3-(6-Methyl-2-pyrid-yl)-2-phenyl-3,4-dihydro-1,3,2-benzoxaza-phosphinine 2-oxide.

In the title compound, C(19)H(17)N(2)O(2)P, the six-membered 1,3,2-oxaza-phosphinine ring adopts a boat conformation with the phosphoryl O atom in an equatorial position. The dihedral angle between the 6-methyl-2-pyridyl and phenyl groups is 75.5 (1)°. These substituents are trans to each other, and are oriented at angles of 57.2 (1) and 74.8 (1)°, respectively, to the benzene ring. The crystal structure is stabilized by intra- and inter-molecular hydrogen bonds. The phosphoryl O atom participates in inter-molecular C-H⋯O inter-actions with the neighbouring mol-ecules, forming centrosymmetric R(2) (2)(14) dimers.

Related literature

For the biological activity of organophospho­rus compounds, see: Hoagland (1988 ▶); Smith (1983 ▶); Molodykh et al. (1990 ▶). For P—O and P=O bond lengths in related structures, see: Brzozowski et al. (1990 ▶); Angelov et al. (2002 ▶); Kant et al. (2009 ▶). For P—N bond lengths in related structures, see: Radha Krishna et al. (2007 ▶); Yang et al. (1988 ▶); Subramanian et al. (1989 ▶); Selladurai & Subramanian (1990 ▶); Selladurai et al. (1991 ▶).

Experimental

Crystal data

C19H17N2O2P

M = 336.32

Triclinic,

a = 7.2238 (8) Å

b = 8.6573 (8) Å

c = 13.7265 (14) Å

α = 95.216 (8)°

β = 94.397 (9)°

γ = 94.330 (9)°

V = 849.42 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.18 mm−1

T = 293 K

0.28 × 0.18 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: none

12457 measured reflections

5006 independent reflections

3069 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.173

S = 1.14

5006 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ZORTEP (Zsolnai, 1997 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶) and PARST95 (Nardelli, 1995 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809040367/bh2245sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040367/bh2245Isup2.hkl

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

C19H17N2O2P	Z = 2
Mr = 336.32	F(000) = 352
Triclinic, P1	Dx = 1.315 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2238 (8) Å	Cell parameters from 5006 reflections
b = 8.6573 (8) Å	θ = 3.3–30.1°
c = 13.7265 (14) Å	µ = 0.18 mm−1
α = 95.216 (8)°	T = 293 K
β = 94.397 (9)°	Plate, colourless
γ = 94.330 (9)°	0.28 × 0.18 × 0.08 mm
V = 849.42 (15) Å3

Oxford Diffraction Xcalibur diffractometer	3069 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
graphite	θmax = 30.1°, θmin = 3.3°
ω–2θ scans	h = −10→10
12457 measured reflections	k = −12→12
5006 independent reflections	l = −19→19

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0909P)2] where P = (Fo2 + 2Fc2)/3
5006 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.33 e Å−3
0 constraints

Refinement. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric.Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=dPlane 1 m1 = 0.38775(0.00078) m2 = 0.69013(0.00101) m3 = -0.61104(0.00092) D = -0.04785(0.00813) Atom d s d/s (d/s)**2 C6 * 0.0033 0.0020 1.652 2.729 C7 * -0.0061 0.0019 - 3.190 10.179 C12 * 0.0060 0.0019 3.207 10.286 O4 * -0.0017 0.0014 - 1.201 1.443 P1 0.9362 0.0005 1909.984 3648038.000 N2 0.9357 0.0015 617.499 381304.969 ============ Sum((d/s)**2) for starred atoms 24.637 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarityPlane 2 m1 = 0.36501(0.00090) m2 = 0.72088(0.00066) m3 = -0.58915(0.00074) D = 0.19711(0.00721) Atom d s d/s (d/s)**2 C7 * -0.0010 0.0019 - 0.547 0.300 C8 * -0.0022 0.0022 - 1.022 1.044 C9 * 0.0076 0.0024 3.196 10.214 C10 * -0.0077 0.0023 - 3.346 11.194 C11 * 0.0029 0.0021 1.390 1.931 C12 * 0.0007 0.0019 0.353 0.125 ============ Sum((d/s)**2) for starred atoms 24.808 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarityPlane 3 m1 = -0.45957(0.00079) m2 = 0.86478(0.00046) m3 = -0.20235(0.00092) D = 2.02662(0.00192) Atom d s d/s (d/s)**2 C13 * 0.0050 0.0018 2.731 7.457 N3 * -0.0045 0.0018 - 2.513 6.313 C14 * 0.0033 0.0025 1.334 1.780 C16 * 0.0013 0.0026 0.508 0.258 C17 * -0.0009 0.0027 - 0.328 0.108 C18 * -0.0040 0.0024 - 1.686 2.842 ============ Sum((d/s)**2) for starred atoms 18.758 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarityPlane 4 m1 = -0.44454(0.00100) m2 = -0.15288(0.00101) m3 = -0.88262(0.00050) D = -4.64491(0.00165) Atom d s d/s (d/s)**2 C19 * 0.0128 0.0022 5.712 32.623 C20 * -0.0095 0.0029 - 3.274 10.717 C21 * -0.0074 0.0031 - 2.395 5.738 C22 * 0.0121 0.0031 3.908 15.276 C23 * 0.0012 0.0025 0.480 0.231 C24 * -0.0084 0.0020 - 4.200 17.636 ============ Sum((d/s)**2) for starred atoms 82.221 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarityDihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 2.52 (0.07) 177.48 (0.07) 1 3 57.16 (0.06) 122.84 (0.06) 1 4 74.84 (0.08) 105.16 (0.08) 2 3 54.91 (0.06) 125.09 (0.06) 2 4 75.67 (0.07) 104.33 (0.07) 3 4 75.48 (0.08) 104.52 (0.08)

	x	y	z	Uiso*/Ueq
P1	0.37783 (6)	0.42101 (5)	0.26648 (4)	0.03578 (17)
O4	0.34114 (19)	0.46439 (16)	0.37866 (10)	0.0459 (4)
N2	0.16623 (19)	0.42897 (18)	0.20981 (11)	0.0360 (4)
O5	0.52630 (17)	0.51923 (15)	0.23013 (11)	0.0491 (4)
C24	0.4304 (3)	0.2230 (2)	0.26798 (15)	0.0399 (4)
C7	0.0443 (2)	0.5645 (2)	0.35210 (14)	0.0380 (4)
C6	0.0029 (2)	0.4431 (2)	0.26737 (15)	0.0413 (4)
H6A	−0.0316	0.3438	0.2913	0.050*
H6B	−0.1017	0.4703	0.2255	0.050*
N3	−0.0324 (2)	0.2849 (2)	0.08712 (13)	0.0476 (4)
C12	0.2155 (3)	0.5737 (2)	0.40604 (14)	0.0374 (4)
C13	0.1314 (2)	0.3663 (2)	0.10995 (14)	0.0367 (4)
C11	0.2642 (3)	0.6790 (2)	0.48673 (15)	0.0475 (5)
H11	0.3809	0.6826	0.5210	0.057*
C8	−0.0832 (3)	0.6682 (3)	0.38261 (16)	0.0485 (5)
H8	−0.1999	0.6649	0.3484	0.058*
C9	−0.0374 (4)	0.7763 (3)	0.46352 (17)	0.0574 (6)
H9	−0.1226	0.8463	0.4824	0.069*
C10	0.1326 (4)	0.7804 (3)	0.51557 (16)	0.0560 (6)
H10	0.1607	0.8513	0.5707	0.067*
C19	0.5868 (3)	0.1738 (2)	0.22629 (17)	0.0509 (5)
H19	0.6631	0.2428	0.1959	0.061*
C14	−0.0738 (3)	0.2269 (3)	−0.00667 (18)	0.0579 (6)
C18	0.2619 (3)	0.3908 (3)	0.04171 (16)	0.0532 (5)
H18	0.3761	0.4468	0.0603	0.064*
C23	0.3141 (4)	0.1170 (3)	0.30964 (18)	0.0623 (7)
H23	0.2076	0.1487	0.3370	0.075*
C20	0.6295 (4)	0.0186 (3)	0.2303 (2)	0.0683 (8)
H20	0.7366	−0.0145	0.2044	0.082*
C16	0.0481 (3)	0.2471 (3)	−0.07839 (17)	0.0590 (6)
H16	0.0157	0.2050	−0.1427	0.071*
C21	0.5141 (5)	−0.0834 (3)	0.2720 (2)	0.0788 (9)
H21	0.5424	−0.1861	0.2743	0.095*
C17	0.2164 (4)	0.3297 (3)	−0.05363 (18)	0.0643 (6)
H17	0.2996	0.3444	−0.1011	0.077*
C22	0.3571 (5)	−0.0350 (3)	0.3103 (2)	0.0821 (9)
H22	0.2778	−0.1060	0.3373	0.099*
C15	−0.2625 (4)	0.1350 (5)	−0.0295 (2)	0.1035 (13)
H15A	−0.3264	0.1337	0.0292	0.155*
H15B	−0.2449	0.0302	−0.0542	0.155*
H15C	−0.3352	0.1830	−0.0780	0.155*

	U11	U22	U33	U12	U13	U23
P1	0.0327 (3)	0.0325 (3)	0.0410 (3)	0.00243 (18)	−0.00086 (19)	0.00089 (19)
O4	0.0493 (8)	0.0471 (8)	0.0395 (8)	0.0155 (6)	−0.0083 (6)	−0.0055 (6)
N2	0.0304 (7)	0.0421 (8)	0.0352 (9)	0.0048 (6)	0.0018 (6)	0.0017 (6)
O5	0.0364 (7)	0.0426 (8)	0.0666 (10)	−0.0066 (6)	0.0011 (6)	0.0077 (7)
C24	0.0403 (9)	0.0348 (9)	0.0436 (11)	0.0058 (8)	−0.0026 (8)	0.0014 (8)
C7	0.0374 (9)	0.0386 (10)	0.0375 (10)	0.0015 (7)	0.0071 (8)	−0.0011 (8)
C6	0.0314 (9)	0.0468 (11)	0.0443 (11)	0.0041 (8)	0.0008 (8)	−0.0013 (8)
N3	0.0411 (9)	0.0550 (10)	0.0431 (10)	0.0014 (8)	−0.0024 (7)	−0.0079 (8)
C12	0.0463 (10)	0.0331 (9)	0.0334 (10)	0.0046 (8)	0.0040 (8)	0.0050 (7)
C13	0.0382 (9)	0.0363 (9)	0.0359 (10)	0.0084 (7)	0.0000 (8)	0.0026 (7)
C11	0.0627 (13)	0.0414 (10)	0.0362 (11)	0.0036 (9)	−0.0041 (9)	−0.0004 (8)
C8	0.0484 (11)	0.0517 (12)	0.0457 (12)	0.0094 (9)	0.0072 (9)	−0.0001 (9)
C9	0.0735 (15)	0.0510 (12)	0.0512 (14)	0.0206 (11)	0.0170 (12)	0.0010 (10)
C10	0.0829 (16)	0.0445 (12)	0.0380 (12)	0.0049 (11)	0.0030 (11)	−0.0075 (9)
C19	0.0358 (10)	0.0487 (12)	0.0645 (15)	0.0038 (9)	−0.0003 (9)	−0.0105 (10)
C14	0.0526 (12)	0.0661 (15)	0.0498 (14)	0.0071 (11)	−0.0090 (10)	−0.0133 (11)
C18	0.0495 (12)	0.0642 (14)	0.0446 (13)	−0.0043 (10)	0.0045 (10)	0.0051 (10)
C23	0.0888 (18)	0.0445 (12)	0.0616 (16)	0.0143 (11)	0.0293 (13)	0.0215 (10)
C20	0.0558 (14)	0.0600 (15)	0.083 (2)	0.0210 (12)	−0.0106 (13)	−0.0255 (14)
C16	0.0659 (14)	0.0711 (16)	0.0373 (12)	0.0153 (12)	−0.0047 (10)	−0.0099 (11)
C21	0.115 (2)	0.0425 (13)	0.076 (2)	0.0263 (15)	−0.0259 (17)	0.0016 (13)
C17	0.0723 (16)	0.0806 (17)	0.0402 (13)	0.0067 (13)	0.0116 (11)	0.0021 (12)
C22	0.130 (3)	0.0433 (13)	0.079 (2)	0.0139 (16)	0.0199 (19)	0.0209 (13)
C15	0.0665 (17)	0.157 (3)	0.070 (2)	−0.0246 (19)	−0.0090 (15)	−0.045 (2)

P1—O5	1.4641 (14)	C9—C10	1.369 (3)
P1—O4	1.5984 (15)	C9—H9	0.9300
P1—N2	1.6702 (14)	C10—H10	0.9300
P1—C24	1.7850 (19)	C19—C20	1.406 (3)
O4—C12	1.407 (2)	C19—H19	0.9300
N2—C13	1.424 (2)	C14—C16	1.384 (4)
N2—C6	1.476 (2)	C14—C15	1.522 (3)
C24—C19	1.383 (3)	C18—C17	1.372 (3)
C24—C23	1.388 (3)	C18—H18	0.9300
C7—C12	1.385 (3)	C23—C22	1.376 (3)
C7—C8	1.395 (3)	C23—H23	0.9300
C7—C6	1.491 (3)	C20—C21	1.362 (4)
C6—H6A	0.9700	C20—H20	0.9300
C6—H6B	0.9700	C16—C17	1.366 (3)
N3—C13	1.331 (2)	C16—H16	0.9300
N3—C14	1.342 (3)	C21—C22	1.364 (4)
C12—C11	1.374 (3)	C21—H21	0.9300
C13—C18	1.397 (3)	C17—H17	0.9300
C11—C10	1.397 (3)	C22—H22	0.9300
C11—H11	0.9300	C15—H15A	0.9600
C8—C9	1.388 (3)	C15—H15B	0.9600
C8—H8	0.9300	C15—H15C	0.9600
O5—P1—O4	114.90 (8)	C8—C9—H9	119.9
O5—P1—N2	114.95 (8)	C9—C10—C11	120.7 (2)
O4—P1—N2	101.68 (7)	C9—C10—H10	119.7
O5—P1—C24	112.80 (9)	C11—C10—H10	119.7
O4—P1—C24	101.38 (8)	C24—C19—C20	119.4 (2)
N2—P1—C24	109.81 (8)	C24—C19—H19	120.3
C12—O4—P1	121.93 (12)	C20—C19—H19	120.3
C13—N2—C6	116.96 (14)	N3—C14—C16	122.4 (2)
C13—N2—P1	118.81 (12)	N3—C14—C15	115.9 (2)
C6—N2—P1	120.30 (13)	C16—C14—C15	121.7 (2)
C19—C24—C23	119.55 (19)	C17—C18—C13	117.9 (2)
C19—C24—P1	119.92 (16)	C17—C18—H18	121.0
C23—C24—P1	120.53 (16)	C13—C18—H18	121.0
C12—C7—C8	117.29 (17)	C22—C23—C24	119.7 (2)
C12—C7—C6	119.26 (16)	C22—C23—H23	120.2
C8—C7—C6	123.43 (17)	C24—C23—H23	120.2
N2—C6—C7	110.86 (15)	C21—C20—C19	120.2 (2)
N2—C6—H6A	109.5	C21—C20—H20	119.9
C7—C6—H6A	109.5	C19—C20—H20	119.9
N2—C6—H6B	109.5	C17—C16—C14	119.3 (2)
C7—C6—H6B	109.5	C17—C16—H16	120.4
H6A—C6—H6B	108.1	C14—C16—H16	120.4
C13—N3—C14	117.66 (19)	C20—C21—C22	120.0 (2)
C11—C12—C7	123.37 (18)	C20—C21—H21	120.0
C11—C12—O4	119.00 (17)	C22—C21—H21	120.0
C7—C12—O4	117.56 (16)	C16—C17—C18	119.5 (2)
N3—C13—C18	123.22 (18)	C16—C17—H17	120.2
N3—C13—N2	115.42 (16)	C18—C17—H17	120.2
C18—C13—N2	121.35 (17)	C21—C22—C23	121.2 (3)
C12—C11—C10	117.8 (2)	C21—C22—H22	119.4
C12—C11—H11	121.1	C23—C22—H22	119.4
C10—C11—H11	121.1	C14—C15—H15A	109.5
C9—C8—C7	120.6 (2)	C14—C15—H15B	109.5
C9—C8—H8	119.7	H15A—C15—H15B	109.5
C7—C8—H8	119.7	C14—C15—H15C	109.5
C10—C9—C8	120.3 (2)	H15A—C15—H15C	109.5
C10—C9—H9	119.9	H15B—C15—H15C	109.5
O5—P1—O4—C12	88.83 (15)	C6—N2—C13—N3	−19.5 (2)
N2—P1—O4—C12	−35.98 (15)	P1—N2—C13—N3	138.32 (15)
C24—P1—O4—C12	−149.22 (14)	C6—N2—C13—C18	160.12 (19)
O5—P1—N2—C13	67.98 (16)	P1—N2—C13—C18	−42.1 (2)
O4—P1—N2—C13	−167.24 (13)	C7—C12—C11—C10	0.5 (3)
C24—P1—N2—C13	−60.47 (16)	O4—C12—C11—C10	−176.41 (18)
O5—P1—N2—C6	−134.97 (14)	C12—C7—C8—C9	0.4 (3)
O4—P1—N2—C6	−10.20 (16)	C6—C7—C8—C9	178.5 (2)
C24—P1—N2—C6	96.57 (15)	C7—C8—C9—C10	−1.3 (4)
O5—P1—C24—C19	−7.5 (2)	C8—C9—C10—C11	1.7 (4)
O4—P1—C24—C19	−130.88 (17)	C12—C11—C10—C9	−1.3 (3)
N2—P1—C24—C19	122.15 (17)	C23—C24—C19—C20	−2.5 (3)
O5—P1—C24—C23	173.33 (17)	P1—C24—C19—C20	178.29 (17)
O4—P1—C24—C23	49.93 (19)	C13—N3—C14—C16	0.9 (3)
N2—P1—C24—C23	−57.0 (2)	C13—N3—C14—C15	−179.9 (2)
C13—N2—C6—C7	−156.56 (16)	N3—C13—C18—C17	1.1 (3)
P1—N2—C6—C7	46.0 (2)	N2—C13—C18—C17	−178.50 (19)
C12—C7—C6—N2	−41.6 (3)	C19—C24—C23—C22	0.9 (4)
C8—C7—C6—N2	140.36 (19)	P1—C24—C23—C22	−179.9 (2)
C8—C7—C12—C11	−0.1 (3)	C24—C19—C20—C21	2.2 (4)
C6—C7—C12—C11	−178.27 (19)	N3—C14—C16—C17	−0.4 (4)
C8—C7—C12—O4	176.88 (18)	C15—C14—C16—C17	−179.5 (3)
C6—C7—C12—O4	−1.3 (3)	C19—C20—C21—C22	−0.2 (4)
P1—O4—C12—C11	−138.17 (16)	C14—C16—C17—C18	0.1 (4)
P1—O4—C12—C7	44.7 (2)	C13—C18—C17—C16	−0.4 (4)
C14—N3—C13—C18	−1.3 (3)	C20—C21—C22—C23	−1.4 (4)
C14—N3—C13—N2	178.29 (17)	C24—C23—C22—C21	1.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O5i	0.93	2.57	3.455 (3)	159
C21—H21···O5ii	0.93	2.56	3.445 (3)	159
C18—H18···O5	0.93	2.50	3.158 (3)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O5i	0.93	2.57	3.455 (3)	159
C21—H21⋯O5ii	0.93	2.56	3.445 (3)	159
C18—H18⋯O5	0.93	2.50	3.158 (3)	128

Symmetry codes: (i) ; (ii) .