Five new compounds belonging to the phosphoric triamide family have been synthesized: two of them with the formula
XC(O)NHP(O)
Y [
X = CF
3 (1) and CClF
2 (2),
Y = NHCH
2C(CH
3)
2CH
2NH] involving a 1,3-diazaphosphorinane ring part, and three 2,6-Cl
2C
6H
3C(O)NHP(O)
Z2 phosphoric triamides [
Z = NHC(CH
3)
3 (3), N(CH
3)(C
6H
11) (4) and N(CH
3)(CH
2C
6H
5) (5)]. The characterization was performed by
31P{
1H},
1H,
13C NMR, IR spectroscopy besides
19F NMR for fluorine containing compounds (1) and (2), and X-ray single-crystal structure analysis for (1), (3), (4) and (5). In each molecule the P atom has a distorted tetrahedral environment. The N atoms bonded to P atom have mainly
sp2 character with a very slight tendency to a pyramidal coordination for some amido groups. Different types of N—H
O hydrogen bonds have been analyzed for (1), (3), (4) and (5) and 118 other structures (including 194 hydrogen bonds) deposited in the Cambridge Structural Database, containing either C(O)—NH—P(O)[N(C)(C)]
2 or C(O)—NH—P(O)[NH(C)]
2. The participation of N
CP—H
O=P [N
CP = the nitrogen atom of the C(O)—NH—P(O) fragment], N—H
O=P, N—H
O=C and N
CP—H
O=C hydrogen bonds in different hydrogen-bonded motifs are discussed. Moreover, the involvement of the O atoms of C=O or P=O in the [N
CP—H][N—H]
O=P, [N—H]
2O=P, [N—H]
2O=C and [N—H]
3O=C groups are considered. A histogram of N
O distances, the distribution of N—H
O angles and the scatterplot of N—H
O angles
versus N
O distances are studied.
Supporting information
Data collection: Collect (Bruker AXS BV, 1997-2004) for (I); CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET) (compiled Aug 2 2010,13:00:58) for (IV), (V); CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) for (III). Cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997) for (I); CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET) (compiled Aug 2 2010,13:00:58) for (IV), (V); CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) for (III). Data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) for (I); CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET) (compiled Aug 2 2010,13:00:58) for (IV), (V); CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) for (III). Program(s) used to solve structure: SIR2002 (Giacovazzo et al., 2003) for (I); SIR92 (Altomare et al., 1993) for (IV), (V); Superflip (Palatinus & Chapuis, 2007) for (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); SHELXL97 (Sheldrick, 2008) for (IV), (V); CRYSTALS (Betteridge et al., 2003) for (III). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (I); Mercury (Macrae et al., 2008) for (IV), (V); CAMERON (Watkin et al., 1996) for (III). Software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) for (I); SHELXL97 (Sheldrick, 2008) for (IV), (V); CRYSTALS (Betteridge et al., 2003) for (III).
Crystal data top
C7H13F3N3O2P | F(000) = 536 |
Mr = 259.17 | Dx = 1.506 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 600 reflections |
a = 11.3416 (3) Å | θ = 1–14° |
b = 9.0552 (3) Å | µ = 0.27 mm−1 |
c = 11.8030 (4) Å | T = 295 K |
β = 109.413 (2)° | Prism, colourless |
V = 1143.26 (6) Å3 | 0.41 × 0.35 × 0.24 mm |
Z = 4 | |
Data collection top
KappaCCD diffractometer | 1748 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 2.9° |
Detector resolution: 9 pixels mm-1 | h = −13→12 |
CCD rotation images, thick slices scans | k = 0→10 |
1977 measured reflections | l = 0→14 |
1977 independent reflections | |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.5607P] where P = (Fo2 + 2Fc2)/3 |
1977 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.26 e Å−3 |
3 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C7H13F3N3O2P | V = 1143.26 (6) Å3 |
Mr = 259.17 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 11.3416 (3) Å | µ = 0.27 mm−1 |
b = 9.0552 (3) Å | T = 295 K |
c = 11.8030 (4) Å | 0.41 × 0.35 × 0.24 mm |
β = 109.413 (2)° | |
Data collection top
KappaCCD diffractometer | 1748 reflections with I > 2σ(I) |
1977 measured reflections | Rint = 0.000 |
1977 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.26 e Å−3 |
1977 reflections | Δρmin = −0.28 e Å−3 |
156 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 | x | y | z | Uiso*/Ueq | |
C3 | 0.84601 (18) | 0.3900 (2) | 0.25660 (16) | 0.0410 (4) | |
H3A | 0.7797 | 0.4625 | 0.2288 | 0.049* | |
H3B | 0.9229 | 0.4424 | 0.2980 | 0.049* | |
C4 | 0.81610 (18) | 0.2857 (2) | 0.34458 (16) | 0.0417 (4) | |
C5 | 0.69751 (19) | 0.1990 (2) | 0.27789 (18) | 0.0473 (5) | |
H5A | 0.6777 | 0.1326 | 0.3335 | 0.057* | |
H5B | 0.6282 | 0.2671 | 0.2469 | 0.057* | |
C7 | 0.7899 (2) | 0.3789 (3) | 0.4417 (2) | 0.0660 (7) | |
H7A | 0.8627 | 0.4361 | 0.4833 | 0.099* | |
H7B | 0.7697 | 0.3152 | 0.4976 | 0.099* | |
H7C | 0.7209 | 0.4440 | 0.4050 | 0.099* | |
C8 | 0.9246 (2) | 0.1802 (3) | 0.40210 (18) | 0.0531 (5) | |
H8A | 0.9411 | 0.1229 | 0.3406 | 0.080* | |
H8B | 0.9030 | 0.1155 | 0.4566 | 0.080* | |
H8C | 0.9977 | 0.2360 | 0.4452 | 0.080* | |
C11 | 0.54109 (17) | 0.22268 (19) | −0.09812 (15) | 0.0353 (4) | |
C13 | 0.45742 (19) | 0.3183 (2) | −0.19981 (18) | 0.0476 (5) | |
N2 | 0.85984 (14) | 0.31238 (15) | 0.15204 (13) | 0.0346 (4) | |
H2 | 0.8913 (17) | 0.3663 (19) | 0.1113 (15) | 0.042* | |
N6 | 0.71308 (15) | 0.11290 (17) | 0.17773 (14) | 0.0439 (4) | |
H6 | 0.6623 (16) | 0.0419 (18) | 0.1551 (19) | 0.053* | |
N10 | 0.63981 (14) | 0.28988 (15) | −0.02049 (13) | 0.0346 (4) | |
H10 | 0.6454 (18) | 0.3836 (11) | −0.0234 (17) | 0.042* | |
O9 | 0.80507 (13) | 0.08740 (14) | 0.00389 (12) | 0.0488 (4) | |
O12 | 0.51616 (13) | 0.09177 (14) | −0.09905 (13) | 0.0502 (4) | |
F14 | 0.49766 (18) | 0.3089 (2) | −0.29274 (12) | 0.0964 (6) | |
F15 | 0.34028 (12) | 0.27180 (16) | −0.23594 (14) | 0.0791 (5) | |
F16 | 0.45729 (12) | 0.45963 (13) | −0.17218 (12) | 0.0661 (4) | |
P1 | 0.76025 (4) | 0.19006 (5) | 0.07696 (4) | 0.03353 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C3 | 0.0404 (10) | 0.0347 (10) | 0.0410 (10) | −0.0003 (8) | 0.0046 (8) | −0.0067 (8) |
C4 | 0.0376 (10) | 0.0491 (11) | 0.0340 (9) | 0.0066 (8) | 0.0062 (8) | 0.0000 (8) |
C5 | 0.0393 (10) | 0.0559 (12) | 0.0445 (11) | −0.0012 (9) | 0.0110 (9) | 0.0098 (9) |
C7 | 0.0661 (15) | 0.0835 (18) | 0.0483 (12) | 0.0146 (13) | 0.0189 (11) | −0.0102 (12) |
C8 | 0.0477 (12) | 0.0660 (14) | 0.0384 (11) | 0.0130 (10) | 0.0047 (9) | 0.0095 (9) |
C11 | 0.0385 (10) | 0.0300 (9) | 0.0331 (9) | −0.0009 (7) | 0.0062 (8) | −0.0010 (7) |
C13 | 0.0459 (11) | 0.0453 (11) | 0.0396 (10) | 0.0012 (9) | −0.0017 (9) | 0.0014 (9) |
N2 | 0.0372 (8) | 0.0302 (8) | 0.0326 (8) | −0.0055 (6) | 0.0065 (6) | 0.0008 (6) |
N6 | 0.0476 (9) | 0.0341 (9) | 0.0414 (9) | −0.0119 (7) | 0.0035 (7) | 0.0064 (7) |
N10 | 0.0400 (8) | 0.0204 (7) | 0.0350 (8) | 0.0006 (6) | 0.0011 (7) | 0.0015 (6) |
O9 | 0.0605 (9) | 0.0312 (7) | 0.0455 (7) | 0.0123 (6) | 0.0053 (6) | −0.0050 (6) |
O12 | 0.0514 (8) | 0.0302 (7) | 0.0575 (8) | −0.0095 (6) | 0.0026 (7) | −0.0004 (6) |
F14 | 0.1216 (14) | 0.1261 (15) | 0.0405 (7) | 0.0244 (11) | 0.0256 (8) | 0.0196 (8) |
F15 | 0.0468 (8) | 0.0643 (9) | 0.0929 (11) | −0.0050 (6) | −0.0213 (7) | −0.0008 (8) |
F16 | 0.0593 (8) | 0.0372 (7) | 0.0776 (9) | 0.0073 (6) | −0.0095 (6) | 0.0110 (6) |
P1 | 0.0389 (3) | 0.0217 (2) | 0.0321 (3) | 0.00121 (17) | 0.0013 (2) | 0.00159 (16) |
Geometric parameters (Å, º) top
C3—N2 | 1.473 (2) | C8—H8C | 0.9600 |
C3—C4 | 1.523 (3) | C11—O12 | 1.218 (2) |
C3—H3A | 0.9700 | C11—N10 | 1.335 (2) |
C3—H3B | 0.9700 | C11—C13 | 1.527 (2) |
C4—C8 | 1.526 (3) | C13—F16 | 1.321 (2) |
C4—C5 | 1.530 (3) | C13—F15 | 1.322 (2) |
C4—C7 | 1.530 (3) | C13—F14 | 1.323 (3) |
C5—N6 | 1.475 (3) | N2—P1 | 1.6194 (14) |
C5—H5A | 0.9700 | N2—H2 | 0.844 (9) |
C5—H5B | 0.9700 | N6—P1 | 1.6162 (16) |
C7—H7A | 0.9600 | N6—H6 | 0.845 (9) |
C7—H7B | 0.9600 | N10—P1 | 1.7209 (14) |
C7—H7C | 0.9600 | N10—H10 | 0.853 (9) |
C8—H8A | 0.9600 | O9—P1 | 1.4689 (13) |
C8—H8B | 0.9600 | | |
| | | |
N2—C3—C4 | 112.64 (15) | C4—C8—H8C | 109.5 |
N2—C3—H3A | 109.1 | H8A—C8—H8C | 109.5 |
C4—C3—H3A | 109.1 | H8B—C8—H8C | 109.5 |
N2—C3—H3B | 109.1 | O12—C11—N10 | 126.10 (16) |
C4—C3—H3B | 109.1 | O12—C11—C13 | 117.56 (16) |
H3A—C3—H3B | 107.8 | N10—C11—C13 | 116.20 (15) |
C3—C4—C8 | 111.22 (16) | F16—C13—F15 | 107.73 (17) |
C3—C4—C5 | 108.93 (14) | F16—C13—F14 | 107.20 (18) |
C8—C4—C5 | 110.40 (17) | F15—C13—F14 | 107.38 (17) |
C3—C4—C7 | 108.11 (17) | F16—C13—C11 | 113.98 (16) |
C8—C4—C7 | 109.91 (16) | F15—C13—C11 | 111.62 (17) |
C5—C4—C7 | 108.19 (17) | F14—C13—C11 | 108.64 (17) |
N6—C5—C4 | 111.38 (15) | C3—N2—P1 | 122.38 (12) |
N6—C5—H5A | 109.4 | C3—N2—H2 | 112.6 (14) |
C4—C5—H5A | 109.4 | P1—N2—H2 | 115.7 (14) |
N6—C5—H5B | 109.4 | C5—N6—P1 | 121.24 (13) |
C4—C5—H5B | 109.4 | C5—N6—H6 | 113.9 (15) |
H5A—C5—H5B | 108.0 | P1—N6—H6 | 117.0 (15) |
C4—C7—H7A | 109.5 | C11—N10—P1 | 121.18 (12) |
C4—C7—H7B | 109.5 | C11—N10—H10 | 118.9 (13) |
H7A—C7—H7B | 109.5 | P1—N10—H10 | 119.8 (13) |
C4—C7—H7C | 109.5 | O9—P1—N6 | 114.98 (8) |
H7A—C7—H7C | 109.5 | O9—P1—N2 | 116.08 (8) |
H7B—C7—H7C | 109.5 | N6—P1—N2 | 103.55 (8) |
C4—C8—H8A | 109.5 | O9—P1—N10 | 107.02 (8) |
C4—C8—H8B | 109.5 | N6—P1—N10 | 109.61 (8) |
H8A—C8—H8B | 109.5 | N2—P1—N10 | 105.12 (7) |
| | | |
N2—C3—C4—C8 | 65.3 (2) | C4—C5—N6—P1 | −52.8 (2) |
N2—C3—C4—C5 | −56.6 (2) | O12—C11—N10—P1 | 10.4 (3) |
N2—C3—C4—C7 | −173.95 (16) | C13—C11—N10—P1 | −165.17 (14) |
C3—C4—C5—N6 | 59.3 (2) | C5—N6—P1—O9 | 163.49 (14) |
C8—C4—C5—N6 | −63.1 (2) | C5—N6—P1—N2 | 35.82 (16) |
C7—C4—C5—N6 | 176.57 (17) | C5—N6—P1—N10 | −75.93 (15) |
O12—C11—C13—F16 | 155.65 (19) | C3—N2—P1—O9 | −159.90 (13) |
N10—C11—C13—F16 | −28.4 (2) | C3—N2—P1—N6 | −32.92 (15) |
O12—C11—C13—F15 | 33.3 (3) | C3—N2—P1—N10 | 82.08 (14) |
N10—C11—C13—F15 | −150.74 (17) | C11—N10—P1—O9 | 55.09 (16) |
O12—C11—C13—F14 | −84.9 (2) | C11—N10—P1—N6 | −70.21 (16) |
N10—C11—C13—F14 | 91.0 (2) | C11—N10—P1—N2 | 179.07 (14) |
C4—C3—N2—P1 | 47.13 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O12i | 0.84 (1) | 2.32 (1) | 3.058 (2) | 146 (2) |
N6—H6···O12ii | 0.85 (1) | 2.26 (1) | 3.074 (2) | 162 (2) |
N10—H10···O9i | 0.85 (1) | 1.92 (1) | 2.7579 (18) | 167 (2) |
Symmetry codes: (i) −x+3/2, y+1/2, −z; (ii) −x+1, −y, −z. |
Crystal data top
C21H32Cl2N3O2P | F(000) = 976 |
Mr = 460.37 | Dx = 1.261 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1526 (4) Å | Cell parameters from 4913 reflections |
b = 12.9020 (6) Å | θ = 3.2–29.0° |
c = 18.5334 (9) Å | µ = 0.36 mm−1 |
β = 92.724 (4)° | T = 295 K |
V = 2424.9 (2) Å3 | Prism, colourless |
Z = 4 | 0.27 × 0.19 × 0.12 mm |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4258 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3551 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 16.3280 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
ω scans | h = −12→12 |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −15→15 |
Tmin = 0.943, Tmax = 1.000 | l = −22→22 |
10444 measured reflections | |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0773P)2 + 1.3233P] where P = (Fo2 + 2Fc2)/3 |
4258 reflections | (Δ/σ)max = 0.001 |
267 parameters | Δρmax = 0.52 e Å−3 |
1 restraint | Δρmin = −0.31 e Å−3 |
Crystal data top
C21H32Cl2N3O2P | V = 2424.9 (2) Å3 |
Mr = 460.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.1526 (4) Å | µ = 0.36 mm−1 |
b = 12.9020 (6) Å | T = 295 K |
c = 18.5334 (9) Å | 0.27 × 0.19 × 0.12 mm |
β = 92.724 (4)° | |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4258 independent reflections |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 3551 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 1.000 | Rint = 0.022 |
10444 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 1 restraint |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.52 e Å−3 |
4258 reflections | Δρmin = −0.31 e Å−3 |
267 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 | x | y | z | Uiso*/Ueq | |
P1 | 0.45683 (6) | 0.17353 (5) | 0.02088 (3) | 0.03391 (19) | |
Cl1 | 0.08033 (9) | −0.02310 (8) | −0.07961 (5) | 0.0763 (3) | |
Cl2 | 0.47634 (10) | 0.13783 (9) | −0.22553 (5) | 0.0879 (3) | |
O4 | 0.54543 (17) | 0.09943 (13) | 0.05953 (10) | 0.0454 (5) | |
O5 | 0.23756 (19) | 0.21520 (15) | −0.10604 (10) | 0.0521 (5) | |
N6 | 0.53851 (19) | 0.27243 (16) | −0.00852 (11) | 0.0393 (5) | |
N7 | 0.33519 (19) | 0.22345 (17) | 0.06449 (11) | 0.0400 (5) | |
N8 | 0.3839 (2) | 0.10512 (15) | −0.04772 (11) | 0.0364 (5) | |
H8 | 0.410 (3) | 0.0427 (10) | −0.0516 (14) | 0.044* | |
C9 | 0.2955 (2) | 0.13328 (19) | −0.10175 (13) | 0.0364 (6) | |
C10 | 0.2751 (2) | 0.0501 (2) | −0.15838 (13) | 0.0399 (6) | |
C11 | 0.3698 (3) | 0.3034 (2) | 0.11981 (14) | 0.0454 (6) | |
H11 | 0.4375 | 0.3471 | 0.0992 | 0.055* | |
C12 | 0.4726 (3) | 0.3556 (2) | −0.04913 (18) | 0.0561 (8) | |
H12A | 0.5078 | 0.4211 | −0.0330 | 0.084* | |
H12B | 0.3798 | 0.3535 | −0.0415 | 0.084* | |
H12C | 0.4868 | 0.3471 | −0.0996 | 0.084* | |
C13 | 0.6848 (2) | 0.2719 (2) | −0.00371 (16) | 0.0466 (7) | |
H13 | 0.7112 | 0.2106 | 0.0246 | 0.056* | |
C14 | 0.3530 (3) | 0.0449 (3) | −0.21726 (15) | 0.0564 (8) | |
C15 | 0.1794 (3) | −0.0257 (2) | −0.15304 (15) | 0.0523 (7) | |
C16 | 0.7397 (3) | 0.3644 (3) | 0.0372 (2) | 0.0754 (11) | |
H16A | 0.7045 | 0.3660 | 0.0849 | 0.090* | |
H16B | 0.7126 | 0.4274 | 0.0121 | 0.090* | |
C17 | 0.2546 (3) | 0.3745 (3) | 0.13347 (17) | 0.0605 (8) | |
H17A | 0.2216 | 0.4044 | 0.0881 | 0.073* | |
H17B | 0.1839 | 0.3346 | 0.1533 | 0.073* | |
C18 | 0.2238 (3) | 0.1559 (3) | 0.07965 (19) | 0.0646 (9) | |
H18A | 0.2422 | 0.1197 | 0.1243 | 0.097* | |
H18B | 0.2105 | 0.1066 | 0.0412 | 0.097* | |
H18C | 0.1456 | 0.1970 | 0.0834 | 0.097* | |
C19 | 0.7449 (3) | 0.2607 (4) | −0.0749 (2) | 0.0828 (12) | |
H19A | 0.7161 | 0.3177 | −0.1059 | 0.099* | |
H19B | 0.7140 | 0.1968 | −0.0975 | 0.099* | |
C20 | 0.3590 (4) | 0.4195 (4) | 0.25527 (19) | 0.0855 (12) | |
H20A | 0.3893 | 0.4770 | 0.2854 | 0.103* | |
H20B | 0.2946 | 0.3807 | 0.2813 | 0.103* | |
C21 | 0.4301 (3) | 0.2616 (3) | 0.19037 (17) | 0.0711 (10) | |
H21A | 0.5057 | 0.2186 | 0.1808 | 0.085* | |
H21B | 0.3660 | 0.2190 | 0.2138 | 0.085* | |
C22 | 0.2402 (5) | −0.1066 (3) | −0.2603 (2) | 0.0858 (12) | |
H22 | 0.2288 | −0.1594 | −0.2941 | 0.103* | |
C23 | 0.2953 (4) | 0.4607 (3) | 0.1855 (2) | 0.0788 (11) | |
H23A | 0.2182 | 0.5011 | 0.1963 | 0.095* | |
H23B | 0.3568 | 0.5063 | 0.1626 | 0.095* | |
C24 | 0.3371 (4) | −0.0327 (3) | −0.26932 (18) | 0.0796 (11) | |
H24 | 0.3900 | −0.0347 | −0.3089 | 0.096* | |
C25 | 0.9485 (3) | 0.3522 (3) | −0.0278 (2) | 0.0843 (12) | |
H25A | 1.0436 | 0.3466 | −0.0217 | 0.101* | |
H25B | 0.9281 | 0.4146 | −0.0554 | 0.101* | |
C26 | 0.1614 (4) | −0.1035 (3) | −0.2030 (2) | 0.0740 (10) | |
H26 | 0.0965 | −0.1534 | −0.1977 | 0.089* | |
C27 | 0.8905 (3) | 0.3599 (4) | 0.0443 (2) | 0.0907 (13) | |
H27A | 0.9235 | 0.4218 | 0.0688 | 0.109* | |
H27B | 0.9174 | 0.3004 | 0.0733 | 0.109* | |
C28 | 0.8950 (4) | 0.2595 (4) | −0.0684 (3) | 0.1030 (15) | |
H28A | 0.9244 | 0.1969 | −0.0435 | 0.124* | |
H28B | 0.9295 | 0.2586 | −0.1163 | 0.124* | |
C29 | 0.4730 (4) | 0.3509 (4) | 0.24004 (19) | 0.0875 (13) | |
H29A | 0.5107 | 0.3233 | 0.2851 | 0.105* | |
H29B | 0.5405 | 0.3912 | 0.2175 | 0.105* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0348 (3) | 0.0276 (3) | 0.0385 (3) | −0.0022 (3) | −0.0063 (3) | 0.0014 (3) |
Cl1 | 0.0702 (6) | 0.0792 (6) | 0.0801 (6) | −0.0321 (5) | 0.0103 (4) | −0.0001 (5) |
Cl2 | 0.0767 (6) | 0.1077 (8) | 0.0819 (7) | −0.0069 (6) | 0.0325 (5) | 0.0095 (6) |
O4 | 0.0498 (10) | 0.0335 (10) | 0.0508 (11) | 0.0007 (8) | −0.0191 (8) | −0.0007 (8) |
O5 | 0.0572 (12) | 0.0405 (11) | 0.0570 (12) | 0.0125 (9) | −0.0140 (9) | 0.0014 (9) |
N6 | 0.0353 (11) | 0.0309 (11) | 0.0516 (12) | −0.0005 (9) | 0.0008 (9) | 0.0025 (9) |
N7 | 0.0366 (11) | 0.0413 (12) | 0.0419 (11) | −0.0083 (9) | −0.0003 (9) | −0.0018 (9) |
N8 | 0.0415 (11) | 0.0267 (10) | 0.0399 (11) | 0.0018 (9) | −0.0101 (9) | 0.0008 (9) |
C9 | 0.0343 (12) | 0.0353 (14) | 0.0394 (13) | −0.0023 (11) | −0.0025 (10) | 0.0064 (11) |
C10 | 0.0427 (14) | 0.0398 (14) | 0.0358 (13) | 0.0069 (11) | −0.0133 (11) | 0.0035 (11) |
C11 | 0.0421 (14) | 0.0534 (17) | 0.0407 (14) | −0.0083 (12) | 0.0004 (11) | −0.0044 (12) |
C12 | 0.0512 (16) | 0.0399 (16) | 0.077 (2) | −0.0046 (13) | −0.0031 (15) | 0.0156 (14) |
C13 | 0.0364 (13) | 0.0392 (15) | 0.0643 (17) | −0.0041 (11) | 0.0043 (12) | −0.0005 (13) |
C14 | 0.0611 (18) | 0.064 (2) | 0.0433 (15) | 0.0121 (15) | −0.0025 (13) | 0.0006 (14) |
C15 | 0.0573 (17) | 0.0474 (16) | 0.0503 (16) | −0.0032 (14) | −0.0177 (13) | −0.0013 (13) |
C16 | 0.0518 (18) | 0.091 (3) | 0.084 (2) | −0.0179 (18) | 0.0088 (17) | −0.036 (2) |
C17 | 0.0639 (19) | 0.066 (2) | 0.0521 (17) | 0.0093 (16) | 0.0018 (15) | −0.0061 (15) |
C18 | 0.0559 (18) | 0.069 (2) | 0.070 (2) | −0.0265 (16) | 0.0132 (16) | −0.0082 (17) |
C19 | 0.0551 (19) | 0.109 (3) | 0.086 (3) | −0.011 (2) | 0.0175 (18) | −0.039 (2) |
C20 | 0.084 (3) | 0.117 (3) | 0.056 (2) | −0.021 (2) | 0.0088 (18) | −0.035 (2) |
C21 | 0.068 (2) | 0.093 (3) | 0.0504 (18) | 0.0130 (19) | −0.0132 (15) | −0.0043 (18) |
C22 | 0.111 (3) | 0.073 (3) | 0.070 (2) | 0.011 (2) | −0.030 (2) | −0.028 (2) |
C23 | 0.092 (3) | 0.069 (2) | 0.077 (2) | −0.003 (2) | 0.025 (2) | −0.020 (2) |
C24 | 0.098 (3) | 0.096 (3) | 0.0443 (18) | 0.030 (2) | −0.0028 (18) | −0.0129 (19) |
C25 | 0.0451 (18) | 0.088 (3) | 0.120 (3) | −0.0161 (18) | 0.010 (2) | 0.004 (2) |
C26 | 0.085 (2) | 0.060 (2) | 0.074 (2) | −0.0086 (18) | −0.025 (2) | −0.0147 (18) |
C27 | 0.052 (2) | 0.112 (3) | 0.108 (3) | −0.026 (2) | −0.005 (2) | −0.027 (3) |
C28 | 0.053 (2) | 0.129 (4) | 0.130 (4) | −0.007 (2) | 0.031 (2) | −0.041 (3) |
C29 | 0.076 (2) | 0.130 (4) | 0.055 (2) | −0.008 (2) | −0.0138 (18) | −0.024 (2) |
Geometric parameters (Å, º) top
P1—O4 | 1.4748 (18) | C17—H17B | 0.9700 |
P1—N6 | 1.630 (2) | C18—H18A | 0.9600 |
P1—N7 | 1.640 (2) | C18—H18B | 0.9600 |
P1—N8 | 1.689 (2) | C18—H18C | 0.9600 |
Cl1—C15 | 1.730 (3) | C19—C28 | 1.523 (5) |
Cl2—C14 | 1.746 (4) | C19—H19A | 0.9700 |
O5—C9 | 1.210 (3) | C19—H19B | 0.9700 |
N6—C12 | 1.455 (3) | C20—C29 | 1.495 (6) |
N6—C13 | 1.483 (3) | C20—C23 | 1.515 (6) |
N7—C18 | 1.466 (3) | C20—H20A | 0.9700 |
N7—C11 | 1.485 (3) | C20—H20B | 0.9700 |
N8—C9 | 1.362 (3) | C21—C29 | 1.525 (5) |
N8—H8 | 0.854 (10) | C21—H21A | 0.9700 |
C9—C10 | 1.508 (4) | C21—H21B | 0.9700 |
C10—C14 | 1.380 (4) | C22—C26 | 1.360 (6) |
C10—C15 | 1.386 (4) | C22—C24 | 1.386 (6) |
C11—C17 | 1.518 (4) | C22—H22 | 0.9300 |
C11—C21 | 1.516 (4) | C23—H23A | 0.9700 |
C11—H11 | 0.9800 | C23—H23B | 0.9700 |
C12—H12A | 0.9600 | C24—H24 | 0.9300 |
C12—H12B | 0.9600 | C25—C27 | 1.489 (6) |
C12—H12C | 0.9600 | C25—C28 | 1.501 (6) |
C13—C19 | 1.487 (4) | C25—H25A | 0.9700 |
C13—C16 | 1.506 (4) | C25—H25B | 0.9700 |
C13—H13 | 0.9800 | C26—H26 | 0.9300 |
C14—C24 | 1.394 (5) | C27—H27A | 0.9700 |
C15—C26 | 1.371 (4) | C27—H27B | 0.9700 |
C16—C27 | 1.531 (5) | C28—H28A | 0.9700 |
C16—H16A | 0.9700 | C28—H28B | 0.9700 |
C16—H16B | 0.9700 | C29—H29A | 0.9700 |
C17—C23 | 1.516 (5) | C29—H29B | 0.9700 |
C17—H17A | 0.9700 | | |
| | | |
O4—P1—N6 | 111.20 (11) | N7—C18—H18C | 109.5 |
O4—P1—N7 | 118.14 (11) | H18A—C18—H18C | 109.5 |
N6—P1—N7 | 105.33 (11) | H18B—C18—H18C | 109.5 |
O4—P1—N8 | 105.20 (10) | C13—C19—C28 | 112.4 (3) |
N6—P1—N8 | 111.67 (11) | C13—C19—H19A | 109.1 |
N7—P1—N8 | 105.24 (11) | C28—C19—H19A | 109.1 |
C12—N6—C13 | 117.9 (2) | C13—C19—H19B | 109.1 |
C12—N6—P1 | 121.45 (17) | C28—C19—H19B | 109.1 |
C13—N6—P1 | 120.03 (17) | H19A—C19—H19B | 107.8 |
C18—N7—C11 | 116.1 (2) | C29—C20—C23 | 110.5 (3) |
C18—N7—P1 | 117.8 (2) | C29—C20—H20A | 109.6 |
C11—N7—P1 | 117.02 (16) | C23—C20—H20A | 109.6 |
C9—N8—P1 | 131.59 (18) | C29—C20—H20B | 109.6 |
C9—N8—H8 | 112.9 (19) | C23—C20—H20B | 109.6 |
P1—N8—H8 | 115.3 (19) | H20A—C20—H20B | 108.1 |
O5—C9—N8 | 125.6 (2) | C11—C21—C29 | 110.1 (3) |
O5—C9—C10 | 121.7 (2) | C11—C21—H21A | 109.6 |
N8—C9—C10 | 112.7 (2) | C29—C21—H21A | 109.6 |
C14—C10—C15 | 116.9 (3) | C11—C21—H21B | 109.6 |
C14—C10—C9 | 121.3 (2) | C29—C21—H21B | 109.6 |
C15—C10—C9 | 121.8 (2) | H21A—C21—H21B | 108.2 |
N7—C11—C17 | 112.1 (2) | C26—C22—C24 | 121.5 (3) |
N7—C11—C21 | 114.9 (3) | C26—C22—H22 | 119.3 |
C17—C11—C21 | 110.7 (2) | C24—C22—H22 | 119.3 |
N7—C11—H11 | 106.1 | C17—C23—C20 | 112.2 (3) |
C17—C11—H11 | 106.1 | C17—C23—H23A | 109.2 |
C21—C11—H11 | 106.1 | C20—C23—H23A | 109.2 |
N6—C12—H12A | 109.5 | C17—C23—H23B | 109.2 |
N6—C12—H12B | 109.5 | C20—C23—H23B | 109.2 |
H12A—C12—H12B | 109.5 | H23A—C23—H23B | 107.9 |
N6—C12—H12C | 109.5 | C22—C24—C14 | 118.0 (3) |
H12A—C12—H12C | 109.5 | C22—C24—H24 | 121.0 |
H12B—C12—H12C | 109.5 | C14—C24—H24 | 121.0 |
N6—C13—C19 | 113.5 (2) | C27—C25—C28 | 110.7 (3) |
N6—C13—C16 | 111.9 (2) | C27—C25—H25A | 109.5 |
C19—C13—C16 | 111.5 (3) | C28—C25—H25A | 109.5 |
N6—C13—H13 | 106.5 | C27—C25—H25B | 109.5 |
C19—C13—H13 | 106.5 | C28—C25—H25B | 109.5 |
C16—C13—H13 | 106.5 | H25A—C25—H25B | 108.1 |
C10—C14—C24 | 122.0 (3) | C22—C26—C15 | 118.9 (4) |
C10—C14—Cl2 | 118.5 (2) | C22—C26—H26 | 120.5 |
C24—C14—Cl2 | 119.5 (3) | C15—C26—H26 | 120.5 |
C26—C15—C10 | 122.7 (3) | C25—C27—C16 | 111.2 (3) |
C26—C15—Cl1 | 118.8 (3) | C25—C27—H27A | 109.4 |
C10—C15—Cl1 | 118.5 (2) | C16—C27—H27A | 109.4 |
C13—C16—C27 | 111.0 (3) | C25—C27—H27B | 109.4 |
C13—C16—H16A | 109.4 | C16—C27—H27B | 109.4 |
C27—C16—H16A | 109.4 | H27A—C27—H27B | 108.0 |
C13—C16—H16B | 109.4 | C25—C28—C19 | 111.6 (3) |
C27—C16—H16B | 109.4 | C25—C28—H28A | 109.3 |
H16A—C16—H16B | 108.0 | C19—C28—H28A | 109.3 |
C23—C17—C11 | 111.1 (3) | C25—C28—H28B | 109.3 |
C23—C17—H17A | 109.4 | C19—C28—H28B | 109.3 |
C11—C17—H17A | 109.4 | H28A—C28—H28B | 108.0 |
C23—C17—H17B | 109.4 | C20—C29—C21 | 111.1 (3) |
C11—C17—H17B | 109.4 | C20—C29—H29A | 109.4 |
H17A—C17—H17B | 108.0 | C21—C29—H29A | 109.4 |
N7—C18—H18A | 109.5 | C20—C29—H29B | 109.4 |
N7—C18—H18B | 109.5 | C21—C29—H29B | 109.4 |
H18A—C18—H18B | 109.5 | H29A—C29—H29B | 108.0 |
| | | |
O4—P1—N6—C12 | 179.3 (2) | C9—C10—C14—C24 | 178.7 (3) |
N7—P1—N6—C12 | −51.6 (2) | C15—C10—C14—Cl2 | −179.1 (2) |
N8—P1—N6—C12 | 62.1 (2) | C9—C10—C14—Cl2 | −0.5 (3) |
O4—P1—N6—C13 | 8.3 (2) | C14—C10—C15—C26 | 0.4 (4) |
N7—P1—N6—C13 | 137.45 (19) | C9—C10—C15—C26 | −178.3 (3) |
N8—P1—N6—C13 | −108.8 (2) | C14—C10—C15—Cl1 | 179.4 (2) |
O4—P1—N7—C18 | −72.0 (2) | C9—C10—C15—Cl1 | 0.7 (3) |
N6—P1—N7—C18 | 163.1 (2) | N6—C13—C16—C27 | 177.6 (3) |
N8—P1—N7—C18 | 45.0 (2) | C19—C13—C16—C27 | −54.1 (4) |
O4—P1—N7—C11 | 73.9 (2) | N7—C11—C17—C23 | −175.4 (3) |
N6—P1—N7—C11 | −51.0 (2) | C21—C11—C17—C23 | 54.9 (4) |
N8—P1—N7—C11 | −169.12 (18) | N6—C13—C19—C28 | −179.5 (3) |
O4—P1—N8—C9 | −178.4 (2) | C16—C13—C19—C28 | 53.1 (5) |
N6—P1—N8—C9 | −57.7 (3) | N7—C11—C21—C29 | 174.8 (3) |
N7—P1—N8—C9 | 56.1 (2) | C17—C11—C21—C29 | −57.0 (4) |
P1—N8—C9—O5 | −9.7 (4) | C11—C17—C23—C20 | −54.0 (4) |
P1—N8—C9—C10 | 170.26 (19) | C29—C20—C23—C17 | 55.0 (4) |
O5—C9—C10—C14 | 91.0 (3) | C26—C22—C24—C14 | 0.8 (6) |
N8—C9—C10—C14 | −88.9 (3) | C10—C14—C24—C22 | −0.6 (5) |
O5—C9—C10—C15 | −90.4 (3) | Cl2—C14—C24—C22 | 178.6 (3) |
N8—C9—C10—C15 | 89.7 (3) | C24—C22—C26—C15 | −0.4 (6) |
C18—N7—C11—C17 | −57.6 (3) | C10—C15—C26—C22 | −0.2 (5) |
P1—N7—C11—C17 | 155.9 (2) | Cl1—C15—C26—C22 | −179.2 (3) |
C18—N7—C11—C21 | 70.0 (3) | C28—C25—C27—C16 | −56.8 (5) |
P1—N7—C11—C21 | −76.5 (3) | C13—C16—C27—C25 | 56.4 (5) |
C12—N6—C13—C19 | −62.3 (4) | C27—C25—C28—C19 | 55.2 (5) |
P1—N6—C13—C19 | 108.9 (3) | C13—C19—C28—C25 | −53.7 (5) |
C12—N6—C13—C16 | 64.9 (4) | C23—C20—C29—C21 | −57.1 (5) |
P1—N6—C13—C16 | −123.8 (3) | C11—C21—C29—C20 | 58.6 (4) |
C15—C10—C14—C24 | 0.0 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···O4i | 0.85 (1) | 1.90 (1) | 2.746 (3) | 175 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Crystal data top
C23H24Cl2N3O2P | F(000) = 992 |
Mr = 476.32 | Dx = 1.354 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0375 (2) Å | Cell parameters from 4008 reflections |
b = 23.0525 (7) Å | θ = 3.0–29.1° |
c = 10.1700 (3) Å | µ = 0.37 mm−1 |
β = 96.809 (2)° | T = 295 K |
V = 2336.64 (11) Å3 | Prism, colourless |
Z = 4 | 0.13 × 0.07 × 0.05 mm |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4092 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3324 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 16.3280 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
ω scans | h = −11→11 |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −27→26 |
Tmin = 0.984, Tmax = 1.000 | l = −11→12 |
9762 measured reflections | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0523P)2 + 0.6582P] where P = (Fo2 + 2Fc2)/3 |
4092 reflections | (Δ/σ)max < 0.001 |
285 parameters | Δρmax = 0.25 e Å−3 |
1 restraint | Δρmin = −0.24 e Å−3 |
Crystal data top
C23H24Cl2N3O2P | V = 2336.64 (11) Å3 |
Mr = 476.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.0375 (2) Å | µ = 0.37 mm−1 |
b = 23.0525 (7) Å | T = 295 K |
c = 10.1700 (3) Å | 0.13 × 0.07 × 0.05 mm |
β = 96.809 (2)° | |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4092 independent reflections |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 3324 reflections with I > 2σ(I) |
Tmin = 0.984, Tmax = 1.000 | Rint = 0.026 |
9762 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 1 restraint |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.25 e Å−3 |
4092 reflections | Δρmin = −0.24 e Å−3 |
285 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 | x | y | z | Uiso*/Ueq | |
P1 | 0.43467 (6) | 0.08429 (3) | 0.08652 (6) | 0.03369 (18) | |
Cl2 | 0.90330 (7) | 0.12598 (4) | 0.01365 (8) | 0.0695 (3) | |
Cl3 | 0.72870 (10) | −0.01484 (5) | 0.37835 (10) | 0.0928 (3) | |
O4 | 0.35699 (15) | 0.03297 (7) | 0.03733 (16) | 0.0436 (4) | |
O5 | 0.69200 (17) | 0.13148 (8) | 0.25482 (18) | 0.0534 (5) | |
N6 | 0.59806 (18) | 0.06507 (8) | 0.10605 (19) | 0.0352 (5) | |
H6 | 0.612 (2) | 0.0352 (7) | 0.061 (2) | 0.042* | |
N7 | 0.39038 (19) | 0.10519 (8) | 0.22853 (18) | 0.0365 (5) | |
N8 | 0.4212 (2) | 0.13849 (9) | −0.0157 (2) | 0.0445 (5) | |
C9 | 0.2768 (3) | 0.17871 (10) | 0.3502 (2) | 0.0409 (6) | |
C10 | 0.5869 (2) | 0.16937 (10) | −0.1675 (2) | 0.0396 (6) | |
C11 | 0.8284 (2) | 0.05323 (11) | 0.1990 (2) | 0.0402 (6) | |
C12 | 0.7001 (2) | 0.08741 (11) | 0.1907 (2) | 0.0382 (6) | |
C13 | 0.9299 (2) | 0.06862 (12) | 0.1239 (3) | 0.0489 (7) | |
C14 | 0.5291 (3) | 0.17822 (11) | −0.0377 (2) | 0.0454 (6) | |
H14A | 0.6008 | 0.1740 | 0.0344 | 0.055* | |
H14B | 0.4957 | 0.2176 | −0.0352 | 0.055* | |
C15 | 0.3967 (3) | 0.16483 (11) | 0.2787 (3) | 0.0463 (7) | |
H15A | 0.3995 | 0.1915 | 0.2054 | 0.056* | |
H15B | 0.4783 | 0.1699 | 0.3389 | 0.056* | |
C16 | 0.6563 (3) | 0.21474 (12) | −0.2178 (3) | 0.0512 (7) | |
H16 | 0.6628 | 0.2503 | −0.1742 | 0.061* | |
C17 | 0.6384 (3) | 0.11067 (13) | −0.3494 (3) | 0.0564 (7) | |
H17 | 0.6323 | 0.0753 | −0.3937 | 0.068* | |
C18 | 0.7066 (3) | 0.15561 (15) | −0.3981 (3) | 0.0620 (8) | |
H18 | 0.7464 | 0.1510 | −0.4755 | 0.074* | |
C19 | 0.5782 (3) | 0.11742 (12) | −0.2341 (2) | 0.0493 (7) | |
H19 | 0.5318 | 0.0866 | −0.2020 | 0.059* | |
C20 | 0.2920 (3) | 0.18696 (12) | 0.4856 (3) | 0.0558 (7) | |
H20 | 0.3765 | 0.1840 | 0.5336 | 0.067* | |
C21 | 0.1509 (3) | 0.18254 (13) | 0.2825 (3) | 0.0609 (8) | |
H21 | 0.1393 | 0.1768 | 0.1913 | 0.073* | |
C22 | 0.7157 (3) | 0.20736 (14) | −0.3323 (3) | 0.0616 (8) | |
H22 | 0.7625 | 0.2379 | −0.3649 | 0.074* | |
C23 | 0.3892 (3) | 0.06117 (11) | 0.3307 (3) | 0.0537 (7) | |
H23A | 0.4630 | 0.0676 | 0.3982 | 0.081* | |
H23B | 0.3973 | 0.0235 | 0.2924 | 0.081* | |
H23C | 0.3064 | 0.0634 | 0.3691 | 0.081* | |
C24 | 0.2914 (3) | 0.14904 (14) | −0.0955 (3) | 0.0653 (8) | |
H24A | 0.2589 | 0.1868 | −0.0753 | 0.098* | |
H24B | 0.2281 | 0.1201 | −0.0754 | 0.098* | |
H24C | 0.3026 | 0.1471 | −0.1878 | 0.098* | |
C25 | 1.0694 (3) | −0.00723 (16) | 0.2180 (4) | 0.0722 (10) | |
H25 | 1.1502 | −0.0274 | 0.2248 | 0.087* | |
C26 | 0.8531 (3) | 0.00651 (13) | 0.2834 (3) | 0.0550 (7) | |
C27 | 0.9720 (3) | −0.02410 (15) | 0.2935 (3) | 0.0713 (9) | |
H27 | 0.9858 | −0.0556 | 0.3505 | 0.086* | |
C28 | 0.0411 (3) | 0.19473 (17) | 0.3472 (4) | 0.0839 (11) | |
H28 | −0.0440 | 0.1968 | 0.3001 | 0.101* | |
C29 | 0.1816 (4) | 0.19968 (15) | 0.5499 (3) | 0.0776 (10) | |
H29 | 0.1922 | 0.2055 | 0.6410 | 0.093* | |
C30 | 1.0500 (3) | 0.03877 (15) | 0.1328 (3) | 0.0659 (9) | |
H30 | 1.1166 | 0.0498 | 0.0816 | 0.079* | |
C31 | 0.0578 (4) | 0.20374 (17) | 0.4805 (4) | 0.0863 (11) | |
H31 | −0.0158 | 0.2127 | 0.5241 | 0.104* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0275 (3) | 0.0383 (4) | 0.0368 (3) | 0.0013 (3) | 0.0102 (2) | −0.0040 (3) |
Cl2 | 0.0517 (4) | 0.0844 (6) | 0.0756 (5) | −0.0053 (4) | 0.0212 (4) | 0.0144 (4) |
Cl3 | 0.0885 (7) | 0.1081 (7) | 0.0875 (7) | 0.0118 (6) | 0.0345 (5) | 0.0428 (6) |
O4 | 0.0308 (9) | 0.0467 (10) | 0.0544 (11) | −0.0009 (8) | 0.0094 (8) | −0.0149 (8) |
O5 | 0.0406 (10) | 0.0580 (12) | 0.0615 (12) | −0.0037 (9) | 0.0061 (9) | −0.0247 (10) |
N6 | 0.0293 (10) | 0.0380 (11) | 0.0392 (11) | 0.0011 (9) | 0.0078 (9) | −0.0088 (9) |
N7 | 0.0394 (11) | 0.0350 (10) | 0.0380 (11) | −0.0005 (9) | 0.0160 (9) | −0.0028 (9) |
N8 | 0.0377 (11) | 0.0549 (13) | 0.0424 (12) | 0.0038 (10) | 0.0111 (9) | 0.0066 (10) |
C9 | 0.0436 (14) | 0.0362 (13) | 0.0457 (15) | 0.0009 (12) | 0.0167 (12) | −0.0045 (11) |
C10 | 0.0386 (13) | 0.0418 (14) | 0.0390 (13) | 0.0056 (12) | 0.0073 (11) | 0.0071 (11) |
C11 | 0.0291 (12) | 0.0491 (15) | 0.0418 (14) | −0.0011 (11) | 0.0018 (11) | −0.0114 (12) |
C12 | 0.0341 (13) | 0.0443 (14) | 0.0375 (13) | −0.0052 (11) | 0.0100 (11) | −0.0050 (12) |
C13 | 0.0323 (13) | 0.0594 (17) | 0.0548 (16) | −0.0008 (13) | 0.0041 (12) | −0.0085 (13) |
C14 | 0.0540 (16) | 0.0407 (14) | 0.0435 (14) | 0.0016 (13) | 0.0136 (12) | 0.0022 (12) |
C15 | 0.0459 (15) | 0.0432 (15) | 0.0540 (16) | −0.0057 (12) | 0.0234 (13) | −0.0104 (12) |
C16 | 0.0508 (16) | 0.0476 (15) | 0.0568 (17) | 0.0018 (13) | 0.0140 (14) | 0.0063 (13) |
C17 | 0.0656 (19) | 0.0616 (18) | 0.0430 (16) | 0.0077 (16) | 0.0107 (14) | −0.0061 (14) |
C18 | 0.0583 (18) | 0.085 (2) | 0.0463 (16) | 0.0127 (17) | 0.0227 (14) | 0.0092 (16) |
C19 | 0.0572 (17) | 0.0488 (16) | 0.0433 (15) | −0.0015 (14) | 0.0120 (13) | 0.0036 (13) |
C20 | 0.0650 (18) | 0.0569 (17) | 0.0468 (16) | 0.0168 (15) | 0.0125 (14) | −0.0018 (13) |
C21 | 0.0512 (17) | 0.079 (2) | 0.0534 (17) | 0.0081 (16) | 0.0082 (14) | −0.0119 (16) |
C22 | 0.0567 (18) | 0.068 (2) | 0.0649 (19) | −0.0007 (16) | 0.0265 (15) | 0.0200 (16) |
C23 | 0.0675 (18) | 0.0514 (16) | 0.0452 (15) | 0.0050 (15) | 0.0193 (14) | 0.0069 (13) |
C24 | 0.0505 (17) | 0.081 (2) | 0.0636 (19) | 0.0125 (16) | 0.0041 (15) | 0.0191 (17) |
C25 | 0.0376 (17) | 0.079 (2) | 0.096 (3) | 0.0156 (17) | −0.0068 (17) | −0.014 (2) |
C26 | 0.0467 (16) | 0.0629 (18) | 0.0551 (17) | 0.0041 (15) | 0.0048 (13) | 0.0046 (15) |
C27 | 0.060 (2) | 0.069 (2) | 0.081 (2) | 0.0161 (17) | −0.0104 (18) | 0.0063 (18) |
C28 | 0.0429 (17) | 0.110 (3) | 0.100 (3) | 0.0142 (19) | 0.0121 (18) | −0.019 (2) |
C29 | 0.107 (3) | 0.085 (2) | 0.0483 (18) | 0.028 (2) | 0.0387 (19) | 0.0024 (17) |
C30 | 0.0278 (14) | 0.087 (2) | 0.084 (2) | −0.0004 (15) | 0.0102 (14) | −0.014 (2) |
C31 | 0.072 (2) | 0.099 (3) | 0.098 (3) | 0.020 (2) | 0.053 (2) | −0.006 (2) |
Geometric parameters (Å, º) top
P1—O4 | 1.4716 (17) | C17—C18 | 1.366 (4) |
P1—N8 | 1.621 (2) | C17—C19 | 1.390 (4) |
P1—N7 | 1.633 (2) | C17—H17 | 0.9300 |
P1—N6 | 1.688 (2) | C18—C22 | 1.366 (4) |
Cl2—C13 | 1.734 (3) | C18—H18 | 0.9300 |
Cl3—C26 | 1.737 (3) | C19—H19 | 0.9300 |
O5—C12 | 1.215 (3) | C20—C29 | 1.383 (4) |
N6—C12 | 1.359 (3) | C20—H20 | 0.9300 |
N6—H6 | 0.850 (10) | C21—C28 | 1.378 (4) |
N7—C23 | 1.454 (3) | C21—H21 | 0.9300 |
N7—C15 | 1.465 (3) | C22—H22 | 0.9300 |
N8—C14 | 1.456 (3) | C23—H23A | 0.9600 |
N8—C24 | 1.471 (3) | C23—H23B | 0.9600 |
C9—C21 | 1.368 (4) | C23—H23C | 0.9600 |
C9—C20 | 1.380 (4) | C24—H24A | 0.9600 |
C9—C15 | 1.512 (3) | C24—H24B | 0.9600 |
C10—C19 | 1.374 (4) | C24—H24C | 0.9600 |
C10—C16 | 1.388 (3) | C25—C27 | 1.369 (5) |
C10—C14 | 1.517 (3) | C25—C30 | 1.369 (5) |
C11—C26 | 1.381 (4) | C25—H25 | 0.9300 |
C11—C13 | 1.390 (4) | C26—C27 | 1.380 (4) |
C11—C12 | 1.503 (3) | C27—H27 | 0.9300 |
C13—C30 | 1.381 (4) | C28—C31 | 1.361 (5) |
C14—H14A | 0.9700 | C28—H28 | 0.9300 |
C14—H14B | 0.9700 | C29—C31 | 1.357 (5) |
C15—H15A | 0.9700 | C29—H29 | 0.9300 |
C15—H15B | 0.9700 | C30—H30 | 0.9300 |
C16—C22 | 1.380 (4) | C31—H31 | 0.9300 |
C16—H16 | 0.9300 | | |
| | | |
O4—P1—N8 | 113.66 (11) | C17—C18—C22 | 119.5 (3) |
O4—P1—N7 | 110.42 (10) | C17—C18—H18 | 120.3 |
N8—P1—N7 | 109.20 (11) | C22—C18—H18 | 120.3 |
O4—P1—N6 | 107.29 (10) | C10—C19—C17 | 120.4 (3) |
N8—P1—N6 | 106.49 (10) | C10—C19—H19 | 119.8 |
N7—P1—N6 | 109.63 (10) | C17—C19—H19 | 119.8 |
C12—N6—P1 | 128.61 (16) | C9—C20—C29 | 120.1 (3) |
C12—N6—H6 | 119.3 (17) | C9—C20—H20 | 120.0 |
P1—N6—H6 | 111.8 (17) | C29—C20—H20 | 120.0 |
C23—N7—C15 | 114.2 (2) | C9—C21—C28 | 121.1 (3) |
C23—N7—P1 | 116.91 (16) | C9—C21—H21 | 119.5 |
C15—N7—P1 | 125.42 (16) | C28—C21—H21 | 119.5 |
C14—N8—C24 | 115.9 (2) | C18—C22—C16 | 120.7 (3) |
C14—N8—P1 | 125.23 (17) | C18—C22—H22 | 119.6 |
C24—N8—P1 | 118.83 (18) | C16—C22—H22 | 119.6 |
C21—C9—C20 | 118.6 (2) | N7—C23—H23A | 109.5 |
C21—C9—C15 | 120.8 (2) | N7—C23—H23B | 109.5 |
C20—C9—C15 | 120.6 (2) | H23A—C23—H23B | 109.5 |
C19—C10—C16 | 118.7 (2) | N7—C23—H23C | 109.5 |
C19—C10—C14 | 122.6 (2) | H23A—C23—H23C | 109.5 |
C16—C10—C14 | 118.7 (2) | H23B—C23—H23C | 109.5 |
C26—C11—C13 | 116.8 (2) | N8—C24—H24A | 109.5 |
C26—C11—C12 | 122.2 (2) | N8—C24—H24B | 109.5 |
C13—C11—C12 | 120.9 (2) | H24A—C24—H24B | 109.5 |
O5—C12—N6 | 124.3 (2) | N8—C24—H24C | 109.5 |
O5—C12—C11 | 121.3 (2) | H24A—C24—H24C | 109.5 |
N6—C12—C11 | 114.4 (2) | H24B—C24—H24C | 109.5 |
C30—C13—C11 | 121.9 (3) | C27—C25—C30 | 121.2 (3) |
C30—C13—Cl2 | 119.2 (2) | C27—C25—H25 | 119.4 |
C11—C13—Cl2 | 118.9 (2) | C30—C25—H25 | 119.4 |
N8—C14—C10 | 114.7 (2) | C11—C26—C27 | 122.3 (3) |
N8—C14—H14A | 108.6 | C11—C26—Cl3 | 118.6 (2) |
C10—C14—H14A | 108.6 | C27—C26—Cl3 | 119.1 (2) |
N8—C14—H14B | 108.6 | C25—C27—C26 | 118.8 (3) |
C10—C14—H14B | 108.6 | C25—C27—H27 | 120.6 |
H14A—C14—H14B | 107.6 | C26—C27—H27 | 120.6 |
N7—C15—C9 | 111.21 (19) | C31—C28—C21 | 119.7 (3) |
N7—C15—H15A | 109.4 | C31—C28—H28 | 120.2 |
C9—C15—H15A | 109.4 | C21—C28—H28 | 120.2 |
N7—C15—H15B | 109.4 | C31—C29—C20 | 120.2 (3) |
C9—C15—H15B | 109.4 | C31—C29—H29 | 119.9 |
H15A—C15—H15B | 108.0 | C20—C29—H29 | 119.9 |
C22—C16—C10 | 120.3 (3) | C25—C30—C13 | 119.0 (3) |
C22—C16—H16 | 119.9 | C25—C30—H30 | 120.5 |
C10—C16—H16 | 119.9 | C13—C30—H30 | 120.5 |
C18—C17—C19 | 120.5 (3) | C29—C31—C28 | 120.3 (3) |
C18—C17—H17 | 119.8 | C29—C31—H31 | 119.9 |
C19—C17—H17 | 119.8 | C28—C31—H31 | 119.9 |
| | | |
O4—P1—N6—C12 | −152.9 (2) | P1—N7—C15—C9 | 141.34 (19) |
N8—P1—N6—C12 | 85.1 (2) | C21—C9—C15—N7 | −68.0 (3) |
N7—P1—N6—C12 | −32.9 (2) | C20—C9—C15—N7 | 111.0 (3) |
O4—P1—N7—C23 | 51.1 (2) | C19—C10—C16—C22 | −0.3 (4) |
N8—P1—N7—C23 | 176.76 (18) | C14—C10—C16—C22 | 176.9 (2) |
N6—P1—N7—C23 | −66.9 (2) | C19—C17—C18—C22 | 0.3 (4) |
O4—P1—N7—C15 | −151.30 (19) | C16—C10—C19—C17 | 0.2 (4) |
N8—P1—N7—C15 | −25.6 (2) | C14—C10—C19—C17 | −176.9 (2) |
N6—P1—N7—C15 | 90.7 (2) | C18—C17—C19—C10 | −0.2 (4) |
O4—P1—N8—C14 | −142.75 (18) | C21—C9—C20—C29 | −1.0 (4) |
N7—P1—N8—C14 | 93.5 (2) | C15—C9—C20—C29 | 180.0 (3) |
N6—P1—N8—C14 | −24.8 (2) | C20—C9—C21—C28 | 0.4 (5) |
O4—P1—N8—C24 | 36.2 (2) | C15—C9—C21—C28 | 179.5 (3) |
N7—P1—N8—C24 | −87.5 (2) | C17—C18—C22—C16 | −0.4 (5) |
N6—P1—N8—C24 | 154.2 (2) | C10—C16—C22—C18 | 0.4 (4) |
P1—N6—C12—O5 | −10.9 (4) | C13—C11—C26—C27 | −0.3 (4) |
P1—N6—C12—C11 | 169.76 (17) | C12—C11—C26—C27 | −178.5 (3) |
C26—C11—C12—O5 | 94.8 (3) | C13—C11—C26—Cl3 | −179.4 (2) |
C13—C11—C12—O5 | −83.3 (3) | C12—C11—C26—Cl3 | 2.4 (4) |
C26—C11—C12—N6 | −85.8 (3) | C30—C25—C27—C26 | −0.6 (5) |
C13—C11—C12—N6 | 96.1 (3) | C11—C26—C27—C25 | 0.6 (5) |
C26—C11—C13—C30 | 0.0 (4) | Cl3—C26—C27—C25 | 179.7 (3) |
C12—C11—C13—C30 | 178.2 (2) | C9—C21—C28—C31 | 0.7 (6) |
C26—C11—C13—Cl2 | 178.7 (2) | C9—C20—C29—C31 | 0.4 (5) |
C12—C11—C13—Cl2 | −3.2 (3) | C27—C25—C30—C13 | 0.3 (5) |
C24—N8—C14—C10 | −73.2 (3) | C11—C13—C30—C25 | 0.0 (4) |
P1—N8—C14—C10 | 105.8 (2) | Cl2—C13—C30—C25 | −178.7 (2) |
C19—C10—C14—N8 | −23.6 (3) | C20—C29—C31—C28 | 0.7 (6) |
C16—C10—C14—N8 | 159.3 (2) | C21—C28—C31—C29 | −1.2 (6) |
C23—N7—C15—C9 | −60.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O4i | 0.85 (1) | 1.91 (1) | 2.756 (2) | 178 (2) |
Symmetry code: (i) −x+1, −y, −z. |
Crystal data top
C15H24Cl2N3O2P | Z = 2 |
Mr = 380.24 | F(000) = 400 |
Triclinic, P1 | Dx = 1.306 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7455 (2) Å | Cell parameters from 11215 reflections |
b = 10.0122 (3) Å | θ = 2.0–29.0° |
c = 11.7163 (3) Å | µ = 0.43 mm−1 |
α = 66.278 (3)° | T = 150 K |
β = 67.729 (2)° | Long block, colourless |
γ = 84.121 (2)° | 0.40 × 0.20 × 0.20 mm |
V = 966.84 (5) Å3 | |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4853 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3805 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 16.0143 pixels mm-1 | θmax = 29.1°, θmin = 2.0° |
ω scans | h = −13→13 |
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −13→13 |
Tmin = 0.933, Tmax = 1.000 | l = −15→15 |
43311 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: other |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.067 | Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax
Method = Robust Weighting (Prince, 1982)
W = [weight] * [1-(deltaF/6*sigmaF)2]2
Ai are:
0.119E + 04 0.124E + 04 666. 226. -17.0 |
S = 0.97 | (Δ/σ)max = 0.0002645 |
4853 reflections | Δρmax = 0.55 e Å−3 |
217 parameters | Δρmin = −0.52 e Å−3 |
3 restraints | |
Crystal data top
C15H24Cl2N3O2P | γ = 84.121 (2)° |
Mr = 380.24 | V = 966.84 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7455 (2) Å | Mo Kα radiation |
b = 10.0122 (3) Å | µ = 0.43 mm−1 |
c = 11.7163 (3) Å | T = 150 K |
α = 66.278 (3)° | 0.40 × 0.20 × 0.20 mm |
β = 67.729 (2)° | |
Data collection top
Xcalibur, Sapphire3, Gemini diffractometer | 4853 independent reflections |
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | 3805 reflections with I > 2.0σ(I) |
Tmin = 0.933, Tmax = 1.000 | Rint = 0.058 |
43311 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 3 restraints |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.55 e Å−3 |
4853 reflections | Δρmin = −0.52 e Å−3 |
217 parameters | |
Special details top
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K. Cosier, J. & Glazer, A·M., 1986. J. Appl. Cryst. 105–107. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.80505 (8) | 0.74524 (7) | −0.18215 (7) | 0.0419 | |
C2 | 0.8154 (3) | 0.9139 (3) | −0.3122 (2) | 0.0294 | |
C3 | 0.8387 (2) | 1.0394 (3) | −0.2991 (2) | 0.0246 | |
C4 | 0.8489 (2) | 1.0312 (2) | −0.1703 (2) | 0.0242 | |
O5 | 0.96792 (18) | 1.0226 (2) | −0.15579 (17) | 0.0340 | |
N6 | 0.7162 (2) | 1.0318 (2) | −0.07689 (19) | 0.0239 | |
P7 | 0.67903 (7) | 0.99785 (7) | 0.08665 (6) | 0.0233 | |
O8 | 0.51546 (17) | 0.99268 (18) | 0.14913 (15) | 0.0284 | |
N9 | 0.7660 (2) | 1.1237 (2) | 0.0924 (2) | 0.0274 | |
C10 | 0.7171 (3) | 1.2717 (3) | 0.0818 (3) | 0.0316 | |
C11 | 0.8518 (3) | 1.3613 (3) | 0.0548 (3) | 0.0485 | |
H113 | 0.8231 | 1.4582 | 0.0480 | 0.0727* | |
H111 | 0.8893 | 1.3169 | 0.1255 | 0.0723* | |
H112 | 0.9309 | 1.3675 | −0.0300 | 0.0726* | |
C12 | 0.6613 (3) | 1.3417 (3) | −0.0333 (3) | 0.0445 | |
H123 | 0.6360 | 1.4405 | −0.0428 | 0.0658* | |
H121 | 0.7382 | 1.3445 | −0.1155 | 0.0657* | |
H122 | 0.5735 | 1.2860 | −0.0119 | 0.0659* | |
C13 | 0.5940 (3) | 1.2628 (3) | 0.2131 (3) | 0.0444 | |
H133 | 0.5613 | 1.3594 | 0.2056 | 0.0662* | |
H131 | 0.6304 | 1.2218 | 0.2838 | 0.0671* | |
H132 | 0.5130 | 1.1996 | 0.2323 | 0.0668* | |
N14 | 0.7544 (2) | 0.8446 (2) | 0.1438 (2) | 0.0318 | |
C15 | 0.6850 (3) | 0.7235 (3) | 0.2760 (2) | 0.0330 | |
C16 | 0.5518 (4) | 0.6559 (3) | 0.2782 (4) | 0.0682 | |
H162 | 0.5118 | 0.5713 | 0.3611 | 0.1015* | |
H161 | 0.4769 | 0.7252 | 0.2688 | 0.1019* | |
H163 | 0.5830 | 0.6280 | 0.2030 | 0.1016* | |
C17 | 0.8006 (3) | 0.6103 (3) | 0.2905 (3) | 0.0498 | |
H172 | 0.7603 | 0.5287 | 0.3763 | 0.0743* | |
H171 | 0.8901 | 0.6526 | 0.2831 | 0.0749* | |
H173 | 0.8298 | 0.5746 | 0.2187 | 0.0753* | |
C18 | 0.6419 (5) | 0.7781 (4) | 0.3876 (3) | 0.0793 | |
H182 | 0.5995 | 0.6964 | 0.4717 | 0.1182* | |
H181 | 0.7272 | 0.8205 | 0.3835 | 0.1195* | |
H183 | 0.5677 | 0.8495 | 0.3795 | 0.1186* | |
H141 | 0.8463 (18) | 0.847 (3) | 0.111 (3) | 0.0394* | |
H61 | 0.642 (2) | 1.029 (3) | −0.097 (2) | 0.0307* | |
C19 | 0.8479 (3) | 1.1717 (3) | −0.4055 (2) | 0.0289 | |
Cl20 | 0.88198 (8) | 1.33294 (7) | −0.39623 (7) | 0.0420 | |
C21 | 0.8334 (3) | 1.1780 (3) | −0.5207 (2) | 0.0350 | |
C22 | 0.8096 (3) | 1.0495 (3) | −0.5300 (3) | 0.0377 | |
C23 | 0.8009 (3) | 0.9165 (3) | −0.4263 (3) | 0.0352 | |
H231 | 0.7889 | 0.8284 | −0.4327 | 0.0417* | |
H221 | 0.8029 | 1.0499 | −0.6088 | 0.0446* | |
H211 | 0.8400 | 1.2700 | −0.5922 | 0.0413* | |
H91 | 0.840 (2) | 1.097 (3) | 0.110 (2) | 0.0335* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0528 (4) | 0.0331 (4) | 0.0398 (4) | −0.0011 (3) | −0.0225 (3) | −0.0085 (3) |
C2 | 0.0241 (12) | 0.0345 (13) | 0.0269 (12) | 0.0019 (10) | −0.0085 (10) | −0.0106 (11) |
C3 | 0.0162 (10) | 0.0334 (12) | 0.0233 (11) | 0.0029 (9) | −0.0074 (9) | −0.0104 (10) |
C4 | 0.0204 (11) | 0.0265 (12) | 0.0254 (12) | 0.0027 (9) | −0.0107 (10) | −0.0083 (10) |
O5 | 0.0227 (9) | 0.0499 (11) | 0.0338 (10) | 0.0057 (8) | −0.0158 (8) | −0.0167 (9) |
N6 | 0.0202 (10) | 0.0334 (11) | 0.0229 (10) | 0.0012 (8) | −0.0130 (8) | −0.0112 (8) |
P7 | 0.0205 (3) | 0.0296 (3) | 0.0222 (3) | 0.0017 (2) | −0.0113 (2) | −0.0094 (3) |
O8 | 0.0229 (8) | 0.0410 (10) | 0.0257 (8) | 0.0011 (7) | −0.0120 (7) | −0.0144 (8) |
N9 | 0.0226 (10) | 0.0351 (11) | 0.0351 (11) | 0.0061 (9) | −0.0190 (9) | −0.0173 (10) |
C10 | 0.0334 (14) | 0.0318 (13) | 0.0392 (14) | 0.0045 (11) | −0.0195 (12) | −0.0184 (12) |
C11 | 0.0439 (17) | 0.0470 (17) | 0.067 (2) | −0.0022 (14) | −0.0228 (16) | −0.0314 (16) |
C12 | 0.062 (2) | 0.0353 (15) | 0.0491 (17) | 0.0116 (14) | −0.0343 (16) | −0.0180 (13) |
C13 | 0.0415 (17) | 0.0515 (18) | 0.0487 (18) | 0.0096 (14) | −0.0168 (14) | −0.0297 (15) |
N14 | 0.0246 (11) | 0.0326 (11) | 0.0299 (11) | 0.0027 (10) | −0.0105 (10) | −0.0042 (9) |
C15 | 0.0445 (16) | 0.0285 (13) | 0.0254 (12) | 0.0013 (11) | −0.0156 (12) | −0.0075 (11) |
C16 | 0.054 (2) | 0.0401 (18) | 0.098 (3) | −0.0135 (16) | −0.034 (2) | −0.0051 (19) |
C17 | 0.062 (2) | 0.0359 (16) | 0.0525 (18) | 0.0070 (14) | −0.0346 (17) | −0.0071 (14) |
C18 | 0.149 (4) | 0.059 (2) | 0.0303 (17) | 0.023 (2) | −0.035 (2) | −0.0201 (16) |
C19 | 0.0226 (12) | 0.0354 (14) | 0.0281 (12) | 0.0046 (10) | −0.0089 (10) | −0.0131 (11) |
Cl20 | 0.0565 (4) | 0.0329 (3) | 0.0399 (4) | 0.0006 (3) | −0.0256 (3) | −0.0100 (3) |
C21 | 0.0351 (14) | 0.0416 (15) | 0.0246 (12) | 0.0076 (12) | −0.0131 (11) | −0.0090 (11) |
C22 | 0.0383 (15) | 0.0537 (17) | 0.0288 (13) | 0.0076 (13) | −0.0175 (12) | −0.0204 (13) |
C23 | 0.0338 (14) | 0.0426 (15) | 0.0367 (14) | 0.0030 (12) | −0.0148 (12) | −0.0216 (13) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.741 (2) | C13—H131 | 0.949 |
C2—C3 | 1.377 (3) | C13—H132 | 0.962 |
C2—C23 | 1.386 (3) | N14—C15 | 1.479 (3) |
C3—C4 | 1.519 (3) | N14—H141 | 0.829 (16) |
C3—C19 | 1.389 (3) | C15—C16 | 1.512 (4) |
C4—O5 | 1.224 (3) | C15—C17 | 1.520 (4) |
C4—N6 | 1.341 (3) | C15—C18 | 1.517 (4) |
N6—P7 | 1.7009 (19) | C16—H162 | 0.965 |
N6—H61 | 0.848 (15) | C16—H161 | 0.960 |
P7—O8 | 1.4770 (16) | C16—H163 | 0.961 |
P7—N9 | 1.625 (2) | C17—H172 | 0.968 |
P7—N14 | 1.631 (2) | C17—H171 | 0.968 |
N9—C10 | 1.480 (3) | C17—H173 | 0.978 |
N9—H91 | 0.815 (16) | C18—H182 | 0.961 |
C10—C11 | 1.526 (3) | C18—H181 | 0.949 |
C10—C12 | 1.524 (3) | C18—H183 | 0.966 |
C10—C13 | 1.525 (3) | C19—Cl20 | 1.734 (3) |
C11—H113 | 0.961 | C19—C21 | 1.385 (3) |
C11—H111 | 0.958 | C21—C22 | 1.384 (4) |
C11—H112 | 0.982 | C21—H211 | 0.951 |
C12—H123 | 0.966 | C22—C23 | 1.378 (3) |
C12—H121 | 0.962 | C22—H221 | 0.949 |
C12—H122 | 0.963 | C23—H231 | 0.937 |
C13—H133 | 0.966 | | |
| | | |
Cl1—C2—C3 | 119.29 (18) | C10—C13—H132 | 108.8 |
Cl1—C2—C23 | 118.4 (2) | H133—C13—H132 | 110.7 |
C3—C2—C23 | 122.3 (2) | H131—C13—H132 | 108.4 |
C2—C3—C4 | 120.3 (2) | P7—N14—C15 | 125.28 (17) |
C2—C3—C19 | 117.6 (2) | P7—N14—H141 | 115.9 (19) |
C4—C3—C19 | 122.1 (2) | C15—N14—H141 | 115.0 (19) |
C3—C4—O5 | 121.8 (2) | N14—C15—C16 | 109.4 (2) |
C3—C4—N6 | 113.22 (18) | N14—C15—C17 | 106.6 (2) |
O5—C4—N6 | 125.0 (2) | C16—C15—C17 | 109.0 (2) |
C4—N6—P7 | 127.02 (15) | N14—C15—C18 | 110.4 (2) |
C4—N6—H61 | 115.6 (16) | C16—C15—C18 | 111.3 (3) |
P7—N6—H61 | 115.8 (16) | C17—C15—C18 | 110.0 (2) |
N6—P7—O8 | 105.18 (9) | C15—C16—H162 | 109.6 |
N6—P7—N9 | 108.68 (10) | C15—C16—H161 | 110.9 |
O8—P7—N9 | 114.97 (10) | H162—C16—H161 | 110.1 |
N6—P7—N14 | 105.41 (11) | C15—C16—H163 | 108.5 |
O8—P7—N14 | 115.10 (10) | H162—C16—H163 | 110.2 |
N9—P7—N14 | 106.94 (11) | H161—C16—H163 | 107.6 |
P7—N9—C10 | 126.98 (15) | C15—C17—H172 | 109.7 |
P7—N9—H91 | 113.7 (18) | C15—C17—H171 | 110.8 |
C10—N9—H91 | 119.1 (18) | H172—C17—H171 | 110.0 |
N9—C10—C11 | 107.0 (2) | C15—C17—H173 | 110.7 |
N9—C10—C12 | 110.21 (19) | H172—C17—H173 | 109.1 |
C11—C10—C12 | 110.0 (2) | H171—C17—H173 | 106.4 |
N9—C10—C13 | 110.0 (2) | C15—C18—H182 | 108.0 |
C11—C10—C13 | 109.8 (2) | C15—C18—H181 | 109.5 |
C12—C10—C13 | 109.8 (2) | H182—C18—H181 | 110.8 |
C10—C11—H113 | 108.9 | C15—C18—H183 | 110.4 |
C10—C11—H111 | 110.7 | H182—C18—H183 | 108.2 |
H113—C11—H111 | 109.7 | H181—C18—H183 | 109.8 |
C10—C11—H112 | 109.8 | C3—C19—Cl20 | 119.51 (19) |
H113—C11—H112 | 109.1 | C3—C19—C21 | 121.6 (2) |
H111—C11—H112 | 108.6 | Cl20—C19—C21 | 118.92 (19) |
C10—C12—H123 | 109.3 | C19—C21—C22 | 119.2 (2) |
C10—C12—H121 | 109.6 | C19—C21—H211 | 119.9 |
H123—C12—H121 | 108.9 | C22—C21—H211 | 120.9 |
C10—C12—H122 | 108.4 | C21—C22—C23 | 120.6 (2) |
H123—C12—H122 | 109.0 | C21—C22—H221 | 121.2 |
H121—C12—H122 | 111.6 | C23—C22—H221 | 118.2 |
C10—C13—H133 | 109.9 | C2—C23—C22 | 118.9 (2) |
C10—C13—H131 | 109.3 | C2—C23—H231 | 119.7 |
H133—C13—H131 | 109.7 | C22—C23—H231 | 121.4 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H161···O8 | 0.960 | 2.462 | 3.137 (4) | 127.16 (8) |
N6—H61···O8i | 0.848 | 1.914 | 2.758 (4) | 173 (2) |
N9—H91···O5ii | 0.815 | 2.237 | 3.038 (4) | 168 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+2, −y+2, −z. |
Experimental details
| (I) | (IV) | (V) | (III) |
Crystal data |
Chemical formula | C7H13F3N3O2P | C21H32Cl2N3O2P | C23H24Cl2N3O2P | C15H24Cl2N3O2P |
Mr | 259.17 | 460.37 | 476.32 | 380.24 |
Crystal system, space group | Monoclinic, P21/a | Monoclinic, P21/n | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 295 | 295 | 295 | 150 |
a, b, c (Å) | 11.3416 (3), 9.0552 (3), 11.8030 (4) | 10.1526 (4), 12.9020 (6), 18.5334 (9) | 10.0375 (2), 23.0525 (7), 10.1700 (3) | 9.7455 (2), 10.0122 (3), 11.7163 (3) |
α, β, γ (°) | 90, 109.413 (2), 90 | 90, 92.724 (4), 90 | 90, 96.809 (2), 90 | 66.278 (3), 67.729 (2), 84.121 (2) |
V (Å3) | 1143.26 (6) | 2424.9 (2) | 2336.64 (11) | 966.84 (5) |
Z | 4 | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.36 | 0.37 | 0.43 |
Crystal size (mm) | 0.41 × 0.35 × 0.24 | 0.27 × 0.19 × 0.12 | 0.13 × 0.07 × 0.05 | 0.40 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | Xcalibur, Sapphire3, Gemini diffractometer | Xcalibur, Sapphire3, Gemini diffractometer | Xcalibur, Sapphire3, Gemini diffractometer |
Absorption correction | – | Multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | Multi-scan CrysAlis PRO, Oxford Diffraction Ltd.,
Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET)
(compiled Aug 2 2010,13:00:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | Multi-scan CrysAlis PRO, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. |
Tmin, Tmax | – | 0.943, 1.000 | 0.984, 1.000 | 0.933, 1.000 |
No. of measured, independent and observed reflections | 1977, 1977, 1748 [I > 2σ(I)] | 10444, 4258, 3551 [I > 2σ(I)] | 9762, 4092, 3324 [I > 2σ(I)] | 43311, 4853, 3805 [I > 2.0σ(I)] |
Rint | 0.000 | 0.022 | 0.026 | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 | 0.683 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.094, 1.03 | 0.053, 0.146, 1.02 | 0.050, 0.114, 1.04 | 0.055, 0.067, 0.97 |
No. of reflections | 1977 | 4258 | 4092 | 4853 |
No. of parameters | 156 | 267 | 285 | 217 |
No. of restraints | 3 | 1 | 1 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 | 0.52, −0.31 | 0.25, −0.24 | 0.55, −0.52 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O12i | 0.844 (9) | 2.322 (14) | 3.058 (2) | 146.1 (18) |
N6—H6···O12ii | 0.845 (9) | 2.260 (11) | 3.074 (2) | 162 (2) |
N10—H10···O9i | 0.853 (9) | 1.920 (11) | 2.7579 (18) | 167.0 (19) |
Symmetry codes: (i) −x+3/2, y+1/2, −z; (ii) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···O4i | 0.854 (10) | 1.895 (11) | 2.746 (3) | 175 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O4i | 0.850 (10) | 1.906 (10) | 2.756 (2) | 178 (2) |
Symmetry code: (i) −x+1, −y, −z. |
Selected geometric parameters (Å, º) for (III) topCl1—C2 | 1.741 (2) | C10—C11 | 1.526 (3) |
C2—C3 | 1.377 (3) | C10—C12 | 1.524 (3) |
C2—C23 | 1.386 (3) | C10—C13 | 1.525 (3) |
C3—C4 | 1.519 (3) | N14—C15 | 1.479 (3) |
C3—C19 | 1.389 (3) | C15—C16 | 1.512 (4) |
C4—O5 | 1.224 (3) | C15—C17 | 1.520 (4) |
C4—N6 | 1.341 (3) | C15—C18 | 1.517 (4) |
N6—P7 | 1.7009 (19) | C19—Cl20 | 1.734 (3) |
P7—O8 | 1.4770 (16) | C19—C21 | 1.385 (3) |
P7—N9 | 1.625 (2) | C21—C22 | 1.384 (4) |
P7—N14 | 1.631 (2) | C22—C23 | 1.378 (3) |
N9—C10 | 1.480 (3) | | |
| | | |
Cl1—C2—C3 | 119.29 (18) | N9—C10—C12 | 110.21 (19) |
Cl1—C2—C23 | 118.4 (2) | C11—C10—C12 | 110.0 (2) |
C3—C2—C23 | 122.3 (2) | N9—C10—C13 | 110.0 (2) |
C2—C3—C4 | 120.3 (2) | C11—C10—C13 | 109.8 (2) |
C2—C3—C19 | 117.6 (2) | C12—C10—C13 | 109.8 (2) |
C4—C3—C19 | 122.1 (2) | P7—N14—C15 | 125.28 (17) |
C3—C4—O5 | 121.8 (2) | N14—C15—C16 | 109.4 (2) |
C3—C4—N6 | 113.22 (18) | N14—C15—C17 | 106.6 (2) |
O5—C4—N6 | 125.0 (2) | C16—C15—C17 | 109.0 (2) |
C4—N6—P7 | 127.02 (15) | N14—C15—C18 | 110.4 (2) |
N6—P7—O8 | 105.18 (9) | C16—C15—C18 | 111.3 (3) |
N6—P7—N9 | 108.68 (10) | C17—C15—C18 | 110.0 (2) |
O8—P7—N9 | 114.97 (10) | C3—C19—Cl20 | 119.51 (19) |
N6—P7—N14 | 105.41 (11) | C3—C19—C21 | 121.6 (2) |
O8—P7—N14 | 115.10 (10) | Cl20—C19—C21 | 118.92 (19) |
N9—P7—N14 | 106.94 (11) | C19—C21—C22 | 119.2 (2) |
P7—N9—C10 | 126.98 (15) | C21—C22—C23 | 120.6 (2) |
N9—C10—C11 | 107.0 (2) | C2—C23—C22 | 118.9 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H161···O8 | 0.960 | 2.462 | 3.137 (4) | 127.16 (8) |
N6—H61···O8i | 0.848 | 1.914 | 2.758 (4) | 173 (2) |
N9—H91···O5ii | 0.815 | 2.237 | 3.038 (4) | 168 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+2, −y+2, −z. |