Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041499/lh2482sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041499/lh2482Isup2.hkl |
CCDC reference: 663687
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.155
- Data-to-parameter ratio = 18.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.35 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C27 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C28 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C9 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C18 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C9 H13 N O3 P PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C9 H13 N O3 P PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 C4 H12 N PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 C4 H12 N PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 5 C H Cl3 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 6 C H Cl3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 14 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 8 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the corresponding dimeric complex with similar P—O and P—N bonds, see: Andrianov et al. (1977). For related literature, see: Quin & Jankowski (1994).
A solution of toluidine 12.5 mmol and 12.5 mmol of Et2NH in 15 ml of ether was added to a solution of 12.5 mmol of ethyl phosphorodichloridate in 15 ml of ether. After 20 h, the solution was filtrated and the filtrate was evaporated to give a solid powder. The powder was dissolved in 30 ml of acetone-water containing 1 g of NaOH. After 10 min, the solvent was evaporated and the residue dried over in vacuo. Recrystalization of a chloroform solution of the title compound gave crystals suitable for X-ray diffraction.
H atoms bonded to N atoms and the C atoms of the chloroform molecules were located in a difference map and refined with distance restraints of N—H = 0.85 (3), and C—H = 0.95 (3) Å, and isotropic displacement parameters. Other H atoms were positioned geometrically and refined using a riding- model approximation, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups)Ueq(C).
Although O,N-substituted phosphoramidic acids have been reported as a useful agents in the synthesis of pyrophosphate groups, (Quin & Jankowski, 1994), crystal structures of these types of materials are not well characterized. As part of an investigation of the use of the O,N-substituted phosphoramidic acids as ligand in the synthesis of new metal phosphate frameworks, the title compound was obtained as a salt of the O,N-substituted phosphoramidic acid.
As shown in Figure 1, the asymmetric unit of the title compound is composed of two chloroform molecules, two diethylamine cations and two N-ethoxyphosphorl-p -tolylamide anions. The geometrical parameters of the two independent anions are similar. The phosphorus atoms have tetrahedral coordination geometry and there are three types of P—O bonds and one P—N bond existing in the [PO3N] tetrahetra. The shortest bond lengths of 1.4945 (17) Å (P1—O3) and 1.4891 (17) Å (P2—O4) refer to the P=O double bonds at the [P1O3N] and [P2O3N] tetrahetra respectively, while the P—O bond lengths of 1.6002 (19) Å and 1.6055 (18) Å are attributed to the P-OEt connections. These longer P—O distances are due to the influence of the –OEt group, according to the literature report (Andrianov et al., 1977). The P—N bond lengths in the [PO3N] tetrahetra are 1.656 (2) Å (P1—N1)and 1.659 (2) Å (P2—N) respectively. The bond angles of O—P—O and O—P—N range from 103.44 (10)- 118.32 (10)° and 103.03 (10)- 119.28 (10)°, indicating that the tetrahetra are slightly distorted. Solvated chloroform molecules fill the voids in the crystal lattice.
In the crystal structure, intermolecular N—H···O hydrogen bonds form two independent one-dimensional chains along the a axis.
For the corresponding dimeric complex with similar P—O and P—N bonds, see: Andrianov et al. (1977). For related literature, see: Quin & Jankowski (1994).
Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1994); data reduction: SAINT (Bruker, 1994); program(s) used to solve structure: SHELXTL (Bruker, 1994); program(s) used to refine structure: SHELXTL (Bruker, 1994); molecular graphics: SHELXTL (Bruker, 1994); software used to prepare material for publication: SHELXTL (Bruker, 1994).
C4H12N+·C9H13NO3P−·CHCl3 | Z = 4 |
Mr = 407.69 | F(000) = 856 |
Triclinic, P1 | Dx = 1.326 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4030 (2) Å | Cell parameters from 14646 reflections |
b = 12.5575 (4) Å | θ = 2.6–26.4° |
c = 19.6980 (7) Å | µ = 0.54 mm−1 |
α = 82.8707 (15)° | T = 173 K |
β = 83.869 (2)° | Block, colourless |
γ = 84.9637 (18)° | 0.4 × 0.4 × 0.2 mm |
V = 2044.82 (11) Å3 |
Bruker SMART CCD diffractometer | 8048 independent reflections |
Radiation source: fine-focus sealed tube | 5266 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.4°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.811, Tmax = 0.895 | k = −15→15 |
14646 measured reflections | l = −24→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0688P)2 + 1.5923P] where P = (Fo2 + 2Fc2)/3 |
8048 reflections | (Δ/σ)max = 0.002 |
447 parameters | Δρmax = 0.87 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C4H12N+·C9H13NO3P−·CHCl3 | γ = 84.9637 (18)° |
Mr = 407.69 | V = 2044.82 (11) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.4030 (2) Å | Mo Kα radiation |
b = 12.5575 (4) Å | µ = 0.54 mm−1 |
c = 19.6980 (7) Å | T = 173 K |
α = 82.8707 (15)° | 0.4 × 0.4 × 0.2 mm |
β = 83.869 (2)° |
Bruker SMART CCD diffractometer | 8048 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5266 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.895 | Rint = 0.026 |
14646 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.87 e Å−3 |
8048 reflections | Δρmin = −0.37 e Å−3 |
447 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 | 1.29263 (7) | 0.89735 (5) | 1.05042 (3) | 0.02205 (16) | |
P2 | 0.71031 (7) | 1.10383 (5) | 1.44730 (3) | 0.02143 (16) | |
C1 | 1.5019 (4) | 0.9023 (3) | 1.19335 (18) | 0.0534 (9) | |
H1B | 1.6076 | 0.9100 | 1.2056 | 0.080* | |
H1C | 1.4394 | 0.8677 | 1.2322 | 0.080* | |
H1F | 1.4511 | 0.9721 | 1.1798 | 0.080* | |
C2 | 1.5139 (3) | 0.8359 (2) | 1.13512 (16) | 0.0392 (7) | |
H2A | 1.5784 | 0.8704 | 1.0961 | 0.047* | |
H2B | 1.5667 | 0.7657 | 1.1485 | 0.047* | |
C3 | 1.4176 (3) | 0.76561 (18) | 0.95398 (13) | 0.0244 (5) | |
C4 | 1.3400 (3) | 0.6769 (2) | 0.98657 (14) | 0.0339 (6) | |
H4A | 1.2809 | 0.6812 | 1.0290 | 0.041* | |
C5 | 1.3499 (3) | 0.5826 (2) | 0.95654 (15) | 0.0372 (7) | |
H5A | 1.2964 | 0.5248 | 0.9794 | 0.045* | |
C6 | 1.4366 (3) | 0.5708 (2) | 0.89340 (15) | 0.0326 (6) | |
C7 | 1.5153 (3) | 0.6589 (2) | 0.86158 (14) | 0.0348 (6) | |
H7A | 1.5755 | 0.6538 | 0.8195 | 0.042* | |
C8 | 1.5066 (3) | 0.7547 (2) | 0.89096 (14) | 0.0315 (6) | |
H8A | 1.5609 | 0.8123 | 0.8682 | 0.038* | |
C9 | 1.4443 (4) | 0.4666 (2) | 0.86181 (17) | 0.0469 (8) | |
H9A | 1.5092 | 0.4733 | 0.8185 | 0.070* | |
H9B | 1.3379 | 0.4511 | 0.8547 | 0.070* | |
H9C | 1.4908 | 0.4093 | 0.8922 | 0.070* | |
C10 | 0.5322 (4) | 1.1069 (3) | 1.29435 (16) | 0.0507 (8) | |
H10A | 0.4308 | 1.0988 | 1.2779 | 0.076* | |
H10B | 0.5844 | 1.0371 | 1.3068 | 0.076* | |
H10C | 0.5986 | 1.1460 | 1.2588 | 0.076* | |
C11 | 0.5053 (3) | 1.1669 (2) | 1.35537 (15) | 0.0384 (7) | |
H11A | 0.4510 | 1.2370 | 1.3429 | 0.046* | |
H11B | 0.4368 | 1.1280 | 1.3910 | 0.046* | |
C12 | 0.5763 (3) | 1.23085 (18) | 1.54516 (12) | 0.0221 (5) | |
C13 | 0.6510 (3) | 1.32177 (19) | 1.51385 (14) | 0.0314 (6) | |
H13A | 0.7082 | 1.3204 | 1.4708 | 0.038* | |
C14 | 0.6406 (3) | 1.4135 (2) | 1.54627 (15) | 0.0351 (6) | |
H14A | 0.6919 | 1.4729 | 1.5245 | 0.042* | |
C15 | 0.5556 (3) | 1.4207 (2) | 1.61081 (14) | 0.0313 (6) | |
C16 | 0.4814 (3) | 1.3295 (2) | 1.64106 (14) | 0.0328 (6) | |
H16A | 0.4234 | 1.3311 | 1.6839 | 0.039* | |
C17 | 0.4911 (3) | 1.2363 (2) | 1.60930 (13) | 0.0287 (6) | |
H17A | 0.4400 | 1.1768 | 1.6311 | 0.034* | |
C18 | 0.5453 (4) | 1.5223 (2) | 1.64501 (17) | 0.0442 (7) | |
H18A | 0.4825 | 1.5120 | 1.6887 | 0.066* | |
H18B | 0.4955 | 1.5805 | 1.6164 | 0.066* | |
H18C | 0.6514 | 1.5391 | 1.6518 | 0.066* | |
C19 | 0.9895 (4) | 1.0396 (3) | 1.18932 (18) | 0.0625 (10) | |
H19A | 0.9186 | 0.9997 | 1.2226 | 0.094* | |
H19B | 1.0103 | 1.1049 | 1.2064 | 0.094* | |
H19C | 1.0887 | 0.9969 | 1.1812 | 0.094* | |
C20 | 0.9133 (4) | 1.0663 (3) | 1.12371 (15) | 0.0469 (8) | |
H20A | 0.8118 | 1.1078 | 1.1325 | 0.056* | |
H20B | 0.8907 | 1.0000 | 1.1072 | 0.056* | |
C21 | 1.0452 (4) | 1.2393 (2) | 1.07998 (19) | 0.0513 (8) | |
H21A | 1.1069 | 1.2367 | 1.1192 | 0.062* | |
H21B | 0.9428 | 1.2791 | 1.0902 | 0.062* | |
C22 | 1.1338 (5) | 1.2952 (3) | 1.0177 (2) | 0.0731 (12) | |
H22A | 1.1507 | 1.3670 | 1.0259 | 0.110* | |
H22B | 1.0720 | 1.2983 | 0.9791 | 0.110* | |
H22C | 1.2356 | 1.2563 | 1.0081 | 0.110* | |
C23 | 1.1327 (4) | 0.9797 (3) | 1.36070 (18) | 0.0609 (10) | |
H23A | 1.1959 | 0.9904 | 1.3172 | 0.091* | |
H23B | 1.1984 | 0.9845 | 1.3971 | 0.091* | |
H23C | 1.0450 | 1.0342 | 1.3623 | 0.091* | |
C24 | 1.0701 (4) | 0.8741 (3) | 1.36913 (16) | 0.0531 (9) | |
H24A | 1.1589 | 0.8194 | 1.3668 | 0.064* | |
H24B | 1.0060 | 0.8690 | 1.3317 | 0.064* | |
C25 | 0.9187 (4) | 0.7405 (2) | 1.4462 (2) | 0.0550 (10) | |
H25A | 0.8568 | 0.7291 | 1.4093 | 0.066* | |
H25B | 1.0127 | 0.6897 | 1.4454 | 0.066* | |
C26 | 0.8194 (4) | 0.7206 (3) | 1.5135 (2) | 0.0675 (11) | |
H26A | 0.7872 | 0.6482 | 1.5194 | 0.101* | |
H26B | 0.7258 | 0.7703 | 1.5141 | 0.101* | |
H26C | 0.8814 | 0.7304 | 1.5501 | 0.101* | |
C27 | 0.9296 (3) | 1.3268 (2) | 1.31187 (16) | 0.0370 (7) | |
C28 | 1.0752 (3) | 0.6802 (2) | 1.18552 (16) | 0.0361 (6) | |
O1 | 1.3562 (2) | 0.82291 (14) | 1.11549 (9) | 0.0304 (4) | |
O2 | 1.31494 (19) | 1.01307 (13) | 1.05514 (9) | 0.0274 (4) | |
O3 | 1.12594 (18) | 0.86509 (13) | 1.04931 (9) | 0.0263 (4) | |
O4 | 0.87397 (18) | 1.13685 (13) | 1.45287 (9) | 0.0274 (4) | |
O5 | 0.68917 (19) | 0.98893 (13) | 1.43997 (9) | 0.0273 (4) | |
O6 | 0.6545 (2) | 1.18052 (13) | 1.38125 (9) | 0.0292 (4) | |
Cl1 | 0.81294 (9) | 1.34074 (7) | 1.24222 (4) | 0.0466 (2) | |
Cl2 | 0.91751 (11) | 1.44700 (7) | 1.34968 (5) | 0.0574 (2) | |
Cl3 | 1.13127 (9) | 1.28867 (8) | 1.28418 (5) | 0.0570 (2) | |
Cl4 | 0.87684 (9) | 0.72423 (8) | 1.21407 (6) | 0.0698 (3) | |
Cl5 | 1.07822 (12) | 0.55915 (7) | 1.14978 (5) | 0.0607 (3) | |
Cl6 | 1.19441 (9) | 0.66534 (7) | 1.25426 (4) | 0.0490 (2) | |
N1 | 1.4088 (3) | 0.86350 (17) | 0.98185 (11) | 0.0276 (5) | |
H1 | 1.480 (4) | 0.902 (3) | 0.9688 (17) | 0.047 (10)* | |
N2 | 0.5856 (2) | 1.13562 (17) | 1.51415 (11) | 0.0260 (5) | |
H2 | 0.521 (4) | 1.094 (3) | 1.5298 (17) | 0.044 (9)* | |
N3 | 1.0184 (3) | 1.13005 (19) | 1.06806 (12) | 0.0304 (5) | |
H3 | 1.102 (4) | 1.097 (3) | 1.0637 (16) | 0.039 (9)* | |
H4 | 0.970 (3) | 1.132 (2) | 1.0265 (17) | 0.039 (8)* | |
N4 | 0.9706 (3) | 0.85319 (19) | 1.43514 (12) | 0.0303 (5) | |
H5 | 0.882 (4) | 0.896 (3) | 1.4384 (16) | 0.046 (9)* | |
H6 | 1.029 (3) | 0.859 (2) | 1.4702 (16) | 0.035 (8)* | |
H7 | 0.889 (3) | 1.272 (2) | 1.3452 (15) | 0.037 (8)* | |
H8 | 1.113 (3) | 0.737 (2) | 1.1534 (16) | 0.042 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0208 (3) | 0.0206 (3) | 0.0255 (3) | −0.0042 (2) | −0.0029 (2) | −0.0034 (2) |
P2 | 0.0196 (3) | 0.0207 (3) | 0.0247 (3) | −0.0046 (2) | −0.0021 (2) | −0.0035 (2) |
C1 | 0.063 (2) | 0.0459 (18) | 0.059 (2) | 0.0036 (16) | −0.0318 (18) | −0.0195 (16) |
C2 | 0.0372 (15) | 0.0373 (15) | 0.0478 (18) | 0.0049 (12) | −0.0223 (13) | −0.0129 (13) |
C3 | 0.0212 (12) | 0.0212 (12) | 0.0309 (14) | −0.0012 (9) | −0.0039 (10) | −0.0026 (10) |
C4 | 0.0374 (15) | 0.0271 (13) | 0.0353 (15) | −0.0060 (11) | 0.0082 (12) | −0.0031 (11) |
C5 | 0.0448 (16) | 0.0203 (13) | 0.0457 (18) | −0.0070 (12) | 0.0035 (13) | −0.0043 (12) |
C6 | 0.0327 (14) | 0.0273 (13) | 0.0392 (16) | 0.0043 (11) | −0.0076 (12) | −0.0104 (12) |
C7 | 0.0355 (14) | 0.0371 (15) | 0.0320 (15) | −0.0024 (12) | 0.0030 (12) | −0.0099 (12) |
C8 | 0.0320 (14) | 0.0311 (14) | 0.0317 (15) | −0.0078 (11) | 0.0015 (11) | −0.0044 (11) |
C9 | 0.0557 (19) | 0.0325 (15) | 0.055 (2) | 0.0032 (14) | −0.0081 (15) | −0.0179 (14) |
C10 | 0.060 (2) | 0.0543 (19) | 0.0435 (19) | −0.0111 (16) | −0.0163 (16) | −0.0156 (16) |
C11 | 0.0352 (15) | 0.0404 (16) | 0.0428 (17) | 0.0015 (12) | −0.0167 (13) | −0.0099 (13) |
C12 | 0.0181 (11) | 0.0225 (12) | 0.0266 (13) | −0.0036 (9) | −0.0050 (9) | −0.0028 (10) |
C13 | 0.0369 (14) | 0.0239 (13) | 0.0320 (15) | −0.0054 (11) | 0.0047 (11) | −0.0026 (11) |
C14 | 0.0418 (15) | 0.0229 (13) | 0.0407 (17) | −0.0077 (11) | 0.0017 (13) | −0.0050 (12) |
C15 | 0.0323 (14) | 0.0262 (13) | 0.0369 (15) | 0.0006 (11) | −0.0062 (11) | −0.0091 (11) |
C16 | 0.0331 (14) | 0.0363 (14) | 0.0288 (14) | −0.0022 (11) | 0.0021 (11) | −0.0082 (12) |
C17 | 0.0281 (13) | 0.0286 (13) | 0.0298 (14) | −0.0095 (10) | 0.0011 (11) | −0.0030 (11) |
C18 | 0.0507 (18) | 0.0343 (15) | 0.0504 (19) | 0.0006 (13) | −0.0066 (15) | −0.0177 (14) |
C19 | 0.070 (2) | 0.067 (2) | 0.046 (2) | −0.0003 (19) | 0.0016 (18) | 0.0014 (18) |
C20 | 0.0357 (16) | 0.067 (2) | 0.0358 (17) | 0.0067 (15) | −0.0047 (13) | −0.0022 (15) |
C21 | 0.056 (2) | 0.0374 (16) | 0.066 (2) | 0.0032 (15) | −0.0239 (17) | −0.0199 (16) |
C22 | 0.085 (3) | 0.049 (2) | 0.091 (3) | −0.029 (2) | −0.042 (2) | 0.015 (2) |
C23 | 0.053 (2) | 0.077 (3) | 0.049 (2) | 0.0022 (19) | 0.0029 (16) | −0.0027 (19) |
C24 | 0.0422 (17) | 0.079 (2) | 0.0377 (18) | 0.0091 (17) | −0.0037 (14) | −0.0139 (17) |
C25 | 0.0407 (17) | 0.0396 (17) | 0.094 (3) | 0.0057 (14) | −0.0284 (18) | −0.0323 (18) |
C26 | 0.060 (2) | 0.047 (2) | 0.097 (3) | −0.0234 (17) | −0.026 (2) | 0.013 (2) |
C27 | 0.0326 (14) | 0.0365 (15) | 0.0407 (17) | −0.0079 (12) | −0.0007 (12) | 0.0019 (13) |
C28 | 0.0315 (14) | 0.0366 (15) | 0.0395 (17) | −0.0062 (12) | −0.0034 (12) | 0.0013 (13) |
O1 | 0.0312 (9) | 0.0303 (9) | 0.0318 (10) | −0.0035 (7) | −0.0121 (8) | −0.0029 (8) |
O2 | 0.0230 (8) | 0.0217 (8) | 0.0385 (10) | −0.0056 (7) | −0.0011 (7) | −0.0064 (7) |
O3 | 0.0219 (8) | 0.0301 (9) | 0.0286 (10) | −0.0070 (7) | −0.0027 (7) | −0.0055 (7) |
O4 | 0.0202 (8) | 0.0328 (9) | 0.0309 (10) | −0.0080 (7) | −0.0031 (7) | −0.0064 (8) |
O5 | 0.0243 (8) | 0.0210 (8) | 0.0371 (10) | −0.0050 (7) | 0.0014 (7) | −0.0070 (7) |
O6 | 0.0313 (9) | 0.0296 (9) | 0.0280 (10) | −0.0069 (7) | −0.0084 (7) | −0.0008 (7) |
Cl1 | 0.0401 (4) | 0.0578 (5) | 0.0423 (4) | −0.0038 (3) | −0.0082 (3) | −0.0038 (4) |
Cl2 | 0.0731 (6) | 0.0455 (4) | 0.0558 (5) | −0.0118 (4) | −0.0042 (4) | −0.0107 (4) |
Cl3 | 0.0326 (4) | 0.0710 (6) | 0.0650 (6) | −0.0005 (4) | −0.0016 (4) | −0.0038 (4) |
Cl4 | 0.0325 (4) | 0.0831 (7) | 0.0890 (7) | 0.0047 (4) | −0.0021 (4) | −0.0014 (6) |
Cl5 | 0.0874 (7) | 0.0465 (5) | 0.0511 (5) | −0.0216 (4) | −0.0063 (5) | −0.0061 (4) |
Cl6 | 0.0441 (4) | 0.0613 (5) | 0.0424 (5) | 0.0017 (4) | −0.0093 (3) | −0.0087 (4) |
N1 | 0.0252 (11) | 0.0230 (11) | 0.0350 (13) | −0.0080 (9) | 0.0036 (9) | −0.0065 (9) |
N2 | 0.0247 (11) | 0.0224 (10) | 0.0312 (12) | −0.0088 (9) | 0.0036 (9) | −0.0048 (9) |
N3 | 0.0269 (12) | 0.0343 (12) | 0.0304 (13) | 0.0036 (10) | −0.0053 (10) | −0.0073 (10) |
N4 | 0.0224 (11) | 0.0387 (13) | 0.0320 (13) | 0.0027 (10) | −0.0075 (10) | −0.0125 (10) |
P1—O3 | 1.4945 (17) | C16—H16A | 0.9300 |
P1—O2 | 1.4959 (17) | C17—H17A | 0.9300 |
P1—O1 | 1.6002 (19) | C18—H18A | 0.9600 |
P1—N1 | 1.656 (2) | C18—H18B | 0.9600 |
P2—O4 | 1.4891 (17) | C18—H18C | 0.9600 |
P2—O5 | 1.4946 (17) | C19—C20 | 1.491 (5) |
P2—O6 | 1.6055 (18) | C19—H19A | 0.9600 |
P2—N2 | 1.659 (2) | C19—H19B | 0.9600 |
C1—C2 | 1.489 (4) | C19—H19C | 0.9600 |
C1—H1B | 0.9600 | C20—N3 | 1.523 (4) |
C1—H1C | 0.9600 | C20—H20A | 0.9700 |
C1—H1F | 0.9600 | C20—H20B | 0.9700 |
C2—O1 | 1.447 (3) | C21—N3 | 1.460 (4) |
C2—H2A | 0.9700 | C21—C22 | 1.495 (5) |
C2—H2B | 0.9700 | C21—H21A | 0.9700 |
C3—C4 | 1.392 (3) | C21—H21B | 0.9700 |
C3—C8 | 1.394 (3) | C22—H22A | 0.9600 |
C3—N1 | 1.399 (3) | C22—H22B | 0.9600 |
C4—C5 | 1.379 (4) | C22—H22C | 0.9600 |
C4—H4A | 0.9300 | C23—C24 | 1.453 (5) |
C5—C6 | 1.390 (4) | C23—H23A | 0.9600 |
C5—H5A | 0.9300 | C23—H23B | 0.9600 |
C6—C7 | 1.385 (4) | C23—H23C | 0.9600 |
C6—C9 | 1.510 (4) | C24—N4 | 1.476 (4) |
C7—C8 | 1.390 (4) | C24—H24A | 0.9700 |
C7—H7A | 0.9300 | C24—H24B | 0.9700 |
C8—H8A | 0.9300 | C25—C26 | 1.493 (5) |
C9—H9A | 0.9600 | C25—N4 | 1.500 (4) |
C9—H9B | 0.9600 | C25—H25A | 0.9700 |
C9—H9C | 0.9600 | C25—H25B | 0.9700 |
C10—C11 | 1.483 (4) | C26—H26A | 0.9600 |
C10—H10A | 0.9600 | C26—H26B | 0.9600 |
C10—H10B | 0.9600 | C26—H26C | 0.9600 |
C10—H10C | 0.9600 | C27—Cl1 | 1.752 (3) |
C11—O6 | 1.433 (3) | C27—Cl2 | 1.754 (3) |
C11—H11A | 0.9700 | C27—Cl3 | 1.767 (3) |
C11—H11B | 0.9700 | C27—H7 | 0.95 (3) |
C12—C17 | 1.390 (3) | C28—Cl5 | 1.749 (3) |
C12—C13 | 1.394 (3) | C28—Cl6 | 1.750 (3) |
C12—N2 | 1.401 (3) | C28—Cl4 | 1.764 (3) |
C13—C14 | 1.376 (4) | C28—H8 | 0.94 (3) |
C13—H13A | 0.9300 | N1—H1 | 0.80 (3) |
C14—C15 | 1.398 (4) | N2—H2 | 0.80 (3) |
C14—H14A | 0.9300 | N3—H3 | 0.79 (3) |
C15—C16 | 1.389 (4) | N3—H4 | 0.95 (3) |
C15—C18 | 1.506 (4) | N4—H5 | 0.88 (3) |
C16—C17 | 1.385 (4) | N4—H6 | 0.90 (3) |
O3—P1—O2 | 118.32 (10) | H18A—C18—H18C | 109.5 |
O3—P1—O1 | 103.44 (10) | H18B—C18—H18C | 109.5 |
O2—P1—O1 | 110.39 (10) | C20—C19—H19A | 109.5 |
O3—P1—N1 | 110.78 (11) | C20—C19—H19B | 109.5 |
O2—P1—N1 | 106.60 (11) | H19A—C19—H19B | 109.5 |
O1—P1—N1 | 106.81 (11) | C20—C19—H19C | 109.5 |
O4—P2—O5 | 119.28 (10) | H19A—C19—H19C | 109.5 |
O4—P2—O6 | 103.03 (10) | H19B—C19—H19C | 109.5 |
O5—P2—O6 | 110.12 (10) | C19—C20—N3 | 112.8 (3) |
O4—P2—N2 | 110.52 (11) | C19—C20—H20A | 109.0 |
O5—P2—N2 | 106.51 (11) | N3—C20—H20A | 109.0 |
O6—P2—N2 | 106.80 (10) | C19—C20—H20B | 109.0 |
C2—C1—H1B | 109.5 | N3—C20—H20B | 109.0 |
C2—C1—H1C | 109.5 | H20A—C20—H20B | 107.8 |
H1B—C1—H1C | 109.5 | N3—C21—C22 | 110.0 (3) |
C2—C1—H1F | 109.5 | N3—C21—H21A | 109.7 |
H1B—C1—H1F | 109.5 | C22—C21—H21A | 109.7 |
H1C—C1—H1F | 109.5 | N3—C21—H21B | 109.7 |
O1—C2—C1 | 110.7 (2) | C22—C21—H21B | 109.7 |
O1—C2—H2A | 109.5 | H21A—C21—H21B | 108.2 |
C1—C2—H2A | 109.5 | C21—C22—H22A | 109.5 |
O1—C2—H2B | 109.5 | C21—C22—H22B | 109.5 |
C1—C2—H2B | 109.5 | H22A—C22—H22B | 109.5 |
H2A—C2—H2B | 108.1 | C21—C22—H22C | 109.5 |
C4—C3—C8 | 117.5 (2) | H22A—C22—H22C | 109.5 |
C4—C3—N1 | 122.7 (2) | H22B—C22—H22C | 109.5 |
C8—C3—N1 | 119.8 (2) | C24—C23—H23A | 109.5 |
C5—C4—C3 | 120.6 (2) | C24—C23—H23B | 109.5 |
C5—C4—H4A | 119.7 | H23A—C23—H23B | 109.5 |
C3—C4—H4A | 119.7 | C24—C23—H23C | 109.5 |
C4—C5—C6 | 122.5 (2) | H23A—C23—H23C | 109.5 |
C4—C5—H5A | 118.7 | H23B—C23—H23C | 109.5 |
C6—C5—H5A | 118.7 | C23—C24—N4 | 112.1 (3) |
C7—C6—C5 | 116.6 (2) | C23—C24—H24A | 109.2 |
C7—C6—C9 | 122.2 (3) | N4—C24—H24A | 109.2 |
C5—C6—C9 | 121.2 (3) | C23—C24—H24B | 109.2 |
C6—C7—C8 | 121.7 (2) | N4—C24—H24B | 109.2 |
C6—C7—H7A | 119.2 | H24A—C24—H24B | 107.9 |
C8—C7—H7A | 119.2 | C26—C25—N4 | 110.9 (3) |
C7—C8—C3 | 121.0 (2) | C26—C25—H25A | 109.5 |
C7—C8—H8A | 119.5 | N4—C25—H25A | 109.5 |
C3—C8—H8A | 119.5 | C26—C25—H25B | 109.5 |
C6—C9—H9A | 109.5 | N4—C25—H25B | 109.5 |
C6—C9—H9B | 109.5 | H25A—C25—H25B | 108.0 |
H9A—C9—H9B | 109.5 | C25—C26—H26A | 109.5 |
C6—C9—H9C | 109.5 | C25—C26—H26B | 109.5 |
H9A—C9—H9C | 109.5 | H26A—C26—H26B | 109.5 |
H9B—C9—H9C | 109.5 | C25—C26—H26C | 109.5 |
C11—C10—H10A | 109.5 | H26A—C26—H26C | 109.5 |
C11—C10—H10B | 109.5 | H26B—C26—H26C | 109.5 |
H10A—C10—H10B | 109.5 | Cl1—C27—Cl2 | 110.84 (16) |
C11—C10—H10C | 109.5 | Cl1—C27—Cl3 | 109.84 (17) |
H10A—C10—H10C | 109.5 | Cl2—C27—Cl3 | 110.34 (16) |
H10B—C10—H10C | 109.5 | Cl1—C27—H7 | 108.2 (18) |
O6—C11—C10 | 110.9 (2) | Cl2—C27—H7 | 108.5 (18) |
O6—C11—H11A | 109.5 | Cl3—C27—H7 | 109.1 (17) |
C10—C11—H11A | 109.5 | Cl5—C28—Cl6 | 110.80 (16) |
O6—C11—H11B | 109.5 | Cl5—C28—Cl4 | 110.50 (16) |
C10—C11—H11B | 109.5 | Cl6—C28—Cl4 | 109.60 (17) |
H11A—C11—H11B | 108.0 | Cl5—C28—H8 | 112.5 (19) |
C17—C12—C13 | 118.1 (2) | Cl6—C28—H8 | 107.8 (19) |
C17—C12—N2 | 119.9 (2) | Cl4—C28—H8 | 105.4 (18) |
C13—C12—N2 | 122.1 (2) | C2—O1—P1 | 119.30 (17) |
C14—C13—C12 | 120.4 (2) | C11—O6—P2 | 120.05 (17) |
C14—C13—H13A | 119.8 | C3—N1—P1 | 126.97 (18) |
C12—C13—H13A | 119.8 | C3—N1—H1 | 117 (2) |
C13—C14—C15 | 122.5 (2) | P1—N1—H1 | 115 (2) |
C13—C14—H14A | 118.8 | C12—N2—P2 | 126.94 (17) |
C15—C14—H14A | 118.8 | C12—N2—H2 | 115 (2) |
C16—C15—C14 | 116.3 (2) | P2—N2—H2 | 118 (2) |
C16—C15—C18 | 122.3 (3) | C21—N3—C20 | 116.5 (3) |
C14—C15—C18 | 121.4 (2) | C21—N3—H3 | 109 (2) |
C17—C16—C15 | 122.0 (2) | C20—N3—H3 | 107 (2) |
C17—C16—H16A | 119.0 | C21—N3—H4 | 109.6 (18) |
C15—C16—H16A | 119.0 | C20—N3—H4 | 106.9 (18) |
C16—C17—C12 | 120.8 (2) | H3—N3—H4 | 107 (3) |
C16—C17—H17A | 119.6 | C24—N4—C25 | 111.7 (3) |
C12—C17—H17A | 119.6 | C24—N4—H5 | 114 (2) |
C15—C18—H18A | 109.5 | C25—N4—H5 | 106 (2) |
C15—C18—H18B | 109.5 | C24—N4—H6 | 109.6 (19) |
H18A—C18—H18B | 109.5 | C25—N4—H6 | 106.2 (18) |
C15—C18—H18C | 109.5 | H5—N4—H6 | 109 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O2 | 0.79 (3) | 2.00 (3) | 2.782 (3) | 179 (4) |
N4—H5···O5 | 0.88 (3) | 1.91 (3) | 2.790 (3) | 177 (3) |
Experimental details
Crystal data | |
Chemical formula | C4H12N+·C9H13NO3P−·CHCl3 |
Mr | 407.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.4030 (2), 12.5575 (4), 19.6980 (7) |
α, β, γ (°) | 82.8707 (15), 83.869 (2), 84.9637 (18) |
V (Å3) | 2044.82 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.4 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.811, 0.895 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14646, 8048, 5266 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.155, 1.04 |
No. of reflections | 8048 |
No. of parameters | 447 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.87, −0.37 |
Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1994), SHELXTL (Bruker, 1994).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O2 | 0.79 (3) | 2.00 (3) | 2.782 (3) | 179 (4) |
N4—H5···O5 | 0.88 (3) | 1.91 (3) | 2.790 (3) | 177 (3) |
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Although O,N-substituted phosphoramidic acids have been reported as a useful agents in the synthesis of pyrophosphate groups, (Quin & Jankowski, 1994), crystal structures of these types of materials are not well characterized. As part of an investigation of the use of the O,N-substituted phosphoramidic acids as ligand in the synthesis of new metal phosphate frameworks, the title compound was obtained as a salt of the O,N-substituted phosphoramidic acid.
As shown in Figure 1, the asymmetric unit of the title compound is composed of two chloroform molecules, two diethylamine cations and two N-ethoxyphosphorl-p -tolylamide anions. The geometrical parameters of the two independent anions are similar. The phosphorus atoms have tetrahedral coordination geometry and there are three types of P—O bonds and one P—N bond existing in the [PO3N] tetrahetra. The shortest bond lengths of 1.4945 (17) Å (P1—O3) and 1.4891 (17) Å (P2—O4) refer to the P=O double bonds at the [P1O3N] and [P2O3N] tetrahetra respectively, while the P—O bond lengths of 1.6002 (19) Å and 1.6055 (18) Å are attributed to the P-OEt connections. These longer P—O distances are due to the influence of the –OEt group, according to the literature report (Andrianov et al., 1977). The P—N bond lengths in the [PO3N] tetrahetra are 1.656 (2) Å (P1—N1)and 1.659 (2) Å (P2—N) respectively. The bond angles of O—P—O and O—P—N range from 103.44 (10)- 118.32 (10)° and 103.03 (10)- 119.28 (10)°, indicating that the tetrahetra are slightly distorted. Solvated chloroform molecules fill the voids in the crystal lattice.
In the crystal structure, intermolecular N—H···O hydrogen bonds form two independent one-dimensional chains along the a axis.