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The title compound, C26H36N2O6P2, possesses a crystallographically imposed inversion centre. The molecules are linked into a one-dimensional structure along the c axis by a centrosymmetric system of weak C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048349/bg2110sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048349/bg2110Isup2.hkl
Contains datablock I

CCDC reference: 667319

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.062
  • wR factor = 0.151
  • Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level B CELLV02_ALERT_1_B The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 4 Calculated cell volume su = 12.82 Cell volume su given = 18.00
Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of P1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C7 = ... R
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Organic phosphorus compounds are widely used in pesticide science because of their significant biological properties. The title compound has been used as a precursor of organic phosphorus pesticides. The title dimeric molecule possesses a crystallographically imposed centre of symmetry, as shown in Fig.1. The central piperazine ring (N1, C12, C13, N1i,C12i,C13i; (i): -x, 1 - y, 2 - z) adopts a chair conformation,with puckering parameters (Cremer & Pople,1975) θ = 180°, φ = 173.6° and Q = 0.5916 (1) Å. The oxaphosphorinane ring (P1, O6, O7, C7, C8, C11) also displays a chair conformation, with puckering parameters θ = 14.20 (13)°, φ = 172.2° and Q = 0.5363 (16) Å. Analysis of P—O bond distances (Table 1) indicate a clear P1O8 double-bond character. The structure is stabilized by a centrosymmetric array of intermolecular hydrogen bonds. (Table 2).

Related literature top

For related literature, see: Cremer & Pople (1975).

Experimental top

A mixture of 2-chloro-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphinane 2-oxide(10 mmol) and piperazine (5 mmol) in THF (30 ml) was stirred for 4 h and the solvent was removed under reduced pressure. After filtration, crystals suitable for X-ray investigation were obtained by recrystallization from methanol and chloroform (1:1 v/v).

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å (methyl) or 0.97 Å (methylene); Uiso(H) = xUeq(carrier atom), where x = 1.5 for methyl and 1.2 for methylene.

Structure description top

Organic phosphorus compounds are widely used in pesticide science because of their significant biological properties. The title compound has been used as a precursor of organic phosphorus pesticides. The title dimeric molecule possesses a crystallographically imposed centre of symmetry, as shown in Fig.1. The central piperazine ring (N1, C12, C13, N1i,C12i,C13i; (i): -x, 1 - y, 2 - z) adopts a chair conformation,with puckering parameters (Cremer & Pople,1975) θ = 180°, φ = 173.6° and Q = 0.5916 (1) Å. The oxaphosphorinane ring (P1, O6, O7, C7, C8, C11) also displays a chair conformation, with puckering parameters θ = 14.20 (13)°, φ = 172.2° and Q = 0.5363 (16) Å. Analysis of P—O bond distances (Table 1) indicate a clear P1O8 double-bond character. The structure is stabilized by a centrosymmetric array of intermolecular hydrogen bonds. (Table 2).

For related literature, see: Cremer & Pople (1975).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted. Symmetry codes: (i) -x + 2, -y + 1, -z.
[Figure 2] Fig. 2. Packing diagram of the title molecule viewed down the b axis.
[Figure 3] Fig. 3. The preparation of (I).
1,4-Bis(5,5-dimethyl-2-oxo-4-phenyl-1,3,2-dioxaphosphorinan-2-yl)piperazine top
Crystal data top
C26H36N2O6P2Z = 1
Mr = 534.51F(000) = 284
Triclinic, P1Dx = 1.312 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.4436 (7) ÅCell parameters from 1049 reflections
b = 10.4563 (11) Åθ = 2.3–20.0°
c = 11.5762 (13) ŵ = 0.20 mm1
α = 65.680 (2)°T = 295 K
β = 86.755 (2)°Plate, colorless
γ = 72.641 (2)°0.20 × 0.20 × 0.10 mm
V = 676.40 (18) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2616 independent reflections
Radiation source: fine-focus sealed tube1754 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
φ and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 77
Tmin = 0.951, Tmax = 0.980k = 1212
7086 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0717P)2]
where P = (Fo2 + 2Fc2)/3
2616 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C26H36N2O6P2γ = 72.641 (2)°
Mr = 534.51V = 676.40 (18) Å3
Triclinic, P1Z = 1
a = 6.4436 (7) ÅMo Kα radiation
b = 10.4563 (11) ŵ = 0.20 mm1
c = 11.5762 (13) ÅT = 295 K
α = 65.680 (2)°0.20 × 0.20 × 0.10 mm
β = 86.755 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2616 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
1754 reflections with I > 2σ(I)
Tmin = 0.951, Tmax = 0.980Rint = 0.047
7086 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.06Δρmax = 0.30 e Å3
2616 reflectionsΔρmin = 0.23 e Å3
165 parameters
Special details top

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 > 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
xyzUiso*/Ueq
C10.8132 (4)0.8979 (3)0.2863 (3)0.0363 (7)
C20.7646 (5)0.9464 (4)0.3830 (3)0.0539 (9)
H20.82590.88520.46540.065*
C30.6243 (6)1.0863 (4)0.3556 (4)0.0690 (11)
H30.59521.11920.42000.083*
C40.5276 (6)1.1771 (4)0.2359 (4)0.0685 (11)
H40.43261.27030.21920.082*
C50.5726 (5)1.1291 (3)0.1405 (3)0.0578 (9)
H50.50791.18990.05880.069*
C60.7137 (5)0.9904 (3)0.1661 (3)0.0441 (8)
H60.74230.95860.10110.053*
C70.9697 (4)0.7486 (3)0.3152 (2)0.0353 (7)
H70.95300.68260.40220.042*
C81.2127 (5)0.7404 (3)0.3031 (3)0.0403 (7)
C91.2908 (5)0.7813 (4)0.4025 (3)0.0565 (9)
H9A1.44600.76250.40260.085*
H9B1.25410.72310.48510.085*
H9C1.22110.88380.38190.085*
C101.2518 (5)0.8427 (4)0.1706 (3)0.0517 (9)
H10A1.17650.94300.15580.078*
H10B1.19830.81960.10820.078*
H10C1.40520.83010.16440.078*
C111.3430 (5)0.5815 (4)0.3337 (3)0.0519 (9)
H11A1.49670.57360.32810.062*
H11B1.32270.52000.42030.062*
C120.8516 (5)0.4487 (3)0.0935 (3)0.0468 (8)
H12A0.71050.51780.05420.056*
H12B0.83000.37790.17580.056*
C131.0454 (5)0.6299 (3)0.0110 (3)0.0474 (8)
H13A1.14480.67540.00540.057*
H13B0.91290.70720.05530.057*
N10.9939 (4)0.5274 (3)0.1097 (2)0.0446 (7)
O61.2784 (3)0.5277 (2)0.2478 (2)0.0523 (6)
O70.9065 (3)0.69522 (19)0.22708 (16)0.0366 (5)
O80.9706 (4)0.4198 (2)0.35255 (19)0.0615 (7)
P11.03157 (13)0.53246 (8)0.24428 (7)0.0406 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0407 (17)0.0387 (18)0.0388 (17)0.0189 (14)0.0090 (13)0.0210 (14)
C20.064 (2)0.069 (2)0.0484 (19)0.0254 (19)0.0118 (16)0.0397 (19)
C30.081 (3)0.073 (3)0.083 (3)0.026 (2)0.026 (2)0.062 (2)
C40.068 (3)0.047 (2)0.094 (3)0.0086 (19)0.016 (2)0.040 (2)
C50.061 (2)0.042 (2)0.060 (2)0.0040 (17)0.0071 (17)0.0196 (18)
C60.0518 (19)0.0436 (19)0.0415 (18)0.0151 (16)0.0099 (14)0.0225 (16)
C70.0467 (17)0.0381 (17)0.0278 (15)0.0185 (14)0.0027 (12)0.0162 (13)
C80.0425 (17)0.048 (2)0.0389 (17)0.0194 (15)0.0017 (13)0.0224 (15)
C90.061 (2)0.075 (2)0.0468 (19)0.0311 (19)0.0022 (16)0.0301 (19)
C100.054 (2)0.068 (2)0.0471 (19)0.0331 (18)0.0125 (15)0.0274 (18)
C110.0426 (19)0.061 (2)0.052 (2)0.0089 (17)0.0087 (15)0.0269 (18)
C120.057 (2)0.049 (2)0.0458 (18)0.0274 (17)0.0095 (15)0.0241 (16)
C130.067 (2)0.0448 (19)0.0462 (18)0.0309 (17)0.0106 (16)0.0255 (16)
N10.0675 (18)0.0442 (16)0.0407 (14)0.0323 (14)0.0144 (12)0.0259 (13)
O60.0456 (13)0.0540 (14)0.0625 (14)0.0031 (11)0.0054 (10)0.0362 (12)
O70.0406 (11)0.0384 (12)0.0393 (11)0.0137 (9)0.0003 (9)0.0226 (10)
O80.105 (2)0.0458 (14)0.0401 (13)0.0361 (13)0.0091 (12)0.0151 (11)
P10.0545 (5)0.0346 (5)0.0364 (5)0.0135 (4)0.0018 (4)0.0181 (4)
Geometric parameters (Å, º) top
P1—N11.615 (2)C8—C101.525 (4)
P1—O61.578 (2)C8—C91.536 (4)
P1—O71.583 (2)C9—H9A0.9600
P1—O81.455 (2)C9—H9B0.9600
C1—C61.380 (4)C9—H9C0.9600
C1—C21.392 (3)C10—H10A0.9600
C1—C71.495 (4)C10—H10B0.9600
C2—C31.386 (4)C10—H10C0.9600
C2—H20.9300C11—O61.458 (3)
C3—C41.368 (5)C11—H11A0.9700
C3—H30.9300C11—H11B0.9700
C4—C51.374 (4)C12—N11.466 (4)
C4—H40.9300C12—C13i1.509 (4)
C5—C61.381 (4)C12—H12A0.9700
C5—H50.9300C12—H12B0.9700
C6—H60.9300C13—N11.462 (4)
C7—O71.473 (3)C13—C12i1.509 (4)
C7—C81.544 (4)C13—H13A0.9700
C7—H70.9800C13—H13B0.9700
C8—C111.519 (4)
C6—C1—C2118.4 (3)C8—C10—H10A109.5
C6—C1—C7122.1 (2)C8—C10—H10B109.5
C2—C1—C7119.5 (3)H10A—C10—H10B109.5
C3—C2—C1119.6 (3)C8—C10—H10C109.5
C3—C2—H2120.2H10A—C10—H10C109.5
C1—C2—H2120.2H10B—C10—H10C109.5
C4—C3—C2121.3 (3)O6—C11—C8112.3 (2)
C4—C3—H3119.3O6—C11—H11A109.1
C2—C3—H3119.3C8—C11—H11A109.1
C3—C4—C5119.3 (3)O6—C11—H11B109.1
C3—C4—H4120.3C8—C11—H11B109.1
C5—C4—H4120.3H11A—C11—H11B107.9
C4—C5—C6120.0 (3)N1—C12—C13i109.5 (2)
C4—C5—H5120.0N1—C12—H12A109.8
C6—C5—H5120.0C13i—C12—H12A109.8
C1—C6—C5121.3 (3)N1—C12—H12B109.8
C1—C6—H6119.3C13i—C12—H12B109.8
C5—C6—H6119.3H12A—C12—H12B108.2
O7—C7—C1107.3 (2)N1—C13—C12i110.8 (2)
O7—C7—C8108.33 (19)N1—C13—H13A109.5
C1—C7—C8116.0 (2)C12i—C13—H13A109.5
O7—C7—H7108.3N1—C13—H13B109.5
C1—C7—H7108.3C12i—C13—H13B109.5
C8—C7—H7108.3H13A—C13—H13B108.1
C11—C8—C10111.0 (2)C13—N1—C12113.1 (2)
C11—C8—C9107.0 (2)C13—N1—P1123.04 (18)
C10—C8—C9109.4 (2)C12—N1—P1121.8 (2)
C11—C8—C7107.8 (2)C11—O6—P1116.17 (17)
C10—C8—C7111.6 (2)C7—O7—P1118.41 (16)
C9—C8—C7109.9 (2)O8—P1—O6115.83 (13)
C8—C9—H9A109.5O8—P1—O7113.86 (12)
C8—C9—H9B109.5O6—P1—O7102.54 (10)
H9A—C9—H9B109.5O8—P1—N1114.05 (12)
C8—C9—H9C109.5O6—P1—N1103.11 (12)
H9A—C9—H9C109.5O7—P1—N1106.11 (11)
H9B—C9—H9C109.5
C6—C1—C2—C31.9 (5)C7—C8—C11—O659.9 (3)
C7—C1—C2—C3178.2 (3)C12i—C13—N1—C1256.6 (4)
C1—C2—C3—C41.7 (5)C12i—C13—N1—P1139.4 (2)
C2—C3—C4—C50.7 (6)C13i—C12—N1—C1355.9 (4)
C3—C4—C5—C60.1 (5)C13i—C12—N1—P1139.9 (2)
C2—C1—C6—C51.3 (5)C8—C11—O6—P158.8 (3)
C7—C1—C6—C5178.8 (3)C1—C7—O7—P1174.51 (16)
C4—C5—C6—C10.4 (5)C8—C7—O7—P159.6 (3)
C6—C1—C7—O729.3 (3)C11—O6—P1—O875.5 (2)
C2—C1—C7—O7150.5 (2)C11—O6—P1—O749.2 (2)
C6—C1—C7—C891.9 (3)C11—O6—P1—N1159.3 (2)
C2—C1—C7—C888.3 (3)C7—O7—P1—O874.4 (2)
O7—C7—C8—C1158.3 (3)C7—O7—P1—O651.54 (19)
C1—C7—C8—C11179.0 (2)C7—O7—P1—N1159.37 (17)
O7—C7—C8—C1063.8 (3)C13—N1—P1—O8179.7 (2)
C1—C7—C8—C1056.9 (3)C12—N1—P1—O817.8 (3)
O7—C7—C8—C9174.7 (2)C13—N1—P1—O653.2 (3)
C1—C7—C8—C964.7 (3)C12—N1—P1—O6144.2 (2)
C10—C8—C11—O662.6 (3)C13—N1—P1—O754.2 (3)
C9—C8—C11—O6178.1 (2)C12—N1—P1—O7108.4 (2)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···O80.972.533.008 (4)111
C9—H9B···O8ii0.962.563.459 (4)157
Symmetry code: (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC26H36N2O6P2
Mr534.51
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)6.4436 (7), 10.4563 (11), 11.5762 (13)
α, β, γ (°)65.680 (2), 86.755 (2), 72.641 (2)
V3)676.40 (18)
Z1
Radiation typeMo Kα
µ (mm1)0.20
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.951, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
7086, 2616, 1754
Rint0.047
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.151, 1.06
No. of reflections2616
No. of parameters165
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.23

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Selected bond lengths (Å) top
P1—N11.615 (2)C12—N11.466 (4)
P1—O61.578 (2)C12—C13i1.509 (4)
P1—O71.583 (2)C13—N11.462 (4)
P1—O81.455 (2)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···O8ii0.962.563.459 (4)157
Symmetry code: (ii) x+2, y+1, z+1.
 

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