Oxonium ammonio­(cyclo­prop­yl)methyl­enebis(hydrogenphospho­nate) monohydrate

The title compound, H₃O⁺·C₄H₁₀NO₆P₂⁻·H₂O, was obtained from the reaction of cyclo­propane­carbonitrile with PCl₃, 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 phospho­nic acid residues and a water mol­ecule of crystallization. The hydroxonium cation and water mol­ecule are hydrogen bonded to the anion and further N—H...O and O—H...O bonds create a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.111
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT772_ALERT_2_A Suspect O-H Bond in CIF:   O5     --  H73O    ..       1.35 Ang.

Author Response: The strong H-bond between O5 and O7 was treated as an equilibrium between hydroxonium ion and water molecule. The position of the H73o atom is freely refined.

Alert level B
PLAT355_ALERT_3_B Long    O-H Bond (0.82A)   O7     -   H73O   ...       1.08 Ang.

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.117
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........         O7
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The organic diphosphonic acids are potentially very powerful chelating agents used in metal extractions and are tested by the pharmaceutical industry for use as efficient drugs preventing calcification and inhibiting bone resorption (Tromelin et al., 1986, Matczak-Jon & Videnova-Adrabinska, 2005). Diphosphonic acids are used in the treatment of Paget disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002). The asymmetric unit of titled compound (Fig. 1) contains one molecule which exists as zwitterions with the proton transferred from one of the phosphonic group to the nitrogen atom. In the crystal structure of the compound the phosphorus atom displays a slightly distorted tetrahedral geometry provided by three oxygen atoms and one carbon atom. Bond lengths and angles have normal values (Allen et al., 1987). The asymmetric unit contains one hydroxonium ion and one water molecule. The structure is stabilized by three-dimensional intramolecular O—H···O and N—H···O hydrogen bonds network (Table 1).

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).

S2. Experimental

The preparation of oxonium ammonio(cyclopropyl)methylenebis(hydrogenphosphonate) hydrate was provided as follows. Dry hydrogen chloride at about 278 K was brought into contact with the surface of a mixture of cyclopropanecarbonitrile (73.7 ml, 1 mol) and PCl₃ (87.4 ml, 1 mol) while stirring the mixture drop-wise addition of water (54 ml, 3 mol) was made in the molar ratio 1:1:3. After an a hour the solution becomes cloudy and sets. After cooling the product it was dissolved in water and separated by addition of acetone. The saturated solution was left at room temperature. Colourless crystals of the title compound were obtained after 1 week.

S3. Refinement

H atoms bonded to O and N atoms were located in a difference map. Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.99 Å for CH₂ [U_iso(H) = 1.2Ueq(N)] and C—H = 1.00 Å for CH [U_iso(H) = 1.2Ueq(C)]. The strong H-bond between O5 and O7 was treated as an equilibrium between hydroxonium ion and water molecule. The position of the H atom was freely refined.

Computing details

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

Figures

	Fig. 1. The asymmetric unit of title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms.
	Fig. 2. Crystal packing of title compound, projection along b axis. Dashed lines indicate hydrogen bonds.

Oxonium ammonio(cyclopropyl)methylenebis(hydrogenphosphonate) monohydrate

Crystal data

H3O^+·C4H10NO6P2^−·H2O	F(000) = 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 = 2.3–26.4°
c = 14.3296 (8) Å	µ = 0.46 mm^−1
β = 94.973 (4)°	T = 100 K
V = 1002.74 (11) Å^3	Needle, colourless
Z = 4	0.56 × 0.07 × 0.06 mm

Data collection

Bruker SMART APEXII CCD diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	1411 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.117
ϕ and ω scans	θmax = 26.6°, θmin = 2.1°
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0546P)^2] where P = (Fo^2 + 2Fc^2)/3
2076 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.64 e Å^−3
6 restraints	Δρmin = −0.48 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^i	0.88 (4)	1.92 (4)	2.767 (4)	161 (3)
N1—H1B···O3^ii	0.84 (3)	2.23 (3)	2.859 (4)	133 (3)
N1—H1B···O6^ii	0.84 (3)	2.32 (3)	3.017 (4)	142 (3)
N1—H1C···O1^i	0.86 (4)	2.05 (4)	2.846 (4)	154 (3)
O2—H2O···O1^iii	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···O3^ii	0.81 (4)	1.70 (4)	2.508 (3)	171 (4)
O7—H71O···O4^iv	0.81 (2)	1.79 (3)	2.600 (3)	171 (4)
O7—H72O···O8^ii	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)

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y+2, −z+1.