A new crystal modification of diammonium hydrogen phosphate, (NH(4))(2)(HPO(4)).

The addition of hexa-fluorido-phosphate salts (ammonium, silver, thallium or potassium) is usually used to precipitate complex cations from aqueous solutions. It has long been known that PF(6) (-) is sensitive towards hydrolysis under acidic conditions [Gebala & Jones (1969 ▶). J. Inorg. Nucl. Chem.31, 771-776; Plakhotnyk et al. (2005 ▶). J. Fluorine Chem.126, 27-31]. During the course of our investigation into coinage metal complexes of diphosphine ligands, we used ammonium hexa-fluorido-phosphate in order to crystallize [Ag(diphos-phine)(2)]PF(6) complexes. From these solutions we always obtained needle-like crystals which turned out to be the title compound, 2NH(4) (+)·HPO(4) (2-). It was received as the hydrolysis product of NH(4)PF(6). The crystals are a new modification of diammonium hydrogen phosphate. In contrast to the previously published polymorph [Khan et al. (1972 ▶). Acta Cryst. B28, 2065-2069], Z' of the title compound is 2. In the new modification of the title compound, there are eight mol-ecules of (NH(4))(2)(HPO(4)) in the unit cell. The structure consists of PO(3)OH and NH(4) tetra-hedra, held together by O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For the study of another crystal modification of the title compound, see: Khan et al. (1972 ▶). For the hydrolysis of hexa­fluorido­phosphates, see: Akbayeva et al. (2006 ▶); Deifel et al. (2008 ▶); Fernandez-Galan et al. (1994 ▶); Gebala & Jones (1969 ▶); Nikitenko et al. (2007 ▶); Plakhotnyk et al. (2005 ▶).

Experimental

Crystal data

2NH4 +·HPO4 2−

M = 132.06

Monoclinic,

a = 11.2868 (3) Å

b = 15.3466 (4) Å

c = 6.41894 (19) Å

β = 90.795 (3)°

V = 1111.74 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.42 mm−1

T = 183 K

0.44 × 0.17 × 0.11 mm

Data collection

Oxford Xcalibur Ruby CCD diffractometer

Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009 ▶) T min = 0.891, T max = 0.955

22537 measured reflections

5384 independent reflections

4400 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.158

S = 1.21

5384 reflections

181 parameters

16 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.82 e Å−3

Δρmin = −0.69 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global. DOI: 10.1107/S1600536810009839/br2137sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009839/br2137Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2NH4+·HPO42−	F(000) = 560
Mr = 132.06	Dx = 1.578 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 11185 reflections
a = 11.2868 (3) Å	θ = 2.7–37.6°
b = 15.3466 (4) Å	µ = 0.42 mm−1
c = 6.41894 (19) Å	T = 183 K
β = 90.795 (3)°	Needle, colourless
V = 1111.74 (5) Å3	0.44 × 0.17 × 0.11 mm
Z = 8

Oxford Xcalibur Ruby CCD diffractometer	5384 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4400 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 10.4498 pixels mm-1	θmax = 36.3°, θmin = 2.7°
ω oscillation scan	h = −18→18
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	k = −25→25
Tmin = 0.891, Tmax = 0.955	l = −9→10
22537 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ2(Fo2) + (0.0508P)2 + 1.9491P] where P = (Fo2 + 2Fc2)/3
5384 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.82 e Å−3
16 restraints	Δρmin = −0.68 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.12341 (16)	0.48227 (11)	0.6812 (3)	0.0260 (4)
H1	0.181 (4)	0.502 (3)	0.635 (6)	0.039*
O2	0.25104 (13)	0.34866 (10)	0.7264 (2)	0.0180 (3)
O3	0.13920 (15)	0.40992 (11)	1.0319 (2)	0.0198 (3)
O4	0.02645 (13)	0.34042 (10)	0.7334 (3)	0.0190 (3)
O5	−0.41866 (14)	0.29289 (11)	0.4731 (3)	0.0209 (3)
H5	−0.368 (3)	0.259 (3)	0.529 (6)	0.031*
O6	−0.47633 (13)	0.40326 (10)	0.2142 (2)	0.0174 (3)
O7	−0.30247 (15)	0.43252 (11)	0.4549 (2)	0.0209 (3)
O8	−0.28270 (13)	0.32102 (10)	0.1683 (2)	0.0182 (3)
P1	0.13662 (4)	0.39195 (3)	0.79806 (7)	0.01228 (10)
P2	−0.36645 (4)	0.36515 (3)	0.32105 (7)	0.01211 (10)
N11	0.03108 (16)	0.66864 (12)	0.7030 (3)	0.0185 (3)
H11A	0.009 (3)	0.7219 (13)	0.720 (5)	0.028*
H11B	0.1058 (17)	0.667 (2)	0.730 (5)	0.028*
H11C	−0.017 (3)	0.638 (2)	0.780 (5)	0.028*
H11D	0.018 (3)	0.658 (2)	0.570 (3)	0.028*
N12	0.47645 (17)	0.41255 (13)	0.7925 (3)	0.0188 (3)
H12A	0.500 (3)	0.402 (2)	0.920 (3)	0.028*
H12B	0.523 (3)	0.382 (2)	0.711 (5)	0.028*
H12C	0.479 (3)	0.4675 (13)	0.760 (5)	0.028*
H12D	0.4031 (19)	0.395 (2)	0.770 (5)	0.028*
N13	0.29995 (16)	0.32905 (12)	1.2991 (3)	0.0182 (3)
H13A	0.252 (3)	0.351 (2)	1.207 (4)	0.027*
H13B	0.285 (3)	0.339 (2)	1.428 (3)	0.027*
H13C	0.3748 (18)	0.345 (2)	1.278 (5)	0.027*
H13D	0.288 (3)	0.2742 (12)	1.282 (5)	0.027*
N14	−0.18493 (17)	0.42049 (12)	0.8356 (3)	0.0178 (3)
H14A	−0.227 (3)	0.425 (2)	0.720 (4)	0.027*
H14B	−0.221 (3)	0.394 (2)	0.933 (4)	0.027*
H14C	−0.169 (3)	0.4726 (14)	0.877 (5)	0.027*
H14D	−0.1132 (19)	0.398 (2)	0.814 (5)	0.027*

	U11	U22	U33	U12	U13	U23
O1	0.0185 (7)	0.0193 (7)	0.0403 (10)	0.0021 (6)	0.0007 (6)	0.0145 (7)
O2	0.0140 (6)	0.0182 (6)	0.0220 (7)	0.0022 (5)	0.0025 (5)	−0.0015 (5)
O3	0.0225 (7)	0.0215 (7)	0.0153 (6)	0.0000 (5)	−0.0005 (5)	−0.0035 (5)
O4	0.0142 (6)	0.0179 (6)	0.0249 (7)	−0.0037 (5)	−0.0022 (5)	−0.0034 (5)
O5	0.0183 (6)	0.0207 (7)	0.0237 (7)	0.0025 (5)	0.0055 (5)	0.0099 (5)
O6	0.0145 (6)	0.0189 (6)	0.0188 (6)	0.0015 (5)	−0.0032 (5)	0.0032 (5)
O7	0.0221 (7)	0.0242 (7)	0.0165 (6)	−0.0048 (6)	−0.0035 (5)	−0.0031 (5)
O8	0.0150 (6)	0.0206 (7)	0.0192 (6)	−0.0010 (5)	0.0046 (5)	−0.0033 (5)
P1	0.01141 (19)	0.01162 (19)	0.01380 (19)	−0.00003 (14)	−0.00053 (14)	−0.00007 (14)
P2	0.01113 (18)	0.0140 (2)	0.01122 (18)	−0.00061 (14)	0.00038 (13)	0.00073 (14)
N11	0.0167 (7)	0.0184 (7)	0.0205 (8)	0.0015 (6)	−0.0007 (6)	−0.0001 (6)
N12	0.0170 (7)	0.0226 (8)	0.0169 (7)	0.0013 (6)	−0.0008 (6)	−0.0018 (6)
N13	0.0160 (7)	0.0199 (7)	0.0187 (7)	−0.0015 (6)	−0.0001 (5)	0.0002 (6)
N14	0.0178 (7)	0.0197 (7)	0.0159 (7)	−0.0006 (6)	0.0001 (5)	−0.0016 (6)

O1—P1	1.5821 (17)	N11—H11D	0.877 (18)
O1—H1	0.78 (4)	N12—H12A	0.869 (18)
O2—P1	1.5287 (15)	N12—H12B	0.878 (18)
O3—P1	1.5257 (16)	N12—H12C	0.868 (18)
O4—P1	1.5262 (15)	N12—H12D	0.879 (18)
O5—P2	1.5955 (16)	N13—H13A	0.863 (18)
O5—H5	0.85 (4)	N13—H13B	0.862 (18)
O6—P2	1.5254 (15)	N13—H13C	0.892 (18)
O7—P2	1.5201 (16)	N13—H13D	0.859 (18)
O8—P2	1.5295 (15)	N14—H14A	0.874 (18)
N11—H11A	0.862 (18)	N14—H14B	0.856 (18)
N11—H11B	0.859 (18)	N14—H14C	0.861 (18)
N11—H11C	0.876 (18)	N14—H14D	0.890 (18)
P1—O1—H1	116 (3)	H11C—N11—H11D	110 (3)
P2—O5—H5	115 (3)	H12A—N12—H12B	107 (3)
O3—P1—O4	111.44 (9)	H12A—N12—H12C	113 (3)
O3—P1—O2	111.70 (9)	H12B—N12—H12C	111 (3)
O4—P1—O2	112.43 (9)	H12A—N12—H12D	112 (3)
O3—P1—O1	107.95 (10)	H12B—N12—H12D	108 (3)
O4—P1—O1	104.71 (10)	H12C—N12—H12D	106 (3)
O2—P1—O1	108.21 (9)	H13A—N13—H13B	118 (3)
O7—P2—O6	111.73 (9)	H13A—N13—H13C	112 (3)
O7—P2—O8	111.74 (9)	H13B—N13—H13C	107 (3)
O6—P2—O8	112.79 (9)	H13A—N13—H13D	101 (3)
O7—P2—O5	107.68 (9)	H13B—N13—H13D	105 (3)
O6—P2—O5	103.69 (9)	H13C—N13—H13D	113 (3)
O8—P2—O5	108.73 (9)	H14A—N14—H14B	114 (3)
H11A—N11—H11B	107 (3)	H14A—N14—H14C	107 (3)
H11A—N11—H11C	105 (3)	H14B—N14—H14C	109 (3)
H11B—N11—H11C	119 (3)	H14A—N14—H14D	112 (3)
H11A—N11—H11D	105 (3)	H14B—N14—H14D	112 (3)
H11B—N11—H11D	110 (3)	H14C—N14—H14D	102 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7i	0.78 (4)	1.80 (4)	2.570 (2)	168 (4)
O5—H5···O8ii	0.85 (4)	1.79 (4)	2.632 (2)	170 (4)
N11—H11A···O4iii	0.86 (2)	1.89 (2)	2.747 (2)	175 (4)
N11—H11B···O8i	0.86 (2)	2.10 (2)	2.951 (2)	171 (3)
N11—H11C···O3iv	0.88 (2)	1.99 (2)	2.852 (3)	169 (3)
N11—H11D···O4i	0.88 (2)	2.01 (2)	2.870 (2)	167 (3)
N12—H12A···O6v	0.87 (2)	1.91 (2)	2.755 (2)	165 (3)
N12—H12B···O5vi	0.88 (2)	2.16 (2)	3.008 (3)	161 (3)
N12—H12C···O6i	0.87 (2)	1.99 (2)	2.827 (2)	161 (3)
N12—H12D···O2	0.88 (2)	1.88 (2)	2.754 (2)	175 (3)
N13—H13A···O3	0.86 (2)	1.92 (2)	2.773 (2)	172 (3)
N13—H13B···O2vii	0.86 (2)	1.96 (2)	2.822 (2)	175 (3)
N13—H13C···O6v	0.89 (2)	1.95 (2)	2.830 (2)	168 (3)
N13—H13D···O2ii	0.86 (2)	1.96 (2)	2.820 (2)	176 (3)
N14—H14A···O7	0.87 (2)	1.90 (2)	2.771 (2)	174 (3)
N14—H14B···O8vii	0.86 (2)	2.01 (2)	2.859 (2)	171 (3)
N14—H14C···O3iv	0.86 (2)	1.92 (2)	2.784 (2)	178 (3)
N14—H14D···O4	0.89 (2)	1.89 (2)	2.771 (2)	171 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O7i	0.78 (4)	1.80 (4)	2.570 (2)	168 (4)
O5—H5⋯O8ii	0.85 (4)	1.79 (4)	2.632 (2)	170 (4)
N11—H11A⋯O4iii	0.86 (2)	1.89 (2)	2.747 (2)	175 (4)
N11—H11B⋯O8i	0.86 (2)	2.10 (2)	2.951 (2)	171 (3)
N11—H11C⋯O3iv	0.88 (2)	1.99 (2)	2.852 (3)	169 (3)
N11—H11D⋯O4i	0.88 (2)	2.01 (2)	2.870 (2)	167 (3)
N12—H12A⋯O6v	0.87 (2)	1.91 (2)	2.755 (2)	165 (3)
N12—H12B⋯O5vi	0.88 (2)	2.16 (2)	3.008 (3)	161 (3)
N12—H12C⋯O6i	0.87 (2)	1.99 (2)	2.827 (2)	161 (3)
N12—H12D⋯O2	0.88 (2)	1.88 (2)	2.754 (2)	175 (3)
N13—H13A⋯O3	0.86 (2)	1.92 (2)	2.773 (2)	172 (3)
N13—H13B⋯O2vii	0.86 (2)	1.96 (2)	2.822 (2)	175 (3)
N13—H13C⋯O6v	0.89 (2)	1.95 (2)	2.830 (2)	168 (3)
N13—H13D⋯O2ii	0.86 (2)	1.96 (2)	2.820 (2)	176 (3)
N14—H14A⋯O7	0.87 (2)	1.90 (2)	2.771 (2)	174 (3)
N14—H14B⋯O8vii	0.86 (2)	2.01 (2)	2.859 (2)	171 (3)
N14—H14C⋯O3iv	0.86 (2)	1.92 (2)	2.784 (2)	178 (3)
N14—H14D⋯O4	0.89 (2)	1.89 (2)	2.771 (2)	171 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .