Acta Cryst. (2010). E66, o450 [ doi:10.1107/S1600536810002692 ]
The title compound, C18H26N2O5P2, was obtained accidently from the reaction between N,N-dimethylphosphoramidochloridic acid 4-methyl phenyl ester, NaNO2 and 18-crown-6 in acetonitrile under reflux conditions. The asymmetric unit contains one half-molecule, the complete molecule being generated by crystallographic twofold symmetry, with the bridging O atom lying on the rotation axis. The P atoms exhibit a tetrahedral coordination and are bridged via one O atom [P-O-P angle = 130.00 (19)°].
[(CH3)2N]P(O)Cl[O—C6H4-p-CH3] was synthesized according to the literature method (Ghadimi et al., 2007). The title compound was prepared according to the following procedure: A mixture of [(CH3)2N]P(O)Cl[O—C6H4-p-CH3] (0.82 g, 3.5 mmol), NaNO2 (0.24 g, 3.5 mmol) and 18-crown-6 (0.20 g) in acetonitrile (30 ml) was refluxed for 4 h and then filtered. The solvent was removed under vacuum and the solid recrystallized in a mixture of chloroform and n-hexane to produce single crystals after a slow evaporation at room temperature. IR (KBr, cm-1): 2995, 2900, 2880, 2820, 1850, 1580, 1480, 1440, 1300, 1235, 1250, 1185, 1100, 990, 940, 730.
The H(C) atom positions were calculated. All hydrogen atoms were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bg2328fig1thm.gif)
| Fig. 1. Molecular view (50 % probability level) of the title compound. Symmetry code A: -x,y,-z+1/2. |
| C18H26N2O5P2 | F(000) = 872 |
| Mr = 412.35 | Dx = 1.364 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1898 reflections |
| a = 26.484 (5) Å | θ = 2.9–30.7° |
| b = 7.4195 (15) Å | µ = 0.25 mm−1 |
| c = 11.096 (2) Å | T = 100 K |
| β = 112.949 (4)° | Plate, colorless |
| V = 2007.8 (7) Å3 | 0.50 × 0.25 × 0.10 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 2415 independent reflections |
| Radiation source: fine-focus sealed tube | 1763 reflections with I > 2σ(I) |
| graphite | Rint = 0.039 |
| phi and ω scans | θmax = 28.0°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −34→21 |
| Tmin = 0.930, Tmax = 0.978 | k = −9→9 |
| 6483 measured reflections | l = −14→14 |
| 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) = 0.124 | H-atom parameters constrained |
| S = 0.94 | w = 1/[σ2(Fo2) + (0.013P)2 + 16.2989P] where P = (Fo2 + 2Fc2)/3 |
| 2415 reflections | (Δ/σ)max = 0.002 |
| 126 parameters | Δρmax = 0.34 e Å−3 |
| 0 restraints | Δρmin = −0.37 e Å−3 |
| C18H26N2O5P2 | V = 2007.8 (7) Å3 |
| Mr = 412.35 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 26.484 (5) Å | µ = 0.25 mm−1 |
| b = 7.4195 (15) Å | T = 100 K |
| c = 11.096 (2) Å | 0.50 × 0.25 × 0.10 mm |
| β = 112.949 (4)° |
| Bruker APEXII CCD area-detector diffractometer | 2415 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1763 reflections with I > 2σ(I) |
| Tmin = 0.930, Tmax = 0.978 | Rint = 0.039 |
| 6483 measured reflections | θmax = 28.0° |
| R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.013P)2 + 16.2989P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.124 | Δρmax = 0.34 e Å−3 |
| S = 0.94 | Δρmin = −0.37 e Å−3 |
| 2415 reflections | Absolute structure: ? |
| 126 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| H-atom parameters constrained |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | 0.05951 (3) | 0.15216 (10) | 0.29554 (7) | 0.01597 (17) | |
| O1 | 0.08997 (8) | −0.0313 (3) | 0.2957 (2) | 0.0188 (4) | |
| O2 | 0.0000 | 0.0607 (4) | 0.2500 | 0.0198 (6) | |
| O3 | 0.07504 (8) | 0.2488 (3) | 0.4196 (2) | 0.0224 (5) | |
| N1 | 0.06400 (10) | 0.2733 (3) | 0.1781 (2) | 0.0192 (5) | |
| C1 | 0.14675 (11) | −0.0402 (4) | 0.3240 (3) | 0.0159 (6) | |
| C2 | 0.18495 (13) | 0.0402 (4) | 0.4337 (3) | 0.0237 (7) | |
| H2A | 0.1735 | 0.1112 | 0.4898 | 0.028* | |
| C3 | 0.24040 (13) | 0.0160 (4) | 0.4612 (3) | 0.0250 (7) | |
| H3A | 0.2669 | 0.0709 | 0.5369 | 0.030* | |
| C4 | 0.25790 (12) | −0.0867 (4) | 0.3802 (3) | 0.0205 (6) | |
| C5 | 0.21822 (12) | −0.1656 (4) | 0.2707 (3) | 0.0222 (6) | |
| H5A | 0.2294 | −0.2372 | 0.2145 | 0.027* | |
| C6 | 0.16261 (12) | −0.1427 (4) | 0.2411 (3) | 0.0205 (6) | |
| H6A | 0.1360 | −0.1965 | 0.1652 | 0.025* | |
| C7 | 0.31835 (12) | −0.1118 (5) | 0.4103 (4) | 0.0305 (8) | |
| H7A | 0.3238 | −0.1263 | 0.3284 | 0.046* | |
| H7B | 0.3317 | −0.2194 | 0.4647 | 0.046* | |
| H7C | 0.3387 | −0.0059 | 0.4574 | 0.046* | |
| C8 | 0.05658 (14) | 0.4694 (4) | 0.1789 (4) | 0.0288 (7) | |
| H8A | 0.0723 | 0.5265 | 0.1217 | 0.043* | |
| H8B | 0.0751 | 0.5151 | 0.2683 | 0.043* | |
| H8C | 0.0174 | 0.4974 | 0.1472 | 0.043* | |
| C9 | 0.04811 (13) | 0.1948 (4) | 0.0462 (3) | 0.0239 (7) | |
| H9A | 0.0670 | 0.2590 | −0.0013 | 0.036* | |
| H9B | 0.0084 | 0.2062 | −0.0016 | 0.036* | |
| H9C | 0.0584 | 0.0672 | 0.0538 | 0.036* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| P1 | 0.0134 (3) | 0.0175 (3) | 0.0189 (4) | −0.0003 (3) | 0.0084 (3) | −0.0005 (3) |
| O1 | 0.0150 (10) | 0.0186 (10) | 0.0268 (11) | −0.0006 (8) | 0.0127 (9) | −0.0007 (9) |
| O2 | 0.0159 (14) | 0.0197 (15) | 0.0274 (16) | 0.000 | 0.0123 (13) | 0.000 |
| O3 | 0.0209 (11) | 0.0254 (11) | 0.0212 (11) | 0.0015 (9) | 0.0087 (9) | −0.0031 (9) |
| N1 | 0.0183 (12) | 0.0189 (12) | 0.0216 (13) | −0.0024 (10) | 0.0090 (11) | 0.0008 (10) |
| C1 | 0.0142 (13) | 0.0140 (12) | 0.0219 (15) | −0.0007 (11) | 0.0097 (11) | 0.0043 (11) |
| C2 | 0.0247 (16) | 0.0254 (15) | 0.0223 (16) | 0.0021 (13) | 0.0104 (13) | −0.0029 (13) |
| C3 | 0.0200 (15) | 0.0249 (15) | 0.0247 (17) | −0.0016 (13) | 0.0029 (13) | −0.0023 (13) |
| C4 | 0.0177 (14) | 0.0172 (13) | 0.0276 (16) | 0.0010 (11) | 0.0098 (13) | 0.0077 (12) |
| C5 | 0.0208 (15) | 0.0224 (15) | 0.0266 (16) | 0.0028 (12) | 0.0127 (13) | −0.0007 (13) |
| C6 | 0.0206 (14) | 0.0200 (14) | 0.0221 (15) | −0.0004 (12) | 0.0096 (12) | −0.0033 (12) |
| C7 | 0.0168 (15) | 0.0286 (17) | 0.042 (2) | 0.0034 (13) | 0.0075 (14) | 0.0097 (15) |
| C8 | 0.0291 (17) | 0.0205 (15) | 0.0381 (19) | −0.0004 (13) | 0.0147 (15) | 0.0045 (14) |
| C9 | 0.0241 (15) | 0.0279 (16) | 0.0221 (16) | −0.0029 (13) | 0.0115 (13) | 0.0008 (13) |
| P1—O3 | 1.462 (2) | C4—C5 | 1.388 (4) |
| P1—O1 | 1.582 (2) | C4—C7 | 1.514 (4) |
| P1—O2 | 1.6059 (14) | C5—C6 | 1.389 (4) |
| P1—N1 | 1.625 (3) | C5—H5A | 0.9500 |
| O1—C1 | 1.413 (3) | C6—H6A | 0.9500 |
| O2—P1i | 1.6059 (14) | C7—H7A | 0.9800 |
| N1—C8 | 1.468 (4) | C7—H7B | 0.9800 |
| N1—C9 | 1.476 (4) | C7—H7C | 0.9800 |
| C1—C6 | 1.379 (4) | C8—H8A | 0.9800 |
| C1—C2 | 1.379 (4) | C8—H8B | 0.9800 |
| C2—C3 | 1.390 (4) | C8—H8C | 0.9800 |
| C2—H2A | 0.9500 | C9—H9A | 0.9800 |
| C3—C4 | 1.389 (4) | C9—H9B | 0.9800 |
| C3—H3A | 0.9500 | C9—H9C | 0.9800 |
| O3—P1—O1 | 117.71 (12) | C4—C5—H5A | 119.1 |
| O3—P1—O2 | 112.64 (10) | C6—C5—H5A | 119.1 |
| O1—P1—O2 | 94.25 (12) | C1—C6—C5 | 118.7 (3) |
| O3—P1—N1 | 113.71 (13) | C1—C6—H6A | 120.6 |
| O1—P1—N1 | 106.27 (12) | C5—C6—H6A | 120.6 |
| O2—P1—N1 | 110.55 (11) | C4—C7—H7A | 109.5 |
| C1—O1—P1 | 122.57 (17) | C4—C7—H7B | 109.5 |
| P1—O2—P1i | 130.00 (19) | H7A—C7—H7B | 109.5 |
| C8—N1—C9 | 114.2 (3) | C4—C7—H7C | 109.5 |
| C8—N1—P1 | 119.4 (2) | H7A—C7—H7C | 109.5 |
| C9—N1—P1 | 119.7 (2) | H7B—C7—H7C | 109.5 |
| C6—C1—C2 | 121.2 (3) | N1—C8—H8A | 109.5 |
| C6—C1—O1 | 116.9 (3) | N1—C8—H8B | 109.5 |
| C2—C1—O1 | 121.8 (3) | H8A—C8—H8B | 109.5 |
| C1—C2—C3 | 119.1 (3) | N1—C8—H8C | 109.5 |
| C1—C2—H2A | 120.5 | H8A—C8—H8C | 109.5 |
| C3—C2—H2A | 120.5 | H8B—C8—H8C | 109.5 |
| C4—C3—C2 | 121.3 (3) | N1—C9—H9A | 109.5 |
| C4—C3—H3A | 119.4 | N1—C9—H9B | 109.5 |
| C2—C3—H3A | 119.4 | H9A—C9—H9B | 109.5 |
| C5—C4—C3 | 117.9 (3) | N1—C9—H9C | 109.5 |
| C5—C4—C7 | 121.0 (3) | H9A—C9—H9C | 109.5 |
| C3—C4—C7 | 121.0 (3) | H9B—C9—H9C | 109.5 |
| C4—C5—C6 | 121.8 (3) | ||
| O3—P1—O1—C1 | −64.5 (2) | P1—O1—C1—C6 | −133.6 (2) |
| O2—P1—O1—C1 | 177.1 (2) | P1—O1—C1—C2 | 50.4 (3) |
| N1—P1—O1—C1 | 64.3 (2) | C6—C1—C2—C3 | −0.4 (5) |
| O3—P1—O2—P1i | 66.93 (11) | O1—C1—C2—C3 | 175.5 (3) |
| O1—P1—O2—P1i | −170.64 (9) | C1—C2—C3—C4 | 0.2 (5) |
| N1—P1—O2—P1i | −61.51 (10) | C2—C3—C4—C5 | −0.3 (5) |
| O3—P1—N1—C8 | −28.6 (3) | C2—C3—C4—C7 | 179.7 (3) |
| O1—P1—N1—C8 | −159.7 (2) | C3—C4—C5—C6 | 0.5 (5) |
| O2—P1—N1—C8 | 99.2 (2) | C7—C4—C5—C6 | −179.4 (3) |
| O3—P1—N1—C9 | −178.3 (2) | C2—C1—C6—C5 | 0.7 (4) |
| O1—P1—N1—C9 | 50.6 (2) | O1—C1—C6—C5 | −175.4 (3) |
| O2—P1—N1—C9 | −50.4 (3) | C4—C5—C6—C1 | −0.7 (5) |
| Symmetry codes: (i) −x, y, −z+1/2. |
Support of this investigation by Imam Hossein University is gratefully acknowledged.
Bruker (2005). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Ghadimi, S., Pourayoubi, M. & Valmoozi, A. A. E. (2009). Z. Naturforsch. Teil B, 64, 565–569.
Ghadimi, S., Valmoozi, A. A. E. & Pourayoubi, M. (2007). Z. Kristallogr. New Cryst. Struct. 222, 339–340.
Pourayoubi, M., Ghadimi, S. & Valmoozi, A. A. E. (2007). Acta Cryst. E63, o4093.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Following our previous works about amido phosphoric acid esters with general formula [(CH3)2N][p-CH3—C6H4—O]P(O)X [for example X = NHCH(CH3)2 (Pourayoubi et al., 2007) and NHC(CH3)3 (Ghadimi et al., 2009)], we report here on the synthesis and crystal structure of title compound, [(CH3)2N][p-CH3—C6H4—O]P(O)(O)P(O)[O—C6H4-p-CH3][N(CH3)2]. The asymmetric unit contains one half-molecule, the complete molecule (Fig. 1) being generated by a twofold rotation axis. The phosphorous atoms exhibit a tetrahedral coordination and are bridged via one O atom (P—O—P angle = 130.0 (2)°). The bond angles around the P atoms are in the range of 94.25 (12)° (for O1—P1—O2 angle) to 117.71 (12)° (for O3—P1—O1 angle). The nitrogen atom indicates some deviation from planarity, the sum of the surrounding angles around N atom being about 353.3°.