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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o839.
Published online 2009 March 25. doi:  10.1107/S160053680900909X
PMCID: PMC2969104

Tris(3-amino­phen­yl)phosphine oxide ethanol solvate

Abstract

The title compound crystallized as an ethanol solvate, C18H18N3OP·C2H6O. It is the reduction product of tris­(3-nitro­phen­yl)phosphine oxide. In the crystal, there are inter­molecular N—H(...)O hydrogen bonds between neighbouring tris­(3-amino­phen­yl)phosphine oxide mol­ecules and O—H(...)O hydrogen bonds involving the ethanol solvent mol­ecule.

Related literature

The structure of tris­(3-nitro­phen­yl)phosphine oxide is described by Jean-Noël et al. (2004 [triangle]). For literature on related compounds, see: Michaelis et al. (1885 [triangle]); Dressick et al. (2000 [triangle]); Hessler & Stelzer (1997 [triangle]).

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Object name is e-65-0o839-scheme1.jpg

Experimental

Crystal data

  • C18H18N3OP·C2H6O
  • M r = 369.39
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o839-efi1.jpg
  • a = 9.1046 (13) Å
  • b = 10.7595 (15) Å
  • c = 12.020 (3) Å
  • α = 109.131 (3)°
  • β = 94.245 (3)°
  • γ = 114.028 (2)°
  • V = 986.3 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 293 K
  • 0.35 × 0.34 × 0.30 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.947, T max = 0.954
  • 5014 measured reflections
  • 3420 independent reflections
  • 1659 reflections with I > 2σ(I)
  • R int = 0.058

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.149
  • S = 0.85
  • 3420 reflections
  • 174 parameters
  • H-atom parameters constrained
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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 global, I. DOI: 10.1107/S160053680900909X/pk2158sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900909X/pk2158Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge the financial support of the NSFC (grant No. 20602017), the Program for New Century Excellent Talents in University (grant No. NCET-07-0425) and the Natural Science Foundation of Jiangsu (grant No. BK 2008259).

supplementary crystallographic information

Comment

Arylphosphines have been investigated extensively as ionic ligands for catalytically active transition metals in aqueous solution (Hessler & Stelzer, 1997), as starting materials for the molecular fabrication of materials (Dressick et al., 2000) and so on. As early as 1885, tris(3-aminophenyl)phosphine oxide had been synthesized in the Sn/HCl system but with low yield (Michaelis et al., 1885). The molecules of the title compound crystallized as an ethanol solvate (Fig. 1). Adjacent molecules are linked via intermolecular O—H···O and N—H···O interactions, such as O2—H2···O1, N2—H2B···O1, N2—H2C···O2 and N1—H1A···O2 from a neighboring molecule (Fig. 2).

Experimental

The precursor, tris(3-nitrophenyl)phosphine oxide (1.032 g, 2.5 mmol), was added to a mixture of ethanol (30 ml), THF (30 ml), hydrazine hydrate (10 ml) and a catalytic amount of Raney Ni in a 100 ml flask. The mixture was heated to reflux and reaction progress was monitored by TLC. The pure product was obtained as colorless crystals suitable for X-ray analysis after removing most of the solvent and without further purification (yield > 99%).

Refinement

All the H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C), (1.5Ueq(C) for methyl groups), and with a distance of O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O), and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(N). Although the diffraction data were rather weak, the structure is unambiguous, nevertheless, the ethanol solvent molecule is rather poorly defined.

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme.
Fig. 2.
The crystal packing of the title compound, viewed along the a axis.

Crystal data

C18H18N3OP·C2H6OZ = 2
Mr = 369.39F(000) = 392
Triclinic, P1Dx = 1.244 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1046 (13) ÅCell parameters from 706 reflections
b = 10.7595 (15) Åθ = 2.6–19.5°
c = 12.020 (3) ŵ = 0.16 mm1
α = 109.131 (3)°T = 293 K
β = 94.245 (3)°Prism, colorless
γ = 114.028 (2)°0.35 × 0.34 × 0.30 mm
V = 986.3 (3) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3420 independent reflections
Radiation source: fine-focus sealed tube1659 reflections with I > 2σ(I)
graphiteRint = 0.058
[var phi] and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −10→10
Tmin = 0.947, Tmax = 0.954k = −11→12
5014 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 0.85w = 1/[σ2(Fo2) + (0.0599P)2] where P = (Fo2 + 2Fc2)/3
3420 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = −0.41 e Å3

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 > 2σ(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
P10.32847 (11)0.46681 (10)0.24048 (9)0.040
O10.2533 (3)0.4519 (2)0.3452 (2)0.048
O20.0137 (3)0.2243 (3)0.3724 (3)0.0692 (9)
H20.08790.29290.36320.104*
C120.5751 (4)0.7116 (4)0.2172 (3)0.0450 (9)
H120.61480.64750.17490.054*
C70.4373 (4)0.6580 (4)0.2618 (3)0.0398 (9)
C10.1745 (4)0.3739 (4)0.0993 (3)0.0430 (9)
C130.4720 (4)0.3909 (3)0.2210 (3)0.0380 (9)
C170.6849 (4)0.3539 (4)0.3165 (3)0.046
C110.6559 (4)0.8607 (4)0.2346 (3)0.049
C180.5679 (4)0.4064 (3)0.3238 (3)0.044
H180.55390.45280.39960.052*
N10.7909 (4)0.9160 (4)0.1905 (3)0.076
H1A0.83731.00810.20210.091*
H1B0.82980.85880.15100.091*
C140.4895 (4)0.3209 (4)0.1081 (3)0.048
H140.42430.30950.03870.058*
C160.7007 (4)0.2837 (4)0.2010 (3)0.052
H160.77760.24720.19310.062*
C60.0464 (4)0.2340 (4)0.0766 (3)0.0486 (10)
H60.04460.19080.13240.058*
C5−0.0779 (4)0.1596 (4)−0.0291 (4)0.057
C20.1779 (5)0.4355 (4)0.0146 (4)0.0548 (11)
H2A0.26420.52770.02880.066*
C100.5934 (5)0.9530 (4)0.2983 (4)0.0592 (12)
H100.64571.05270.31110.071*
N20.7780 (4)0.3664 (4)0.4182 (3)0.0764 (11)
H2B0.76460.40740.48860.092*
H2C0.84970.33320.41160.092*
C90.4574 (5)0.9015 (4)0.3424 (4)0.0599 (11)
H90.41760.96570.38440.072*
C80.3784 (5)0.7539 (4)0.3248 (3)0.0534 (10)
H80.28570.71890.35530.064*
C150.6044 (4)0.2679 (4)0.0989 (3)0.056
H150.61700.22080.02280.068*
C30.0530 (5)0.3608 (5)−0.0918 (4)0.0677 (13)
H30.05550.4027−0.14860.081*
N3−0.2044 (5)0.0239 (4)−0.0519 (4)0.106
H3A−0.2077−0.0164−0.00050.127*
H3B−0.2811−0.0214−0.11780.127*
C4−0.0726 (5)0.2259 (5)−0.1117 (4)0.0687 (13)
H4−0.15680.1768−0.18220.082*
C200.0756 (6)0.2038 (6)0.4755 (5)0.0963 (19)
H20A0.12650.29690.54580.116*
H20B−0.01500.13280.49410.116*
C190.1946 (8)0.1515 (7)0.4477 (6)0.147 (3)
H19A0.14140.05550.38250.221*
H19B0.24260.14470.51800.221*
H19C0.28000.21890.42390.221*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0410.0390.0400.0170.0120.016
O10.0510.0500.0440.0210.0210.021
O20.0604 (18)0.062 (2)0.081 (2)0.0167 (15)0.0085 (17)0.0396 (17)
C120.050 (2)0.036 (2)0.042 (2)0.0173 (19)0.0080 (19)0.0098 (18)
C70.043 (2)0.037 (2)0.037 (2)0.0159 (18)0.0056 (18)0.0149 (18)
C10.043 (2)0.047 (2)0.041 (2)0.023 (2)0.0107 (18)0.0159 (19)
C130.041 (2)0.030 (2)0.039 (2)0.0122 (17)0.0108 (18)0.0129 (17)
C170.0540.0460.0400.0250.0120.016
C110.0490.0450.0420.0120.0070.019
C180.0490.0390.0420.0230.0130.011
N10.0820.0560.0780.0210.0310.024
C140.0610.0570.0400.0380.0160.021
C160.0560.0550.0560.0340.0210.024
C60.041 (2)0.048 (2)0.053 (3)0.018 (2)0.012 (2)0.019 (2)
C50.0380.0420.0670.0130.0070.001
C20.051 (2)0.058 (3)0.052 (3)0.021 (2)0.007 (2)0.022 (2)
C100.071 (3)0.038 (2)0.056 (3)0.017 (2)−0.001 (2)0.017 (2)
N20.096 (3)0.104 (3)0.046 (2)0.076 (2)0.004 (2)0.014 (2)
C90.068 (3)0.049 (3)0.056 (3)0.030 (2)0.004 (2)0.011 (2)
C80.056 (2)0.048 (3)0.052 (3)0.024 (2)0.007 (2)0.016 (2)
C150.0730.0640.0420.0390.0200.021
C30.070 (3)0.071 (3)0.058 (3)0.033 (3)0.006 (3)0.023 (3)
N30.0890.0710.1100.009−0.0090.020
C40.062 (3)0.076 (3)0.057 (3)0.035 (3)−0.004 (2)0.013 (3)
C200.072 (3)0.072 (4)0.140 (6)0.024 (3)0.002 (4)0.054 (4)
C190.158 (6)0.134 (6)0.132 (6)0.039 (5)−0.018 (5)0.077 (5)

Geometric parameters (Å, °)

P1—O11.500 (2)C6—C51.385 (5)
P1—C131.794 (3)C6—H60.9300
P1—C71.799 (3)C5—N31.362 (5)
P1—C11.799 (4)C5—C41.393 (5)
O2—C201.441 (5)C2—C31.394 (5)
O2—H20.8200C2—H2A0.9300
C12—C71.381 (5)C10—C91.361 (5)
C12—C111.398 (5)C10—H100.9300
C12—H120.9300N2—H2B0.8600
C7—C81.388 (5)N2—H2C0.8600
C1—C21.381 (5)C9—C81.383 (5)
C1—C61.399 (5)C9—H90.9300
C13—C141.376 (5)C8—H80.9300
C13—C181.380 (4)C15—H150.9300
C17—N21.370 (4)C3—C41.361 (5)
C17—C181.390 (4)C3—H30.9300
C17—C161.396 (5)N3—H3A0.8600
C11—N11.362 (4)N3—H3B0.8600
C11—C101.387 (5)C4—H40.9300
C18—H180.9300C20—C191.424 (8)
N1—H1A0.8600C20—H20A0.9700
N1—H1B0.8600C20—H20B0.9700
C14—C151.377 (5)C19—H19A0.9600
C14—H140.9300C19—H19B0.9600
C16—C151.372 (5)C19—H19C0.9600
C16—H160.9300
O1—P1—C13112.04 (15)N3—C5—C4120.3 (4)
O1—P1—C7110.89 (16)C6—C5—C4119.1 (4)
C13—P1—C7107.89 (16)C1—C2—C3120.6 (4)
O1—P1—C1112.16 (15)C1—C2—H2A119.7
C13—P1—C1106.99 (16)C3—C2—H2A119.7
C7—P1—C1106.60 (16)C9—C10—C11121.7 (4)
C20—O2—H2109.5C9—C10—H10119.2
C7—C12—C11121.1 (4)C11—C10—H10119.2
C7—C12—H12119.5C17—N2—H2B120.0
C11—C12—H12119.5C17—N2—H2C120.0
C12—C7—C8119.3 (3)H2B—N2—H2C120.0
C12—C7—P1122.6 (3)C10—C9—C8120.1 (4)
C8—C7—P1118.1 (3)C10—C9—H9120.0
C2—C1—C6119.5 (3)C8—C9—H9120.0
C2—C1—P1122.8 (3)C9—C8—C7120.0 (4)
C6—C1—P1117.7 (3)C9—C8—H8120.0
C14—C13—C18120.2 (3)C7—C8—H8120.0
C14—C13—P1122.0 (3)C16—C15—C14120.6 (4)
C18—C13—P1117.8 (3)C16—C15—H15119.7
N2—C17—C18121.5 (3)C14—C15—H15119.7
N2—C17—C16121.0 (3)C4—C3—C2119.3 (4)
C18—C17—C16117.5 (3)C4—C3—H3120.4
N1—C11—C10120.0 (4)C2—C3—H3120.4
N1—C11—C12122.2 (4)C5—N3—H3A120.0
C10—C11—C12117.8 (4)C5—N3—H3B120.0
C13—C18—C17121.3 (3)H3A—N3—H3B120.0
C13—C18—H18119.4C3—C4—C5121.6 (4)
C17—C18—H18119.4C3—C4—H4119.2
C11—N1—H1A120.0C5—C4—H4119.2
C11—N1—H1B120.0C19—C20—O2109.0 (5)
H1A—N1—H1B120.0C19—C20—H20A109.9
C13—C14—C15119.4 (3)O2—C20—H20A109.9
C13—C14—H14120.3C19—C20—H20B109.9
C15—C14—H14120.3O2—C20—H20B109.9
C15—C16—C17121.0 (4)H20A—C20—H20B108.3
C15—C16—H16119.5C20—C19—H19A109.5
C17—C16—H16119.5C20—C19—H19B109.5
C5—C6—C1120.0 (4)H19A—C19—H19B109.5
C5—C6—H6120.0C20—C19—H19C109.5
C1—C6—H6120.0H19A—C19—H19C109.5
N3—C5—C6120.6 (4)H19B—C19—H19C109.5
C11—C12—C7—C80.0 (5)N2—C17—C18—C13−178.7 (3)
C11—C12—C7—P1179.4 (3)C16—C17—C18—C13−0.6 (5)
O1—P1—C7—C12148.9 (3)C18—C13—C14—C15−0.6 (5)
C13—P1—C7—C1225.9 (3)P1—C13—C14—C15178.5 (3)
C1—P1—C7—C12−88.7 (3)N2—C17—C16—C15178.3 (3)
O1—P1—C7—C8−31.7 (3)C18—C17—C16—C150.2 (5)
C13—P1—C7—C8−154.7 (3)C2—C1—C6—C5−1.4 (5)
C1—P1—C7—C890.7 (3)P1—C1—C6—C5178.1 (3)
O1—P1—C1—C2137.1 (3)C1—C6—C5—N3−179.3 (4)
C13—P1—C1—C2−99.7 (3)C1—C6—C5—C40.3 (6)
C7—P1—C1—C215.5 (4)C6—C1—C2—C31.4 (6)
O1—P1—C1—C6−42.5 (3)P1—C1—C2—C3−178.1 (3)
C13—P1—C1—C680.8 (3)N1—C11—C10—C9179.1 (3)
C7—P1—C1—C6−164.0 (3)C12—C11—C10—C9−0.3 (6)
O1—P1—C13—C14145.0 (3)C11—C10—C9—C80.4 (6)
C7—P1—C13—C14−92.6 (3)C10—C9—C8—C7−0.2 (6)
C1—P1—C13—C1421.7 (3)C12—C7—C8—C90.0 (5)
O1—P1—C13—C18−35.8 (3)P1—C7—C8—C9−179.4 (3)
C7—P1—C13—C1886.5 (3)C17—C16—C15—C14−0.1 (6)
C1—P1—C13—C18−159.2 (3)C13—C14—C15—C160.3 (5)
C7—C12—C11—N1−179.3 (3)C1—C2—C3—C4−0.1 (6)
C7—C12—C11—C100.1 (5)C2—C3—C4—C5−1.0 (6)
C14—C13—C18—C170.8 (5)N3—C5—C4—C3−179.5 (4)
P1—C13—C18—C17−178.4 (3)C6—C5—C4—C31.0 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···N1i0.862.623.469 (6)168
O2—H2···O10.821.852.672 (3)178
N2—H2B···O1ii0.862.142.987 (4)168
N2—H2C···O2iii0.862.233.089 (5)173

Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2158).

References

  • Bruker (2005). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dressick, W. J., George, C., Brandow, S. L., Schull, T. L. & Knight, D. A. (2000). J. Org. Chem.65, 5059–5062. [PubMed]
  • Hessler, A. & Stelzer, O. (1997). J. Org. Chem.62, 2362–2369. [PubMed]
  • Jean-Noël, G., Fronczek, F. R. & Isovitsch, R. (2004). Acta Cryst. E60, o1646–o1647.
  • Michaelis, A., Michaelis, A. & von Soden, H. (1885). Liebigs Ann. Chem.229, 295–334.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography