Tris(3-aminophenyl)phosphine oxide ethanol solvate Jun Han, a Wenguang Li, b Shufang Wang b and Juli Jiang a * a Key Laboratory of Mesoscopic Chemistry of the Ministry of Education, and School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People’s Republic of China, and b Jiangguantun Middle School, Liaocheng 252022, Shangdong Province, People’s Republic of China Correspondence e-mail: [email protected]Received 19 February 2009; accepted 12 March 2009 Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.006 A ˚ ; R factor = 0.059; wR factor = 0.149; data-to-parameter ratio = 19.7. The title compound crystallized as an ethanol solvate, C 18 H 18 N 3 OPC 2 H 6 O. It is the reduction product of tris(3- nitrophenyl)phosphine oxide. In the crystal, there are inter- molecular N—HO hydrogen bonds between neighbouring tris(3-aminophenyl)phosphine oxide molecules and O— HO hydrogen bonds involving the ethanol solvent mol- ecule. Related literature The structure of tris(3-nitrophenyl)phosphine oxide is described by Jean-Noe ¨l et al. (2004). For literature on related compounds, see: Michaelis et al. (1885); Dressick et al. (2000); Hessler & Stelzer (1997). Experimental Crystal data C 18 H 18 N 3 OPC 2 H 6 O M r = 369.39 Triclinic, P 1 a = 9.1046 (13) A ˚ b = 10.7595 (15) A ˚ c = 12.020 (3) A ˚ = 109.131 (3) = 94.245 (3) = 114.028 (2) V = 986.3 (3) A ˚ 3 Z =2 Mo Kradiation = 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) T min = 0.947, T max = 0.954 5014 measured reflections 3420 independent reflections 1659 reflections with I >2(I) R int = 0.058 Refinement R[F 2 >2(F 2 )] = 0.059 wR(F 2 ) = 0.149 S = 0.85 3420 reflections 174 parameters H-atom parameters constrained Ámax = 0.53 e A ˚ 3 Ámin = 0.41 e A ˚ 3 Table 1 Hydrogen-bond geometry (A ˚ , ). D—HA D—H HA DA D—HA N3—H3AN1 i 0.86 2.62 3.469 (6) 168 N2—H2BO1 ii 0.86 2.14 2.987 (4) 168 N2—H2CO2 iii 0.86 2.23 3.089 (5) 173 O2—H2O1 0.82 1.85 2.672 (3) 178 Symmetry codes: (i) x 1; y 1; z; (ii) x þ 1; y þ 1; z þ 1; (iii) x þ 1; y; z. Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL. 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 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. Hessler, A. & Stelzer, O. (1997). J. Org. Chem. 62, 2362–2369. Jean-Noe ¨l, 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. organic compounds Acta Cryst. (2009). E65, o839 doi:10.1107/S160053680900909X Han et al. o839 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368
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Tris(3-aminophenyl)phosphine oxideethanol solvate
Jun Han,a Wenguang Li,b Shufang Wangb and Juli Jianga*
aKey Laboratory of Mesoscopic Chemistry of the Ministry of Education, and School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People’s
Republic of China, and bJiangguantun Middle School, Liaocheng 252022,
Arylphosphines have been investigated extensively as ionic ligands for catalytically active transition metals in aqueoussolution (Hessler & Stelzer, 1997), as starting materials for the molecular fabrication of materials (Dressick et al., 2000) andso 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 moleculesare linked via intermolecular O—H···O and N—H···O interactions, such as O2—H2···O1, N2—H2B···O1, N2—H2C···O2and 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 (30ml), hydrazine hydrate (10 ml) and a catalytic amount of Raney Ni in a 100 ml flask. The mixture was heated to reflux andreaction progress was monitored by TLC. The pure product was obtained as colorless crystals suitable for X-ray analysisafter 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.
Primary atom site location: structure-invariant directmethods Extinction correction: none
supplementary materials
sup-3
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 mat-rix. 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; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell 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 largeas 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)
