rac-Phenyl (benzylamido)(p-tolyl-amido)-phosphinate.

The title compound, C(20)H(21)N(2)O(2)P, was synthesized from (RS)-(C(6)H(5)O)P(O)Cl(NHC(6)H(4)-p-CH(3)) and benzyl-amine. The product crystallizes as a racemate in a polar space group. The phospho-rus atom has a distorted tetra-hedral configuration: the bond angles at the P atom are in the range 103.2 (1)-118.4 (1)°. The P-N(benzyl-amido) bond [1.615 (2) Å] is slightly shorter than the P-N(p-tolyl-amido) bond [1.630 (2) Å]. Both N-H groups adopt an anti orientation relative to the phosphoryl group. In the crystal, the adjacent mol-ecules are linked via N-H⋯O hydrogen bonds, forming R(2) (2)(8) rings, into a one-dimensional arrangement parallel to the x axis.

Related literature

For a related mixed-amido phosphinate derivative and its mol­ecular geometry, see: Sabbaghi et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H21N2O2P

M = 352.36

Orthorhombic,

a = 9.6986 (5) Å

b = 13.0751 (6) Å

c = 14.3446 (5) Å

V = 1819.04 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.17 mm−1

T = 120 K

0.30 × 0.30 × 0.10 mm

Data collection

Xcalibur, Sapphire2, large Be window diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.785, T max = 1.000

20413 measured reflections

3200 independent reflections

2823 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 1.00

3200 reflections

233 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 1526 Friedel pairs

Flack parameter: 0.01 (10)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811034465/ld2023sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034465/ld2023Isup2.hkl

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

C20H21N2O2P	Dx = 1.287 Mg m−3
Mr = 352.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 10547 reflections
a = 9.6986 (5) Å	θ = 3.0–27.2°
b = 13.0751 (6) Å	µ = 0.17 mm−1
c = 14.3446 (5) Å	T = 120 K
V = 1819.04 (14) Å3	Plate, colorless
Z = 4	0.30 × 0.30 × 0.10 mm
F(000) = 744

Xcalibur, Sapphire2, large Be window diffractometer	3200 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2823 reflections with I > 2σ(I)
graphite	Rint = 0.047
Detector resolution: 8.4353 pixels mm-1	θmax = 25.0°, θmin = 3.0°
ω scan	h = −11→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −15→15
Tmin = 0.785, Tmax = 1.000	l = −17→17
20413 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.073P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
3200 reflections	Δρmax = 0.51 e Å−3
233 parameters	Δρmin = −0.29 e Å−3
1 restraint	Absolute structure: Flack (1983), 1523 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (10)

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
P1	0.91905 (5)	0.99930 (4)	0.56899 (5)	0.01847 (16)
O1	0.84602 (16)	1.07673 (12)	0.64256 (11)	0.0217 (4)
O2	0.80162 (17)	0.94641 (13)	0.52605 (12)	0.0247 (4)
N1	1.0250 (2)	0.92421 (16)	0.62255 (15)	0.0241 (5)
H1N	1.098 (3)	0.944 (2)	0.630 (2)	0.029*
N2	1.0197 (2)	1.06729 (15)	0.50236 (15)	0.0217 (5)
H2N	1.107 (3)	1.062 (2)	0.5071 (19)	0.026*
C1	0.9250 (2)	1.1424 (2)	0.69810 (16)	0.0207 (6)
C2	0.9809 (3)	1.1052 (2)	0.78124 (17)	0.0264 (6)
H2C	0.9699	1.0356	0.7987	0.032*
C3	1.0533 (3)	1.1733 (2)	0.83765 (18)	0.0297 (6)
H3A	1.0940	1.1494	0.8938	0.036*
C4	1.0667 (3)	1.2738 (2)	0.81375 (18)	0.0290 (6)
H4A	1.1156	1.3192	0.8535	0.035*
C5	1.0088 (3)	1.3098 (2)	0.73111 (18)	0.0283 (6)
H5A	1.0182	1.3798	0.7143	0.034*
C6	0.9375 (3)	1.2432 (2)	0.67366 (17)	0.0249 (6)
H6A	0.8974	1.2674	0.6174	0.030*
C7	0.9737 (3)	0.83908 (19)	0.67821 (18)	0.0273 (6)
H7A	0.8801	0.8564	0.7006	0.033*
H7B	1.0336	0.8315	0.7337	0.033*
C8	0.9671 (3)	0.73740 (18)	0.62858 (16)	0.0225 (5)
C9	0.8580 (3)	0.6727 (2)	0.6440 (2)	0.0360 (7)
H9A	0.7840	0.6945	0.6826	0.043*
C10	0.8539 (4)	0.5761 (2)	0.6042 (2)	0.0503 (9)
H10A	0.7787	0.5316	0.6167	0.060*
C11	0.9596 (4)	0.5448 (2)	0.54621 (18)	0.0436 (8)
H11A	0.9573	0.4789	0.5184	0.052*
C12	1.0667 (3)	0.6091 (2)	0.52932 (19)	0.0368 (7)
H12A	1.1394	0.5876	0.4895	0.044*
C13	1.0716 (3)	0.70547 (18)	0.5693 (2)	0.0282 (5)
H13A	1.1467	0.7498	0.5561	0.034*
C14	0.9794 (3)	1.15603 (17)	0.45273 (16)	0.0196 (5)
C15	1.0762 (3)	1.23182 (19)	0.43674 (17)	0.0246 (5)
H15A	1.1680	1.2239	0.4588	0.030*
C16	1.0383 (3)	1.3201 (2)	0.38799 (19)	0.0296 (6)
H16A	1.1061	1.3707	0.3753	0.036*
C17	0.9042 (3)	1.33547 (18)	0.35774 (16)	0.0258 (6)
C18	0.8104 (3)	1.25870 (19)	0.37405 (16)	0.0249 (6)
H18A	0.7182	1.2670	0.3530	0.030*
C19	0.8467 (3)	1.16882 (19)	0.42071 (16)	0.0229 (5)
H19A	0.7799	1.1167	0.4303	0.027*
C20	0.8653 (3)	1.4309 (2)	0.3061 (2)	0.0364 (7)
H20A	0.7646	1.4369	0.3040	0.055*
H20B	0.9017	1.4276	0.2424	0.055*
H20C	0.9041	1.4905	0.3381	0.055*

	U11	U22	U33	U12	U13	U23
P1	0.0170 (3)	0.0230 (3)	0.0154 (3)	−0.0002 (3)	0.0001 (3)	0.0003 (2)
O1	0.0207 (9)	0.0288 (9)	0.0155 (8)	0.0002 (7)	−0.0003 (7)	−0.0013 (7)
O2	0.0199 (9)	0.0295 (10)	0.0247 (8)	−0.0025 (7)	−0.0001 (7)	−0.0008 (7)
N1	0.0185 (11)	0.0276 (12)	0.0261 (12)	−0.0036 (10)	−0.0027 (10)	0.0003 (9)
N2	0.0153 (11)	0.0287 (11)	0.0211 (10)	0.0021 (9)	−0.0001 (9)	0.0026 (9)
C1	0.0165 (13)	0.0302 (14)	0.0154 (12)	−0.0025 (10)	0.0021 (9)	−0.0065 (10)
C2	0.0320 (15)	0.0292 (13)	0.0180 (11)	0.0010 (11)	−0.0026 (11)	0.0026 (11)
C3	0.0307 (15)	0.0421 (16)	0.0163 (12)	0.0023 (13)	−0.0032 (11)	−0.0008 (12)
C4	0.0274 (14)	0.0378 (15)	0.0217 (13)	−0.0048 (12)	−0.0014 (11)	−0.0077 (11)
C5	0.0308 (16)	0.0282 (14)	0.0260 (15)	−0.0039 (12)	0.0044 (12)	−0.0031 (12)
C6	0.0239 (14)	0.0340 (14)	0.0167 (11)	0.0031 (11)	0.0007 (10)	0.0015 (11)
C7	0.0368 (17)	0.0260 (14)	0.0190 (13)	0.0026 (12)	−0.0008 (12)	0.0046 (11)
C8	0.0241 (13)	0.0262 (13)	0.0173 (12)	0.0033 (11)	−0.0028 (10)	0.0056 (10)
C9	0.0355 (16)	0.0454 (16)	0.0272 (14)	−0.0088 (13)	0.0049 (12)	−0.0043 (13)
C10	0.066 (2)	0.0461 (18)	0.0387 (16)	−0.0296 (17)	0.0033 (17)	−0.0012 (14)
C11	0.083 (2)	0.0280 (14)	0.0199 (14)	−0.0073 (16)	−0.0028 (14)	−0.0025 (11)
C12	0.054 (2)	0.0357 (15)	0.0201 (13)	0.0115 (14)	0.0042 (13)	0.0011 (11)
C13	0.0289 (14)	0.0316 (13)	0.0240 (12)	0.0016 (10)	0.0020 (12)	0.0081 (13)
C14	0.0214 (14)	0.0257 (13)	0.0118 (12)	0.0031 (11)	0.0044 (10)	−0.0037 (10)
C15	0.0229 (14)	0.0327 (13)	0.0184 (12)	0.0010 (11)	−0.0016 (10)	−0.0015 (11)
C16	0.0361 (17)	0.0274 (13)	0.0254 (13)	−0.0051 (12)	0.0057 (12)	−0.0009 (11)
C17	0.0368 (16)	0.0279 (14)	0.0128 (12)	0.0071 (11)	0.0029 (10)	−0.0027 (10)
C18	0.0252 (14)	0.0341 (14)	0.0154 (12)	0.0058 (11)	0.0008 (10)	−0.0026 (11)
C19	0.0237 (14)	0.0295 (13)	0.0154 (11)	0.0002 (11)	0.0010 (10)	−0.0004 (10)
C20	0.0481 (18)	0.0310 (14)	0.0302 (14)	0.0037 (14)	0.0008 (13)	0.0023 (12)

P1—O2	1.4679 (17)	C8—C13	1.387 (4)
P1—N1	1.615 (2)	C9—C10	1.386 (4)
P1—O1	1.6250 (17)	C9—H9A	0.9500
P1—N2	1.630 (2)	C10—C11	1.382 (4)
O1—C1	1.400 (3)	C10—H10A	0.9500
N1—C7	1.457 (3)	C11—C12	1.358 (4)
N1—H1N	0.76 (3)	C11—H11A	0.9500
N2—C14	1.416 (3)	C12—C13	1.385 (4)
N2—H2N	0.86 (3)	C12—H12A	0.9500
C1—C6	1.369 (4)	C13—H13A	0.9500
C1—C2	1.398 (4)	C14—C19	1.377 (4)
C2—C3	1.393 (4)	C14—C15	1.385 (3)
C2—H2C	0.9500	C15—C16	1.399 (4)
C3—C4	1.364 (4)	C15—H15A	0.9500
C3—H3A	0.9500	C16—C17	1.386 (4)
C4—C5	1.394 (4)	C16—H16A	0.9500
C4—H4A	0.9500	C17—C18	1.375 (4)
C5—C6	1.384 (4)	C17—C20	1.499 (3)
C5—H5A	0.9500	C18—C19	1.397 (4)
C6—H6A	0.9500	C18—H18A	0.9500
C7—C8	1.510 (4)	C19—H19A	0.9500
C7—H7A	0.9900	C20—H20A	0.9800
C7—H7B	0.9900	C20—H20B	0.9800
C8—C9	1.373 (4)	C20—H20C	0.9800
O2—P1—N1	114.00 (11)	C8—C9—C10	121.1 (3)
O2—P1—O1	103.17 (9)	C8—C9—H9A	119.4
N1—P1—O1	110.30 (11)	C10—C9—H9A	119.4
O2—P1—N2	118.39 (11)	C11—C10—C9	119.8 (3)
N1—P1—N2	103.28 (11)	C11—C10—H10A	120.1
O1—P1—N2	107.58 (10)	C9—C10—H10A	120.1
C1—O1—P1	120.90 (14)	C12—C11—C10	119.4 (3)
C7—N1—P1	120.54 (18)	C12—C11—H11A	120.3
C7—N1—H1N	120 (2)	C10—C11—H11A	120.3
P1—N1—H1N	117 (2)	C11—C12—C13	121.0 (3)
C14—N2—P1	125.18 (18)	C11—C12—H12A	119.5
C14—N2—H2N	112.1 (18)	C13—C12—H12A	119.5
P1—N2—H2N	120.5 (19)	C12—C13—C8	120.2 (2)
C6—C1—C2	121.3 (2)	C12—C13—H13A	119.9
C6—C1—O1	119.6 (2)	C8—C13—H13A	119.9
C2—C1—O1	118.9 (2)	C19—C14—C15	119.5 (2)
C3—C2—C1	117.9 (2)	C19—C14—N2	121.7 (2)
C3—C2—H2C	121.1	C15—C14—N2	118.8 (2)
C1—C2—H2C	121.1	C14—C15—C16	119.7 (2)
C4—C3—C2	121.2 (2)	C14—C15—H15A	120.2
C4—C3—H3A	119.4	C16—C15—H15A	120.2
C2—C3—H3A	119.4	C17—C16—C15	121.5 (2)
C3—C4—C5	120.1 (3)	C17—C16—H16A	119.2
C3—C4—H4A	120.0	C15—C16—H16A	119.2
C5—C4—H4A	120.0	C18—C17—C16	117.5 (2)
C6—C5—C4	119.7 (2)	C18—C17—C20	121.7 (2)
C6—C5—H5A	120.2	C16—C17—C20	120.8 (2)
C4—C5—H5A	120.2	C17—C18—C19	121.9 (2)
C1—C6—C5	119.8 (2)	C17—C18—H18A	119.0
C1—C6—H6A	120.1	C19—C18—H18A	119.0
C5—C6—H6A	120.1	C14—C19—C18	119.8 (2)
N1—C7—C8	115.4 (2)	C14—C19—H19A	120.1
N1—C7—H7A	108.4	C18—C19—H19A	120.1
C8—C7—H7A	108.4	C17—C20—H20A	109.5
N1—C7—H7B	108.4	C17—C20—H20B	109.5
C8—C7—H7B	108.4	H20A—C20—H20B	109.5
H7A—C7—H7B	107.5	C17—C20—H20C	109.5
C9—C8—C13	118.5 (2)	H20A—C20—H20C	109.5
C9—C8—C7	119.9 (2)	H20B—C20—H20C	109.5
C13—C8—C7	121.6 (2)
O2—P1—O1—C1	−179.64 (16)	N1—C7—C8—C13	41.2 (3)
N1—P1—O1—C1	58.23 (19)	C13—C8—C9—C10	2.3 (4)
N2—P1—O1—C1	−53.74 (19)	C7—C8—C9—C10	−175.7 (3)
O2—P1—N1—C7	−40.2 (2)	C8—C9—C10—C11	−1.5 (5)
O1—P1—N1—C7	75.3 (2)	C9—C10—C11—C12	0.3 (5)
N2—P1—N1—C7	−169.97 (18)	C10—C11—C12—C13	0.0 (4)
O2—P1—N2—C14	64.2 (2)	C11—C12—C13—C8	0.8 (4)
N1—P1—N2—C14	−168.78 (18)	C9—C8—C13—C12	−1.9 (4)
O1—P1—N2—C14	−52.1 (2)	C7—C8—C13—C12	176.0 (2)
P1—O1—C1—C6	100.9 (2)	P1—N2—C14—C19	−30.3 (3)
P1—O1—C1—C2	−83.8 (2)	P1—N2—C14—C15	149.3 (2)
C6—C1—C2—C3	−1.6 (4)	C19—C14—C15—C16	−0.3 (4)
O1—C1—C2—C3	−176.8 (2)	N2—C14—C15—C16	−179.9 (2)
C1—C2—C3—C4	1.4 (4)	C14—C15—C16—C17	2.2 (4)
C2—C3—C4—C5	−0.7 (4)	C15—C16—C17—C18	−2.6 (4)
C3—C4—C5—C6	0.1 (4)	C15—C16—C17—C20	179.6 (2)
C2—C1—C6—C5	1.1 (4)	C16—C17—C18—C19	1.1 (3)
O1—C1—C6—C5	176.3 (2)	C20—C17—C18—C19	178.9 (2)
C4—C5—C6—C1	−0.3 (4)	C15—C14—C19—C18	−1.2 (3)
P1—N1—C7—C8	94.9 (3)	N2—C14—C19—C18	178.4 (2)
N1—C7—C8—C9	−140.9 (3)	C17—C18—C19—C14	0.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.76 (3)	2.43 (3)	3.127 (3)	153 (3)
N2—H2N···O2i	0.86 (3)	1.91 (3)	2.761 (3)	176 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.76 (3)	2.43 (3)	3.127 (3)	153 (3)
N2—H2N⋯O2i	0.86 (3)	1.91 (3)	2.761 (3)	176 (3)

Symmetry code: (i) .