Diethyl­ammonium di­phenyl­phosphinate

In the title compound, C₄H₁₂N⁺·C₁₂H₁₀O₂P⁻, the Et₂NH₂⁺ and Ph₂PO₂⁻ moieties in the asymmetric unit are linked by P—O...H—N hydrogen bonds [O...N distance 2.6722 (15) Å]. These hydrogen-bonded pairs are in turn linked by intermolecular P—O...H—N hydrogen bonds [O...N distance 2.6943 (15) Å] to form infinite chains along 2₁ screw axes in the y direction.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.106
• Data-to-parameter ratio = 20.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

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.

S2. Experimental

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).

S3. Refinement

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.

Computing details

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.

Figures

	Fig. 1. View of (I) showing the atom-labelling scheme. Displacement ellipsoids are at the 50% probability level and H atoms bonded to C atoms have been omitted for clarity.
	Fig. 2. View of the hydrogen bonding in (I). H atoms bonded to C atoms have been omitted for clarity.

Diethylammonium diphenylphosphinate

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.32 × 0.30 × 0.26 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.757P] where P = (Fo^2 + 2Fc^2)/3
3705 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

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···O2^i	0.92	1.78	2.6943 (15)	176

Symmetry code: (i) −x+1, y+1/2, −z+1/2.