Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112039534/fg3272sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112039534/fg3272Iasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112039534/fg3272Ibsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112039534/fg3272Icsup4.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112039534/fg3272Iasup5.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112039534/fg3272Ibsup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112039534/fg3272Icsup7.cml |
CCDC references: 914646; 914647; 914648
Ethyl 2-amino-3-oxo-3-(pyridin-2-yl)propanoate, (V), was first prepared by hydrogenation of ethyl 2-hydroxyimino-3-oxo-3-(pyridin-2-yl)propanoate (Altaf et al., 2012) in dry ethyl acetate using 5% Rh/Al2O3 catalyst (0.3 g) in an autoclave for 24 h at room temperature. The initial pressure of hydrogen was 3.5 bar (1 bar = 100 000 Pa). After stopping the reaction, the solution was filtered to remove the catalyst, then the filtrate was concentrated under reduced pressure as quickly as possible to afford (V) as a white solid (yield 2.02 g, 97%; m.p. 401–404 K). This compound is not stable in solution and was used directly to be transformed into diethyl 3,6-bis(pyridin-2-yl)pyrazine-2,5-dicarboxylate, (IV), by dissolving (V) (4.16 g, 20 mmol) in chloroform (200 ml). The solution was stirred under a condenser at room temperature until the starting material had been consumed, then the solvent was removed under reduced pressure to yield the crude product. Recrystallization from ethanol gave (IV) as colourless crystals (Wang & Stoeckli-Evans, 2012b) (yield 1.40 g, 37%; m.p. 187–189 K ???).
Compound (IV) (775 mg, 2.05 mmol) was then added to an aqueous solution of KOH (5 g, 13 ml H2O). The mixture was refluxed at 375 K for 3 h and then allowed to cool to room temperature. It was then acidified with 4 N HCl until a white solid formed (ca pH = 2). This was filtered off, washed with water and chloroform and dried under vacuum to yield (Ia) as a white solid (yield 640 mg, 92%; m.p. 515–516 K). Colourless crystals of (Ia) were obtained by slow evaporation of a solution in water. Compound (Ib) was obtained by dissolving (Ia) in aqueous 1M HCl. On slow evaporation of the solvent at room temperature, colourless crystals were obtained (m.p. 537 K). Compound (Ic) was obtained by dissolving (Ia) in DMSO. On slow evaporation of the solvent at room temperature, colourless crystals were obtained (m.p. 499–501 K).
In all three compounds, the O-bound, N-bound and water H atoms were located in difference electron-density maps and refined with distance restraints of O—H = 0.84 (2) Å and N—H = 0.88 (2) Å. C-bound H atoms were included in calculated positions and treated as riding, with C—H = 0.94 and 0.97 Å for CH and CH3 H atoms, respectively, and with Uiso(H) = kUeq(C), where k = 1.5 for methyl H atoms and 1.2 otherwise.
For all compounds, data collection: STADI-4 Software (Stoe & Cie, 1997); cell refinement: STADI-4 Software (Stoe & Cie, 1997); data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
C16H10N4O4 | F(000) = 664 |
Mr = 322.28 | Dx = 1.499 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 17 reflections |
a = 8.304 (3) Å | θ = 14.0–19.0° |
b = 9.684 (1) Å | µ = 0.11 mm−1 |
c = 17.802 (2) Å | T = 213 K |
β = 93.89 (1)° | Rod, colourless |
V = 1428.3 (6) Å3 | 0.49 × 0.27 × 0.10 mm |
Z = 4 |
Stoe AED-2 four-circle diffractometer | Rint = 0.087 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.3° |
Graphite monochromator | h = −9→9 |
2θ/ω scans | k = 0→11 |
2502 measured reflections | l = 0→21 |
2371 independent reflections | 2 standard reflections every 60 min |
1731 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.165 | w = 1/[σ2(Fo2) + (0.0837P)2 + 0.1644P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2371 reflections | Δρmax = 0.24 e Å−3 |
226 parameters | Δρmin = −0.33 e Å−3 |
2 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.007 (2) |
C16H10N4O4 | V = 1428.3 (6) Å3 |
Mr = 322.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.304 (3) Å | µ = 0.11 mm−1 |
b = 9.684 (1) Å | T = 213 K |
c = 17.802 (2) Å | 0.49 × 0.27 × 0.10 mm |
β = 93.89 (1)° |
Stoe AED-2 four-circle diffractometer | Rint = 0.087 |
2502 measured reflections | 2 standard reflections every 60 min |
2371 independent reflections | intensity decay: 2% |
1731 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.061 | 2 restraints |
wR(F2) = 0.165 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.24 e Å−3 |
2371 reflections | Δρmin = −0.33 e Å−3 |
226 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 | ||
O1 | 0.6004 (3) | −0.3146 (2) | 0.05568 (12) | 0.0370 (8) | |
O2 | 0.7772 (3) | −0.3595 (2) | 0.15328 (13) | 0.0359 (9) | |
O3 | 0.5723 (3) | 0.3148 (2) | 0.21142 (12) | 0.0344 (8) | |
O4 | 0.7608 (3) | 0.3811 (2) | 0.13479 (13) | 0.0409 (9) | |
N1 | 0.7303 (3) | 0.1069 (3) | 0.08187 (13) | 0.0242 (8) | |
N2 | 0.7305 (3) | −0.0916 (3) | 0.19477 (13) | 0.0234 (8) | |
N3 | 0.8607 (3) | −0.1718 (3) | −0.02336 (13) | 0.0266 (9) | |
N4 | 0.6567 (4) | −0.0069 (3) | 0.33651 (13) | 0.0262 (9) | |
C1 | 0.7395 (4) | −0.0271 (3) | 0.06572 (15) | 0.0220 (9) | |
C2 | 0.7278 (4) | −0.1275 (3) | 0.12231 (15) | 0.0234 (10) | |
C3 | 0.7287 (4) | 0.0440 (3) | 0.21090 (15) | 0.0222 (9) | |
C4 | 0.7188 (4) | 0.1433 (3) | 0.15377 (15) | 0.0218 (9) | |
C5 | 0.7623 (4) | −0.0648 (3) | −0.01387 (15) | 0.0222 (9) | |
C6 | 0.6891 (4) | 0.0109 (3) | −0.07274 (16) | 0.0304 (10) | |
C7 | 0.7123 (5) | −0.0301 (4) | −0.14580 (17) | 0.0377 (11) | |
C8 | 0.8116 (5) | −0.1408 (4) | −0.15661 (17) | 0.0382 (13) | |
C9 | 0.8836 (4) | −0.2080 (4) | −0.09475 (17) | 0.0325 (11) | |
C10 | 0.6967 (4) | −0.2791 (3) | 0.10605 (16) | 0.0261 (10) | |
C11 | 0.7422 (4) | 0.0757 (3) | 0.29247 (16) | 0.0243 (9) | |
C12 | 0.8446 (4) | 0.1715 (3) | 0.32588 (17) | 0.0300 (11) | |
C13 | 0.8587 (4) | 0.1823 (4) | 0.40439 (18) | 0.0358 (11) | |
C14 | 0.7696 (4) | 0.0969 (4) | 0.44688 (18) | 0.0366 (11) | |
C15 | 0.6672 (4) | 0.0026 (4) | 0.41177 (16) | 0.0325 (11) | |
C16 | 0.6829 (4) | 0.2937 (3) | 0.16834 (15) | 0.0261 (10) | |
H2O | 0.750 (5) | −0.447 (2) | 0.145 (2) | 0.073 (15)* | |
H4N | 0.584 (4) | −0.065 (3) | 0.3160 (19) | 0.044 (11)* | |
H6 | 0.62520 | 0.08840 | −0.06340 | 0.0360* | |
H7 | 0.66110 | 0.01670 | −0.18710 | 0.0450* | |
H8 | 0.83020 | −0.17040 | −0.20550 | 0.0460* | |
H9 | 0.95220 | −0.28290 | −0.10300 | 0.0390* | |
H12 | 0.90510 | 0.22970 | 0.29630 | 0.0360* | |
H13 | 0.92900 | 0.24770 | 0.42790 | 0.0430* | |
H14 | 0.77860 | 0.10310 | 0.49970 | 0.0440* | |
H15 | 0.60440 | −0.05550 | 0.44040 | 0.0390* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0560 (17) | 0.0270 (13) | 0.0277 (12) | −0.0042 (12) | 0.0016 (12) | −0.0033 (10) |
O2 | 0.0595 (18) | 0.0190 (13) | 0.0287 (13) | 0.0020 (12) | −0.0005 (11) | 0.0016 (10) |
O3 | 0.0496 (15) | 0.0288 (13) | 0.0256 (12) | 0.0069 (11) | 0.0091 (11) | 0.0001 (10) |
O4 | 0.0731 (19) | 0.0175 (13) | 0.0348 (13) | −0.0024 (12) | 0.0229 (13) | 0.0022 (10) |
N1 | 0.0398 (17) | 0.0157 (14) | 0.0174 (12) | −0.0018 (12) | 0.0050 (11) | 0.0005 (10) |
N2 | 0.0378 (16) | 0.0165 (13) | 0.0161 (12) | −0.0020 (11) | 0.0034 (11) | 0.0004 (10) |
N3 | 0.0392 (17) | 0.0251 (15) | 0.0162 (12) | 0.0010 (12) | 0.0074 (11) | −0.0029 (11) |
N4 | 0.0411 (18) | 0.0197 (14) | 0.0183 (13) | −0.0011 (13) | 0.0047 (12) | 0.0004 (11) |
C1 | 0.0299 (18) | 0.0178 (16) | 0.0181 (15) | 0.0010 (13) | 0.0006 (13) | −0.0008 (12) |
C2 | 0.0362 (19) | 0.0183 (16) | 0.0159 (14) | 0.0008 (14) | 0.0033 (13) | −0.0009 (12) |
C3 | 0.0308 (18) | 0.0181 (16) | 0.0183 (14) | −0.0033 (13) | 0.0064 (12) | −0.0024 (13) |
C4 | 0.0312 (18) | 0.0189 (16) | 0.0159 (14) | −0.0023 (13) | 0.0055 (12) | −0.0008 (12) |
C5 | 0.0324 (18) | 0.0194 (17) | 0.0149 (14) | −0.0040 (14) | 0.0026 (12) | −0.0008 (12) |
C6 | 0.046 (2) | 0.0227 (18) | 0.0223 (16) | −0.0008 (15) | 0.0012 (15) | 0.0029 (13) |
C7 | 0.053 (2) | 0.043 (2) | 0.0167 (15) | −0.0049 (18) | −0.0008 (15) | 0.0053 (15) |
C8 | 0.058 (3) | 0.041 (2) | 0.0165 (16) | −0.0079 (19) | 0.0093 (16) | −0.0021 (15) |
C9 | 0.046 (2) | 0.0299 (19) | 0.0228 (16) | −0.0011 (16) | 0.0104 (15) | −0.0066 (14) |
C10 | 0.040 (2) | 0.0236 (17) | 0.0153 (15) | −0.0020 (14) | 0.0074 (14) | −0.0030 (13) |
C11 | 0.0381 (19) | 0.0167 (15) | 0.0184 (14) | 0.0044 (14) | 0.0047 (13) | 0.0011 (13) |
C12 | 0.038 (2) | 0.0265 (19) | 0.0256 (16) | −0.0018 (15) | 0.0024 (14) | −0.0031 (14) |
C13 | 0.039 (2) | 0.039 (2) | 0.0284 (18) | 0.0042 (17) | −0.0052 (15) | −0.0129 (16) |
C14 | 0.051 (2) | 0.043 (2) | 0.0158 (15) | 0.0066 (18) | 0.0024 (15) | −0.0038 (15) |
C15 | 0.049 (2) | 0.033 (2) | 0.0163 (15) | 0.0069 (17) | 0.0081 (15) | 0.0000 (14) |
C16 | 0.042 (2) | 0.0238 (18) | 0.0123 (14) | 0.0032 (15) | 0.0011 (14) | −0.0002 (13) |
O1—C10 | 1.210 (4) | C3—C11 | 1.481 (4) |
O2—C10 | 1.298 (4) | C4—C16 | 1.513 (4) |
O3—C16 | 1.253 (4) | C5—C6 | 1.385 (4) |
O4—C16 | 1.243 (4) | C6—C7 | 1.386 (4) |
O2—H2O | 0.89 (2) | C7—C8 | 1.374 (6) |
N1—C4 | 1.337 (4) | C8—C9 | 1.380 (5) |
N1—C1 | 1.332 (4) | C11—C12 | 1.367 (4) |
N2—C2 | 1.335 (4) | C12—C13 | 1.399 (4) |
N2—C3 | 1.345 (4) | C13—C14 | 1.371 (5) |
N3—C9 | 1.344 (4) | C14—C15 | 1.370 (5) |
N3—C5 | 1.337 (4) | C6—H6 | 0.9400 |
N4—C11 | 1.354 (4) | C7—H7 | 0.9400 |
N4—C15 | 1.340 (4) | C8—H8 | 0.9400 |
N4—H4N | 0.89 (3) | C9—H9 | 0.9400 |
C1—C2 | 1.408 (4) | C12—H12 | 0.9400 |
C1—C5 | 1.488 (4) | C13—H13 | 0.9400 |
C2—C10 | 1.515 (4) | C14—H14 | 0.9400 |
C3—C4 | 1.398 (4) | C15—H15 | 0.9400 |
C10—O2—H2O | 111 (2) | O1—C10—O2 | 126.5 (3) |
C1—N1—C4 | 118.2 (3) | N4—C11—C3 | 115.9 (3) |
C2—N2—C3 | 117.5 (3) | N4—C11—C12 | 119.0 (3) |
C5—N3—C9 | 116.6 (3) | C3—C11—C12 | 124.8 (3) |
C11—N4—C15 | 122.5 (3) | C11—C12—C13 | 119.5 (3) |
C15—N4—H4N | 117 (2) | C12—C13—C14 | 119.6 (3) |
C11—N4—H4N | 120 (2) | C13—C14—C15 | 119.5 (3) |
N1—C1—C2 | 120.7 (2) | N4—C15—C14 | 119.9 (3) |
C2—C1—C5 | 122.1 (3) | O3—C16—O4 | 127.6 (3) |
N1—C1—C5 | 117.2 (2) | O3—C16—C4 | 115.0 (3) |
C1—C2—C10 | 123.5 (2) | O4—C16—C4 | 117.3 (3) |
N2—C2—C1 | 120.9 (3) | C5—C6—H6 | 121.00 |
N2—C2—C10 | 115.4 (3) | C7—C6—H6 | 121.00 |
N2—C3—C4 | 121.2 (2) | C6—C7—H7 | 121.00 |
N2—C3—C11 | 114.3 (2) | C8—C7—H7 | 121.00 |
C4—C3—C11 | 124.6 (3) | C7—C8—H8 | 120.00 |
N1—C4—C3 | 120.7 (3) | C9—C8—H8 | 120.00 |
N1—C4—C16 | 116.5 (2) | N3—C9—H9 | 118.00 |
C3—C4—C16 | 122.7 (2) | C8—C9—H9 | 118.00 |
N3—C5—C6 | 123.7 (3) | C11—C12—H12 | 120.00 |
N3—C5—C1 | 115.4 (2) | C13—C12—H12 | 120.00 |
C1—C5—C6 | 120.9 (3) | C12—C13—H13 | 120.00 |
C5—C6—C7 | 118.5 (3) | C14—C13—H13 | 120.00 |
C6—C7—C8 | 118.6 (3) | C13—C14—H14 | 120.00 |
C7—C8—C9 | 119.2 (3) | C15—C14—H14 | 120.00 |
N3—C9—C8 | 123.4 (3) | N4—C15—H15 | 120.00 |
O2—C10—C2 | 112.6 (3) | C14—C15—H15 | 120.00 |
O1—C10—C2 | 120.8 (3) | ||
C4—N1—C1—C2 | 3.7 (5) | C1—C2—C10—O1 | −40.8 (5) |
C4—N1—C1—C5 | −176.4 (3) | C1—C2—C10—O2 | 142.2 (3) |
C1—N1—C4—C3 | 4.8 (5) | N2—C3—C4—N1 | −8.1 (5) |
C1—N1—C4—C16 | −170.9 (3) | N2—C3—C4—C16 | 167.4 (3) |
C3—N2—C2—C1 | 6.4 (5) | C11—C3—C4—N1 | 170.3 (3) |
C3—N2—C2—C10 | −168.4 (3) | C11—C3—C4—C16 | −14.3 (5) |
C2—N2—C3—C4 | 2.1 (5) | N2—C3—C11—N4 | −41.0 (4) |
C2—N2—C3—C11 | −176.4 (3) | N2—C3—C11—C12 | 132.5 (3) |
C9—N3—C5—C1 | −179.9 (3) | C4—C3—C11—N4 | 140.6 (3) |
C9—N3—C5—C6 | −2.1 (5) | C4—C3—C11—C12 | −46.0 (5) |
C5—N3—C9—C8 | 0.1 (5) | N1—C4—C16—O3 | 132.1 (3) |
C15—N4—C11—C3 | 174.6 (3) | N1—C4—C16—O4 | −45.5 (4) |
C15—N4—C11—C12 | 0.8 (5) | C3—C4—C16—O3 | −43.6 (4) |
C11—N4—C15—C14 | −1.2 (5) | C3—C4—C16—O4 | 138.9 (3) |
N1—C1—C2—N2 | −9.7 (5) | N3—C5—C6—C7 | 3.3 (5) |
N1—C1—C2—C10 | 164.7 (3) | C1—C5—C6—C7 | −179.0 (3) |
C5—C1—C2—N2 | 170.4 (3) | C5—C6—C7—C8 | −2.4 (5) |
C5—C1—C2—C10 | −15.3 (5) | C6—C7—C8—C9 | 0.5 (6) |
N1—C1—C5—N3 | 141.7 (3) | C7—C8—C9—N3 | 0.7 (6) |
N1—C1—C5—C6 | −36.3 (5) | N4—C11—C12—C13 | −0.1 (5) |
C2—C1—C5—N3 | −38.4 (4) | C3—C11—C12—C13 | −173.4 (3) |
C2—C1—C5—C6 | 143.7 (3) | C11—C12—C13—C14 | −0.1 (5) |
N2—C2—C10—O1 | 133.9 (3) | C12—C13—C14—C15 | −0.4 (5) |
N2—C2—C10—O2 | −43.2 (4) | C13—C14—C15—N4 | 1.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4i | 0.89 (2) | 1.68 (2) | 2.536 (3) | 162 (4) |
N4—H4N···O3ii | 0.89 (3) | 1.79 (3) | 2.666 (4) | 171 (3) |
C7—H7···O3iii | 0.94 | 2.51 | 3.429 (4) | 166 |
C8—H8···O2iv | 0.94 | 2.54 | 3.377 (4) | 149 |
C13—H13···N3v | 0.94 | 2.48 | 3.353 (4) | 155 |
C14—H14···O4vi | 0.94 | 2.42 | 3.358 (4) | 172 |
C15—H15···O1vii | 0.94 | 2.41 | 3.222 (4) | 145 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) x, −y−1/2, z−1/2; (v) −x+2, y+1/2, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x, −y−1/2, z+1/2. |
C16H12N4O42+·2Cl−·2H2O | Z = 1 |
Mr = 431.23 | F(000) = 222 |
Triclinic, P1 | Dx = 1.497 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.857 (1) Å | Cell parameters from 21 reflections |
b = 8.576 (1) Å | θ = 14.0–20.0° |
c = 9.187 (2) Å | µ = 0.38 mm−1 |
α = 63.40 (1)° | T = 213 K |
β = 81.94 (1)° | Rod, colourless |
γ = 87.47 (1)° | 0.49 × 0.34 × 0.27 mm |
V = 478.19 (14) Å3 |
Stoe AED-2 four-circle diffractometer | Rint = 0.035 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.5° |
Graphite monochromator | h = −8→8 |
2θ/ω scans | k = −10→10 |
3504 measured reflections | l = −10→10 |
1681 independent reflections | 3 standard reflections every 60 min |
1463 reflections with I > 2˘I) | intensity decay: 7% |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0596P)2 + 0.0431P] where P = (Fo2 + 2Fc2)/3 |
1681 reflections | (Δ/σ)max < 0.001 |
143 parameters | Δρmax = 0.27 e Å−3 |
2 restraints | Δρmin = −0.32 e Å−3 |
C16H12N4O42+·2Cl−·2H2O | γ = 87.47 (1)° |
Mr = 431.23 | V = 478.19 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.857 (1) Å | Mo Kα radiation |
b = 8.576 (1) Å | µ = 0.38 mm−1 |
c = 9.187 (2) Å | T = 213 K |
α = 63.40 (1)° | 0.49 × 0.34 × 0.27 mm |
β = 81.94 (1)° |
Stoe AED-2 four-circle diffractometer | Rint = 0.035 |
3504 measured reflections | 3 standard reflections every 60 min |
1681 independent reflections | intensity decay: 7% |
1463 reflections with I > 2˘I) |
R[F2 > 2σ(F2)] = 0.034 | 2 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.27 e Å−3 |
1681 reflections | Δρmin = −0.32 e Å−3 |
143 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 | ||
O1 | 1.00015 (17) | 0.49490 (17) | 0.31111 (14) | 0.0275 (4) | |
O2 | 0.92722 (19) | 0.23783 (17) | 0.53000 (16) | 0.0339 (4) | |
N1 | 0.5886 (2) | 0.35779 (19) | 0.61518 (16) | 0.0213 (4) | |
N2 | 0.2702 (2) | 0.38465 (19) | 0.92225 (16) | 0.0224 (4) | |
C1 | 0.4106 (2) | 0.4098 (2) | 0.65399 (19) | 0.0209 (5) | |
C2 | 0.6788 (2) | 0.4478 (2) | 0.46210 (19) | 0.0201 (5) | |
C5 | 0.3229 (2) | 0.3023 (2) | 0.82833 (19) | 0.0203 (5) | |
C6 | 0.3015 (3) | 0.1241 (2) | 0.8968 (2) | 0.0258 (5) | |
C7 | 0.2197 (3) | 0.0334 (2) | 1.0613 (2) | 0.0304 (5) | |
C8 | 0.1635 (3) | 0.1233 (3) | 1.1525 (2) | 0.0317 (6) | |
C9 | 0.1921 (3) | 0.3007 (2) | 1.0801 (2) | 0.0286 (5) | |
C10 | 0.8865 (2) | 0.3959 (2) | 0.42515 (19) | 0.0222 (5) | |
Cl1 | 0.35647 (7) | 0.77154 (6) | 0.77915 (6) | 0.0328 (2) | |
O1W | 0.2839 (2) | 0.1436 (2) | 0.5001 (2) | 0.0400 (5) | |
H2N | 0.288 (3) | 0.500 (2) | 0.880 (2) | 0.037 (6)* | |
H2O | 1.044 (3) | 0.211 (4) | 0.511 (3) | 0.065 (8)* | |
H6 | 0.34130 | 0.06410 | 0.83390 | 0.0310* | |
H7 | 0.20300 | −0.08850 | 1.10970 | 0.0360* | |
H8 | 0.10640 | 0.06370 | 1.26270 | 0.0380* | |
H9 | 0.15690 | 0.36330 | 1.14140 | 0.0340* | |
H1WA | 0.305 (5) | 0.044 (4) | 0.565 (4) | 0.071 (10)* | |
H2WB | 0.370 (4) | 0.164 (3) | 0.423 (3) | 0.050 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0230 (6) | 0.0307 (7) | 0.0216 (6) | 0.0003 (5) | 0.0030 (5) | −0.0070 (5) |
O2 | 0.0259 (7) | 0.0293 (8) | 0.0311 (7) | 0.0092 (6) | 0.0035 (6) | −0.0027 (6) |
N1 | 0.0225 (7) | 0.0224 (7) | 0.0181 (7) | 0.0013 (6) | −0.0007 (6) | −0.0089 (6) |
N2 | 0.0256 (7) | 0.0216 (8) | 0.0180 (7) | 0.0016 (6) | −0.0003 (6) | −0.0080 (6) |
C1 | 0.0229 (8) | 0.0216 (9) | 0.0180 (8) | 0.0000 (7) | 0.0007 (7) | −0.0096 (7) |
C2 | 0.0217 (8) | 0.0210 (9) | 0.0178 (8) | −0.0006 (7) | 0.0000 (6) | −0.0096 (7) |
C5 | 0.0189 (8) | 0.0232 (9) | 0.0158 (8) | 0.0027 (7) | −0.0014 (6) | −0.0064 (7) |
C6 | 0.0272 (9) | 0.0245 (9) | 0.0243 (9) | 0.0020 (7) | −0.0020 (7) | −0.0102 (8) |
C7 | 0.0297 (10) | 0.0224 (9) | 0.0286 (9) | −0.0017 (8) | −0.0049 (8) | −0.0017 (8) |
C8 | 0.0312 (10) | 0.0364 (11) | 0.0167 (8) | −0.0025 (8) | 0.0017 (7) | −0.0034 (8) |
C9 | 0.0305 (9) | 0.0353 (11) | 0.0172 (8) | 0.0012 (8) | 0.0006 (7) | −0.0105 (8) |
C10 | 0.0230 (9) | 0.0250 (9) | 0.0196 (8) | 0.0036 (7) | −0.0026 (7) | −0.0112 (7) |
Cl1 | 0.0360 (3) | 0.0244 (3) | 0.0353 (3) | −0.0007 (2) | −0.0004 (2) | −0.0121 (2) |
O1W | 0.0319 (8) | 0.0415 (10) | 0.0335 (8) | 0.0145 (7) | −0.0002 (7) | −0.0076 (7) |
O1—C10 | 1.208 (2) | C1—C5 | 1.495 (2) |
O2—C10 | 1.310 (2) | C2—C10 | 1.512 (2) |
O2—H2O | 0.84 (2) | C5—C6 | 1.373 (3) |
O1W—H2WB | 0.81 (3) | C6—C7 | 1.397 (2) |
O1W—H1WA | 0.81 (4) | C7—C8 | 1.381 (3) |
N1—C1 | 1.337 (2) | C8—C9 | 1.371 (3) |
N1—C2 | 1.335 (2) | C6—H6 | 0.9400 |
N2—C9 | 1.338 (2) | C7—H7 | 0.9400 |
N2—C5 | 1.345 (2) | C8—H8 | 0.9400 |
N2—H2N | 0.893 (19) | C9—H9 | 0.9400 |
C1—C2i | 1.398 (2) | ||
C10—O2—H2O | 113 (2) | C5—C6—C7 | 119.02 (17) |
H1WA—O1W—H2WB | 104 (3) | C6—C7—C8 | 119.82 (18) |
C1—N1—C2 | 117.62 (14) | C7—C8—C9 | 119.12 (16) |
C5—N2—C9 | 122.74 (17) | N2—C9—C8 | 119.93 (17) |
C9—N2—H2N | 117.2 (11) | O1—C10—C2 | 121.69 (16) |
C5—N2—H2N | 120.0 (11) | O2—C10—C2 | 113.08 (13) |
N1—C1—C5 | 113.61 (14) | O1—C10—O2 | 125.22 (15) |
C2i—C1—C5 | 125.20 (14) | C5—C6—H6 | 120.00 |
N1—C1—C2i | 121.20 (14) | C7—C6—H6 | 121.00 |
N1—C2—C1i | 121.18 (14) | C8—C7—H7 | 120.00 |
N1—C2—C10 | 116.60 (14) | C6—C7—H7 | 120.00 |
C1i—C2—C10 | 122.08 (14) | C7—C8—H8 | 120.00 |
N2—C5—C6 | 119.33 (15) | C9—C8—H8 | 120.00 |
C1—C5—C6 | 122.73 (16) | N2—C9—H9 | 120.00 |
N2—C5—C1 | 117.90 (16) | C8—C9—H9 | 120.00 |
C2—N1—C1—C5 | −179.32 (16) | N1—C1—C2i—C10i | 174.85 (16) |
C2—N1—C1—C2i | 0.7 (3) | C5—C1—C2i—N1i | 179.30 (17) |
C1—N1—C2—C10 | 175.11 (16) | C5—C1—C2i—C10i | −5.2 (3) |
C1—N1—C2—C1i | −0.7 (3) | N1—C2—C10—O1 | −158.32 (17) |
C9—N2—C5—C1 | −179.39 (15) | N1—C2—C10—O2 | 20.5 (2) |
C9—N2—C5—C6 | −1.8 (2) | C1i—C2—C10—O1 | 17.4 (3) |
C5—N2—C9—C8 | 0.2 (3) | C1i—C2—C10—O2 | −163.80 (16) |
N1—C1—C5—N2 | 123.35 (17) | N2—C5—C6—C7 | 2.0 (3) |
N1—C1—C5—C6 | −54.1 (2) | C1—C5—C6—C7 | 179.39 (16) |
C2i—C1—C5—N2 | −56.7 (2) | C5—C6—C7—C8 | −0.6 (3) |
C2i—C1—C5—C6 | 125.9 (2) | C6—C7—C8—C9 | −1.0 (3) |
N1—C1—C2i—N1i | −0.7 (3) | C7—C8—C9—N2 | 1.2 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···Cl1ii | 0.81 (4) | 2.34 (3) | 3.1453 (19) | 172 (3) |
O1W—H2WB···Cl1i | 0.81 (3) | 2.34 (3) | 3.1472 (17) | 173 (2) |
N2—H2N···Cl1 | 0.89 (2) | 2.13 (2) | 3.0226 (19) | 175 (2) |
O2—H2O···O1Wiii | 0.84 (2) | 1.72 (2) | 2.559 (2) | 172 (3) |
C6—H6···Cl1ii | 0.94 | 2.77 | 3.628 (2) | 153 |
C8—H8···O2iv | 0.94 | 2.43 | 3.172 (3) | 136 |
C9—H9···O1v | 0.94 | 2.42 | 3.346 (2) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y, −z+2; (v) x−1, y, z+1. |
C16H10N4O4·2C2H6OS | F(000) = 500 |
Mr = 478.54 | Dx = 1.410 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 20 reflections |
a = 13.067 (1) Å | θ = 14.0–18.5° |
b = 6.138 (1) Å | µ = 0.28 mm−1 |
c = 14.453 (1) Å | T = 213 K |
β = 103.59 (1)° | Rod, colourless |
V = 1126.8 (2) Å3 | 0.53 × 0.38 × 0.30 mm |
Z = 2 |
Stoe AED-2 four-circle diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.9° |
Graphite monochromator | h = −15→15 |
2θ/ω scans | k = 0→7 |
1979 measured reflections | l = 0→17 |
1979 independent reflections | 2 standard reflections every 60 min |
1296 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0401P)2] where P = (Fo2 + 2Fc2)/3 |
1979 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.20 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
C16H10N4O4·2C2H6OS | V = 1126.8 (2) Å3 |
Mr = 478.54 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.067 (1) Å | µ = 0.28 mm−1 |
b = 6.138 (1) Å | T = 213 K |
c = 14.453 (1) Å | 0.53 × 0.38 × 0.30 mm |
β = 103.59 (1)° |
Stoe AED-2 four-circle diffractometer | Rint = 0.000 |
1979 measured reflections | 2 standard reflections every 60 min |
1979 independent reflections | intensity decay: none |
1296 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.20 e Å−3 |
1979 reflections | Δρmin = −0.27 e Å−3 |
151 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 | ||
O1 | 0.38051 (15) | 0.3095 (3) | 0.68347 (12) | 0.0393 (7) | |
O2 | 0.54242 (14) | 0.1658 (4) | 0.70910 (14) | 0.0422 (7) | |
N1 | 0.55440 (16) | 0.5453 (3) | 0.59271 (14) | 0.0291 (7) | |
N2 | 0.36463 (16) | −0.0091 (3) | 0.52033 (15) | 0.0317 (8) | |
C1 | 0.42877 (19) | 0.3352 (4) | 0.47999 (18) | 0.0284 (8) | |
C2 | 0.4843 (2) | 0.3838 (4) | 0.57293 (17) | 0.0275 (8) | |
C5 | 0.35261 (19) | 0.1527 (4) | 0.45630 (17) | 0.0286 (8) | |
C6 | 0.2742 (2) | 0.1535 (5) | 0.37278 (18) | 0.0369 (9) | |
C7 | 0.2060 (2) | −0.0222 (5) | 0.3539 (2) | 0.0417 (10) | |
C8 | 0.2182 (2) | −0.1897 (5) | 0.4179 (2) | 0.0387 (10) | |
C9 | 0.2977 (2) | −0.1765 (4) | 0.49948 (19) | 0.0341 (9) | |
C10 | 0.4624 (2) | 0.2776 (4) | 0.66021 (17) | 0.0310 (9) | |
S1 | 0.38909 (6) | −0.05423 (12) | 0.86118 (5) | 0.0385 (2) | |
O3 | 0.50225 (14) | 0.0048 (3) | 0.86415 (13) | 0.0528 (8) | |
C11 | 0.3409 (2) | −0.1835 (5) | 0.75067 (19) | 0.0463 (11) | |
C12 | 0.3951 (3) | −0.2859 (6) | 0.9351 (2) | 0.0669 (14) | |
H2O | 0.526 (3) | 0.119 (5) | 0.7597 (17) | 0.074 (12)* | |
H6 | 0.26750 | 0.27080 | 0.33000 | 0.0440* | |
H7 | 0.15220 | −0.02620 | 0.29790 | 0.0500* | |
H8 | 0.17330 | −0.31140 | 0.40640 | 0.0460* | |
H9 | 0.30540 | −0.29230 | 0.54310 | 0.0410* | |
H11A | 0.38370 | −0.31020 | 0.74610 | 0.0690* | |
H11B | 0.34370 | −0.08280 | 0.69960 | 0.0690* | |
H11C | 0.26860 | −0.22860 | 0.74540 | 0.0690* | |
H12A | 0.42300 | −0.24430 | 1.00090 | 0.1010* | |
H12B | 0.44060 | −0.39470 | 0.91690 | 0.1010* | |
H12C | 0.32500 | −0.34580 | 0.92780 | 0.1010* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0445 (12) | 0.0356 (12) | 0.0429 (11) | 0.0053 (10) | 0.0208 (9) | 0.0025 (9) |
O2 | 0.0323 (11) | 0.0548 (14) | 0.0382 (12) | −0.0004 (10) | 0.0059 (9) | 0.0177 (11) |
N1 | 0.0296 (12) | 0.0280 (12) | 0.0290 (12) | −0.0014 (11) | 0.0053 (9) | −0.0016 (11) |
N2 | 0.0338 (13) | 0.0274 (13) | 0.0343 (13) | −0.0015 (11) | 0.0088 (10) | −0.0017 (10) |
C1 | 0.0277 (14) | 0.0267 (14) | 0.0312 (14) | 0.0036 (12) | 0.0076 (12) | 0.0016 (13) |
C2 | 0.0287 (14) | 0.0266 (15) | 0.0268 (14) | 0.0034 (12) | 0.0059 (11) | −0.0004 (12) |
C5 | 0.0300 (15) | 0.0297 (15) | 0.0278 (14) | 0.0002 (13) | 0.0101 (12) | −0.0028 (13) |
C6 | 0.0404 (17) | 0.0397 (17) | 0.0312 (15) | −0.0005 (15) | 0.0097 (13) | 0.0028 (14) |
C7 | 0.0347 (16) | 0.0476 (19) | 0.0388 (16) | −0.0053 (15) | 0.0007 (13) | −0.0112 (15) |
C8 | 0.0355 (17) | 0.0324 (17) | 0.0476 (18) | −0.0072 (14) | 0.0084 (14) | −0.0122 (15) |
C9 | 0.0398 (17) | 0.0243 (15) | 0.0401 (16) | −0.0006 (13) | 0.0130 (13) | −0.0025 (13) |
C10 | 0.0371 (17) | 0.0256 (15) | 0.0292 (15) | −0.0056 (14) | 0.0058 (13) | −0.0052 (12) |
S1 | 0.0362 (4) | 0.0395 (4) | 0.0393 (4) | −0.0020 (4) | 0.0080 (3) | 0.0012 (4) |
O3 | 0.0339 (11) | 0.0723 (16) | 0.0464 (12) | −0.0144 (11) | −0.0019 (9) | 0.0258 (11) |
C11 | 0.054 (2) | 0.0406 (18) | 0.0460 (18) | −0.0133 (16) | 0.0149 (15) | −0.0061 (15) |
C12 | 0.068 (2) | 0.079 (3) | 0.052 (2) | −0.023 (2) | 0.0106 (18) | 0.020 (2) |
S1—O3 | 1.513 (2) | C6—C7 | 1.385 (4) |
S1—C11 | 1.762 (3) | C7—C8 | 1.367 (4) |
S1—C12 | 1.769 (3) | C8—C9 | 1.379 (4) |
O1—C10 | 1.211 (3) | C6—H6 | 0.9400 |
O2—C10 | 1.310 (3) | C7—H7 | 0.9400 |
O2—H2O | 0.86 (3) | C8—H8 | 0.9400 |
N1—C2 | 1.334 (3) | C9—H9 | 0.9400 |
N1—C1i | 1.341 (3) | C11—H11A | 0.9700 |
N2—C9 | 1.337 (3) | C11—H11B | 0.9700 |
N2—C5 | 1.341 (3) | C11—H11C | 0.9700 |
C1—C5 | 1.484 (4) | C12—H12A | 0.9700 |
C1—C2 | 1.401 (4) | C12—H12B | 0.9700 |
C2—C10 | 1.506 (3) | C12—H12C | 0.9700 |
C5—C6 | 1.388 (4) | ||
C11—S1—C12 | 98.11 (15) | O2—C10—C2 | 113.2 (2) |
O3—S1—C11 | 105.80 (12) | C5—C6—H6 | 121.00 |
O3—S1—C12 | 105.72 (15) | C7—C6—H6 | 121.00 |
C10—O2—H2O | 108 (3) | C8—C7—H7 | 121.00 |
C1i—N1—C2 | 118.0 (2) | C6—C7—H7 | 120.00 |
C5—N2—C9 | 116.7 (2) | C7—C8—H8 | 121.00 |
C2—C1—C5 | 123.4 (2) | C9—C8—H8 | 121.00 |
N1i—C1—C5 | 117.2 (2) | N2—C9—H9 | 118.00 |
N1i—C1—C2 | 119.4 (2) | C8—C9—H9 | 118.00 |
N1—C2—C1 | 122.6 (2) | S1—C11—H11A | 110.00 |
N1—C2—C10 | 113.5 (2) | S1—C11—H11B | 109.00 |
C1—C2—C10 | 123.6 (2) | S1—C11—H11C | 109.00 |
N2—C5—C6 | 123.1 (2) | H11A—C11—H11B | 110.00 |
C1—C5—C6 | 121.1 (2) | H11A—C11—H11C | 109.00 |
N2—C5—C1 | 115.9 (2) | H11B—C11—H11C | 109.00 |
C5—C6—C7 | 118.6 (3) | S1—C12—H12A | 110.00 |
C6—C7—C8 | 119.0 (3) | S1—C12—H12B | 109.00 |
C7—C8—C9 | 118.6 (3) | S1—C12—H12C | 109.00 |
N2—C9—C8 | 124.0 (2) | H12A—C12—H12B | 110.00 |
O1—C10—C2 | 121.1 (2) | H12A—C12—H12C | 110.00 |
O1—C10—O2 | 125.5 (2) | H12B—C12—H12C | 109.00 |
C1i—N1—C2—C1 | 0.2 (4) | C2—C1—C5—C6 | 157.3 (3) |
C1i—N1—C2—C10 | −173.3 (2) | N1i—C1—C5—N2 | 156.1 (2) |
C2—N1—C1i—C2i | −0.2 (4) | N1i—C1—C5—C6 | −24.1 (4) |
C2—N1—C1i—C5i | 178.4 (2) | N1—C2—C10—O1 | 106.4 (3) |
C9—N2—C5—C1 | −179.0 (2) | N1—C2—C10—O2 | −68.9 (3) |
C9—N2—C5—C6 | 1.2 (4) | C1—C2—C10—O1 | −67.1 (3) |
C5—N2—C9—C8 | −0.7 (4) | C1—C2—C10—O2 | 117.7 (3) |
C5—C1—C2—N1 | 178.3 (2) | N2—C5—C6—C7 | −0.9 (4) |
C5—C1—C2—C10 | −8.8 (4) | C1—C5—C6—C7 | 179.4 (2) |
N1i—C1—C2—N1 | −0.2 (4) | C5—C6—C7—C8 | 0.0 (4) |
N1i—C1—C2—C10 | 172.6 (2) | C6—C7—C8—C9 | 0.5 (4) |
C2—C1—C5—N2 | −22.5 (4) | C7—C8—C9—N2 | −0.2 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.86 (3) | 1.76 (3) | 2.613 (3) | 175 (3) |
C8—H8···O3ii | 0.94 | 2.48 | 3.358 (3) | 156 |
C11—H11A···O1iii | 0.97 | 2.50 | 3.336 (4) | 144 |
C11—H11C···O1iv | 0.97 | 2.42 | 3.252 (3) | 144 |
C12—H12A···O3v | 0.97 | 2.45 | 3.371 (4) | 158 |
Symmetry codes: (ii) x−1/2, −y−1/2, z−1/2; (iii) x, y−1, z; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1, −y, −z+2. |
Experimental details
(Ia) | (Ib) | (Ic) | |
Crystal data | |||
Chemical formula | C16H10N4O4 | C16H12N4O42+·2Cl−·2H2O | C16H10N4O4·2C2H6OS |
Mr | 322.28 | 431.23 | 478.54 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 213 | 213 | 213 |
a, b, c (Å) | 8.304 (3), 9.684 (1), 17.802 (2) | 6.857 (1), 8.576 (1), 9.187 (2) | 13.067 (1), 6.138 (1), 14.453 (1) |
α, β, γ (°) | 90, 93.89 (1), 90 | 63.40 (1), 81.94 (1), 87.47 (1) | 90, 103.59 (1), 90 |
V (Å3) | 1428.3 (6) | 478.19 (14) | 1126.8 (2) |
Z | 4 | 1 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.38 | 0.28 |
Crystal size (mm) | 0.49 × 0.27 × 0.10 | 0.49 × 0.34 × 0.27 | 0.53 × 0.38 × 0.30 |
Data collection | |||
Diffractometer | Stoe AED-2 four-circle diffractometer | Stoe AED-2 four-circle diffractometer | Stoe AED-2 four-circle diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed reflections | 2502, 2371, 1731 [I > 2σ(I)] | 3504, 1681, 1463 [I > 2˘I)] | 1979, 1979, 1296 [I > 2σ(I)] |
Rint | 0.087 | 0.035 | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 | 0.595 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.165, 1.09 | 0.034, 0.093, 1.02 | 0.041, 0.093, 0.96 |
No. of reflections | 2371 | 1681 | 1979 |
No. of parameters | 226 | 143 | 151 |
No. of restraints | 2 | 2 | 1 |
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) | 0.24, −0.33 | 0.27, −0.32 | 0.20, −0.27 |
Computer programs: STADI-4 Software (Stoe & Cie, 1997), X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4i | 0.89 (2) | 1.68 (2) | 2.536 (3) | 162 (4) |
N4—H4N···O3ii | 0.89 (3) | 1.79 (3) | 2.666 (4) | 171 (3) |
C7—H7···O3iii | 0.94 | 2.51 | 3.429 (4) | 166 |
C8—H8···O2iv | 0.94 | 2.54 | 3.377 (4) | 149 |
C13—H13···N3v | 0.94 | 2.48 | 3.353 (4) | 155 |
C14—H14···O4vi | 0.94 | 2.42 | 3.358 (4) | 172 |
C15—H15···O1vii | 0.94 | 2.41 | 3.222 (4) | 145 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) x, −y−1/2, z−1/2; (v) −x+2, y+1/2, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x, −y−1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···Cl1i | 0.81 (4) | 2.34 (3) | 3.1453 (19) | 172 (3) |
O1W—H2WB···Cl1ii | 0.81 (3) | 2.34 (3) | 3.1472 (17) | 173 (2) |
N2—H2N···Cl1 | 0.893 (19) | 2.132 (19) | 3.0226 (19) | 175.2 (19) |
O2—H2O···O1Wiii | 0.84 (2) | 1.72 (2) | 2.559 (2) | 172 (3) |
C6—H6···Cl1i | 0.94 | 2.77 | 3.628 (2) | 153 |
C8—H8···O2iv | 0.94 | 2.43 | 3.172 (3) | 136 |
C9—H9···O1v | 0.94 | 2.42 | 3.346 (2) | 168 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+2; (v) x−1, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.86 (3) | 1.76 (3) | 2.613 (3) | 175 (3) |
C8—H8···O3i | 0.94 | 2.48 | 3.358 (3) | 156 |
C11—H11A···O1ii | 0.97 | 2.50 | 3.336 (4) | 144 |
C11—H11C···O1iii | 0.97 | 2.42 | 3.252 (3) | 144 |
C12—H12A···O3iv | 0.97 | 2.45 | 3.371 (4) | 158 |
Symmetry codes: (i) x−1/2, −y−1/2, z−1/2; (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z+3/2; (iv) −x+1, −y, −z+2. |
Various pyrazine carboxylic acids have been used for many years as ligands in coordination chemistry. A search of the Cambridge Structural Database (CSD, Version 5.33, Update 4, August 2012; Allen, 2002), for pyrazine-2,5-dicarboxylic acid yielded 63 hits, including more than 50 coordination complexes. A search for 2,5-bis(pyridin-2-yl)pyrazine yielded 27 hits, including 26 coordination complexes. Among the pyridyl and carboxylic acid derivatives of pyrazine, 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine (TPPZ) and pyrazine-2,3,5,6-tetracarboxylic acid (H4pztca) also feature. Both ligands are relatively old; TPPZ was first synthesized in 1959 by Goodwin & Lions (1959), while the first mention of the synthesis of H4pztca dates back to 1887 (Wolf, 1887, 1893). These compounds have also been studied extensively in the domain of coordination chemistry. A search of the CSD revealed 173 hits for TPPZ, including more than 150 mono-, bi-, tri- or polynuclear coordination complexes. There were 56 hits for H4pztca, including more than 40 mono-, bi- or polynuclear coordination complexes. For example, it was shown for the first time that a binuclear copper(II) complex of TPPZ could be formed, namely bis[diaqua[µ2-2,3,5,6-tetrakis(2-pyridyl)pyrazine-κ6N,N',N'',N''',N'''',N''''']copper(II)] tetraperchlorate dihydrate (Graf et al., 1993). It possesses an inversion centre and the pyridine rings rotate out of the plane of the planar pyrazine ring to accommodate the CuII atoms. The first crystal structure analysis of a metal complex of H4pztca involved iron(II) and resulted in the formation of a one-dimensional coordination polymer, namely catena-poly[[trans-diaqua(µ2-2,5-dicarboxypyrazine-3,6-dicarboxylato-κ2N,O)diiron(II)] dihydrate] (Marioni et al., 1986).
3,6-Bis(pyridin-2-yl)pyrazine-2,5-dicarboxylic acid, (I), and the isostructural compound 5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylic acid, (II) (Alfonso et al., 2001), with a combination of pyridine and carboxylic acid substituents, were synthesized to study their coordination behaviour with first-row transition metals. They do indeed exhibit a highly diverse coordination geometry (Wang, 1996; Alfonso, 1999). A prominent characteristic of these compounds is their amphoteric character, as they can exist as inner-salt zwitterions and as doubly charged species.
The inner-salt zwitterion of (I), 5-carboxy-3-(pyridin-1-ium-2-yl)-6-(pyridin-2-yl)pyrazine-2-carboxylate, (Ia) (Fig. 1), was obtained on treating the diethyl ester of (I) with KOH (see Experimental). The pyrazine ring (atoms N1/N2/C1–C4) is not planar [maximum deviation = 0.052 (3) Å for atom C2] but has a twist–boat conformation [puckering parameters (Cremer & Pople, 1975): pucking amplitude = 0.091 (3) Å, θ = 94.1 (19)° and ϕ = 280.4 (19)°]. The opposing pyridine and pyridinium rings are almost perpendicular to one another, with a dihedral angle of 80.24 (18)°, and they are inclined to the pyrazine ring mean plane by 36.83 (17) and 43.74 (17)°, respectively. The carboxy (–COOH) and carboxylate (COO–) groups are inclined to the mean plane of the pyrazine ring by 43.60 (17) and 45.46 (17)°, respectively.
In the crystal structure of (Ia), the pyridinium H atoms and the carboxy and carboxylate groups are involved in N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 2), leading to the formation of double-stranded chains propagating in the [010] direction. These chains incorporate R33(19) ring motifs (Bernstein et al., 1995) involving three molecules. The presence of C—H···O interactions leads to the formation of two-dimensional networks lying parallel to the bc plane (Table 1). These networks are in turn linked via C—H···N interactions to form a three-dimensional structure (Fig. 3).
On treating (Ia) with aqueous 1M HCl, the diprotonated dihydrate form 2,2'-(3,6-dicarboxypyrazine-2,5-diyl)bis(pyridin-1-ium) dichloride dihydrate, (Ib), was obtained (Fig. 4). The cation lies about an inversion centre and the pyrazine ring is planar. The pyridinium rings and the carboxy groups (–COOH) are inclined to the pyrazine ring by 55.53 (9) and 19.8 (2)°, respectively.
In the crystal structure of (Ib), the molecules are involved in N—H···Cl and O—H···Owater hydrogen bonds (Table 2 and Fig. 5). The Cl- anions are in turn bridged by Owater—H..Cl hydrogen bonds, forming R42(8) ring motifs. This leads to the formation of chains propagating in the [010] direction. The presence of C—H···Cl and C—H···O interactions leads to the formation of a three-dimensional framework-like structure (Table 2 and Fig. 6)
When (Ia) was recrystallized from dimethyl sulfoxide (DMSO), the DMSO disolvate of (I) was obtained, viz. 3,6-bis(pyridin-2-yl)pyrazine-2,5-dicarboxylic acid dimethyl sulfoxide disolvate, (Ic) (Fig. 7). Here, the molecule of (I) lies about an inversion centre and the pyrazine ring is planar. The pyridine rings are inclined to the pyrazine ring by 23.59 (12)°, while the carboxy (–COOH) groups are inclined to the pyrazine ring by 69.0 (3)°.
In the crystal structure of (Ic), the carboxy groups are linked to the DMSO molecules by O—H···O hydrogen bonds (Table 3 and Fig. 8). A series of C—H···O interactions involving both components of the crystal structure leads to the formation of a three-dimensional supramolecular structure (Table 3 and Fig. 9).
The dimethyl ester, (III), and the diethyl ester, (IV), of (I) both crystallize in the triclinic space group P1 (Wang & Stoeckli-Evans, 2012a,b). In both cases, the whole molecules are generated by crystallographic inversion symmetry. The pyridine rings lie almost in the plane of the pyrazine ring, with dihedral angles of 7.89 (13)° for (III) and 1.7 (2)° for (IV). In (III), the methyl carboxylate mean plane [maximum deviation for non-H atoms = 0.041 (3) Å [For which atom?]] makes a dihedral angle of 74.09 (19)° with the pyrazine ring. In (IV), the ethyl carboxylate mean plane [maximum deviation for non-H atoms = 0.042 (5) Å [For which atom?]] makes a dihedral angle of 79.5 (3)°. In the crystal structures of both esters, the molecules are linked by pairs of C—H···O hydrogen bonds to form chains propagating along [101] and incorporating R22(10) ring motifs.