3-(2-Chloro­phen­oxy)-1,5-dihydr­oxy-2,4,3-benzodioxaphosphepine 3-oxide

In the title compound, C₁₄H₁₂ClO₄P, the seven-membered phosphepine ring exhibits a twist-chair conformation, with the phosphoryl O atom occupying an axial and the chloro­phen­oxy group an equatorial position. The P=O distance is 1.449 (2) Å and the average length of the three P-O bonds is 1.574 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.051
• wR factor = 0.115
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

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Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

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

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

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S1. Comment

Organophosphorus compounds are ubiquitous in nature and they have unique multifaceted applications as insecticides (Fest & Schmidt, 1982), anticancer agents (Papanastassiou & Bardos, 1962) and lubricating oil additives and polymer stabilizers (Spivack, 1982). Benzoannulated and related analogs (Ludeman & Zon, 1975) of cyclophosphamide posses antitumor activity against lymphoid leukemia in mice. The title compound, (I), which has both antifungal and antibacterial activity, promoted us to undertake the present crystal structure determination to examine the influence of the substituents on the conformation of the heterocyclic ring.

In the dioxaphosphepin ring system of (I), the corresponding bond lengths and angles (Table 1) of the two P—O—CH₂—C fragments are equal within experimental error. The endocyclic O—P—O and P—O—C bond angles [108.4 (4) and 123.2 (2)°] are in good agreement with the values of the corresponding seven-membered-ring structures [Selladurai & Subramanian, 1991; Sivakumar et al., 1989; Grand & Robert, 1978]. As a result of the presence of the C10═C11 double bond, considerable differences in the C—O and P—O distances are observed in the dioxaphosphepine ring. The average values for the C—O [1.461 (4) Å] and P—O [1.555 (2) Å] bond distances are similar to the values observed in the structures reported by Grand & Robert (1978).

The C14—Cl bond length of 1.732 (2) Å and its associated endocyclic C13—C14—C15 angle of 120.3 (3)° agree well with values of P–sustituted chlorobenzene (Domenicano et al., 1975: Sivakumar et al., 1989), but are slightly different from the corresponding values of 1.68 (3) Å and 118.2 (3)° in dithiaphosphepine (Reddy et al., 1985). The torsion angles (Table 1) indicate that the heterocyclic ring exhibits a twist-chair conformation with the C1/O2/O4/C5 atoms nearly coplanar, and the C10/C11 and P3 atoms puckered in opposite directions in a conformation similar to that observed in tetramethylene phosphoric acid (Coulter, 1975). However, this conformation is different from those generally found in the distorted-boat, twist-boat, and boat forms of the dioxaphosphepine ring (Krishnaiah et al., 2005; Selladurai & Subramanian, 1991; Sivakumar et al., 1989), which have bulky substituents to the heterocyclic ring. The presence of the fused benzene ring, which forms a dihedral angle of 25.8 (1)° with the heterocyclic ring, might account for the different geometry exhibited by the seven-membered ring. The planar chlorophenyl group is oriented at 56.9 (1)° to the heterocyclic ring, keeping the Cl atom away from the phosphoryl O atom.

S2. Experimental

A solution of 2-chlorophenylphosphorodichloridate (0.48 g, 2 mmol) in dry tetrahydrofuran (20 ml) was added dropwise over a period of 20 minutes at 273 K to a stirred solution of 1,2-benzenedimethanol (0.27 g, 2 mmol) and triethylamine (0.404 g, 4 mmol) in dry tetrahydrofuran (30 ml). After completion of the addition, the temperature was slowly raised to room temperature and the reaction mixture stirred for 4 h. The progress of the reaction was monitored by TLC analysis (ethyl acetate-hexane 1:2). The precipitated triethylamine hydrochloride was filtered and the filtrate evaporated under vacuum. The residue obtained was washed with water and recrystallized from ethanol to afford 0.38 g (62%) of pure title compound.

S3. Refinement

All the H-atoms were clearly identified from difference Fourier syntheses and refined isotropically.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEPII (Zsolnai, 1997); software used to prepare material for publication: enCIFer (CCDC, 2003) and PARST (Nardelli, 1995)'.

Figures

Fig. 1. View of the molecule, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radius.

3-(2-Chlorophenoxy)-1,5-dihydroxy-2,4,3-benzodioxaphosphepine 3-oxide

Crystal data

C14H12ClO4P	F(000) = 640
Mr = 310.66	Dx = 1.508 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 989 reflections
a = 13.585 (2) Å	θ = 2.9–25.0°
b = 8.719 (1) Å	µ = 0.41 mm^−1
c = 13.106 (2) Å	T = 293 K
β = 118.15 (2)°	Prism, yellow
V = 1368.8 (4) Å^3	0.25 × 0.25 × 0.13 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	2410 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→15
Tmin = 0.906, Tmax = 0.949	k = −7→10
6682 measured reflections	l = −15→15

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)] = 0.051	All H-atom parameters refined
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.766P] where P = (Fo^2 + 2Fc^2)/3
S = 1.31	(Δ/σ)max < 0.001
2410 reflections	Δρmax = 0.18 e Å^−3
229 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (3)

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
H1A	0.237 (2)	0.954 (4)	0.295 (2)	0.039 (8)*
H1B	0.215 (2)	0.787 (3)	0.316 (2)	0.046 (8)*
H5B	0.358 (3)	1.115 (4)	0.249 (3)	0.049 (9)*
H8	0.569 (3)	0.637 (4)	0.564 (3)	0.059 (9)*
H9	0.378 (3)	0.669 (4)	0.457 (3)	0.048 (9)*
H5A	0.461 (3)	1.095 (4)	0.229 (3)	0.052 (9)*
H15	0.144 (2)	1.569 (4)	0.051 (3)	0.048 (8)*
H7	0.689 (3)	0.796 (4)	0.529 (3)	0.054 (9)*
H16	0.058 (3)	1.555 (4)	−0.149 (3)	0.053 (9)*
H18	0.051 (3)	1.102 (4)	−0.129 (3)	0.055 (9)*
H6	0.612 (3)	0.969 (4)	0.379 (3)	0.065 (10)*
H17	0.015 (3)	1.318 (4)	−0.237 (3)	0.073 (11)*
P3	0.21146 (7)	0.92684 (8)	0.07582 (6)	0.0432 (2)
Cl	0.21078 (8)	1.35784 (10)	0.22422 (7)	0.0650 (3)
O12	0.14626 (16)	1.0709 (2)	0.08935 (17)	0.0447 (5)
O2	0.20807 (16)	0.8156 (2)	0.16665 (17)	0.0471 (5)
O4	0.33469 (16)	0.9805 (2)	0.12017 (17)	0.0471 (5)
C13	0.1226 (2)	1.2029 (3)	0.0212 (2)	0.0382 (6)
O20	0.1661 (2)	0.8606 (3)	−0.03888 (19)	0.0613 (6)
C5	0.4028 (3)	1.0453 (4)	0.2353 (3)	0.0478 (7)
C1	0.2547 (3)	0.8535 (4)	0.2893 (3)	0.0458 (7)
C11	0.4492 (2)	0.9258 (3)	0.3284 (2)	0.0402 (6)
C10	0.3784 (2)	0.8348 (3)	0.3531 (2)	0.0401 (6)
C14	0.1490 (2)	1.3442 (3)	0.0749 (2)	0.0392 (6)
C15	0.1252 (2)	1.4764 (3)	0.0101 (3)	0.0461 (7)
C18	0.0690 (3)	1.1948 (4)	−0.0978 (3)	0.0492 (8)
C16	0.0729 (3)	1.4671 (4)	−0.1083 (3)	0.0487 (8)
C6	0.5637 (3)	0.9089 (4)	0.3941 (3)	0.0493 (7)
C8	0.5391 (3)	0.7124 (4)	0.5055 (3)	0.0565 (9)
C17	0.0440 (3)	1.3279 (4)	−0.1623 (3)	0.0524 (8)
C7	0.6085 (3)	0.8036 (4)	0.4829 (3)	0.0543 (8)
C9	0.4248 (3)	0.7268 (4)	0.4411 (3)	0.0499 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P3	0.0513 (5)	0.0339 (4)	0.0411 (4)	0.0032 (3)	0.0190 (4)	0.0012 (3)
Cl	0.0814 (6)	0.0606 (5)	0.0402 (4)	0.0181 (4)	0.0180 (4)	−0.0057 (4)
O12	0.0512 (12)	0.0374 (11)	0.0448 (11)	0.0059 (9)	0.0221 (10)	0.0077 (9)
O2	0.0485 (12)	0.0364 (11)	0.0491 (12)	−0.0017 (9)	0.0172 (10)	0.0037 (9)
O4	0.0522 (12)	0.0467 (12)	0.0469 (12)	0.0023 (10)	0.0272 (10)	0.0058 (9)
C13	0.0341 (14)	0.0374 (15)	0.0401 (15)	0.0042 (12)	0.0150 (12)	0.0055 (12)
O20	0.0762 (16)	0.0505 (13)	0.0472 (13)	0.0079 (11)	0.0209 (12)	−0.0036 (10)
C5	0.0446 (18)	0.0414 (17)	0.056 (2)	−0.0021 (14)	0.0225 (16)	0.0040 (14)
C1	0.0480 (18)	0.0446 (18)	0.0490 (18)	0.0013 (15)	0.0263 (15)	0.0066 (14)
C11	0.0438 (16)	0.0343 (15)	0.0423 (16)	0.0023 (12)	0.0200 (13)	−0.0033 (12)
C10	0.0479 (16)	0.0352 (14)	0.0398 (15)	0.0042 (13)	0.0229 (13)	−0.0013 (12)
C14	0.0357 (14)	0.0394 (15)	0.0399 (15)	0.0051 (12)	0.0156 (12)	−0.0010 (12)
C15	0.0447 (17)	0.0339 (16)	0.059 (2)	0.0014 (13)	0.0240 (15)	−0.0036 (14)
C18	0.0503 (18)	0.0426 (18)	0.0434 (17)	−0.0018 (14)	0.0128 (14)	−0.0012 (14)
C16	0.0493 (18)	0.0433 (17)	0.0520 (19)	0.0093 (14)	0.0226 (15)	0.0146 (15)
C6	0.0457 (18)	0.0454 (17)	0.0553 (19)	0.0004 (15)	0.0226 (15)	−0.0045 (15)
C8	0.065 (2)	0.0465 (19)	0.0435 (18)	0.0142 (17)	0.0136 (17)	0.0053 (15)
C17	0.056 (2)	0.054 (2)	0.0373 (17)	0.0047 (16)	0.0141 (15)	0.0068 (15)
C7	0.0473 (19)	0.052 (2)	0.0502 (19)	0.0094 (16)	0.0123 (16)	−0.0071 (15)
C9	0.060 (2)	0.0443 (18)	0.0452 (18)	0.0018 (16)	0.0248 (16)	0.0043 (14)

Geometric parameters (Å, º)

P3—O20	1.449 (2)	C11—C10	1.397 (4)
P3—O2	1.553 (2)	C10—C9	1.389 (4)
P3—O4	1.562 (2)	C14—C15	1.377 (4)
P3—O12	1.594 (2)	C15—C16	1.371 (4)
Cl—C14	1.732 (3)	C15—H15	0.93 (3)
O12—C13	1.398 (3)	C18—C17	1.380 (4)
O2—C1	1.461 (4)	C18—H18	0.89 (3)
O4—C5	1.461 (4)	C16—C17	1.366 (5)
C13—C18	1.377 (4)	C16—H16	0.90 (3)
C13—C14	1.380 (4)	C6—C7	1.379 (5)
C5—C11	1.499 (4)	C6—H6	0.93 (4)
C5—H5B	0.93 (3)	C8—C7	1.368 (5)
C5—H5A	0.94 (3)	C8—C9	1.379 (5)
C1—C10	1.492 (4)	C8—H8	0.94 (3)
C1—H1A	0.92 (3)	C17—H17	0.88 (4)
C1—H1B	0.97 (3)	C7—H7	0.97 (3)
C11—C6	1.385 (4)	C9—H9	0.90 (3)
O20—P3—O2	113.2 (1)	C11—C10—C1	121.7 (3)
O20—P3—O4	111.2 (1)	C15—C14—C13	120.3 (3)
O2—P3—O4	108.4 (1)	C15—C14—Cl	119.1 (2)
O20—P3—O12	116.3 (1)	C13—C14—Cl	120.6 (2)
O2—P3—O12	100.83 (11)	C16—C15—C14	119.6 (3)
O4—P3—O12	106.1 (1)	C16—C15—H15	123.6 (19)
C13—O12—P3	123.3 (2)	C14—C15—H15	116.7 (19)
C1—O2—P3	123.2 (2)	C13—C18—C17	119.8 (3)
C5—O4—P3	123.0 (2)	C13—C18—H18	117 (2)
C18—C13—C14	119.6 (3)	C17—C18—H18	123 (2)
C18—C13—O12	121.4 (3)	C17—C16—C15	120.5 (3)
C14—C13—O12	118.9 (2)	C17—C16—H16	121 (2)
O4—C5—C11	113.0 (2)	C15—C16—H16	118 (2)
O4—C5—H5B	107.3 (19)	C7—C6—C11	120.9 (3)
C11—C5—H5B	111.1 (19)	C7—C6—H6	118 (2)
O4—C5—H5A	103.6 (19)	C11—C6—H6	121 (2)
C11—C5—H5A	110.2 (19)	C7—C8—C9	120.4 (3)
H5B—C5—H5A	111 (3)	C7—C8—H8	120 (2)
O2—C1—C10	112.4 (2)	C9—C8—H8	119 (2)
O2—C1—H1A	108.1 (17)	C16—C17—C18	120.2 (3)
C10—C1—H1A	109.3 (18)	C16—C17—H17	122 (3)
O2—C1—H1B	103.9 (17)	C18—C17—H17	117 (3)
C10—C1—H1B	113.7 (17)	C8—C7—C6	119.7 (3)
H1A—C1—H1B	109 (2)	C8—C7—H7	120.9 (19)
C6—C11—C10	119.4 (3)	C6—C7—H7	119.4 (19)
C6—C11—C5	119.8 (3)	C8—C9—C10	120.6 (3)
C10—C11—C5	120.8 (3)	C8—C9—H9	121 (2)
C9—C10—C11	119.0 (3)	C10—C9—H9	118 (2)
C9—C10—C1	119.3 (3)
O20—P3—O12—C13	−54.5 (2)	O2—C1—C10—C11	64.6 (4)
O2—P3—O12—C13	−177.3 (2)	C18—C13—C14—C15	−2.1 (4)
O4—P3—O12—C13	69.7 (2)	O12—C13—C14—C15	−179.0 (2)
O20—P3—O2—C1	176.5 (2)	C18—C13—C14—Cl	177.1 (2)
O4—P3—O2—C1	52.6 (2)	O12—C13—C14—Cl	0.2 (4)
O12—P3—O2—C1	−58.6 (2)	C13—C14—C15—C16	1.3 (4)
O20—P3—O4—C5	−177.2 (2)	Cl—C14—C15—C16	−177.8 (2)
O2—P3—O4—C5	−52.1 (2)	C14—C13—C18—C17	1.2 (5)
O12—P3—O4—C5	55.5 (2)	O12—C13—C18—C17	178.0 (3)
P3—O12—C13—C18	53.1 (3)	C14—C15—C16—C17	0.3 (5)
P3—O12—C13—C14	−130.0 (2)	C10—C11—C6—C7	0.1 (4)
P3—O4—C5—C11	78.6 (3)	C5—C11—C6—C7	177.7 (3)
P3—O2—C1—C10	−79.3 (3)	C15—C16—C17—C18	−1.2 (5)
O4—C5—C11—C6	118.7 (3)	C13—C18—C17—C16	0.4 (5)
O4—C5—C11—C10	−63.7 (4)	C9—C8—C7—C6	−0.9 (5)
C6—C11—C10—C9	−1.6 (4)	C11—C6—C7—C8	1.2 (5)
C5—C11—C10—C9	−179.1 (3)	C7—C8—C9—C10	−0.6 (5)
C6—C11—C10—C1	176.8 (3)	C11—C10—C9—C8	1.8 (4)
C5—C11—C10—C1	−0.7 (4)	C1—C10—C9—C8	−176.6 (3)
O2—C1—C10—C9	−117.0 (3)