6-(2,4-Dichloro­phen­oxy)­dibenzo­[d,f]­[1,3,2]­dioxaphosphepine-6-sulfide

In the title compound, C₁₈H₁₁Cl₂O₃PS, the seven-membered phosphepine ring exhibits a distorted-boat conformation, with the phosphor­yl sulfide group axial and the dichloro­phen­oxy group equatorial. Fusion of the phosphepine ring to the biphen­yl system causes strain, as evidenced by both widening and compression of the endocyclic angles in the heterocyclic ring. The P=S bond length is 1.8939 (12) Å and the planar dichloro­phen­yl ring is oriented at an angle of 28.70 (6)° to the phosphepine ring.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.112
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



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
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16

   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
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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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 (Version 1.0; Allen et al., 2004) and PARST (Nardelli, 1995).

6-(2,4-Dichlorophenoxy)dibenzo[d,f][1,3,2]dioxaphosphepine-6-sulfide

Crystal data

C18H11Cl2O3PS	F(000) = 832
Mr = 409.20	Dx = 1.519 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 988 reflections
a = 10.816 (6) Å	θ = 2.3–25.0°
b = 13.615 (8) Å	µ = 0.58 mm^−1
c = 12.321 (7) Å	T = 293 K
β = 99.583 (9)°	Rectangular, yellow
V = 1789.0 (18) Å^3	0.48 × 0.25 × 0.25 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	3119 independent reflections
Radiation source: fine-focus sealed tube	2831 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.753, Tmax = 0.864	k = −16→11
8553 measured reflections	l = −14→14

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)] = 0.043	All H-atom parameters refined
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0628P)^2 + 0.5542P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
3119 reflections	Δρmax = 0.46 e Å^−3
271 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), 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
H2	−0.103 (2)	0.688 (2)	0.537 (2)	0.066 (7)*
H15	0.534 (3)	0.662 (2)	0.469 (2)	0.075 (8)*
H5	−0.380 (2)	0.8103 (19)	0.241 (2)	0.058 (6)*
H8	−0.447 (3)	0.6504 (19)	0.141 (2)	0.070 (7)*
H11	−0.076 (3)	0.5867 (19)	0.005 (2)	0.065 (7)*
H4	−0.362 (3)	0.883 (2)	0.412 (2)	0.071 (8)*
H3	−0.230 (3)	0.825 (2)	0.564 (3)	0.093 (10)*
H9	−0.441 (3)	0.590 (2)	−0.037 (3)	0.092 (10)*
H18	0.138 (3)	0.584 (2)	0.544 (2)	0.068 (8)*
H10	−0.261 (2)	0.558 (2)	−0.104 (2)	0.070 (7)*
H17	0.311 (3)	0.547 (2)	0.671 (3)	0.081 (9)*
P	0.02337 (4)	0.59495 (4)	0.29913 (4)	0.04315 (19)
S	0.08408 (5)	0.46789 (4)	0.27403 (5)	0.0600 (2)
Cl1	0.35244 (7)	0.72052 (7)	0.28874 (6)	0.0842 (3)
Cl2	0.56846 (9)	0.57733 (7)	0.67872 (8)	0.1151 (4)
O2	−0.02728 (12)	0.66252 (11)	0.19715 (11)	0.0478 (4)
O1	−0.08920 (13)	0.59033 (10)	0.36641 (12)	0.0494 (4)
O3	0.11994 (12)	0.67146 (10)	0.36156 (13)	0.0525 (4)
C12	−0.14454 (18)	0.63868 (15)	0.13420 (16)	0.0446 (4)
C14	0.34087 (19)	0.66563 (15)	0.41213 (17)	0.0493 (5)
C7	−0.25209 (18)	0.66102 (15)	0.17678 (16)	0.0462 (5)
C6	−0.24581 (17)	0.70683 (15)	0.28564 (16)	0.0462 (4)
C11	−0.1474 (2)	0.60049 (18)	0.03081 (18)	0.0555 (5)
C13	0.22484 (17)	0.64337 (14)	0.43638 (16)	0.0445 (4)
C8	−0.3666 (2)	0.64117 (19)	0.1094 (2)	0.0596 (6)
C1	−0.16360 (18)	0.67370 (15)	0.37699 (16)	0.0465 (5)
C9	−0.3705 (2)	0.6026 (2)	0.0058 (2)	0.0672 (7)
C15	0.4476 (2)	0.64499 (19)	0.4871 (2)	0.0628 (6)
C2	−0.1570 (2)	0.7153 (2)	0.47905 (19)	0.0631 (6)
C16	0.4345 (2)	0.60174 (18)	0.5842 (2)	0.0647 (7)
C18	0.2134 (2)	0.59914 (19)	0.5337 (2)	0.0598 (6)
C5	−0.3214 (2)	0.78628 (18)	0.30210 (19)	0.0561 (5)
C10	−0.2624 (3)	0.5824 (2)	−0.0338 (2)	0.0647 (6)
C17	0.3192 (3)	0.5776 (2)	0.6089 (2)	0.0682 (7)
C4	−0.3146 (2)	0.8304 (2)	0.4028 (2)	0.0664 (6)
C3	−0.2329 (3)	0.7950 (2)	0.4916 (2)	0.0733 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0339 (3)	0.0458 (3)	0.0467 (3)	−0.00054 (19)	−0.0024 (2)	0.0054 (2)
S	0.0545 (3)	0.0505 (3)	0.0710 (4)	0.0058 (2)	−0.0016 (3)	−0.0048 (2)
Cl1	0.0758 (4)	0.1119 (6)	0.0672 (4)	−0.0126 (4)	0.0183 (3)	0.0203 (4)
Cl2	0.1008 (6)	0.1070 (6)	0.1091 (7)	0.0260 (5)	−0.0656 (5)	−0.0131 (5)
O2	0.0359 (7)	0.0579 (8)	0.0475 (8)	−0.0032 (6)	0.0012 (6)	0.0118 (6)
O1	0.0431 (7)	0.0539 (8)	0.0502 (8)	0.0034 (6)	0.0045 (6)	0.0148 (6)
O3	0.0417 (7)	0.0458 (8)	0.0633 (9)	0.0002 (6)	−0.0112 (6)	0.0037 (6)
C12	0.0399 (9)	0.0492 (10)	0.0416 (10)	−0.0005 (8)	−0.0020 (8)	0.0098 (8)
C14	0.0450 (10)	0.0523 (11)	0.0483 (11)	−0.0032 (9)	0.0012 (8)	−0.0031 (9)
C7	0.0393 (10)	0.0528 (11)	0.0438 (10)	0.0003 (8)	−0.0015 (8)	0.0061 (8)
C6	0.0364 (9)	0.0555 (11)	0.0453 (10)	−0.0013 (8)	0.0032 (8)	0.0054 (8)
C11	0.0569 (13)	0.0642 (13)	0.0445 (11)	0.0060 (10)	0.0062 (10)	0.0068 (9)
C13	0.0401 (10)	0.0424 (10)	0.0470 (10)	0.0004 (8)	−0.0045 (8)	−0.0026 (8)
C8	0.0404 (11)	0.0760 (15)	0.0580 (13)	0.0008 (10)	−0.0047 (9)	0.0029 (11)
C1	0.0387 (9)	0.0545 (11)	0.0453 (10)	0.0003 (8)	0.0043 (8)	0.0085 (9)
C9	0.0572 (14)	0.0825 (17)	0.0538 (13)	−0.0067 (12)	−0.0149 (11)	−0.0009 (12)
C15	0.0408 (11)	0.0688 (15)	0.0733 (16)	−0.0015 (10)	−0.0062 (10)	−0.0082 (12)
C2	0.0598 (13)	0.0827 (17)	0.0435 (12)	0.0063 (12)	−0.0009 (10)	0.0064 (11)
C16	0.0637 (14)	0.0569 (13)	0.0620 (14)	0.0120 (11)	−0.0230 (11)	−0.0110 (11)
C18	0.0557 (13)	0.0647 (14)	0.0584 (13)	−0.0018 (11)	0.0077 (10)	0.0086 (10)
C5	0.0449 (11)	0.0676 (14)	0.0544 (12)	0.0103 (10)	0.0048 (9)	0.0040 (10)
C10	0.0726 (16)	0.0728 (16)	0.0435 (12)	0.0008 (12)	−0.0059 (11)	0.0005 (11)
C17	0.0841 (18)	0.0656 (15)	0.0494 (13)	0.0059 (13)	−0.0055 (12)	0.0075 (11)
C4	0.0613 (14)	0.0728 (16)	0.0656 (15)	0.0143 (12)	0.0127 (12)	−0.0038 (12)
C3	0.0759 (16)	0.0910 (19)	0.0521 (14)	0.0106 (14)	0.0080 (12)	−0.0106 (13)

Geometric parameters (Å, º)

P—O2	1.5799 (15)	C8—C9	1.374 (4)
P—O3	1.5812 (16)	C8—H8	1.01 (3)
P—O1	1.5842 (16)	C1—C2	1.370 (3)
P—S	1.8939 (12)	C9—C10	1.368 (4)
Cl1—C14	1.717 (2)	C9—H9	0.87 (3)
Cl2—C16	1.733 (2)	C15—C16	1.362 (4)
O2—C12	1.410 (2)	C15—H15	1.02 (3)
O1—C1	1.410 (3)	C2—C3	1.385 (4)
O3—C13	1.391 (2)	C2—H2	0.92 (3)
C12—C11	1.371 (3)	C16—C17	1.372 (4)
C12—C7	1.387 (3)	C18—C17	1.378 (4)
C14—C13	1.371 (3)	C18—H18	0.87 (3)
C14—C15	1.382 (3)	C5—C4	1.369 (4)
C7—C8	1.398 (3)	C5—H5	0.96 (3)
C7—C6	1.470 (3)	C10—H10	0.93 (3)
C6—C1	1.388 (3)	C17—H17	0.89 (3)
C6—C5	1.391 (3)	C4—C3	1.374 (4)
C11—C10	1.382 (4)	C4—H4	0.90 (3)
C11—H11	0.90 (3)	C3—H3	0.98 (3)
C13—C18	1.366 (3)
O2—P—O3	96.71 (9)	C6—C1—O1	119.01 (18)
O2—P—O1	104.14 (8)	C10—C9—C8	120.8 (2)
O3—P—O1	105.94 (9)	C10—C9—H9	117 (2)
O2—P—S	119.06 (7)	C8—C9—H9	122 (2)
O3—P—S	117.54 (7)	C16—C15—C14	118.5 (2)
O1—P—S	111.51 (6)	C16—C15—H15	121.5 (16)
C12—O2—P	117.68 (12)	C14—C15—H15	120.0 (16)
C1—O1—P	121.10 (12)	C1—C2—C3	119.0 (2)
C13—O3—P	122.75 (13)	C1—C2—H2	118.7 (16)
C11—C12—C7	122.92 (19)	C3—C2—H2	122.3 (16)
C11—C12—O2	118.53 (18)	C15—C16—C17	122.0 (2)
C7—C12—O2	118.41 (18)	C15—C16—Cl2	118.4 (2)
C13—C14—C15	120.2 (2)	C17—C16—Cl2	119.6 (2)
C13—C14—Cl1	119.55 (16)	C13—C18—C17	119.8 (2)
C15—C14—Cl1	120.27 (18)	C13—C18—H18	117.2 (19)
C12—C7—C8	116.7 (2)	C17—C18—H18	122.9 (19)
C12—C7—C6	121.58 (17)	C4—C5—C6	121.9 (2)
C8—C7—C6	121.72 (19)	C4—C5—H5	119.5 (15)
C1—C6—C5	116.6 (2)	C6—C5—H5	118.6 (15)
C1—C6—C7	121.85 (19)	C9—C10—C11	119.9 (2)
C5—C6—C7	121.59 (18)	C9—C10—H10	123.6 (17)
C12—C11—C10	118.8 (2)	C11—C10—H10	116.4 (17)
C12—C11—H11	121.2 (17)	C16—C17—C18	118.9 (2)
C10—C11—H11	120.0 (17)	C16—C17—H17	122 (2)
C18—C13—C14	120.6 (2)	C18—C17—H17	119 (2)
C18—C13—O3	121.33 (19)	C5—C4—C3	119.9 (2)
C14—C13—O3	118.03 (18)	C5—C4—H4	121.2 (19)
C9—C8—C7	120.9 (2)	C3—C4—H4	118.9 (18)
C9—C8—H8	120.3 (15)	C4—C3—C2	120.0 (2)
C7—C8—H8	118.7 (15)	C4—C3—H3	120 (2)
C2—C1—C6	122.6 (2)	C2—C3—H3	120 (2)
C2—C1—O1	118.30 (18)
O3—P—O2—C12	−159.88 (14)	C12—C7—C8—C9	−0.8 (3)
O1—P—O2—C12	−51.53 (16)	C6—C7—C8—C9	176.9 (2)
S—P—O2—C12	73.40 (15)	C5—C6—C1—C2	0.8 (3)
O2—P—O1—C1	−38.57 (16)	C7—C6—C1—C2	−179.7 (2)
O3—P—O1—C1	62.80 (16)	C5—C6—C1—O1	176.86 (18)
S—P—O1—C1	−168.19 (13)	C7—C6—C1—O1	−3.7 (3)
O2—P—O3—C13	−155.58 (16)	P—O1—C1—C2	−112.8 (2)
O1—P—O3—C13	97.60 (16)	P—O1—C1—C6	71.0 (2)
S—P—O3—C13	−27.79 (18)	C7—C8—C9—C10	0.2 (4)
P—O2—C12—C11	−108.54 (19)	C13—C14—C15—C16	0.5 (3)
P—O2—C12—C7	75.7 (2)	Cl1—C14—C15—C16	179.76 (19)
C11—C12—C7—C8	1.0 (3)	C6—C1—C2—C3	−1.6 (4)
O2—C12—C7—C8	176.61 (19)	O1—C1—C2—C3	−177.7 (2)
C11—C12—C7—C6	−176.7 (2)	C14—C15—C16—C17	0.6 (4)
O2—C12—C7—C6	−1.1 (3)	C14—C15—C16—Cl2	−179.22 (18)
C12—C7—C6—C1	−45.7 (3)	C14—C13—C18—C17	0.7 (4)
C8—C7—C6—C1	136.7 (2)	O3—C13—C18—C17	−176.1 (2)
C12—C7—C6—C5	133.7 (2)	C1—C6—C5—C4	0.6 (3)
C8—C7—C6—C5	−43.9 (3)	C7—C6—C5—C4	−178.9 (2)
C7—C12—C11—C10	−0.6 (3)	C8—C9—C10—C11	0.2 (4)
O2—C12—C11—C10	−176.2 (2)	C12—C11—C10—C9	0.0 (4)
C15—C14—C13—C18	−1.1 (3)	C15—C16—C17—C18	−0.9 (4)
Cl1—C14—C13—C18	179.59 (18)	Cl2—C16—C17—C18	178.8 (2)
C15—C14—C13—O3	175.79 (19)	C13—C18—C17—C16	0.3 (4)
Cl1—C14—C13—O3	−3.5 (3)	C6—C5—C4—C3	−1.2 (4)
P—O3—C13—C18	−65.9 (3)	C5—C4—C3—C2	0.4 (4)
P—O3—C13—C14	117.23 (19)	C1—C2—C3—C4	1.0 (4)