Two polymorphs of bis­(2-carbamoylguanidinium) fluoro­phospho­nate dihydrate

Two polymorphs of bis­(2-carbamoylguanidinium) fluoro­phos­phon­ate dihydrate, 2C₂H₇N₄O⁺·FO₃P^2-·2H₂O, are pre­sented. Polymorph (I), crystallizing in the space group Pnma, is slightly less densely packed than polymorph (II), which crystallizes in Pbca. In (I), the fluoro­phosphon­ate anion is situated on a crystallographic mirror plane and the O atom of the water mol­ecule is disordered over two positions, in contrast with its H atoms. The hydrogen-bond patterns in both poly­morphs share similar features. There are O-H...O and N-H...O hydrogen bonds in both structures. The water mol­ecules donate their H atoms to the O atoms of the fluoro­phosphon­ates exclusively. The water mol­ecules and the fluoro­phosphon­ates participate in the formation of R⁴₄(10) graph-set motifs. These motifs extend along the a axis in each structure. The water mol­ecules are also acceptors of either one [in (I) and (II)] or two [in (II)] N-H...O hydrogen bonds. The water mol­ecules are significant building elements in the formation of a three-dimensional hydrogen-bond network in both structures. Despite these similarities, there are substantial differences between the hydrogen-bond networks of (I) and (II). The N-H...O and O-H...O hydrogen bonds in (I) are stronger and weaker, respectively, than those in (II). Moreover, in (I), the shortest N-H...O hydrogen bonds are shorter than the shortest O-H...O hydrogen bonds, which is an unusual feature. The properties of the hydrogen-bond network in (II) can be related to an unusually long P-O bond length for an unhydrogenated fluoro­phosphon­ate anion that is present in this structure. In both structures, the N-H...F inter­actions are far weaker than the N-H...O hydrogen bonds. It follows from the structure analysis that (II) seems to be thermodynamically more stable than (I).

S1. Comment

Interest in the synthesis of the title structures was aroused by the preparation and structure determination of a series of mixed crystals of 2-carbamoylguanidinium hydrogen fluorophosphonate and 2-carbamoylguanidinium hydrogen phosphite (Fábry et al., 2012a). Pure 2-carbamoylguanidinium hydrogen phosphite (Fridrichová, Němec, Císařová & Němec, 2010) shows interesting physical properties (Fridrichová , Němec, Císařová & Chvostová, 2010; Kroupa & Fridrichová, 2011), namely spontaneous non-collinear second-harmonic generation of light. This property of second-harmonic generation is related to the constitutent cation, which shows significant hyperpolarizability (Fridrichová, Němec, Císařová & Němec, 2010). Therefore, we were interested in the preparation of crystals with different cation–anion molar ratios of 2-carbamoylguanidinium and fluorophosphonate than in the above-mentioned structures (Fábry et al., 2012a). The suggested ratios included the cation–anion molar ratio 2:1 which was expected to yield a structure with a nonhydrogenated fluorophosphonate. Two such structures have now been prepared and their structures are reported below.

Bis(2-carbamoylguanidinium) fluorophosphonate dihydrate crystallizes in space group Pnma to give polymorph (I). It also crystallizes in space group Pbca to give polymorph (II), which has a doubled unit-cell volume and is slightly more densely packed; the volume ratio per formula unit is 0.9917 compared with (I). In (I), the fluorophosphonate anion is situated on a crystallographic mirror plane and the O atom of the water molecule is disordered in contrast with its H atoms. This means that two slightly different hydrogen-bond patterns co-exist in the same structure.

The molecules (Figs. 1 and 2) are linked together by water–fluorophosphonate O—H···O hydrogen bonds and N—H···O hydrogen bonds (Tables 1 and 2) in both structures. Fluorine – as is usual (Dunitz & Taylor, 1997) – avoids participation in strong hydrogen bonds, though there is, for example, a relatively short N41—H1N41···F1 interaction in (II) (Table 2). The oxo groups [atoms O3 in (I) and O41 and O42 in (II)] participate in intra- and intermolecular N—H···O hydrogen bonds with quite acute angles (Tables 1 and 2).

The water–fluorophosphonate O—H···O hydrogen bonds result in the same R⁴₄(10) graph-set motif (Etter et al., 1990) in both structures (Figs. 3 and 4). These interactions contribute significantly to the formation of a three-dimensional hydrogen-bond network in each structure. However, there is an important difference between the two polymorphs in this respect. In (I), the 2-carbamoylguanidinium cations and fluorophosphonate anions form ribbons parallel to the a axis (Fig. 5), while the water molecules are indispensable for the construction of a three-dimensional hydrogen-bond network by linking these ribbons together. On the other hand, in (II) only the 2-carbamoylguanidinium cations and fluorophosphonate anions are needed to form a three-dimensional hydrogen-bond network (Fig. 6), although the water molecules reinforce the three-dimensional hydrogen-bond network (Table 2) significantly in this structure.

There is another important difference between the hydrogen-bond networks in (I) and (II), related to the strengths of the water–fluorophosphonate O—H···O hydrogen bonds in (I) and (II) (Tables 1 and 2). These hydrogen bonds are weaker in (I); the H···O distances are about 0.2 Å longer in (I) than those in (II). On the other hand, the N—H···O hydrogen bonds in (I) are shorter than the water–fluorophosphonate O—H···O hydrogen bonds in (I). The latter feature is quite unusual; a search of the Cambridge Structural Database (CSD, Version 5.32 with addenda from April 1 2011; Allen, 2002) for structures in which both O—H···O and N—H···O hydrogen bonds were simultaneously present yielded for O—H···O mean O—H and H···O values of 0.797 (1) and 1.990 (3) Å, respectively, while for N—H···O, the retrieved values were 0.897 (1) Å for N—H and 2.133 (2) Å for H···O. The search was carried out on organic structures only, with R < 0.05, without any error or disorder, and excluding polymeric and ionic structures.

In addition, the water–fluorophosphonate O—H···O angles in (I) are more acute than in (II). This is a manifestation of weaker hydrogen bonds (Jeffrey, 1995) of this type in (I) than in (II). This also seems to be related to the fact that the anion is situated in a special position in (I). Hence, only two symmetry-independent fluorophosphonate O atoms can be involved in the water–fluorophosphonate O—H···O hydrogen bonds, in contrast with (II), where there are three independent fluorophosphonate O atoms participating in this interaction. Moreover, since there is only one independent water molecule in (I), but two in general positions in (II), the molecules in the latter structure can better adjust in order to optimize their interactions.

The ability of the water molecules to interact with their neighbouring molecules is also manifested by the number of N—H···O(water) hydrogen bonds. While the disordered water O atoms in (I) are acceptors of just one amine H atom, in (II) one of the water O atoms (OW2) accepts one H atom and the second (OW1) accepts two.

A plot of P—F versus longest P—O distance in the fluorophosphonate anion was shown in the article by Fábry et al. (2012a), showing that the P—F distance is inversely proportional to the longest P—O distance in the anion. Therefore, this distance is quite sensitive to the hydrogenation of the fluorophosphonate because the P—O bond length of the hydroxyl group is larger than those of the remaining O atoms. Therefore, the fluorophosphonates and hydrogen fluorophosphonates can be readily distinguished. The distances within the anions for (I) and (II) are given in Tables 3 and 4, respectively.

In (II), the P—O and P—F distances are unusual because P1—O2 is quite long for a structure where the fluorophosphonate is not hydrogenated. The P1—F1 distance is correspondingly shortened. Hence, (II) is situated on the boundary between hydrogenated and unhydrogenated fluorophosphonates. This peculiarity of (II) seems to be related to the hydrogen-bond network in which the fluorophosphonate is involved. Atom O2 is hydrogen-bonded more strongly to neighbouring molecules than atoms O1 and O3. Atom O2 is also an acceptor of the strongest hydrogen bonds stemming from two water molecules [OW2—H2W2···O2 and OW1—H1W1···O2ⁱ; symmetry code: (i) x + 1, y, z] and of another strong N—H···O2 hydrogen bond [Desiraju & Steiner, 1999; N11—H2N11···O2ⁱⁱ; symmetry code: (ii) x + 1/2, y, -z + 1/2]. These O—H···O and N—H···O angles lie in the range 156–172°, which is typical for rather strong hydrogen bonds. A similar influence of the hydrogen bonds on P—O(acceptor) distances, and concomitantly on P—F distances, has recently been found in tris(guanylurea)(1+) hydrogen fluorophosphonate fluorophosphonate monohydrate (Fábry et al., 2012b). On the other hand, the P—O distances are quite short and the P—F distance quite long in (I).

Comparison of the hydrogen-bond distances pertinent to the bonding of the fluorophosphonates in (I) and (II) shows that the fluorophosphonate is less firmly bound in (I).

The χ² indices for the best planes through the non-H atoms of the cations are 19477.0, 36.29 and 84.29 for (I), the first cation in (II) and the second cation in (II), respectively. [The first and second cations in (II) contain atoms O41 and O42, respectively.] This is an enormous contrast, indicating that the cation in (I) is quite strained. The largest deviation from the best plane through the cationic non-H atoms in (I) is for atom N3, which is situated 0.12 (3) Å from this plane. In the case of the cations in (II), the atoms with the largest deviations from the best planes through the non-H atoms are N31 and N42, which are 0.031 (9) and 0.055 (10) Å from their respective best planes. The χ² indices in the related structures of 2-carbamoylguanidinium hydrogen fluorophosphonate and 2-carbamoylguanidinium hydrogen phosphite are 1139.577 (Fábry et al., 2012a) and 6515.041 (Fridrichová, Němec, Císařová & Němec, 2010; Fábry et al., 2012a), respectively. It is also of interest that the equivalent isotropic displacement parameters of the non-H atoms in (I) are lower than those in (II) (Table 5).

The above-mentioned facts [the disorder of the water O atoms, the features of the O—H···O and N—H···O hydrogen bonds, the position of the anions on special and general positions in (I) and (II), respectively] indicate that (II) seems to be thermodynamically more stable than (I), even though the molecules in (II) are only slightly more densely packed than those in (I).

The existence of two polymorphs indicates complexity is present in solutions of 2-carbamoylguanidinium:fluorophosphonate in a molar ratio of 2:1. Our experiments have shown reproducibility for the preparations of 2-carbamoylguanidinium hydrogen fluorophosphonate (Fábry et al., 2012a) but difficult reproducibility for different solutions. Another prepared compound was tris(guanylurea)(1+) hydrogen fluorophosphonate fluorophosphonate monohydrate (Fábry et al., 2012b).

Related literature

For related literature, see: Allen (2002); Desiraju & Steiner (1999); Dunitz & Taylor (1997); Etter et al. (1990); Fábry et al. (2012a, 2012b); Fridrichová, Němec, Císařová & Chvostová (2010); Fridrichová, Němec, Císařová & Němec (2010); Jeffrey (1995); Kroupa & Fridrichová (2011); Schülke & Kayser (1991); Scoponi et al. (1991).

S2. Experimental

The title compounds were prepared by neutralization of stoichiometric amounts of solutions of guanylurea hydroxide and H₂PO₃F. Guanylurea hydroxide was prepared from hydrochloride hemihydrate (1.18 g) by an exchange reaction on Anex. This solution was then concentrated using a vacuum rotatory evaporator.

Guanylurea chloride hemihydrate was prepared by acid hydrolysis of cyanoguanidine. A dilute aqueous solution (100 ml of water to every 0.1 mol of cyanoguanidine) of equimolar ratios of cyanoguanidine (99%, Sigma–Aldrich) and hydrochloric acid (p.a., Lachema) was gradually heated. After about 45 min, when the reaction mixture started boiling, the originally colourless mixture suddenly became grey and cloudy for a while and then an exothermic process occurred. This reaction was accompanied by very intense boiling of the reaction mixture. The heating was immediately interrupted and the reaction mixture placed on a cold magnetic stirrer while it was still boiling due to the exothermic reaction, and the mixture was stirred for another 15 min.

The liquid, which in the meantime had turned colourless again, was heated at boiling point for 2 h. The excess water was then evaporated under vacuum and a white crystalline product was filtered off. This was purified by recrystallization from water and characterized by powder X-ray diffraction. The powder diffraction pattern was found to be identical to the structure with CSD refcode JODZOR (Scoponi et al., 1991). The IR spectrum was also recorded, in order to exclude the possibility of contamination of the product by cyanoguanidine. The IR spectrum was in accordance with that obtained by Scoponi et al. (1991), whereas the intense doublet of the CN^- group typical for cyanoguanidine was absent.

A solution of H₂PO₃F was prepared from a solution of (NH₄)₂PO₃F.H₂O passed through a column of Catex. (NH₄)₂PO₃F.H₂O was prepared according to the method described by Schülke & Kayser (1991) and the raw material of (NH₄)₂PO₃F.H₂O prepared by this method was recrystallized in order to remove (NH₄)H₂PO₄ contamination. The volume of the eluted solution of H₂PO₃F was about 50 ml for the cases of (I) and (II). The solutions were placed in an evacuated desiccator over P₄O₁₀. Crystals appeared within about 10 d. The crystals of (I) and (II) were placed in special glass capillaries because they seemed to be hygroscopic.

The synthesis used 0.59 g (NH₄)₂PO₃F.H₂O and 0.936 g of guanylurea hydroxide. Each polymorph was prepared in a different batch.

S3. Refinement

All H atoms were discernible in difference electron-density maps for both structures. The applied constraints and restraints were as similar as possible for the refinement of each structure. The N—H distances for primary and secondary amine H atoms were constrained to 0.86 and 0.89 Å, respectively, with U_iso(H) = 1.2U_eq(N). The water O—H distances were restrained to 0.820 (1) Å, and the interatomic angles in the water molecules were restrained to 107.90 (1)° (this value was retrieved from the CSD), with U_iso(H) = 1.5U_eq(O). Additionally, in the case of (I) the displacement parameters of the disordered water O atoms OW and OW' were constrained to be equal; these water O atoms were refined anisotropically.

Computing details

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).

Figures

	Fig. 1. A view of the constituent molecules and atoms of (I), with the atom-numbering scheme. Displacement ellipsoids are depicted at the 50% probability level. Atom O2a is related to atom O2 by the transformation (x, -y + 1/2, z).
	Fig. 2. A view of the constituent molecules and atoms of (II), with the atom-numbering scheme. Displacement ellipsoids are depicted at the 50% probability level.
	Fig. 3. A section of the structure of (I), showing the R4^4(10) graph-set motifs extending along the a axis. [Symmetry codes: (i) x, -y + 1/2, z; (ii) -x + 3/2, y + 1/2, z - 1/2; (iii) -x + 3/2, -y, z + 1/2.]
	Fig. 4. A section of the structure of (II), showing the R4^4(10) graph-set motifs extending along the a axis. [Symmetry codes: (i) x - 1, y, z; (ii) -x + 1/2, y - 1/2, z; (iii) -x + 3/2, y - 1/2, z.]
	Fig. 5. A section of the structure of (I), showing the hydrogen-bond network without water molecules. The fluorophosphate anions and guanylurea molecules form ribbons extending along the c axis.
	Fig. 6. A section of the structure of (II), showing the formation of a three-dimensional hydrogen-bond network without water molecules. [Symmetry codes: (i) x + 1/2, -y + 1/2, -z + 1; (ii) -x + 1/2, y + 1/2, z; (iii) x - 1/2, y, -z + 1/2; (iv) -x, y + 1/2, -z + 1/2; (v) x - 1, y, z.]

(I) Bis(2-carbamoylguanidinium) fluorophosphonate

Crystal data

2(C2H7N4O^+)·FO3P^2^−·2H2O	F(000) = 712
Mr = 340.2	Dx = 1.574 Mg m^−3
Orthorhombic, Pnma	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2n	Cell parameters from 12987 reflections
a = 12.2788 (1) Å	θ = 3.6–66.9°
b = 17.4866 (2) Å	µ = 2.30 mm^−1
c = 6.6851 (1) Å	T = 120 K
V = 1435.39 (3) Å^3	Block, colourless
Z = 4	0.51 × 0.34 × 0.24 mm

Data collection

Oxford Xcalibur Gemini Ultra diffractometer	1326 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1219 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.050
Detector resolution: 10.3784 pixels mm^-1	θmax = 67.1°, θmin = 5.1°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −20→20
Tmin = 0.444, Tmax = 0.580	l = −7→7
20298 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	Weighting scheme based on measured s.u.'s w = 1/[σ^2(I) + 0.0004I^2]
wR(F^2) = 0.086	(Δ/σ)max = 0.042
S = 2.93	Δρmax = 0.31 e Å^−3
1326 reflections	Δρmin = −0.36 e Å^−3
110 parameters	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
5 restraints	Extinction coefficient: 2000 (300)
36 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.79564 (4)	0.25	0.64167 (9)	0.01375 (18)
F1	0.69594 (10)	0.25	0.4892 (2)	0.0242 (4)
O1	0.74310 (12)	0.25	0.8461 (2)	0.0184 (5)
O2	0.85611 (8)	0.17715 (5)	0.59359 (18)	0.0186 (3)
O3	0.88034 (8)	0.02675 (6)	1.21935 (18)	0.0203 (3)
C1	0.86096 (11)	0.07693 (8)	1.09535 (18)	0.0165 (5)
N1	0.84118 (12)	0.14962 (8)	1.14404 (18)	0.0236 (4)
H1N1	0.853384	0.165343	1.263852	0.0283*
H2N1	0.816224	0.180743	1.055605	0.0283*
N2	0.86000 (10)	0.06207 (7)	0.8909 (2)	0.0165 (4)
H1N2	0.850937	0.101651	0.808841	0.0198*
C2	0.87185 (11)	−0.00828 (6)	0.8065 (2)	0.0162 (5)
N3	0.87779 (11)	−0.07068 (5)	0.9178 (2)	0.0197 (4)
H1N3	0.881549	−0.114893	0.861882	0.0236*
H2N3	0.877899	−0.067047	1.046109	0.0236*
N4	0.87500 (10)	−0.01219 (6)	0.61146 (19)	0.0200 (4)
H1N4	0.881167	−0.05585	0.553335	0.024*
H2N4	0.870909	0.028901	0.541168	0.024*
OW	0.5761 (2)	0.14236 (16)	0.8878 (5)	0.0349 (8)	0.5
OW'	0.5734 (2)	0.15990 (15)	1.0159 (5)	0.0349 (8)	0.5
H1OW	0.51922 (19)	0.1500 (12)	0.9490 (13)	0.0523*
H2OW	0.6235 (8)	0.1691 (10)	0.9383 (12)	0.0523*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0175 (3)	0.0113 (3)	0.0124 (4)	0	−0.0002 (2)	0
F1	0.0259 (6)	0.0248 (6)	0.0219 (9)	0	−0.0083 (5)	0
O1	0.0218 (7)	0.0182 (7)	0.0152 (10)	0	0.0030 (6)	0
O2	0.0245 (5)	0.0127 (5)	0.0185 (7)	0.0022 (4)	0.0025 (4)	−0.0004 (4)
O3	0.0259 (5)	0.0215 (5)	0.0134 (7)	0.0031 (4)	−0.0003 (5)	0.0032 (4)
C1	0.0168 (7)	0.0172 (7)	0.0154 (10)	−0.0005 (5)	−0.0002 (6)	0.0005 (6)
N1	0.0386 (8)	0.0177 (6)	0.0145 (9)	0.0040 (5)	−0.0027 (6)	−0.0020 (5)
N2	0.0229 (6)	0.0134 (6)	0.0132 (8)	0.0007 (4)	−0.0005 (5)	0.0024 (5)
C2	0.0134 (6)	0.0188 (7)	0.0164 (11)	−0.0004 (5)	0.0004 (6)	0.0003 (6)
N3	0.0265 (6)	0.0137 (6)	0.0188 (9)	0.0007 (4)	0.0014 (6)	0.0009 (5)
N4	0.0237 (6)	0.0205 (6)	0.0160 (10)	0.0005 (5)	0.0005 (5)	−0.0015 (5)
OW	0.0208 (7)	0.0273 (11)	0.056 (2)	−0.0029 (7)	−0.0023 (13)	0.0156 (12)
OW'	0.0208 (7)	0.0273 (11)	0.056 (2)	−0.0029 (7)	−0.0023 (13)	0.0156 (12)

Geometric parameters (Å, º)

P1—F1	1.5931 (15)	C2—N3	1.3226 (16)
P1—O1	1.5112 (17)	C2—N4	1.3065 (19)
P1—O2	1.5092 (10)	N3—H1N3	0.86
P1—O2^i	1.5092 (10)	N3—H2N3	0.86
O3—C1	1.2303 (17)	N4—H1N4	0.86
C1—N1	1.3344 (19)	N4—H2N4	0.86
C1—N2	1.3915 (18)	OW—OW'	0.910 (5)
N1—H1N1	0.86	OW—H1OW	0.820 (6)
N1—H2N1	0.86	OW—H2OW	0.820 (13)
N2—H1N2	0.89	OW'—H1OW	0.821 (7)
N2—C2	1.3611 (16)	OW'—H2OW	0.821 (10)
F1—P1—O1	104.52 (8)	C1—N2—C2	125.08 (12)
F1—P1—O2	103.99 (5)	H1N2—N2—C2	117.4581
F1—P1—O2^i	103.99 (5)	N2—C2—N3	121.24 (13)
O1—P1—O2	113.74 (5)	N2—C2—N4	117.64 (11)
O1—P1—O2^i	113.74 (5)	N3—C2—N4	121.11 (11)
O2—P1—O2^i	115.16 (6)	C2—N3—H1N3	119.9998
O3—C1—N1	123.38 (12)	C2—N3—H2N3	119.9994
O3—C1—N2	122.03 (13)	H1N3—N3—H2N3	120.0009
N1—C1—N2	114.58 (12)	C2—N4—H1N4	119.9999
C1—N1—H1N1	120	C2—N4—H2N4	120.0003
C1—N1—H2N1	120.0003	H1N4—N4—H2N4	119.9998
H1N1—N1—H2N1	119.9997	H1OW—OW—H2OW	107.9 (13)
C1—N2—H1N2	117.459	H1OW—OW'—H2OW	107.8 (9)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2^ii	0.86	2.21	3.0491 (17)	164
N1—H2N1···O1	0.86	2.06	2.9152 (18)	175
N2—H1N2···O2	0.89	1.95	2.8286 (17)	167
N3—H1N3···F1^iii	0.86	2.69	3.2984 (10)	129
N3—H1N3···OW′^iv	0.86	2.50	3.164 (4)	134
N3—H2N3···O3	0.86	2.01	2.6395 (17)	129
N3—H2N3···OW^iii	0.86	2.70	3.430 (4)	144
N4—H1N4···OW^iv	0.86	1.95	2.789 (3)	166
N4—H1N4···OW′^iv	0.86	1.92	2.735 (3)	158
N4—H2N4···O2	0.86	2.62	3.3211 (14)	139
N4—H2N4···O3^v	0.86	2.15	2.7091 (17)	122
OW—H1OW···O2^vi	0.820 (6)	2.078 (5)	2.771 (3)	142.1 (8)
OW′—H1OW···O2^vi	0.821 (7)	2.078 (5)	2.783 (3)	143.9 (15)
OW—H2OW···O1	0.820 (13)	2.130 (14)	2.798 (3)	138.6 (9)
OW′—H2OW···O1	0.821 (10)	2.130 (14)	2.848 (3)	146.1 (15)

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

(II) Bis(2-carbamoylguanidinium) fluorophosphonate

Crystal data

2(C2H7N4O^+)·FO3P^2^−·2H2O	F(000) = 1424
Mr = 340.2	Dx = 1.587 Mg m^−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1710 reflections
a = 6.5362 (3) Å	θ = 3.1–62.4°
b = 16.6485 (6) Å	µ = 2.32 mm^−1
c = 26.1629 (15) Å	T = 120 K
V = 2847.0 (2) Å^3	Plate, colourless
Z = 8	0.43 × 0.14 × 0.04 mm

Data collection

Oxford Xcalibur Gemini Ultra diffractometer	2210 independent reflections
Radiation source: X-ray tube	968 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.110
Detector resolution: 10.3784 pixels mm^-1	θmax = 62.3°, θmin = 5.3°
ω scans	h = −7→4
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −18→16
Tmin = 0.718, Tmax = 0.908	l = −29→27
7251 measured reflections

Refinement

Refinement on F^2	60 constraints
R[F^2 > 2σ(F^2)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.193	Weighting scheme based on measured s.u.'s w = 1/[σ^2(I) + 0.0004I^2]
S = 1.43	(Δ/σ)max = 0.036
2210 reflections	Δρmax = 0.84 e Å^−3
202 parameters	Δρmin = −0.60 e Å^−3
6 restraints

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

	x	y	z	Uiso*/Ueq
P1	0.2388 (4)	0.28849 (10)	0.36710 (7)	0.0273 (7)
F1	0.2556 (8)	0.3407 (2)	0.41754 (16)	0.0393 (16)
O1	0.3413 (9)	0.2109 (3)	0.3806 (2)	0.0355 (19)
O2	0.3468 (9)	0.3371 (3)	0.3271 (2)	0.042 (2)
O3	0.0079 (9)	0.2824 (3)	0.3579 (2)	0.041 (2)
O41	0.3459 (9)	0.0964 (3)	0.2048 (2)	0.037 (2)
C11	0.3645 (13)	0.1390 (4)	0.2425 (2)	0.030 (3)
N11	0.4141 (13)	0.2160 (3)	0.2420 (2)	0.041 (3)
H1N11	0.409457	0.243501	0.269815	0.0495*
H2N11	0.450919	0.238523	0.213921	0.0495*
N21	0.3370 (10)	0.1082 (3)	0.2924 (2)	0.033 (2)
H1N21	0.353245	0.142259	0.318245	0.0396*
C21	0.2874 (12)	0.0305 (3)	0.3043 (3)	0.027 (3)
N31	0.2686 (12)	−0.0249 (2)	0.2686 (2)	0.030 (2)
H1N31	0.29433	−0.013236	0.2372	0.0359*
H2N31	0.230506	−0.072733	0.27662	0.0359*
N41	0.2655 (12)	0.0129 (2)	0.3526 (2)	0.034 (2)
H1N41	0.290971	0.048551	0.375515	0.0407*
H2N41	0.225479	−0.034254	0.361468	0.0407*
O42	0.7714 (10)	0.4622 (3)	0.54348 (18)	0.0330 (19)
C12	0.7595 (14)	0.4166 (4)	0.5063 (2)	0.028 (3)
N12	0.7614 (15)	0.3370 (3)	0.51053 (19)	0.038 (2)
H1N12	0.76991	0.307551	0.483597	0.0457*
H2N12	0.75401	0.314917	0.540199	0.0457*
N22	0.7449 (11)	0.4462 (3)	0.4570 (2)	0.031 (2)
H1N22	0.738916	0.410468	0.431762	0.0372*
C22	0.7387 (14)	0.5266 (2)	0.4434 (3)	0.027 (3)
N32	0.7288 (13)	0.5428 (2)	0.3948 (2)	0.035 (2)
H1N32	0.739588	0.504719	0.372681	0.0417*
H2N32	0.711459	0.591473	0.3847	0.0417*
N42	0.7349 (14)	0.5822 (2)	0.4789 (2)	0.034 (2)
H1N42	0.75366	0.569386	0.510346	0.0412*
H2N42	0.713532	0.631507	0.470617	0.0412*
OW1	0.7273 (9)	0.2291 (3)	0.4235 (2)	0.035 (2)
H1W1	0.818 (7)	0.231 (5)	0.402 (2)	0.0527*
H2W1	0.623 (6)	0.247 (5)	0.411 (3)	0.0527*
OW2	0.7287 (10)	0.3986 (3)	0.3421 (3)	0.045 (2)
H2W2	0.828 (7)	0.369 (4)	0.343 (4)	0.0681*
H1W2	0.626 (6)	0.371 (4)	0.339 (4)	0.0681*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0422 (15)	0.0162 (8)	0.0236 (10)	−0.0014 (11)	−0.0012 (11)	−0.0019 (7)
F1	0.052 (3)	0.032 (2)	0.034 (3)	0.006 (2)	−0.004 (3)	−0.0104 (18)
O1	0.057 (4)	0.015 (2)	0.034 (3)	0.001 (3)	−0.001 (3)	0.000 (2)
O2	0.060 (4)	0.024 (3)	0.041 (4)	0.001 (3)	0.002 (3)	0.012 (2)
O3	0.036 (4)	0.040 (3)	0.047 (4)	−0.002 (3)	−0.009 (3)	0.001 (3)
O41	0.061 (5)	0.023 (3)	0.028 (3)	−0.001 (3)	0.002 (3)	−0.004 (2)
C11	0.034 (6)	0.030 (4)	0.027 (5)	0.004 (4)	−0.003 (4)	0.000 (3)
N11	0.057 (6)	0.026 (4)	0.040 (5)	−0.007 (4)	0.014 (5)	0.004 (3)
N21	0.050 (5)	0.023 (3)	0.026 (4)	0.004 (3)	−0.001 (4)	−0.006 (3)
C21	0.028 (6)	0.023 (4)	0.030 (5)	0.002 (4)	−0.003 (4)	−0.001 (3)
N31	0.045 (5)	0.019 (3)	0.026 (3)	−0.003 (4)	0.001 (4)	−0.003 (2)
N41	0.052 (5)	0.024 (3)	0.026 (4)	0.006 (4)	−0.004 (4)	−0.001 (3)
O42	0.051 (4)	0.025 (3)	0.023 (3)	−0.002 (3)	−0.003 (3)	−0.001 (2)
C12	0.036 (6)	0.027 (4)	0.022 (4)	−0.001 (4)	−0.004 (4)	0.002 (3)
N12	0.066 (5)	0.017 (3)	0.032 (4)	0.003 (4)	−0.004 (5)	−0.001 (2)
N22	0.054 (5)	0.020 (3)	0.019 (3)	−0.011 (4)	0.000 (4)	−0.005 (2)
C22	0.027 (5)	0.025 (4)	0.031 (4)	−0.010 (4)	0.005 (5)	−0.003 (3)
N32	0.055 (5)	0.029 (3)	0.020 (4)	0.000 (4)	0.003 (4)	0.001 (3)
N42	0.062 (5)	0.018 (3)	0.023 (3)	0.000 (4)	0.004 (4)	−0.001 (2)
OW1	0.040 (4)	0.031 (3)	0.035 (3)	0.002 (3)	−0.005 (3)	0.006 (2)
OW2	0.050 (4)	0.022 (3)	0.064 (4)	0.002 (3)	−0.003 (5)	−0.001 (3)

Geometric parameters (Å, º)

P1—F1	1.584 (4)	O42—C12	1.237 (7)
P1—O1	1.497 (5)	C12—N12	1.330 (8)
P1—O2	1.499 (6)	C12—N22	1.385 (8)
P1—O3	1.531 (6)	N12—H1N12	0.86
O41—C11	1.222 (8)	N12—H2N12	0.86
C11—N11	1.322 (9)	N22—H1N22	0.89
C11—N21	1.413 (9)	N22—C22	1.385 (7)
N11—H1N11	0.86	C22—N32	1.303 (9)
N11—H2N11	0.86	C22—N42	1.310 (7)
H1N11—H2N11	1.4896	N32—H1N32	0.86
N21—H1N21	0.89	N32—H2N32	0.86
N21—C21	1.370 (7)	N42—H1N42	0.86
C21—N31	1.320 (8)	N42—H2N42	0.86
C21—N41	1.304 (9)	OW1—H1W1	0.82 (5)
N31—H1N31	0.86	OW1—H2W1	0.82 (5)
N31—H2N31	0.86	H1W1—H2W1	1.33 (7)
N41—H1N41	0.86	OW2—H2W2	0.82 (5)
N41—H2N41	0.86	OW2—H1W2	0.82 (5)
F1—P1—O1	104.2 (3)	C21—N41—H1N41	120.0003
F1—P1—O2	104.6 (3)	C21—N41—H2N41	119.9999
F1—P1—O3	103.6 (3)	H1N41—N41—H2N41	119.9997
O1—P1—O2	114.8 (3)	O42—C12—N12	123.1 (5)
O1—P1—O3	114.9 (3)	O42—C12—N22	121.2 (6)
O2—P1—O3	113.0 (3)	N12—C12—N22	115.7 (5)
P1—O3—H1W1^i	125.3 (16)	C12—N12—H1N12	120.0005
P1—O3—H2W2^i	126.2 (16)	C12—N12—H2N12	120
H1W1^i—O3—H2W2^i	93 (3)	H1N12—N12—H2N12	119.9995
O41—C11—N11	125.4 (6)	C12—N22—H1N22	117.0683
O41—C11—N21	121.5 (6)	C12—N22—C22	125.9 (5)
N11—C11—N21	113.1 (6)	H1N22—N22—C22	117.0671
C11—N11—H1N11	119.9996	N22—C22—N32	116.8 (5)
C11—N11—H2N11	120.0009	N22—C22—N42	120.1 (6)
H1N11—N11—H2N11	119.9995	N32—C22—N42	123.0 (4)
C11—N21—H1N21	117.1361	H2N32—C22—H1N42	122.8835
C11—N21—C21	125.7 (6)	C22—N32—H1N32	120
H1N21—N21—C21	117.1355	C22—N32—H2N32	120
N21—C21—N31	121.3 (6)	H1N32—N32—H2N32	120
N21—C21—N41	117.3 (5)	C22—N42—H1N42	120.0006
N31—C21—N41	121.3 (5)	C22—N42—H2N42	119.9993
C21—N31—H1N31	119.9998	H1N42—N42—H2N42	120.0001
C21—N31—H2N31	119.9996	H1W1—OW1—H2W1	108 (6)
H1N31—N31—H2N31	120.0006	H2W2—OW2—H1W2	108 (5)

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H1N11···O2	0.86	2.20	3.036 (8)	164
N11—H2N11···O3^ii	0.86	2.05	2.904 (8)	172
N21—H1N21···O1	0.89	1.99	2.873 (8)	170
N31—H1N31···O41	0.86	2.04	2.668 (7)	129
N31—H1N31···C11	0.86	2.58	2.882 (8)	102
N31—H1N31···OW2^iii	0.86	2.55	3.164 (9)	129
N31—H2N31···O2^iv	0.86	2.06	2.862 (7)	154
N41—H1N41···O1	0.86	2.73	3.413 (6)	138
N41—H1N41···O42^v	0.86	2.13	2.751 (7)	129
N41—H2N41···F1^iv	0.86	2.55	3.337 (6)	152
N41—H2N41···O2^iv	0.86	2.37	3.091 (7)	142
N12—H1N12···OW1	0.86	2.06	2.908 (7)	168
N12—H2N12···O1^vi	0.86	2.19	3.004 (7)	157
N22—H1N22···OW2	0.89	2.35	3.109 (9)	143
N32—H1N32···OW2	0.86	1.94	2.766 (7)	161
N32—H2N32···O41^vii	0.86	2.37	2.796 (8)	111
N32—H2N32···OW1^viii	0.86	2.54	3.205 (7)	135
N42—H1N42···F1^ix	0.86	2.41	3.000 (7)	126
N42—H1N42···O42	0.86	1.99	2.629 (7)	130
N42—H2N42···OW1^viii	0.86	2.08	2.852 (7)	150
OW1—H1W1···O3^x	0.82 (5)	1.89 (6)	2.665 (8)	156 (8)
OW1—H2W1···O1	0.82 (5)	2.09 (5)	2.778 (8)	141 (7)
OW2—H2W2···O3^x	0.82 (5)	1.89 (6)	2.692 (8)	164 (8)
OW2—H1W2···O2	0.82 (5)	1.94 (5)	2.727 (9)	162 (6)

Symmetry codes: (ii) x+1/2, y, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1/2, y−1/2, z; (v) x−1/2, −y+1/2, −z+1; (vi) x+1/2, −y+1/2, −z+1; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+3/2, y+1/2, z; (ix) −x+1, −y+1, −z+1; (x) x+1, y, z.