Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048349/bg2110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048349/bg2110Isup2.hkl |
CCDC reference: 667319
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
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).
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.
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 P1═O8 double-bond character. The structure is stabilized by a centrosymmetric array of intermolecular hydrogen bonds. (Table 2).
For related literature, see: Cremer & Pople (1975).
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).
C26H36N2O6P2 | Z = 1 |
Mr = 534.51 | F(000) = 284 |
Triclinic, P1 | Dx = 1.312 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4436 (7) Å | Cell parameters from 1049 reflections |
b = 10.4563 (11) Å | θ = 2.3–20.0° |
c = 11.5762 (13) Å | µ = 0.20 mm−1 |
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 |
Bruker SMART CCD area-detector diffractometer | 2616 independent reflections |
Radiation source: fine-focus sealed tube | 1754 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
φ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −7→7 |
Tmin = 0.951, Tmax = 0.980 | k = −12→12 |
7086 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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-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 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C26H36N2O6P2 | γ = 72.641 (2)° |
Mr = 534.51 | V = 676.40 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.4436 (7) Å | Mo Kα radiation |
b = 10.4563 (11) Å | µ = 0.20 mm−1 |
c = 11.5762 (13) Å | T = 295 K |
α = 65.680 (2)° | 0.20 × 0.20 × 0.10 mm |
β = 86.755 (2)° |
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 = 0.980 | Rint = 0.047 |
7086 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.30 e Å−3 |
2616 reflections | Δρmin = −0.23 e Å−3 |
165 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8132 (4) | 0.8979 (3) | 0.2863 (3) | 0.0363 (7) | |
C2 | 0.7646 (5) | 0.9464 (4) | 0.3830 (3) | 0.0539 (9) | |
H2 | 0.8259 | 0.8852 | 0.4654 | 0.065* | |
C3 | 0.6243 (6) | 1.0863 (4) | 0.3556 (4) | 0.0690 (11) | |
H3 | 0.5952 | 1.1192 | 0.4200 | 0.083* | |
C4 | 0.5276 (6) | 1.1771 (4) | 0.2359 (4) | 0.0685 (11) | |
H4 | 0.4326 | 1.2703 | 0.2192 | 0.082* | |
C5 | 0.5726 (5) | 1.1291 (3) | 0.1405 (3) | 0.0578 (9) | |
H5 | 0.5079 | 1.1899 | 0.0588 | 0.069* | |
C6 | 0.7137 (5) | 0.9904 (3) | 0.1661 (3) | 0.0441 (8) | |
H6 | 0.7423 | 0.9586 | 0.1011 | 0.053* | |
C7 | 0.9697 (4) | 0.7486 (3) | 0.3152 (2) | 0.0353 (7) | |
H7 | 0.9530 | 0.6826 | 0.4022 | 0.042* | |
C8 | 1.2127 (5) | 0.7404 (3) | 0.3031 (3) | 0.0403 (7) | |
C9 | 1.2908 (5) | 0.7813 (4) | 0.4025 (3) | 0.0565 (9) | |
H9A | 1.4460 | 0.7625 | 0.4026 | 0.085* | |
H9B | 1.2541 | 0.7231 | 0.4851 | 0.085* | |
H9C | 1.2211 | 0.8838 | 0.3819 | 0.085* | |
C10 | 1.2518 (5) | 0.8427 (4) | 0.1706 (3) | 0.0517 (9) | |
H10A | 1.1765 | 0.9430 | 0.1558 | 0.078* | |
H10B | 1.1983 | 0.8196 | 0.1082 | 0.078* | |
H10C | 1.4052 | 0.8301 | 0.1644 | 0.078* | |
C11 | 1.3430 (5) | 0.5815 (4) | 0.3337 (3) | 0.0519 (9) | |
H11A | 1.4967 | 0.5736 | 0.3281 | 0.062* | |
H11B | 1.3227 | 0.5200 | 0.4203 | 0.062* | |
C12 | 0.8516 (5) | 0.4487 (3) | 0.0935 (3) | 0.0468 (8) | |
H12A | 0.7105 | 0.5178 | 0.0542 | 0.056* | |
H12B | 0.8300 | 0.3779 | 0.1758 | 0.056* | |
C13 | 1.0454 (5) | 0.6299 (3) | −0.0110 (3) | 0.0474 (8) | |
H13A | 1.1448 | 0.6754 | 0.0054 | 0.057* | |
H13B | 0.9129 | 0.7072 | −0.0553 | 0.057* | |
N1 | 0.9939 (4) | 0.5274 (3) | 0.1097 (2) | 0.0446 (7) | |
O6 | 1.2784 (3) | 0.5277 (2) | 0.2478 (2) | 0.0523 (6) | |
O7 | 0.9065 (3) | 0.69522 (19) | 0.22708 (16) | 0.0366 (5) | |
O8 | 0.9706 (4) | 0.4198 (2) | 0.35255 (19) | 0.0615 (7) | |
P1 | 1.03157 (13) | 0.53246 (8) | 0.24428 (7) | 0.0406 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0407 (17) | 0.0387 (18) | 0.0388 (17) | −0.0189 (14) | 0.0090 (13) | −0.0210 (14) |
C2 | 0.064 (2) | 0.069 (2) | 0.0484 (19) | −0.0254 (19) | 0.0118 (16) | −0.0397 (19) |
C3 | 0.081 (3) | 0.073 (3) | 0.083 (3) | −0.026 (2) | 0.026 (2) | −0.062 (2) |
C4 | 0.068 (3) | 0.047 (2) | 0.094 (3) | −0.0086 (19) | 0.016 (2) | −0.040 (2) |
C5 | 0.061 (2) | 0.042 (2) | 0.060 (2) | −0.0040 (17) | 0.0071 (17) | −0.0196 (18) |
C6 | 0.0518 (19) | 0.0436 (19) | 0.0415 (18) | −0.0151 (16) | 0.0099 (14) | −0.0225 (16) |
C7 | 0.0467 (17) | 0.0381 (17) | 0.0278 (15) | −0.0185 (14) | 0.0027 (12) | −0.0162 (13) |
C8 | 0.0425 (17) | 0.048 (2) | 0.0389 (17) | −0.0194 (15) | 0.0017 (13) | −0.0224 (15) |
C9 | 0.061 (2) | 0.075 (2) | 0.0468 (19) | −0.0311 (19) | −0.0022 (16) | −0.0301 (19) |
C10 | 0.054 (2) | 0.068 (2) | 0.0471 (19) | −0.0331 (18) | 0.0125 (15) | −0.0274 (18) |
C11 | 0.0426 (19) | 0.061 (2) | 0.052 (2) | −0.0089 (17) | −0.0087 (15) | −0.0269 (18) |
C12 | 0.057 (2) | 0.049 (2) | 0.0458 (18) | −0.0274 (17) | 0.0095 (15) | −0.0241 (16) |
C13 | 0.067 (2) | 0.0448 (19) | 0.0462 (18) | −0.0309 (17) | 0.0106 (16) | −0.0255 (16) |
N1 | 0.0675 (18) | 0.0442 (16) | 0.0407 (14) | −0.0323 (14) | 0.0144 (12) | −0.0259 (13) |
O6 | 0.0456 (13) | 0.0540 (14) | 0.0625 (14) | −0.0031 (11) | −0.0054 (10) | −0.0362 (12) |
O7 | 0.0406 (11) | 0.0384 (12) | 0.0393 (11) | −0.0137 (9) | 0.0003 (9) | −0.0226 (10) |
O8 | 0.105 (2) | 0.0458 (14) | 0.0401 (13) | −0.0361 (13) | 0.0091 (12) | −0.0151 (11) |
P1 | 0.0545 (5) | 0.0346 (5) | 0.0364 (5) | −0.0135 (4) | 0.0018 (4) | −0.0181 (4) |
P1—N1 | 1.615 (2) | C8—C10 | 1.525 (4) |
P1—O6 | 1.578 (2) | C8—C9 | 1.536 (4) |
P1—O7 | 1.583 (2) | C9—H9A | 0.9600 |
P1—O8 | 1.455 (2) | C9—H9B | 0.9600 |
C1—C6 | 1.380 (4) | C9—H9C | 0.9600 |
C1—C2 | 1.392 (3) | C10—H10A | 0.9600 |
C1—C7 | 1.495 (4) | C10—H10B | 0.9600 |
C2—C3 | 1.386 (4) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | C11—O6 | 1.458 (3) |
C3—C4 | 1.368 (5) | C11—H11A | 0.9700 |
C3—H3 | 0.9300 | C11—H11B | 0.9700 |
C4—C5 | 1.374 (4) | C12—N1 | 1.466 (4) |
C4—H4 | 0.9300 | C12—C13i | 1.509 (4) |
C5—C6 | 1.381 (4) | C12—H12A | 0.9700 |
C5—H5 | 0.9300 | C12—H12B | 0.9700 |
C6—H6 | 0.9300 | C13—N1 | 1.462 (4) |
C7—O7 | 1.473 (3) | C13—C12i | 1.509 (4) |
C7—C8 | 1.544 (4) | C13—H13A | 0.9700 |
C7—H7 | 0.9800 | C13—H13B | 0.9700 |
C8—C11 | 1.519 (4) | ||
C6—C1—C2 | 118.4 (3) | C8—C10—H10A | 109.5 |
C6—C1—C7 | 122.1 (2) | C8—C10—H10B | 109.5 |
C2—C1—C7 | 119.5 (3) | H10A—C10—H10B | 109.5 |
C3—C2—C1 | 119.6 (3) | C8—C10—H10C | 109.5 |
C3—C2—H2 | 120.2 | H10A—C10—H10C | 109.5 |
C1—C2—H2 | 120.2 | H10B—C10—H10C | 109.5 |
C4—C3—C2 | 121.3 (3) | O6—C11—C8 | 112.3 (2) |
C4—C3—H3 | 119.3 | O6—C11—H11A | 109.1 |
C2—C3—H3 | 119.3 | C8—C11—H11A | 109.1 |
C3—C4—C5 | 119.3 (3) | O6—C11—H11B | 109.1 |
C3—C4—H4 | 120.3 | C8—C11—H11B | 109.1 |
C5—C4—H4 | 120.3 | H11A—C11—H11B | 107.9 |
C4—C5—C6 | 120.0 (3) | N1—C12—C13i | 109.5 (2) |
C4—C5—H5 | 120.0 | N1—C12—H12A | 109.8 |
C6—C5—H5 | 120.0 | C13i—C12—H12A | 109.8 |
C1—C6—C5 | 121.3 (3) | N1—C12—H12B | 109.8 |
C1—C6—H6 | 119.3 | C13i—C12—H12B | 109.8 |
C5—C6—H6 | 119.3 | H12A—C12—H12B | 108.2 |
O7—C7—C1 | 107.3 (2) | N1—C13—C12i | 110.8 (2) |
O7—C7—C8 | 108.33 (19) | N1—C13—H13A | 109.5 |
C1—C7—C8 | 116.0 (2) | C12i—C13—H13A | 109.5 |
O7—C7—H7 | 108.3 | N1—C13—H13B | 109.5 |
C1—C7—H7 | 108.3 | C12i—C13—H13B | 109.5 |
C8—C7—H7 | 108.3 | H13A—C13—H13B | 108.1 |
C11—C8—C10 | 111.0 (2) | C13—N1—C12 | 113.1 (2) |
C11—C8—C9 | 107.0 (2) | C13—N1—P1 | 123.04 (18) |
C10—C8—C9 | 109.4 (2) | C12—N1—P1 | 121.8 (2) |
C11—C8—C7 | 107.8 (2) | C11—O6—P1 | 116.17 (17) |
C10—C8—C7 | 111.6 (2) | C7—O7—P1 | 118.41 (16) |
C9—C8—C7 | 109.9 (2) | O8—P1—O6 | 115.83 (13) |
C8—C9—H9A | 109.5 | O8—P1—O7 | 113.86 (12) |
C8—C9—H9B | 109.5 | O6—P1—O7 | 102.54 (10) |
H9A—C9—H9B | 109.5 | O8—P1—N1 | 114.05 (12) |
C8—C9—H9C | 109.5 | O6—P1—N1 | 103.11 (12) |
H9A—C9—H9C | 109.5 | O7—P1—N1 | 106.11 (11) |
H9B—C9—H9C | 109.5 | ||
C6—C1—C2—C3 | −1.9 (5) | C7—C8—C11—O6 | 59.9 (3) |
C7—C1—C2—C3 | 178.2 (3) | C12i—C13—N1—C12 | −56.6 (4) |
C1—C2—C3—C4 | 1.7 (5) | C12i—C13—N1—P1 | 139.4 (2) |
C2—C3—C4—C5 | −0.7 (6) | C13i—C12—N1—C13 | 55.9 (4) |
C3—C4—C5—C6 | 0.1 (5) | C13i—C12—N1—P1 | −139.9 (2) |
C2—C1—C6—C5 | 1.3 (5) | C8—C11—O6—P1 | −58.8 (3) |
C7—C1—C6—C5 | −178.8 (3) | C1—C7—O7—P1 | −174.51 (16) |
C4—C5—C6—C1 | −0.4 (5) | C8—C7—O7—P1 | 59.6 (3) |
C6—C1—C7—O7 | −29.3 (3) | C11—O6—P1—O8 | −75.5 (2) |
C2—C1—C7—O7 | 150.5 (2) | C11—O6—P1—O7 | 49.2 (2) |
C6—C1—C7—C8 | 91.9 (3) | C11—O6—P1—N1 | 159.3 (2) |
C2—C1—C7—C8 | −88.3 (3) | C7—O7—P1—O8 | 74.4 (2) |
O7—C7—C8—C11 | −58.3 (3) | C7—O7—P1—O6 | −51.54 (19) |
C1—C7—C8—C11 | −179.0 (2) | C7—O7—P1—N1 | −159.37 (17) |
O7—C7—C8—C10 | 63.8 (3) | C13—N1—P1—O8 | −179.7 (2) |
C1—C7—C8—C10 | −56.9 (3) | C12—N1—P1—O8 | 17.8 (3) |
O7—C7—C8—C9 | −174.7 (2) | C13—N1—P1—O6 | −53.2 (3) |
C1—C7—C8—C9 | 64.7 (3) | C12—N1—P1—O6 | 144.2 (2) |
C10—C8—C11—O6 | −62.6 (3) | C13—N1—P1—O7 | 54.2 (3) |
C9—C8—C11—O6 | 178.1 (2) | C12—N1—P1—O7 | −108.4 (2) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O8 | 0.97 | 2.53 | 3.008 (4) | 111 |
C9—H9B···O8ii | 0.96 | 2.56 | 3.459 (4) | 157 |
Symmetry code: (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C26H36N2O6P2 |
Mr | 534.51 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 676.40 (18) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.951, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7086, 2616, 1754 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.151, 1.06 |
No. of reflections | 2616 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.23 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
P1—N1 | 1.615 (2) | C12—N1 | 1.466 (4) |
P1—O6 | 1.578 (2) | C12—C13i | 1.509 (4) |
P1—O7 | 1.583 (2) | C13—N1 | 1.462 (4) |
P1—O8 | 1.455 (2) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O8ii | 0.96 | 2.56 | 3.459 (4) | 157 |
Symmetry code: (ii) −x+2, −y+1, −z+1. |
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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 P1═O8 double-bond character. The structure is stabilized by a centrosymmetric array of intermolecular hydrogen bonds. (Table 2).