2,8-Dimethyl-10-p-tolyl-10H-phenoxaphosphine.

THE TITLE COMPOUND (SYSTEMATIC NAME: 3,6-dimethyl-10-p-tolyl-9-oxa-10-phosphaanthracene), C(21)H(19)OP, is a precursor for the preparation of a bidentate xanthene-based ligand, in which the dihedral angle between the toluene ring and the phenoxaphosphine ring system is 83.26 (3)°. The geometry at the P atom is pyramidal, resulting in a longer C-P bond length as compared to the two ring C-P bonds.

Related literature

For related structures based on the xanthene backbone, see: Marimuthu et al. (2008a ▶,b ▶,c ▶). For a related phenoxaphosphine compound, see: Mann et al. (1976 ▶). The title compound was synthesised by a modified literature method (Bronger et al., 2004 ▶). For other structurally related ligands, see: Levy et al. (1965 ▶); Seibold et al. (2008 ▶); Shau et al. (2002 ▶).

Experimental

Crystal data

C21H19OP

M = 318.33

Monoclinic,

a = 10.9363 (3) Å

b = 11.6323 (3) Å

c = 14.0458 (4) Å

β = 111.532 (1)°

V = 1662.13 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.17 mm−1

T = 173 K

0.51 × 0.49 × 0.48 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: none

29900 measured reflections

4013 independent reflections

3507 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.108

S = 1.07

4013 reflections

211 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009817/rz2300sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009817/rz2300Isup2.hkl

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

C21H19OP	F(000) = 672
Mr = 318.33	Dx = 1.272 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8225 reflections
a = 10.9363 (3) Å	θ = 2.3–28.4°
b = 11.6323 (3) Å	µ = 0.17 mm−1
c = 14.0458 (4) Å	T = 173 K
β = 111.532 (1)°	Needle, colourless
V = 1662.13 (8) Å3	0.51 × 0.49 × 0.48 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3507 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
graphite	θmax = 28.0°, θmin = 2.0°
φ and ω scans	h = −14→14
29900 measured reflections	k = −15→15
4013 independent reflections	l = −18→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0534P)2 + 0.586P] where P = (Fo2 + 2Fc2)/3
4013 reflections	(Δ/σ)max = 0.040
211 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.59638 (12)	1.06591 (11)	0.15703 (10)	0.0274 (3)
C2	0.53669 (13)	1.05047 (12)	0.22849 (10)	0.0303 (3)
H2	0.5484	0.9791	0.2636	0.036*
C3	0.46153 (13)	1.13388 (12)	0.25049 (10)	0.0313 (3)
C4	0.44183 (14)	1.23579 (12)	0.19518 (11)	0.0361 (3)
H4	0.3880	1.2940	0.2069	0.043*
C5	0.49875 (14)	1.25429 (12)	0.12363 (11)	0.0357 (3)
H5	0.4843	1.3247	0.0868	0.043*
C6	0.57734 (13)	1.16977 (11)	0.10547 (10)	0.0289 (3)
C7	0.69900 (12)	1.12246 (11)	−0.00204 (10)	0.0284 (3)
C8	0.73269 (14)	1.16321 (12)	−0.08200 (10)	0.0340 (3)
H8	0.7092	1.2391	−0.1071	0.041*
C9	0.80050 (14)	1.09313 (13)	−0.12506 (10)	0.0347 (3)
H9	0.8246	1.1222	−0.1789	0.042*
C10	0.83423 (13)	0.98126 (12)	−0.09135 (10)	0.0310 (3)
C11	0.79734 (12)	0.94259 (11)	−0.01249 (10)	0.0294 (3)
H11	0.8177	0.8657	0.0106	0.035*
C12	0.73184 (12)	1.01137 (11)	0.03436 (9)	0.0264 (2)
C13	0.40629 (15)	1.11516 (14)	0.33266 (11)	0.0399 (3)
H13A	0.3553	1.0437	0.3190	0.060*
H13B	0.3491	1.1798	0.3333	0.060*
H13C	0.4784	1.1098	0.3993	0.060*
C14	0.90781 (15)	0.90328 (14)	−0.13659 (11)	0.0387 (3)
H14A	0.9981	0.8935	−0.0878	0.058*
H14B	0.9093	0.9371	−0.2001	0.058*
H14C	0.8641	0.8283	−0.1515	0.058*
C15	0.85437 (13)	0.98293 (12)	0.24735 (9)	0.0286 (3)
C16	0.94457 (15)	0.89406 (13)	0.28148 (11)	0.0377 (3)
H16	0.9249	0.8209	0.2493	0.045*
C17	1.06328 (16)	0.91088 (17)	0.36216 (12)	0.0474 (4)
H17	1.1246	0.8494	0.3837	0.057*
C18	1.09347 (15)	1.01549 (17)	0.41141 (11)	0.0463 (4)
C19	1.00354 (15)	1.10404 (16)	0.37752 (11)	0.0440 (4)
H19	1.0230	1.1767	0.4106	0.053*
C20	0.88574 (14)	1.08866 (13)	0.29636 (11)	0.0358 (3)
H20	0.8258	1.1509	0.2739	0.043*
C21	1.22049 (18)	1.0331 (2)	0.50093 (13)	0.0681 (6)
H21A	1.2587	1.1074	0.4940	0.102*
H21B	1.2821	0.9713	0.5024	0.102*
H21C	1.2033	1.0322	0.5647	0.102*
O1	0.63326 (10)	1.20048 (8)	0.03575 (8)	0.0356 (2)
P1	0.69921 (3)	0.95166 (3)	0.14160 (2)	0.02660 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0250 (6)	0.0274 (6)	0.0299 (6)	−0.0007 (5)	0.0102 (5)	−0.0010 (5)
C2	0.0298 (6)	0.0307 (6)	0.0311 (6)	−0.0013 (5)	0.0122 (5)	0.0003 (5)
C3	0.0279 (6)	0.0352 (7)	0.0316 (6)	−0.0036 (5)	0.0119 (5)	−0.0059 (5)
C4	0.0349 (7)	0.0322 (7)	0.0445 (8)	0.0023 (5)	0.0185 (6)	−0.0054 (6)
C5	0.0383 (7)	0.0273 (6)	0.0439 (8)	0.0038 (5)	0.0179 (6)	0.0021 (6)
C6	0.0287 (6)	0.0280 (6)	0.0313 (6)	−0.0008 (5)	0.0125 (5)	0.0000 (5)
C7	0.0277 (6)	0.0290 (6)	0.0288 (6)	−0.0008 (5)	0.0105 (5)	0.0001 (5)
C8	0.0373 (7)	0.0331 (7)	0.0332 (7)	−0.0006 (5)	0.0147 (6)	0.0059 (5)
C9	0.0370 (7)	0.0418 (8)	0.0279 (6)	−0.0051 (6)	0.0150 (5)	0.0011 (5)
C10	0.0295 (6)	0.0372 (7)	0.0267 (6)	−0.0050 (5)	0.0110 (5)	−0.0063 (5)
C11	0.0308 (6)	0.0289 (6)	0.0279 (6)	−0.0016 (5)	0.0100 (5)	−0.0026 (5)
C12	0.0263 (6)	0.0285 (6)	0.0239 (5)	−0.0034 (5)	0.0084 (5)	−0.0013 (5)
C13	0.0402 (8)	0.0469 (9)	0.0385 (7)	0.0005 (6)	0.0214 (6)	−0.0047 (6)
C14	0.0404 (8)	0.0456 (8)	0.0346 (7)	−0.0017 (6)	0.0190 (6)	−0.0073 (6)
C15	0.0304 (6)	0.0337 (6)	0.0250 (6)	0.0017 (5)	0.0140 (5)	0.0048 (5)
C16	0.0413 (8)	0.0374 (7)	0.0366 (7)	0.0062 (6)	0.0168 (6)	0.0111 (6)
C17	0.0379 (8)	0.0626 (10)	0.0412 (8)	0.0109 (7)	0.0140 (7)	0.0220 (8)
C18	0.0342 (7)	0.0774 (12)	0.0272 (7)	−0.0079 (8)	0.0111 (6)	0.0112 (7)
C19	0.0416 (8)	0.0588 (10)	0.0334 (7)	−0.0115 (7)	0.0159 (6)	−0.0083 (7)
C20	0.0350 (7)	0.0398 (7)	0.0338 (7)	−0.0013 (6)	0.0141 (6)	−0.0030 (6)
C21	0.0400 (9)	0.1219 (19)	0.0356 (8)	−0.0161 (10)	0.0060 (7)	0.0136 (10)
O1	0.0444 (6)	0.0277 (5)	0.0431 (5)	0.0054 (4)	0.0261 (5)	0.0070 (4)
P1	0.02996 (18)	0.02340 (17)	0.02918 (18)	0.00000 (12)	0.01410 (14)	0.00138 (12)

C1—C6	1.3845 (18)	C12—P1	1.8092 (13)
C1—C2	1.3953 (18)	C13—H13A	0.9800
C1—P1	1.8046 (13)	C13—H13B	0.9800
C2—C3	1.3780 (18)	C13—H13C	0.9800
C2—H2	0.9500	C14—H14A	0.9800
C3—C4	1.390 (2)	C14—H14B	0.9800
C3—C13	1.5021 (19)	C14—H14C	0.9800
C4—C5	1.379 (2)	C15—C16	1.3873 (19)
C4—H4	0.9500	C15—C20	1.390 (2)
C5—C6	1.3896 (19)	C15—P1	1.8352 (13)
C5—H5	0.9500	C16—C17	1.389 (2)
C6—O1	1.3784 (15)	C16—H16	0.9500
C7—O1	1.3794 (16)	C17—C18	1.379 (3)
C7—C8	1.3876 (18)	C17—H17	0.9500
C7—C12	1.3876 (18)	C18—C19	1.382 (3)
C8—C9	1.382 (2)	C18—C21	1.507 (2)
C8—H8	0.9500	C19—C20	1.383 (2)
C9—C10	1.388 (2)	C19—H19	0.9500
C9—H9	0.9500	C20—H20	0.9500
C10—C11	1.3858 (18)	C21—H21A	0.9800
C10—C14	1.4999 (19)	C21—H21B	0.9800
C11—C12	1.3901 (18)	C21—H21C	0.9800
C11—H11	0.9500
C6—C1—C2	117.93 (12)	H13A—C13—H13B	109.5
C6—C1—P1	124.10 (10)	C3—C13—H13C	109.5
C2—C1—P1	117.92 (10)	H13A—C13—H13C	109.5
C3—C2—C1	123.08 (12)	H13B—C13—H13C	109.5
C3—C2—H2	118.5	C10—C14—H14A	109.5
C1—C2—H2	118.5	C10—C14—H14B	109.5
C2—C3—C4	117.25 (12)	H14A—C14—H14B	109.5
C2—C3—C13	120.76 (13)	C10—C14—H14C	109.5
C4—C3—C13	121.98 (13)	H14A—C14—H14C	109.5
C5—C4—C3	121.42 (13)	H14B—C14—H14C	109.5
C5—C4—H4	119.3	C16—C15—C20	118.26 (13)
C3—C4—H4	119.3	C16—C15—P1	117.45 (11)
C4—C5—C6	119.89 (13)	C20—C15—P1	124.28 (11)
C4—C5—H5	120.1	C15—C16—C17	120.68 (15)
C6—C5—H5	120.1	C15—C16—H16	119.7
O1—C6—C1	125.24 (12)	C17—C16—H16	119.7
O1—C6—C5	114.37 (12)	C18—C17—C16	120.93 (15)
C1—C6—C5	120.38 (12)	C18—C17—H17	119.5
O1—C7—C8	114.67 (12)	C16—C17—H17	119.5
O1—C7—C12	124.88 (11)	C17—C18—C19	118.41 (14)
C8—C7—C12	120.45 (12)	C17—C18—C21	121.11 (18)
C9—C8—C7	119.82 (13)	C19—C18—C21	120.48 (19)
C9—C8—H8	120.1	C18—C19—C20	121.14 (16)
C7—C8—H8	120.1	C18—C19—H19	119.4
C8—C9—C10	121.47 (12)	C20—C19—H19	119.4
C8—C9—H9	119.3	C19—C20—C15	120.58 (15)
C10—C9—H9	119.3	C19—C20—H20	119.7
C11—C10—C9	117.27 (12)	C15—C20—H20	119.7
C11—C10—C14	120.08 (13)	C18—C21—H21A	109.5
C9—C10—C14	122.64 (12)	C18—C21—H21B	109.5
C10—C11—C12	122.92 (12)	H21A—C21—H21B	109.5
C10—C11—H11	118.5	C18—C21—H21C	109.5
C12—C11—H11	118.5	H21A—C21—H21C	109.5
C7—C12—C11	118.04 (12)	H21B—C21—H21C	109.5
C7—C12—P1	124.12 (10)	C6—O1—C7	122.19 (10)
C11—C12—P1	117.81 (10)	C1—P1—C12	98.00 (6)
C3—C13—H13A	109.5	C1—P1—C15	100.87 (6)
C3—C13—H13B	109.5	C12—P1—C15	101.04 (6)
C6—C1—C2—C3	−0.7 (2)	C20—C15—C16—C17	−0.3 (2)
P1—C1—C2—C3	176.68 (10)	P1—C15—C16—C17	−179.07 (11)
C1—C2—C3—C4	2.4 (2)	C15—C16—C17—C18	1.1 (2)
C1—C2—C3—C13	−176.31 (13)	C16—C17—C18—C19	−1.0 (2)
C2—C3—C4—C5	−2.1 (2)	C16—C17—C18—C21	178.23 (14)
C13—C3—C4—C5	176.57 (13)	C17—C18—C19—C20	0.1 (2)
C3—C4—C5—C6	0.2 (2)	C21—C18—C19—C20	−179.10 (14)
C2—C1—C6—O1	177.32 (12)	C18—C19—C20—C15	0.6 (2)
P1—C1—C6—O1	0.09 (19)	C16—C15—C20—C19	−0.5 (2)
C2—C1—C6—C5	−1.29 (19)	P1—C15—C20—C19	178.12 (11)
P1—C1—C6—C5	−178.52 (10)	C1—C6—O1—C7	10.4 (2)
C4—C5—C6—O1	−177.21 (13)	C5—C6—O1—C7	−170.89 (12)
C4—C5—C6—C1	1.5 (2)	C8—C7—O1—C6	171.17 (12)
O1—C7—C8—C9	179.10 (12)	C12—C7—O1—C6	−9.1 (2)
C12—C7—C8—C9	−0.6 (2)	C6—C1—P1—C12	−8.60 (12)
C7—C8—C9—C10	1.1 (2)	C2—C1—P1—C12	174.17 (10)
C8—C9—C10—C11	−0.1 (2)	C6—C1—P1—C15	94.34 (12)
C8—C9—C10—C14	−179.98 (13)	C2—C1—P1—C15	−82.90 (11)
C9—C10—C11—C12	−1.45 (19)	C7—C12—P1—C1	9.72 (12)
C14—C10—C11—C12	178.41 (12)	C11—C12—P1—C1	−172.23 (10)
O1—C7—C12—C11	179.45 (12)	C7—C12—P1—C15	−93.08 (12)
C8—C7—C12—C11	−0.86 (19)	C11—C12—P1—C15	84.97 (11)
O1—C7—C12—P1	−2.50 (19)	C16—C15—P1—C1	159.40 (10)
C8—C7—C12—P1	177.19 (10)	C20—C15—P1—C1	−19.24 (12)
C10—C11—C12—C7	1.94 (19)	C16—C15—P1—C12	−100.12 (11)
C10—C11—C12—P1	−176.23 (10)	C20—C15—P1—C12	81.24 (12)