(S)-2-[(2,4-Dichloro­phen­yl)(hy­droxy)meth­yl]-5,5-dimethyl-1,3,2-dioxa­phosphinane 2-oxide

Abstract

In the title mol­ecule, C₁₂H₁₅Cl₂O₄P, the cyclic dioxaphosphinane ring adopts a chair conformation. In the crystal, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into chains propagating along the b axis.

Related literature

For the synthesis and biological activity of hy­droxy­dioxa­phos­phinane derivatives, see: Peng et al. (2007 ▶); Liu et al. (2006 ▶). For the synthesis of chiral cyclic hy­droxy­dioxa­phos­phin­anes, see: Zhou et al. (2008 ▶).

Experimental

Crystal data

• C₁₂H₁₅Cl₂O₄P

• M _r = 325.11

• Monoclinic,

• a = 7.0263 (9) Å

• b = 9.9443 (13) Å

• c = 10.6462 (14) Å

• β = 93.975 (2)°

• V = 742.08 (17) ų

• Z = 2

• Mo Kα radiation

• μ = 0.55 mm⁻¹

• T = 298 K

• 0.16 × 0.12 × 0.10 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• 4069 measured reflections

• 2597 independent reflections

• 2478 reflections with I > 2σ(I)

• R _int = 0.067

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.105

• S = 1.01

• 2597 reflections

• 177 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1140 Friedel pairs

• Flack parameter: −0.15 (8)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4i	0.80 (5)	1.89 (5)	2.686 (3)	173 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The cyclic alpha-hydroxydioxaphosphinanes exhibit various biological activities (Peng et al., 2007; Liu et al., 2006). The title compound, (I), is a chiral cyclic hydroxydioxaphosphinane derivative. Herewith we present its crystal structure.

In (I) (Fig. 1), the cyclic dioxaphosphinane ring adopts a chair conformation. In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules into chains propagated along b axis (Fig. 2).

Experimental

The title compound was prepared according to the known procedure (Zhou et al., 2008). Diethylaluminum chloride (1 mmol) was added to a solution of (S,E)-2-(adamantan-1-yl)-4- (tert-butyl)-6(((1-hydroxy-3-methylbutan-2-yl)imino)methyl)phenol (1 mmol) in dichloromethane, The mixture was stirred at room temperature for 1 h. The aldehyde and cyclic phosphite was added and the mixture was stirred for another 2 h. The reaction was quenched by diluted hydrochloride acid. The pure title compound was afforded by column chromatography on silica gel (acetone/petroleum ether 1:2). Recrystallization from ethyl acetate over a period of one week gave colourless crystals of the title compound.

Refinement

C-bound H atoms were geometrically positioned (C—H 0.93–0.98 Å) and refined as riding, with U_iso(H) = 1.2-1.5 U_eq(C). O-bound H atom was located on a difference map and refined as riding (U_iso(H) = 1.5U_eq(O)) with O—H bond length restrained to 0.80 (4) Å.

Figures

Fig. 1.

Molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.

Fig. 2.

Part of the crystal packing, showing the intermolecular O—H···O hydrogen bonds as dashed lines.

Crystal data

C12H15Cl2O4P	F(000) = 336
Mr = 325.11	Dx = 1.455 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.0263 (9) Å	Cell parameters from 2185 reflections
b = 9.9443 (13) Å	θ = 2.8–28.1°
c = 10.6462 (14) Å	µ = 0.55 mm−1
β = 93.975 (2)°	T = 298 K
V = 742.08 (17) Å3	Block, colourless
Z = 2	0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2478 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
graphite	θmax = 25.5°, θmin = 1.9°
φ and ω scans	h = −8→8
4069 measured reflections	k = −11→12
2597 independent reflections	l = −12→11

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0604P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2597 reflections	Δρmax = 0.39 e Å−3
177 parameters	Δρmin = −0.25 e Å−3
1 restraint	Absolute structure: Flack (1983), 1140 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.15 (8)

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	1.0374 (4)	0.6151 (3)	0.2326 (3)	0.0326 (6)
C2	1.2166 (4)	0.6199 (3)	0.2946 (3)	0.0353 (6)
C3	1.2552 (5)	0.6911 (4)	0.4050 (3)	0.0426 (7)
H3	1.3771	0.6916	0.4451	0.051*
C4	1.1093 (5)	0.7608 (3)	0.4537 (3)	0.0432 (8)
C5	0.9289 (5)	0.7620 (4)	0.3937 (3)	0.0454 (8)
H5	0.8316	0.8117	0.4264	0.054*
C6	0.8951 (4)	0.6891 (3)	0.2856 (3)	0.0395 (7)
H6	0.7728	0.6890	0.2461	0.047*
C8	0.9910 (4)	0.5319 (3)	0.1163 (3)	0.0330 (6)
H8	1.0894	0.4627	0.1112	0.040*
C9	0.7747 (5)	0.4722 (4)	−0.1830 (3)	0.0461 (8)
H9A	0.7300	0.4104	−0.1209	0.055*
H9B	0.7880	0.4222	−0.2601	0.055*
C10	0.6092 (4)	0.6611 (4)	−0.0866 (3)	0.0439 (8)
H10A	0.5200	0.7344	−0.1037	0.053*
H10B	0.5575	0.6030	−0.0242	0.053*
C11	0.6301 (5)	0.5816 (4)	−0.2073 (3)	0.0456 (8)
C12	0.4368 (6)	0.5156 (6)	−0.2449 (5)	0.0766 (14)
H12A	0.4470	0.4632	−0.3199	0.115*
H12B	0.3418	0.5841	−0.2605	0.115*
H12C	0.4008	0.4583	−0.1780	0.115*
C13	0.6874 (6)	0.6734 (5)	−0.3136 (3)	0.0617 (11)
H13A	0.8071	0.7157	−0.2893	0.093*
H13B	0.5913	0.7411	−0.3297	0.093*
H13C	0.6996	0.6211	−0.3884	0.093*
Cl1	1.40915 (11)	0.53739 (10)	0.23277 (9)	0.0563 (3)
Cl2	1.15586 (17)	0.85446 (12)	0.59048 (10)	0.0703 (3)
O1	0.8112 (3)	0.4671 (2)	0.1240 (2)	0.0404 (5)
H1	0.818 (6)	0.390 (5)	0.102 (4)	0.061*
O2	0.9609 (3)	0.5257 (2)	−0.1376 (2)	0.0425 (5)
O3	0.7922 (3)	0.7156 (2)	−0.0361 (2)	0.0390 (5)
O4	1.1503 (3)	0.7162 (2)	−0.0359 (2)	0.0450 (6)
P1	0.98124 (10)	0.63058 (8)	−0.02830 (7)	0.0317 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0314 (14)	0.0335 (17)	0.0328 (14)	−0.0005 (13)	0.0022 (11)	0.0054 (13)
C2	0.0315 (14)	0.0363 (16)	0.0380 (15)	0.0030 (14)	0.0008 (11)	0.0036 (14)
C3	0.0403 (18)	0.0474 (18)	0.0386 (17)	−0.0026 (15)	−0.0067 (13)	0.0031 (15)
C4	0.055 (2)	0.0433 (19)	0.0312 (16)	−0.0031 (16)	0.0021 (14)	−0.0047 (14)
C5	0.0400 (19)	0.051 (2)	0.0456 (19)	0.0057 (16)	0.0073 (15)	−0.0045 (16)
C6	0.0305 (16)	0.0443 (18)	0.0433 (18)	0.0024 (14)	−0.0014 (13)	−0.0034 (15)
C8	0.0277 (13)	0.0318 (15)	0.0397 (16)	0.0010 (13)	0.0031 (12)	0.0010 (13)
C9	0.0453 (18)	0.0470 (19)	0.0452 (19)	−0.0084 (16)	−0.0034 (14)	−0.0094 (16)
C10	0.0304 (15)	0.055 (2)	0.0464 (18)	0.0036 (14)	0.0009 (13)	−0.0034 (16)
C11	0.0402 (18)	0.056 (2)	0.0404 (17)	−0.0018 (16)	−0.0029 (13)	−0.0051 (16)
C12	0.048 (2)	0.099 (4)	0.080 (3)	−0.014 (3)	−0.0139 (19)	−0.019 (3)
C13	0.071 (3)	0.073 (3)	0.040 (2)	−0.001 (2)	−0.0067 (17)	0.0043 (18)
Cl1	0.0313 (4)	0.0680 (6)	0.0690 (6)	0.0119 (4)	−0.0002 (4)	−0.0118 (5)
Cl2	0.0797 (7)	0.0820 (7)	0.0480 (5)	−0.0019 (6)	−0.0050 (5)	−0.0268 (5)
O1	0.0354 (12)	0.0373 (12)	0.0489 (13)	−0.0063 (10)	0.0063 (9)	−0.0050 (11)
O2	0.0359 (11)	0.0502 (14)	0.0411 (12)	0.0067 (11)	0.0015 (9)	−0.0107 (11)
O3	0.0330 (12)	0.0408 (13)	0.0425 (12)	0.0059 (9)	−0.0020 (9)	−0.0058 (10)
O4	0.0364 (12)	0.0445 (13)	0.0544 (14)	−0.0067 (10)	0.0055 (10)	0.0060 (11)
P1	0.0292 (4)	0.0331 (4)	0.0327 (4)	0.0000 (3)	0.0020 (3)	−0.0015 (3)

Geometric parameters (Å, °)

C1—C2	1.381 (4)	C9—H9B	0.9700
C1—C6	1.393 (4)	C10—O3	1.463 (4)
C1—C8	1.506 (4)	C10—C11	1.524 (5)
C2—C3	1.382 (5)	C10—H10A	0.9700
C2—Cl1	1.750 (3)	C10—H10B	0.9700
C3—C4	1.369 (5)	C11—C13	1.530 (5)
C3—H3	0.9300	C11—C12	1.536 (5)
C4—C5	1.379 (5)	C12—H12A	0.9600
C4—Cl2	1.741 (3)	C12—H12B	0.9600
C5—C6	1.366 (5)	C12—H12C	0.9600
C5—H5	0.9300	C13—H13A	0.9600
C6—H6	0.9300	C13—H13B	0.9600
C8—O1	1.425 (3)	C13—H13C	0.9600
C8—P1	1.822 (3)	O1—H1	0.80 (5)
C8—H8	0.9800	O2—P1	1.561 (2)
C9—O2	1.463 (4)	O3—P1	1.572 (2)
C9—C11	1.499 (5)	O4—P1	1.468 (2)
C9—H9A	0.9700
C2—C1—C6	116.4 (3)	C11—C10—H10A	109.3
C2—C1—C8	123.4 (3)	O3—C10—H10B	109.3
C6—C1—C8	120.2 (2)	C11—C10—H10B	109.3
C1—C2—C3	122.9 (3)	H10A—C10—H10B	108.0
C1—C2—Cl1	120.4 (2)	C9—C11—C10	109.6 (3)
C3—C2—Cl1	116.7 (2)	C9—C11—C13	110.6 (3)
C4—C3—C2	118.2 (3)	C10—C11—C13	111.1 (3)
C4—C3—H3	120.9	C9—C11—C12	108.1 (3)
C2—C3—H3	120.9	C10—C11—C12	107.8 (3)
C3—C4—C5	121.2 (3)	C13—C11—C12	109.6 (3)
C3—C4—Cl2	119.0 (3)	C11—C12—H12A	109.5
C5—C4—Cl2	119.8 (3)	C11—C12—H12B	109.5
C6—C5—C4	119.1 (3)	H12A—C12—H12B	109.5
C6—C5—H5	120.5	C11—C12—H12C	109.5
C4—C5—H5	120.5	H12A—C12—H12C	109.5
C5—C6—C1	122.3 (3)	H12B—C12—H12C	109.5
C5—C6—H6	118.9	C11—C13—H13A	109.5
C1—C6—H6	118.9	C11—C13—H13B	109.5
O1—C8—C1	110.1 (2)	H13A—C13—H13B	109.5
O1—C8—P1	108.08 (19)	C11—C13—H13C	109.5
C1—C8—P1	113.1 (2)	H13A—C13—H13C	109.5
O1—C8—H8	108.5	H13B—C13—H13C	109.5
C1—C8—H8	108.5	C8—O1—H1	110 (3)
P1—C8—H8	108.5	C9—O2—P1	121.52 (19)
O2—C9—C11	111.9 (3)	C10—O3—P1	122.6 (2)
O2—C9—H9A	109.2	O4—P1—O2	112.27 (14)
C11—C9—H9A	109.2	O4—P1—O3	111.68 (14)
O2—C9—H9B	109.2	O2—P1—O3	106.63 (12)
C11—C9—H9B	109.2	O4—P1—C8	112.04 (13)
H9A—C9—H9B	107.9	O2—P1—C8	105.43 (14)
O3—C10—C11	111.6 (2)	O3—P1—C8	108.43 (13)
O3—C10—H10A	109.3
C6—C1—C2—C3	1.5 (5)	O2—C9—C11—C12	−175.9 (3)
C8—C1—C2—C3	−176.6 (3)	O3—C10—C11—C9	56.3 (4)
C6—C1—C2—Cl1	−177.0 (2)	O3—C10—C11—C13	−66.1 (4)
C8—C1—C2—Cl1	5.0 (4)	O3—C10—C11—C12	173.8 (3)
C1—C2—C3—C4	−0.7 (5)	C11—C9—O2—P1	48.4 (4)
Cl1—C2—C3—C4	177.8 (3)	C11—C10—O3—P1	−44.1 (4)
C2—C3—C4—C5	−1.0 (5)	C9—O2—P1—O4	−153.1 (3)
C2—C3—C4—Cl2	−178.4 (2)	C9—O2—P1—O3	−30.4 (3)
C3—C4—C5—C6	1.8 (5)	C9—O2—P1—C8	84.7 (3)
Cl2—C4—C5—C6	179.3 (3)	C10—O3—P1—O4	151.7 (2)
C4—C5—C6—C1	−1.0 (5)	C10—O3—P1—O2	28.8 (3)
C2—C1—C6—C5	−0.6 (5)	C10—O3—P1—C8	−84.3 (3)
C8—C1—C6—C5	177.5 (3)	O1—C8—P1—O4	171.92 (19)
C2—C1—C8—O1	137.8 (3)	C1—C8—P1—O4	49.8 (2)
C6—C1—C8—O1	−40.1 (4)	O1—C8—P1—O2	−65.7 (2)
C2—C1—C8—P1	−101.1 (3)	C1—C8—P1—O2	172.18 (19)
C6—C1—C8—P1	80.9 (3)	O1—C8—P1—O3	48.2 (2)
O2—C9—C11—C10	−58.6 (4)	C1—C8—P1—O3	−73.9 (2)
O2—C9—C11—C13	64.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4i	0.80 (5)	1.89 (5)	2.686 (3)	173 (4)

Symmetry codes: (i) −x+2, y−1/2, −z.