Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011077/av1139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011077/av1139Isup2.hkl |
CCDC reference: 217145
H3PO4 (0.814 ml, 12 mmol; aq. 85% wt) was added dropwise to an aqueous solution (20 ml) of ethylene glycol (20%) with 2-methanolpyridine (1.012 ml, 10 mmol) and stirred for 2 h at 323 K. The resulting mixture was left to crystallize at room temperature. The colourless transparent crystals of (I) that resulted from the mixture were washed with a small amount of water and acetone, and dried in air.
Hydroxyl and amine H atoms were found in difference maps and were refined by allowing them to ride in these positions. H atoms bonded to C atoms were placed in calculated positions 0.97 Å from their parent atoms and modelled as riding. The Uiso(H) values were constrained to be 1.2Ueq of the parent atom in all cases.
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 (Dowty, 1999); software used to prepare material for publication: SHELXL97.
C6H8NO+·H2O4P− | Z = 2 |
Mr = 207.12 | F(000) = 216 |
Triclinic, P1 | Dx = 1.608 Mg m−3 |
a = 7.8826 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.0041 (4) Å | Cell parameters from 2793 reflections |
c = 8.2092 (5) Å | θ = 2.8–30.0° |
α = 65.5050 (1)° | µ = 0.31 mm−1 |
β = 69.5660 (1)° | T = 293 K |
γ = 69.0370 (1)° | Chunk, colourless |
V = 427.67 (4) Å3 | 0.39 × 0.37 × 0.28 mm |
Bruker SMART1000 CCD diffractometer | 2447 independent reflections |
Radiation source: fine-focus sealed tube | 2150 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ω scans | θmax = 30.0°, θmin = 2.8° |
Absorption correction: multi-scan SADABS (Bruker, 1999) | h = −9→11 |
Tmin = 0.884, Tmax = 0.918 | k = −10→11 |
3828 measured reflections | l = −7→11 |
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)] = 0.039 | Hydrogen site location: geom and difmap |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0759P)2 + 0.0416P] where P = (Fo2 + 2Fc2)/3 |
2447 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
C6H8NO+·H2O4P− | γ = 69.0370 (1)° |
Mr = 207.12 | V = 427.67 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8826 (4) Å | Mo Kα radiation |
b = 8.0041 (4) Å | µ = 0.31 mm−1 |
c = 8.2092 (5) Å | T = 293 K |
α = 65.5050 (1)° | 0.39 × 0.37 × 0.28 mm |
β = 69.5660 (1)° |
Bruker SMART1000 CCD diffractometer | 2447 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 1999) | 2150 reflections with I > 2σ(I) |
Tmin = 0.884, Tmax = 0.918 | Rint = 0.012 |
3828 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.44 e Å−3 |
2447 reflections | Δρmin = −0.45 e Å−3 |
118 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 | 0.45065 (4) | 0.54983 (4) | 0.24996 (4) | 0.03134 (12) | |
O1 | 0.31579 (14) | 0.49693 (16) | 0.43426 (13) | 0.0418 (2) | |
O2 | 0.35888 (14) | 0.68249 (14) | 0.09334 (13) | 0.0386 (2) | |
O3 | 0.5794 (2) | 0.36271 (17) | 0.21248 (16) | 0.0627 (4) | |
H3 | 0.5960 | 0.3394 | 0.1128 | 0.075* | |
O4 | 0.58419 (15) | 0.64905 (16) | 0.25971 (14) | 0.0434 (3) | |
H4 | 0.6142 | 0.5989 | 0.3546 | 0.052* | |
O5 | 0.01745 (16) | 0.26015 (17) | 0.79348 (16) | 0.0475 (3) | |
H5 | −0.1026 | 0.2573 | 0.8354 | 0.057* | |
N1 | 0.02109 (16) | 0.27950 (16) | 0.45168 (16) | 0.0365 (2) | |
H1 | −0.0677 | 0.3575 | 0.5077 | 0.044* | |
C1 | 0.0273 (2) | 0.3218 (2) | 0.2730 (2) | 0.0421 (3) | |
H11 | −0.0618 | 0.4230 | 0.2179 | 0.051* | |
C2 | 0.1649 (2) | 0.2158 (2) | 0.1728 (2) | 0.0463 (3) | |
H12 | 0.1716 | 0.2449 | 0.0490 | 0.056* | |
C3 | 0.2941 (2) | 0.0643 (2) | 0.2591 (2) | 0.0492 (4) | |
H13 | 0.3890 | −0.0091 | 0.1931 | 0.059* | |
C4 | 0.2820 (2) | 0.0222 (2) | 0.4431 (2) | 0.0450 (3) | |
H14 | 0.3664 | −0.0818 | 0.5022 | 0.054* | |
C5 | 0.14358 (19) | 0.13548 (18) | 0.53948 (19) | 0.0358 (3) | |
C6 | 0.1239 (2) | 0.1018 (2) | 0.7392 (2) | 0.0454 (3) | |
H15 | 0.0660 | −0.0029 | 0.8149 | 0.054* | |
H16 | 0.2474 | 0.0653 | 0.7610 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0339 (2) | 0.03528 (19) | 0.02256 (17) | −0.00207 (12) | −0.00855 (12) | −0.01146 (13) |
O1 | 0.0375 (5) | 0.0597 (6) | 0.0270 (4) | −0.0162 (4) | −0.0073 (4) | −0.0099 (4) |
O2 | 0.0399 (5) | 0.0437 (5) | 0.0275 (4) | 0.0023 (4) | −0.0131 (4) | −0.0138 (4) |
O3 | 0.0929 (10) | 0.0465 (6) | 0.0406 (6) | 0.0238 (6) | −0.0372 (6) | −0.0239 (5) |
O4 | 0.0442 (6) | 0.0541 (6) | 0.0307 (5) | −0.0193 (5) | −0.0113 (4) | −0.0049 (4) |
O5 | 0.0411 (6) | 0.0600 (7) | 0.0482 (6) | −0.0098 (5) | −0.0120 (5) | −0.0255 (5) |
N1 | 0.0359 (6) | 0.0378 (5) | 0.0339 (5) | −0.0067 (4) | −0.0091 (4) | −0.0116 (4) |
C1 | 0.0456 (8) | 0.0418 (7) | 0.0333 (7) | −0.0088 (6) | −0.0112 (6) | −0.0073 (5) |
C2 | 0.0547 (9) | 0.0467 (8) | 0.0326 (7) | −0.0135 (6) | −0.0063 (6) | −0.0113 (6) |
C3 | 0.0497 (8) | 0.0466 (8) | 0.0465 (8) | −0.0073 (6) | −0.0033 (7) | −0.0216 (7) |
C4 | 0.0443 (8) | 0.0372 (7) | 0.0487 (8) | −0.0044 (5) | −0.0140 (6) | −0.0121 (6) |
C5 | 0.0377 (6) | 0.0341 (6) | 0.0362 (6) | −0.0116 (5) | −0.0115 (5) | −0.0078 (5) |
C6 | 0.0499 (8) | 0.0492 (8) | 0.0390 (7) | −0.0093 (6) | −0.0188 (6) | −0.0123 (6) |
P1—O1 | 1.5054 (10) | C1—C2 | 1.368 (2) |
P1—O2 | 1.5072 (9) | C1—H11 | 0.9300 |
P1—O3 | 1.5634 (11) | C2—C3 | 1.385 (2) |
P1—O4 | 1.5668 (11) | C2—H12 | 0.9300 |
O3—H3 | 0.8694 | C3—C4 | 1.380 (2) |
O4—H4 | 0.7908 | C3—H13 | 0.9300 |
O5—C6 | 1.3982 (19) | C4—C5 | 1.387 (2) |
O5—H5 | 0.8924 | C4—H14 | 0.9300 |
N1—C5 | 1.3346 (16) | C5—C6 | 1.506 (2) |
N1—C1 | 1.3488 (18) | C6—H15 | 0.9700 |
N1—H1 | 0.8897 | C6—H16 | 0.9700 |
O1—P1—O2 | 114.29 (6) | C3—C2—H12 | 120.6 |
O1—P1—O3 | 108.06 (7) | C4—C3—C2 | 120.03 (15) |
O2—P1—O3 | 111.68 (5) | C4—C3—H13 | 120.0 |
O1—P1—O4 | 109.44 (6) | C2—C3—H13 | 120.0 |
O2—P1—O4 | 107.44 (6) | C3—C4—C5 | 119.73 (14) |
O3—P1—O4 | 105.57 (7) | C3—C4—H14 | 120.1 |
P1—O3—H3 | 123.7 | C5—C4—H14 | 120.1 |
P1—O4—H4 | 111.0 | N1—C5—C4 | 118.41 (13) |
C6—O5—H5 | 109.9 | N1—C5—C6 | 118.60 (13) |
C5—N1—C1 | 123.12 (13) | C4—C5—C6 | 122.99 (13) |
C5—N1—H1 | 121.1 | O5—C6—C5 | 113.43 (12) |
C1—N1—H1 | 115.7 | O5—C6—H15 | 108.9 |
N1—C1—C2 | 119.92 (14) | C5—C6—H15 | 108.9 |
N1—C1—H11 | 120.0 | O5—C6—H16 | 108.9 |
C2—C1—H11 | 120.0 | C5—C6—H16 | 108.9 |
C1—C2—C3 | 118.75 (14) | H15—C6—H16 | 107.7 |
C1—C2—H12 | 120.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.87 | 1.67 | 2.5386 (14) | 173 |
O4—H4···O1ii | 0.79 | 1.78 | 2.5667 (14) | 176 |
O5—H5···O2iii | 0.89 | 1.83 | 2.7071 (15) | 165 |
N1—H1···O1iii | 0.89 | 1.89 | 2.7172 (16) | 153 |
N1—H1···O5 | 0.89 | 2.40 | 2.7358 (16) | 103 |
C4—H14···O3iv | 0.93 | 2.52 | 3.3472 (19) | 148 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C6H8NO+·H2O4P− |
Mr | 207.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.8826 (4), 8.0041 (4), 8.2092 (5) |
α, β, γ (°) | 65.5050 (1), 69.5660 (1), 69.0370 (1) |
V (Å3) | 427.67 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.39 × 0.37 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan SADABS (Bruker, 1999) |
Tmin, Tmax | 0.884, 0.918 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3828, 2447, 2150 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.115, 1.08 |
No. of reflections | 2447 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.45 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.87 | 1.67 | 2.5386 (14) | 172.7 |
O4—H4···O1ii | 0.79 | 1.78 | 2.5667 (14) | 175.6 |
O5—H5···O2iii | 0.89 | 1.83 | 2.7071 (15) | 165.2 |
N1—H1···O1iii | 0.89 | 1.89 | 2.7172 (16) | 153.0 |
C4—H14···O3iv | 0.93 | 2.52 | 3.3472 (19) | 147.8 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z+1. |
During the synthesis of metal phosphates templated by organic amines (Cheetham et al., 1999), amine phosphates may occur as unexpected by-products and may also act as intermediates in the formation of open-framework structures (Oliver et al., 1998; Neeraj et al., 1999; 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). Here we describe the structure of 2-methanolpyridinium dihydrogenphosphate, (C6H8NO)(H2PO4), (I) (Fig. 1).
The pyridine ring is essentially planar (for atoms N1 and C1–C6, the r.m.s. deviation from the best least-squares plane is 0.009 Å), and the bond distances and angles in the cation are comparable to those seen for the neutral molecule coordinated to metal ions (Yilmaz et al., 2002a,b). Similar geometrical parameters were also observed in (C6H8NO)[RuCl3(C6H6NO)(NO)] (Suzuki et al., 1999) in which the organic moiety acts as both an O—H deprotonated (N,O)-ligand to ruthenium and an N—H protonated counter-ion.
For the dihydrogen phosphate group, the protonated P—O vertices (O3 and O4) show their expected lengthening relative to the other P—O bonds (O1 and O2), which are of similar length as a result of delocalization of the negative charge between them.
The crystal packing is shown in Figs. 2 and 3. The dihydrogen phosphate anions are linked by relatively strong, roughly parallel, pairs of P—O—H···O—P and P—O···H—O—P hydrogen bonds, thus creating a polymeric chain that propagates along [001]. Along the chain, these bonds alternate between P—O3—H3···O2—P and P—O2···H3—O2—P pairs, and P—O4—H4···O1—P and P—O1···H4—O4—P pairs. By comparison, in N-(2-hydroxyethyl)-ethylenediammonium hydrogen phosphate monohydrate (Demir et al., 2002), infinite chains of HPO4 groups are linked by a single P—O—H···O—P connection, while in triethanolammonium dihydrogenphosphate (Demir et al., 2003), the [H2PO4]− moieties are connected by alternating single and double P—O—H···O—P hydrogen-bond links.
In (I), the 2-methanolpyridinium cations are pendant to the phosphate chains; each (C6H8NO)+ cation is bonded to its neighbouring (H2PO4)− unit by both an N1—H1···O1 and an O5—H5···O2 hydrogen bond. The first of these links (Table 2) may be acute because of a weak intramolecular N1—H1···O5 bond [d(N—H) = 0.89 Å, d(H···O) = 2.40 Å, d(N···O) = 2.736 (2) Å and θ(N—H····O) = 103°].
Adjacent chains interact via van der Waals forces and relatively weak π–π ring-stacking interactions [ring–centroid separation = 3.829 Å; the adjacent ring is generated by the symmetry operator (-x, −y, 1 − z)]. The pattern of π–π stacking (Fig. 2) between adjacent chains results in a head-to-tail configuration for the participating 2-methanolpyridinium cations, although it is not clear that the π–π interaction by itself actually drives this motif. This configuration resuls in extended (110) sheets (Fig. 3). If it is not an artefact of crystal packing, a weak C4—H14···O3 bond (Table 2) provides further cohesion between neighbouring chains in the (110) sheets.