C17—C18	113.3 (6)
C21—P—Se	113.12 (19)	C16—C17—H17A	108.9
C11—P—Se	112.9 (2)	C18—C17—H17A	108.9
C12—C11—P	113.3 (4)	C16—C17—H17B	108.9
C12—C11—H11A	108.9	C18—C17—H17B	108.9
P—C11—H11A	108.9	H17A—C17—H17B	107.7
C12—C11—H11B	108.9	C17—C18—C13	116.4 (6)
P—C11—H11B	108.9	C17—C18—H18A	108.2
H11A—C11—H11B	107.7	C13—C18—H18A	108.2
C11—C12—C13	114.6 (6)	C17—C18—H18B	108.2
C11—C12—H12A	108.6	C13—C18—H18B	108.2
C13—C12—H12A	108.6	H18A—C18—H18B	107.3
C11—C12—H12B	108.6	C22—C21—P	117.4 (4)
C13—C12—H12B	108.6	C22—C21—H21A	107.9
H12A—C12—H12B	107.6	P—C21—H21A	107.9
C14—C13—C18	110.0 (7)	C22—C21—H21B	107.9
C14—C13—C12	109.6 (6)	P—C21—H21B	107.9
C18—C13—C12	114.7 (6)	H21A—C21—H21B	107.2
C14—C13—H13	107.4	C24—C22—C21	111.5 (5)
C18—C13—H13	107.4	C24—C22—C23	110.5 (5)
C12—C13—H13	107.4	C21—C22—C23	110.1 (5)
C13—C14—C15	112.0 (5)	C24—C22—H22	108.2
C13—C14—H14A	109.2	C21—C22—H22	108.2
C15—C14—H14A	109.2	C23—C22—H22	108.2
C13—C14—H14B	109.2	C22—C23—H23A	109.5
C15—C14—H14B	109.2	C22—C23—H23B	109.5
H14A—C14—H14B	107.9	H23A—C23—H23B	109.5
C16—C15—C14	107.5 (5)	C22—C23—H23C	109.5
C16—C15—P	116.8 (4)	H23A—C23—H23C	109.5
C14—C15—P	106.0 (4)	H23B—C23—H23C	109.5
C16—C15—H15	108.7	C22—C24—H24A	109.5
C14—C15—H15	108.7	C22—C24—H24B	109.5
P—C15—H15	108.7	H24A—C24—H24B	109.5
C17—C16—C15	114.7 (6)	C22—C24—H24C	109.5
C17—C16—H16A	108.6	H24A—C24—H24C	109.5
C15—C16—H16A	108.6	H24B—C24—H24C	109.5
C15—P—C11—C12	−45.9 (6)	C11—P—C15—C14	50.9 (4)
C21—P—C11—C12	−162.9 (5)	Se—P—C15—C14	−70.7 (4)
Se—P—C11—C12	74.6 (5)	C14—C15—C16—C17	−54.2 (7)
P—C11—C12—C13	52.2 (8)	P—C15—C16—C17	64.7 (7)
C11—C12—C13—C14	−62.0 (8)	C15—C16—C17—C18	48.6 (9)
C11—C12—C13—C18	62.3 (8)	C16—C17—C18—C13	−45.1 (10)
C18—C13—C14—C15	−55.5 (8)	C14—C13—C18—C17	48.8 (9)
C12—C13—C14—C15	71.5 (8)	C12—C13—C18—C17	−75.3 (8)
C13—C14—C15—C16	58.2 (7)	C15—P—C21—C22	87.0 (5)
C13—C14—C15—P	−67.5 (6)	C11—P—C21—C22	−162.1 (4)
C21—P—C15—C16	41.8 (6)	Se—P—C21—C22	−39.8 (5)
C11—P—C15—C16	−68.9 (5)	P—C21—C22—C24	−69.3 (6)
Se—P—C15—C16	169.6 (4)	P—C21—C22—C23	167.7 (4)
C21—P—C15—C14	161.6 (4)

P	Se—P	1JSe—P
PMe3i	2.111 (3)	684
PCy3ii	2.108 (1)	676
VCH-iBuiii	2.1360 (16)	672,687
Phoban-Phiv	2.1090 (9)	689,717
PPhCy2v	2.1260 (8)	701
P(o-Tol)3vi	2.116 (5)	708
PPh2Cyv	2.111 (2)	725
PPh3vii	2.106 (1)	733
P(NMe2)3viii	2.120 (1)	797

Table 1

X-ray and spectroscopic data (Å, Hz) for selected phosphine selenides.

P	Se—P	1JSe—P
PMe3i	2.111 (3)	684
PCy3ii	2.108 (1)	676
VCH-iBuiii	2.1360 (16)	672, 687
Phoban-Phiv	2.1090 (9)	689, 717
PPhCy2v	2.1260 (8)	701
P(o-Tol)3vi	2.116 (5)	708
PPh2Cyv	2.111 (2)	725
PPh3vii	2.106 (1)	733
P(NMe2)3viii	2.120 (1)	797

Notes: (i) Cogne et al. (1980 ▶); (ii) Davies et al. (1991 ▶); (iii) this work; (iv) Bungu & Otto (2007b ▶); (v) Muller et al. (2008 ▶); (vi) Cameron & Dahlen (1975 ▶); (vii) Codding & Kerr (1979 ▶); (viii) Rømming & Songstad (1979 ▶).