Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009644/lh6055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009644/lh6055Isup2.hkl |
CCDC reference: 214814
(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.
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.
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.
CN3H6+·H2PO3− | F(000) = 148 |
Mr = 141.07 | Dx = 1.534 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.5268 (3) Å | Cell parameters from 2092 reflections |
b = 7.4711 (5) Å | θ = 2.3–32.3° |
c = 9.1856 (6) Å | µ = 0.38 mm−1 |
β = 100.631 (2)° | T = 293 K |
V = 305.33 (3) Å3 | Block, colourless |
Z = 2 | 0.32 × 0.21 × 0.16 mm |
Bruker SMART1000 CCD diffractometer | 1836 independent reflections |
Radiation source: fine-focus sealed tube | 1691 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 32.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −4→6 |
Tmin = 0.891, Tmax = 0.944 | k = −11→10 |
3144 measured reflections | l = −13→13 |
Refinement on F2 | Hydrogen site location: geom and difmap (O-H species) |
Least-squares matrix: full | H-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 = 0.99 | Δρmax = 0.28 e Å−3 |
1836 reflections | Δρmin = −0.23 e Å−3 |
73 parameters | Absolute structure: Flack (1983), 1055 Friedel pairs |
1 restraint | Absolute structure parameter: −0.03 (9) |
Primary atom site location: structure-invariant direct methods |
CN3H6+·H2PO3− | V = 305.33 (3) Å3 |
Mr = 141.07 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 4.5268 (3) Å | µ = 0.38 mm−1 |
b = 7.4711 (5) Å | T = 293 K |
c = 9.1856 (6) Å | 0.32 × 0.21 × 0.16 mm |
β = 100.631 (2)° |
Bruker SMART1000 CCD diffractometer | 1836 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1691 reflections with I > 2σ(I) |
Tmin = 0.891, Tmax = 0.944 | Rint = 0.015 |
3144 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.076 | Δρmax = 0.28 e Å−3 |
S = 0.99 | Δρmin = −0.23 e Å−3 |
1836 reflections | Absolute structure: Flack (1983), 1055 Friedel pairs |
73 parameters | Absolute structure parameter: −0.03 (9) |
1 restraint |
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 | 0.05592 (7) | 0.82326 (5) | 0.67043 (3) | 0.03008 (9) | |
H1 | −0.2401 | 0.8142 | 0.6492 | 0.036* | |
O1 | 0.1445 (3) | 1.02556 (15) | 0.65761 (13) | 0.0447 (3) | |
H2 | 0.0576 | 1.0775 | 0.5827 | 0.054* | |
O2 | 0.1744 (3) | 0.76649 (18) | 0.82545 (12) | 0.0456 (3) | |
O3 | 0.1579 (3) | 0.71352 (15) | 0.55118 (12) | 0.0401 (3) | |
C1 | 0.3189 (4) | 0.8857 (2) | 0.17856 (16) | 0.0346 (3) | |
N1 | 0.4001 (4) | 0.9221 (2) | 0.32228 (14) | 0.0434 (3) | |
H3 | 0.3291 | 0.8596 | 0.3865 | 0.052* | |
H4 | 0.5236 | 1.0081 | 0.3509 | 0.052* | |
N2 | 0.4276 (4) | 0.9817 (2) | 0.07947 (15) | 0.0450 (3) | |
H5 | 0.3748 | 0.9581 | −0.0133 | 0.054* | |
H6 | 0.5511 | 1.0677 | 0.1078 | 0.054* | |
N3 | 0.1295 (4) | 0.7541 (2) | 0.13305 (16) | 0.0471 (4) | |
H7 | 0.0782 | 0.7317 | 0.0400 | 0.057* | |
H8 | 0.0574 | 0.6909 | 0.1965 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.03987 (16) | 0.02707 (14) | 0.02260 (13) | 0.00271 (16) | 0.00391 (10) | 0.00014 (13) |
O1 | 0.0700 (8) | 0.0256 (5) | 0.0353 (5) | 0.0021 (5) | 0.0011 (5) | 0.0008 (4) |
O2 | 0.0709 (8) | 0.0398 (6) | 0.0251 (5) | 0.0093 (5) | 0.0062 (5) | 0.0062 (4) |
O3 | 0.0588 (7) | 0.0342 (6) | 0.0281 (5) | −0.0011 (5) | 0.0099 (5) | −0.0076 (4) |
C1 | 0.0439 (8) | 0.0307 (6) | 0.0296 (6) | 0.0007 (5) | 0.0079 (5) | 0.0006 (5) |
N1 | 0.0633 (9) | 0.0382 (7) | 0.0282 (6) | −0.0087 (6) | 0.0070 (6) | −0.0010 (5) |
N2 | 0.0636 (9) | 0.0415 (7) | 0.0317 (6) | −0.0156 (7) | 0.0134 (6) | −0.0019 (6) |
N3 | 0.0647 (10) | 0.0446 (8) | 0.0321 (6) | −0.0179 (7) | 0.0093 (7) | 0.0000 (5) |
P1—O2 | 1.4878 (11) | C1—N1 | 1.3314 (19) |
P1—O3 | 1.5073 (11) | N1—H3 | 0.8600 |
P1—O1 | 1.5736 (13) | N1—H4 | 0.8600 |
P1—H1 | 1.3200 | N2—H5 | 0.8600 |
O1—H2 | 0.8241 | N2—H6 | 0.8600 |
C1—N3 | 1.321 (2) | N3—H7 | 0.8600 |
C1—N2 | 1.3227 (19) | N3—H8 | 0.8600 |
O2—P1—O3 | 115.84 (7) | C1—N1—H3 | 120.0 |
O2—P1—O1 | 107.07 (7) | C1—N1—H4 | 120.0 |
O3—P1—O1 | 110.59 (7) | H3—N1—H4 | 120.0 |
O2—P1—H1 | 107.7 | C1—N2—H5 | 120.0 |
O3—P1—H1 | 107.7 | C1—N2—H6 | 120.0 |
O1—P1—H1 | 107.7 | H5—N2—H6 | 120.0 |
P1—O1—H2 | 115.2 | C1—N3—H7 | 120.0 |
N3—C1—N2 | 119.20 (14) | C1—N3—H8 | 120.0 |
N3—C1—N1 | 120.67 (15) | H7—N3—H8 | 120.0 |
N2—C1—N1 | 120.13 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2···O3i | 0.82 | 1.75 | 2.5602 (17) | 169 |
N1—H4···O3ii | 0.86 | 2.18 | 3.039 (2) | 174 |
N1—H3···O3 | 0.86 | 2.12 | 2.9837 (19) | 178 |
N2—H6···O2ii | 0.86 | 1.96 | 2.820 (2) | 179 |
N2—H5···O2iii | 0.86 | 2.14 | 2.8907 (19) | 146 |
N3—H8···O1iv | 0.86 | 2.15 | 3.005 (2) | 176 |
N3—H7···O2iii | 0.86 | 2.11 | 2.8714 (19) | 147 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) x, y, z−1; (iv) −x, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | CN3H6+·H2PO3− |
Mr | 141.07 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 4.5268 (3), 7.4711 (5), 9.1856 (6) |
β (°) | 100.631 (2) |
V (Å3) | 305.33 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.32 × 0.21 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.891, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3144, 1836, 1691 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.076, 0.99 |
No. of reflections | 1836 |
No. of parameters | 73 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.23 |
Absolute structure | Flack (1983), 1055 Friedel pairs |
Absolute structure parameter | −0.03 (9) |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999).
P1—O2 | 1.4878 (11) | C1—N3 | 1.321 (2) |
P1—O3 | 1.5073 (11) | C1—N2 | 1.3227 (19) |
P1—O1 | 1.5736 (13) | C1—N1 | 1.3314 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2···O3i | 0.82 | 1.75 | 2.5602 (17) | 169 |
N1—H4···O3ii | 0.86 | 2.18 | 3.039 (2) | 174 |
N1—H3···O3 | 0.86 | 2.12 | 2.9837 (19) | 178 |
N2—H6···O2ii | 0.86 | 1.96 | 2.820 (2) | 179 |
N2—H5···O2iii | 0.86 | 2.14 | 2.8907 (19) | 146 |
N3—H8···O1iv | 0.86 | 2.15 | 3.005 (2) | 176 |
N3—H7···O2iii | 0.86 | 2.11 | 2.8714 (19) | 147 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) x, y, z−1; (iv) −x, y−1/2, −z+1. |
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.