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2-Pyridone (2-oxopyrimidine) forms hydrogen-bonded complexes with dicarboxylic acids, the molar ratio of 2-pyridone/dicarboxylic acid being 2:1 for the complexes with oxalic acid (ethanedioic acid), 2C5H5NO·C2H2O4, (I), and trans-β-hydromuconic acid (trans-hex-3-enedioic acid), 2C5H5NO·C6H8O4, (II), and 1:1 for the complexes with trans-glutaconic acid (trans-pent-2-enedioic acid), C5H5NO·C5H6O4, (III), and L-tartaric acid (L-2,3-dihydroxybutanedioic acid), C5H5NO·C4H6O6·H2O, (IV). Common features in the hydrogen-bonding patterns were found for the centrosymmetric and non-centrosymmetric acids, respectively. The 2-pyridone molecule takes the lactam form in these crystals.
Supporting information
CCDC references: 164675; 164676; 164677; 164678
Crystals of the four compounds were grown by slow evaporation from ethanol
solutions of 2-pyridone and the respective dicarboxylic acid, with molar
ratios of 1:1. Commercially available L-tartaric acid (Aldrich) was
used for the preparation of (IV).
All H atoms were located from difference Fourier maps and refined isotropically.
The ranges of the Uiso values for the H atoms were 0.051 (3)–0.084 (4) Å2 for (I), 0.054 (3)–0.085 (4) Å2 for (II), 0.055 (5)–0.154 (10) Å2
for (III) and 0.015 (3)–0.146 (10) Å2 for (IV). The values larger than 0.1 Å2 were observed for H10 and H11 in (III), and H9, H10 and H12 in (IV).
The least-squares refinement of (IV) was carried out by assuming the chirality
of L-tartaric acid and removing redundant diffraction data. The
calculations were performed at the Centre of Instrumental Analysis, Okayama
University.
For all compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Windows; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
2C5H5NO·C2H2O4 | Z = 1 |
Mr = 280.24 | F(000) = 146 |
Triclinic, P1 | Dx = 1.493 Mg m−3 |
a = 9.162 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.898 (3) Å | Cell parameters from 18 reflections |
c = 3.7672 (17) Å | θ = 9.4–11.5° |
α = 98.86 (4)° | µ = 0.12 mm−1 |
β = 97.66 (3)° | T = 298 K |
γ = 109.61 (3)° | Prismatic, colourless |
V = 311.6 (2) Å3 | 0.50 × 0.38 × 0.35 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.006 |
Radiation source: Rigaku rotating anode | θmax = 27.5°, θmin = 2.2° |
Graphite monochromator | h = −11→11 |
ω/2θ scans | k = −12→12 |
1645 measured reflections | l = 0→4 |
1428 independent reflections | 3 standard reflections every 97 reflections |
1336 reflections with I > 0.1σ(I) | intensity decay: <0.9% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.059 | All H-atom parameters refined |
wR(F2) = 0.098 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00031|Fo|2] |
S = 1.96 | (Δ/σ)max = 0.001 |
1336 reflections | Δρmax = 0.24 e Å−3 |
115 parameters | Δρmin = −0.22 e Å−3 |
Crystal data top
2C5H5NO·C2H2O4 | γ = 109.61 (3)° |
Mr = 280.24 | V = 311.6 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.162 (3) Å | Mo Kα radiation |
b = 9.898 (3) Å | µ = 0.12 mm−1 |
c = 3.7672 (17) Å | T = 298 K |
α = 98.86 (4)° | 0.50 × 0.38 × 0.35 mm |
β = 97.66 (3)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.006 |
1645 measured reflections | 3 standard reflections every 97 reflections |
1428 independent reflections | intensity decay: <0.9% |
1336 reflections with I > 0.1σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.098 | All H-atom parameters refined |
S = 1.96 | Δρmax = 0.24 e Å−3 |
1336 reflections | Δρmin = −0.22 e Å−3 |
115 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.80311 (7) | 0.41104 (7) | 0.0347 (2) | 0.04484 (18) | |
O2 | 0.56467 (8) | 0.19067 (7) | 0.0910 (2) | 0.0542 (2) | |
O3 | 0.67367 (8) | 0.04132 (7) | −0.1697 (2) | 0.0561 (2) | |
N1 | 0.95991 (8) | 0.64707 (8) | 0.2854 (2) | 0.03573 (19) | |
C2 | 0.81684 (9) | 0.53621 (9) | 0.2102 (2) | 0.0324 (2) | |
C3 | 0.69251 (10) | 0.57249 (10) | 0.3352 (3) | 0.0394 (2) | |
C4 | 0.71801 (12) | 0.71081 (11) | 0.5140 (3) | 0.0428 (3) | |
C5 | 0.86907 (12) | 0.82065 (10) | 0.5837 (3) | 0.0443 (3) | |
C6 | 0.98733 (11) | 0.78527 (10) | 0.4669 (3) | 0.0427 (3) | |
C7 | 0.57155 (9) | 0.06303 (9) | −0.0288 (3) | 0.0370 (2) | |
H1 | 1.0371 (15) | 0.6232 (12) | 0.194 (3) | 0.053 (3)* | |
H2 | 0.5883 (14) | 0.4935 (12) | 0.284 (3) | 0.051 (3)* | |
H3 | 0.6346 (15) | 0.7365 (13) | 0.596 (3) | 0.060 (3)* | |
H4 | 0.8863 (13) | 0.9167 (13) | 0.716 (3) | 0.057 (3)* | |
H5 | 1.0942 (15) | 0.8534 (12) | 0.501 (3) | 0.059 (3)* | |
H6 | 0.6554 (18) | 0.2687 (17) | 0.058 (4) | 0.084 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0383 (3) | 0.0275 (3) | 0.0682 (4) | 0.0092 (3) | 0.0244 (3) | 0.0033 (3) |
O2 | 0.0458 (4) | 0.0289 (3) | 0.0893 (6) | 0.0096 (3) | 0.0380 (4) | 0.0050 (3) |
O3 | 0.0412 (4) | 0.0401 (4) | 0.0894 (6) | 0.0118 (3) | 0.0376 (4) | 0.0060 (4) |
N1 | 0.0302 (4) | 0.0318 (4) | 0.0476 (4) | 0.0124 (3) | 0.0140 (3) | 0.0077 (3) |
C2 | 0.0312 (4) | 0.0304 (4) | 0.0389 (5) | 0.0120 (3) | 0.0129 (3) | 0.0098 (3) |
C3 | 0.0320 (4) | 0.0397 (5) | 0.0499 (5) | 0.0129 (4) | 0.0184 (4) | 0.0104 (4) |
C4 | 0.0463 (5) | 0.0464 (5) | 0.0479 (5) | 0.0260 (4) | 0.0227 (4) | 0.0130 (4) |
C5 | 0.0545 (6) | 0.0334 (5) | 0.0480 (5) | 0.0187 (4) | 0.0174 (4) | 0.0045 (4) |
C6 | 0.0382 (5) | 0.0330 (5) | 0.0534 (6) | 0.0089 (4) | 0.0121 (4) | 0.0062 (4) |
C7 | 0.0309 (4) | 0.0316 (4) | 0.0469 (5) | 0.0095 (3) | 0.0143 (4) | 0.0026 (4) |
Geometric parameters (Å, º) top
O1—C2 | 1.2683 (15) | C4—H3 | 0.955 (18) |
N1—C2 | 1.3573 (16) | C5—C6 | 1.3507 (19) |
N1—C6 | 1.3554 (17) | C5—H4 | 0.953 (16) |
N1—H1 | 0.908 (19) | C6—H5 | 0.963 (17) |
C2—C3 | 1.4191 (16) | O2—C7 | 1.2996 (15) |
C3—C4 | 1.3573 (19) | O2—H6 | 0.96 (2) |
C3—H2 | 0.981 (16) | O3—C7 | 1.1983 (15) |
C4—C5 | 1.404 (2) | C7—C7i | 1.544 (2) |
| | | |
O3···C7ii | 3.302 (2) | O3···C5iv | 3.3588 (19) |
O3···C7iii | 3.307 (2) | O3···H4iv | 2.679 (17) |
| | | |
C2—N1—C6 | 123.88 (11) | C5—C4—H3 | 118.1 (11) |
C2—N1—H1 | 114.7 (10) | C4—C5—C6 | 118.39 (12) |
C6—N1—H1 | 121.3 (10) | C4—C5—H4 | 119.7 (10) |
O1—C2—N1 | 118.99 (10) | C6—C5—H4 | 121.8 (10) |
O1—C2—C3 | 125.19 (11) | N1—C6—C5 | 120.53 (12) |
N1—C2—C3 | 115.81 (11) | N1—C6—H5 | 115.3 (10) |
C2—C3—C4 | 120.89 (12) | C5—C6—H5 | 124.1 (10) |
C2—C3—H2 | 116.9 (9) | C7—O2—H6 | 111.1 (12) |
C4—C3—H2 | 122.2 (9) | O2—C7—O3 | 125.93 (11) |
C3—C4—C5 | 120.49 (12) | O2—C7—C7i | 111.68 (12) |
C3—C4—H3 | 121.4 (11) | O3—C7—C7i | 122.39 (14) |
| | | |
O1—C2—N1—C6 | 179.19 (12) | C2—C3—C4—C5 | −0.9 (2) |
O1—C2—C3—C4 | −178.48 (12) | C3—C2—N1—C6 | −0.15 (18) |
N1—C2—C3—C4 | 0.81 (19) | C3—C4—C5—C6 | 0.3 (2) |
N1—C6—C5—C4 | 0.3 (2) | O2—C7—C7i—O3i | −0.4 (3) |
C2—N1—C6—C5 | −0.4 (2) | | |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y, −z−1; (iii) x, y, z−1; (iv) x, y−1, z−1. |
Crystal data top
2C5H5NO·C6H8O4 | F(000) = 352 |
Mr = 334.33 | Dx = 1.330 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.824 (3) Å | Cell parameters from 25 reflections |
b = 5.5720 (17) Å | θ = 10–11° |
c = 15.556 (5) Å | µ = 0.10 mm−1 |
β = 101.31 (3)° | T = 298 K |
V = 835.0 (5) Å3 | Prismatic, colourless |
Z = 2 | 0.43 × 0.35 × 0.20 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.009 |
Radiation source: Rigaku rotating anode | θmax = 30.0°, θmin = 2.1° |
Graphite monochromator | h = 0→13 |
ω/2θ scans | k = 0→7 |
2802 measured reflections | l = −21→21 |
2429 independent reflections | 3 standard reflections every 97 reflections |
2187 reflections with I > 0.1σ(I) | intensity decay: <0.1% |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.059 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00022|Fo|2] |
wR(F2) = 0.102 | (Δ/σ)max = 0.010 |
S = 1.89 | Δρmax = 0.26 e Å−3 |
2187 reflections | Δρmin = −0.30 e Å−3 |
146 parameters | Extinction correction: Zachariasen (1967), equ(3), Acta Cryst. (1968). A24, p213. |
0 restraints | Extinction coefficient: 1.6 (4) × 10-6 |
Crystal data top
2C5H5NO·C6H8O4 | V = 835.0 (5) Å3 |
Mr = 334.33 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.824 (3) Å | µ = 0.10 mm−1 |
b = 5.5720 (17) Å | T = 298 K |
c = 15.556 (5) Å | 0.43 × 0.35 × 0.20 mm |
β = 101.31 (3)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.009 |
2802 measured reflections | 3 standard reflections every 97 reflections |
2429 independent reflections | intensity decay: <0.1% |
2187 reflections with I > 0.1σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.102 | All H-atom parameters refined |
S = 1.89 | Δρmax = 0.26 e Å−3 |
2187 reflections | Δρmin = −0.30 e Å−3 |
146 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.42044 (7) | 0.13718 (12) | 0.07540 (4) | 0.05736 (19) | |
O2 | 0.26139 (7) | 0.46278 (13) | 0.12498 (4) | 0.0566 (2) | |
O3 | 0.21963 (9) | 0.56938 (15) | −0.01457 (4) | 0.0768 (3) | |
N1 | 0.55942 (7) | −0.18999 (13) | 0.10368 (5) | 0.04455 (19) | |
C2 | 0.47795 (9) | −0.01743 (15) | 0.13013 (5) | 0.0422 (2) | |
C3 | 0.46415 (10) | −0.02961 (17) | 0.21914 (5) | 0.0508 (3) | |
C4 | 0.52890 (11) | −0.20255 (18) | 0.27268 (6) | 0.0554 (3) | |
C5 | 0.61049 (11) | −0.37510 (19) | 0.24190 (6) | 0.0560 (3) | |
C6 | 0.62347 (10) | −0.36531 (17) | 0.15700 (6) | 0.0509 (3) | |
C7 | 0.20316 (9) | 0.59895 (16) | 0.05882 (5) | 0.0447 (2) | |
C8 | 0.11163 (10) | 0.79070 (17) | 0.08523 (6) | 0.0470 (2) | |
C9 | 0.06462 (9) | 0.97199 (16) | 0.01504 (5) | 0.0427 (2) | |
H1 | 0.5684 (9) | −0.1862 (17) | 0.0456 (6) | 0.054 (3)* | |
H2 | 0.4087 (10) | 0.0918 (19) | 0.2374 (6) | 0.060 (3)* | |
H3 | 0.5158 (11) | −0.207 (2) | 0.3317 (7) | 0.070 (3)* | |
H4 | 0.6525 (12) | −0.502 (2) | 0.2755 (7) | 0.077 (4)* | |
H5 | 0.6743 (10) | −0.4714 (17) | 0.1293 (6) | 0.054 (3)* | |
H6 | 0.0333 (11) | 0.7090 (19) | 0.0999 (6) | 0.061 (3)* | |
H7 | 0.1626 (10) | 0.867 (2) | 0.1389 (7) | 0.064 (3)* | |
H8 | 0.1336 (10) | 1.0497 (18) | −0.0066 (6) | 0.054 (3)* | |
H9 | 0.3205 (13) | 0.357 (2) | 0.1031 (8) | 0.085 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0710 (4) | 0.0600 (4) | 0.0411 (3) | 0.0280 (3) | 0.0109 (3) | 0.0047 (3) |
O2 | 0.0685 (4) | 0.0580 (4) | 0.0432 (3) | 0.0257 (3) | 0.0108 (3) | 0.0052 (3) |
O3 | 0.1102 (6) | 0.0810 (5) | 0.0445 (4) | 0.0425 (5) | 0.0282 (4) | 0.0073 (4) |
N1 | 0.0496 (4) | 0.0496 (4) | 0.0353 (3) | 0.0100 (3) | 0.0105 (3) | 0.0005 (3) |
C2 | 0.0459 (4) | 0.0442 (5) | 0.0356 (4) | 0.0061 (4) | 0.0057 (3) | −0.0026 (3) |
C3 | 0.0629 (6) | 0.0535 (5) | 0.0371 (4) | 0.0119 (5) | 0.0127 (4) | −0.0048 (4) |
C4 | 0.0716 (6) | 0.0602 (6) | 0.0350 (4) | 0.0055 (5) | 0.0123 (4) | 0.0020 (4) |
C5 | 0.0677 (6) | 0.0526 (5) | 0.0464 (5) | 0.0119 (5) | 0.0082 (4) | 0.0101 (4) |
C6 | 0.0559 (5) | 0.0490 (5) | 0.0481 (5) | 0.0134 (4) | 0.0110 (4) | 0.0001 (4) |
C7 | 0.0493 (5) | 0.0441 (5) | 0.0406 (4) | 0.0064 (4) | 0.0087 (3) | −0.0001 (4) |
C8 | 0.0516 (5) | 0.0503 (5) | 0.0400 (4) | 0.0123 (4) | 0.0110 (4) | 0.0034 (4) |
C9 | 0.0471 (4) | 0.0409 (4) | 0.0419 (4) | 0.0048 (4) | 0.0127 (4) | 0.0024 (4) |
Geometric parameters (Å, º) top
O1—C2 | 1.2639 (13) | C6—H5 | 0.933 (14) |
N1—C2 | 1.3652 (15) | O2—C7 | 1.3158 (14) |
N1—C6 | 1.3540 (16) | O2—H9 | 0.937 (19) |
N1—H1 | 0.925 (13) | O3—C7 | 1.1954 (14) |
C2—C3 | 1.4191 (16) | C7—C8 | 1.5046 (17) |
C3—C4 | 1.3488 (18) | C8—C9 | 1.4927 (16) |
C3—H2 | 0.947 (14) | C8—H6 | 0.959 (14) |
C4—C5 | 1.395 (2) | C8—H7 | 0.982 (15) |
C4—H3 | 0.952 (14) | C9—C9i | 1.302 (2) |
C5—C6 | 1.3526 (19) | C9—H8 | 0.921 (14) |
C5—H4 | 0.925 (15) | | |
| | | |
C6···O3ii | 3.1492 (19) | H5···O3ii | 2.301 (14) |
| | | |
C7—O2—H9 | 106.5 (10) | N1—C6—C5 | 120.38 (12) |
C2—N1—C6 | 123.57 (10) | N1—C6—H5 | 113.6 (8) |
C2—N1—H1 | 116.9 (8) | C5—C6—H5 | 126.0 (8) |
C6—N1—H1 | 119.5 (8) | O2—C7—O3 | 123.23 (11) |
O1—C2—N1 | 119.22 (10) | O2—C7—C8 | 112.79 (10) |
O1—C2—C3 | 125.04 (10) | O3—C7—C8 | 123.97 (11) |
N1—C2—C3 | 115.74 (10) | C7—C8—C9 | 113.36 (10) |
C2—C3—C4 | 120.86 (11) | C7—C8—H6 | 106.2 (9) |
C2—C3—H2 | 115.4 (8) | C7—C8—H7 | 107.9 (8) |
C4—C3—H2 | 123.7 (8) | C9—C8—H6 | 110.3 (8) |
C3—C4—C5 | 120.90 (11) | C9—C8—H7 | 111.2 (9) |
C3—C4—H3 | 118.6 (9) | H6—C8—H7 | 107.7 (11) |
C5—C4—H3 | 120.5 (9) | C8—C9—C9 | 124.41 (15) |
C4—C5—C6 | 118.54 (12) | C8—C9—H8 | 116.2 (8) |
C4—C5—H4 | 123.6 (10) | C9—C9i—H8i | 119.4 (8) |
C6—C5—H4 | 117.8 (10) | | |
| | | |
O1—C2—N1—C6 | −178.90 (12) | C3—C2—N1—C6 | 0.56 (17) |
O1—C2—C3—C4 | 179.54 (13) | C3—C4—C5—C6 | 0.0 (2) |
N1—C2—C3—C4 | 0.12 (18) | O2—C7—C8—C9 | 170.00 (11) |
N1—C6—C5—C4 | 0.6 (2) | O3—C7—C8—C9 | −11.4 (2) |
C2—N1—C6—C5 | −1.0 (2) | C7—C8—C9—C9i | 125.59 (17) |
C2—C3—C4—C5 | −0.4 (2) | | |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y, −z. |
Crystal data top
C5H5NO·C5H6O4 | F(000) = 472 |
Mr = 225.20 | Dx = 1.382 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.889 (3) Å | Cell parameters from 25 reflections |
b = 16.839 (10) Å | θ = 10.8–11.4° |
c = 8.288 (2) Å | µ = 0.11 mm−1 |
β = 100.49 (3)° | T = 298 K |
V = 1082.5 (7) Å3 | Prismatic, colourless |
Z = 4 | 0.43 × 0.40 × 0.27 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.016 |
Radiation source: Rigaku rotating anode | θmax = 26.0°, θmin = 2.4° |
Graphite monochromator | h = 0→9 |
ω/2θ scans | k = 0→20 |
2298 measured reflections | l = −10→10 |
2128 independent reflections | 3 standard reflections every 97 reflections |
1848 reflections with I > 0.1σ(I) | intensity decay: <0.3% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.079 | All H-atom parameters refined |
wR(F2) = 0.088 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00022|Fo|2] |
S = 1.47 | (Δ/σ)max = 0.010 |
1848 reflections | Δρmax = 0.19 e Å−3 |
189 parameters | Δρmin = −0.25 e Å−3 |
Crystal data top
C5H5NO·C5H6O4 | V = 1082.5 (7) Å3 |
Mr = 225.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.889 (3) Å | µ = 0.11 mm−1 |
b = 16.839 (10) Å | T = 298 K |
c = 8.288 (2) Å | 0.43 × 0.40 × 0.27 mm |
β = 100.49 (3)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.016 |
2298 measured reflections | 3 standard reflections every 97 reflections |
2128 independent reflections | intensity decay: <0.3% |
1848 reflections with I > 0.1σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.088 | All H-atom parameters refined |
S = 1.47 | Δρmax = 0.19 e Å−3 |
1848 reflections | Δρmin = −0.25 e Å−3 |
189 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.58952 (13) | 0.41995 (6) | 0.25918 (14) | 0.0590 (4) | |
O2 | 0.32107 (16) | 0.36545 (7) | 0.37827 (16) | 0.0671 (4) | |
O3 | 0.21697 (15) | 0.48751 (7) | 0.33856 (17) | 0.0821 (5) | |
O4 | −0.29487 (14) | 0.21882 (7) | 0.69388 (15) | 0.0623 (4) | |
O5 | −0.09776 (14) | 0.17391 (6) | 0.55638 (15) | 0.0676 (4) | |
N1 | 0.50970 (17) | 0.54898 (8) | 0.23311 (17) | 0.0530 (4) | |
C2 | 0.61778 (18) | 0.48915 (9) | 0.20861 (18) | 0.0466 (5) | |
C3 | 0.7527 (2) | 0.50969 (11) | 0.1264 (2) | 0.0551 (5) | |
C4 | 0.7700 (2) | 0.58583 (12) | 0.0771 (2) | 0.0641 (6) | |
C5 | 0.6560 (2) | 0.64483 (12) | 0.1079 (3) | 0.0681 (7) | |
C6 | 0.5276 (2) | 0.62513 (10) | 0.1852 (2) | 0.0625 (6) | |
C7 | 0.20371 (19) | 0.42006 (10) | 0.3849 (2) | 0.0532 (5) | |
C8 | 0.0546 (2) | 0.39462 (11) | 0.4550 (2) | 0.0574 (6) | |
C9 | 0.0403 (2) | 0.32930 (11) | 0.5340 (2) | 0.0538 (5) | |
C10 | −0.1076 (3) | 0.31216 (11) | 0.6188 (3) | 0.0611 (6) | |
C11 | −0.16296 (19) | 0.22764 (9) | 0.61704 (19) | 0.0474 (5) | |
H1 | 0.409 (2) | 0.5304 (10) | 0.285 (2) | 0.089 (6)* | |
H2 | 0.8302 (19) | 0.4711 (9) | 0.1102 (18) | 0.055 (5)* | |
H3 | 0.869 (2) | 0.5988 (10) | 0.028 (2) | 0.085 (6)* | |
H4 | 0.674 (2) | 0.6959 (12) | 0.078 (2) | 0.089 (7)* | |
H5 | 0.441 (2) | 0.6641 (11) | 0.215 (2) | 0.092 (6)* | |
H6 | −0.030 (2) | 0.4344 (10) | 0.447 (2) | 0.084 (6)* | |
H7 | 0.129 (2) | 0.2915 (10) | 0.5470 (19) | 0.064 (5)* | |
H8 | −0.198 (2) | 0.3466 (11) | 0.582 (2) | 0.079 (6)* | |
H9 | −0.071 (2) | 0.3287 (10) | 0.739 (2) | 0.092 (6)* | |
H10 | 0.406 (3) | 0.3904 (13) | 0.341 (3) | 0.116 (8)* | |
H11 | −0.311 (3) | 0.1652 (16) | 0.709 (3) | 0.154 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0565 (7) | 0.0403 (6) | 0.0893 (9) | 0.0025 (5) | 0.0378 (6) | 0.0005 (6) |
O2 | 0.0631 (8) | 0.0507 (8) | 0.0988 (10) | 0.0032 (6) | 0.0449 (8) | 0.0089 (6) |
O3 | 0.0765 (9) | 0.0530 (8) | 0.1337 (12) | 0.0071 (7) | 0.0637 (9) | 0.0200 (8) |
O4 | 0.0589 (7) | 0.0448 (7) | 0.0947 (9) | −0.0043 (6) | 0.0443 (7) | −0.0040 (6) |
O5 | 0.0773 (8) | 0.0478 (7) | 0.0903 (9) | 0.0038 (6) | 0.0490 (7) | −0.0040 (6) |
N1 | 0.0495 (8) | 0.0446 (8) | 0.0701 (9) | 0.0021 (7) | 0.0246 (7) | 0.0019 (7) |
C2 | 0.0432 (9) | 0.0442 (9) | 0.0545 (10) | −0.0018 (7) | 0.0150 (8) | −0.0065 (8) |
C3 | 0.0455 (10) | 0.0564 (11) | 0.0688 (12) | −0.0037 (9) | 0.0244 (9) | −0.0081 (9) |
C4 | 0.0565 (11) | 0.0715 (13) | 0.0688 (13) | −0.0197 (10) | 0.0234 (10) | 0.0004 (10) |
C5 | 0.0714 (13) | 0.0525 (12) | 0.0821 (14) | −0.0101 (10) | 0.0184 (11) | 0.0076 (10) |
C6 | 0.0646 (11) | 0.0474 (11) | 0.0780 (13) | 0.0023 (9) | 0.0199 (10) | 0.0048 (9) |
C7 | 0.0518 (10) | 0.0490 (10) | 0.0654 (11) | 0.0018 (8) | 0.0283 (9) | 0.0013 (9) |
C8 | 0.0550 (10) | 0.0525 (10) | 0.0722 (12) | −0.0011 (9) | 0.0316 (9) | 0.0039 (9) |
C9 | 0.0556 (10) | 0.0478 (10) | 0.0647 (12) | −0.0044 (9) | 0.0285 (9) | −0.0050 (9) |
C10 | 0.0681 (12) | 0.0493 (11) | 0.0767 (14) | −0.0123 (10) | 0.0417 (11) | −0.0071 (10) |
C11 | 0.0460 (9) | 0.0471 (9) | 0.0531 (10) | −0.0015 (7) | 0.0200 (8) | 0.0005 (8) |
Geometric parameters (Å, º) top
O1—C2 | 1.271 (2) | O2—H10 | 0.89 (3) |
N1—C2 | 1.359 (2) | O3—C7 | 1.209 (2) |
N1—C6 | 1.357 (3) | O4—C11 | 1.324 (2) |
N1—H1 | 1.02 (2) | O4—H11 | 0.92 (3) |
C2—C3 | 1.407 (2) | O5—C11 | 1.196 (2) |
C3—C4 | 1.360 (3) | C7—C8 | 1.468 (3) |
C3—H2 | 0.919 (18) | C8—C9 | 1.296 (3) |
C4—C5 | 1.395 (3) | C8—H6 | 0.94 (2) |
C4—H3 | 0.97 (2) | C9—C10 | 1.496 (3) |
C5—C6 | 1.335 (3) | C9—H7 | 0.938 (17) |
C5—H4 | 0.91 (2) | C10—C11 | 1.488 (3) |
C6—H5 | 1.01 (2) | C10—H8 | 0.93 (2) |
O2—C7 | 1.313 (2) | C10—H9 | 1.03 (2) |
| | | |
C4···O5i | 3.339 (3) | H5···O4ii | 2.47 (2) |
H3···O5i | 2.41 (2) | C3···O5iii | 3.397 (3) |
C6···O4ii | 3.457 (3) | H2···O5iii | 2.565 (15) |
| | | |
C2—N1—C6 | 123.72 (17) | C11—O4—H11 | 108.5 (19) |
C2—N1—H1 | 113.2 (12) | O2—C7—O3 | 122.82 (16) |
C6—N1—H1 | 123.0 (12) | O2—C7—C8 | 115.73 (19) |
O1—C2—N1 | 118.53 (15) | O3—C7—C8 | 121.44 (18) |
O1—C2—C3 | 125.31 (17) | C7—C8—C9 | 126.7 (2) |
N1—C2—C3 | 116.13 (17) | C7—C8—H6 | 111.8 (13) |
C2—C3—C4 | 120.25 (19) | C9—C8—H6 | 121.2 (13) |
C2—C3—H2 | 118.6 (11) | C8—C9—C10 | 123.3 (2) |
C4—C3—H2 | 121.1 (11) | C8—C9—H7 | 120.1 (12) |
C3—C4—C5 | 120.8 (2) | C10—C9—H7 | 116.5 (12) |
C3—C4—H3 | 118.1 (13) | C9—C10—C11 | 115.62 (17) |
C5—C4—H3 | 120.8 (13) | C9—C10—H8 | 110.1 (13) |
C4—C5—C6 | 118.9 (2) | C9—C10—H9 | 107.4 (12) |
C4—C5—H4 | 118.9 (14) | C11—C10—H8 | 112.9 (14) |
C6—C5—H4 | 122.2 (14) | C11—C10—H9 | 107.4 (12) |
N1—C6—C5 | 120.2 (2) | H8—C10—H9 | 102.4 (18) |
N1—C6—H5 | 115.6 (12) | O4—C11—O5 | 123.60 (17) |
C5—C6—H5 | 124.2 (13) | O4—C11—C10 | 110.95 (16) |
C7—O2—H10 | 105.2 (17) | O5—C11—C10 | 125.45 (16) |
| | | |
O1—C2—N1—C6 | 179.68 (19) | C3—C4—C5—C6 | −0.8 (4) |
O1—C2—C3—C4 | 179.7 (2) | O2—C7—C8—C9 | 12.1 (3) |
N1—C2—C3—C4 | 0.3 (3) | O3—C7—C8—C9 | −167.0 (2) |
N1—C6—C5—C4 | 0.3 (4) | O4—C11—C10—C9 | −179.7 (2) |
C2—N1—C6—C5 | 0.6 (3) | O5—C11—C10—C9 | 1.1 (4) |
C2—C3—C4—C5 | 0.5 (3) | C7—C8—C9—C10 | 172.5 (2) |
C3—C2—N1—C6 | −0.9 (3) | C8—C9—C10—C11 | 145.6 (2) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x+1, −y+1/2, z−1/2. |
Crystal data top
C5H5NO·C4H6O6·H2O | Dx = 1.516 Mg m−3 |
Mr = 263.20 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 8.528 (5) Å | θ = 10.8–11.5° |
b = 20.668 (8) Å | µ = 0.14 mm−1 |
c = 6.5438 (15) Å | T = 295 K |
V = 1153.4 (7) Å3 | Prismatic, colourless |
Z = 4 | 0.53 × 0.28 × 0.20 mm |
F(000) = 552 | |
Data collection top
Rigaku AFC-5R diffractometer | 2064 reflections with I > 0.1σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.011 |
Graphite monochromator | θmax = 32.0°, θmin = 2.0° |
ω/2θ scans | h = 0→12 |
Absorption correction: ψ scans (North et al., 1968) | k = 0→30 |
Tmin = 0.952, Tmax = 0.999 | l = −1→9 |
2660 measured reflections | 3 standard reflections every 97 reflections |
2303 independent reflections | intensity decay: <0.5% |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.044 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00001|Fo|2] |
wR(F2) = 0.044 | (Δ/σ)max = 0.010 |
S = 1.80 | Δρmax = 0.32 e Å−3 |
2064 reflections | Δρmin = −0.31 e Å−3 |
216 parameters | Extinction correction: Zachariasen (1967), equ(3), Acta Cryst. (1968). A24, p213. |
0 restraints | Extinction coefficient: 1.68 × 10 (12)-6 |
Crystal data top
C5H5NO·C4H6O6·H2O | V = 1153.4 (7) Å3 |
Mr = 263.20 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.528 (5) Å | µ = 0.14 mm−1 |
b = 20.668 (8) Å | T = 295 K |
c = 6.5438 (15) Å | 0.53 × 0.28 × 0.20 mm |
Data collection top
Rigaku AFC-5R diffractometer | 2064 reflections with I > 0.1σ(I) |
Absorption correction: ψ scans (North et al., 1968) | Rint = 0.011 |
Tmin = 0.952, Tmax = 0.999 | 3 standard reflections every 97 reflections |
2660 measured reflections | intensity decay: <0.5% |
2303 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.044 | All H-atom parameters refined |
S = 1.80 | Δρmax = 0.32 e Å−3 |
2064 reflections | Δρmin = −0.31 e Å−3 |
216 parameters | |
Special details top
Geometry. The O2—H10 length, 1.20 (2) Å, is elongated in the short O—H···O hydrogen
bond. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.49399 (12) | 0.43810 (5) | 0.25423 (17) | 0.0541 (3) | |
O2 | 0.31341 (10) | 0.53184 (5) | 0.21738 (18) | 0.0558 (3) | |
O3 | 0.51062 (10) | 0.60285 (4) | 0.19044 (15) | 0.0467 (3) | |
O4 | 0.31260 (12) | 0.70141 (5) | 0.13139 (18) | 0.0496 (3) | |
O5 | 0.25390 (12) | 0.66734 (5) | 0.53540 (15) | 0.0458 (3) | |
O6 | −0.09014 (13) | 0.66162 (5) | 0.22679 (19) | 0.0556 (4) | |
O7 | −0.01411 (11) | 0.73370 (4) | 0.46179 (16) | 0.0540 (3) | |
O8 | −0.34509 (12) | 0.73051 (6) | 0.1702 (2) | 0.0470 (3) | |
N1 | 0.72157 (13) | 0.49451 (6) | 0.2167 (2) | 0.0423 (4) | |
C2 | 0.64150 (17) | 0.43759 (7) | 0.2387 (2) | 0.0431 (4) | |
C3 | 0.73498 (19) | 0.38140 (7) | 0.2403 (3) | 0.0488 (5) | |
C4 | 0.89252 (18) | 0.38451 (8) | 0.2219 (3) | 0.0548 (6) | |
C5 | 0.96815 (19) | 0.44382 (9) | 0.2021 (3) | 0.0518 (5) | |
C6 | 0.88088 (19) | 0.49770 (8) | 0.1992 (3) | 0.0490 (5) | |
C7 | 0.37157 (17) | 0.58980 (7) | 0.1943 (2) | 0.0409 (4) | |
C8 | 0.24346 (17) | 0.64044 (6) | 0.1745 (2) | 0.0375 (4) | |
C9 | 0.15579 (16) | 0.64452 (7) | 0.3785 (2) | 0.0369 (4) | |
C10 | 0.00891 (16) | 0.68594 (7) | 0.3606 (2) | 0.0406 (4) | |
H1 | 0.6595 (14) | 0.5334 (6) | 0.211 (2) | 0.059 (5)* | |
H2 | 0.6820 (14) | 0.3442 (5) | 0.2578 (19) | 0.041 (4)* | |
H3 | 0.9538 (16) | 0.3431 (6) | 0.227 (2) | 0.070 (5)* | |
H4 | 1.0811 (15) | 0.4476 (6) | 0.178 (2) | 0.062 (5)* | |
H5 | 0.9227 (12) | 0.5395 (5) | 0.1839 (19) | 0.033 (4)* | |
H6 | 0.1714 (12) | 0.6266 (5) | 0.0702 (17) | 0.027 (4)* | |
H7 | 0.1185 (11) | 0.6012 (4) | 0.4129 (15) | 0.015 (3)* | |
H8 | 0.2600 (17) | 0.7179 (7) | 0.045 (3) | 0.077 (7)* | |
H9 | 0.318 (2) | 0.7022 (8) | 0.491 (3) | 0.145 (9)* | |
H10 | 0.4094 (19) | 0.4904 (8) | 0.246 (3) | 0.101 (6)* | |
H11 | −0.1720 (17) | 0.6843 (7) | 0.219 (3) | 0.073 (6)* | |
H12 | −0.427 (2) | 0.7064 (10) | 0.156 (4) | 0.146 (10)* | |
H13 | −0.3645 (19) | 0.7532 (7) | 0.266 (2) | 0.074 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0408 (6) | 0.0429 (6) | 0.0786 (8) | 0.0001 (5) | −0.0053 (6) | −0.0040 (6) |
O2 | 0.0380 (5) | 0.0405 (5) | 0.0889 (8) | −0.0019 (5) | 0.0013 (6) | −0.0001 (6) |
O3 | 0.0329 (5) | 0.0459 (6) | 0.0611 (7) | −0.0000 (5) | 0.0045 (6) | −0.0007 (6) |
O4 | 0.0455 (6) | 0.0484 (6) | 0.0549 (8) | −0.0049 (5) | −0.0052 (6) | 0.0161 (6) |
O5 | 0.0402 (6) | 0.0524 (6) | 0.0449 (6) | −0.0019 (6) | −0.0059 (6) | −0.0039 (6) |
O6 | 0.0415 (6) | 0.0569 (7) | 0.0685 (8) | 0.0114 (6) | −0.0137 (7) | −0.0156 (7) |
O7 | 0.0478 (6) | 0.0416 (6) | 0.0726 (8) | 0.0073 (5) | −0.0033 (6) | −0.0165 (6) |
O8 | 0.0369 (6) | 0.0577 (7) | 0.0464 (7) | −0.0031 (6) | 0.0040 (6) | −0.0055 (6) |
N1 | 0.0451 (8) | 0.0398 (7) | 0.0419 (8) | 0.0001 (6) | −0.0015 (7) | −0.0043 (7) |
C2 | 0.0485 (9) | 0.0408 (8) | 0.0400 (9) | −0.0027 (8) | −0.0031 (8) | −0.0066 (8) |
C3 | 0.0556 (10) | 0.0349 (8) | 0.0560 (11) | −0.0006 (8) | −0.0042 (10) | −0.0054 (8) |
C4 | 0.0541 (10) | 0.0549 (11) | 0.0552 (12) | 0.0102 (9) | −0.0008 (10) | −0.0073 (10) |
C5 | 0.0432 (10) | 0.0602 (11) | 0.0521 (11) | 0.0012 (9) | 0.0038 (9) | −0.0028 (10) |
C6 | 0.0542 (10) | 0.0519 (10) | 0.0408 (10) | −0.0121 (9) | 0.0020 (9) | 0.0009 (9) |
C7 | 0.0425 (8) | 0.0455 (9) | 0.0347 (9) | 0.0005 (7) | 0.0022 (8) | −0.0010 (8) |
C8 | 0.0349 (7) | 0.0386 (8) | 0.0391 (9) | −0.0038 (7) | −0.0040 (8) | 0.0028 (7) |
C9 | 0.0324 (8) | 0.0320 (7) | 0.0464 (10) | −0.0044 (7) | 0.0008 (8) | 0.0012 (7) |
C10 | 0.0350 (8) | 0.0398 (8) | 0.0471 (10) | −0.0031 (7) | 0.0038 (9) | 0.0039 (7) |
Geometric parameters (Å, º) top
O1—C2 | 1.262 (2) | O4—C8 | 1.419 (2) |
N1—C2 | 1.368 (2) | O4—H8 | 0.80 (2) |
N1—C6 | 1.365 (3) | O5—C9 | 1.406 (2) |
N1—H1 | 0.962 (16) | O5—H9 | 0.95 (2) |
C2—C3 | 1.409 (3) | O6—C10 | 1.316 (2) |
C3—C4 | 1.350 (3) | O6—H11 | 0.842 (19) |
C3—H2 | 0.900 (15) | O7—C10 | 1.205 (2) |
C4—C5 | 1.391 (3) | C7—C8 | 1.518 (3) |
C4—H3 | 1.003 (17) | C8—C9 | 1.532 (3) |
C5—C6 | 1.340 (3) | C8—H6 | 0.962 (15) |
C5—H4 | 0.979 (16) | C9—C10 | 1.522 (3) |
C6—H5 | 0.941 (14) | C9—H7 | 0.976 (12) |
O2—C7 | 1.305 (2) | O8—H12 | 0.86 (3) |
O2—H10 | 1.20 (2) | O8—H13 | 0.798 (19) |
O3—C7 | 1.216 (2) | | |
| | | |
C9···O1i | 3.255 (2) | O1···C6iii | 3.373 (3) |
H7···O1i | 2.563 (13) | N1···C6iii | 3.280 (3) |
O3···C4ii | 3.186 (3) | C2···C6iii | 3.302 (3) |
| | | |
C2—N1—C6 | 123.18 (19) | C10—O6—H11 | 111.1 (14) |
C2—N1—H1 | 116.6 (10) | O2—C7—O3 | 125.19 (18) |
C6—N1—H1 | 120.2 (10) | O2—C7—C8 | 111.66 (17) |
O1—C2—N1 | 119.92 (18) | O3—C7—C8 | 123.15 (17) |
O1—C2—C3 | 124.78 (19) | O4—C8—C7 | 109.27 (16) |
N1—C2—C3 | 115.30 (18) | O4—C8—C9 | 109.09 (15) |
C2—C3—C4 | 121.5 (2) | O4—C8—H6 | 112.8 (9) |
C2—C3—H2 | 115.0 (10) | C7—C8—C9 | 108.33 (16) |
C4—C3—H2 | 123.5 (10) | C7—C8—H6 | 108.4 (9) |
C3—C4—C5 | 120.8 (2) | C9—C8—H6 | 108.8 (9) |
C3—C4—H3 | 118.4 (11) | O5—C9—C8 | 111.36 (15) |
C5—C4—H3 | 120.9 (11) | O5—C9—C10 | 110.93 (16) |
C4—C5—C6 | 118.4 (2) | O5—C9—H7 | 109.4 (8) |
C4—C5—H4 | 122.7 (10) | C8—C9—C10 | 111.46 (16) |
C6—C5—H4 | 118.6 (10) | C8—C9—H7 | 108.0 (8) |
N1—C6—C5 | 120.8 (2) | C10—C9—H7 | 105.4 (8) |
N1—C6—H5 | 115.5 (9) | O6—C10—O7 | 125.02 (18) |
C5—C6—H5 | 123.7 (9) | O6—C10—C9 | 111.38 (17) |
C7—O2—H10 | 114.5 (9) | O7—C10—C9 | 123.57 (19) |
C8—O4—H8 | 106.7 (15) | H12—O8—H13 | 105 (2) |
C9—O5—H9 | 112.1 (17) | | |
| | | |
O1—C2—N1—C6 | 180.0 (2) | O2—C7—C8—C9 | 66.5 (2) |
O1—C2—C3—C4 | 179.6 (2) | O3—C7—C8—O4 | 5.8 (3) |
N1—C2—C3—C4 | 0.2 (4) | O3—C7—C8—C9 | −112.9 (2) |
N1—C6—C5—C4 | 0.5 (4) | O4—C8—C9—O5 | −53.87 (19) |
C2—N1—C6—C5 | 0.2 (4) | O4—C8—C9—C10 | 70.59 (19) |
C2—C3—C4—C5 | 0.5 (4) | O5—C9—C8—C7 | 65.0 (2) |
C3—C2—N1—C6 | −0.6 (3) | O5—C9—C10—O6 | −174.34 (15) |
C3—C4—C5—C6 | −0.8 (4) | O5—C9—C10—O7 | 3.6 (3) |
C7—C8—C9—C10 | −170.56 (15) | O6—C10—C9—C8 | 61.0 (2) |
O2—C7—C8—O4 | −174.75 (17) | O7—C10—C9—C8 | −121.1 (2) |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+3/2, −y+1, z+1/2. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | 2C5H5NO·C2H2O4 | 2C5H5NO·C6H8O4 | C5H5NO·C5H6O4 | C5H5NO·C4H6O6·H2O |
Mr | 280.24 | 334.33 | 225.20 | 263.20 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n | Monoclinic, P21/c | Orthorhombic, P212121 |
Temperature (K) | 298 | 298 | 298 | 295 |
a, b, c (Å) | 9.162 (3), 9.898 (3), 3.7672 (17) | 9.824 (3), 5.5720 (17), 15.556 (5) | 7.889 (3), 16.839 (10), 8.288 (2) | 8.528 (5), 20.668 (8), 6.5438 (15) |
α, β, γ (°) | 98.86 (4), 97.66 (3), 109.61 (3) | 90, 101.31 (3), 90 | 90, 100.49 (3), 90 | 90, 90, 90 |
V (Å3) | 311.6 (2) | 835.0 (5) | 1082.5 (7) | 1153.4 (7) |
Z | 1 | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.10 | 0.11 | 0.14 |
Crystal size (mm) | 0.50 × 0.38 × 0.35 | 0.43 × 0.35 × 0.20 | 0.43 × 0.40 × 0.27 | 0.53 × 0.28 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – | – | – | ψ scans (North et al., 1968) |
Tmin, Tmax | – | – | – | 0.952, 0.999 |
No. of measured, independent and observed [I > 0.1σ(I)] reflections | 1645, 1428, 1336 | 2802, 2429, 2187 | 2298, 2128, 1848 | 2660, 2303, 2064 |
Rint | 0.006 | 0.009 | 0.016 | 0.011 |
(sin θ/λ)max (Å−1) | 0.650 | 0.703 | 0.617 | 0.746 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.098, 1.96 | 0.059, 0.102, 1.89 | 0.079, 0.088, 1.47 | 0.044, 0.044, 1.80 |
No. of reflections | 1336 | 2187 | 1848 | 2064 |
No. of parameters | 115 | 146 | 189 | 216 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.24, −0.22 | 0.26, −0.30 | 0.19, −0.25 | 0.32, −0.31 |
Selected geometric parameters (Å, º) for (I) topO1—C2 | 1.2683 (15) | C3—C4 | 1.3573 (19) |
N1—C2 | 1.3573 (16) | C4—C5 | 1.404 (2) |
N1—C6 | 1.3554 (17) | C5—C6 | 1.3507 (19) |
C2—C3 | 1.4191 (16) | | |
| | | |
C2—N1—C6 | 123.88 (11) | C2—C3—C4 | 120.89 (12) |
O1—C2—N1 | 118.99 (10) | C3—C4—C5 | 120.49 (12) |
O1—C2—C3 | 125.19 (11) | C4—C5—C6 | 118.39 (12) |
N1—C2—C3 | 115.81 (11) | N1—C6—C5 | 120.53 (12) |
Selected geometric parameters (Å, º) for (II) topO1—C2 | 1.2639 (13) | C3—C4 | 1.3488 (18) |
N1—C2 | 1.3652 (15) | C4—C5 | 1.395 (2) |
N1—C6 | 1.3540 (16) | C5—C6 | 1.3526 (19) |
C2—C3 | 1.4191 (16) | | |
| | | |
C2—N1—C6 | 123.57 (10) | C2—C3—C4 | 120.86 (11) |
O1—C2—N1 | 119.22 (10) | C3—C4—C5 | 120.90 (11) |
O1—C2—C3 | 125.04 (10) | C4—C5—C6 | 118.54 (12) |
N1—C2—C3 | 115.74 (10) | N1—C6—C5 | 120.38 (12) |
Selected geometric parameters (Å, º) for (III) topO1—C2 | 1.271 (2) | C3—C4 | 1.360 (3) |
N1—C2 | 1.359 (2) | C4—C5 | 1.395 (3) |
N1—C6 | 1.357 (3) | C5—C6 | 1.335 (3) |
C2—C3 | 1.407 (2) | | |
| | | |
C2—N1—C6 | 123.72 (17) | C3—C4—C5 | 120.8 (2) |
O1—C2—N1 | 118.53 (15) | C4—C5—C6 | 118.9 (2) |
N1—C2—C3 | 116.13 (17) | N1—C6—C5 | 120.2 (2) |
C2—C3—C4 | 120.25 (19) | | |
Selected geometric parameters (Å, º) for (IV) topO1—C2 | 1.262 (2) | C3—C4 | 1.350 (3) |
N1—C2 | 1.368 (2) | C4—C5 | 1.391 (3) |
N1—C6 | 1.365 (3) | C5—C6 | 1.340 (3) |
C2—C3 | 1.409 (3) | | |
| | | |
C2—N1—C6 | 123.18 (19) | C2—C3—C4 | 121.5 (2) |
O1—C2—N1 | 119.92 (18) | C3—C4—C5 | 120.8 (2) |
O1—C2—C3 | 124.78 (19) | C4—C5—C6 | 118.4 (2) |
N1—C2—C3 | 115.30 (18) | N1—C6—C5 | 120.8 (2) |
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2-Pyridone has been extensively studied because it exhibits lactam-lactim tautomerism, and the lactam group can be regarded as a model of cis-peptides and of the purine and pyrimidine bases of nucleic acids (Yang & Craven, 1998; Field & Hillier, 1987). The crystal structure of 2-pyridone has been determined from high-resolution X-ray data at 123 K, and the molecule is in the lactam form (Yang & Craven, 1998). In the present study, the title complexes, (I)-(IV), have been prepared under the expectation that the lactam group of 2-pyridone could be a building unit of a supramolecular synthon, and the patterns characteristic of the hydrogen-bonding and the geometries of the 2-pyridone moiety in the complexes have been elucidated. \sch
The hydrogen-bond patterns in (I) and (II) are shown in Figs. 1 and 2, respectively. In the crystals of (I) and (II), a molecule of the acid has a centre of symmetry. Two molecules of 2-pyridone related by an inversion centre form a dimer via an N—H···O hydrogen bond. The dimeric unit and the acid molecule are connected by an O—H···O hydrogen bond between the carboxyl group and the O atom of 2-pyridone, to form a chain (Figs. 1 and 2; Tables 2 and 4). In (I), the chains are arranged side by side to form a sheet on (111). The sheets are stacked along the c axis with short contacts O3···C7ii 3.302 (2) and O3···C7iii 3.307 (2) Å [symmetry codes: (ii) 1 - x, - y, - z - 1; (iii) x, y, z - 1]. In the chain of (II), a C—H···O interaction is observed (Table 4). The chains are arranged around the twofold screw axis with normal van der Waals contacts and no sheet structure is formed. In spite of difference in the packing mode of the chains in (I) and (II), the patterns of the hydrogen bonds in the chains show a common feature in these crystals. Thus, the hydrogen-bond scheme, (1), as found in (I) and (II), can be recognized as the supramolecular synthon (Desiraju, 1995) possible in complexes of 2-pyridone/centrosymmetric dicarboxylic acid in the ratio 2:1.
The molecules of the acids in (III) and (IV) have no centre of symmetry (Figs. 3 and 4). In both crystals, one carboxyl group forms an O—H···O and an N—H···O hydrogen bond with a 2-pyridone molecule (Tables 6 and 8). The O2—H10···O1 hydrogen bond in (IV) is short, the O2—H10 bond length being elongated, as found for a short noncentrosymmetric O—H···O hydrogen bond in ammonium hydrogen tartronate [O—H 1.18 (3) and O···O 2.443 (2) Å; Taka et al., 1998]. It could not be confirmed whether atom H10 is disordered, because the difference Fourier map drawn by H10 showed a single peak. In (III), the other carboxyl group forms an O—H···O hydrogen bond with a 2-pyridone molecule at (x - 1, 1/2 - y, 1/2 + z) to form a zigzag chain, and the chains form a sheet on (102) with C—H···O interactions (Fig. 5 and Table 6). The other carboxyl group in (IV) forms a hydrogen bond with a water molecule. The water molecule forms bifurcated hydrogen bonds with the acid molecules related by a translation along a and by the twofold screw axes along the a axis, forming a sheet developed parallel to (040) (Fig. 6 and Table 8). Between the sheets related by the twofold screw axes along the c axis, there are a C—H···O interaction and some short contacts between overlapped molecules of 2-pyridone: C9—H7 0.976 (12), H7···O1v 2.563 (13) and C9···O1v 3.255 (2) Å, and C9—H7···O1v 127.9 (10)°; O3···C4vi 3.186 (3), O1···C6vii 3.373 (3), N1···C6vii 3.280 (3) and C2···C6vii 3.302 Å [symmetry codes: (v) 1/2 - x, 1 - y, z + 1/2; (vi) 3/2 - x, 1 - y, z - 1/2; (vii) 3/2 - x, 1 - y, 1/2 + z]. Because the hydrogen-bond scheme, (2), is found in both (III) and (IV), it can be recognized as the supramolecular synthon possible in complexes of 2-pyridone/noncentrosymmetric dicarboxylic acid in the ratio 1:1.
The geometries of the 2-pyridone moieties observed in compounds (I)-(IV) (Tables 1, 3, 5 and 7) show a common feature characteristic of the lactam form, as found in the crystal of 2-pyridone (Yang & Craven, 1998). The C—C distance [1.544 (2) Å] of oxalic acid in (I) is rather long for the Csp2—Csp2 bond, as observed in dimorphs of oxalic acid [1.537 (1) Å; Derissen & Smit, 1974], and close to that determined for oxalic acid dihydrate at 15 K [1.5423 (5) Å; Zobel et al., 1992].