organic compounds
Cyclohexylmethylammonium N,N′-dicyclohexyl-N,N′-dimethyl-N′′-(2,2,2-trifluoroacetyl)phosphonic triamide)
aDepartment of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad 91779, Iran
*Correspondence e-mail: myazdam56@yahoo.de
In the salt, C7H16N+·C16H28F3N3O2P−, the P atom shows tetrahedral coordination. Two ion pairs are linked by N—H⋯O hydrogen bonds across a center of inversion. The phosphoryl and carbonyl groups are staggered [O—P—N—C = 64.8 (3)°].
Related literature
For alkali metal salts of dimethyl-N-trichloracetylamidophosphate, see: Trush et al. (2005). For a related structure, see: Yazdanbakhsh & Sabbaghi (2007). For bond-length data, see: Corbridge (1995). For synthetic details, see: Shokol et al. (1969).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808040737/ng2519sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808040737/ng2519Isup2.hkl
CF3C(O)N(H)P(O)Cl2 was prepared similar to the literature method (Shokol et al., 1969) from the reaction of phosphorus pentachloride and 2,2,2-triflouoroacetamide in CCl4 and then the treatment of formic acid. Synthesis of CF3C(O)N(H)P(O)[N(CH3)(C6H11)]2 To a solution of (1.15 g, 5 mmol) triflouroacetyl phosphoramidic dichloride in CCl4 (20 ml), a solution of N-methylcyclohexylamine (2.26 g, 20 mmol) in CCl4 (10 ml) was added dropwise at 0°C. After 24 h stirring, the solvent was removed in vacuum and the solid product was washed with distilled water. The residue recrystallized in CH3CN. Anal. Calc. for C16H29F3N3O2P: C, 50.10; H, 7.56; N, 10.95. Found: C, 49.72; H, 7.84; N, 10.74%. 31P NMR ([D6]DMSO): 12.22. 13C NMR ([D6]DMSO): 54.35 (d, 2J(P,C) = 4.2 Hz 2 C, CH3), 30.22 (d, 2J(P,C) = 2.7 Hz, 2 C, CH), 27.30 (d, 3J(P,C) = 4.4 Hz, 4 C, CH2), 25.60 (s), 25.00 (s). 1H NMR ([D6]DMSO): 1.02 (m, 2 H), 1.17 (m, 4 H), 1.48 (m, 8 H), 1.73 (m, 4 H), 2.49 (s, 6 H), 3.27 (m, 2 H), 10.23 (b, 1 H, NH). IR (KBr, cm-1): 3067, 2925, 2802, 1735 (C?O), 1498, 1271, 1236, 1202, 1158, 1005, 980, 893, 851. Raman (cm-1): 2929, 2858, 1736, 1446, 1341, 1259, 1188, 1151, 1025, 857, 808, 742, 533, 493, 442, 308. MS (70 ev) m/z (%): 383 (20, [M]+), 368 (2, [M—CH3]+), 340 (36, [M—C(O)NH]+), 271 (35, [P(O)(N(CH3)(C6H11))2]+), 112 (100, [N(CH3)(C6H11)]+), 97 (58, [CF3C(O)]+), 69 (98, [CF3]+). Synthesis of [NH2CH3C6H11][CF3CONPO(NCH3C6H11)2] Lithium hydroxide (0.04 g, 1.6 mmol) was added to a solution of CF3CONHPO(NCH3C6H11)2 (0.62 g, 1.6 mmol) in 10 ml of aqueous methanol (1:3). The solution was stirred at room temperature for 24 h. Colorless single-crystal was obtained after a week at room temperature. Yield: 0.48 g, 60%. Anal. Calc. for C23H44F3N4O2P: C, 55.59; H, 8.86; N, 11.28. Found: C, 55.47; H, 8.80; N, 11.52%. 31P NMR ([D6]DMSO): 18.61. 13C NMR ([D6]DMSO): 23.84 (s), 24.83 (s), 25.37 (s), 25.87 (s), 27.20 (d, J(P,C)=3.9 Hz), 28.69 (s), 29.70 (s), 30.38 (s), 53.48 (s), 56.72 (s), 137.58 (dq, CF3), 157.14 (q, C?O). IR (KBr, cm-1): 3338, 3058, 2936, 2849, 2690, 2624, 1689 (C?O), 1631, 1601, 1553, 1520, 1430, 1375, 1220, 1067, 987, 896, 769, 682.
The hydrogen atoms of NH2 group were found in difference Fourier synthesis. The H(C) atom positions were calculated. All hydrogen atoms were refined in isotropic approximation in riding model with with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded.
Data collection: SMART (Bruker, 1998); cell
SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C7H16N+·C16H28F3N3O2P− | F(000) = 1072 |
Mr = 496.59 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 365 reflections |
a = 9.183 (3) Å | θ = 2–25° |
b = 30.893 (7) Å | µ = 0.15 mm−1 |
c = 9.241 (2) Å | T = 120 K |
β = 93.039 (7)° | Prism, colorless |
V = 2617.9 (12) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 5148 independent reflections |
Radiation source: fine-focus sealed tube | 2673 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.947, Tmax = 0.969 | k = −38→37 |
23153 measured reflections | l = −11→11 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0126P)2 + 2.4P] where P = (Fo2 + 2Fc2)/3 |
5148 reflections | (Δ/σ)max = 0.004 |
304 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C7H16N+·C16H28F3N3O2P− | V = 2617.9 (12) Å3 |
Mr = 496.59 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.183 (3) Å | µ = 0.15 mm−1 |
b = 30.893 (7) Å | T = 120 K |
c = 9.241 (2) Å | 0.40 × 0.30 × 0.25 mm |
β = 93.039 (7)° |
Bruker SMART 1000 CCD area-detector diffractometer | 5148 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2673 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.969 | Rint = 0.064 |
23153 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.33 e Å−3 |
5148 reflections | Δρmin = −0.32 e Å−3 |
304 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 | ||
P1 | 0.59626 (9) | 0.11209 (3) | 0.00482 (9) | 0.0277 (2) | |
F1 | 0.8519 (2) | 0.13212 (8) | −0.3599 (2) | 0.0674 (7) | |
F2 | 1.0171 (2) | 0.15024 (6) | −0.2005 (2) | 0.0605 (6) | |
F3 | 1.0165 (2) | 0.08688 (6) | −0.2932 (2) | 0.0498 (5) | |
O1 | 0.5406 (2) | 0.06625 (6) | 0.0163 (2) | 0.0306 (5) | |
O2 | 0.9035 (2) | 0.07648 (7) | −0.0331 (2) | 0.0381 (6) | |
N1 | 0.7111 (3) | 0.12011 (8) | −0.1208 (3) | 0.0285 (6) | |
N2 | 0.4692 (3) | 0.14801 (7) | −0.0417 (3) | 0.0250 (6) | |
N3 | 0.6583 (3) | 0.12719 (7) | 0.1670 (3) | 0.0280 (6) | |
N4 | 0.3080 (3) | 0.01010 (8) | 0.0416 (3) | 0.0300 (6) | |
H4NA | 0.3810 | 0.0319 | 0.0427 | 0.029 (9)* | |
H4NB | 0.3547 | −0.0172 | 0.0350 | 0.051 (11)* | |
C1 | 0.8390 (3) | 0.10240 (10) | −0.1197 (3) | 0.0302 (8) | |
C2 | 0.9298 (3) | 0.11769 (11) | −0.2449 (4) | 0.0330 (8) | |
C3 | 0.3392 (3) | 0.14748 (10) | 0.0448 (3) | 0.0348 (8) | |
H3A | 0.2959 | 0.1765 | 0.0455 | 0.052* | |
H3B | 0.3672 | 0.1387 | 0.1444 | 0.052* | |
H3C | 0.2679 | 0.1269 | 0.0023 | 0.052* | |
C4 | 0.4473 (3) | 0.16366 (9) | −0.1935 (3) | 0.0259 (7) | |
H4A | 0.5466 | 0.1700 | −0.2277 | 0.031* | |
C5 | 0.3796 (3) | 0.13003 (10) | −0.2974 (3) | 0.0317 (8) | |
H5A | 0.2808 | 0.1225 | −0.2674 | 0.038* | |
H5B | 0.4395 | 0.1034 | −0.2929 | 0.038* | |
C6 | 0.3694 (4) | 0.14714 (11) | −0.4532 (3) | 0.0411 (9) | |
H6A | 0.4689 | 0.1512 | −0.4873 | 0.049* | |
H6B | 0.3186 | 0.1256 | −0.5170 | 0.049* | |
C7 | 0.2875 (4) | 0.18992 (11) | −0.4631 (4) | 0.0443 (9) | |
H7A | 0.2889 | 0.2012 | −0.5633 | 0.053* | |
H7B | 0.1845 | 0.1851 | −0.4406 | 0.053* | |
C8 | 0.3553 (4) | 0.22305 (10) | −0.3587 (4) | 0.0411 (9) | |
H8A | 0.2965 | 0.2499 | −0.3638 | 0.049* | |
H8B | 0.4547 | 0.2302 | −0.3877 | 0.049* | |
C9 | 0.3634 (4) | 0.20606 (10) | −0.2029 (3) | 0.0340 (8) | |
H9A | 0.4125 | 0.2277 | −0.1381 | 0.041* | |
H9B | 0.2636 | 0.2015 | −0.1703 | 0.041* | |
C10 | 0.6862 (4) | 0.09517 (10) | 0.2826 (3) | 0.0391 (9) | |
H10A | 0.6866 | 0.1096 | 0.3770 | 0.059* | |
H10B | 0.7811 | 0.0815 | 0.2709 | 0.059* | |
H10C | 0.6095 | 0.0731 | 0.2769 | 0.059* | |
C11 | 0.7380 (3) | 0.16853 (9) | 0.1839 (3) | 0.0292 (8) | |
H11A | 0.7251 | 0.1840 | 0.0889 | 0.035* | |
C12 | 0.9025 (3) | 0.16295 (10) | 0.2143 (4) | 0.0357 (8) | |
H12A | 0.9204 | 0.1477 | 0.3079 | 0.043* | |
H12B | 0.9424 | 0.1449 | 0.1374 | 0.043* | |
C13 | 0.9808 (4) | 0.20648 (11) | 0.2202 (4) | 0.0472 (10) | |
H13A | 1.0859 | 0.2019 | 0.2448 | 0.057* | |
H13B | 0.9710 | 0.2205 | 0.1239 | 0.057* | |
C14 | 0.9170 (4) | 0.23579 (11) | 0.3327 (4) | 0.0504 (10) | |
H14A | 0.9658 | 0.2643 | 0.3314 | 0.060* | |
H14B | 0.9357 | 0.2230 | 0.4302 | 0.060* | |
C15 | 0.7527 (4) | 0.24187 (11) | 0.3035 (4) | 0.0482 (10) | |
H15A | 0.7342 | 0.2574 | 0.2106 | 0.058* | |
H15B | 0.7133 | 0.2597 | 0.3815 | 0.058* | |
C16 | 0.6749 (4) | 0.19793 (10) | 0.2965 (4) | 0.0403 (9) | |
H16A | 0.6849 | 0.1838 | 0.3927 | 0.048* | |
H16B | 0.5697 | 0.2024 | 0.2722 | 0.048* | |
C17 | 0.2070 (3) | 0.01882 (10) | −0.0858 (3) | 0.0367 (9) | |
H17A | 0.2635 | 0.0236 | −0.1715 | 0.055* | |
H17B | 0.1490 | 0.0447 | −0.0674 | 0.055* | |
H17C | 0.1420 | −0.0060 | −0.1026 | 0.055* | |
C18 | 0.2394 (3) | 0.00821 (10) | 0.1845 (3) | 0.0299 (8) | |
H18A | 0.1527 | −0.0114 | 0.1745 | 0.036* | |
C19 | 0.3478 (4) | −0.01118 (10) | 0.2964 (3) | 0.0364 (9) | |
H19A | 0.4363 | 0.0071 | 0.3050 | 0.044* | |
H19B | 0.3770 | −0.0404 | 0.2646 | 0.044* | |
C20 | 0.2801 (4) | −0.01433 (11) | 0.4438 (3) | 0.0430 (9) | |
H20A | 0.1985 | −0.0353 | 0.4375 | 0.052* | |
H20B | 0.3541 | −0.0252 | 0.5167 | 0.052* | |
C21 | 0.2246 (4) | 0.02903 (11) | 0.4918 (4) | 0.0454 (10) | |
H21A | 0.3080 | 0.0489 | 0.5107 | 0.054* | |
H21B | 0.1745 | 0.0254 | 0.5833 | 0.054* | |
C22 | 0.1197 (4) | 0.04878 (11) | 0.3780 (3) | 0.0437 (9) | |
H22A | 0.0902 | 0.0779 | 0.4102 | 0.052* | |
H22B | 0.0309 | 0.0306 | 0.3674 | 0.052* | |
C23 | 0.1878 (4) | 0.05249 (10) | 0.2320 (3) | 0.0357 (8) | |
H23A | 0.1151 | 0.0641 | 0.1590 | 0.043* | |
H23B | 0.2714 | 0.0728 | 0.2397 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0272 (5) | 0.0257 (5) | 0.0301 (5) | −0.0010 (4) | 0.0017 (4) | 0.0008 (4) |
F1 | 0.0449 (13) | 0.112 (2) | 0.0460 (13) | 0.0198 (13) | 0.0116 (11) | 0.0314 (13) |
F2 | 0.0560 (14) | 0.0487 (13) | 0.0793 (16) | −0.0186 (11) | 0.0286 (12) | −0.0111 (12) |
F3 | 0.0466 (13) | 0.0509 (13) | 0.0535 (13) | 0.0069 (10) | 0.0170 (10) | −0.0057 (11) |
O1 | 0.0307 (12) | 0.0241 (12) | 0.0372 (13) | −0.0017 (10) | 0.0042 (10) | 0.0018 (10) |
O2 | 0.0367 (14) | 0.0360 (14) | 0.0416 (14) | 0.0078 (11) | 0.0014 (11) | 0.0029 (11) |
N1 | 0.0212 (14) | 0.0337 (16) | 0.0304 (15) | 0.0044 (12) | 0.0008 (12) | 0.0002 (12) |
N2 | 0.0265 (15) | 0.0242 (14) | 0.0249 (14) | −0.0005 (11) | 0.0056 (12) | 0.0033 (11) |
N3 | 0.0345 (16) | 0.0223 (14) | 0.0268 (15) | −0.0040 (12) | −0.0019 (12) | 0.0018 (12) |
N4 | 0.0331 (16) | 0.0260 (16) | 0.0308 (16) | 0.0019 (13) | 0.0009 (13) | 0.0012 (12) |
C1 | 0.031 (2) | 0.0290 (19) | 0.0299 (19) | −0.0028 (16) | −0.0004 (16) | −0.0024 (15) |
C2 | 0.0264 (19) | 0.032 (2) | 0.040 (2) | 0.0042 (16) | −0.0021 (16) | −0.0007 (16) |
C3 | 0.036 (2) | 0.0320 (19) | 0.037 (2) | 0.0024 (16) | 0.0092 (17) | 0.0039 (16) |
C4 | 0.0234 (17) | 0.0253 (17) | 0.0294 (18) | 0.0005 (14) | 0.0044 (14) | 0.0060 (14) |
C5 | 0.0325 (19) | 0.0283 (18) | 0.0338 (19) | 0.0005 (15) | −0.0027 (15) | 0.0034 (15) |
C6 | 0.050 (2) | 0.039 (2) | 0.034 (2) | −0.0105 (18) | −0.0064 (17) | −0.0030 (17) |
C7 | 0.040 (2) | 0.048 (2) | 0.044 (2) | −0.0035 (18) | −0.0075 (18) | 0.0165 (19) |
C8 | 0.044 (2) | 0.032 (2) | 0.047 (2) | 0.0049 (17) | −0.0007 (18) | 0.0093 (17) |
C9 | 0.037 (2) | 0.0297 (19) | 0.036 (2) | −0.0004 (15) | 0.0036 (16) | 0.0043 (16) |
C10 | 0.054 (2) | 0.0310 (19) | 0.031 (2) | −0.0043 (17) | −0.0053 (17) | 0.0073 (16) |
C11 | 0.035 (2) | 0.0261 (18) | 0.0258 (18) | −0.0052 (15) | −0.0029 (15) | 0.0027 (14) |
C12 | 0.036 (2) | 0.038 (2) | 0.033 (2) | −0.0044 (16) | 0.0010 (16) | −0.0048 (16) |
C13 | 0.043 (2) | 0.053 (2) | 0.045 (2) | −0.0163 (19) | −0.0068 (19) | 0.0032 (19) |
C14 | 0.060 (3) | 0.035 (2) | 0.054 (3) | −0.0102 (19) | −0.015 (2) | −0.0093 (19) |
C15 | 0.053 (3) | 0.036 (2) | 0.055 (3) | 0.0040 (18) | −0.005 (2) | −0.0125 (19) |
C16 | 0.040 (2) | 0.033 (2) | 0.047 (2) | 0.0020 (17) | −0.0012 (18) | −0.0059 (17) |
C17 | 0.041 (2) | 0.041 (2) | 0.0278 (19) | 0.0017 (17) | −0.0061 (16) | 0.0043 (16) |
C18 | 0.032 (2) | 0.0329 (19) | 0.0247 (18) | −0.0010 (15) | 0.0033 (15) | 0.0027 (15) |
C19 | 0.041 (2) | 0.031 (2) | 0.036 (2) | 0.0006 (16) | −0.0051 (17) | 0.0008 (16) |
C20 | 0.058 (3) | 0.038 (2) | 0.032 (2) | −0.0026 (18) | −0.0092 (18) | 0.0079 (17) |
C21 | 0.062 (3) | 0.047 (2) | 0.027 (2) | −0.001 (2) | 0.0042 (18) | −0.0015 (17) |
C22 | 0.051 (2) | 0.045 (2) | 0.036 (2) | 0.0031 (18) | 0.0105 (18) | −0.0010 (18) |
C23 | 0.042 (2) | 0.034 (2) | 0.031 (2) | 0.0049 (16) | −0.0007 (16) | 0.0026 (15) |
P1—O1 | 1.511 (2) | C10—H10B | 0.9800 |
P1—N1 | 1.629 (3) | C10—H10C | 0.9800 |
P1—N3 | 1.643 (2) | C11—C16 | 1.519 (4) |
P1—N2 | 1.651 (2) | C11—C12 | 1.531 (4) |
F1—C2 | 1.326 (3) | C11—H11A | 1.0000 |
F2—C2 | 1.337 (3) | C12—C13 | 1.525 (4) |
F3—C2 | 1.333 (3) | C12—H12A | 0.9900 |
O2—C1 | 1.258 (3) | C12—H12B | 0.9900 |
N1—C1 | 1.295 (4) | C13—C14 | 1.520 (5) |
N2—C3 | 1.472 (3) | C13—H13A | 0.9900 |
N2—C4 | 1.487 (3) | C13—H13B | 0.9900 |
N3—C10 | 1.468 (4) | C14—C15 | 1.530 (5) |
N3—C11 | 1.476 (3) | C14—H14A | 0.9900 |
N4—C17 | 1.484 (4) | C14—H14B | 0.9900 |
N4—C18 | 1.494 (4) | C15—C16 | 1.534 (4) |
N4—H4NA | 0.9502 | C15—H15A | 0.9900 |
N4—H4NB | 0.9499 | C15—H15B | 0.9900 |
C1—C2 | 1.536 (4) | C16—H16A | 0.9900 |
C3—H3A | 0.9800 | C16—H16B | 0.9900 |
C3—H3B | 0.9800 | C17—H17A | 0.9800 |
C3—H3C | 0.9800 | C17—H17B | 0.9800 |
C4—C9 | 1.520 (4) | C17—H17C | 0.9800 |
C4—C5 | 1.525 (4) | C18—C23 | 1.520 (4) |
C4—H4A | 1.0000 | C18—C19 | 1.520 (4) |
C5—C6 | 1.531 (4) | C18—H18A | 1.0000 |
C5—H5A | 0.9900 | C19—C20 | 1.530 (4) |
C5—H5B | 0.9900 | C19—H19A | 0.9900 |
C6—C7 | 1.521 (4) | C19—H19B | 0.9900 |
C6—H6A | 0.9900 | C20—C21 | 1.509 (4) |
C6—H6B | 0.9900 | C20—H20A | 0.9900 |
C7—C8 | 1.517 (4) | C20—H20B | 0.9900 |
C7—H7A | 0.9900 | C21—C22 | 1.516 (4) |
C7—H7B | 0.9900 | C21—H21A | 0.9900 |
C8—C9 | 1.531 (4) | C21—H21B | 0.9900 |
C8—H8A | 0.9900 | C22—C23 | 1.521 (4) |
C8—H8B | 0.9900 | C22—H22A | 0.9900 |
C9—H9A | 0.9900 | C22—H22B | 0.9900 |
C9—H9B | 0.9900 | C23—H23A | 0.9900 |
C10—H10A | 0.9800 | C23—H23B | 0.9900 |
O1—P1—N1 | 115.26 (13) | N3—C11—C12 | 113.6 (2) |
O1—P1—N3 | 107.72 (12) | C16—C11—C12 | 110.5 (3) |
N1—P1—N3 | 113.65 (13) | N3—C11—H11A | 106.5 |
O1—P1—N2 | 114.29 (12) | C16—C11—H11A | 106.5 |
N1—P1—N2 | 100.79 (12) | C12—C11—H11A | 106.5 |
N3—P1—N2 | 104.66 (12) | C13—C12—C11 | 111.5 (3) |
C1—N1—P1 | 123.4 (2) | C13—C12—H12A | 109.3 |
C3—N2—C4 | 116.3 (2) | C11—C12—H12A | 109.3 |
C3—N2—P1 | 115.67 (19) | C13—C12—H12B | 109.3 |
C4—N2—P1 | 121.53 (19) | C11—C12—H12B | 109.3 |
C10—N3—C11 | 116.1 (2) | H12A—C12—H12B | 108.0 |
C10—N3—P1 | 120.7 (2) | C14—C13—C12 | 110.6 (3) |
C11—N3—P1 | 119.19 (19) | C14—C13—H13A | 109.5 |
C17—N4—C18 | 115.7 (2) | C12—C13—H13A | 109.5 |
C17—N4—H4NA | 106.9 | C14—C13—H13B | 109.5 |
C18—N4—H4NA | 110.4 | C12—C13—H13B | 109.5 |
C17—N4—H4NB | 112.1 | H13A—C13—H13B | 108.1 |
C18—N4—H4NB | 103.6 | C13—C14—C15 | 111.4 (3) |
H4NA—N4—H4NB | 108.1 | C13—C14—H14A | 109.3 |
O2—C1—N1 | 132.1 (3) | C15—C14—H14A | 109.3 |
O2—C1—C2 | 114.8 (3) | C13—C14—H14B | 109.3 |
N1—C1—C2 | 113.1 (3) | C15—C14—H14B | 109.3 |
F1—C2—F3 | 106.1 (3) | H14A—C14—H14B | 108.0 |
F1—C2—F2 | 106.4 (3) | C14—C15—C16 | 110.6 (3) |
F3—C2—F2 | 106.3 (3) | C14—C15—H15A | 109.5 |
F1—C2—C1 | 114.6 (3) | C16—C15—H15A | 109.5 |
F3—C2—C1 | 113.0 (3) | C14—C15—H15B | 109.5 |
F2—C2—C1 | 109.9 (3) | C16—C15—H15B | 109.5 |
N2—C3—H3A | 109.5 | H15A—C15—H15B | 108.1 |
N2—C3—H3B | 109.5 | C11—C16—C15 | 111.4 (3) |
H3A—C3—H3B | 109.5 | C11—C16—H16A | 109.4 |
N2—C3—H3C | 109.5 | C15—C16—H16A | 109.4 |
H3A—C3—H3C | 109.5 | C11—C16—H16B | 109.4 |
H3B—C3—H3C | 109.5 | C15—C16—H16B | 109.4 |
N2—C4—C9 | 112.1 (2) | H16A—C16—H16B | 108.0 |
N2—C4—C5 | 113.8 (2) | N4—C17—H17A | 109.5 |
C9—C4—C5 | 111.3 (2) | N4—C17—H17B | 109.5 |
N2—C4—H4A | 106.4 | H17A—C17—H17B | 109.5 |
C9—C4—H4A | 106.4 | N4—C17—H17C | 109.5 |
C5—C4—H4A | 106.4 | H17A—C17—H17C | 109.5 |
C4—C5—C6 | 111.1 (2) | H17B—C17—H17C | 109.5 |
C4—C5—H5A | 109.4 | N4—C18—C23 | 111.9 (2) |
C6—C5—H5A | 109.4 | N4—C18—C19 | 108.9 (2) |
C4—C5—H5B | 109.4 | C23—C18—C19 | 111.2 (3) |
C6—C5—H5B | 109.4 | N4—C18—H18A | 108.2 |
H5A—C5—H5B | 108.0 | C23—C18—H18A | 108.2 |
C7—C6—C5 | 111.2 (3) | C19—C18—H18A | 108.2 |
C7—C6—H6A | 109.4 | C18—C19—C20 | 110.4 (3) |
C5—C6—H6A | 109.4 | C18—C19—H19A | 109.6 |
C7—C6—H6B | 109.4 | C20—C19—H19A | 109.6 |
C5—C6—H6B | 109.4 | C18—C19—H19B | 109.6 |
H6A—C6—H6B | 108.0 | C20—C19—H19B | 109.6 |
C8—C7—C6 | 111.3 (3) | H19A—C19—H19B | 108.1 |
C8—C7—H7A | 109.4 | C21—C20—C19 | 111.4 (3) |
C6—C7—H7A | 109.4 | C21—C20—H20A | 109.3 |
C8—C7—H7B | 109.4 | C19—C20—H20A | 109.3 |
C6—C7—H7B | 109.4 | C21—C20—H20B | 109.3 |
H7A—C7—H7B | 108.0 | C19—C20—H20B | 109.3 |
C7—C8—C9 | 111.4 (3) | H20A—C20—H20B | 108.0 |
C7—C8—H8A | 109.3 | C20—C21—C22 | 111.5 (3) |
C9—C8—H8A | 109.3 | C20—C21—H21A | 109.3 |
C7—C8—H8B | 109.3 | C22—C21—H21A | 109.3 |
C9—C8—H8B | 109.3 | C20—C21—H21B | 109.3 |
H8A—C8—H8B | 108.0 | C22—C21—H21B | 109.3 |
C4—C9—C8 | 110.4 (3) | H21A—C21—H21B | 108.0 |
C4—C9—H9A | 109.6 | C21—C22—C23 | 111.7 (3) |
C8—C9—H9A | 109.6 | C21—C22—H22A | 109.3 |
C4—C9—H9B | 109.6 | C23—C22—H22A | 109.3 |
C8—C9—H9B | 109.6 | C21—C22—H22B | 109.3 |
H9A—C9—H9B | 108.1 | C23—C22—H22B | 109.3 |
N3—C10—H10A | 109.5 | H22A—C22—H22B | 107.9 |
N3—C10—H10B | 109.5 | C18—C23—C22 | 109.7 (3) |
H10A—C10—H10B | 109.5 | C18—C23—H23A | 109.7 |
N3—C10—H10C | 109.5 | C22—C23—H23A | 109.7 |
H10A—C10—H10C | 109.5 | C18—C23—H23B | 109.7 |
H10B—C10—H10C | 109.5 | C22—C23—H23B | 109.7 |
N3—C11—C16 | 112.6 (3) | H23A—C23—H23B | 108.2 |
O1—P1—N1—C1 | −64.8 (3) | C4—C5—C6—C7 | −54.9 (4) |
N3—P1—N1—C1 | 60.3 (3) | C5—C6—C7—C8 | 55.0 (4) |
N2—P1—N1—C1 | 171.7 (2) | C6—C7—C8—C9 | −55.9 (4) |
O1—P1—N2—C3 | 51.3 (2) | N2—C4—C9—C8 | 174.9 (2) |
N1—P1—N2—C3 | 175.5 (2) | C5—C4—C9—C8 | −56.4 (3) |
N3—P1—N2—C3 | −66.3 (2) | C7—C8—C9—C4 | 56.4 (4) |
O1—P1—N2—C4 | −99.4 (2) | C10—N3—C11—C16 | −75.6 (3) |
N1—P1—N2—C4 | 24.9 (2) | P1—N3—C11—C16 | 126.7 (2) |
N3—P1—N2—C4 | 143.0 (2) | C10—N3—C11—C12 | 51.0 (4) |
O1—P1—N3—C10 | 14.9 (3) | P1—N3—C11—C12 | −106.8 (3) |
N1—P1—N3—C10 | −114.1 (2) | N3—C11—C12—C13 | 176.0 (3) |
N2—P1—N3—C10 | 136.9 (2) | C16—C11—C12—C13 | −56.3 (4) |
O1—P1—N3—C11 | 171.6 (2) | C11—C12—C13—C14 | 56.4 (4) |
N1—P1—N3—C11 | 42.6 (3) | C12—C13—C14—C15 | −56.2 (4) |
N2—P1—N3—C11 | −66.4 (2) | C13—C14—C15—C16 | 55.9 (4) |
P1—N1—C1—O2 | 1.1 (5) | N3—C11—C16—C15 | −175.8 (3) |
P1—N1—C1—C2 | −176.0 (2) | C12—C11—C16—C15 | 56.0 (4) |
O2—C1—C2—F1 | 157.9 (3) | C14—C15—C16—C11 | −55.9 (4) |
N1—C1—C2—F1 | −24.4 (4) | C17—N4—C18—C23 | −69.9 (3) |
O2—C1—C2—F3 | 36.2 (4) | C17—N4—C18—C19 | 166.7 (3) |
N1—C1—C2—F3 | −146.1 (3) | N4—C18—C19—C20 | −179.0 (3) |
O2—C1—C2—F2 | −82.3 (3) | C23—C18—C19—C20 | 57.2 (3) |
N1—C1—C2—F2 | 95.3 (3) | C18—C19—C20—C21 | −55.3 (4) |
C3—N2—C4—C9 | 48.6 (3) | C19—C20—C21—C22 | 54.5 (4) |
P1—N2—C4—C9 | −161.0 (2) | C20—C21—C22—C23 | −55.5 (4) |
C3—N2—C4—C5 | −78.8 (3) | N4—C18—C23—C22 | −179.7 (3) |
P1—N2—C4—C5 | 71.7 (3) | C19—C18—C23—C22 | −57.7 (4) |
N2—C4—C5—C6 | −176.2 (2) | C21—C22—C23—C18 | 56.5 (4) |
C9—C4—C5—C6 | 56.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4NA···O1 | 0.95 | 1.84 | 2.771 (3) | 167 |
N4—H4NB···O1i | 0.95 | 1.87 | 2.804 (3) | 168 |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C7H16N+·C16H28F3N3O2P− |
Mr | 496.59 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 9.183 (3), 30.893 (7), 9.241 (2) |
β (°) | 93.039 (7) |
V (Å3) | 2617.9 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.947, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23153, 5148, 2673 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.113, 1.08 |
No. of reflections | 5148 |
No. of parameters | 304 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.32 |
Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4NA···O1 | 0.95 | 1.84 | 2.771 (3) | 167 |
N4—H4NB···O1i | 0.95 | 1.87 | 2.804 (3) | 168 |
Symmetry code: (i) −x+1, −y, −z. |
Acknowledgements
Support of this investigation by Ferdowsi University is gratefully acknowledged.
References
Brandenburg, K. (2001). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Corbridge, D. E. C. (1995). Phosphorus, an Outline of its Chemistry, Biochemistry and Technology, 5th ed., p. 1179. New York: Elsevier Science. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shokol, V. A., Kisilenko, A. A. & Derkach, G. I. (1969). Zh. Obshch. Khim. 39, 1492–1497. CAS Google Scholar
Trush, V. A., Gubina, K. E., Amirkhanov, V. M., Swiatek-Kozlowska, J. & Domasevitch, K. V. (2005). Polyhedron, 24, 1007–1014. Web of Science CSD CrossRef CAS Google Scholar
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Alkali onic-salts (Na+, Rb+) of dimethyl-N-trichloracetylamidophosphate [HL] were synthesized from aqueous-alcoholic solutions (Trush et al., 2005). Furthermore synthesis and investigation of onic-salts SbPh4+ allowed the determination of the preferable donor center of the deprotonated ligand (the oxygen atom of the phosphoryl group). Using non-coordinating ions PPh4+ permits to synthesize and characterize structurally of the "free" non-solvated [HL] anion. This information could be used for the molecular design of coordination systems based on carbacylamidophosphates. Here, we report on a new onic-salt (NH2CH3C6H11+) of [CF3CONPO(NCH3C6H11)2]- obtained from a reaction between LiOH and ligand. Single crystal of the product [NH2CH3C6H11][CF3CONPO(NCH3C6H11)2] was obtained from a solution of CH3OH—H2O (3:1) after a slow evaporation at room temperature. The proton transfer compound contains N-methyl cyclohexyl ammonium cation and deprotonated N'-2,2,2,-tri-flouroacetyl bis N"-methyl cyclohexyl phosphortriamide (Fig. 1). The structure of the title compound is composed of centrosymmetric dimmers (of two bridged cations between two anions) forming by intermolecular N+—H···OP hydrogen bonds (N···O = 2.771 (3) Å & 2.804 (3) Å), Fig. 2. The phosphoryl and the carbonyl groups in the structure are not in anti position (O(1)—P(1)—N(1)—C(1) = 64.8 (3)°) against the previous reported carbacylamidophosphates (Yazdanbakhsh & Sabbaghi, 2007). The phosphorus atom has slightly distorted tetrahedral configuration. The bond angles around P(1) atom is in the range of 100.79 (12)°-115.26 (13)° that the highest and the lowest values were obtained for the angles O—P—N(1)amide and N(2)amine—P—N(1)amide. The P(1)—N(1), P(1)—N(2) and P(1)—N(3) bond lengths are 1.629 (3) Å, 1.651 (2) Å and 1.643 (2) Å. They are significantly shorter than the typical P—N single bond length (1.77 Å) (Corbridge, 1995). Sum of the surrounding angles around N(2) and N(3) atoms are 353.5° and 356.0° that indicate some deviation from planarity. Furthermore the angle C(1)—N(1)—P(1) (123.4 (2)°) confirm the sp2 hybridization for the nitrogen atom. The PO bond length (1.511 (2) Å) is larger than the normal P?O bond length (1.45 Å). The CO group cooperates in weak C—H···O hydrogen bonds forming four hydrogen bonds with two neighboring cations (C(17)—H(17 C)···O(2)—C(1), C(17)···O(2) = 3.320 Å; C(18)—H(18 A)···O(2)—C(1), C(18)···O(2) = 3.214 Å; C(17)—H(17B)···O(2)—C(1), C(17)···O(2) = 3.365 Å; C(23)—H(23 A)···O(2)—C(1), C(23)···O(2) = 3.562 Å) (Fig. 3). Moreover, the C—H···F hydrogen bonds exist in the crystal network (C(5)—H(5 A)···F(3), C(5)···F(3) = 3.593 Å) (Fig. 4).