2-Chloro-1,3-dioxa-2σ³λ³-phosphaanthracen-4-one

The mol­ecule of the title compound, C₁₁H₆ClO₃P, is essentially planar, except for the P, Cl and carbonyl O atoms. Bond lengths at phospho­rus are P—O = 1.6110 (18) and 1.6290 (18) Å, and P—Cl = 2.0890 (9) Å. The mol­ecules are linked to form ribbons parallel to the b axis by two C—H...O and one P...O interaction.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.083
• Data-to-parameter ratio = 16.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.54
         From the CIF: _reflns_number_total               2367
         Count of symmetry unique reflns         1396
         Completeness (_total/calc)            169.56%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       971
         Fraction of Friedel pairs measured     0.696
         Are heavy atom types Z>Si present          yes
          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.

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S1. Comment

The title compound, (I), was obtained as a synthetic intermediate en route to phosphorus-substituted calix[4]arenes (Kunze, 2002).

The structure of (I) is shown in Fig. 1. Bond lengths and angles may be considered normal (Table 1). All non-H atoms, except P, Cl and O3, are coplanar (r.m.s. deviation 0.028 Å); these three atoms lie 0.491 (1), 2.525 (1) and −0.256 (2) Å, respectively, out of the mean plane (the minus sign indicating the opposite side of the plane).

The molecular packing involves three contacts, namely two `weak' C—H···O hydrogen bonds (Table 2) and a P···O3 contact of 3.072 (2) Å (operator of O3: −x + 2, y + 1/2, −z + 1/2). The overall effect of these is to link the molecules in ribbons parallel to the y axis (Fig. 2). The Cl···Cl contact between ribbons is, at 3.897 (1) Å (operator x + 1/2, −y + 1/2, −z), probably too long to be regarded as significant.

The structure of an isomeric material is presented in the following paper (Jones et al., 2002).

S2. Experimental

The title compound was prepared by the reaction of 3-hydroxynaphthalene-2-carboxylic acid with phosphorus trichloride in toluene (Hoechst, 1966) and recrystallized from dichloromethane/diethyl ether (2:1 v/v) (Kunze, 2002).

S3. Refinement

The absolute structure was determined on the basis of 974 Friedel pairs. The bulk material is racemic, so that the concept of absolute configuration is not applicable. H atoms were included using a riding model with fixed C—H bond lengths of 0.95 Å; U_iso(H) values were fixed at 1.2 times the U_eq value of the parent atom.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 30% probability levels. H-atom radii are arbitrary.
	Fig. 2. Packing diagram of the title compound, viewed parallel to the x axis. Secondary interactions are indicated by dashed bonds.

2-Chloro-1,3-dioxa-2σ³λ³-phosphaanthracen-4-one

Crystal data

C11H6ClO3P	Dx = 1.630 Mg m^−3
Mr = 252.58	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 56 reflections
a = 6.0031 (15) Å	θ = 10–11.5°
b = 10.0697 (15) Å	µ = 0.51 mm^−1
c = 17.028 (3) Å	T = 173 K
V = 1029.3 (4) Å^3	Prism, colourless
Z = 4	0.5 × 0.3 × 0.2 mm
F(000) = 512

Data collection

Stoe Stadi-4 diffractometer	Rint = 0.038
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.1°
Graphite monochromator	h = −7→3
ω/θ scans	k = −13→0
3936 measured reflections	l = −22→22
2367 independent reflections	3 standard reflections every 90 min
2114 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0289P)^2 + 0.1959P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2367 reflections	Δρmax = 0.22 e Å^−3
145 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Absolute structure: Flack (1983), 971 Friedel pairs [Please check]
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (10)

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.

Non-bonded distances:

3.0719 (0.0019) O3 - P_$1 3.8970 (0.0010) Cl - Cl_$2

Operators for generating equivalent atoms:

$1 − x + 2, y + 1/2, −z + 1/2 $2 x + 1/2, −y + 1/2, −z

#=============================================

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 2.9424 (0.0025) x + 1.3706 (0.0034) y + 14.6602 (0.0050) z = 1.4424 (0.0035)

* −0.0145 (0.0020) C1 * −0.0041 (0.0019) C2 * −0.0181 (0.0019) C3 * −0.0225 (0.0018) C4 * 0.0206 (0.0018) C5 * 0.0283 (0.0020) C6 * 0.0042 (0.0020) C7 * −0.0254 (0.0019) C8 * −0.0215 (0.0019) C9 * −0.0041 (0.0020) C10 * 0.0768 (0.0018) C11 * 0.0122 (0.0015) O1 * −0.0319 (0.0016) O2 − 0.4905 (0.0014) P −2.5248 (0.0014) Cl 0.2556 (0.0023) O3

Rms deviation of fitted atoms = 0.0284

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
P	0.67867 (10)	0.24783 (6)	0.17797 (4)	0.03157 (15)
Cl	0.85239 (13)	0.26700 (7)	0.07228 (4)	0.04888 (19)
O1	0.4731 (3)	0.34694 (16)	0.16174 (10)	0.0324 (4)
O2	0.8378 (3)	0.34102 (15)	0.23247 (9)	0.0319 (4)
O3	1.0008 (3)	0.52884 (17)	0.26724 (9)	0.0378 (4)
C1	0.7046 (4)	0.6836 (2)	0.17491 (13)	0.0249 (5)
H1	0.8309	0.7280	0.1959	0.030*
C2	0.6850 (4)	0.5482 (2)	0.18433 (12)	0.0243 (4)
C3	0.4976 (4)	0.4830 (2)	0.15187 (12)	0.0260 (5)
C4	0.3362 (4)	0.5502 (2)	0.11288 (12)	0.0257 (4)
H4	0.2128	0.5036	0.0914	0.031*
C5	0.1849 (4)	0.7650 (2)	0.06539 (12)	0.0275 (4)
H5	0.0574	0.7216	0.0446	0.033*
C6	0.2063 (4)	0.8993 (2)	0.05764 (13)	0.0335 (5)
H6	0.0930	0.9486	0.0318	0.040*
C7	0.3940 (5)	0.9654 (2)	0.08749 (13)	0.0349 (6)
H7	0.4065	1.0589	0.0816	0.042*
C8	0.5586 (4)	0.8968 (2)	0.12493 (13)	0.0307 (5)
H8	0.6854	0.9425	0.1445	0.037*
C9	0.5411 (4)	0.7575 (2)	0.13470 (11)	0.0242 (4)
C10	0.3511 (4)	0.6898 (2)	0.10407 (12)	0.0243 (4)
C11	0.8551 (4)	0.4777 (2)	0.23058 (12)	0.0283 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0306 (3)	0.0249 (3)	0.0392 (3)	−0.0022 (3)	−0.0020 (3)	0.0030 (3)
Cl	0.0529 (4)	0.0518 (4)	0.0419 (3)	−0.0004 (4)	0.0091 (3)	−0.0059 (3)
O1	0.0262 (9)	0.0256 (8)	0.0453 (9)	−0.0053 (7)	−0.0047 (8)	0.0056 (7)
O2	0.0326 (9)	0.0279 (7)	0.0353 (8)	0.0032 (8)	−0.0060 (8)	0.0047 (6)
O3	0.0299 (9)	0.0377 (9)	0.0457 (10)	−0.0024 (9)	−0.0137 (9)	0.0064 (8)
C1	0.0220 (11)	0.0279 (10)	0.0249 (10)	−0.0029 (9)	−0.0010 (10)	−0.0024 (8)
C2	0.0184 (10)	0.0288 (10)	0.0257 (10)	0.0021 (9)	−0.0002 (9)	0.0013 (8)
C3	0.0259 (12)	0.0235 (10)	0.0284 (10)	−0.0024 (10)	0.0021 (9)	0.0023 (8)
C4	0.0180 (10)	0.0317 (11)	0.0273 (10)	−0.0045 (10)	0.0012 (9)	−0.0016 (8)
C5	0.0212 (10)	0.0363 (11)	0.0249 (9)	0.0005 (11)	−0.0033 (9)	−0.0025 (9)
C6	0.0329 (13)	0.0341 (12)	0.0334 (11)	0.0077 (12)	−0.0091 (10)	−0.0009 (10)
C7	0.0412 (15)	0.0261 (11)	0.0375 (12)	0.0009 (11)	−0.0076 (11)	0.0009 (10)
C8	0.0323 (12)	0.0286 (12)	0.0313 (11)	−0.0030 (11)	−0.0070 (10)	−0.0024 (9)
C9	0.0233 (10)	0.0261 (10)	0.0231 (9)	0.0013 (10)	−0.0006 (8)	−0.0002 (9)
C10	0.0210 (11)	0.0289 (10)	0.0231 (9)	−0.0008 (10)	0.0020 (10)	−0.0009 (8)
C11	0.0254 (12)	0.0300 (11)	0.0293 (10)	−0.0012 (11)	0.0006 (10)	0.0031 (9)

Geometric parameters (Å, º)

P—O1	1.6110 (18)	C4—C10	1.417 (3)
P—O2	1.6290 (18)	C4—H4	0.9500
P—Cl	2.0890 (9)	C5—C6	1.365 (3)
O1—C3	1.388 (3)	C5—C10	1.415 (3)
O2—C11	1.381 (3)	C5—H5	0.9500
O3—C11	1.191 (3)	C6—C7	1.404 (4)
C1—C2	1.379 (3)	C6—H6	0.9500
C1—C9	1.410 (3)	C7—C8	1.364 (3)
C1—H1	0.9500	C7—H7	0.9500
C2—C3	1.414 (3)	C8—C9	1.416 (3)
C2—C11	1.472 (3)	C8—H8	0.9500
C3—C4	1.356 (3)	C9—C10	1.428 (3)
O1—P—O2	100.95 (9)	C10—C5—H5	119.7
O1—P—Cl	100.21 (7)	C5—C6—C7	120.7 (2)
O2—P—Cl	98.33 (7)	C5—C6—H6	119.7
C3—O1—P	123.43 (16)	C7—C6—H6	119.7
C11—O2—P	127.24 (15)	C8—C7—C6	120.7 (2)
C2—C1—C9	121.3 (2)	C8—C7—H7	119.6
C2—C1—H1	119.4	C6—C7—H7	119.6
C9—C1—H1	119.4	C7—C8—C9	120.2 (2)
C1—C2—C3	118.8 (2)	C7—C8—H8	119.9
C1—C2—C11	118.7 (2)	C9—C8—H8	119.9
C3—C2—C11	122.49 (19)	C1—C9—C8	121.9 (2)
C4—C3—O1	118.4 (2)	C1—C9—C10	118.8 (2)
C4—C3—C2	121.9 (2)	C8—C9—C10	119.30 (19)
O1—C3—C2	119.7 (2)	C5—C10—C4	122.4 (2)
C3—C4—C10	120.1 (2)	C5—C10—C9	118.57 (19)
C3—C4—H4	119.9	C4—C10—C9	119.0 (2)
C10—C4—H4	119.9	O3—C11—O2	118.3 (2)
C6—C5—C10	120.6 (2)	O3—C11—C2	125.5 (2)
C6—C5—H5	119.7	O2—C11—C2	116.1 (2)
O2—P—O1—C3	35.57 (18)	C2—C1—C9—C10	0.6 (3)
Cl—P—O1—C3	−65.07 (17)	C7—C8—C9—C1	−178.2 (2)
O1—P—O2—C11	−29.7 (2)	C7—C8—C9—C10	0.8 (3)
Cl—P—O2—C11	72.5 (2)	C6—C5—C10—C4	−179.5 (2)
C9—C1—C2—C3	0.8 (3)	C6—C5—C10—C9	0.0 (3)
C9—C1—C2—C11	−176.72 (19)	C3—C4—C10—C5	−178.6 (2)
P—O1—C3—C4	157.61 (16)	C3—C4—C10—C9	1.9 (3)
P—O1—C3—C2	−24.2 (3)	C1—C9—C10—C5	178.53 (19)
C1—C2—C3—C4	−0.9 (3)	C8—C9—C10—C5	−0.5 (3)
C11—C2—C3—C4	176.5 (2)	C1—C9—C10—C4	−2.0 (3)
C1—C2—C3—O1	−179.0 (2)	C8—C9—C10—C4	179.0 (2)
C11—C2—C3—O1	−1.6 (3)	P—O2—C11—O3	−170.25 (17)
O1—C3—C4—C10	177.7 (2)	P—O2—C11—C2	11.4 (3)
C2—C3—C4—C10	−0.4 (3)	C1—C2—C11—O3	7.1 (4)
C10—C5—C6—C7	0.4 (4)	C3—C2—C11—O3	−170.3 (2)
C5—C6—C7—C8	−0.1 (4)	C1—C2—C11—O2	−174.6 (2)
C6—C7—C8—C9	−0.5 (3)	C3—C2—C11—O2	7.9 (3)
C2—C1—C9—C8	179.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2^i	0.95	2.60	3.542 (3)	174
C8—H8···O3^i	0.95	2.56	3.484 (3)	164

Symmetry code: (i) −x+2, y+1/2, −z+1/2.