Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013587/bt6077sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013587/bt6077Isup2.hkl |
CCDC reference: 172215
The title compound was prepared by the reaction of a solution of phosphorus acid in water and 1,6-hexamethylenediamine in water with the molar ratio 2:1 at ambient temperature. Crystals suitable for X-ray diffraction analysis were obtained by very slow evaporation of the solution over a period of several days.
The H atom bonded to the P atom was refined isotropically without restraints. The H atoms of the ammonium and hydroxyl groups were refined isotropically with restrained bond distances of 0.85 and 0.80 Å, respectively, whereas the other H atoms were constrained to idealized geometries using the appropriate riding model.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000).
C6H18N22+·2H2PO3− | F(000) = 300 |
Mr = 280.20 | Dx = 1.432 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9330 (3) Å | Cell parameters from 2831 reflections |
b = 8.9074 (5) Å | θ = 1–25° |
c = 14.8407 (8) Å | µ = 0.35 mm−1 |
β = 94.751 (1)° | T = 183 K |
V = 649.86 (6) Å3 | Parallelipide, colorless |
Z = 2 | 0.16 × 0.08 × 0.02 mm |
Siemens SMART CCD diffractometer | 1284 independent reflections |
Radiation source: fine-focus sealed tube | 1049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: no pixels mm-1 | θmax = 26.1°, θmin = 2.7° |
ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | k = −11→9 |
Tmin = 0.946, Tmax = 0.993 | l = −16→18 |
4004 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0641P)2 + 0.4391P] where P = (Fo2 + 2Fc2)/3 |
1284 reflections | (Δ/σ)max < 0.001 |
93 parameters | Δρmax = 0.40 e Å−3 |
4 restraints | Δρmin = −0.34 e Å−3 |
C6H18N22+·2H2PO3− | V = 649.86 (6) Å3 |
Mr = 280.20 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.9330 (3) Å | µ = 0.35 mm−1 |
b = 8.9074 (5) Å | T = 183 K |
c = 14.8407 (8) Å | 0.16 × 0.08 × 0.02 mm |
β = 94.751 (1)° |
Siemens SMART CCD diffractometer | 1284 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1049 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.993 | Rint = 0.042 |
4004 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 4 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.40 e Å−3 |
1284 reflections | Δρmin = −0.34 e Å−3 |
93 parameters |
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 | 0.05324 (12) | 0.12340 (7) | 0.61326 (4) | 0.0182 (2) | |
O1 | −0.2067 (3) | 0.0477 (2) | 0.63477 (13) | 0.0272 (5) | |
O2 | 0.1354 (4) | 0.2562 (2) | 0.67105 (12) | 0.0267 (5) | |
O3 | 0.2752 (4) | −0.0031 (2) | 0.61785 (15) | 0.0302 (5) | |
N1 | −0.1298 (5) | −0.2250 (3) | 0.72491 (15) | 0.0219 (5) | |
C1 | −0.1121 (5) | −0.3440 (3) | 0.65508 (17) | 0.0222 (6) | |
H1A | −0.0475 | −0.4384 | 0.6848 | 0.027* | |
H1B | 0.0222 | −0.3137 | 0.6125 | 0.027* | |
C2 | −0.3850 (5) | −0.3714 (3) | 0.60280 (17) | 0.0220 (6) | |
H2A | −0.4570 | −0.2751 | 0.5775 | 0.026* | |
H2B | −0.5151 | −0.4101 | 0.6446 | 0.026* | |
C3 | −0.3630 (5) | −0.4838 (3) | 0.52585 (18) | 0.0224 (6) | |
H3A | −0.2366 | −0.4436 | 0.4833 | 0.027* | |
H3B | −0.2853 | −0.5788 | 0.5511 | 0.027* | |
H1 | 0.027 (5) | 0.154 (3) | 0.5297 (16) | 0.011 (6)* | |
H13 | −0.269 (5) | −0.240 (3) | 0.7564 (17) | 0.021 (7)* | |
H12 | 0.021 (5) | −0.225 (4) | 0.7608 (19) | 0.039 (9)* | |
H11 | −0.152 (7) | −0.138 (2) | 0.699 (2) | 0.034 (9)* | |
H3 | 0.432 (4) | 0.022 (4) | 0.624 (2) | 0.041 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0164 (4) | 0.0182 (4) | 0.0200 (4) | 0.0012 (2) | 0.0003 (2) | 0.0002 (3) |
O1 | 0.0167 (9) | 0.0277 (11) | 0.0374 (11) | 0.0023 (7) | 0.0039 (8) | 0.0064 (9) |
O2 | 0.0295 (10) | 0.0208 (10) | 0.0284 (10) | 0.0024 (8) | −0.0051 (8) | −0.0053 (8) |
O3 | 0.0166 (10) | 0.0204 (10) | 0.0535 (13) | 0.0011 (8) | 0.0027 (9) | −0.0037 (9) |
N1 | 0.0207 (11) | 0.0224 (13) | 0.0223 (12) | −0.0025 (9) | 0.0000 (9) | 0.0022 (9) |
C1 | 0.0217 (13) | 0.0207 (13) | 0.0239 (13) | 0.0021 (10) | 0.0002 (10) | −0.0002 (10) |
C2 | 0.0173 (12) | 0.0226 (14) | 0.0258 (13) | 0.0027 (10) | 0.0004 (10) | −0.0028 (11) |
C3 | 0.0172 (13) | 0.0219 (13) | 0.0279 (13) | 0.0035 (10) | 0.0002 (10) | −0.0016 (11) |
P1—O1 | 1.5060 (19) | C1—C2 | 1.517 (3) |
P1—O2 | 1.4974 (19) | C1—H1A | 0.99 |
P1—O3 | 1.5686 (19) | C1—H1B | 0.99 |
P1—H1 | 1.27 (2) | C2—C3 | 1.529 (4) |
O3—H3 | 0.80 (2) | C2—H2A | 0.99 |
N1—C1 | 1.490 (3) | C2—H2B | 0.99 |
N1—H13 | 0.87 (2) | C3—C3i | 1.526 (5) |
N1—H12 | 0.87 (2) | C3—H3A | 0.99 |
N1—H11 | 0.87 (2) | C3—H3B | 0.99 |
O1—P1—H1 | 106.4 (11) | N1—C1—H1B | 109.3 |
O1—P1—O3 | 105.82 (11) | C2—C1—H1B | 109.3 |
O2—P1—H1 | 113.1 (11) | H1A—C1—H1B | 107.9 |
O2—P1—O1 | 115.29 (12) | C1—C2—C3 | 111.9 (2) |
O2—P1—O3 | 112.83 (10) | C1—C2—H2A | 109.2 |
O3—P1—H1 | 102.3 (11) | C3—C2—H2A | 109.2 |
P1—O3—H3 | 118 (3) | C1—C2—H2B | 109.2 |
C1—N1—H13 | 110.9 (19) | C3—C2—H2B | 109.2 |
C1—N1—H12 | 109 (2) | H2A—C2—H2B | 107.9 |
H13—N1—H12 | 110 (3) | C3i—C3—C2 | 112.6 (3) |
C1—N1—H11 | 110 (2) | C3i—C3—H3A | 109.1 |
H13—N1—H11 | 108 (3) | C2—C3—H3A | 109.1 |
H12—N1—H11 | 110 (3) | C3i—C3—H3B | 109.1 |
N1—C1—C2 | 111.7 (2) | C2—C3—H3B | 109.1 |
N1—C1—H1A | 109.3 | H3A—C3—H3B | 107.8 |
C2—C1—H1A | 109.3 |
Symmetry code: (i) −x−1, −y−1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1[a]ii | 0.80 (2) | 1.79 (2) | 2.587 (3) | 171 (4) |
N1—H11···O1[b] | 0.87 (2) | 1.91 (2) | 2.784 (3) | 177 (3) |
N1—H12···O2[c]iii | 0.87 (2) | 1.91 (2) | 2.781 (3) | 173 (3) |
N1—H13···O1[d]iv | 0.87 (2) | 2.50 (3) | 3.060 (3) | 123 (2) |
N1—H13···O2[e]iv | 0.87 (2) | 2.18 (2) | 3.045 (3) | 171 (3) |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1/2, y−1/2, −z+3/2; (iv) −x−1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C6H18N22+·2H2PO3− |
Mr | 280.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 183 |
a, b, c (Å) | 4.9330 (3), 8.9074 (5), 14.8407 (8) |
β (°) | 94.751 (1) |
V (Å3) | 649.86 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.16 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.946, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4004, 1284, 1049 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.117, 1.04 |
No. of reflections | 1284 |
No. of parameters | 93 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.34 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2001), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).
P1—O1 | 1.5060 (19) | P1—O3 | 1.5686 (19) |
P1—O2 | 1.4974 (19) | P1—H1 | 1.27 (2) |
O1—P1—H1 | 106.4 (11) | O2—P1—O3 | 112.83 (10) |
O1—P1—O3 | 105.82 (11) | O3—P1—H1 | 102.3 (11) |
O2—P1—H1 | 113.1 (11) | P1—O3—H3 | 118 (3) |
O2—P1—O1 | 115.29 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1[a]i | 0.80 (2) | 1.79 (2) | 2.587 (3) | 171 (4) |
N1—H11···O1[b] | 0.87 (2) | 1.91 (2) | 2.784 (3) | 177 (3) |
N1—H12···O2[c]ii | 0.87 (2) | 1.91 (2) | 2.781 (3) | 173 (3) |
N1—H13···O1[d]iii | 0.87 (2) | 2.50 (3) | 3.060 (3) | 123 (2) |
N1—H13···O2[e]iii | 0.87 (2) | 2.18 (2) | 3.045 (3) | 171 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x−1/2, y−1/2, −z+3/2. |
Current interest in supramolecular chemistry and material chemistry has focused on the search for new synthons and the design of building blocks which can be utilized for the engineering of one-, two- or three-dimensional assemblies. These include both organic and organic–inorganic hybrid materials, as well as organometallic moieties. The hydrogen bond plays a key role in this field and a number of hydrogen-bonding synthons have been introduced for the rational design of solids (Braga et al., 1998; Desiraju, 1989; Meleńdez & Hamilton, 1998). It has been found that phosphonic acids are potentially good candidates for the assembly of hydrogen-bonded networks (Ferguson et al., 1998; Gregson et al., 2000; Mahmoudkhani & Langer, 2001a,b; Sharma & Clearfield, 2000; Sharma et al., 2001). Phosphorus acid is the inorganic analogue of phosphonic acids, could thus behave in a similar manner in view of the architecture of the resulting structure and the potential for hydrogen-bonding interactions. This requires a systematic investigation and careful analysis of the already known structures. For example, in the crystal structures of anilinium hydrogenphosphite (Paixäo et al., 2000) and ethylenediammonium hydrogenphosphite (Fleck et al., 2000), the hydrogenphosphite group is involved in hydrogen-bonding networks, forming sheets or layers with a railroad-type section, respectively.
In the crystal structure of the title compound, (I), the hexamethylenediammonium cation is centrosymmetric and the asymmetric unit contains half of the dication and a hydrogenphosphite anion (Fig. 1). The structure exhibits a pillared-layered hydrogen-bonded network, as shown in Fig. 2. The anion acts as both hydrogen-bond donor (through the O3 atom) and acceptor (through the O1 and O2 atoms). The O2 atom is a bifurcated acceptor of hydrogen bonds via the H12 and H13 atoms, while the N1 atom acts as a bifurcated hydrogen-bond donor through the H13 atom. The O1 atom acts as an acceptor of three hydrogen bonds via the H3, H11 and H13 atoms (see Table 2 for the hydrogen-bond geometry and notations). The hydrogen-bonding pattern is presented in Fig. 3. Although the first-level graph set, based on the methodology of Bernstein et al. (1995) and Grell et al. (1999), contains only D and C(4) descriptors, the second and higher levels comprise several motifs, including chains and rings. The assignment of graph-set descriptors were performed using PLUTO, as described by Motherwell et al. (1999). The O3 atom acts only as a donor to the O1 atom, hydrogen bond [a], thus forming C(4) chain motifs along the a axis. A R12(4) ring motif is formed by the combination of [d] and [e] hydrogen bonds. A pair of hydrogenphosphite anions and an ammonium cation are linked together via [a], [c] and [d] hydrogen bonds, forming a R32(8) ring motif. A R33(10) motif is also formed by [a], [c] and [e] hydrogen bonds. A combination of [a], [b], [e], [c] and [b] hydrogen bonds gives a R53(12) ring motif.