Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014696/cv6056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014696/cv6056Isup2.hkl |
CCDC reference: 175355
Ph2PHBH3 (305 mg, 1.53 mmol) was dissolved in dichloromethane (5 ml) and Et2NH (230 mg, 2.1 equivalents) was added via syringe at room temperature. The reaction mixture was stirred for 3 d, filtered and set aside for crystallization in air. Colourless crystals of [Et2NH2][Ph2PO2] suitable for X-ray diffraction grew over a period of several days. 1H NMR (CDCl3, p.p.m.): δ 10.3 (br, 2H, NH), 7.76–7.22 (m, 10H, Ph), 2.77 (q, 4H, CH2), 1.24 (t, 6H, CH3); 31P NMR: 19.3 p.p.m. (s).
H atoms were included in calculated positions, with C—H distances ranging from 0.95 to 0.99 Å and N—H distances of 0.92 Å.
Data collection: COLLECT (Nonius BV, 1997-2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H12N+·C12H10O2P− | F(000) = 624 |
Mr = 291.32 | Dx = 1.193 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.4163 (2) Å | Cell parameters from 3745 reflections |
b = 8.3038 (2) Å | θ = 2.6–27.5° |
c = 16.4517 (3) Å | µ = 0.17 mm−1 |
β = 106.949 (1)° | T = 150 K |
V = 1622.53 (6) Å3 | Needle, colourless |
Z = 4 | 0.32 × 0.30 × 0.26 mm |
Nonius Kappa-CCD diffractometer | 3705 independent reflections |
Radiation source: fine-focus sealed tube | 3236 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ scans, and ω scans with κ offsets | h = −16→16 |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = −10→10 |
Tmin = 0.947, Tmax = 0.957 | l = −21→20 |
13875 measured reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.757P] where P = (Fo2 + 2Fc2)/3 |
3705 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C4H12N+·C12H10O2P− | V = 1622.53 (6) Å3 |
Mr = 291.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.4163 (2) Å | µ = 0.17 mm−1 |
b = 8.3038 (2) Å | T = 150 K |
c = 16.4517 (3) Å | 0.32 × 0.30 × 0.26 mm |
β = 106.949 (1)° |
Nonius Kappa-CCD diffractometer | 3705 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 3236 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.957 | Rint = 0.026 |
13875 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
3705 reflections | Δρmin = −0.34 e Å−3 |
181 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 | 0.28006 (3) | 0.23499 (4) | 0.15073 (2) | 0.02810 (12) | |
O1 | 0.30182 (9) | 0.35183 (12) | 0.22348 (6) | 0.0359 (2) | |
O2 | 0.37224 (8) | 0.11993 (13) | 0.14731 (7) | 0.0396 (3) | |
C1 | 0.15490 (11) | 0.12124 (16) | 0.14906 (8) | 0.0283 (3) | |
C2 | 0.08063 (12) | 0.18057 (19) | 0.19056 (9) | 0.0372 (3) | |
H2A | 0.0969 | 0.2793 | 0.2208 | 0.045* | |
C3 | −0.01735 (14) | 0.0974 (2) | 0.18840 (11) | 0.0488 (4) | |
H3A | −0.0672 | 0.1388 | 0.2174 | 0.059* | |
C4 | −0.04186 (14) | −0.0448 (2) | 0.14414 (12) | 0.0515 (5) | |
H4A | −0.1091 | −0.1012 | 0.1422 | 0.062* | |
C5 | 0.03070 (15) | −0.1062 (2) | 0.10250 (12) | 0.0535 (5) | |
H5A | 0.0137 | −0.2050 | 0.0724 | 0.064* | |
C6 | 0.12922 (13) | −0.02312 (18) | 0.10457 (11) | 0.0416 (4) | |
H6A | 0.1789 | −0.0652 | 0.0755 | 0.050* | |
C7 | 0.23893 (11) | 0.34668 (16) | 0.05172 (8) | 0.0292 (3) | |
C8 | 0.16520 (12) | 0.47706 (18) | 0.04111 (9) | 0.0350 (3) | |
H8A | 0.1374 | 0.5092 | 0.0867 | 0.042* | |
C9 | 0.13202 (14) | 0.5604 (2) | −0.03541 (10) | 0.0426 (4) | |
H9A | 0.0822 | 0.6495 | −0.0419 | 0.051* | |
C10 | 0.17168 (14) | 0.5136 (2) | −0.10224 (10) | 0.0462 (4) | |
H10A | 0.1485 | 0.5699 | −0.1547 | 0.055* | |
C11 | 0.24468 (15) | 0.3856 (2) | −0.09265 (11) | 0.0484 (4) | |
H11A | 0.2718 | 0.3537 | −0.1385 | 0.058* | |
C12 | 0.27887 (13) | 0.3025 (2) | −0.01571 (10) | 0.0401 (3) | |
H12A | 0.3299 | 0.2150 | −0.0093 | 0.048* | |
N1 | 0.40933 (10) | 0.63319 (14) | 0.26095 (8) | 0.0368 (3) | |
H1A | 0.3835 | 0.5296 | 0.2485 | 0.044* | |
H1B | 0.4847 | 0.6274 | 0.2902 | 0.044* | |
C13 | 0.34901 (15) | 0.7070 (2) | 0.31663 (16) | 0.0649 (6) | |
H13A | 0.2681 | 0.7168 | 0.2853 | 0.078* | |
H13B | 0.3789 | 0.8166 | 0.3330 | 0.078* | |
C14 | 0.3623 (2) | 0.6084 (4) | 0.39434 (16) | 0.0807 (8) | |
H14A | 0.3216 | 0.6595 | 0.4303 | 0.121* | |
H14B | 0.4424 | 0.6002 | 0.4258 | 0.121* | |
H14C | 0.3317 | 0.5004 | 0.3781 | 0.121* | |
C15 | 0.39664 (17) | 0.7217 (2) | 0.17902 (15) | 0.0659 (6) | |
H15A | 0.3166 | 0.7203 | 0.1447 | 0.079* | |
H15B | 0.4194 | 0.8354 | 0.1916 | 0.079* | |
C16 | 0.46680 (19) | 0.6475 (3) | 0.12900 (13) | 0.0768 (7) | |
H16A | 0.4568 | 0.7080 | 0.0762 | 0.115* | |
H16B | 0.4434 | 0.5355 | 0.1156 | 0.115* | |
H16C | 0.5463 | 0.6503 | 0.1625 | 0.115* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.02198 (18) | 0.02413 (18) | 0.0336 (2) | −0.00250 (12) | 0.00097 (13) | −0.00018 (13) |
O1 | 0.0393 (5) | 0.0293 (5) | 0.0335 (5) | −0.0102 (4) | 0.0018 (4) | −0.0025 (4) |
O2 | 0.0243 (5) | 0.0347 (6) | 0.0543 (6) | 0.0042 (4) | 0.0028 (4) | 0.0005 (5) |
C1 | 0.0247 (6) | 0.0240 (6) | 0.0309 (6) | −0.0010 (5) | −0.0003 (5) | 0.0043 (5) |
C2 | 0.0359 (7) | 0.0371 (8) | 0.0384 (7) | −0.0022 (6) | 0.0106 (6) | 0.0031 (6) |
C3 | 0.0358 (8) | 0.0608 (11) | 0.0514 (9) | −0.0013 (8) | 0.0155 (7) | 0.0157 (8) |
C4 | 0.0331 (8) | 0.0553 (10) | 0.0579 (10) | −0.0158 (7) | 0.0006 (7) | 0.0221 (9) |
C5 | 0.0465 (9) | 0.0362 (9) | 0.0656 (11) | −0.0168 (7) | −0.0025 (8) | −0.0007 (8) |
C6 | 0.0343 (7) | 0.0297 (7) | 0.0555 (9) | −0.0047 (6) | 0.0047 (7) | −0.0060 (7) |
C7 | 0.0233 (6) | 0.0280 (6) | 0.0338 (7) | −0.0067 (5) | 0.0044 (5) | −0.0021 (5) |
C8 | 0.0323 (7) | 0.0345 (7) | 0.0365 (7) | 0.0006 (6) | 0.0073 (6) | 0.0022 (6) |
C9 | 0.0402 (8) | 0.0379 (8) | 0.0434 (8) | −0.0012 (6) | 0.0025 (7) | 0.0087 (7) |
C10 | 0.0472 (9) | 0.0494 (10) | 0.0373 (8) | −0.0155 (8) | 0.0051 (7) | 0.0094 (7) |
C11 | 0.0505 (9) | 0.0601 (11) | 0.0384 (8) | −0.0123 (8) | 0.0191 (7) | −0.0028 (7) |
C12 | 0.0364 (8) | 0.0429 (8) | 0.0419 (8) | −0.0034 (7) | 0.0128 (6) | −0.0059 (7) |
N1 | 0.0232 (5) | 0.0229 (6) | 0.0591 (8) | −0.0020 (4) | 0.0039 (5) | −0.0022 (5) |
C13 | 0.0370 (9) | 0.0490 (11) | 0.1121 (18) | −0.0027 (8) | 0.0271 (10) | −0.0345 (12) |
C14 | 0.0650 (13) | 0.110 (2) | 0.0764 (15) | −0.0202 (13) | 0.0359 (12) | −0.0413 (15) |
C15 | 0.0477 (10) | 0.0406 (10) | 0.0873 (15) | −0.0127 (8) | −0.0150 (10) | 0.0266 (10) |
C16 | 0.0651 (13) | 0.108 (2) | 0.0509 (11) | −0.0415 (13) | 0.0060 (10) | 0.0136 (12) |
P1—O1 | 1.5027 (10) | C10—C11 | 1.376 (3) |
P1—O2 | 1.5046 (10) | C10—H10A | 0.9500 |
P1—C1 | 1.8119 (13) | C11—C12 | 1.394 (2) |
P1—C7 | 1.8136 (14) | C11—H11A | 0.9500 |
C1—C2 | 1.388 (2) | C12—H12A | 0.9500 |
C1—C6 | 1.392 (2) | N1—C13 | 1.475 (2) |
C2—C3 | 1.390 (2) | N1—C15 | 1.503 (2) |
C2—H2A | 0.9500 | N1—H1A | 0.9200 |
C3—C4 | 1.374 (3) | N1—H1B | 0.9200 |
C3—H3A | 0.9500 | C13—C14 | 1.487 (3) |
C4—C5 | 1.378 (3) | C13—H13A | 0.9900 |
C4—H4A | 0.9500 | C13—H13B | 0.9900 |
C5—C6 | 1.396 (2) | C14—H14A | 0.9800 |
C5—H5A | 0.9500 | C14—H14B | 0.9800 |
C6—H6A | 0.9500 | C14—H14C | 0.9800 |
C7—C12 | 1.390 (2) | C15—C16 | 1.495 (3) |
C7—C8 | 1.395 (2) | C15—H15A | 0.9900 |
C8—C9 | 1.390 (2) | C15—H15B | 0.9900 |
C8—H8A | 0.9500 | C16—H16A | 0.9800 |
C9—C10 | 1.385 (2) | C16—H16B | 0.9800 |
C9—H9A | 0.9500 | C16—H16C | 0.9800 |
O1—P1—O2 | 118.54 (6) | C10—C11—C12 | 120.14 (15) |
O1—P1—C1 | 107.63 (6) | C10—C11—H11A | 119.9 |
O2—P1—C1 | 109.08 (6) | C12—C11—H11A | 119.9 |
O1—P1—C7 | 108.86 (6) | C7—C12—C11 | 120.60 (15) |
O2—P1—C7 | 108.01 (6) | C7—C12—H12A | 119.7 |
C1—P1—C7 | 103.72 (6) | C11—C12—H12A | 119.7 |
C2—C1—C6 | 118.75 (13) | C13—N1—C15 | 114.47 (16) |
C2—C1—P1 | 119.83 (11) | C13—N1—H1A | 108.6 |
C6—C1—P1 | 121.39 (11) | C15—N1—H1A | 108.6 |
C1—C2—C3 | 120.86 (15) | C13—N1—H1B | 108.6 |
C1—C2—H2A | 119.6 | C15—N1—H1B | 108.6 |
C3—C2—H2A | 119.6 | H1A—N1—H1B | 107.6 |
C4—C3—C2 | 119.83 (16) | N1—C13—C14 | 110.84 (17) |
C4—C3—H3A | 120.1 | N1—C13—H13A | 109.5 |
C2—C3—H3A | 120.1 | C14—C13—H13A | 109.5 |
C3—C4—C5 | 120.33 (15) | N1—C13—H13B | 109.5 |
C3—C4—H4A | 119.8 | C14—C13—H13B | 109.5 |
C5—C4—H4A | 119.8 | H13A—C13—H13B | 108.1 |
C4—C5—C6 | 120.02 (16) | C13—C14—H14A | 109.5 |
C4—C5—H5A | 120.0 | C13—C14—H14B | 109.5 |
C6—C5—H5A | 120.0 | H14A—C14—H14B | 109.5 |
C1—C6—C5 | 120.20 (16) | C13—C14—H14C | 109.5 |
C1—C6—H6A | 119.9 | H14A—C14—H14C | 109.5 |
C5—C6—H6A | 119.9 | H14B—C14—H14C | 109.5 |
C12—C7—C8 | 118.58 (13) | C16—C15—N1 | 111.51 (16) |
C12—C7—P1 | 120.62 (11) | C16—C15—H15A | 109.3 |
C8—C7—P1 | 120.79 (11) | N1—C15—H15A | 109.3 |
C9—C8—C7 | 120.68 (14) | C16—C15—H15B | 109.3 |
C9—C8—H8A | 119.7 | N1—C15—H15B | 109.3 |
C7—C8—H8A | 119.7 | H15A—C15—H15B | 108.0 |
C10—C9—C8 | 119.95 (16) | C15—C16—H16A | 109.5 |
C10—C9—H9A | 120.0 | C15—C16—H16B | 109.5 |
C8—C9—H9A | 120.0 | H16A—C16—H16B | 109.5 |
C11—C10—C9 | 120.04 (15) | C15—C16—H16C | 109.5 |
C11—C10—H10A | 120.0 | H16A—C16—H16C | 109.5 |
C9—C10—H10A | 120.0 | H16B—C16—H16C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.92 | 1.77 | 2.6722 (15) | 166 |
N1—H1B···O2i | 0.92 | 1.78 | 2.6943 (15) | 176 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C4H12N+·C12H10O2P− |
Mr | 291.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 12.4163 (2), 8.3038 (2), 16.4517 (3) |
β (°) | 106.949 (1) |
V (Å3) | 1622.53 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.32 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.947, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13875, 3705, 3236 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.106, 1.03 |
No. of reflections | 3705 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.34 |
Computer programs: COLLECT (Nonius BV, 1997-2001), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick 1999), SHELXTL.
P1—O1 | 1.5027 (10) | N1—C13 | 1.475 (2) |
P1—O2 | 1.5046 (10) | N1—C15 | 1.503 (2) |
O1—P1—O2 | 118.54 (6) | O2—P1—C7 | 108.01 (6) |
O1—P1—C1 | 107.63 (6) | C1—P1—C7 | 103.72 (6) |
O2—P1—C1 | 109.08 (6) | C13—N1—C15 | 114.47 (16) |
O1—P1—C7 | 108.86 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.92 | 1.77 | 2.6722 (15) | 166.0 |
N1—H1B···O2i | 0.92 | 1.78 | 2.6943 (15) | 176.3 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Diethylammonium diphenylphosphinate, [Et2NH2][Ph2PO2], (I), was synthesized during the course of our work on the preparation and reactivity of phosphinoborane compounds (Dorn et al., 2000). The reaction between the phosphine–borane adduct Ph2PHBH3 and diethylamine (1:2 ratio) in dichloromethane under air yielded [Et2NH2][Ph2PO2] as colourless crystals, along with the amine–borane adduct Et2NHBH3, which was detected by 11B NMR spectroscopy. The breaking of the P—B bond in phosphine–borane adducts by amines is known; however, the subsequent oxidation of Ph2PH and formation of the ammonium salt was unexpected. The title compound could also be synthesized directly from Ph2P(O)(OH) and Et2NH in CDCl3 solution, and was identified by 31P NMR spectroscopy.