(+)-(R)-(tert-Butyl­vinyl­phosphino­yl)benzene

The chiral title compound, C₁₂H₁₇OP, with potential uses in asymmetric induction in homogeneous catalysed reactions, shows an s-cis conformation for the C=C—P=O unit, in common with related materials.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.049
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    P1     -   O1      ..       5.94 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C6      ..       6.18 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    -   C14     ..       5.45 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C21    -   C22     ..       5.66 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C12 H17 O P

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.38
           From the CIF: _reflns_number_total               2179
           Count of symmetry unique reflns         1317
           Completeness (_total/calc)            165.45%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       862
           Fraction of Friedel pairs measured     0.655
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Anna Szmigielski carried out the synthesis of the title compound, prepared the crystallization and composed the comment. L. Ricken carried out all analytical data. M. Sch\"urmann measured the diffraction data and H. Preut did the final refinements, composed the manuscript and is contact author. M. Pietrusiewicz developed this chemistry and the starting materials. P. Eilbracht is the head of the catalysis group and together with Mr. Pietrusiewicz coordinates the cooperation.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO & SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2003).

(+)-(R)-(tert-Butylvinylphosphinoyl)benzene

Crystal data

C12H17OP	F(000) = 448
Mr = 208.23	Dx = 1.159 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9543 reflections
a = 6.0852 (4) Å	θ = 3.0–25.4°
b = 7.3750 (6) Å	µ = 0.20 mm^−1
c = 26.598 (2) Å	T = 291 K
V = 1193.67 (15) Å^3	Column, colourless
Z = 4	0.28 × 0.10 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer	1367 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 25.4°, θmin = 3.1°
Detector resolution: 19 vertical, 18 horizontal pixels mm^-1	h = −7→7
ω scans	k = −8→8
9543 measured reflections	l = −31→32
2179 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.049	w = 1/[σ^2(Fo^2)]
S = 0.82	(Δ/σ)max < 0.001
2179 reflections	Δρmax = 0.21 e Å^−3
130 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Absolute structure: Flack (1983), 862 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.10 (8)

Special details

Experimental. 403 frames via ω-rotation (Δω = 1°) and two times 80 s per frame (four sets at different κ-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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	−0.21240 (8)	−0.01471 (7)	−0.093663 (19)	0.04939 (16)
O1	0.02732 (17)	0.01059 (17)	−0.08598 (4)	0.0613 (4)
C1	−0.3090 (4)	0.1088 (2)	−0.14826 (8)	0.0477 (6)
C2	−0.5182 (4)	0.1824 (3)	−0.15283 (8)	0.0583 (6)
H2A	−0.6215	0.1634	−0.1276	0.070*
C3	−0.5737 (4)	0.2838 (3)	−0.19467 (9)	0.0701 (7)
H3A	−0.7135	0.3340	−0.1972	0.084*
C4	−0.4235 (5)	0.3108 (3)	−0.23257 (9)	0.0765 (7)
H4A	−0.4613	0.3793	−0.2606	0.092*
C5	−0.2188 (4)	0.2369 (3)	−0.22884 (9)	0.0762 (7)
H5A	−0.1180	0.2527	−0.2547	0.091*
C6	−0.1608 (3)	0.1382 (3)	−0.18657 (9)	0.0645 (7)
H6A	−0.0195	0.0911	−0.1840	0.077*
C11	−0.2866 (3)	−0.2520 (2)	−0.10271 (7)	0.0504 (5)
C12	−0.2141 (3)	−0.3561 (2)	−0.05535 (8)	0.0811 (7)
H12A	−0.2376	−0.4836	−0.0603	0.122*
H12B	−0.2984	−0.3155	−0.0270	0.122*
H12C	−0.0609	−0.3342	−0.0492	0.122*
C13	−0.5360 (3)	−0.2771 (2)	−0.11053 (8)	0.0691 (7)
H13A	−0.5688	−0.4039	−0.1137	0.104*
H13B	−0.5807	−0.2149	−0.1405	0.104*
H13C	−0.6137	−0.2282	−0.0822	0.104*
C14	−0.1623 (3)	−0.3259 (3)	−0.14825 (8)	0.0749 (7)
H14A	−0.1899	−0.4536	−0.1514	0.112*
H14B	−0.0076	−0.3059	−0.1438	0.112*
H14C	−0.2113	−0.2648	−0.1781	0.112*
C21	−0.3712 (3)	0.0638 (2)	−0.04198 (8)	0.0527 (6)
H21A	−0.5234	0.0701	−0.0447	0.063*
C22	−0.2745 (4)	0.1130 (2)	−0.00008 (8)	0.0698 (7)
H22B	−0.1223	0.1069	0.0027	0.084*
H22C	−0.3581	0.1540	0.0269	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0429 (3)	0.0540 (3)	0.0512 (3)	−0.0007 (3)	0.0022 (3)	−0.0027 (3)
O1	0.0392 (8)	0.0729 (9)	0.0719 (10)	−0.0050 (8)	−0.0029 (6)	−0.0033 (9)
C1	0.0497 (15)	0.0457 (12)	0.0477 (15)	−0.0068 (12)	0.0061 (12)	−0.0001 (10)
C2	0.0549 (17)	0.0599 (14)	0.0600 (17)	−0.0003 (13)	0.0024 (13)	0.0051 (13)
C3	0.0679 (18)	0.0657 (16)	0.0766 (19)	−0.0013 (15)	−0.0169 (17)	0.0103 (15)
C4	0.101 (2)	0.0690 (17)	0.0601 (19)	−0.0174 (18)	−0.0171 (19)	0.0109 (14)
C5	0.089 (2)	0.0836 (19)	0.0559 (17)	−0.0110 (17)	0.0135 (16)	0.0111 (14)
C6	0.0645 (19)	0.0681 (17)	0.0609 (17)	−0.0055 (12)	0.0062 (14)	0.0002 (14)
C11	0.0443 (12)	0.0501 (12)	0.0567 (14)	0.0017 (11)	−0.0008 (13)	−0.0006 (12)
C12	0.1008 (19)	0.0564 (14)	0.0861 (18)	0.0050 (15)	−0.0150 (16)	0.0108 (13)
C13	0.0540 (15)	0.0600 (14)	0.0934 (19)	−0.0100 (12)	0.0053 (13)	−0.0073 (13)
C14	0.0680 (18)	0.0686 (15)	0.0882 (19)	0.0051 (13)	0.0037 (13)	−0.0214 (13)
C21	0.0497 (13)	0.0582 (14)	0.0501 (15)	−0.0002 (10)	0.0019 (11)	−0.0026 (11)
C22	0.0717 (17)	0.0747 (16)	0.0631 (16)	−0.0051 (14)	0.0037 (16)	−0.0085 (12)

Geometric parameters (Å, º)

P1—O1	1.4847 (11)	C11—C12	1.540 (2)
P1—C21	1.7772 (19)	C11—C13	1.543 (2)
P1—C1	1.812 (2)	C12—H12A	0.9600
P1—C11	1.8232 (18)	C12—H12B	0.9600
C1—C6	1.378 (3)	C12—H12C	0.9600
C1—C2	1.389 (2)	C13—H13A	0.9600
C2—C3	1.383 (2)	C13—H13B	0.9600
C2—H2A	0.9300	C13—H13C	0.9600
C3—C4	1.376 (3)	C14—H14A	0.9600
C3—H3A	0.9300	C14—H14B	0.9600
C4—C5	1.363 (3)	C14—H14C	0.9600
C4—H4A	0.9300	C21—C22	1.311 (2)
C5—C6	1.385 (3)	C21—H21A	0.9300
C5—H5A	0.9300	C22—H22B	0.9300
C6—H6A	0.9300	C22—H22C	0.9300
C11—C14	1.529 (2)
O1—P1—C21	112.75 (9)	C14—C11—P1	108.93 (14)
O1—P1—C1	111.46 (9)	C12—C11—P1	107.43 (13)
C21—P1—C1	106.24 (9)	C13—C11—P1	112.13 (12)
O1—P1—C11	112.46 (9)	C11—C12—H12A	109.5
C21—P1—C11	106.27 (9)	C11—C12—H12B	109.5
C1—P1—C11	107.23 (9)	H12A—C12—H12B	109.5
C6—C1—C2	118.24 (19)	C11—C12—H12C	109.5
C6—C1—P1	117.35 (18)	H12A—C12—H12C	109.5
C2—C1—P1	124.33 (18)	H12B—C12—H12C	109.5
C3—C2—C1	120.4 (2)	C11—C13—H13A	109.5
C3—C2—H2A	119.8	C11—C13—H13B	109.5
C1—C2—H2A	119.8	H13A—C13—H13B	109.5
C4—C3—C2	120.4 (2)	C11—C13—H13C	109.5
C4—C3—H3A	119.8	H13A—C13—H13C	109.5
C2—C3—H3A	119.8	H13B—C13—H13C	109.5
C5—C4—C3	119.7 (2)	C11—C14—H14A	109.5
C5—C4—H4A	120.1	C11—C14—H14B	109.5
C3—C4—H4A	120.1	H14A—C14—H14B	109.5
C4—C5—C6	120.1 (2)	C11—C14—H14C	109.5
C4—C5—H5A	119.9	H14A—C14—H14C	109.5
C6—C5—H5A	119.9	H14B—C14—H14C	109.5
C1—C6—C5	121.1 (2)	C22—C21—P1	120.24 (17)
C1—C6—H6A	119.5	C22—C21—H21A	119.9
C5—C6—H6A	119.5	P1—C21—H21A	119.9
C14—C11—C12	109.18 (16)	C21—C22—H22B	120.0
C14—C11—C13	109.70 (17)	C21—C22—H22C	120.0
C12—C11—C13	109.41 (16)	H22B—C22—H22C	120.0
O1—P1—C1—C6	28.1 (2)	C4—C5—C6—C1	1.7 (3)
C21—P1—C1—C6	151.29 (16)	O1—P1—C11—C14	−58.53 (16)
C11—P1—C1—C6	−95.39 (17)	C21—P1—C11—C14	177.64 (14)
O1—P1—C1—C2	−148.71 (16)	C1—P1—C11—C14	64.34 (17)
C21—P1—C1—C2	−25.5 (2)	O1—P1—C11—C12	59.61 (16)
C11—P1—C1—C2	87.80 (19)	C21—P1—C11—C12	−64.22 (16)
C6—C1—C2—C3	−0.6 (3)	C1—P1—C11—C12	−177.52 (14)
P1—C1—C2—C3	176.19 (16)	O1—P1—C11—C13	179.86 (13)
C1—C2—C3—C4	0.9 (3)	C21—P1—C11—C13	56.03 (17)
C2—C3—C4—C5	0.1 (3)	C1—P1—C11—C13	−57.27 (17)
C3—C4—C5—C6	−1.4 (4)	O1—P1—C21—C22	−8.9 (2)
C2—C1—C6—C5	−0.7 (3)	C1—P1—C21—C22	−131.24 (17)
P1—C1—C6—C5	−177.69 (15)	C11—P1—C21—C22	114.78 (17)