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The structure of the title compound, CH6N3+.H2PO3, originally determined by Krumbe & Haussuhl [Z. Kristallogr. (1987), 178, 132–134], has been redetermined. The intermolecular packing is controlled by N—H...O and O—H...O hydrogen bonds, resulting in a non-centrosymmetric three-dimensional structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009644/lh6055sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009644/lh6055Isup2.hkl
Contains datablock I

CCDC reference: 214814

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](P-O) = 0.001 Å
  • R factor = 0.029
  • wR factor = 0.076
  • Data-to-parameter ratio = 25.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_420 Alert C D-H Without Acceptor P(1) - H(1) ? General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.48 From the CIF: _reflns_number_total 1836 Count of symmetry unique reflns 1173 Completeness (_total/calc) 156.52% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 663 Fraction of Friedel pairs measured 0.565 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Amine phosphates have recently been proposed as key intermediates in the synthesis of organically templated open frameworks (Rao et al., 2000). In addition, they show interesting crystal-packing motifs controlled by the interplay of N—H···O and O—H···O hydrogen bonds (Demir et al., 2002). Less is known about the crystal structures of amine–hydrogen phosphite complexes which involve the [HPO3]2− ion or its protonated derivative, [H2PO3]. Here, we report the crystal structure of guanidinium dihydrogen phosphite, CN3H6+·H2PO3, (I) (Fig. 1). This phase was first prepared and characterized by Krumbe & Haussuhl (1987), but a redeterination was considered worthwhile as atomic parameters were not published.

The CN3H6+ moiety [dav(C—N) = 1.339 (2) Å; θav(N—C—N) = 120.0 (2)°] shows its usual `propeller' shape approximating to D3 h local symmetry (Harrison & Phillips, 1997) indicating that the usual bonding model for this species to result in a C—N bond order of 1.33 is appropriate here. The dihydrogen phosphite anion possesses typical (Doran et al., 2001) geometrical parameters [dav(P—O) = 1.547 (2) Å; θav(O—P—O) = 111.4 (2)°], with the P—O1H vertex significantly lengthened compared with the other P—O bonds.

The unit-cell packing (Fig. 2) involves chains of [H2PO3] groups propagating in the polar [010] direction, linked together via O1—H2···O3 hydrogen bonds. All six of the guanidinium H atoms are involved in N—H···O interactions (Figs. 1 and 2); O1 accepts one, O2 three, and O3 two N—H···O bonds. The resulting O(PH3) coordinations for O2 and O3 are approximately tetrahedral. As expected (Doran et al., 2001), the P—H vertex is not involved in the hydrogen-bonding scheme.

Experimental top

(CN3H6)2(CO3) (0.91 g, 0.005 mmol) and H3PO3 (0.82 g, 0.01 mmol) were dissolved in 20 ml distilled water. Block-shaped crystals of (I) grew over the course of a few days as the solvent evaporated.

Refinement top

Atom H2 was located in a difference map and the other H atoms were placed in calculated positions [d(N—H) = 0.86 Å and d(P—H) = 1.32 Å]. The H atoms were included in the refinement in the riding-motion approximation, with Uiso(H) = 1.2Ueq of the carrier atom.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Fragment of (I) (50% displacement ellipsoids and arbitrary spheres for the H atoms), showing the atom-labelling scheme and hydrogen-bonding interactions (dashed lines). Symmetry-generated hydrogen phosphite moieties are indicated by unshaded ellipsoids; symmetry codes are as in Table 2. Note how each roughly parallel pair of guanidinium N–H bonds (H3 + H5; H6 + H8; H4 + H7) hydrogen bonds to a different acceptor configuration.
[Figure 2] Fig. 2. The crystal packing in (I) viewed approximately down [100], with the dihydrogen phosphite tetrahedra coloured yellow. The coloured spheres, of arbitrary radii, represent O atoms (red), C atoms (blue), N atoms (green), and H atoms (grey). Hydrogen bonds are highlighted in pink.
Guanidinium dihydrogen phosphite top
Crystal data top
CN3H6+·H2PO3F(000) = 148
Mr = 141.07Dx = 1.534 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 4.5268 (3) ÅCell parameters from 2092 reflections
b = 7.4711 (5) Åθ = 2.3–32.3°
c = 9.1856 (6) ŵ = 0.38 mm1
β = 100.631 (2)°T = 293 K
V = 305.33 (3) Å3Block, colourless
Z = 20.32 × 0.21 × 0.16 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
1836 independent reflections
Radiation source: fine-focus sealed tube1691 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 32.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 46
Tmin = 0.891, Tmax = 0.944k = 1110
3144 measured reflectionsl = 1313
Refinement top
Refinement on F2Hydrogen site location: geom and difmap (O-H species)
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029 w = 1/[σ2(Fo2) + (0.0506P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.28 e Å3
1836 reflectionsΔρmin = 0.23 e Å3
73 parametersAbsolute structure: Flack (1983), 1055 Friedel pairs
1 restraintAbsolute structure parameter: 0.03 (9)
Primary atom site location: structure-invariant direct methods
Crystal data top
CN3H6+·H2PO3V = 305.33 (3) Å3
Mr = 141.07Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.5268 (3) ŵ = 0.38 mm1
b = 7.4711 (5) ÅT = 293 K
c = 9.1856 (6) Å0.32 × 0.21 × 0.16 mm
β = 100.631 (2)°
Data collection top
Bruker SMART1000 CCD
diffractometer
1836 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1691 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.944Rint = 0.015
3144 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.076Δρmax = 0.28 e Å3
S = 0.99Δρmin = 0.23 e Å3
1836 reflectionsAbsolute structure: Flack (1983), 1055 Friedel pairs
73 parametersAbsolute structure parameter: 0.03 (9)
1 restraint
Special details top

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 (Å2) top
xyzUiso*/Ueq
P10.05592 (7)0.82326 (5)0.67043 (3)0.03008 (9)
H10.24010.81420.64920.036*
O10.1445 (3)1.02556 (15)0.65761 (13)0.0447 (3)
H20.05761.07750.58270.054*
O20.1744 (3)0.76649 (18)0.82545 (12)0.0456 (3)
O30.1579 (3)0.71352 (15)0.55118 (12)0.0401 (3)
C10.3189 (4)0.8857 (2)0.17856 (16)0.0346 (3)
N10.4001 (4)0.9221 (2)0.32228 (14)0.0434 (3)
H30.32910.85960.38650.052*
H40.52361.00810.35090.052*
N20.4276 (4)0.9817 (2)0.07947 (15)0.0450 (3)
H50.37480.95810.01330.054*
H60.55111.06770.10780.054*
N30.1295 (4)0.7541 (2)0.13305 (16)0.0471 (4)
H70.07820.73170.04000.057*
H80.05740.69090.19650.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.03987 (16)0.02707 (14)0.02260 (13)0.00271 (16)0.00391 (10)0.00014 (13)
O10.0700 (8)0.0256 (5)0.0353 (5)0.0021 (5)0.0011 (5)0.0008 (4)
O20.0709 (8)0.0398 (6)0.0251 (5)0.0093 (5)0.0062 (5)0.0062 (4)
O30.0588 (7)0.0342 (6)0.0281 (5)0.0011 (5)0.0099 (5)0.0076 (4)
C10.0439 (8)0.0307 (6)0.0296 (6)0.0007 (5)0.0079 (5)0.0006 (5)
N10.0633 (9)0.0382 (7)0.0282 (6)0.0087 (6)0.0070 (6)0.0010 (5)
N20.0636 (9)0.0415 (7)0.0317 (6)0.0156 (7)0.0134 (6)0.0019 (6)
N30.0647 (10)0.0446 (8)0.0321 (6)0.0179 (7)0.0093 (7)0.0000 (5)
Geometric parameters (Å, º) top
P1—O21.4878 (11)C1—N11.3314 (19)
P1—O31.5073 (11)N1—H30.8600
P1—O11.5736 (13)N1—H40.8600
P1—H11.3200N2—H50.8600
O1—H20.8241N2—H60.8600
C1—N31.321 (2)N3—H70.8600
C1—N21.3227 (19)N3—H80.8600
O2—P1—O3115.84 (7)C1—N1—H3120.0
O2—P1—O1107.07 (7)C1—N1—H4120.0
O3—P1—O1110.59 (7)H3—N1—H4120.0
O2—P1—H1107.7C1—N2—H5120.0
O3—P1—H1107.7C1—N2—H6120.0
O1—P1—H1107.7H5—N2—H6120.0
P1—O1—H2115.2C1—N3—H7120.0
N3—C1—N2119.20 (14)C1—N3—H8120.0
N3—C1—N1120.67 (15)H7—N3—H8120.0
N2—C1—N1120.13 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O3i0.821.752.5602 (17)169
N1—H4···O3ii0.862.183.039 (2)174
N1—H3···O30.862.122.9837 (19)178
N2—H6···O2ii0.861.962.820 (2)179
N2—H5···O2iii0.862.142.8907 (19)146
N3—H8···O1iv0.862.153.005 (2)176
N3—H7···O2iii0.862.112.8714 (19)147
Symmetry codes: (i) x, y+1/2, z+1; (ii) x+1, y+1/2, z+1; (iii) x, y, z1; (iv) x, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaCN3H6+·H2PO3
Mr141.07
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)4.5268 (3), 7.4711 (5), 9.1856 (6)
β (°) 100.631 (2)
V3)305.33 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.32 × 0.21 × 0.16
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.891, 0.944
No. of measured, independent and
observed [I > 2σ(I)] reflections
3144, 1836, 1691
Rint0.015
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.076, 0.99
No. of reflections1836
No. of parameters73
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.23
Absolute structureFlack (1983), 1055 Friedel pairs
Absolute structure parameter0.03 (9)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999).

Selected bond lengths (Å) top
P1—O21.4878 (11)C1—N31.321 (2)
P1—O31.5073 (11)C1—N21.3227 (19)
P1—O11.5736 (13)C1—N11.3314 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O3i0.821.752.5602 (17)169
N1—H4···O3ii0.862.183.039 (2)174
N1—H3···O30.862.122.9837 (19)178
N2—H6···O2ii0.861.962.820 (2)179
N2—H5···O2iii0.862.142.8907 (19)146
N3—H8···O1iv0.862.153.005 (2)176
N3—H7···O2iii0.862.112.8714 (19)147
Symmetry codes: (i) x, y+1/2, z+1; (ii) x+1, y+1/2, z+1; (iii) x, y, z1; (iv) x, y1/2, z+1.
 

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