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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2352.
Published online 2010 August 18. doi:  10.1107/S1600536810032319
PMCID: PMC3007901

2-Isopropyl-5-methyl­cyclo­hexyl N-cyclo­hexyl-P-phenyl­phospho­namidate

Abstract

The title compound, C22H36NO2P, features a P atom bonded to a phenyl ring, a cyclo­hexyl­amine unit and the O atom of a menthyl group. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds connect mol­ecules into a one-dimensional chain in the b direction.

Related literature

For the general synthesis of phospho­rus–amine compounds, see: Steinberg (1950 [triangle]); Benamer et al. (2010 [triangle]). For the structures of related phospho­rus–amine compounds, see: Balakrishna et al. (2001 [triangle]).

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Object name is e-66-o2352-scheme1.jpg

Experimental

Crystal data

  • C22H36NO2P
  • M r = 377.49
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2352-efi1.jpg
  • a = 10.0205 (10) Å
  • b = 10.4317 (11) Å
  • c = 22.101 (2) Å
  • V = 2310.2 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 298 K
  • 0.40 × 0.14 × 0.07 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.949, T max = 0.991
  • 11780 measured reflections
  • 4064 independent reflections
  • 2537 reflections with I > 2σ(I)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.083
  • S = 1.00
  • 4064 reflections
  • 238 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.21 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1727 Friedel pairs
  • Flack parameter: −0.01 (11)

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810032319/vm2032sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032319/vm2032Isup2.hkl

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

Acknowledgments

The authors acknowledge the financial support of the Natural Science Foundation of China (grant No. 20772055).

supplementary crystallographic information

Comment

The molecular structure of the P-chiral title compound consists of an O-menthyl phenylphosphinate core and cyclohexylamine (Steinberg, 1950). The absolute configuration of the central P atom is S and the four groups around the central P atom form an irregular tetrahedron (Benamer et al., 2010). In the crystal structure intermolecular N—H···O hydrogen bonds connect molecules into a one-dimensional chain in the b-direction (Table 1, Fig. 2).

Experimental

Carbon tetrachloride was added to a solution of (Rp)-O-menthyl-phenyl phosphonothioate dissolved in dry ether and cyclohexylamine. The reaction mixture was stirred for 38 h at room temperature. A single crystal of the title compound suitable for X-ray diffraction was obtained by slow evaporation of an ether solution of the title compound.

Refinement

The imino H atom was located in a differece Fourier map and refined isotropically, with the N—H distance restrained to 0.86 Å. Other H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93–0.98 Å, with Uiso(H) = 1.5 Ueq(methyl) and Uiso(H) = 1.2 Ueq(C) for all other H atoms.

Figures

Fig. 1.
The molecular structure of the compound. H atoms have been omitted for clarity.
Fig. 2.
A view of the one-dimensional chain structure formed by N—H···O interactions in the title compound.

Crystal data

C22H36NO2PF(000) = 824
Mr = 377.49Dx = 1.085 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2271 reflections
a = 10.0205 (10) Åθ = 3.0–25.0°
b = 10.4317 (11) ŵ = 0.13 mm1
c = 22.101 (2) ÅT = 298 K
V = 2310.2 (4) Å3Block, colourless
Z = 40.40 × 0.14 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer4064 independent reflections
Radiation source: fine-focus sealed tube2537 reflections with I > 2σ(I)
graphiteRint = 0.061
[var phi] and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→11
Tmin = 0.949, Tmax = 0.991k = −11→12
11780 measured reflectionsl = −26→23

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.083w = 1/[σ2(Fo2) + (0.0224P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
4064 reflectionsΔρmax = 0.17 e Å3
238 parametersΔρmin = −0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), with 1727 Friedel pairs [Please check]
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (11)

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 (Å2)

xyzUiso*/Ueq
N11.06771 (19)0.23385 (19)0.24171 (9)0.0499 (6)
H11.05950.31590.24050.060*
O10.83345 (16)0.21330 (17)0.19514 (8)0.0453 (5)
O20.96301 (17)0.01022 (17)0.22946 (8)0.0536 (5)
P10.93290 (8)0.14723 (7)0.24088 (3)0.0429 (2)
C10.8879 (4)0.4422 (3)0.06456 (14)0.0768 (11)
H1A0.97960.41830.05410.092*
C20.8593 (3)0.3933 (3)0.12811 (12)0.0606 (9)
H2A0.92170.43260.15610.073*
H2B0.77010.41930.13980.073*
C30.8704 (3)0.2485 (3)0.13321 (12)0.0481 (8)
H30.96290.22260.12560.058*
C40.7777 (3)0.1789 (3)0.08865 (12)0.0592 (9)
H40.68610.20410.09870.071*
C50.8062 (4)0.2286 (3)0.02431 (12)0.0774 (11)
H5A0.89560.20330.01250.093*
H5B0.74390.1894−0.00370.093*
C60.7939 (4)0.3748 (3)0.02013 (14)0.0895 (12)
H6A0.81470.4021−0.02080.107*
H6B0.70260.39970.02880.107*
C70.8768 (4)0.5885 (3)0.06108 (16)0.1226 (17)
H7A0.78750.61410.07120.184*
H7B0.89750.61650.02080.184*
H7C0.93840.62660.08910.184*
C80.7848 (3)0.0312 (3)0.09409 (14)0.0688 (10)
H80.77670.01050.13720.083*
C90.6676 (4)−0.0338 (3)0.06175 (16)0.0917 (12)
H9A0.58530.00330.07540.138*
H9B0.6680−0.12390.07080.138*
H9C0.6762−0.02170.01890.138*
C100.9165 (3)−0.0253 (3)0.07251 (16)0.0912 (12)
H10A0.9257−0.01130.02980.137*
H10B0.9178−0.11570.08070.137*
H10C0.98890.01540.09340.137*
C111.2028 (2)0.1796 (3)0.24442 (13)0.0552 (8)
H111.19640.09280.26110.066*
C121.2647 (3)0.1704 (4)0.18205 (14)0.0822 (11)
H12A1.20980.11570.15680.099*
H12B1.26650.25500.16380.099*
C131.4051 (4)0.1172 (5)0.1840 (2)0.134 (2)
H13A1.44260.11650.14350.161*
H13B1.40320.02970.19890.161*
C141.4916 (4)0.1989 (6)0.2252 (3)0.150 (2)
H14A1.49840.28490.20880.180*
H14B1.58070.16280.22730.180*
C151.4315 (4)0.2045 (5)0.2888 (2)0.1302 (18)
H15A1.48600.25880.31440.156*
H15B1.43000.11920.30620.156*
C161.2890 (3)0.2581 (4)0.28578 (16)0.0877 (12)
H16A1.25050.25840.32600.105*
H16B1.29180.34590.27140.105*
C170.8400 (3)0.1681 (3)0.30935 (12)0.0452 (7)
C180.8202 (3)0.2870 (3)0.33534 (14)0.0636 (9)
H180.85680.35940.31720.076*
C190.7467 (3)0.3002 (3)0.38791 (15)0.0776 (11)
H190.73450.38100.40480.093*
C200.6920 (4)0.1947 (4)0.41515 (14)0.0763 (11)
H200.64250.20380.45050.092*
C210.7103 (4)0.0758 (4)0.39042 (15)0.0832 (11)
H210.67330.00390.40880.100*
C220.7844 (3)0.0634 (3)0.33780 (14)0.0673 (10)
H220.7969−0.01760.32130.081*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0427 (11)0.0383 (14)0.0687 (15)0.0012 (12)−0.0004 (14)−0.0012 (12)
O10.0465 (11)0.0518 (13)0.0377 (11)0.0046 (10)−0.0014 (9)0.0019 (10)
O20.0624 (12)0.0374 (12)0.0609 (13)0.0023 (10)0.0017 (10)−0.0037 (10)
P10.0461 (4)0.0365 (5)0.0460 (4)0.0015 (4)−0.0010 (4)−0.0011 (4)
C10.115 (3)0.055 (2)0.061 (2)0.002 (2)−0.006 (2)0.0105 (17)
C20.084 (2)0.048 (2)0.050 (2)0.0012 (18)−0.0082 (17)0.0013 (15)
C30.0580 (18)0.047 (2)0.0387 (18)0.0040 (16)0.0001 (15)0.0008 (14)
C40.075 (2)0.057 (2)0.0455 (19)0.006 (2)−0.0092 (16)−0.0023 (16)
C50.115 (3)0.067 (3)0.049 (2)0.002 (2)−0.010 (2)−0.0007 (17)
C60.144 (3)0.071 (3)0.053 (2)0.004 (3)−0.016 (2)0.0142 (19)
C70.217 (5)0.060 (3)0.091 (3)−0.013 (3)−0.030 (3)0.029 (2)
C80.097 (3)0.058 (2)0.052 (2)−0.007 (2)−0.012 (2)−0.0013 (17)
C90.113 (3)0.079 (3)0.083 (3)−0.023 (3)−0.010 (2)−0.020 (2)
C100.106 (3)0.065 (3)0.102 (3)0.017 (3)−0.020 (3)−0.023 (2)
C110.0372 (15)0.055 (2)0.074 (2)0.0045 (15)−0.0008 (17)0.0021 (18)
C120.063 (2)0.093 (3)0.091 (3)0.007 (2)0.0164 (19)−0.020 (2)
C130.071 (3)0.160 (5)0.170 (5)0.018 (3)0.031 (3)−0.051 (4)
C140.060 (3)0.183 (6)0.207 (6)0.006 (3)0.011 (3)−0.030 (5)
C150.074 (3)0.155 (5)0.162 (5)0.010 (4)−0.045 (3)−0.018 (4)
C160.055 (2)0.114 (3)0.095 (3)−0.004 (2)−0.0194 (19)−0.008 (2)
C170.0514 (17)0.040 (2)0.0443 (17)−0.0032 (17)−0.0040 (14)0.0008 (15)
C180.080 (2)0.050 (2)0.060 (2)−0.006 (2)0.0146 (18)−0.0004 (17)
C190.106 (3)0.064 (3)0.063 (2)−0.002 (2)0.024 (2)−0.013 (2)
C200.105 (3)0.073 (3)0.051 (2)−0.002 (3)0.026 (2)0.005 (2)
C210.124 (3)0.064 (3)0.061 (2)−0.012 (3)0.027 (2)0.010 (2)
C220.098 (3)0.049 (2)0.055 (2)−0.008 (2)0.015 (2)−0.0009 (16)

Geometric parameters (Å, °)

N1—C111.468 (3)C9—H9C0.9600
N1—P11.625 (2)C10—H10A0.9600
N1—H10.8600C10—H10B0.9600
O1—C31.465 (3)C10—H10C0.9600
O1—P11.5779 (17)C11—C161.501 (4)
O2—P11.4823 (19)C11—C121.515 (4)
P1—C171.790 (3)C11—H110.9800
C1—C21.522 (4)C12—C131.513 (4)
C1—C61.532 (4)C12—H12A0.9700
C1—C71.532 (4)C12—H12B0.9700
C1—H1A0.9800C13—C141.519 (6)
C2—C31.518 (3)C13—H13A0.9700
C2—H2A0.9700C13—H13B0.9700
C2—H2B0.9700C14—C151.529 (6)
C3—C41.537 (3)C14—H14A0.9700
C3—H30.9800C14—H14B0.9700
C4—C51.540 (4)C15—C161.534 (5)
C4—C81.547 (4)C15—H15A0.9700
C4—H40.9800C15—H15B0.9700
C5—C61.533 (4)C16—H16A0.9700
C5—H5A0.9700C16—H16B0.9700
C5—H5B0.9700C17—C221.378 (4)
C6—H6A0.9700C17—C181.382 (4)
C6—H6B0.9700C18—C191.382 (4)
C7—H7A0.9600C18—H180.9300
C7—H7B0.9600C19—C201.370 (4)
C7—H7C0.9600C19—H190.9300
C8—C101.521 (4)C20—C211.367 (4)
C8—C91.533 (4)C20—H200.9300
C8—H80.9800C21—C221.386 (4)
C9—H9A0.9600C21—H210.9300
C9—H9B0.9600C22—H220.9300
C11—N1—P1123.52 (17)H9A—C9—H9C109.5
C11—N1—H1118.2H9B—C9—H9C109.5
P1—N1—H1118.2C8—C10—H10A109.5
C3—O1—P1123.26 (16)C8—C10—H10B109.5
O2—P1—O1116.15 (11)H10A—C10—H10B109.5
O2—P1—N1111.64 (11)C8—C10—H10C109.5
O1—P1—N1106.81 (11)H10A—C10—H10C109.5
O2—P1—C17111.54 (12)H10B—C10—H10C109.5
O1—P1—C1799.19 (11)N1—C11—C16110.2 (2)
N1—P1—C17110.81 (12)N1—C11—C12111.4 (2)
C2—C1—C6108.8 (3)C16—C11—C12110.7 (2)
C2—C1—C7111.5 (3)N1—C11—H11108.2
C6—C1—C7112.4 (3)C16—C11—H11108.2
C2—C1—H1A108.0C12—C11—H11108.2
C6—C1—H1A108.0C13—C12—C11112.2 (3)
C7—C1—H1A108.0C13—C12—H12A109.2
C3—C2—C1112.8 (2)C11—C12—H12A109.2
C3—C2—H2A109.0C13—C12—H12B109.2
C1—C2—H2A109.0C11—C12—H12B109.2
C3—C2—H2B109.0H12A—C12—H12B107.9
C1—C2—H2B109.0C12—C13—C14110.0 (4)
H2A—C2—H2B107.8C12—C13—H13A109.7
O1—C3—C2107.5 (2)C14—C13—H13A109.7
O1—C3—C4109.1 (2)C12—C13—H13B109.7
C2—C3—C4112.2 (2)C14—C13—H13B109.7
O1—C3—H3109.3H13A—C13—H13B108.2
C2—C3—H3109.3C13—C14—C15110.3 (4)
C4—C3—H3109.3C13—C14—H14A109.6
C3—C4—C5108.7 (2)C15—C14—H14A109.6
C3—C4—C8113.1 (2)C13—C14—H14B109.6
C5—C4—C8113.5 (2)C15—C14—H14B109.6
C3—C4—H4107.1H14A—C14—H14B108.1
C5—C4—H4107.1C14—C15—C16109.9 (4)
C8—C4—H4107.1C14—C15—H15A109.7
C6—C5—C4112.1 (3)C16—C15—H15A109.7
C6—C5—H5A109.2C14—C15—H15B109.7
C4—C5—H5A109.2C16—C15—H15B109.7
C6—C5—H5B109.2H15A—C15—H15B108.2
C4—C5—H5B109.2C11—C16—C15111.3 (3)
H5A—C5—H5B107.9C11—C16—H16A109.4
C1—C6—C5111.6 (3)C15—C16—H16A109.4
C1—C6—H6A109.3C11—C16—H16B109.4
C5—C6—H6A109.3C15—C16—H16B109.4
C1—C6—H6B109.3H16A—C16—H16B108.0
C5—C6—H6B109.3C22—C17—C18117.6 (3)
H6A—C6—H6B108.0C22—C17—P1120.0 (2)
C1—C7—H7A109.5C18—C17—P1122.4 (2)
C1—C7—H7B109.5C17—C18—C19121.0 (3)
H7A—C7—H7B109.5C17—C18—H18119.5
C1—C7—H7C109.5C19—C18—H18119.5
H7A—C7—H7C109.5C20—C19—C18120.2 (3)
H7B—C7—H7C109.5C20—C19—H19119.9
C10—C8—C9110.3 (3)C18—C19—H19119.9
C10—C8—C4113.7 (3)C21—C20—C19120.0 (3)
C9—C8—C4111.6 (3)C21—C20—H20120.0
C10—C8—H8106.9C19—C20—H20120.0
C9—C8—H8106.9C20—C21—C22119.5 (3)
C4—C8—H8106.9C20—C21—H21120.3
C8—C9—H9A109.5C22—C21—H21120.3
C8—C9—H9B109.5C17—C22—C21121.7 (3)
H9A—C9—H9B109.5C17—C22—H22119.1
C8—C9—H9C109.5C21—C22—H22119.1
C3—O1—P1—O2−73.7 (2)P1—N1—C11—C16−139.8 (2)
C3—O1—P1—N151.5 (2)P1—N1—C11—C1296.9 (3)
C3—O1—P1—C17166.7 (2)N1—C11—C12—C13178.8 (3)
C11—N1—P1—O2−12.7 (2)C16—C11—C12—C1355.9 (4)
C11—N1—P1—O1−140.6 (2)C11—C12—C13—C14−56.8 (5)
C11—N1—P1—C17112.3 (2)C12—C13—C14—C1557.5 (6)
C6—C1—C2—C355.9 (4)C13—C14—C15—C16−57.7 (6)
C7—C1—C2—C3−179.6 (3)N1—C11—C16—C15−179.2 (3)
P1—O1—C3—C2−117.1 (2)C12—C11—C16—C15−55.6 (4)
P1—O1—C3—C4121.0 (2)C14—C15—C16—C1157.0 (5)
C1—C2—C3—O1−176.8 (2)O2—P1—C17—C22−12.2 (3)
C1—C2—C3—C4−56.9 (4)O1—P1—C17—C22110.8 (2)
O1—C3—C4—C5173.4 (2)N1—P1—C17—C22−137.2 (2)
C2—C3—C4—C554.4 (3)O2—P1—C17—C18168.3 (2)
O1—C3—C4—C8−59.6 (3)O1—P1—C17—C18−68.8 (3)
C2—C3—C4—C8−178.6 (3)N1—P1—C17—C1843.3 (3)
C3—C4—C5—C6−55.0 (4)C22—C17—C18—C19−0.2 (5)
C8—C4—C5—C6178.2 (3)P1—C17—C18—C19179.3 (2)
C2—C1—C6—C5−55.9 (4)C17—C18—C19—C20−0.1 (5)
C7—C1—C6—C5−179.9 (3)C18—C19—C20—C210.2 (6)
C4—C5—C6—C157.6 (4)C19—C20—C21—C220.0 (6)
C3—C4—C8—C10−69.3 (3)C18—C17—C22—C210.4 (4)
C5—C4—C8—C1055.2 (4)P1—C17—C22—C21−179.2 (3)
C3—C4—C8—C9165.2 (2)C20—C21—C22—C17−0.3 (5)
C5—C4—C8—C9−70.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.862.152.969 (3)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2032).

References

  • Balakrishna, M. S., Abhyankar, R. M. & Walawalker, M. G. (2001). Tetrahedron Lett.42, 2733–2734.
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