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

Pourayoubi, M.; Ghadimi, S.; Ebrahimi Valmoozi, A.A.

doi:10.1107/S1600536810002692

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o450

https://doi.org/10.1107/S1600536810002692

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

Mehrdad Pourayoubi,^a Saied Ghadimi ^b ^* and Ali Asghar Ebrahimi Valmoozi ^b

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, 91779, Iran, and ^bDepartment of Chemistry, Imam Hossein University, P.O. Box 16575-347, Tehran, Iran
^*Correspondence e-mail: ghadimi_saied@yahoo.com

(Received 20 January 2010; accepted 21 January 2010; online 27 January 2010)

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 , 2009 ); Pourayoubi et al. (2007 ).

Experimental

Crystal data

C₁₈H₂₆N₂O₅P₂
M_r = 412.35
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.052
wR(F²) = 0.124
S = 0.94
2415 reflections
126 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.37 e Å⁻³

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002692/bg2328Isup2.hkl

checkCIF report

Comment top

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°.

Related literature top

For related compounds see: Ghadimi et al. (2007, 2009); Pourayoubi et al. (2007).

Experimental top

[(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.

Structure description top

For related compounds see: Ghadimi et al. (2007, 2009); Pourayoubi et al. (2007).

Computing details top

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).

Figures top

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

O,O'-Di-p-tolylpyrophosphoric bis(dimethylamide) top

Crystal data top

C₁₈H₂₆N₂O₅P₂	F(000) = 872
M_r = 412.35	D_x = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	2415 independent reflections
Radiation source: fine-focus sealed tube	1763 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 28.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −34→21
T_min = 0.930, T_max = 0.978	k = −9→9
6483 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.013P)² + 16.2989P] where P = (F_o² + 2F_c²)/3
2415 reflections	(Δ/σ)_max = 0.002
126 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₈H₂₆N₂O₅P₂	V = 2007.8 (7) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2415 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1763 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.978	R_int = 0.039
6483 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.013P)² + 16.2989P] where P = (F_o² + 2F_c²)/3
2415 reflections	Δρ_max = 0.34 e Å⁻³
126 parameters	Δρ_min = −0.37 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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 code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₆N₂O₅P₂
M_r	412.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	26.484 (5), 7.4195 (15), 11.096 (2)
β (°)	112.949 (4)
V (Å³)	2007.8 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.50 × 0.25 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.930, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	6483, 2415, 1763
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.124, 0.94
No. of reflections	2415
No. of parameters	126
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.013P)² + 16.2989P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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