Ammonium dihydrogen (1-ammonio-pentane-1,1-di-yl)diphospho-nate.

The title compound, NH(4) (+)·C(5)H(14)NO(6)P(2) (-), was obtained from 1-ammonio-1-phosphono-pentane-1-phospho-nic acid and ammonium hydroxide in aqueous solution. The asymmetric unit of title compound contains one molecule, which consists of an ammonium cation and an aminodiphosphonic anion with the H atoms transferred from the phosphonic acid group to the amino group. The crystal structure shows a three-dimensional network of O-H⋯O and N-H⋯O hydrogen bonds which stabilize the structure.

Related literature

For general background to the use of organic diphospho­nic acids as chelating agents in metal extraction and as drugs to prevent calcification and inhibit bone resorption, see: Matczak-Jon & Videnova-Adrabinska (2005 ▶); Tromelin et al. (1986 ▶); Szabo et al. (2002 ▶). For related structures, see: Bon et al. (2008 ▶). For bond–length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

NH4 +·C5H14NO6P2 −

M = 264.15

Monoclinic,

a = 9.6007 (6) Å

b = 5.7239 (4) Å

c = 20.3259 (15) Å

β = 98.100 (3)°

V = 1105.84 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 296 K

0.50 × 0.12 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.824, T max = 0.982

5297 measured reflections

2256 independent reflections

1532 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.122

S = 1.02

2256 reflections

173 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028323/rk2155sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028323/rk2155Isup2.hkl

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

NH4+·C5H14NO6P2−	F(000) = 560
Mr = 264.15	Dx = 1.587 Mg m−3
Monoclinic, P21/c	Melting point: 495 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.6007 (6) Å	Cell parameters from 824 reflections
b = 5.7239 (4) Å	θ = 2.7–21.1°
c = 20.3259 (15) Å	µ = 0.41 mm−1
β = 98.100 (3)°	T = 296 K
V = 1105.84 (13) Å3	Needle, colourless
Z = 4	0.50 × 0.12 × 0.04 mm

Bruker APEXII CCD diffractometer	2256 independent reflections
Radiation source: fine–focus sealed tube	1532 reflections with I > 2σ(I)
graphite	Rint = 0.056
Detector resolution: 8.26 pixels mm-1	θmax = 26.4°, θmin = 2.0°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −7→5
Tmin = 0.824, Tmax = 0.982	l = −24→25
5297 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0435P)2 + 0.4298P] where P = (Fo2 + 2Fc2)/3
2256 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	0.22481 (10)	0.43513 (17)	0.29915 (4)	0.0195 (3)
P2	0.00587 (9)	0.47871 (16)	0.39608 (4)	0.0184 (2)
C1	0.1590 (3)	0.3149 (6)	0.37310 (16)	0.0161 (7)
C2	0.2832 (4)	0.3109 (7)	0.43011 (17)	0.0243 (8)
H2A	0.3635	0.2439	0.4129	0.029*
H2B	0.3070	0.4715	0.4421	0.029*
C3	0.2649 (4)	0.1806 (7)	0.49344 (17)	0.0295 (9)
H3A	0.1787	0.2316	0.5088	0.035*
H3B	0.2567	0.0146	0.4841	0.035*
C4	0.3877 (4)	0.2227 (8)	0.54735 (18)	0.0374 (11)
H4A	0.3885	0.3860	0.5602	0.045*
H4B	0.4745	0.1909	0.5297	0.045*
C5	0.3827 (5)	0.0731 (9)	0.6084 (2)	0.0506 (13)
H5A	0.2985	0.1074	0.6271	0.076*
H5B	0.4634	0.1059	0.6407	0.076*
H5C	0.3831	−0.0889	0.5962	0.076*
N1	0.1106 (3)	0.0689 (5)	0.35619 (16)	0.0200 (7)
N2	0.3682 (4)	0.9144 (7)	0.2109 (2)	0.0297 (8)
O1	0.3514 (2)	0.2924 (4)	0.28929 (11)	0.0247 (6)
O2	0.2493 (3)	0.6898 (4)	0.31012 (12)	0.0279 (6)
O3	0.1056 (3)	0.3928 (5)	0.23993 (12)	0.0282 (7)
O4	−0.0725 (3)	0.2932 (4)	0.43385 (13)	0.0263 (6)
O5	−0.0902 (2)	0.5374 (5)	0.33383 (12)	0.0280 (6)
O6	0.0601 (3)	0.6800 (4)	0.43945 (11)	0.0237 (6)
H3O	0.107 (5)	0.279 (9)	0.217 (2)	0.065 (18)*
H4O	−0.061 (5)	0.303 (9)	0.475 (2)	0.070 (18)*
H11N	0.180 (4)	−0.059 (7)	0.3428 (19)	0.047 (12)*
H12N	0.078 (5)	−0.001 (8)	0.392 (2)	0.060 (14)*
H13N	0.038 (4)	0.063 (7)	0.321 (2)	0.040 (12)*
H21N	0.336 (5)	0.810 (9)	0.247 (3)	0.083 (18)*
H22N	0.449 (5)	0.874 (7)	0.2012 (19)	0.040 (13)*
H23N	0.295 (6)	0.919 (10)	0.176 (3)	0.10 (2)*
H24N	0.377 (5)	1.058 (8)	0.231 (2)	0.048 (14)*

	U11	U22	U33	U12	U13	U23
P1	0.0216 (5)	0.0158 (5)	0.0220 (5)	−0.0005 (4)	0.0066 (4)	0.0005 (4)
P2	0.0181 (5)	0.0165 (5)	0.0213 (5)	0.0008 (4)	0.0054 (4)	0.0007 (4)
C1	0.0180 (17)	0.0085 (18)	0.0212 (17)	−0.0008 (15)	0.0006 (14)	0.0005 (13)
C2	0.0189 (18)	0.026 (2)	0.0263 (19)	−0.0043 (17)	−0.0025 (15)	−0.0006 (16)
C3	0.028 (2)	0.034 (3)	0.0250 (19)	−0.002 (2)	0.0005 (17)	0.0037 (17)
C4	0.037 (2)	0.043 (3)	0.029 (2)	0.004 (2)	−0.0054 (19)	0.0001 (19)
C5	0.052 (3)	0.068 (4)	0.030 (2)	0.011 (3)	0.000 (2)	0.007 (2)
N1	0.0237 (16)	0.0152 (17)	0.0211 (16)	−0.0026 (14)	0.0028 (14)	−0.0007 (13)
N2	0.026 (2)	0.026 (2)	0.040 (2)	0.0035 (18)	0.0115 (18)	0.0002 (17)
O1	0.0194 (13)	0.0244 (15)	0.0314 (13)	0.0026 (12)	0.0074 (11)	−0.0023 (11)
O2	0.0360 (15)	0.0154 (15)	0.0347 (14)	−0.0015 (13)	0.0132 (12)	−0.0007 (11)
O3	0.0297 (15)	0.0329 (18)	0.0216 (13)	0.0049 (14)	0.0019 (12)	−0.0045 (13)
O4	0.0315 (15)	0.0229 (16)	0.0265 (15)	−0.0089 (12)	0.0108 (12)	−0.0013 (12)
O5	0.0198 (12)	0.0329 (17)	0.0305 (14)	0.0030 (12)	0.0002 (11)	0.0063 (12)
O6	0.0317 (14)	0.0131 (14)	0.0278 (13)	−0.0043 (12)	0.0097 (11)	−0.0040 (10)

P1—O2	1.488 (3)	C4—C5	1.514 (5)
P1—O1	1.501 (2)	C4—H4A	0.9700
P1—O3	1.559 (3)	C4—H4B	0.9700
P1—C1	1.844 (3)	C5—H5A	0.9600
P2—O5	1.495 (2)	C5—H5B	0.9600
P2—O6	1.499 (2)	C5—H5C	0.9600
P2—O4	1.564 (3)	N1—H11N	1.05 (4)
P2—C1	1.858 (3)	N1—H12N	0.93 (5)
C1—N1	1.507 (4)	N1—H13N	0.93 (4)
C1—C2	1.541 (5)	N2—H21N	1.02 (6)
C2—C3	1.519 (5)	N2—H22N	0.86 (4)
C2—H2A	0.9700	N2—H23N	0.93 (6)
C2—H2B	0.9700	N2—H24N	0.92 (5)
C3—C4	1.511 (5)	O3—H3O	0.80 (5)
C3—H3A	0.9700	O4—H4O	0.82 (5)
C3—H3B	0.9700
O2—P1—O1	116.04 (14)	C2—C3—H3B	109.4
O2—P1—O3	110.56 (16)	H3A—C3—H3B	108.0
O1—P1—O3	109.44 (15)	C3—C4—C5	113.1 (4)
O2—P1—C1	107.97 (15)	C3—C4—H4A	109.0
O1—P1—C1	106.42 (15)	C5—C4—H4A	109.0
O3—P1—C1	105.83 (15)	C3—C4—H4B	109.0
O5—P2—O6	116.53 (15)	C5—C4—H4B	109.0
O5—P2—O4	106.61 (15)	H4A—C4—H4B	107.8
O6—P2—O4	112.60 (14)	C4—C5—H5A	109.5
O5—P2—C1	108.42 (14)	C4—C5—H5B	109.5
O6—P2—C1	108.33 (14)	H5A—C5—H5B	109.5
O4—P2—C1	103.51 (14)	C4—C5—H5C	109.5
N1—C1—C2	109.8 (3)	H5A—C5—H5C	109.5
N1—C1—P1	107.0 (2)	H5B—C5—H5C	109.5
C2—C1—P1	107.5 (2)	C1—N1—H11N	122 (2)
N1—C1—P2	107.4 (2)	C1—N1—H12N	110 (3)
C2—C1—P2	112.0 (2)	H11N—N1—H12N	101 (3)
P1—C1—P2	113.01 (17)	C1—N1—H13N	113 (2)
C3—C2—C1	118.3 (3)	H11N—N1—H13N	102 (3)
C3—C2—H2A	107.7	H12N—N1—H13N	107 (4)
C1—C2—H2A	107.7	H21N—N2—H22N	112 (4)
C3—C2—H2B	107.7	H21N—N2—H23N	107 (4)
C1—C2—H2B	107.7	H22N—N2—H23N	116 (4)
H2A—C2—H2B	107.1	H21N—N2—H24N	103 (4)
C4—C3—C2	111.4 (3)	H22N—N2—H24N	108 (4)
C4—C3—H3A	109.4	H23N—N2—H24N	109 (4)
C2—C3—H3A	109.4	P1—O3—H3O	120 (4)
C4—C3—H3B	109.4	P2—O4—H4O	116 (4)
O2—P1—C1—N1	170.1 (2)	O5—P2—C1—C2	162.9 (2)
O1—P1—C1—N1	−64.7 (2)	O6—P2—C1—C2	35.6 (3)
O3—P1—C1—N1	51.7 (3)	O4—P2—C1—C2	−84.2 (3)
O2—P1—C1—C2	−72.0 (3)	O5—P2—C1—P1	41.3 (2)
O1—P1—C1—C2	53.2 (3)	O6—P2—C1—P1	−86.01 (19)
O3—P1—C1—C2	169.6 (2)	O4—P2—C1—P1	154.25 (17)
O2—P1—C1—P2	52.1 (2)	N1—C1—C2—C3	−53.3 (4)
O1—P1—C1—P2	177.27 (16)	P1—C1—C2—C3	−169.4 (3)
O3—P1—C1—P2	−66.4 (2)	P2—C1—C2—C3	65.9 (4)
O5—P2—C1—N1	−76.5 (2)	C1—C2—C3—C4	−171.9 (3)
O6—P2—C1—N1	156.2 (2)	C2—C3—C4—C5	−172.9 (3)
O4—P2—C1—N1	36.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O2i	1.05 (4)	1.75 (4)	2.777 (4)	163 (3)
N1—H13N···O3ii	0.93 (4)	1.98 (4)	2.828 (4)	152 (3)
N1—H12N···O6i	0.93 (5)	2.08 (5)	2.879 (4)	143 (4)
O3—H3O···O5ii	0.80 (5)	1.72 (5)	2.519 (4)	174 (5)
O4—H4O···O6iii	0.82 (5)	1.75 (5)	2.566 (3)	173 (5)
N2—H22N···O1iv	0.86 (4)	1.95 (4)	2.781 (4)	161 (4)
N2—H21N···O2	1.02 (6)	1.77 (6)	2.769 (4)	165 (4)
N2—H23N···O5v	0.93 (6)	2.07 (6)	2.787 (5)	134 (5)
N2—H24N···O1vi	0.92 (5)	1.83 (5)	2.705 (5)	159 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O2i	1.05 (4)	1.75 (4)	2.777 (4)	163 (3)
N1—H13N⋯O3ii	0.93 (4)	1.98 (4)	2.828 (4)	152 (3)
N1—H12N⋯O6i	0.93 (5)	2.08 (5)	2.879 (4)	143 (4)
O3—H3O⋯O5ii	0.80 (5)	1.72 (5)	2.519 (4)	174 (5)
O4—H4O⋯O6iii	0.82 (5)	1.75 (5)	2.566 (3)	173 (5)
N2—H22N⋯O1iv	0.86 (4)	1.95 (4)	2.781 (4)	161 (4)
N2—H21N⋯O2	1.02 (6)	1.77 (6)	2.769 (4)	165 (4)
N2—H23N⋯O5v	0.93 (6)	2.07 (6)	2.787 (5)	134 (5)
N2—H24N⋯O1vi	0.92 (5)	1.83 (5)	2.705 (5)	159 (4)

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