Hydroxonium 1-ammonio-ethane-1,1-diyl-diphospho-nate.

The title complex, H(3)O(+)·NH(3)C(CH(3))(PO(3)H)(2) (-), contains a hydroxonium ion and an NH(3)C(CH(3))(PO(3)H)(2) (-) anion. The three H atoms of H(3)O(+) form a pseudo-tetra-hedron by being distributed over four positions with occupation factors of 0.75. Multiple N-H⋯O and O-H⋯O hydrogen bonds in the crystal structure form an intricate three-dimensional supra-molecular network.

Related literature

For the structures of organophospho­nates, see: Clearfield (2002 ▶); Finn et al. (2003 ▶). For similar bis­phospho­nates, see: Fernández et al. (2003 ▶); For complexes with 1-amino­ethyl­idene-1,1-diphospho­nic acid, see: Yin et al. (2005 ▶); Ding et al. (2006 ▶); Li et al. (2008 ▶). For the synthesis, see: Chai et al. (1980 ▶).

Experimental

Crystal data

H3O+·C2H8N2O6P2 −

M = 223.06

Monoclinic,

a = 7.3372 (6) Å

b = 10.6553 (8) Å

c = 10.6128 (8) Å

β = 97.705 (1)°

V = 822.22 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.53 mm−1

T = 293 K

0.36 × 0.27 × 0.18 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.831, T max = 0.910

5340 measured reflections

1972 independent reflections

1837 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.097

S = 1.10

1972 reflections

136 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.61 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008770/rn2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008770/rn2053Isup2.hkl

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

H3O+·C2H8N2O6P2−	F(000) = 464
Mr = 223.06	Dx = 1.802 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3640 reflections
a = 7.3372 (6) Å	θ = 2.7–29.8°
b = 10.6553 (8) Å	µ = 0.53 mm−1
c = 10.6128 (8) Å	T = 293 K
β = 97.705 (1)°	Plate, colorless
V = 822.22 (11) Å3	0.36 × 0.27 × 0.18 mm
Z = 4

Bruker SMART 4K CCD area-detector diffractometer	1837 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scans	θmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.831, Tmax = 0.910	k = −9→14
5340 measured reflections	l = −13→11
1972 independent reflections

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0481P)2 + 0.8715P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
1972 reflections	Δρmax = 0.40 e Å−3
136 parameters	Δρmin = −0.61 e Å−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (2)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.9948 (2)	0.56114 (16)	0.24265 (16)	0.0131 (3)
C2	0.9672 (3)	0.62357 (19)	0.36861 (18)	0.0209 (4)
H2A	1.0741	0.6722	0.3993	0.031*
H2B	0.9488	0.5602	0.4299	0.031*
H2C	0.8615	0.6774	0.3556	0.031*
N1	1.0165 (2)	0.66564 (14)	0.14939 (14)	0.0152 (3)
H1A	0.9151	0.7124	0.1391	0.023*
H1B	1.0347	0.6329	0.0750	0.023*
H1C	1.1124	0.7131	0.1792	0.023*
O1W	0.4462 (2)	0.70203 (18)	0.52441 (17)	0.0363 (4)
O1	0.63612 (19)	0.57626 (13)	0.17124 (14)	0.0209 (3)
O2	0.75556 (18)	0.37252 (13)	0.27913 (13)	0.0208 (3)
O3	0.80235 (18)	0.42568 (13)	0.05066 (12)	0.0208 (3)
O4	1.23166 (19)	0.41015 (14)	0.13108 (14)	0.0209 (3)
O5	1.20389 (18)	0.37077 (13)	0.35944 (13)	0.0204 (3)
O6	1.36080 (17)	0.56986 (13)	0.29441 (13)	0.0199 (3)
P1	0.78594 (6)	0.47061 (4)	0.18354 (4)	0.01339 (15)
P2	1.21301 (6)	0.47175 (4)	0.26319 (4)	0.01358 (15)
H3	1.227 (5)	0.456 (3)	0.079 (3)	0.051 (10)*
H4	0.562 (5)	0.568 (3)	0.208 (3)	0.049 (10)*
H5	0.5658 (17)	0.698 (3)	0.554 (3)	0.018 (7)*	0.75
H6	0.386 (4)	0.673 (3)	0.587 (2)	0.018 (7)*	0.75
H7	0.426 (4)	0.663 (2)	0.4485 (15)	0.013 (7)*	0.75
H8	0.422 (5)	0.7827 (13)	0.509 (4)	0.038 (10)*	0.75

	U11	U22	U33	U12	U13	U23
C1	0.0145 (7)	0.0114 (7)	0.0138 (7)	−0.0006 (6)	0.0032 (6)	0.0007 (6)
C2	0.0254 (9)	0.0214 (9)	0.0164 (8)	0.0030 (7)	0.0042 (7)	−0.0040 (7)
N1	0.0165 (7)	0.0123 (7)	0.0173 (7)	−0.0002 (5)	0.0040 (5)	0.0017 (5)
O1W	0.0356 (9)	0.0393 (10)	0.0331 (9)	0.0008 (8)	0.0010 (7)	−0.0001 (7)
O1	0.0155 (6)	0.0200 (7)	0.0283 (7)	0.0043 (5)	0.0073 (5)	0.0065 (5)
O2	0.0210 (6)	0.0164 (6)	0.0261 (7)	0.0001 (5)	0.0068 (5)	0.0073 (5)
O3	0.0217 (6)	0.0236 (7)	0.0169 (6)	−0.0005 (5)	0.0022 (5)	−0.0037 (5)
O4	0.0248 (7)	0.0184 (7)	0.0201 (7)	0.0019 (5)	0.0051 (5)	−0.0036 (5)
O5	0.0191 (6)	0.0189 (6)	0.0227 (7)	0.0010 (5)	0.0005 (5)	0.0066 (5)
O6	0.0148 (6)	0.0193 (6)	0.0259 (7)	−0.0038 (5)	0.0037 (5)	−0.0049 (5)
P1	0.0127 (2)	0.0124 (2)	0.0152 (2)	−0.00029 (15)	0.00251 (16)	0.00126 (15)
P2	0.0123 (2)	0.0125 (2)	0.0158 (2)	0.00017 (15)	0.00167 (16)	0.00006 (15)

C1—N1	1.512 (2)	O1W—H6	0.896 (10)
C1—C2	1.531 (2)	O1W—H7	0.900 (10)
C1—P1	1.8479 (17)	O1W—H8	0.888 (10)
C1—P2	1.8505 (17)	O1—P1	1.5666 (14)
C2—H2A	0.9600	O1—H4	0.71 (3)
C2—H2B	0.9600	O2—P1	1.4940 (13)
C2—H2C	0.9600	O3—P1	1.5093 (13)
N1—H1A	0.8900	O4—P2	1.5706 (14)
N1—H1B	0.8900	O4—H3	0.73 (4)
N1—H1C	0.8900	O5—P2	1.4914 (13)
O1W—H5	0.893 (10)	O6—P2	1.5106 (13)
N1—C1—C2	106.82 (14)	H5—O1W—H7	109 (3)
N1—C1—P1	108.51 (11)	H6—O1W—H7	118 (3)
C2—C1—P1	108.82 (12)	H5—O1W—H8	106 (3)
N1—C1—P2	106.91 (11)	H6—O1W—H8	111 (3)
C2—C1—P2	109.54 (12)	H7—O1W—H8	106 (3)
P1—C1—P2	115.87 (9)	P1—O1—H4	116 (3)
C1—C2—H2A	109.5	P2—O4—H3	113 (3)
C1—C2—H2B	109.5	O2—P1—O3	116.77 (8)
H2A—C2—H2B	109.5	O2—P1—O1	113.10 (8)
C1—C2—H2C	109.5	O3—P1—O1	107.04 (8)
H2A—C2—H2C	109.5	O2—P1—C1	109.10 (8)
H2B—C2—H2C	109.5	O3—P1—C1	108.44 (8)
C1—N1—H1A	109.5	O1—P1—C1	101.18 (8)
C1—N1—H1B	109.5	O5—P2—O6	116.47 (8)
H1A—N1—H1B	109.5	O5—P2—O4	109.10 (8)
C1—N1—H1C	109.5	O6—P2—O4	109.82 (8)
H1A—N1—H1C	109.5	O5—P2—C1	109.54 (8)
H1B—N1—H1C	109.5	O6—P2—C1	104.71 (8)
H5—O1W—H6	107 (3)	O4—P2—C1	106.71 (8)
N1—C1—P1—O2	−176.13 (11)	N1—C1—P2—O5	177.18 (11)
C2—C1—P1—O2	−60.25 (14)	C2—C1—P2—O5	61.79 (14)
P2—C1—P1—O2	63.66 (11)	P1—C1—P2—O5	−61.75 (11)
N1—C1—P1—O3	55.70 (13)	N1—C1—P2—O6	51.57 (12)
C2—C1—P1—O3	171.58 (12)	C2—C1—P2—O6	−63.82 (13)
P2—C1—P1—O3	−64.51 (11)	P1—C1—P2—O6	172.64 (9)
N1—C1—P1—O1	−56.68 (12)	N1—C1—P2—O4	−64.85 (12)
C2—C1—P1—O1	59.20 (13)	C2—C1—P2—O4	179.76 (12)
P2—C1—P1—O1	−176.89 (9)	P1—C1—P2—O4	56.22 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2i	0.89	1.98	2.809 (2)	155
N1—H1A···O5i	0.89	1.90	2.713 (2)	151
N1—H1B···O3ii	0.89	2.01	2.824 (2)	152
O4—H3···O3ii	0.73 (4)	1.86 (4)	2.591 (2)	176 (4)
O1—H4···O6iii	0.71 (3)	1.84 (3)	2.550 (2)	172 (4)
O1W—H5···O5iv	0.89 (1)	1.95 (2)	2.804 (2)	159 (3)
O1W—H8···O1v	0.89 (1)	2.64 (4)	3.061 (2)	110 (3)
O1W—H8···O3vi	0.89 (1)	2.27 (2)	3.041 (2)	145 (3)
O1W—H6···O2vii	0.90 (1)	1.94 (1)	2.828 (2)	175 (3)
O1W—H7···O6iii	0.90 (1)	1.92 (1)	2.815 (2)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2i	0.89	1.98	2.809 (2)	155
N1—H1A⋯O5i	0.89	1.90	2.713 (2)	151
N1—H1B⋯O3ii	0.89	2.01	2.824 (2)	152
O4—H3⋯O3ii	0.73 (4)	1.86 (4)	2.591 (2)	176 (4)
O1—H4⋯O6iii	0.71 (3)	1.84 (3)	2.550 (2)	172 (4)
O1W—H5⋯O5iv	0.893 (10)	1.954 (15)	2.804 (2)	159 (3)
O1W—H8⋯O1v	0.888 (10)	2.64 (4)	3.061 (2)	110 (3)
O1W—H8⋯O3vi	0.888 (10)	2.27 (2)	3.041 (2)	145 (3)
O1W—H6⋯O2vii	0.896 (10)	1.935 (11)	2.828 (2)	175 (3)
O1W—H7⋯O6iii	0.900 (10)	1.920 (11)	2.815 (2)	173 (3)

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