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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o450.
Published online 2010 January 27. doi:  10.1107/S1600536810002692
PMCID: PMC2979840

O,O′-Di-p-tolyl­pyrophospho­ric bis­(dimethyl­amide)

Abstract

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)°].

Related literature

For related structures, see: Ghadimi et al. (2007 [triangle], 2009 [triangle]); Pourayoubi et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o450-scheme1.jpg

Experimental

Crystal data

  • C18H26N2O5P2
  • M r = 412.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o450-efi1.jpg
  • a = 26.484 (5) Å
  • b = 7.4195 (15) Å
  • c = 11.096 (2) Å
  • β = 112.949 (4)°
  • V = 2007.8 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 100 K
  • 0.50 × 0.25 × 0.10 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.930, T max = 0.978
  • 6483 measured reflections
  • 2415 independent reflections
  • 1763 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.124
  • S = 0.94
  • 2415 reflections
  • 126 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002692/bg2328sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002692/bg2328Isup2.hkl

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

Acknowledgments

Support of this investigation by Imam Hossein University is gratefully acknowledged.

supplementary crystallographic information

Comment

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°.

Experimental

[(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.

Refinement

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.

Figures

Fig. 1.
Molecular view (50 % probability level) of the title compound. Symmetry code A: -x,y,-z+1/2.

Crystal data

C18H26N2O5P2F(000) = 872
Mr = 412.35Dx = 1.364 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1898 reflections
a = 26.484 (5) Åθ = 2.9–30.7°
b = 7.4195 (15) ŵ = 0.25 mm1
c = 11.096 (2) ÅT = 100 K
β = 112.949 (4)°Plate, colorless
V = 2007.8 (7) Å30.50 × 0.25 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer2415 independent reflections
Radiation source: fine-focus sealed tube1763 reflections with I > 2σ(I)
graphiteRint = 0.039
phi and ω scansθmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −34→21
Tmin = 0.930, Tmax = 0.978k = −9→9
6483 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 0.94w = 1/[σ2(Fo2) + (0.013P)2 + 16.2989P] where P = (Fo2 + 2Fc2)/3
2415 reflections(Δ/σ)max = 0.002
126 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.37 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
P10.05951 (3)0.15216 (10)0.29554 (7)0.01597 (17)
O10.08997 (8)−0.0313 (3)0.2957 (2)0.0188 (4)
O20.00000.0607 (4)0.25000.0198 (6)
O30.07504 (8)0.2488 (3)0.4196 (2)0.0224 (5)
N10.06400 (10)0.2733 (3)0.1781 (2)0.0192 (5)
C10.14675 (11)−0.0402 (4)0.3240 (3)0.0159 (6)
C20.18495 (13)0.0402 (4)0.4337 (3)0.0237 (7)
H2A0.17350.11120.48980.028*
C30.24040 (13)0.0160 (4)0.4612 (3)0.0250 (7)
H3A0.26690.07090.53690.030*
C40.25790 (12)−0.0867 (4)0.3802 (3)0.0205 (6)
C50.21822 (12)−0.1656 (4)0.2707 (3)0.0222 (6)
H5A0.2294−0.23720.21450.027*
C60.16261 (12)−0.1427 (4)0.2411 (3)0.0205 (6)
H6A0.1360−0.19650.16520.025*
C70.31835 (12)−0.1118 (5)0.4103 (4)0.0305 (8)
H7A0.3238−0.12630.32840.046*
H7B0.3317−0.21940.46470.046*
H7C0.3387−0.00590.45740.046*
C80.05658 (14)0.4694 (4)0.1789 (4)0.0288 (7)
H8A0.07230.52650.12170.043*
H8B0.07510.51510.26830.043*
H8C0.01740.49740.14720.043*
C90.04811 (13)0.1948 (4)0.0462 (3)0.0239 (7)
H9A0.06700.2590−0.00130.036*
H9B0.00840.2062−0.00160.036*
H9C0.05840.06720.05380.036*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0134 (3)0.0175 (3)0.0189 (4)−0.0003 (3)0.0084 (3)−0.0005 (3)
O10.0150 (10)0.0186 (10)0.0268 (11)−0.0006 (8)0.0127 (9)−0.0007 (9)
O20.0159 (14)0.0197 (15)0.0274 (16)0.0000.0123 (13)0.000
O30.0209 (11)0.0254 (11)0.0212 (11)0.0015 (9)0.0087 (9)−0.0031 (9)
N10.0183 (12)0.0189 (12)0.0216 (13)−0.0024 (10)0.0090 (11)0.0008 (10)
C10.0142 (13)0.0140 (12)0.0219 (15)−0.0007 (11)0.0097 (11)0.0043 (11)
C20.0247 (16)0.0254 (15)0.0223 (16)0.0021 (13)0.0104 (13)−0.0029 (13)
C30.0200 (15)0.0249 (15)0.0247 (17)−0.0016 (13)0.0029 (13)−0.0023 (13)
C40.0177 (14)0.0172 (13)0.0276 (16)0.0010 (11)0.0098 (13)0.0077 (12)
C50.0208 (15)0.0224 (15)0.0266 (16)0.0028 (12)0.0127 (13)−0.0007 (13)
C60.0206 (14)0.0200 (14)0.0221 (15)−0.0004 (12)0.0096 (12)−0.0033 (12)
C70.0168 (15)0.0286 (17)0.042 (2)0.0034 (13)0.0075 (14)0.0097 (15)
C80.0291 (17)0.0205 (15)0.0381 (19)−0.0004 (13)0.0147 (15)0.0045 (14)
C90.0241 (15)0.0279 (16)0.0221 (16)−0.0029 (13)0.0115 (13)0.0008 (13)

Geometric parameters (Å, °)

P1—O31.462 (2)C4—C51.388 (4)
P1—O11.582 (2)C4—C71.514 (4)
P1—O21.6059 (14)C5—C61.389 (4)
P1—N11.625 (3)C5—H5A0.9500
O1—C11.413 (3)C6—H6A0.9500
O2—P1i1.6059 (14)C7—H7A0.9800
N1—C81.468 (4)C7—H7B0.9800
N1—C91.476 (4)C7—H7C0.9800
C1—C61.379 (4)C8—H8A0.9800
C1—C21.379 (4)C8—H8B0.9800
C2—C31.390 (4)C8—H8C0.9800
C2—H2A0.9500C9—H9A0.9800
C3—C41.389 (4)C9—H9B0.9800
C3—H3A0.9500C9—H9C0.9800
O3—P1—O1117.71 (12)C4—C5—H5A119.1
O3—P1—O2112.64 (10)C6—C5—H5A119.1
O1—P1—O294.25 (12)C1—C6—C5118.7 (3)
O3—P1—N1113.71 (13)C1—C6—H6A120.6
O1—P1—N1106.27 (12)C5—C6—H6A120.6
O2—P1—N1110.55 (11)C4—C7—H7A109.5
C1—O1—P1122.57 (17)C4—C7—H7B109.5
P1—O2—P1i130.00 (19)H7A—C7—H7B109.5
C8—N1—C9114.2 (3)C4—C7—H7C109.5
C8—N1—P1119.4 (2)H7A—C7—H7C109.5
C9—N1—P1119.7 (2)H7B—C7—H7C109.5
C6—C1—C2121.2 (3)N1—C8—H8A109.5
C6—C1—O1116.9 (3)N1—C8—H8B109.5
C2—C1—O1121.8 (3)H8A—C8—H8B109.5
C1—C2—C3119.1 (3)N1—C8—H8C109.5
C1—C2—H2A120.5H8A—C8—H8C109.5
C3—C2—H2A120.5H8B—C8—H8C109.5
C4—C3—C2121.3 (3)N1—C9—H9A109.5
C4—C3—H3A119.4N1—C9—H9B109.5
C2—C3—H3A119.4H9A—C9—H9B109.5
C5—C4—C3117.9 (3)N1—C9—H9C109.5
C5—C4—C7121.0 (3)H9A—C9—H9C109.5
C3—C4—C7121.0 (3)H9B—C9—H9C109.5
C4—C5—C6121.8 (3)
O3—P1—O1—C1−64.5 (2)P1—O1—C1—C6−133.6 (2)
O2—P1—O1—C1177.1 (2)P1—O1—C1—C250.4 (3)
N1—P1—O1—C164.3 (2)C6—C1—C2—C3−0.4 (5)
O3—P1—O2—P1i66.93 (11)O1—C1—C2—C3175.5 (3)
O1—P1—O2—P1i−170.64 (9)C1—C2—C3—C40.2 (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—C7179.7 (3)
O1—P1—N1—C8−159.7 (2)C3—C4—C5—C60.5 (5)
O2—P1—N1—C899.2 (2)C7—C4—C5—C6−179.4 (3)
O3—P1—N1—C9−178.3 (2)C2—C1—C6—C50.7 (4)
O1—P1—N1—C950.6 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2328).

References

  • Bruker (2005). SADABS, APEX2 andSAINT 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. [PubMed]

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