Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109049154/sf3121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109049154/sf3121Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109049154/sf3121IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109049154/sf3121IIIsup4.hkl |
CCDC references: 765461; 765462; 765463
Compounds (I)–(III) were synthesized by heating together for 10 min under reflux L-tartaric acid (1 mmol) and, respectively, 3-aminopyridine, pyridine-3-carboxylic acid (nicotinic acid) and pyridine-2-carboxylic acid (picolinic acid) (1 mmol) in either 50% ethanol–water (50 ml) for (I) or 50% propan-2-ol–water (50 ml) for (I) [(II)?] and (III). After partial room-temperature evaporation of the solvents, all compounds gave hard colourless crystals: prisms for (I) (m.p. 371–373 K), blocks for (II) (m.p. 470–471 K) or plates for (III) (m.p. 393 K).
H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included at calculated positions, with C—H (aromatic) = 0.93 Å and C—H (aliphatic) = 0.98 Å, and treated as riding, with Uiso(H) = 1.2Ueq(C). The absolute configuration determined for the parent L-(+)-tartaric acid, (2R,3R) (Bijvoet et al., 1951; Lutz & Schreurs, 2008), was invoked in all cases. Friedel pairs were averaged in all data sets used in the final refinements, but unacceptable though meaningless values were obtained for the absolute structure parameters (Flack, 1983) determined from complete data sets for these light-atom structures. It should also be noted that with (I) the structure was refined using diffraction data re-acquired at 200 K, necessitated because of the very large displacement parameters for all atoms in the structure obtained from room-temperature data. This problem is still apparent but considerably lessened in the low-temperature structure reported here. With (II) and (III), the problem was not significant and room-temperature data were used.
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
C5H7N2+·C4H5O6−·2H2O | Dx = 1.447 Mg m−3 |
Mr = 280.24 | Melting point = 371–372 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1717 reflections |
a = 7.3073 (12) Å | θ = 3.1–28.9° |
b = 12.1065 (13) Å | µ = 0.13 mm−1 |
c = 14.541 (2) Å | T = 200 K |
V = 1286.4 (3) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.25 × 0.20 mm |
F(000) = 592 |
Oxford Gemini-S CCD area-detector diffractometer | 1434 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray source | Rint = 0.039 |
Graphite monochromator | θmax = 29.0°, θmin = 3.1° |
ω scans | h = −8→9 |
4764 measured reflections | k = −10→15 |
1722 independent reflections | l = −19→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: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0638P)2] where P = (Fo2 + 2Fc2)/3 |
1722 reflections | (Δ/σ)max < 0.001 |
212 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
0 constraints |
C5H7N2+·C4H5O6−·2H2O | V = 1286.4 (3) Å3 |
Mr = 280.24 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3073 (12) Å | µ = 0.13 mm−1 |
b = 12.1065 (13) Å | T = 200 K |
c = 14.541 (2) Å | 0.35 × 0.25 × 0.20 mm |
Oxford Gemini-S CCD area-detector diffractometer | 1434 reflections with I > 2σ(I) |
4764 measured reflections | Rint = 0.039 |
1722 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.25 e Å−3 |
1722 reflections | Δρmin = −0.20 e Å−3 |
212 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O11 | 0.5557 (2) | 0.85792 (14) | 0.42493 (11) | 0.0301 (5) | |
O12 | 0.5671 (2) | 0.70447 (15) | 0.33953 (16) | 0.0500 (7) | |
O21 | 0.2106 (3) | 0.68246 (15) | 0.33108 (18) | 0.0535 (7) | |
O31 | 0.2727 (2) | 0.90477 (14) | 0.26306 (11) | 0.0340 (5) | |
O41 | −0.0871 (2) | 0.86440 (14) | 0.26665 (11) | 0.0316 (5) | |
O42 | −0.0976 (2) | 0.86902 (14) | 0.41985 (11) | 0.0313 (5) | |
C11 | 0.4836 (3) | 0.77476 (18) | 0.38086 (15) | 0.0280 (6) | |
C21 | 0.2758 (3) | 0.77115 (18) | 0.38417 (17) | 0.0297 (6) | |
C31 | 0.1941 (3) | 0.87976 (16) | 0.34977 (15) | 0.0243 (6) | |
C41 | −0.0141 (3) | 0.86949 (15) | 0.34387 (14) | 0.0237 (5) | |
N1 | 0.0189 (4) | 0.8063 (2) | 0.09496 (18) | 0.0489 (8) | |
N3 | 0.0277 (5) | 0.5575 (2) | −0.04172 (18) | 0.0616 (11) | |
C2 | 0.0252 (4) | 0.6988 (3) | 0.07347 (18) | 0.0477 (9) | |
C3 | 0.0268 (4) | 0.6656 (2) | −0.01831 (17) | 0.0423 (8) | |
C4 | 0.0209 (5) | 0.7491 (2) | −0.08446 (19) | 0.0466 (9) | |
C5 | 0.0146 (5) | 0.8588 (2) | −0.0588 (2) | 0.0519 (9) | |
C6 | 0.0139 (5) | 0.8867 (3) | 0.0331 (2) | 0.0532 (9) | |
O1W | 0.3802 (3) | 0.49623 (16) | 0.26518 (14) | 0.0401 (6) | |
O2W | −0.1220 (3) | 0.58882 (18) | 0.2981 (2) | 0.0718 (9) | |
H11 | 0.691 (7) | 0.860 (4) | 0.420 (3) | 0.068 (14)* | |
H21 | 0.23760 | 0.75990 | 0.44810 | 0.0360* | |
H21A | 0.277 (5) | 0.637 (3) | 0.318 (2) | 0.063 (11)* | |
H31 | 0.22510 | 0.93870 | 0.39330 | 0.0290* | |
H31A | 0.220 (5) | 0.961 (3) | 0.238 (2) | 0.053 (9)* | |
H1 | 0.012 (5) | 0.818 (3) | 0.148 (3) | 0.061 (10)* | |
H2 | 0.02860 | 0.64610 | 0.12000 | 0.0570* | |
H3A | 0.051 (6) | 0.501 (3) | 0.007 (3) | 0.075 (11)* | |
H3B | 0.032 (5) | 0.541 (3) | −0.100 (2) | 0.055 (9)* | |
H4 | 0.02120 | 0.73060 | −0.14650 | 0.0560* | |
H5 | 0.01090 | 0.91370 | −0.10340 | 0.0620* | |
H6 | 0.01000 | 0.96030 | 0.05130 | 0.0640* | |
H11W | 0.296 (5) | 0.448 (3) | 0.252 (2) | 0.049 (8)* | |
H12W | 0.470 (7) | 0.476 (3) | 0.246 (3) | 0.074 (13)* | |
H21W | −0.193 (6) | 0.638 (4) | 0.305 (3) | 0.086 (11)* | |
H22W | −0.014 (8) | 0.615 (5) | 0.306 (3) | 0.097 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0187 (8) | 0.0367 (8) | 0.0349 (8) | 0.0008 (7) | −0.0014 (7) | 0.0008 (7) |
O12 | 0.0205 (9) | 0.0405 (9) | 0.0889 (15) | 0.0018 (7) | 0.0011 (10) | −0.0197 (10) |
O21 | 0.0198 (9) | 0.0293 (9) | 0.1113 (18) | 0.0006 (7) | −0.0041 (11) | −0.0182 (10) |
O31 | 0.0210 (8) | 0.0433 (9) | 0.0378 (9) | 0.0042 (7) | 0.0054 (7) | 0.0123 (7) |
O41 | 0.0213 (8) | 0.0437 (9) | 0.0297 (8) | 0.0041 (7) | −0.0019 (7) | −0.0016 (7) |
O42 | 0.0181 (8) | 0.0447 (9) | 0.0312 (8) | −0.0007 (7) | 0.0018 (7) | −0.0039 (7) |
C11 | 0.0207 (10) | 0.0268 (10) | 0.0366 (11) | 0.0036 (9) | 0.0004 (10) | 0.0072 (9) |
C21 | 0.0174 (10) | 0.0294 (11) | 0.0424 (12) | −0.0015 (9) | −0.0011 (10) | 0.0064 (9) |
C31 | 0.0177 (10) | 0.0261 (9) | 0.0292 (10) | 0.0002 (8) | 0.0008 (9) | −0.0001 (9) |
C41 | 0.0198 (10) | 0.0210 (8) | 0.0302 (10) | 0.0020 (8) | −0.0003 (9) | −0.0015 (8) |
N1 | 0.0378 (14) | 0.0706 (16) | 0.0382 (12) | −0.0029 (12) | 0.0023 (11) | −0.0178 (12) |
N3 | 0.101 (3) | 0.0460 (12) | 0.0379 (12) | 0.0078 (15) | 0.0015 (16) | 0.0075 (11) |
C2 | 0.0478 (18) | 0.0613 (17) | 0.0339 (12) | 0.0004 (14) | 0.0021 (13) | 0.0039 (12) |
C3 | 0.0409 (16) | 0.0494 (14) | 0.0367 (12) | 0.0004 (13) | −0.0001 (12) | −0.0021 (11) |
C4 | 0.0576 (19) | 0.0487 (14) | 0.0335 (11) | −0.0035 (13) | 0.0002 (14) | 0.0013 (11) |
C5 | 0.0570 (19) | 0.0510 (15) | 0.0477 (14) | −0.0021 (16) | −0.0016 (15) | 0.0008 (12) |
C6 | 0.0503 (18) | 0.0535 (15) | 0.0557 (16) | −0.0051 (15) | −0.0006 (16) | −0.0110 (14) |
O1W | 0.0257 (10) | 0.0411 (9) | 0.0536 (11) | −0.0011 (9) | 0.0003 (9) | −0.0175 (9) |
O2W | 0.0249 (11) | 0.0446 (12) | 0.146 (2) | 0.0014 (9) | −0.0014 (14) | −0.0451 (13) |
O11—C11 | 1.305 (3) | N1—H1 | 0.79 (4) |
O12—C11 | 1.207 (3) | N3—H3B | 0.87 (3) |
O21—C21 | 1.406 (3) | N3—H3A | 1.00 (4) |
O31—C31 | 1.418 (3) | C11—C21 | 1.520 (3) |
O41—C41 | 1.245 (3) | C21—C31 | 1.528 (3) |
O42—C41 | 1.262 (3) | C31—C41 | 1.529 (3) |
O11—H11 | 0.99 (5) | C21—H21 | 0.9800 |
O21—H21A | 0.76 (4) | C31—H31 | 0.9800 |
O31—H31A | 0.86 (4) | C2—C3 | 1.394 (4) |
O1W—H11W | 0.87 (4) | C3—C4 | 1.396 (4) |
O1W—H12W | 0.75 (5) | C4—C5 | 1.380 (3) |
O2W—H21W | 0.80 (5) | C5—C6 | 1.378 (4) |
O2W—H22W | 0.86 (6) | C2—H2 | 0.9300 |
N1—C2 | 1.339 (4) | C4—H4 | 0.9300 |
N1—C6 | 1.326 (4) | C5—H5 | 0.9300 |
N3—C3 | 1.352 (3) | C6—H6 | 0.9300 |
C11—O11—H11 | 113 (3) | O41—C41—O42 | 125.6 (2) |
C21—O21—H21A | 118 (3) | O21—C21—H21 | 109.00 |
C31—O31—H31A | 111 (2) | C11—C21—H21 | 109.00 |
H11W—O1W—H12W | 108 (4) | C31—C21—H21 | 109.00 |
H21W—O2W—H22W | 108 (5) | O31—C31—H31 | 109.00 |
C2—N1—C6 | 123.8 (3) | C41—C31—H31 | 109.00 |
C6—N1—H1 | 122 (3) | C21—C31—H31 | 109.00 |
C2—N1—H1 | 114 (3) | N1—C2—C3 | 120.3 (3) |
C3—N3—H3A | 119 (2) | N3—C3—C2 | 121.3 (3) |
H3A—N3—H3B | 122 (3) | N3—C3—C4 | 121.8 (2) |
C3—N3—H3B | 118 (2) | C2—C3—C4 | 116.8 (2) |
O12—C11—C21 | 120.0 (2) | C3—C4—C5 | 120.8 (3) |
O11—C11—O12 | 125.8 (2) | C4—C5—C6 | 119.9 (3) |
O11—C11—C21 | 114.21 (18) | N1—C6—C5 | 118.5 (3) |
O21—C21—C31 | 110.19 (19) | N1—C2—H2 | 120.00 |
C11—C21—C31 | 110.81 (18) | C3—C2—H2 | 120.00 |
O21—C21—C11 | 110.07 (19) | C5—C4—H4 | 120.00 |
C21—C31—C41 | 109.70 (16) | C3—C4—H4 | 120.00 |
O31—C31—C21 | 108.45 (17) | C4—C5—H5 | 120.00 |
O31—C31—C41 | 111.75 (17) | C6—C5—H5 | 120.00 |
O41—C41—C31 | 118.76 (18) | C5—C6—H6 | 121.00 |
O42—C41—C31 | 115.62 (18) | N1—C6—H6 | 121.00 |
C2—N1—C6—C5 | 0.2 (5) | O31—C31—C41—O41 | 12.1 (2) |
C6—N1—C2—C3 | 0.0 (5) | C21—C31—C41—O42 | 73.1 (2) |
O11—C11—C21—O21 | 177.0 (2) | O31—C31—C41—O42 | −166.62 (17) |
O12—C11—C21—C31 | −124.9 (2) | C21—C31—C41—O41 | −108.2 (2) |
O11—C11—C21—C31 | 54.8 (3) | N1—C2—C3—C4 | −0.2 (4) |
O12—C11—C21—O21 | −2.8 (3) | N1—C2—C3—N3 | −178.0 (3) |
C11—C21—C31—O31 | 51.6 (2) | N3—C3—C4—C5 | 178.1 (3) |
C11—C21—C31—C41 | 173.86 (18) | C2—C3—C4—C5 | 0.3 (5) |
O21—C21—C31—C41 | 51.8 (2) | C3—C4—C5—C6 | −0.1 (5) |
O21—C21—C31—O31 | −70.5 (2) | C4—C5—C6—N1 | −0.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O41 | 0.79 (4) | 1.95 (4) | 2.707 (3) | 161 (4) |
N3—H3A···O42i | 1.00 (4) | 1.95 (4) | 2.934 (3) | 168 (4) |
N3—H3B···O1Wii | 0.87 (3) | 2.11 (3) | 2.960 (3) | 164 (3) |
O11—H11···O42iii | 0.99 (5) | 1.55 (5) | 2.538 (2) | 175 (2) |
O21—H21A···O1W | 0.76 (4) | 2.02 (4) | 2.745 (3) | 162 (4) |
O21—H21A···O12 | 0.76 (4) | 2.29 (4) | 2.622 (3) | 107 (3) |
O31—H31A···O2Wiv | 0.86 (4) | 1.78 (4) | 2.640 (3) | 171 (3) |
O1W—H11W···O41i | 0.87 (4) | 1.85 (4) | 2.711 (3) | 169 (3) |
O1W—H12W···O31v | 0.75 (5) | 2.07 (5) | 2.798 (3) | 162 (5) |
O2W—H21W···O12vi | 0.80 (5) | 1.99 (4) | 2.736 (3) | 155 (4) |
O2W—H22W···O21 | 0.86 (6) | 1.87 (6) | 2.724 (3) | 174 (3) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x−1, y, z. |
C6H6NO2+·C4H5O6− | Dx = 1.638 Mg m−3 |
Mr = 273.20 | Melting point = 470–471 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3162 reflections |
a = 6.5792 (2) Å | θ = 3.2–28.5° |
b = 7.7637 (2) Å | µ = 0.15 mm−1 |
c = 21.6830 (5) Å | T = 297 K |
V = 1107.55 (5) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.40 × 0.30 mm |
F(000) = 568 |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 1317 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray source | Rint = 0.020 |
Graphite monochromator | θmax = 28.7°, θmin = 3.2° |
ω scans | h = −8→8 |
5552 measured reflections | k = −6→10 |
1537 independent reflections | l = −28→28 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0397P)2] where P = (Fo2 + 2Fc2)/3 |
1537 reflections | (Δ/σ)max = 0.002 |
192 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C6H6NO2+·C4H5O6− | V = 1107.55 (5) Å3 |
Mr = 273.20 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.5792 (2) Å | µ = 0.15 mm−1 |
b = 7.7637 (2) Å | T = 297 K |
c = 21.6830 (5) Å | 0.40 × 0.40 × 0.30 mm |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 1317 reflections with I > 2σ(I) |
5552 measured reflections | Rint = 0.020 |
1537 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.16 e Å−3 |
1537 reflections | Δρmin = −0.16 e Å−3 |
192 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O11 | 0.6742 (2) | 0.15971 (17) | 0.03744 (6) | 0.0376 (5) | |
O12 | 0.7555 (2) | 0.22385 (16) | 0.13467 (6) | 0.0408 (5) | |
O21 | 0.9124 (2) | 0.52781 (17) | 0.09742 (6) | 0.0294 (4) | |
O31 | 0.4801 (2) | 0.53849 (18) | 0.10680 (6) | 0.0311 (4) | |
O41 | 0.6248 (2) | 0.84011 (15) | 0.06913 (5) | 0.0349 (5) | |
O42 | 0.66173 (19) | 0.75197 (15) | −0.02806 (5) | 0.0286 (4) | |
C11 | 0.7361 (3) | 0.2634 (2) | 0.08147 (8) | 0.0258 (5) | |
C21 | 0.7797 (3) | 0.4425 (2) | 0.05612 (7) | 0.0236 (5) | |
C31 | 0.5792 (3) | 0.5418 (2) | 0.04895 (8) | 0.0241 (5) | |
C41 | 0.6244 (3) | 0.7273 (2) | 0.02875 (8) | 0.0229 (5) | |
O71 | 0.7577 (3) | 0.31198 (16) | 0.32594 (6) | 0.0493 (6) | |
O72 | 0.8220 (3) | 0.50398 (17) | 0.39924 (6) | 0.0441 (5) | |
N1 | 0.7280 (3) | 0.7089 (2) | 0.19859 (7) | 0.0460 (6) | |
C2 | 0.7403 (4) | 0.5767 (2) | 0.23779 (9) | 0.0395 (6) | |
C3 | 0.7689 (3) | 0.6084 (2) | 0.29942 (7) | 0.0262 (5) | |
C4 | 0.7844 (3) | 0.7769 (2) | 0.31907 (8) | 0.0311 (6) | |
C5 | 0.7702 (3) | 0.9095 (2) | 0.27691 (8) | 0.0370 (6) | |
C6 | 0.7419 (3) | 0.8722 (2) | 0.21607 (8) | 0.0382 (7) | |
C7 | 0.7825 (3) | 0.4584 (2) | 0.34307 (8) | 0.0305 (5) | |
H11 | 0.648 (4) | 0.052 (4) | 0.0516 (12) | 0.074 (8)* | |
H21 | 0.84560 | 0.43210 | 0.01580 | 0.0280* | |
H21A | 0.992 (5) | 0.600 (4) | 0.0762 (11) | 0.068 (8)* | |
H31 | 0.49390 | 0.48510 | 0.01790 | 0.0290* | |
H31A | 0.386 (5) | 0.617 (4) | 0.1071 (13) | 0.077 (9)* | |
H1 | 0.694 (4) | 0.687 (3) | 0.1598 (13) | 0.061 (8)* | |
H2 | 0.72950 | 0.46420 | 0.22340 | 0.0470* | |
H4 | 0.80440 | 0.80100 | 0.36060 | 0.0370* | |
H5 | 0.77990 | 1.02340 | 0.28990 | 0.0440* | |
H6 | 0.73240 | 0.96030 | 0.18710 | 0.0460* | |
H72 | 0.825 (5) | 0.402 (4) | 0.4263 (11) | 0.080 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0598 (10) | 0.0169 (6) | 0.0361 (7) | −0.0057 (6) | −0.0080 (7) | 0.0002 (6) |
O12 | 0.0664 (10) | 0.0257 (7) | 0.0302 (7) | −0.0042 (7) | −0.0044 (7) | 0.0078 (5) |
O21 | 0.0308 (7) | 0.0251 (7) | 0.0322 (7) | −0.0056 (6) | −0.0044 (6) | 0.0018 (6) |
O31 | 0.0322 (7) | 0.0240 (7) | 0.0370 (7) | 0.0025 (6) | 0.0110 (6) | 0.0036 (6) |
O41 | 0.0569 (10) | 0.0173 (6) | 0.0304 (7) | −0.0048 (7) | 0.0007 (7) | −0.0022 (5) |
O42 | 0.0411 (7) | 0.0206 (6) | 0.0242 (6) | 0.0020 (6) | 0.0004 (6) | 0.0028 (5) |
C11 | 0.0297 (9) | 0.0190 (8) | 0.0286 (9) | 0.0025 (8) | 0.0023 (8) | 0.0006 (7) |
C21 | 0.0291 (9) | 0.0176 (8) | 0.0241 (8) | −0.0002 (8) | 0.0016 (7) | −0.0017 (6) |
C31 | 0.0305 (9) | 0.0182 (8) | 0.0237 (8) | −0.0036 (8) | −0.0033 (7) | 0.0009 (7) |
C41 | 0.0263 (8) | 0.0164 (8) | 0.0260 (9) | 0.0013 (7) | −0.0023 (8) | 0.0017 (7) |
O71 | 0.0840 (13) | 0.0233 (7) | 0.0405 (8) | −0.0044 (8) | 0.0022 (8) | −0.0038 (6) |
O72 | 0.0757 (11) | 0.0279 (7) | 0.0288 (7) | −0.0064 (7) | −0.0066 (7) | 0.0029 (6) |
N1 | 0.0750 (14) | 0.0416 (10) | 0.0213 (8) | −0.0077 (10) | −0.0034 (9) | −0.0015 (7) |
C2 | 0.0568 (14) | 0.0285 (9) | 0.0332 (10) | −0.0076 (11) | 0.0020 (10) | −0.0064 (8) |
C3 | 0.0295 (9) | 0.0241 (8) | 0.0249 (8) | −0.0002 (8) | 0.0021 (8) | −0.0021 (7) |
C4 | 0.0416 (11) | 0.0260 (9) | 0.0256 (9) | −0.0003 (9) | −0.0004 (8) | −0.0045 (7) |
C5 | 0.0521 (13) | 0.0243 (9) | 0.0346 (10) | 0.0024 (10) | 0.0039 (9) | −0.0004 (8) |
C6 | 0.0493 (13) | 0.0331 (11) | 0.0322 (10) | −0.0021 (10) | 0.0018 (10) | 0.0089 (8) |
C7 | 0.0367 (10) | 0.0243 (9) | 0.0304 (9) | −0.0009 (9) | 0.0029 (8) | −0.0014 (8) |
O11—C11 | 1.314 (2) | C11—C21 | 1.522 (2) |
O12—C11 | 1.201 (2) | C21—C31 | 1.536 (3) |
O21—C21 | 1.415 (2) | C31—C41 | 1.534 (2) |
O31—C31 | 1.414 (2) | C21—H21 | 0.9800 |
O41—C41 | 1.238 (2) | C31—H31 | 0.9800 |
O42—C41 | 1.271 (2) | C2—C3 | 1.372 (2) |
O11—H11 | 0.91 (3) | C3—C4 | 1.380 (2) |
O21—H21A | 0.89 (3) | C3—C7 | 1.503 (2) |
O31—H31A | 0.87 (3) | C4—C5 | 1.380 (2) |
O71—C7 | 1.207 (2) | C5—C6 | 1.363 (2) |
O72—C7 | 1.295 (2) | C2—H2 | 0.9300 |
O72—H72 | 0.99 (3) | C4—H4 | 0.9300 |
N1—C2 | 1.335 (2) | C5—H5 | 0.9300 |
N1—C6 | 1.326 (2) | C6—H6 | 0.9300 |
N1—H1 | 0.89 (3) | ||
C11—O11—H11 | 112.2 (17) | C41—C31—H31 | 110.00 |
C21—O21—H21A | 109.2 (17) | O31—C31—H31 | 110.00 |
C31—O31—H31A | 108.8 (19) | C21—C31—H31 | 110.00 |
C7—O72—H72 | 110.2 (16) | N1—C2—C3 | 119.38 (15) |
C2—N1—C6 | 123.28 (16) | C2—C3—C4 | 118.76 (15) |
C2—N1—H1 | 118.2 (15) | C2—C3—C7 | 118.85 (14) |
C6—N1—H1 | 118.1 (15) | C4—C3—C7 | 122.39 (14) |
O12—C11—C21 | 124.09 (15) | C3—C4—C5 | 119.86 (16) |
O11—C11—O12 | 125.07 (15) | C4—C5—C6 | 119.46 (15) |
O11—C11—C21 | 110.84 (14) | N1—C6—C5 | 119.27 (15) |
O21—C21—C31 | 111.04 (13) | O71—C7—O72 | 125.03 (16) |
C11—C21—C31 | 109.46 (15) | O71—C7—C3 | 121.86 (16) |
O21—C21—C11 | 108.37 (13) | O72—C7—C3 | 113.11 (14) |
C21—C31—C41 | 109.49 (15) | N1—C2—H2 | 120.00 |
O31—C31—C21 | 107.29 (13) | C3—C2—H2 | 120.00 |
O31—C31—C41 | 111.08 (14) | C3—C4—H4 | 120.00 |
O41—C41—O42 | 125.34 (15) | C5—C4—H4 | 120.00 |
O41—C41—C31 | 117.54 (15) | C4—C5—H5 | 120.00 |
O42—C41—C31 | 117.11 (14) | C6—C5—H5 | 120.00 |
C11—C21—H21 | 109.00 | N1—C6—H6 | 120.00 |
O21—C21—H21 | 109.00 | C5—C6—H6 | 120.00 |
C31—C21—H21 | 109.00 | ||
C2—N1—C6—C5 | 0.0 (3) | O31—C31—C41—O42 | −161.59 (16) |
C6—N1—C2—C3 | −0.1 (4) | O31—C31—C41—O41 | 19.5 (2) |
O11—C11—C21—O21 | −158.61 (15) | N1—C2—C3—C7 | −180.0 (2) |
O12—C11—C21—C31 | −99.6 (2) | N1—C2—C3—C4 | −0.1 (3) |
O12—C11—C21—O21 | 21.6 (3) | C2—C3—C4—C5 | 0.3 (3) |
O11—C11—C21—C31 | 80.15 (18) | C2—C3—C7—O71 | −4.2 (3) |
O21—C21—C31—O31 | −65.11 (17) | C2—C3—C7—O72 | 176.0 (2) |
C11—C21—C31—O31 | 54.50 (17) | C4—C3—C7—O71 | 175.9 (2) |
C11—C21—C31—C41 | 175.14 (13) | C4—C3—C7—O72 | −3.9 (3) |
O21—C21—C31—C41 | 55.53 (17) | C7—C3—C4—C5 | −179.82 (19) |
C21—C31—C41—O41 | −98.77 (19) | C3—C4—C5—C6 | −0.3 (3) |
C21—C31—C41—O42 | 80.1 (2) | C4—C5—C6—N1 | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21 | 0.89 (3) | 2.33 (3) | 2.874 (2) | 120 (2) |
N1—H1···O31 | 0.89 (3) | 2.15 (3) | 2.893 (2) | 141 (2) |
N1—H1···O41 | 0.89 (3) | 2.34 (3) | 3.0624 (19) | 138 (2) |
O11—H11···O41i | 0.91 (3) | 1.70 (3) | 2.5951 (18) | 171 (3) |
O21—H21A···O42ii | 0.89 (3) | 1.91 (3) | 2.8064 (18) | 178 (3) |
O31—H31A···O42iii | 0.87 (3) | 2.48 (3) | 3.1542 (18) | 135 (2) |
O31—H31A···O71iv | 0.87 (3) | 2.30 (3) | 3.014 (2) | 139 (2) |
O72—H72···O42v | 0.99 (3) | 1.55 (3) | 2.5387 (17) | 176.3 (19) |
C5—H5···O71vi | 0.93 | 2.38 | 3.302 (2) | 172 |
C6—H6···O12vi | 0.93 | 2.35 | 3.252 (2) | 165 |
C21—H21···O11vii | 0.98 | 2.55 | 3.389 (2) | 143 |
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, −y+3/2, −z; (iii) x−1/2, −y+3/2, −z; (iv) −x+1, y+1/2, −z+1/2; (v) −x+3/2, −y+1, z+1/2; (vi) x, y+1, z; (vii) x+1/2, −y+1/2, −z. |
C6H6NO2+·C4H5O6−·H2O | Dx = 1.569 Mg m−3 |
Mr = 291.21 | Melting point: 393 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2870 reflections |
a = 7.1536 (4) Å | θ = 3.0–32.5° |
b = 7.8273 (3) Å | µ = 0.14 mm−1 |
c = 22.0145 (10) Å | T = 297 K |
V = 1232.67 (10) Å3 | Plate, colourless |
Z = 4 | 0.45 × 0.25 × 0.08 mm |
F(000) = 608 |
Oxford Gemini-S CCD area-detector diffractometer | 1416 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray source | Rint = 0.051 |
Graphite monochromator | θmax = 28.0°, θmin = 3.0° |
ω scans | h = −8→9 |
6582 measured reflections | k = −10→8 |
1709 independent reflections | l = −13→28 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.057P)2 + 0.2031P] where P = (Fo2 + 2Fc2)/3 |
1709 reflections | (Δ/σ)max = 0.018 |
209 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H6NO2+·C4H5O6−·H2O | V = 1232.67 (10) Å3 |
Mr = 291.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.1536 (4) Å | µ = 0.14 mm−1 |
b = 7.8273 (3) Å | T = 297 K |
c = 22.0145 (10) Å | 0.45 × 0.25 × 0.08 mm |
Oxford Gemini-S CCD area-detector diffractometer | 1416 reflections with I > 2σ(I) |
6582 measured reflections | Rint = 0.051 |
1709 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.27 e Å−3 |
1709 reflections | Δρmin = −0.24 e Å−3 |
209 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O11 | 0.3506 (5) | 0.2113 (3) | 0.63764 (11) | 0.0563 (8) | |
O12 | 0.2088 (4) | 0.1846 (3) | 0.72684 (11) | 0.0532 (8) | |
O21 | 0.1116 (3) | −0.1453 (3) | 0.70206 (10) | 0.0327 (6) | |
O31 | 0.5010 (3) | −0.1538 (3) | 0.70280 (12) | 0.0431 (8) | |
O41 | 0.3902 (4) | −0.4548 (3) | 0.65870 (10) | 0.0433 (7) | |
O42 | 0.2845 (4) | −0.3362 (3) | 0.57279 (9) | 0.0477 (8) | |
C11 | 0.2563 (4) | 0.1275 (3) | 0.67903 (12) | 0.0289 (8) | |
C21 | 0.2164 (4) | −0.0553 (3) | 0.65868 (11) | 0.0257 (7) | |
C31 | 0.3973 (4) | −0.1523 (3) | 0.64838 (12) | 0.0270 (8) | |
C41 | 0.3542 (4) | −0.3322 (3) | 0.62556 (13) | 0.0291 (8) | |
O71 | 0.7952 (5) | −0.0020 (2) | 0.56837 (10) | 0.0609 (8) | |
O72 | 0.7516 (5) | 0.1131 (3) | 0.47707 (10) | 0.0629 (11) | |
N1 | 0.8059 (4) | 0.3089 (3) | 0.61942 (11) | 0.0321 (7) | |
C2 | 0.7895 (5) | 0.2960 (3) | 0.55920 (13) | 0.0317 (8) | |
C3 | 0.7882 (6) | 0.4413 (4) | 0.52454 (14) | 0.0450 (9) | |
C4 | 0.8085 (7) | 0.5978 (4) | 0.55221 (15) | 0.0494 (12) | |
C5 | 0.8294 (5) | 0.6058 (4) | 0.61403 (16) | 0.0440 (10) | |
C6 | 0.8250 (5) | 0.4589 (4) | 0.64728 (14) | 0.0404 (10) | |
C7 | 0.7787 (5) | 0.1169 (3) | 0.53434 (12) | 0.0356 (9) | |
O1W | 0.8011 (4) | 0.0703 (3) | 0.71291 (10) | 0.0367 (7) | |
H11 | 0.354 (6) | 0.316 (6) | 0.6469 (19) | 0.063 (13)* | |
H21 | 0.14610 | −0.05200 | 0.62050 | 0.0310* | |
H21A | 0.016 (5) | −0.093 (5) | 0.7065 (15) | 0.047 (10)* | |
H31 | 0.47020 | −0.09240 | 0.61730 | 0.0320* | |
H31A | 0.510 (7) | −0.245 (6) | 0.7111 (19) | 0.067 (15)* | |
H1 | 0.803 (6) | 0.220 (5) | 0.6417 (17) | 0.054 (11)* | |
H3 | 0.77380 | 0.43420 | 0.48260 | 0.0540* | |
H4 | 0.80800 | 0.69740 | 0.52920 | 0.0590* | |
H5 | 0.84630 | 0.71060 | 0.63320 | 0.0530* | |
H6 | 0.83540 | 0.46340 | 0.68940 | 0.0490* | |
H72 | 0.765 (9) | 0.005 (7) | 0.459 (2) | 0.100 (16)* | |
H11W | 0.705 (7) | −0.002 (6) | 0.7157 (17) | 0.068 (13)* | |
H12W | 0.826 (7) | 0.122 (6) | 0.744 (2) | 0.079 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.105 (2) | 0.0180 (9) | 0.0458 (13) | −0.0057 (13) | 0.0230 (14) | 0.0006 (10) |
O12 | 0.0716 (16) | 0.0394 (11) | 0.0487 (13) | −0.0202 (14) | 0.0195 (13) | −0.0224 (11) |
O21 | 0.0323 (11) | 0.0273 (10) | 0.0386 (11) | −0.0013 (10) | 0.0081 (10) | −0.0028 (9) |
O31 | 0.0422 (13) | 0.0339 (13) | 0.0531 (14) | 0.0007 (11) | −0.0187 (11) | 0.0007 (12) |
O41 | 0.0656 (15) | 0.0203 (9) | 0.0441 (12) | −0.0016 (12) | 0.0006 (12) | 0.0039 (9) |
O42 | 0.0786 (17) | 0.0315 (11) | 0.0331 (11) | 0.0058 (13) | −0.0042 (12) | −0.0099 (9) |
C11 | 0.0347 (16) | 0.0228 (11) | 0.0293 (13) | 0.0018 (12) | −0.0055 (12) | 0.0000 (11) |
C21 | 0.0341 (14) | 0.0201 (10) | 0.0230 (11) | 0.0001 (13) | −0.0031 (11) | −0.0004 (10) |
C31 | 0.0338 (14) | 0.0206 (12) | 0.0266 (13) | −0.0029 (13) | 0.0018 (11) | 0.0021 (11) |
C41 | 0.0354 (15) | 0.0221 (12) | 0.0299 (14) | 0.0020 (12) | 0.0085 (12) | −0.0051 (11) |
O71 | 0.119 (2) | 0.0211 (9) | 0.0425 (12) | −0.0002 (14) | 0.0051 (16) | −0.0004 (9) |
O72 | 0.122 (3) | 0.0326 (11) | 0.0341 (11) | −0.0011 (16) | −0.0053 (15) | −0.0103 (10) |
N1 | 0.0455 (14) | 0.0229 (11) | 0.0280 (12) | 0.0016 (12) | 0.0006 (12) | 0.0013 (10) |
C2 | 0.0439 (16) | 0.0230 (11) | 0.0281 (13) | −0.0006 (14) | 0.0018 (13) | −0.0022 (11) |
C3 | 0.077 (2) | 0.0264 (13) | 0.0315 (14) | −0.0030 (19) | 0.0021 (17) | 0.0041 (13) |
C4 | 0.083 (3) | 0.0224 (13) | 0.0429 (17) | −0.0007 (18) | 0.0042 (19) | 0.0064 (13) |
C5 | 0.059 (2) | 0.0239 (14) | 0.0490 (19) | −0.0050 (15) | −0.0012 (17) | −0.0126 (13) |
C6 | 0.051 (2) | 0.0350 (14) | 0.0352 (15) | 0.0007 (16) | −0.0032 (14) | −0.0106 (13) |
C7 | 0.0529 (19) | 0.0240 (12) | 0.0300 (14) | −0.0014 (15) | 0.0044 (15) | −0.0056 (11) |
O1W | 0.0430 (13) | 0.0345 (11) | 0.0326 (11) | −0.0038 (12) | 0.0015 (10) | 0.0018 (9) |
O11—C11 | 1.310 (4) | N1—H1 | 0.85 (4) |
O12—C11 | 1.193 (4) | C11—C21 | 1.526 (3) |
O21—C21 | 1.404 (3) | C21—C31 | 1.517 (4) |
O31—C31 | 1.409 (4) | C31—C41 | 1.527 (3) |
O41—C41 | 1.233 (3) | C21—H21 | 0.9800 |
O42—C41 | 1.265 (4) | C31—H31 | 0.9800 |
O11—H11 | 0.85 (5) | C2—C7 | 1.507 (3) |
O21—H21A | 0.80 (4) | C2—C3 | 1.370 (4) |
O31—H31A | 0.74 (5) | C3—C4 | 1.376 (4) |
O71—C7 | 1.201 (3) | C4—C5 | 1.371 (5) |
O72—C7 | 1.276 (3) | C5—C6 | 1.363 (5) |
O72—H72 | 0.94 (5) | C3—H3 | 0.9300 |
O1W—H12W | 0.82 (5) | C4—H4 | 0.9300 |
O1W—H11W | 0.89 (5) | C5—H5 | 0.9300 |
N1—C6 | 1.332 (4) | C6—H6 | 0.9300 |
N1—C2 | 1.335 (4) | ||
C11—O11—H11 | 109 (3) | C31—C21—H21 | 109.00 |
C21—O21—H21A | 106 (3) | C41—C31—H31 | 109.00 |
C31—O31—H31A | 105 (3) | O31—C31—H31 | 109.00 |
C7—O72—H72 | 115 (3) | C21—C31—H31 | 109.00 |
H11W—O1W—H12W | 115 (4) | N1—C2—C7 | 115.8 (2) |
C2—N1—C6 | 122.2 (2) | C3—C2—C7 | 124.7 (3) |
C2—N1—H1 | 121 (3) | N1—C2—C3 | 119.4 (2) |
C6—N1—H1 | 117 (3) | C2—C3—C4 | 119.5 (3) |
O11—C11—O12 | 125.0 (3) | C3—C4—C5 | 119.5 (3) |
O12—C11—C21 | 123.9 (2) | C4—C5—C6 | 119.5 (3) |
O11—C11—C21 | 111.2 (2) | N1—C6—C5 | 119.9 (3) |
C11—C21—C31 | 110.7 (2) | O71—C7—C2 | 119.3 (2) |
O21—C21—C31 | 107.8 (2) | O72—C7—C2 | 112.9 (2) |
O21—C21—C11 | 111.8 (2) | O71—C7—O72 | 127.8 (2) |
O31—C31—C41 | 112.2 (2) | C2—C3—H3 | 120.00 |
C21—C31—C41 | 109.8 (2) | C4—C3—H3 | 120.00 |
O31—C31—C21 | 109.0 (2) | C5—C4—H4 | 120.00 |
O41—C41—O42 | 127.4 (3) | C3—C4—H4 | 120.00 |
O41—C41—C31 | 118.8 (3) | C4—C5—H5 | 120.00 |
O42—C41—C31 | 113.9 (2) | C6—C5—H5 | 120.00 |
O21—C21—H21 | 109.00 | N1—C6—H6 | 120.00 |
C11—C21—H21 | 109.00 | C5—C6—H6 | 120.00 |
C2—N1—C6—C5 | −0.4 (5) | O31—C31—C41—O42 | −170.7 (3) |
C6—N1—C2—C3 | −1.4 (5) | C21—C31—C41—O41 | −112.6 (3) |
C6—N1—C2—C7 | 177.0 (3) | C21—C31—C41—O42 | 67.9 (3) |
O11—C11—C21—C31 | 61.2 (3) | N1—C2—C3—C4 | 1.6 (6) |
O11—C11—C21—O21 | −178.6 (3) | C7—C2—C3—C4 | −176.7 (4) |
O12—C11—C21—O21 | 2.2 (4) | N1—C2—C7—O71 | −4.0 (5) |
O12—C11—C21—C31 | −118.1 (3) | N1—C2—C7—O72 | 175.9 (3) |
O21—C21—C31—O31 | −63.5 (3) | C3—C2—C7—O71 | 174.4 (4) |
C11—C21—C31—C41 | −177.7 (2) | C3—C2—C7—O72 | −5.7 (5) |
O21—C21—C31—C41 | 59.8 (3) | C2—C3—C4—C5 | −0.1 (7) |
C11—C21—C31—O31 | 59.0 (3) | C3—C4—C5—C6 | −1.7 (6) |
O31—C31—C41—O41 | 8.9 (4) | C4—C5—C6—N1 | 1.9 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.85 (4) | 1.96 (4) | 2.779 (3) | 162 (4) |
N1—H1···O71 | 0.85 (4) | 2.37 (4) | 2.682 (3) | 102 (3) |
O11—H11···O41i | 0.85 (5) | 1.83 (5) | 2.669 (3) | 171 (4) |
O21—H21A···O1Wii | 0.80 (4) | 2.00 (4) | 2.800 (3) | 171 (4) |
O31—H31A···O41 | 0.74 (5) | 2.18 (5) | 2.669 (3) | 124 (4) |
O31—H31A···O12iii | 0.74 (5) | 2.49 (5) | 2.883 (4) | 115 (4) |
O72—H72···O42iv | 0.94 (5) | 1.50 (5) | 2.441 (3) | 177 (6) |
O1W—H11W···O31 | 0.89 (5) | 1.90 (5) | 2.781 (3) | 168 (4) |
O1W—H12W···O21v | 0.82 (5) | 2.22 (5) | 2.975 (3) | 154 (4) |
C4—H4···O71i | 0.93 | 2.51 | 3.154 (4) | 127 |
C4—H4···O42vi | 0.93 | 2.50 | 3.329 (4) | 149 |
C6—H6···O12v | 0.93 | 2.55 | 3.295 (4) | 137 |
C6—H6···O21v | 0.93 | 2.56 | 3.446 (4) | 158 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1/2, −y−1/2, −z+1; (v) −x+1, y+1/2, −z+3/2; (vi) x+1/2, −y+1/2, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C5H7N2+·C4H5O6−·2H2O | C6H6NO2+·C4H5O6− | C6H6NO2+·C4H5O6−·H2O |
Mr | 280.24 | 273.20 | 291.21 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 200 | 297 | 297 |
a, b, c (Å) | 7.3073 (12), 12.1065 (13), 14.541 (2) | 6.5792 (2), 7.7637 (2), 21.6830 (5) | 7.1536 (4), 7.8273 (3), 22.0145 (10) |
V (Å3) | 1286.4 (3) | 1107.55 (5) | 1232.67 (10) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.15 | 0.14 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 | 0.40 × 0.40 × 0.30 | 0.45 × 0.25 × 0.08 |
Data collection | |||
Diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S Ultra CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4764, 1722, 1434 | 5552, 1537, 1317 | 6582, 1709, 1416 |
Rint | 0.039 | 0.020 | 0.051 |
(sin θ/λ)max (Å−1) | 0.681 | 0.675 | 0.660 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.098, 1.02 | 0.029, 0.066, 1.06 | 0.047, 0.107, 1.05 |
No. of reflections | 1722 | 1537 | 1709 |
No. of parameters | 212 | 192 | 209 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.20 | 0.16, −0.16 | 0.27, −0.24 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O41 | 0.79 (4) | 1.95 (4) | 2.707 (3) | 161 (4) |
N3—H3A···O42i | 1.00 (4) | 1.95 (4) | 2.934 (3) | 168 (4) |
N3—H3B···O1Wii | 0.87 (3) | 2.11 (3) | 2.960 (3) | 164 (3) |
O11—H11···O42iii | 0.99 (5) | 1.55 (5) | 2.538 (2) | 175 (2) |
O21—H21A···O1W | 0.76 (4) | 2.02 (4) | 2.745 (3) | 162 (4) |
O21—H21A···O12 | 0.76 (4) | 2.29 (4) | 2.622 (3) | 107 (3) |
O31—H31A···O2Wiv | 0.86 (4) | 1.78 (4) | 2.640 (3) | 171 (3) |
O1W—H11W···O41i | 0.87 (4) | 1.85 (4) | 2.711 (3) | 169 (3) |
O1W—H12W···O31v | 0.75 (5) | 2.07 (5) | 2.798 (3) | 162 (5) |
O2W—H21W···O12vi | 0.80 (5) | 1.99 (4) | 2.736 (3) | 155 (4) |
O2W—H22W···O21 | 0.86 (6) | 1.87 (6) | 2.724 (3) | 174 (3) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21 | 0.89 (3) | 2.33 (3) | 2.874 (2) | 120 (2) |
N1—H1···O31 | 0.89 (3) | 2.15 (3) | 2.893 (2) | 141 (2) |
N1—H1···O41 | 0.89 (3) | 2.34 (3) | 3.0624 (19) | 138 (2) |
O11—H11···O41i | 0.91 (3) | 1.70 (3) | 2.5951 (18) | 171 (3) |
O21—H21A···O42ii | 0.89 (3) | 1.91 (3) | 2.8064 (18) | 178 (3) |
O31—H31A···O42iii | 0.87 (3) | 2.48 (3) | 3.1542 (18) | 135 (2) |
O31—H31A···O71iv | 0.87 (3) | 2.30 (3) | 3.014 (2) | 139 (2) |
O72—H72···O42v | 0.99 (3) | 1.55 (3) | 2.5387 (17) | 176.3 (19) |
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, −y+3/2, −z; (iii) x−1/2, −y+3/2, −z; (iv) −x+1, y+1/2, −z+1/2; (v) −x+3/2, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.85 (4) | 1.96 (4) | 2.779 (3) | 162 (4) |
N1—H1···O71 | 0.85 (4) | 2.37 (4) | 2.682 (3) | 102 (3) |
O11—H11···O41i | 0.85 (5) | 1.83 (5) | 2.669 (3) | 171 (4) |
O21—H21A···O1Wii | 0.80 (4) | 2.00 (4) | 2.800 (3) | 171 (4) |
O31—H31A···O41 | 0.74 (5) | 2.18 (5) | 2.669 (3) | 124 (4) |
O31—H31A···O12iii | 0.74 (5) | 2.49 (5) | 2.883 (4) | 115 (4) |
O72—H72···O42iv | 0.94 (5) | 1.50 (5) | 2.441 (3) | 177 (6) |
O1W—H11W···O31 | 0.89 (5) | 1.90 (5) | 2.781 (3) | 168 (4) |
O1W—H12W···O21v | 0.82 (5) | 2.22 (5) | 2.975 (3) | 154 (4) |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1/2, −y−1/2, −z+1; (v) −x+1, y+1/2, −z+3/2. |
The use of common L-tartaric acid for the production of crystalline salts suitable for the single-crystal characterization of Lewis bases has been employed extensively. Such salts, particularly the 1:1 hydrogen L-tartrates, have been employed as biologically compatibile pharmaceuticals, as well as achiral materials with potential for nonlinear optical applications (Aakeröy et al., 1992; Kadirvelraj et al., 1998). However, the known structures of the hydrogen L-tartrate salts of the associative-group substituted monocyclic heteroaromatic base pyridine are not common. These include the 1:1 proton-transfer salts with the substituted pyridines 3-hydroxypyridine (Tafeenko et al., 1990), 3-methoxypyridine (Renuka et al., 1995), 2-amino-5-nitropyridine (Watanabe et al., 1993; Zyss et al., 1993), 3,4-diaminopyridine (Koleva et al., 2008), 4-(N,N-dimethylamino)pyridine (Pecaut, 1993; Parthasarathi et al., 1993; Manivannan et al., 2006), 4-carboxypyridine (isonicotinic acid) (Athimoolam & Natarajan, 2007a), 3-(aminocarboxy)pyridine (nicotinamide) (Athimoolam & Natarajan, 2007b) and 4-(aminocarboxy)pyridine (isonicotinamide) (Bhogala et al., 2005). In the structures of the majority of the anhydrous hydrogen tartrates (Aakeröy et al., 1992; Aakeröy & Hitchcock, 1993), homomeric C11(7) [or C(7)] (Etter et al., 1990) head-to-tail carboxylic acid–carboxylate hydrogen-bonding associations form primary chain substructures. These are extended into two-dimensional sheets and then, in the majority of examples, further extended into three-dimensional framework structures. The cation species, or the solvent water molecules in the hydrated salts, are often involved in the formation of these two-dimensional sheet structures. The presence of associative functional group substituents on the pyridinium cation promotes the formation of the framework structures. In some cases, e.g. the isonicotinic acid salt (Athimoolam & Natarajan, 2007a), where there are two independent hydrogen tartrate residues in the asymmetric unit, these anions form inter-associated duplex C11(7)-linked chains and sheet structures, as well as three-dimensional framework structures.
Considering this background, it was surprising that the structures of the 1:1 proton-transfer hydrogen L-tartrate salts of the analogous 3-carboxypyridine (nicotinic acid) or 2-carboxypyridine (picolinic acid) were not known. We therefore carried out 1:1 stoichiometric reactions of L-tartaric acid with a number of interactive-group substituted pyridines, with the intention of obtaining crystalline compounds suitable for X-ray analysis to enable examination of the hydrogen-bonding systems present. Crystalline compounds were obtained with the salts from the reactions of 3-aminopyridine, nicotinic acid and picolinic acid, from aqueous ethanol or propan-2-ol solvent systems, namely 3-aminopyridinium hydrogen (2R,3R)-tartrate dihydrate, C5H7N2+.C4H5O6-.2H2O, (I), anhydrous 3-carboxypyridinium hydrogen (2R,3R)-tartrate, C6H6N O2+.C4H5O6-, (II), and 2-carboxypyridinium hydrogen (2R,3R)-tartrate monohydrate, C6H6NO2+.C4H5O6-.H2O, (III), and their structures are reported here.
In compounds (I)–(III) (Figs. 1–3), not unexpectedly, the hetero-N atom of the base is protonated and forms direct N+—H···O hydrogen-bonding interactions (Tables 1–3). However, unlike the structures of both (I) and (II) where the interaction is with a carboxyl O acceptor, in (III) one of the solvent water molecules becomes the acceptor. This is probably due to steric factors associated with the ortho-related carboxy group. In all three structures the hydrogen tartrate anions form the common primary C11(7) hydrogen-bonded chain substructures, two-dimensional sheets and overall three-dimensional framework structures (Figs. 4–8). Because of the presence of solvent water molecules in (I) and (III), the three-dimensional makeup is sufficiently different for all three compounds to be considered separately.
With the structure of the 3-aminopyridinium dihydrate salt, (I) (Fig. 1), the primary head-to-tail hydrogen tartrate anion chains form along the a-axis direction in the unit cell and are extended into two-dimensional sheet structures through hydrogen-bonding interactions involving the two solvent water molecules (O1W and O2W) (Fig. 4). These interactions (Table 1) include the hydroxy groups acting as both donors and acceptors with both water molecules, closing conjoint R44(8), R34(11) and R33(12) cyclic associations. Extension into a three-dimensional framework involves both functional groups of the 3-aminopyridinium cation, which form links across the c cell direction with their aromatic rings layering down a, giving some ring overlap with weak π–π interactions [ring centroid separation 3.719 (2) Å].
In the structure of the anhydrous compound, (II), with nicotinic acid, the primary hydrogen tartrate sheet structure forms through hydroxy O—H···O(carboxyl) interchain cyclic associations [graph sets R22(11) and R44(19); Fig. 6]. The pyridinium N+—H group is involved in a four-centre cation–anion hydrogen-bonding association with a carboxylate O atom and two hydroxy O-atom acceptors of the anion (Fig. 2), enclosing two conjoint cyclic R12(5) interactions. The two hydroxy H atoms and the two carboxylic acid H-atom donors (one from the anion and the other from the cation) are involved in hydrogen-bonding interactions (Table 2), expanding the primary hydrogen tartrate sheets into the three-dimensional framework structure through cation crosslinks (Fig 7). The cation carboxylic acid O—H.. O(carboxyl) (anion) hydrogen bond is strong [O—H···O = 2.5387 (17) Å] and forms a cyclic R22(6) association linking separate tartrate residues in the chains via carboxyl and hydroxy groups.
In the monohydrate picolinate structure, (III), the solvent water molecule (O1W), which acts as an acceptor for the pyridinium H atom, also provides a three-centre bridge between the primary hydrogen tartrate anion chain substructures through separate hydroxy groups (Fig. 8). These tartrate chains extend down the b cell direction of the unit cell. The bifunctional 2-carboxypyridinium cations provide the crosslinks between the sheets, across the c cell direction. Additional peripheral hydrogen-bonding associations (Table 3), including a strong cation carboxylic acid O—H···O(carboxylate) (anion) hydrogen bond [O···O = 2.441 (3) Å], give the three-dimensional structure (Fig. 9). The picolinate cation has an intramolecular hydrogen bond [N···O = 2.682 (3) Å] between the pyridinium H atom and an O acceptor of the cis-related carboxylic acid group, which essentially maintains molecular planarity [torsion angle N1—C2—C7—O72 = 175.9 (3)°].
The accepted (2R,3R) absolute configuration for the L-tartrate residues in compounds (I)–(III) (Bijvoet et al., 1951; Lutz & Schreurs, 2008) was assumed and these anions adopt the common extended hydrogen tartrate conformation. The intramolecular hydroxy O—H···O(carboxyl) hydrogen bond, which is common in hydrogen L-tartrates, is also found in the hydrated compounds (I) [O21—H···O12] and (III) [O31—H···O41], but is absent in the anhydrous compound, (II). Despite this, there are no significant conformational differences in the three hydrogen tartrate anions, the characteristic O21—C21—C31—O31 torsion angles being -70.5 (2)° in (I), -65.11 (17)° in (II) and -63.5 (3)° in (III), which compare with the values of -65.1 (4) and -73.5 (4)° in the two independent anions in the asymmetric unit of 4-carboxyanilinium hydrogen L-tartrate (Athimoolam & Natarajan, 2007a), and -74.3 (3)° in the unsubstituted pyridinium hydrogen L-tartrate (Suresh et al., 2006).
This series of monocyclic heteroaromatic Lewis base–hydrogen L-tartrate salts provides further examples of molecular assembly facilitated by the presence of the classical C11(7) hydrogen-bonded head-to-tail hydrogen tartrate chains. These chains are expanded into two-dimensional sheets, which may also contain solvent water molecules. Three-dimensional frameworks result from inter-sheet crosslinking through the interactive bifunctional substituent group of the pyridinium cations.