Diisopropyl­ammonium hydrogen phenyl­phospho­nate

In the title salt, [(CH₃)₂CH]₂NH₂]⁺·[C₆H₅PO₂(OH)]⁻, the anions are linked by pairs of O—H...O hydrogen bonds, forming inversion dimers. These dimers are bridged by the cations via N—H...O hydrogen bonds, leading to a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.029
• wR factor = 0.080
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT143_ALERT_4_C su on c - Axis Small or Missing ................    0.00010 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.88 mm
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In the assymmetric unit of the title salt (Fig. 1), the anion, hydrogen phenylphosphonate (PhPO₃H^-), adopts a tetrahedral geometry, with three oxygen atoms and a benzene group with O—P—O and O—P—C angles in the ranges 109.58 (4) - 115.20 (4) and 105.24 (4) - 108.51 (4)°, respectively. Two P—O distances in the anion are close, (P1—O1 = 1.4932 (7) and P1—O3 = 1.5191 (7) Å) indicating the presence of extensive π-delocalization of the P═O double bonds. The bond distance P1—O2 (1.5809 (7) Å for P—OH bond) is significantly longer than the other two P—O bonds. The P—O bond distances in the title salt agree very well with the corresponding bond distances reported in closely related compounds (Diop et al., 2012; Beckmann et al., 2003).

In the crystal, the anions are connected by O2—H6···O3 hydrogen bonds forming dimers about inversion centers. These pairs are then bridged through cations via N—H···O hydrogen bonds leading to a three-dimensional structure (Tab. 1 & Fig. 2).

Related literature

For crystal structures of closely related compounds, see: Diop et al. (2012); Beckmann et al. (2003).

S2. Experimental

The title compound was synthesized by mixing [(CH₃)₂CH]₂NH and PhPO₃H₂ in water (1/1 ratio). The precipitate obtained was filtered. The crystals suitable for X-ray crystallographic analysis were grown from a solution of water by slow evaporation at room temperature.

S3. Refinement

All H atoms were located from difference maps and were allowed to refine freely with U_iso.

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The assymmetric unit of the title salt. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the O—-H···O and N—H···O hydrogen bonds (light-blue colored lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity.

Diisopropylammonium hydrogen phenylphosphonate

Crystal data

C6H16N^+·C6H6O3P^−	F(000) = 560
Mr = 259.28	Dx = 1.259 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4223 reflections
a = 11.9166 (2) Å	θ = 0.4–30.0°
b = 9.0982 (1) Å	µ = 0.20 mm^−1
c = 12.8539 (1) Å	T = 293 K
β = 101.013 (1)°	Prism, colourless
V = 1367.95 (3) Å^3	0.88 × 0.63 × 0.25 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3990 independent reflections
Radiation source: fine-focus sealed tube	3626 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ϕ scans, and ω scans with κ	θmax = 30.1°, θmin = 3.2°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −16→16
Tmin = 0.845, Tmax = 0.952	k = −12→12
7738 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	All H-atom parameters refined
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0397P)^2 + 0.4747P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3990 reflections	Δρmax = 0.38 e Å^−3
243 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (2)

Special details

Experimental. The analytical data - % calculated (% found): C: 55.59 (55.64); H: 8.55 (8.91); N: 5.40 (5.58).

Infrared data (cm^-1) [br= broad; s= strong; m=medium]

2694br νNH; 1148m, 1129 s, 1059, 1027m νPO₃; 898 s δPO₃; 752 m νPC; 708 s, 696 s νPh.

Melting point = 437–438 K

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.966159 (19)	0.40247 (2)	0.846319 (17)	0.01271 (8)
O2	1.04330 (6)	0.32302 (7)	0.94386 (5)	0.01729 (14)
N1	0.66048 (7)	0.51553 (9)	0.78554 (6)	0.01430 (15)
C1	1.06532 (7)	0.49048 (10)	0.77593 (7)	0.01453 (17)
C6	1.14485 (9)	0.59178 (11)	0.82778 (8)	0.0222 (2)
C12	0.62928 (8)	0.41946 (10)	0.68876 (8)	0.01742 (18)
C13	0.69808 (9)	0.47210 (12)	0.60787 (8)	0.0225 (2)
C2	1.06337 (9)	0.46114 (11)	0.66912 (8)	0.01979 (19)
C4	1.21864 (9)	0.63037 (13)	0.66783 (9)	0.0270 (2)
C3	1.13968 (9)	0.53095 (13)	0.61530 (9)	0.0256 (2)
C5	1.22118 (10)	0.66111 (13)	0.77426 (10)	0.0287 (2)
O1	0.89926 (6)	0.29081 (8)	0.77497 (5)	0.02025 (15)
C8	0.60257 (8)	0.48352 (11)	0.87717 (8)	0.01757 (18)
C9	0.64492 (9)	0.59615 (12)	0.96314 (8)	0.0215 (2)
C11	0.50164 (9)	0.42810 (13)	0.64537 (9)	0.0245 (2)
C10	0.62574 (10)	0.32619 (12)	0.91508 (9)	0.0257 (2)
O3	0.89542 (5)	0.52144 (7)	0.88605 (5)	0.01657 (14)
H6	1.0624 (16)	0.376 (2)	0.9984 (15)	0.054 (5)*
H17	0.7362 (12)	0.5109 (14)	0.8110 (11)	0.022 (3)*
H16	0.6429 (12)	0.6104 (16)	0.7649 (11)	0.028 (3)*
H21	0.5218 (11)	0.4980 (14)	0.8513 (10)	0.018 (3)*
H18	0.6510 (11)	0.3197 (15)	0.7094 (10)	0.020 (3)*
H10	0.6767 (12)	0.5719 (16)	0.5864 (11)	0.029 (4)*
H7	0.7279 (12)	0.5857 (15)	0.9907 (11)	0.027 (3)*
H12	0.6818 (13)	0.4116 (16)	0.5460 (12)	0.034 (4)*
H9	0.6088 (13)	0.5821 (17)	1.0245 (12)	0.036 (4)*
H11	0.7788 (13)	0.4705 (16)	0.6362 (12)	0.032 (4)*
H8	0.6298 (13)	0.6961 (18)	0.9372 (12)	0.035 (4)*
H13	0.4820 (12)	0.3727 (17)	0.5783 (12)	0.034 (4)*
H20	0.7076 (13)	0.3059 (16)	0.9306 (11)	0.029 (3)*
H19	0.5963 (13)	0.3128 (18)	0.9806 (13)	0.041 (4)*
H15	0.4790 (13)	0.5297 (17)	0.6277 (12)	0.034 (4)*
H14	0.4571 (13)	0.3869 (16)	0.6953 (12)	0.034 (4)*
H22	0.5884 (13)	0.2571 (18)	0.8637 (13)	0.038 (4)*
H5	1.1462 (12)	0.6131 (15)	0.9024 (11)	0.028 (3)*
H3	1.2709 (13)	0.6789 (17)	0.6323 (12)	0.037 (4)*
H4	1.2746 (13)	0.7291 (18)	0.8131 (12)	0.040 (4)*
H2	1.1388 (13)	0.5080 (17)	0.5413 (12)	0.034 (4)*
H1	1.0101 (12)	0.3924 (16)	0.6328 (11)	0.027 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01307 (12)	0.01214 (12)	0.01264 (12)	−0.00065 (7)	0.00175 (8)	−0.00020 (7)
O2	0.0219 (3)	0.0150 (3)	0.0141 (3)	0.0025 (2)	0.0012 (2)	0.0012 (2)
N1	0.0134 (3)	0.0143 (3)	0.0154 (3)	0.0003 (3)	0.0031 (3)	0.0005 (3)
C1	0.0141 (4)	0.0135 (4)	0.0161 (4)	0.0019 (3)	0.0032 (3)	0.0015 (3)
C6	0.0229 (5)	0.0226 (5)	0.0214 (5)	−0.0063 (4)	0.0051 (4)	−0.0012 (4)
C12	0.0184 (4)	0.0157 (4)	0.0179 (4)	0.0004 (3)	0.0027 (3)	−0.0029 (3)
C13	0.0214 (5)	0.0297 (5)	0.0171 (4)	0.0020 (4)	0.0049 (4)	−0.0015 (4)
C2	0.0207 (4)	0.0222 (5)	0.0171 (4)	0.0005 (4)	0.0052 (3)	−0.0001 (3)
C4	0.0241 (5)	0.0279 (5)	0.0321 (6)	0.0004 (4)	0.0129 (4)	0.0102 (4)
C3	0.0275 (5)	0.0309 (6)	0.0209 (5)	0.0033 (4)	0.0110 (4)	0.0049 (4)
C5	0.0262 (5)	0.0280 (5)	0.0326 (6)	−0.0105 (4)	0.0077 (4)	0.0014 (4)
O1	0.0231 (3)	0.0169 (3)	0.0193 (3)	−0.0056 (3)	0.0003 (3)	−0.0021 (3)
C8	0.0148 (4)	0.0209 (4)	0.0182 (4)	0.0006 (3)	0.0064 (3)	0.0026 (3)
C9	0.0228 (5)	0.0247 (5)	0.0179 (4)	0.0034 (4)	0.0065 (4)	−0.0007 (4)
C11	0.0190 (4)	0.0267 (5)	0.0263 (5)	−0.0035 (4)	0.0005 (4)	−0.0067 (4)
C10	0.0306 (5)	0.0215 (5)	0.0264 (5)	−0.0017 (4)	0.0089 (4)	0.0066 (4)
O3	0.0137 (3)	0.0197 (3)	0.0161 (3)	0.0026 (2)	0.0023 (2)	−0.0017 (2)

Geometric parameters (Å, º)

P1—O1	1.4932 (7)	C2—C3	1.3962 (14)
P1—O3	1.5191 (7)	C2—H1	0.948 (14)
P1—O2	1.5809 (7)	C4—C3	1.3845 (17)
P1—C1	1.8068 (9)	C4—C5	1.3910 (16)
O2—H6	0.847 (19)	C4—H3	0.949 (15)
N1—C8	1.5030 (12)	C3—H2	0.972 (15)
N1—C12	1.5077 (12)	C5—H4	0.957 (16)
N1—H17	0.900 (14)	C8—C10	1.5202 (14)
N1—H16	0.916 (15)	C8—C9	1.5208 (14)
C1—C2	1.3945 (13)	C8—H21	0.965 (13)
C1—C6	1.3966 (13)	C9—H7	0.989 (15)
C6—C5	1.3920 (14)	C9—H9	0.976 (15)
C6—H5	0.976 (14)	C9—H8	0.973 (16)
C12—C11	1.5188 (14)	C11—H13	0.987 (15)
C12—C13	1.5193 (14)	C11—H15	0.977 (16)
C12—H18	0.967 (13)	C11—H14	0.982 (15)
C13—H10	0.969 (15)	C10—H20	0.976 (15)
C13—H12	0.957 (15)	C10—H19	0.980 (16)
C13—H11	0.961 (15)	C10—H22	0.957 (16)
O1—P1—O3	115.20 (4)	C3—C4—C5	119.74 (9)
O1—P1—O2	109.72 (4)	C3—C4—H3	121.1 (9)
O3—P1—O2	109.58 (4)	C5—C4—H3	119.1 (9)
O1—P1—C1	108.51 (4)	C4—C3—C2	120.12 (10)
O3—P1—C1	108.10 (4)	C4—C3—H2	119.8 (9)
O2—P1—C1	105.24 (4)	C2—C3—H2	120.1 (9)
P1—O2—H6	114.8 (12)	C4—C5—C6	120.10 (10)
C8—N1—C12	117.16 (7)	C4—C5—H4	122.1 (10)
C8—N1—H17	106.5 (8)	C6—C5—H4	117.8 (10)
C12—N1—H17	110.1 (8)	N1—C8—C10	110.56 (8)
C8—N1—H16	107.3 (9)	N1—C8—C9	107.49 (8)
C12—N1—H16	107.5 (9)	C10—C8—C9	112.76 (9)
H17—N1—H16	107.9 (12)	N1—C8—H21	106.3 (7)
C2—C1—C6	118.58 (9)	C10—C8—H21	110.3 (8)
C2—C1—P1	121.24 (7)	C9—C8—H21	109.2 (7)
C6—C1—P1	120.17 (7)	C8—C9—H7	111.5 (8)
C5—C6—C1	120.74 (10)	C8—C9—H9	111.2 (9)
C5—C6—H5	120.4 (8)	H7—C9—H9	105.2 (12)
C1—C6—H5	118.8 (8)	C8—C9—H8	111.5 (9)
N1—C12—C11	110.17 (8)	H7—C9—H8	108.6 (12)
N1—C12—C13	107.55 (8)	H9—C9—H8	108.5 (12)
C11—C12—C13	111.46 (9)	C12—C11—H13	110.3 (8)
N1—C12—H18	107.9 (8)	C12—C11—H15	110.3 (9)
C11—C12—H18	110.2 (8)	H13—C11—H15	105.8 (12)
C13—C12—H18	109.5 (7)	C12—C11—H14	111.6 (9)
C12—C13—H10	110.1 (8)	H13—C11—H14	108.0 (12)
C12—C13—H12	109.8 (9)	H15—C11—H14	110.7 (12)
H10—C13—H12	107.5 (12)	C8—C10—H20	110.9 (8)
C12—C13—H11	111.6 (9)	C8—C10—H19	108.6 (9)
H10—C13—H11	108.2 (12)	H20—C10—H19	108.0 (12)
H12—C13—H11	109.6 (12)	C8—C10—H22	111.4 (9)
C1—C2—C3	120.72 (10)	H20—C10—H22	109.3 (12)
C1—C2—H1	119.7 (8)	H19—C10—H22	108.3 (13)
C3—C2—H1	119.6 (8)
O1—P1—C1—C2	6.07 (9)	C8—N1—C12—C13	−179.89 (8)
O3—P1—C1—C2	−119.51 (8)	C6—C1—C2—C3	0.34 (14)
O2—P1—C1—C2	123.46 (8)	P1—C1—C2—C3	179.35 (8)
O1—P1—C1—C6	−174.93 (8)	C5—C4—C3—C2	−0.39 (17)
O3—P1—C1—C6	59.48 (8)	C1—C2—C3—C4	0.11 (16)
O2—P1—C1—C6	−57.55 (8)	C3—C4—C5—C6	0.21 (18)
C2—C1—C6—C5	−0.53 (15)	C1—C6—C5—C4	0.26 (17)
P1—C1—C6—C5	−179.55 (8)	C12—N1—C8—C10	58.07 (11)
C8—N1—C12—C11	58.44 (11)	C12—N1—C8—C9	−178.48 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H17···O3	0.900 (14)	1.960 (14)	2.8510 (10)	170.3 (12)
O2—H6···O3^i	0.847 (19)	1.744 (19)	2.5895 (10)	177.4 (19)
N1—H16···O1^ii	0.916 (15)	1.764 (15)	2.6782 (10)	176.7 (13)

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+3/2, y+1/2, −z+3/2.