(Z)-(1,2-Dichloro-vin-yl)diphenyl-phosphine oxide.

The title compound, C(14)H(11)Cl(2)OP, was synthesized by the reaction of diphenyl-phosphine oxide with 1,2-dichloro-ethyne under CuI catalysis. The reaction provided the Z isomer regioselectively. Two O-P-C bond angles [114.3 (1) and 112.5 (1)°] are significantly larger than the C-P-C [107.7 (1), 105.6 (1) and 106.6 (1)°] and another O-P-C angle [109.5 (1)°], indicating significant distortion of the tetra-hedral configuration of the P atom. In the crystal, mol-ecules are linked by weak inter-molecular C-H⋯O hydrogen bonds into centrosymmetric dimers, which are connected by further C-H⋯O inter-actions into chains along [101].

Related literature

For the anti­microbial, insecticidal and anti-inflammatory activity of alkenylphosphine oxides, see: Haynes et al. (1989 ▶, 1991 ▶); Shi et al. (2000 ▶); Taylor et al. (2006 ▶); Rahman et al. (2000 ▶). For their use as inter­mediates in the preparation of some palladium catalysts, see: Inoue et al. (2002 ▶). Nucleophiles, such as amines (Rahman et al., 2000 ▶, 2004 ▶), phosphines (Barbaro et al., 2002 ▶; Alajarin et al., 2004 ▶; Han & Zhao, 2005 ▶) and carbanion species readily add to the olefinic bond in alkenylphosphine oxides to give useful bifunctional adducts.

Experimental

Crystal data

C14H11Cl2OP

M = 297.10

Monoclinic,

a = 12.0621 (11) Å

b = 7.9521 (8) Å

c = 14.9913 (15) Å

β = 102.858 (1)°

V = 1401.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.56 mm−1

T = 298 K

0.45 × 0.40 × 0.32 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.786, T max = 0.841

6788 measured reflections

2475 independent reflections

2009 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.094

S = 1.08

2475 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030765/ld2021sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030765/ld2021Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811030765/ld2021Isup3.cml

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

C14H11Cl2OP	F(000) = 608
Mr = 297.10	Dx = 1.408 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.0621 (11) Å	Cell parameters from 3636 reflections
b = 7.9521 (8) Å	θ = 2.5–28.0°
c = 14.9913 (15) Å	µ = 0.56 mm−1
β = 102.858 (1)°	T = 298 K
V = 1401.9 (2) Å3	Prism, colourless
Z = 4	0.45 × 0.40 × 0.32 mm

Bruker APEXII CCD area-detector diffractometer	2475 independent reflections
Radiation source: fine-focus sealed tube	2009 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −14→11
Tmin = 0.786, Tmax = 0.841	k = −9→9
6788 measured reflections	l = −12→17

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0395P)2 + 0.729P] where P = (Fo2 + 2Fc2)/3
2475 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.64091 (5)	0.30633 (8)	0.48897 (6)	0.0610 (2)
Cl2	0.87750 (6)	0.09961 (8)	0.52709 (5)	0.0558 (2)
O1	0.90014 (13)	0.6840 (2)	0.53670 (11)	0.0441 (4)
P1	0.77986 (4)	0.62950 (7)	0.51027 (4)	0.03243 (16)
C1	0.77287 (18)	0.4017 (3)	0.51179 (15)	0.0340 (5)
C2	0.8685 (2)	0.3151 (3)	0.52622 (15)	0.0386 (5)
H2	0.9363	0.3754	0.5367	0.046*
C5	0.71157 (19)	0.6946 (3)	0.39607 (15)	0.0358 (5)
C6	0.7790 (2)	0.7721 (3)	0.34425 (18)	0.0528 (7)
H6	0.8557	0.7909	0.3694	0.063*
C7	0.7327 (3)	0.8213 (4)	0.2555 (2)	0.0726 (9)
H7	0.7782	0.8733	0.2211	0.087*
C8	0.6190 (3)	0.7938 (4)	0.2178 (2)	0.0693 (9)
H8	0.5883	0.8266	0.1579	0.083*
C9	0.5516 (2)	0.7187 (4)	0.26807 (19)	0.0580 (7)
H9	0.4749	0.7011	0.2422	0.070*
C10	0.5964 (2)	0.6681 (3)	0.35770 (17)	0.0462 (6)
H10	0.5500	0.6171	0.3918	0.055*
C11	0.69328 (18)	0.7001 (3)	0.58622 (15)	0.0357 (5)
C12	0.6898 (3)	0.6104 (3)	0.66513 (18)	0.0570 (7)
H12	0.7270	0.5076	0.6761	0.068*
C13	0.6313 (3)	0.6733 (4)	0.7274 (2)	0.0720 (9)
H13	0.6287	0.6122	0.7798	0.086*
C14	0.5770 (3)	0.8255 (4)	0.7119 (2)	0.0646 (8)
H14	0.5375	0.8672	0.7538	0.078*
C15	0.5807 (2)	0.9163 (4)	0.6352 (2)	0.0574 (7)
H15	0.5446	1.0202	0.6255	0.069*
C16	0.6382 (2)	0.8539 (3)	0.57215 (17)	0.0450 (6)
H16	0.6399	0.9157	0.5198	0.054*

	U11	U22	U33	U12	U13	U23
Cl1	0.0402 (4)	0.0432 (4)	0.0962 (6)	−0.0081 (3)	0.0078 (3)	0.0024 (3)
Cl2	0.0635 (4)	0.0370 (3)	0.0740 (5)	0.0102 (3)	0.0305 (4)	0.0031 (3)
O1	0.0339 (8)	0.0455 (9)	0.0512 (10)	−0.0043 (7)	0.0057 (7)	−0.0002 (8)
P1	0.0304 (3)	0.0327 (3)	0.0339 (3)	−0.0002 (2)	0.0064 (2)	0.0015 (2)
C1	0.0356 (12)	0.0325 (11)	0.0348 (12)	−0.0024 (9)	0.0100 (9)	−0.0005 (9)
C2	0.0436 (13)	0.0330 (12)	0.0430 (14)	0.0015 (10)	0.0181 (11)	0.0019 (10)
C5	0.0396 (12)	0.0333 (11)	0.0351 (12)	0.0037 (9)	0.0095 (10)	0.0002 (9)
C6	0.0531 (15)	0.0594 (16)	0.0476 (15)	−0.0026 (13)	0.0152 (12)	0.0103 (13)
C7	0.088 (2)	0.086 (2)	0.0489 (18)	0.0013 (18)	0.0252 (16)	0.0236 (16)
C8	0.088 (2)	0.078 (2)	0.0381 (16)	0.0183 (18)	0.0070 (16)	0.0105 (15)
C9	0.0536 (16)	0.0668 (18)	0.0458 (16)	0.0115 (14)	−0.0053 (13)	−0.0015 (14)
C10	0.0438 (14)	0.0517 (14)	0.0422 (14)	0.0045 (11)	0.0078 (11)	0.0023 (12)
C11	0.0358 (12)	0.0386 (12)	0.0313 (12)	−0.0010 (9)	0.0046 (9)	−0.0027 (10)
C12	0.0811 (19)	0.0525 (15)	0.0396 (14)	0.0128 (14)	0.0181 (13)	0.0058 (12)
C13	0.104 (3)	0.078 (2)	0.0404 (16)	−0.0032 (19)	0.0308 (17)	−0.0010 (15)
C14	0.0630 (18)	0.082 (2)	0.0546 (18)	−0.0031 (16)	0.0253 (14)	−0.0256 (16)
C15	0.0553 (16)	0.0576 (16)	0.0591 (18)	0.0106 (13)	0.0122 (14)	−0.0158 (14)
C16	0.0478 (14)	0.0424 (13)	0.0443 (14)	0.0025 (11)	0.0089 (11)	−0.0008 (11)

Cl1—C1	1.727 (2)	C8—H8	0.9300
Cl2—C2	1.717 (2)	C9—C10	1.391 (4)
O1—P1	1.4813 (16)	C9—H9	0.9300
P1—C11	1.798 (2)	C10—H10	0.9300
P1—C5	1.803 (2)	C11—C16	1.385 (3)
P1—C1	1.814 (2)	C11—C12	1.390 (3)
C1—C2	1.319 (3)	C12—C13	1.382 (4)
C2—H2	0.9300	C12—H12	0.9300
C5—C6	1.388 (3)	C13—C14	1.371 (5)
C5—C10	1.397 (3)	C13—H13	0.9300
C6—C7	1.380 (4)	C14—C15	1.366 (4)
C6—H6	0.9300	C14—H14	0.9300
C7—C8	1.379 (5)	C15—C16	1.384 (4)
C7—H7	0.9300	C15—H15	0.9300
C8—C9	1.364 (4)	C16—H16	0.9300
O1—P1—C11	114.31 (10)	C8—C9—C10	120.6 (3)
O1—P1—C5	112.55 (10)	C8—C9—H9	119.7
C11—P1—C5	107.75 (10)	C10—C9—H9	119.7
O1—P1—C1	109.54 (10)	C9—C10—C5	119.4 (2)
C11—P1—C1	105.58 (10)	C9—C10—H10	120.3
C5—P1—C1	106.62 (10)	C5—C10—H10	120.3
C2—C1—Cl1	122.49 (18)	C16—C11—C12	118.6 (2)
C2—C1—P1	118.80 (17)	C16—C11—P1	120.36 (18)
Cl1—C1—P1	118.64 (12)	C12—C11—P1	120.72 (18)
C1—C2—Cl2	124.99 (19)	C13—C12—C11	120.4 (3)
C1—C2—H2	117.5	C13—C12—H12	119.8
Cl2—C2—H2	117.5	C11—C12—H12	119.8
C6—C5—C10	119.3 (2)	C14—C13—C12	120.1 (3)
C6—C5—P1	117.27 (18)	C14—C13—H13	120.0
C10—C5—P1	123.39 (18)	C12—C13—H13	120.0
C7—C6—C5	120.2 (3)	C15—C14—C13	120.4 (3)
C7—C6—H6	119.9	C15—C14—H14	119.8
C5—C6—H6	119.9	C13—C14—H14	119.8
C8—C7—C6	120.2 (3)	C14—C15—C16	120.0 (3)
C8—C7—H7	119.9	C14—C15—H15	120.0
C6—C7—H7	119.9	C16—C15—H15	120.0
C9—C8—C7	120.2 (3)	C15—C16—C11	120.6 (2)
C9—C8—H8	119.9	C15—C16—H16	119.7
C7—C8—H8	119.9	C11—C16—H16	119.7
O1—P1—C1—C2	−6.2 (2)	C7—C8—C9—C10	−0.3 (5)
C11—P1—C1—C2	−129.75 (19)	C8—C9—C10—C5	−0.1 (4)
C5—P1—C1—C2	115.8 (2)	C6—C5—C10—C9	0.5 (4)
O1—P1—C1—Cl1	176.78 (12)	P1—C5—C10—C9	−178.29 (19)
C11—P1—C1—Cl1	53.24 (16)	O1—P1—C11—C16	88.7 (2)
C5—P1—C1—Cl1	−61.18 (16)	C5—P1—C11—C16	−37.2 (2)
Cl1—C1—C2—Cl2	−1.4 (3)	C1—P1—C11—C16	−150.85 (19)
P1—C1—C2—Cl2	−178.31 (13)	O1—P1—C11—C12	−84.5 (2)
O1—P1—C5—C6	5.5 (2)	C5—P1—C11—C12	149.6 (2)
C11—P1—C5—C6	132.48 (19)	C1—P1—C11—C12	35.9 (2)
C1—P1—C5—C6	−114.6 (2)	C16—C11—C12—C13	0.8 (4)
O1—P1—C5—C10	−175.63 (18)	P1—C11—C12—C13	174.1 (2)
C11—P1—C5—C10	−48.7 (2)	C11—C12—C13—C14	−0.6 (5)
C1—P1—C5—C10	64.3 (2)	C12—C13—C14—C15	−0.2 (5)
C10—C5—C6—C7	−0.4 (4)	C13—C14—C15—C16	0.8 (5)
P1—C5—C6—C7	178.4 (2)	C14—C15—C16—C11	−0.6 (4)
C5—C6—C7—C8	0.0 (5)	C12—C11—C16—C15	−0.2 (4)
C6—C7—C8—C9	0.4 (5)	P1—C11—C16—C15	−173.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.51	3.138 (3)	125.
C8—H8···O1ii	0.93	2.57	3.344 (4)	141.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.51	3.138 (3)	125
C8—H8⋯O1ii	0.93	2.57	3.344 (4)	141

Symmetry codes: (i) ; (ii) .