Oxonium ammonio-(cyclo-prop-yl)methyl-enebis(hydrogenphospho-nate) monohydrate.

The title compound, H(3)O(+)·C(4)H(10)NO(6)P(2) (-)·H(2)O, was obtained from the reaction of cyclo-propane-carbonitrile with PCl(3), followed by dropwise addition of water. The asymmetric unit comprises an oxonium cation, a zwitterionic monoanion containing a positively charged ammonium group and two negatively charged phospho-nic acid residues and a water mol-ecule of crystallization. The hydroxonium cation and water mol-ecule are hydrogen bonded to the anion and further N-H⋯O and O-H⋯O bonds create 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 bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

H3O+·C4H10NO6P2 −·H2O

M = 267.11

Monoclinic,

a = 12.5054 (8) Å

b = 5.6169 (4) Å

c = 14.3296 (8) Å

β = 94.973 (4)°

V = 1002.74 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.46 mm−1

T = 100 (2) K

0.56 × 0.07 × 0.06 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.782, T max = 0.973

14938 measured reflections

2076 independent reflections

1411 reflections with I > 2σ(I)

R int = 0.117

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.111

S = 1.01

2076 reflections

166 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.48 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/S1600536808037094/fj2162sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037094/fj2162Isup2.hkl

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

H3O+·C4H10NO6P2–·H2O	F000 = 560
Mr = 267.11	Dx = 1.769 Mg m−3
Monoclinic, P21/n	Melting point: 493 K
Hall symbol: -P 2yn	Mo Kα radiation λ = 0.71073 Å
a = 12.5054 (8) Å	Cell parameters from 1935 reflections
b = 5.6169 (4) Å	θ = 2.3–26.4º
c = 14.3296 (8) Å	µ = 0.46 mm−1
β = 94.973 (4)º	T = 100 (2) K
V = 1002.74 (11) Å3	Needle, colourless
Z = 4	0.56 × 0.07 × 0.06 mm

Bruker SMART APEXII CCD diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	1411 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.117
T = 100(2) K	θmax = 26.6º
φ and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	h = −15→15
Tmin = 0.782, Tmax = 0.973	k = −7→7
14938 measured reflections	l = −17→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0546P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2076 reflections	Δρmax = 0.64 e Å−3
166 parameters	Δρmin = −0.48 e Å−3
6 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
P1	0.39124 (6)	1.00254 (15)	0.88098 (5)	0.0097 (2)
P2	0.42829 (7)	0.97159 (15)	0.67003 (6)	0.0107 (2)
C1	0.4541 (3)	0.8406 (5)	0.7872 (2)	0.0098 (7)
C2	0.5754 (3)	0.8349 (6)	0.8120 (2)	0.0122 (7)
H2A	0.6098	0.9951	0.8090	0.015*
C3	0.6295 (3)	0.6770 (6)	0.8865 (2)	0.0161 (8)
H3A	0.6897	0.7449	0.9275	0.019*
H3B	0.5843	0.5615	0.9175	0.019*
C4	0.6466 (3)	0.6358 (7)	0.7858 (2)	0.0186 (8)
H4A	0.6120	0.4947	0.7546	0.022*
H4B	0.7174	0.6780	0.7646	0.022*
N1	0.4080 (2)	0.5913 (5)	0.7841 (2)	0.0098 (6)
H1A	0.436 (3)	0.499 (6)	0.743 (3)	0.015*
H1B	0.341 (2)	0.588 (6)	0.778 (2)	0.015*
H1C	0.427 (3)	0.513 (6)	0.835 (3)	0.015*
O1	0.46292 (18)	1.2100 (4)	0.91003 (15)	0.0121 (5)
O2	0.38814 (18)	0.8132 (4)	0.95991 (15)	0.0121 (5)
O3	0.27864 (18)	1.0669 (4)	0.84573 (15)	0.0138 (5)
O4	0.46954 (18)	1.2202 (4)	0.67350 (15)	0.0130 (5)
O5	0.48317 (18)	0.8051 (4)	0.60598 (15)	0.0137 (5)
O6	0.30505 (19)	0.9707 (4)	0.64379 (16)	0.0133 (5)
O7	0.3973 (2)	0.6970 (5)	0.45230 (18)	0.0263 (7)
H2O	0.434 (3)	0.810 (7)	1.000 (2)	0.032*
H6O	0.282 (3)	0.835 (8)	0.643 (3)	0.032*
H71O	0.438 (3)	0.709 (7)	0.411 (2)	0.032*
H72O	0.378 (3)	0.558 (5)	0.448 (3)	0.032*
H73O	0.432 (3)	0.742 (7)	0.522 (3)	0.032*
O8	0.1988 (2)	0.7952 (5)	1.0595 (2)	0.0285 (7)
H81O	0.163 (3)	0.679 (6)	1.066 (3)	0.034*
H82O	0.247 (3)	0.754 (7)	1.028 (3)	0.034*

	U11	U22	U33	U12	U13	U23
P1	0.0087 (5)	0.0105 (4)	0.0095 (4)	0.0000 (4)	−0.0012 (3)	−0.0002 (3)
P2	0.0116 (5)	0.0105 (5)	0.0096 (4)	−0.0001 (4)	−0.0008 (3)	−0.0003 (3)
C1	0.0068 (16)	0.0092 (17)	0.0126 (16)	−0.0009 (13)	−0.0029 (13)	0.0001 (13)
C2	0.0071 (17)	0.0149 (18)	0.0143 (17)	−0.0033 (14)	0.0004 (13)	−0.0038 (13)
C3	0.0088 (18)	0.020 (2)	0.0183 (18)	−0.0005 (15)	−0.0028 (14)	0.0006 (15)
C4	0.0114 (19)	0.024 (2)	0.0200 (19)	0.0026 (15)	0.0017 (15)	−0.0064 (15)
N1	0.0075 (15)	0.0090 (14)	0.0127 (14)	0.0008 (12)	0.0004 (12)	0.0001 (12)
O1	0.0133 (12)	0.0111 (12)	0.0112 (11)	0.0008 (10)	−0.0018 (9)	−0.0009 (9)
O2	0.0114 (13)	0.0148 (12)	0.0098 (11)	−0.0003 (10)	−0.0017 (9)	0.0006 (10)
O3	0.0115 (12)	0.0161 (13)	0.0136 (12)	0.0022 (10)	−0.0010 (9)	−0.0030 (9)
O4	0.0149 (13)	0.0148 (13)	0.0094 (11)	−0.0003 (10)	0.0011 (9)	0.0009 (9)
O5	0.0134 (12)	0.0140 (12)	0.0133 (12)	0.0033 (10)	−0.0011 (9)	−0.0012 (10)
O6	0.0135 (13)	0.0112 (12)	0.0145 (11)	−0.0009 (10)	−0.0028 (9)	−0.0004 (10)
O7	0.0203 (16)	0.0480 (18)	0.0108 (13)	−0.0117 (14)	0.0024 (11)	−0.0047 (14)
O8	0.0180 (16)	0.0335 (17)	0.0356 (17)	0.0026 (13)	0.0110 (13)	0.0120 (14)

P1—O3	1.498 (2)	C3—H3B	0.9900
P1—O1	1.507 (2)	C4—H4A	0.9900
P1—O2	1.555 (2)	C4—H4B	0.9900
P1—C1	1.853 (3)	N1—H1A	0.88 (4)
P2—O4	1.488 (2)	N1—H1B	0.84 (3)
P2—O5	1.516 (2)	N1—H1C	0.86 (4)
P2—O6	1.554 (2)	O2—H2O	0.78 (3)
P2—C1	1.835 (3)	O5—H73O	1.35 (4)
C1—N1	1.514 (4)	O6—H6O	0.81 (4)
C1—C2	1.528 (4)	O7—H71O	0.81 (2)
C2—C4	1.498 (5)	O7—H72O	0.82 (3)
C2—C3	1.503 (5)	O7—H73O	1.09 (4)
C2—H2A	1.0000	O8—H81O	0.80 (3)
C3—C4	1.496 (5)	O8—H82O	0.82 (3)
C3—H3A	0.9900
O3—P1—O1	115.19 (13)	C4—C3—H3A	117.8
O3—P1—O2	109.16 (13)	C2—C3—H3A	117.8
O1—P1—O2	112.32 (12)	C4—C3—H3B	117.8
O3—P1—C1	108.60 (13)	C2—C3—H3B	117.8
O1—P1—C1	107.49 (14)	H3A—C3—H3B	114.9
O2—P1—C1	103.34 (14)	C3—C4—C2	60.3 (2)
O4—P2—O5	115.18 (13)	C3—C4—H4A	117.7
O4—P2—O6	110.17 (13)	C2—C4—H4A	117.7
O5—P2—O6	110.06 (13)	C3—C4—H4B	117.7
O4—P2—C1	108.21 (13)	C2—C4—H4B	117.7
O5—P2—C1	104.70 (13)	H4A—C4—H4B	114.9
O6—P2—C1	108.16 (14)	C1—N1—H1A	113 (2)
N1—C1—C2	110.8 (3)	C1—N1—H1B	113 (3)
N1—C1—P2	107.9 (2)	H1A—N1—H1B	112 (3)
C2—C1—P2	108.3 (2)	C1—N1—H1C	111 (2)
N1—C1—P1	106.9 (2)	H1A—N1—H1C	100 (3)
C2—C1—P1	108.4 (2)	H1B—N1—H1C	106 (3)
P2—C1—P1	114.51 (17)	P1—O2—H2O	119 (3)
C4—C2—C3	59.8 (2)	P2—O5—H73O	119.6 (16)
C4—C2—C1	123.8 (3)	P2—O6—H6O	110 (3)
C3—C2—C1	123.7 (3)	H71O—O7—H72O	103 (4)
C4—C2—H2A	113.2	H71O—O7—H73O	115 (4)
C3—C2—H2A	113.2	H72O—O7—H73O	112 (4)
C1—C2—H2A	113.2	H81O—O8—H82O	106 (4)
C4—C3—C2	59.9 (2)
O4—P2—C1—N1	177.8 (2)	O1—P1—C1—C2	39.6 (2)
O5—P2—C1—N1	−58.9 (2)	O2—P1—C1—C2	−79.4 (2)
O6—P2—C1—N1	58.4 (2)	O3—P1—C1—P2	43.8 (2)
O4—P2—C1—C2	−62.2 (2)	O1—P1—C1—P2	−81.46 (18)
O5—P2—C1—C2	61.1 (2)	O2—P1—C1—P2	159.60 (16)
O6—P2—C1—C2	178.4 (2)	N1—C1—C2—C4	31.4 (4)
O4—P2—C1—P1	58.9 (2)	P2—C1—C2—C4	−86.8 (3)
O5—P2—C1—P1	−177.81 (16)	P1—C1—C2—C4	148.4 (3)
O6—P2—C1—P1	−60.5 (2)	N1—C1—C2—C3	−42.3 (4)
O3—P1—C1—N1	−75.7 (2)	P2—C1—C2—C3	−160.5 (3)
O1—P1—C1—N1	159.06 (19)	P1—C1—C2—C3	74.7 (3)
O2—P1—C1—N1	40.1 (2)	C1—C2—C3—C4	112.7 (4)
O3—P1—C1—C2	164.8 (2)	C1—C2—C4—C3	−112.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4i	0.88 (4)	1.92 (4)	2.767 (4)	161 (3)
N1—H1B···O3ii	0.84 (3)	2.23 (3)	2.859 (4)	133 (3)
N1—H1B···O6ii	0.84 (3)	2.32 (3)	3.017 (4)	142 (3)
N1—H1C···O1i	0.86 (4)	2.05 (4)	2.846 (4)	154 (3)
O2—H2O···O1iii	0.78 (3)	1.75 (3)	2.521 (3)	178 (5)
O7—H73O···O5	1.09 (4)	1.35 (4)	2.441 (3)	175 (3)
O6—H6O···O3ii	0.81 (4)	1.70 (4)	2.508 (3)	171 (4)
O7—H71O···O4iv	0.81 (2)	1.79 (3)	2.600 (3)	171 (4)
O7—H72O···O8ii	0.82 (3)	1.76 (3)	2.555 (4)	164 (4)
O8—H82O···O2	0.82 (3)	2.12 (3)	2.871 (3)	153 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.88 (4)	1.92 (4)	2.767 (4)	161 (3)
N1—H1B⋯O3ii	0.84 (3)	2.23 (3)	2.859 (4)	133 (3)
N1—H1B⋯O6ii	0.84 (3)	2.32 (3)	3.017 (4)	142 (3)
N1—H1C⋯O1i	0.86 (4)	2.05 (4)	2.846 (4)	154 (3)
O2—H2O⋯O1iii	0.78 (3)	1.75 (3)	2.521 (3)	178 (5)
O6—H6O⋯O3ii	0.81 (4)	1.70 (4)	2.508 (3)	171 (4)
O7—H71O⋯O4iv	0.81 (2)	1.79 (3)	2.600 (3)	171 (4)
O7—H72O⋯O8ii	0.82 (3)	1.76 (3)	2.555 (4)	164 (4)
O7—H73O⋯O5	1.09 (4)	1.35 (4)	2.441 (3)	175 (3)
O8—H82O⋯O2	0.82 (3)	2.12 (3)	2.871 (3)	153 (4)

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