Ammonium 1-ammonio-ethane-1,1-diylbis(hydrogenphospho-nate) dihydrate.

The title compound, NH(4) (+)·C(2)H(8)NO(6)P(2) (-)·2H(2)O, was obtained by the reaction between 1-amino-ethane-1,1-diyldiphospho-nic acid and ammonium hydroxide (1:1) in an aqueous solution. The asymmetric unit contains one anion with two H atoms transferred from the phospho-nic acid groups to the amino group of the anion and to an ammonia mol-ecule, giving an ammonium cation. The structure displays N-H⋯O and O-H⋯O hydrogen bonding, which creates a three-dimensional network.

Related literature

Diphospho­nic acids are efficient drugs for the prevention of calcification and the inhibition bone resorption (Tromelin et al., 1986 ▶, Matczak-Jon & Videnova-Adrabinska, 2005 ▶) and are used in the treatment of Pagets disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002 ▶). For related structures, see: Bruckmann et al. (1999 ▶); Olive et al. (2000 ▶); Coiro et al. (1989 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

NH4 +·C2H8NO6P2 −·2H2O

M = 258.11

Monoclinic,

a = 8.8922 (3) Å

b = 6.9390 (3) Å

c = 18.9576 (8) Å

β = 117.957 (2)°

V = 1033.23 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.45 mm−1

T = 173 (2) K

0.23 × 0.19 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.906, T max = 0.963

14152 measured reflections

2126 independent reflections

1710 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.074

S = 1.05

2126 reflections

180 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037045/rk2118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037045/rk2118Isup2.hkl

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

H4N+·C2H8NO6P2–·2H2O	F000 = 544
Mr = 258.11	Dx = 1.659 Mg m−3
Monoclinic, P21/c	Melting point: 511 K
Hall symbol: -P 2ybc	Mo Kα radiation λ = 0.71073 Å
a = 8.8922 (3) Å	Cell parameters from 4102 reflections
b = 6.9390 (3) Å	θ = 2.4–26.4º
c = 18.9576 (8) Å	µ = 0.45 mm−1
β = 117.957 (2)º	T = 173 (2) K
V = 1033.23 (7) Å3	Needle, colourless
Z = 4	0.23 × 0.19 × 0.09 mm

Bruker SMART APEXII CCD area-detector diffractometer	2126 independent reflections
Radiation source: Fine-focus sealed tube	1710 reflections with I > 2σ(I)
Monochromator: Graphite	Rint = 0.057
T = 173(2) K	θmax = 26.5º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.906, Tmax = 0.963	k = −8→8
14152 measured reflections	l = −23→23

Refinement on F2	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0326P)2 + 0.4969P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2126 reflections	Δρmax = 0.50 e Å−3
180 parameters	Δρmin = −0.42 e Å−3
2 restraints	Extinction correction: None
Primary atom site location: Direct

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 > 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	0.45684 (7)	0.78215 (7)	0.83905 (3)	0.00967 (14)
P2	0.75545 (7)	0.49061 (7)	0.90274 (3)	0.00998 (14)
C1	0.6842 (3)	0.7385 (3)	0.86839 (12)	0.0102 (4)
C2	0.7977 (3)	0.8851 (3)	0.93146 (13)	0.0151 (5)
H2A	0.9172	0.8604	0.9460	0.023*
H2B	0.7816	0.8730	0.9790	0.023*
H2C	0.7668	1.0157	0.9097	0.023*
N1	0.7091 (2)	0.7652 (3)	0.79539 (11)	0.0110 (4)
N2	0.4118 (3)	0.2940 (3)	0.92879 (12)	0.0156 (4)
O1	0.41873 (18)	0.6941 (2)	0.90108 (8)	0.0136 (3)
O2	0.42601 (18)	0.99358 (19)	0.82470 (8)	0.0138 (3)
O3	0.35764 (18)	0.6661 (2)	0.75879 (9)	0.0118 (3)
O4	0.61946 (17)	0.3541 (2)	0.84970 (8)	0.0127 (3)
O5	0.92422 (18)	0.4672 (2)	0.90282 (8)	0.0137 (3)
O6	0.7742 (2)	0.4803 (2)	0.98869 (9)	0.0142 (3)
H3O	0.366 (3)	0.724 (4)	0.7255 (16)	0.033 (8)*
H6O	0.873 (4)	0.492 (4)	1.0228 (18)	0.044 (9)*
H11N	0.653 (3)	0.669 (4)	0.7568 (15)	0.022 (6)*
H12N	0.822 (3)	0.761 (3)	0.8110 (14)	0.016 (6)*
H13N	0.672 (3)	0.878 (4)	0.7751 (14)	0.019 (7)*
H21N	0.303 (4)	0.265 (4)	0.9075 (17)	0.036 (8)*
H22N	0.453 (3)	0.222 (4)	0.9061 (16)	0.028 (8)*
H23N	0.418 (3)	0.422 (5)	0.9160 (17)	0.039 (8)*
H24N	0.463 (3)	0.275 (3)	0.9819 (15)	0.013 (6)*
O7	0.0562 (2)	0.2189 (3)	0.83327 (12)	0.0225 (4)
O8	−0.0558 (2)	0.3200 (3)	0.67241 (11)	0.0235 (4)
H71O	0.019 (4)	0.249 (4)	0.786 (2)	0.042 (9)*
H72O	0.004 (3)	0.278 (4)	0.8504 (16)	0.025 (8)*
H81O	−0.145 (3)	0.279 (4)	0.6455 (15)	0.034 (9)*
H82O	−0.064 (4)	0.431 (3)	0.668 (2)	0.063 (12)*

	U11	U22	U33	U12	U13	U23
P1	0.0092 (3)	0.0081 (3)	0.0112 (3)	0.0005 (2)	0.0044 (2)	0.0006 (2)
P2	0.0099 (3)	0.0091 (3)	0.0099 (3)	0.0006 (2)	0.0038 (2)	0.0007 (2)
C1	0.0101 (10)	0.0095 (10)	0.0110 (10)	−0.0006 (8)	0.0049 (8)	0.0002 (8)
C2	0.0152 (11)	0.0123 (11)	0.0167 (11)	−0.0028 (9)	0.0065 (9)	−0.0034 (9)
N1	0.0104 (10)	0.0097 (9)	0.0125 (9)	0.0006 (8)	0.0051 (8)	0.0019 (8)
N2	0.0169 (11)	0.0169 (11)	0.0144 (11)	−0.0005 (9)	0.0084 (9)	−0.0014 (8)
O1	0.0138 (8)	0.0141 (8)	0.0144 (8)	0.0004 (6)	0.0078 (6)	0.0025 (6)
O2	0.0155 (8)	0.0104 (7)	0.0152 (7)	0.0010 (6)	0.0069 (6)	0.0004 (6)
O3	0.0130 (8)	0.0103 (7)	0.0108 (7)	−0.0015 (6)	0.0044 (6)	0.0010 (6)
O4	0.0131 (8)	0.0100 (7)	0.0142 (7)	−0.0009 (6)	0.0058 (6)	−0.0007 (6)
O5	0.0117 (8)	0.0144 (8)	0.0141 (7)	0.0018 (6)	0.0052 (6)	−0.0001 (6)
O6	0.0107 (8)	0.0194 (8)	0.0114 (7)	0.0008 (6)	0.0042 (7)	0.0014 (6)
O7	0.0173 (9)	0.0237 (9)	0.0262 (10)	0.0030 (7)	0.0100 (8)	−0.0056 (8)
O8	0.0164 (10)	0.0216 (10)	0.0324 (10)	0.0009 (8)	0.0115 (9)	−0.0013 (8)

P1—O2	1.4939 (14)	N1—H11N	0.94 (3)
P1—O1	1.4982 (14)	N1—H12N	0.90 (3)
P1—O3	1.5760 (15)	N1—H13N	0.87 (3)
P1—C1	1.853 (2)	N2—H21N	0.88 (3)
P2—O4	1.4933 (15)	N2—H22N	0.85 (3)
P2—O5	1.5088 (15)	N2—H23N	0.93 (3)
P2—O6	1.5598 (15)	N2—H24N	0.90 (2)
P2—C1	1.843 (2)	O3—H3O	0.78 (3)
C1—N1	1.512 (3)	O6—H6O	0.81 (3)
C1—C2	1.534 (3)	O7—H71O	0.83 (3)
C2—H2A	0.9800	O7—H72O	0.80 (3)
C2—H2B	0.9800	O8—H81O	0.768 (17)
C2—H2C	0.9800	O8—H82O	0.775 (18)
O2—P1—O1	116.99 (8)	H2A—C2—H2B	109.5
O2—P1—O3	110.75 (8)	C1—C2—H2C	109.5
O1—P1—O3	108.61 (9)	H2A—C2—H2C	109.5
O2—P1—C1	107.25 (9)	H2B—C2—H2C	109.5
O1—P1—C1	108.31 (9)	C1—N1—H11N	111.7 (15)
O3—P1—C1	104.13 (9)	C1—N1—H12N	108.2 (15)
O4—P2—O5	115.05 (8)	H11N—N1—H12N	110 (2)
O4—P2—O6	109.31 (8)	C1—N1—H13N	109.0 (15)
O5—P2—O6	112.01 (8)	H11N—N1—H13N	110 (2)
O4—P2—C1	108.55 (9)	H12N—N1—H13N	108 (2)
O5—P2—C1	106.13 (9)	H21N—N2—H22N	106 (3)
O6—P2—C1	105.23 (9)	H21N—N2—H23N	107 (2)
N1—C1—C2	107.87 (16)	H22N—N2—H23N	110 (3)
N1—C1—P2	105.33 (13)	H21N—N2—H24N	110 (2)
C2—C1—P2	110.63 (14)	H22N—N2—H24N	112 (2)
N1—C1—P1	108.22 (14)	H23N—N2—H24N	112 (2)
C2—C1—P1	110.60 (14)	P1—O3—H3O	107 (2)
P2—C1—P1	113.86 (10)	P2—O6—H6O	112 (2)
C1—C2—H2A	109.5	H71O—O7—H72O	108 (3)
C1—C2—H2B	109.5	H81O—O8—H82O	106 (3)
O4—P2—C1—N1	−77.19 (14)	O2—P1—C1—N1	−71.57 (14)
O5—P2—C1—N1	47.00 (15)	O1—P1—C1—N1	161.33 (13)
O6—P2—C1—N1	165.88 (13)	O3—P1—C1—N1	45.86 (15)
O4—P2—C1—C2	166.50 (13)	O2—P1—C1—C2	46.40 (16)
O5—P2—C1—C2	−69.31 (15)	O1—P1—C1—C2	−80.71 (15)
O6—P2—C1—C2	49.58 (16)	O3—P1—C1—C2	163.82 (14)
O4—P2—C1—P1	41.22 (13)	O2—P1—C1—P2	171.69 (10)
O5—P2—C1—P1	165.41 (10)	O1—P1—C1—P2	44.58 (13)
O6—P2—C1—P1	−75.71 (12)	O3—P1—C1—P2	−70.88 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4i	0.78 (3)	1.74 (3)	2.523 (2)	179 (3)
O6—H6O···O5ii	0.81 (3)	1.71 (3)	2.526 (2)	175 (3)
N1—H11N···O2iii	0.94 (3)	1.83 (3)	2.759 (2)	169 (2)
N1—H12N···O8i	0.90 (3)	2.00 (3)	2.873 (3)	164 (2)
N1—H13N···O3i	0.87 (3)	2.08 (3)	2.928 (2)	167 (2)
N2—H21N···O7	0.88 (3)	2.00 (3)	2.860 (3)	165 (3)
N2—H22N···O2iv	0.85 (3)	2.14 (3)	2.914 (3)	151 (2)
N2—H23N···O1	0.93 (3)	1.91 (3)	2.832 (3)	171 (3)
N2—H24N···O1v	0.90 (2)	1.97 (3)	2.850 (3)	165 (2)
O7—H71O···O8	0.83 (3)	1.99 (3)	2.817 (3)	177 (3)
O7—H72O···O5vi	0.80 (3)	1.97 (3)	2.745 (2)	165 (3)
O8—H81O···O1vii	0.768 (17)	2.244 (19)	2.984 (2)	162 (3)
O8—H82O···O7viii	0.775 (18)	1.999 (19)	2.770 (3)	173 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O4i	0.78 (3)	1.74 (3)	2.523 (2)	179 (3)
O6—H6O⋯O5ii	0.81 (3)	1.71 (3)	2.526 (2)	175 (3)
N1—H11N⋯O2iii	0.94 (3)	1.83 (3)	2.759 (2)	169 (2)
N1—H12N⋯O8i	0.90 (3)	2.00 (3)	2.873 (3)	164 (2)
N1—H13N⋯O3i	0.87 (3)	2.08 (3)	2.928 (2)	167 (2)
N2—H21N⋯O7	0.88 (3)	2.00 (3)	2.860 (3)	165 (3)
N2—H22N⋯O2iv	0.85 (3)	2.14 (3)	2.914 (3)	151 (2)
N2—H23N⋯O1	0.93 (3)	1.91 (3)	2.832 (3)	171 (3)
N2—H24N⋯O1v	0.90 (2)	1.97 (3)	2.850 (3)	165 (2)
O7—H71O⋯O8	0.83 (3)	1.99 (3)	2.817 (3)	177 (3)
O7—H72O⋯O5vi	0.80 (3)	1.97 (3)	2.745 (2)	165 (3)
O8—H81O⋯O1vii	0.768 (17)	2.244 (19)	2.984 (2)	162 (3)
O8—H82O⋯O7viii	0.775 (18)	1.999 (19)	2.770 (3)	173 (4)

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