Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113010056/sk3484sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010056/sk3484IIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010056/sk3484IIbsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010056/sk3484IIcsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010056/sk3484IIdsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010056/sk3484IIesup6.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010056/sk3484IIasup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010056/sk3484IIbsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010056/sk3484IIcsup9.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010056/sk3484IIdsup10.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010056/sk3484IIesup11.cml |
CCDC references: 950375; 950376; 950377; 950378; 950379
For related literature, see: Allen (2002); Baddeley et al. (2009); Bernstein et al. (1995); Howie et al. (2010, 2010a, 2010b); Howie, Lima, Kaiser, da Silva, de Souza, Wardell & Wardell (2010c); Howie, Lima, Kaiser, de Souza, Wardell & Wardell (2010c); Lima et al. (2011); Orlewska et al. (2001); Souza et al. (2011); Szczesio et al. (2011); Vergara et al. (2009); de Souza (2013).
A reaction mixture of the appropriate N'-[(E)-benzylidene]-2-pyrazinecarbohydrazide derivative (0.75 mmol; Vergara et al., 2009; Lima et al., 2011), Na2CO3 (ca 4 mmol) and MeI (3 mmol) in acetone (4 ml) was heated at 313 K for 18 h under a nitrogen atmosphere. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to leave a residue, which was added to ice–water. The solid which separated was collected and washed with cold Et2O (3 × 10 ml), yielding the N-methylpyrazine-2-carbohydrazide derivative as a colourless crystalline solid. Further recrystallizations of the N-methylpyrazine-2-carbohydrazides were carried out from appropriate solvents. A consistant recrystallization solvent, which could provide suitable crystals for the X-ray study for the five derivatives reported here, was not found. All the solvents used were specially dried. [Double negative removed - OK?]
Compound (IIa) (yield 54%, m.p. 391–393 K) was recrystallized from EtOH for the X-ray analysis, (IIb) (yield 63%, 378–380 K) from MeOCH2CH2OH, (IIc) (yield 73%, m.p. 383–384 K) from dimethyl [Text missing?], (IId) ([Yield?], m.p. 424–425 K) from EtOH and (IIe) ([Yield?], m.p. 458–460 K) from EtOH.
In all five title compounds, H atoms were treated as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, or C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. In (IIc), the water H atoms were located in a difference map and allowed to ride at these positions, with Uiso(H) = 1.5Ueq(O). The positions of the H atoms, methyl groups and water molecules were checked on difference maps during the refinement and after the refinement was complete.
Data collection: CrystalClear-SM Expert (Rigaku, 2011) for (IIa), (IIb), (IIc), (IIe); COLLECT (Nonius, 2000) for (IId). Cell refinement: CrystalClear-SM Expert (Rigaku, 2011) for (IIa), (IIb), (IIc), (IIe); SCALEPACK (Otwinowski & Minor, 1997) for (IId). Data reduction: CrystalClear-SM Expert (Rigaku, 2011) for (IIa), (IIb), (IIc), (IIe); DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (IId). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008).
C13H12N4O | Z = 2 |
Mr = 240.27 | F(000) = 252 |
Triclinic, P1 | Dx = 1.332 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 7.4961 (3) Å | Cell parameters from 6254 reflections |
b = 7.6923 (3) Å | θ = 3.2–27.4° |
c = 10.8821 (7) Å | µ = 0.09 mm−1 |
α = 73.421 (5)° | T = 120 K |
β = 84.844 (6)° | Block, orange |
γ = 88.530 (6)° | 0.56 × 0.43 × 0.23 mm |
V = 598.97 (5) Å3 |
Rigaku R-AXIS conversion diffractometer | 2712 independent reflections |
Radiation source: Sealed tube | 2270 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
profile data from ω–scans | h = −9→9 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −9→9 |
Tmin = 0.952, Tmax = 0.980 | l = −14→14 |
7672 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0656P)2 + 0.0688P] where P = (Fo2 + 2Fc2)/3 |
2712 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C13H12N4O | γ = 88.530 (6)° |
Mr = 240.27 | V = 598.97 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.4961 (3) Å | Mo Kα radiation |
b = 7.6923 (3) Å | µ = 0.09 mm−1 |
c = 10.8821 (7) Å | T = 120 K |
α = 73.421 (5)° | 0.56 × 0.43 × 0.23 mm |
β = 84.844 (6)° |
Rigaku R-AXIS conversion diffractometer | 2712 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 2270 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.980 | Rint = 0.016 |
7672 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.31 e Å−3 |
2712 reflections | Δρmin = −0.21 e Å−3 |
164 parameters |
Experimental. Compound (IIa): 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 8.85 (, s, H3), 8.69 (1H, s, H5), 8.66 (1H, s, H6), 7.81 (1H, N═CH), 7.39–7.33 (5H, m, phenyl), 3.62 (3H, s, NCH3); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 167.5, 150.2, 144.9, 144.7, 143.8, 141.1, 133.8, 130.2, 128.8, 127.3, 28.5; IR (KBr, ν, cm-1): 1676 (C═O), 1606 (–N═C–CH3). LC/MS: m/z [M]-: 240. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.59462 (13) | 0.82450 (11) | 0.15785 (9) | 0.0353 (2) | |
N1 | 0.71743 (12) | 0.48356 (12) | 0.42370 (9) | 0.0222 (2) | |
N2 | 0.65947 (12) | 0.65306 (12) | 0.35592 (9) | 0.0233 (2) | |
N21 | 0.51069 (14) | 0.38869 (14) | 0.21804 (10) | 0.0300 (2) | |
N24 | 0.78603 (14) | 0.37332 (14) | 0.02828 (10) | 0.0313 (3) | |
C1 | 0.75771 (14) | 0.46307 (16) | 0.53921 (10) | 0.0239 (2) | |
H1 | 0.7479 | 0.5633 | 0.5740 | 0.029* | |
C2 | 0.62923 (15) | 0.67640 (15) | 0.23037 (11) | 0.0244 (2) | |
C11 | 0.81848 (14) | 0.28776 (16) | 0.61799 (10) | 0.0237 (2) | |
C12 | 0.87332 (16) | 0.27812 (17) | 0.73924 (11) | 0.0299 (3) | |
H12 | 0.8700 | 0.3838 | 0.7680 | 0.036* | |
C13 | 0.93248 (17) | 0.11570 (19) | 0.81768 (12) | 0.0338 (3) | |
H13 | 0.9713 | 0.1109 | 0.8993 | 0.041* | |
C14 | 0.93520 (16) | −0.03992 (18) | 0.77750 (12) | 0.0321 (3) | |
H14 | 0.9753 | −0.1514 | 0.8316 | 0.039* | |
C15 | 0.87901 (16) | −0.03243 (17) | 0.65759 (12) | 0.0295 (3) | |
H15 | 0.8799 | −0.1393 | 0.6303 | 0.035* | |
C16 | 0.82177 (15) | 0.13007 (16) | 0.57781 (11) | 0.0256 (3) | |
H16 | 0.7847 | 0.1345 | 0.4957 | 0.031* | |
C22 | 0.64153 (15) | 0.51242 (15) | 0.18023 (10) | 0.0223 (2) | |
C23 | 0.77724 (16) | 0.50456 (16) | 0.08704 (11) | 0.0277 (3) | |
H23 | 0.8673 | 0.5955 | 0.0639 | 0.033* | |
C25 | 0.65355 (16) | 0.25194 (16) | 0.06350 (11) | 0.0267 (3) | |
H25 | 0.6518 | 0.1578 | 0.0230 | 0.032* | |
C26 | 0.51892 (16) | 0.25938 (17) | 0.15723 (12) | 0.0302 (3) | |
H26 | 0.4283 | 0.1690 | 0.1796 | 0.036* | |
C27 | 0.65016 (16) | 0.80741 (16) | 0.40887 (12) | 0.0285 (3) | |
H27A | 0.6018 | 0.9128 | 0.3468 | 0.043* | |
H27B | 0.7705 | 0.8357 | 0.4262 | 0.043* | |
H27C | 0.5719 | 0.7775 | 0.4892 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0499 (6) | 0.0231 (5) | 0.0324 (5) | 0.0007 (4) | −0.0118 (4) | −0.0049 (3) |
N1 | 0.0209 (5) | 0.0222 (5) | 0.0234 (5) | −0.0011 (3) | −0.0015 (3) | −0.0066 (4) |
N2 | 0.0255 (5) | 0.0208 (5) | 0.0245 (5) | −0.0013 (4) | −0.0028 (4) | −0.0079 (4) |
N21 | 0.0280 (5) | 0.0304 (5) | 0.0331 (5) | −0.0066 (4) | 0.0022 (4) | −0.0124 (4) |
N24 | 0.0354 (6) | 0.0316 (6) | 0.0280 (5) | −0.0056 (4) | 0.0015 (4) | −0.0111 (4) |
C1 | 0.0231 (5) | 0.0262 (6) | 0.0248 (5) | −0.0027 (4) | −0.0009 (4) | −0.0111 (4) |
C2 | 0.0230 (5) | 0.0233 (6) | 0.0266 (6) | −0.0028 (4) | −0.0034 (4) | −0.0061 (4) |
C11 | 0.0189 (5) | 0.0298 (6) | 0.0229 (5) | −0.0031 (4) | 0.0002 (4) | −0.0084 (4) |
C12 | 0.0324 (6) | 0.0348 (7) | 0.0241 (6) | −0.0039 (5) | −0.0024 (5) | −0.0105 (5) |
C13 | 0.0345 (7) | 0.0422 (7) | 0.0230 (6) | −0.0044 (5) | −0.0060 (5) | −0.0052 (5) |
C14 | 0.0264 (6) | 0.0333 (7) | 0.0300 (6) | −0.0015 (5) | −0.0025 (5) | 0.0018 (5) |
C15 | 0.0259 (6) | 0.0288 (6) | 0.0333 (6) | −0.0015 (5) | −0.0005 (5) | −0.0087 (5) |
C16 | 0.0228 (5) | 0.0314 (6) | 0.0237 (5) | −0.0016 (4) | −0.0022 (4) | −0.0094 (5) |
C22 | 0.0248 (5) | 0.0220 (5) | 0.0199 (5) | −0.0009 (4) | −0.0067 (4) | −0.0040 (4) |
C23 | 0.0305 (6) | 0.0261 (6) | 0.0261 (6) | −0.0076 (5) | 0.0003 (4) | −0.0067 (5) |
C25 | 0.0313 (6) | 0.0255 (6) | 0.0254 (6) | −0.0007 (4) | −0.0072 (4) | −0.0089 (4) |
C26 | 0.0273 (6) | 0.0286 (6) | 0.0368 (6) | −0.0074 (5) | −0.0020 (5) | −0.0122 (5) |
C27 | 0.0307 (6) | 0.0254 (6) | 0.0331 (6) | −0.0008 (5) | −0.0044 (5) | −0.0138 (5) |
O2—C2 | 1.2233 (14) | C13—C14 | 1.3858 (19) |
N1—C1 | 1.2841 (14) | C13—H13 | 0.9500 |
N1—N2 | 1.3830 (13) | C14—C15 | 1.3921 (17) |
N2—C2 | 1.3652 (14) | C14—H14 | 0.9500 |
N2—C27 | 1.4579 (13) | C15—C16 | 1.3858 (17) |
N21—C22 | 1.3376 (15) | C15—H15 | 0.9500 |
N21—C26 | 1.3402 (15) | C16—H16 | 0.9500 |
N24—C25 | 1.3341 (15) | C22—C23 | 1.3833 (16) |
N24—C23 | 1.3378 (15) | C23—H23 | 0.9500 |
C1—C11 | 1.4628 (16) | C25—C26 | 1.3811 (17) |
C1—H1 | 0.9500 | C25—H25 | 0.9500 |
C2—C22 | 1.5084 (15) | C26—H26 | 0.9500 |
C11—C12 | 1.3984 (15) | C27—H27A | 0.9800 |
C11—C16 | 1.4008 (16) | C27—H27B | 0.9800 |
C12—C13 | 1.3846 (18) | C27—H27C | 0.9800 |
C12—H12 | 0.9500 | ||
C1—N1—N2 | 117.51 (9) | C16—C15—C14 | 120.36 (11) |
C2—N2—N1 | 116.86 (9) | C16—C15—H15 | 119.8 |
C2—N2—C27 | 120.23 (9) | C14—C15—H15 | 119.8 |
N1—N2—C27 | 122.54 (9) | C15—C16—C11 | 120.10 (10) |
C22—N21—C26 | 115.12 (10) | C15—C16—H16 | 119.9 |
C25—N24—C23 | 115.75 (10) | C11—C16—H16 | 119.9 |
N1—C1—C11 | 121.02 (10) | N21—C22—C23 | 122.18 (10) |
N1—C1—H1 | 119.5 | N21—C22—C2 | 118.63 (10) |
C11—C1—H1 | 119.5 | C23—C22—C2 | 118.84 (10) |
O2—C2—N2 | 122.49 (10) | N24—C23—C22 | 122.30 (10) |
O2—C2—C22 | 119.42 (10) | N24—C23—H23 | 118.9 |
N2—C2—C22 | 118.09 (9) | C22—C23—H23 | 118.9 |
C12—C11—C16 | 119.02 (11) | N24—C25—C26 | 121.81 (10) |
C12—C11—C1 | 118.09 (10) | N24—C25—H25 | 119.1 |
C16—C11—C1 | 122.89 (10) | C26—C25—H25 | 119.1 |
C13—C12—C11 | 120.51 (11) | N21—C26—C25 | 122.81 (10) |
C13—C12—H12 | 119.7 | N21—C26—H26 | 118.6 |
C11—C12—H12 | 119.7 | C25—C26—H26 | 118.6 |
C12—C13—C14 | 120.21 (11) | N2—C27—H27A | 109.5 |
C12—C13—H13 | 119.9 | N2—C27—H27B | 109.5 |
C14—C13—H13 | 119.9 | H27A—C27—H27B | 109.5 |
C13—C14—C15 | 119.79 (11) | N2—C27—H27C | 109.5 |
C13—C14—H14 | 120.1 | H27A—C27—H27C | 109.5 |
C15—C14—H14 | 120.1 | H27B—C27—H27C | 109.5 |
C1—N1—N2—C2 | 175.51 (10) | C12—C11—C16—C15 | −0.11 (17) |
C1—N1—N2—C27 | 2.55 (15) | C1—C11—C16—C15 | −179.28 (10) |
N2—N1—C1—C11 | 179.41 (9) | C26—N21—C22—C23 | −1.31 (16) |
N1—N2—C2—O2 | −172.75 (10) | C26—N21—C22—C2 | 171.88 (10) |
C27—N2—C2—O2 | 0.38 (17) | O2—C2—C22—N21 | −107.86 (13) |
N1—N2—C2—C22 | 6.53 (14) | N2—C2—C22—N21 | 72.83 (14) |
C27—N2—C2—C22 | 179.66 (9) | O2—C2—C22—C23 | 65.56 (15) |
N1—C1—C11—C12 | 175.16 (10) | N2—C2—C22—C23 | −113.74 (12) |
N1—C1—C11—C16 | −5.65 (17) | C25—N24—C23—C22 | 1.21 (17) |
C16—C11—C12—C13 | 0.94 (17) | N21—C22—C23—N24 | 0.31 (18) |
C1—C11—C12—C13 | −179.85 (10) | C2—C22—C23—N24 | −172.87 (10) |
C11—C12—C13—C14 | −1.04 (19) | C23—N24—C25—C26 | −1.67 (17) |
C12—C13—C14—C15 | 0.31 (19) | C22—N21—C26—C25 | 0.85 (17) |
C13—C14—C15—C16 | 0.52 (18) | N24—C25—C26—N21 | 0.68 (19) |
C14—C15—C16—C11 | −0.62 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C25—H25···O2i | 0.95 | 2.59 | 3.1823 (16) | 121 |
Symmetry code: (i) x, y−1, z. |
C14H14N4O2 | Z = 2 |
Mr = 270.29 | F(000) = 284 |
Triclinic, P1 | Dx = 1.394 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 4.032 (5) Å | Cell parameters from 1623 reflections |
b = 10.628 (15) Å | θ = 2.4–31.2° |
c = 15.034 (19) Å | µ = 0.10 mm−1 |
α = 94.08 (3)° | T = 100 K |
β = 90.36 (3)° | Block, brown |
γ = 92.07 (3)° | 0.18 × 0.13 × 0.12 mm |
V = 642.2 (15) Å3 |
Rigaku Saturn724+ diffractometer | 2246 independent reflections |
Radiation source: Rotating anode | 1859 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.033 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
profile data from ω–scans | h = −3→4 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −12→12 |
Tmin = 0.983, Tmax = 0.988 | l = −17→17 |
4990 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0898P)2 + 0.0839P] where P = (Fo2 + 2Fc2)/3 |
2246 reflections | (Δ/σ)max < 0.001 |
185 parameters | Δρmax = 0.18 e Å−3 |
6 restraints | Δρmin = −0.26 e Å−3 |
C14H14N4O2 | γ = 92.07 (3)° |
Mr = 270.29 | V = 642.2 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.032 (5) Å | Mo Kα radiation |
b = 10.628 (15) Å | µ = 0.10 mm−1 |
c = 15.034 (19) Å | T = 100 K |
α = 94.08 (3)° | 0.18 × 0.13 × 0.12 mm |
β = 90.36 (3)° |
Rigaku Saturn724+ diffractometer | 2246 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 1859 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.988 | Rint = 0.033 |
4990 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 6 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.18 e Å−3 |
2246 reflections | Δρmin = −0.26 e Å−3 |
185 parameters |
Experimental. Compound (IIb): 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 8.85 (1H, s, H3), 8.69 (1H, s, H5), 8.64 (1H, s, H6), 8.23 (1H, s, N═CH), 7.35–7.30 (2H, m, H4' and H5'), 6.90–6.82 (2H, m, H3' and H6'), 3.88 (3H, s, OCH3), 3.62 (3H, s, NCH3); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 167.6, 158.2, 150.5, 145.1, 144.7, 143.9, 137.5, 131.6, 126.1, 122.4, 121.0, 111.1, 55.6, 28.8; IR (KBr, ν, cm-1): 1680 (C═O), 1600 (–N═C–CH3). LC/MS: m/z [M + H]+: 271. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O2 | 0.8377 (4) | 0.40652 (13) | 0.38061 (9) | 0.0375 (4) | |
O12 | −0.0014 (4) | 0.97966 (14) | 0.37116 (11) | 0.0457 (5) | |
N1 | 0.4082 (4) | 0.65216 (15) | 0.29794 (10) | 0.0274 (4) | |
N2 | 0.5864 (4) | 0.59046 (15) | 0.35931 (10) | 0.0274 (4) | |
C1 | 0.3178 (5) | 0.76459 (18) | 0.31972 (13) | 0.0296 (5) | |
H1 | 0.3606 | 0.8017 | 0.3782 | 0.035* | |
C2 | 0.6893 (5) | 0.47329 (18) | 0.33125 (12) | 0.0284 (5) | |
C11 | 0.1489 (5) | 0.83521 (18) | 0.25415 (14) | 0.0312 (5) | |
C12 | −0.0030 (5) | 0.94854 (18) | 0.28078 (16) | 0.0367 (5) | |
C13 | −0.1466 (6) | 1.0204 (2) | 0.21866 (19) | 0.0460 (6) | |
H13 | −0.2464 | 1.0974 | 0.2374 | 0.055* | |
C14 | −0.1441 (6) | 0.9796 (2) | 0.12891 (19) | 0.0471 (6) | |
H14 | −0.2417 | 1.0289 | 0.0861 | 0.056* | |
C15 | 0.0005 (5) | 0.8673 (2) | 0.10160 (16) | 0.0417 (6) | |
H15 | −0.0001 | 0.8389 | 0.0402 | 0.050* | |
C16 | 0.1455 (5) | 0.79676 (19) | 0.16372 (14) | 0.0347 (5) | |
H16 | 0.2453 | 0.7201 | 0.1443 | 0.042* | |
C27 | 0.6666 (5) | 0.6458 (2) | 0.44850 (12) | 0.0340 (5) | |
H27A | 0.8087 | 0.5893 | 0.4790 | 0.051* | |
H27B | 0.4614 | 0.6577 | 0.4822 | 0.051* | |
H27C | 0.7836 | 0.7276 | 0.4443 | 0.051* | |
C22 | 0.6213 (5) | 0.42870 (17) | 0.23544 (12) | 0.0258 (4) | |
C25 | 0.5341 (5) | 0.34126 (19) | 0.06766 (13) | 0.0317 (5) | |
H25 | 0.4943 | 0.3080 | 0.0081 | 0.038* | |
C23 | 0.749 (3) | 0.4998 (11) | 0.1676 (9) | 0.0271 (13) | 0.527 (9) |
H23 | 0.8672 | 0.5776 | 0.1818 | 0.032* | 0.527 (9) |
C26 | 0.419 (2) | 0.2706 (9) | 0.1407 (4) | 0.0271 (13) | 0.527 (9) |
H26 | 0.3043 | 0.1917 | 0.1279 | 0.032* | 0.527 (9) |
N21 | 0.4691 (17) | 0.3124 (6) | 0.2250 (3) | 0.0282 (13) | 0.527 (9) |
N24 | 0.702 (2) | 0.4571 (6) | 0.0834 (6) | 0.0282 (13) | 0.527 (9) |
N21A | 0.779 (3) | 0.4873 (10) | 0.1712 (8) | 0.0282 (13) | 0.473 (9) |
N24A | 0.376 (2) | 0.2812 (8) | 0.1252 (4) | 0.0282 (13) | 0.473 (9) |
C23A | 0.420 (2) | 0.3263 (9) | 0.2109 (5) | 0.0271 (13) | 0.473 (9) |
H23A | 0.3059 | 0.2846 | 0.2561 | 0.032* | 0.473 (9) |
C26A | 0.742 (3) | 0.4378 (8) | 0.0867 (8) | 0.0271 (13) | 0.473 (9) |
H26A | 0.8665 | 0.4728 | 0.0405 | 0.032* | 0.473 (9) |
C121 | −0.1477 (7) | 1.0963 (2) | 0.4016 (2) | 0.0682 (9) | |
H12A | −0.1318 | 1.1074 | 0.4668 | 0.102* | |
H12B | −0.3816 | 1.0941 | 0.3832 | 0.102* | |
H12C | −0.0295 | 1.1668 | 0.3755 | 0.102* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0508 (10) | 0.0342 (8) | 0.0286 (8) | 0.0079 (7) | 0.0002 (7) | 0.0066 (6) |
O12 | 0.0437 (9) | 0.0239 (8) | 0.0672 (11) | 0.0052 (7) | 0.0078 (8) | −0.0161 (7) |
N1 | 0.0256 (9) | 0.0229 (9) | 0.0333 (9) | −0.0010 (6) | 0.0042 (7) | 0.0004 (7) |
N2 | 0.0311 (9) | 0.0247 (9) | 0.0260 (9) | 0.0004 (7) | 0.0017 (7) | −0.0016 (6) |
C1 | 0.0263 (10) | 0.0239 (10) | 0.0374 (11) | −0.0035 (8) | 0.0093 (8) | −0.0038 (8) |
C2 | 0.0307 (11) | 0.0283 (11) | 0.0264 (10) | 0.0009 (8) | 0.0048 (8) | 0.0031 (8) |
C11 | 0.0242 (10) | 0.0215 (10) | 0.0474 (12) | −0.0032 (8) | 0.0089 (9) | 0.0009 (8) |
C12 | 0.0276 (11) | 0.0194 (10) | 0.0622 (14) | −0.0026 (8) | 0.0083 (10) | −0.0031 (10) |
C13 | 0.0318 (12) | 0.0197 (11) | 0.0870 (19) | 0.0006 (9) | 0.0094 (12) | 0.0069 (11) |
C14 | 0.0351 (12) | 0.0328 (13) | 0.0756 (17) | −0.0032 (10) | 0.0025 (11) | 0.0220 (12) |
C15 | 0.0337 (12) | 0.0368 (13) | 0.0557 (14) | −0.0024 (9) | 0.0055 (10) | 0.0127 (10) |
C16 | 0.0301 (11) | 0.0262 (11) | 0.0481 (13) | 0.0011 (8) | 0.0090 (9) | 0.0054 (9) |
C27 | 0.0387 (12) | 0.0363 (12) | 0.0255 (10) | −0.0044 (9) | 0.0010 (8) | −0.0051 (8) |
C22 | 0.0293 (10) | 0.0194 (10) | 0.0292 (10) | 0.0063 (8) | 0.0042 (8) | 0.0025 (8) |
C25 | 0.0399 (12) | 0.0273 (11) | 0.0282 (10) | 0.0080 (9) | 0.0018 (8) | −0.0006 (8) |
C23 | 0.036 (2) | 0.022 (2) | 0.0249 (18) | 0.0044 (17) | 0.0028 (16) | 0.0102 (14) |
C26 | 0.036 (2) | 0.022 (2) | 0.0249 (18) | 0.0044 (17) | 0.0028 (16) | 0.0102 (14) |
N21 | 0.042 (2) | 0.0186 (17) | 0.0245 (16) | 0.0060 (15) | −0.0020 (14) | 0.0014 (15) |
N24 | 0.042 (2) | 0.0186 (17) | 0.0245 (16) | 0.0060 (15) | −0.0020 (14) | 0.0014 (15) |
N21A | 0.042 (2) | 0.0186 (17) | 0.0245 (16) | 0.0060 (15) | −0.0020 (14) | 0.0014 (15) |
N24A | 0.042 (2) | 0.0186 (17) | 0.0245 (16) | 0.0060 (15) | −0.0020 (14) | 0.0014 (15) |
C23A | 0.036 (2) | 0.022 (2) | 0.0249 (18) | 0.0044 (17) | 0.0028 (16) | 0.0102 (14) |
C26A | 0.036 (2) | 0.022 (2) | 0.0249 (18) | 0.0044 (17) | 0.0028 (16) | 0.0102 (14) |
C121 | 0.0519 (16) | 0.0407 (15) | 0.106 (2) | 0.0179 (12) | −0.0098 (15) | −0.0408 (15) |
O2—C2 | 1.230 (3) | C27—H27C | 0.9800 |
O12—C12 | 1.375 (3) | C22—N21A | 1.337 (13) |
O12—C121 | 1.439 (3) | C22—N21 | 1.359 (7) |
N1—C1 | 1.283 (3) | C22—C23A | 1.362 (9) |
N1—N2 | 1.382 (3) | C22—C23 | 1.402 (14) |
N2—C2 | 1.366 (3) | C25—N24A | 1.273 (7) |
N2—C27 | 1.455 (3) | C25—C26A | 1.315 (10) |
C1—C11 | 1.460 (3) | C25—N24 | 1.388 (8) |
C1—H1 | 0.9500 | C25—C26 | 1.443 (8) |
C2—C22 | 1.504 (3) | C25—H25 | 0.9500 |
C11—C16 | 1.391 (3) | C23—N24 | 1.324 (10) |
C11—C12 | 1.405 (3) | C23—H23 | 0.9500 |
C12—C13 | 1.385 (4) | C26—N21 | 1.324 (7) |
C13—C14 | 1.388 (4) | C26—H26 | 0.9500 |
C13—H13 | 0.9500 | N21A—C26A | 1.346 (10) |
C14—C15 | 1.385 (4) | N24A—C23A | 1.351 (8) |
C14—H14 | 0.9500 | C23A—H23A | 0.9500 |
C15—C16 | 1.379 (3) | C26A—H26A | 0.9500 |
C15—H15 | 0.9500 | C121—H12A | 0.9800 |
C16—H16 | 0.9500 | C121—H12B | 0.9800 |
C27—H27A | 0.9800 | C121—H12C | 0.9800 |
C27—H27B | 0.9800 | ||
C12—O12—C121 | 117.3 (2) | N21—C22—C23 | 126.6 (5) |
C1—N1—N2 | 118.49 (17) | C23A—C22—C23 | 117.6 (7) |
C2—N2—N1 | 116.06 (16) | N21A—C22—C2 | 118.9 (5) |
C2—N2—C27 | 121.02 (16) | N21—C22—C2 | 113.6 (3) |
N1—N2—C27 | 122.91 (17) | C23A—C22—C2 | 122.9 (3) |
N1—C1—C11 | 119.65 (19) | C23—C22—C2 | 119.3 (5) |
N1—C1—H1 | 120.2 | N24A—C25—C26A | 124.7 (6) |
C11—C1—H1 | 120.2 | N24A—C25—N24 | 126.0 (4) |
O2—C2—N2 | 122.42 (18) | C26A—C25—C26 | 117.4 (6) |
O2—C2—C22 | 120.34 (18) | N24—C25—C26 | 120.9 (5) |
N2—C2—C22 | 117.22 (16) | N24A—C25—H25 | 113.4 |
C16—C11—C12 | 117.9 (2) | C26A—C25—H25 | 121.8 |
C16—C11—C1 | 121.83 (19) | N24—C25—H25 | 119.6 |
C12—C11—C1 | 120.3 (2) | C26—C25—H25 | 119.6 |
O12—C12—C13 | 123.8 (2) | N24—C23—C22 | 119.1 (8) |
O12—C12—C11 | 115.3 (2) | N24—C23—H23 | 120.4 |
C13—C12—C11 | 120.9 (2) | C22—C23—H23 | 120.4 |
C12—C13—C14 | 119.7 (2) | N21—C26—C25 | 122.0 (5) |
C12—C13—H13 | 120.1 | N21—C26—H26 | 119.0 |
C14—C13—H13 | 120.1 | C25—C26—H26 | 119.0 |
C15—C14—C13 | 120.2 (2) | C26—N21—C22 | 114.0 (4) |
C15—C14—H14 | 119.9 | C23—N24—C25 | 117.2 (5) |
C13—C14—H14 | 119.9 | C22—N21A—C26A | 118.0 (7) |
C16—C15—C14 | 119.8 (2) | C25—N24A—C23A | 115.6 (5) |
C16—C15—H15 | 120.1 | N24A—C23A—C22 | 123.0 (5) |
C14—C15—H15 | 120.1 | N24A—C23A—H23A | 118.5 |
C15—C16—C11 | 121.6 (2) | C22—C23A—H23A | 118.5 |
C15—C16—H16 | 119.2 | C25—C26A—N21A | 120.4 (7) |
C11—C16—H16 | 119.2 | C25—C26A—H26A | 119.8 |
N2—C27—H27A | 109.5 | N21A—C26A—H26A | 119.8 |
N2—C27—H27B | 109.5 | O12—C121—H12A | 109.5 |
H27A—C27—H27B | 109.5 | O12—C121—H12B | 109.5 |
N2—C27—H27C | 109.5 | H12A—C121—H12B | 109.5 |
H27A—C27—H27C | 109.5 | O12—C121—H12C | 109.5 |
H27B—C27—H27C | 109.5 | H12A—C121—H12C | 109.5 |
N21A—C22—N21 | 125.2 (5) | H12B—C121—H12C | 109.5 |
N21A—C22—C23A | 118.0 (6) | ||
C1—N1—N2—C2 | −177.12 (16) | N21—C22—C23—N24 | 5.1 (8) |
C1—N1—N2—C27 | 2.1 (3) | C23A—C22—C23—N24 | −7.8 (13) |
N2—N1—C1—C11 | 175.87 (15) | C2—C22—C23—N24 | 176.8 (4) |
N1—N2—C2—O2 | −176.87 (17) | N24A—C25—C26—N21 | −120 (4) |
C27—N2—C2—O2 | 3.9 (3) | C26A—C25—C26—N21 | 11.9 (11) |
N1—N2—C2—C22 | 4.6 (2) | N24—C25—C26—N21 | −0.2 (6) |
C27—N2—C2—C22 | −174.65 (16) | C25—C26—N21—C22 | 3.1 (6) |
N1—C1—C11—C16 | −14.3 (3) | N21A—C22—N21—C26 | −14.9 (10) |
N1—C1—C11—C12 | 168.73 (18) | C23A—C22—N21—C26 | 49 (2) |
C121—O12—C12—C13 | −2.3 (3) | C23—C22—N21—C26 | −5.6 (7) |
C121—O12—C12—C11 | 178.69 (19) | C2—C22—N21—C26 | −177.7 (3) |
C16—C11—C12—O12 | 177.98 (17) | C22—C23—N24—C25 | −1.6 (8) |
C1—C11—C12—O12 | −4.9 (3) | N24A—C25—N24—C23 | 11.7 (8) |
C16—C11—C12—C13 | −1.0 (3) | C26A—C25—N24—C23 | −76 (4) |
C1—C11—C12—C13 | 176.06 (18) | C26—C25—N24—C23 | −0.6 (6) |
O12—C12—C13—C14 | −178.22 (19) | N21—C22—N21A—C26A | 11.1 (12) |
C11—C12—C13—C14 | 0.7 (3) | C23A—C22—N21A—C26A | −3.2 (7) |
C12—C13—C14—C15 | 0.2 (3) | C23—C22—N21A—C26A | −92 (8) |
C13—C14—C15—C16 | −0.7 (3) | C2—C22—N21A—C26A | 173.1 (4) |
C14—C15—C16—C11 | 0.4 (3) | C26A—C25—N24A—C23A | 3.0 (7) |
C12—C11—C16—C15 | 0.5 (3) | N24—C25—N24A—C23A | −10.6 (10) |
C1—C11—C16—C15 | −176.56 (18) | C26—C25—N24A—C23A | 56 (3) |
O2—C2—C22—N21A | −111.5 (6) | C25—N24A—C23A—C22 | −0.3 (7) |
N2—C2—C22—N21A | 67.1 (6) | N21A—C22—C23A—N24A | 0.6 (7) |
O2—C2—C22—N21 | 52.5 (4) | N21—C22—C23A—N24A | −123 (3) |
N2—C2—C22—N21 | −128.9 (4) | C23—C22—C23A—N24A | 9.2 (12) |
O2—C2—C22—C23A | 64.6 (6) | C2—C22—C23A—N24A | −175.6 (4) |
N2—C2—C22—C23A | −116.8 (5) | N24A—C25—C26A—N21A | −5.9 (7) |
O2—C2—C22—C23 | −120.2 (6) | N24—C25—C26A—N21A | 95 (4) |
N2—C2—C22—C23 | 58.4 (6) | C26—C25—C26A—N21A | −16.2 (9) |
N21A—C22—C23—N24 | 87 (7) | C22—N21A—C26A—C25 | 5.8 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···N21i | 0.95 | 2.61 | 3.514 (8) | 159 |
Symmetry code: (i) x−1, y+1, z. |
C14H11N5O·2H2O | F(000) = 632 |
Mr = 301.31 | Dx = 1.368 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 5437 reflections |
a = 19.395 (3) Å | θ = 3.1–27.5° |
b = 3.9517 (5) Å | µ = 0.10 mm−1 |
c = 23.270 (3) Å | T = 120 K |
β = 124.890 (9)° | Lath, yellow |
V = 1462.9 (3) Å3 | 0.56 × 0.23 × 0.08 mm |
Z = 4 |
Rigaku R-AXIS conversion diffractometer | 3341 independent reflections |
Radiation source: Sealed tube | 2189 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
profile data from ω scans | h = −25→25 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −4→5 |
Tmin = 0.946, Tmax = 0.992 | l = −30→30 |
12564 measured reflections |
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)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.248 | w = 1/[σ2(Fo2) + (0.1408P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.23 | (Δ/σ)max < 0.001 |
3341 reflections | Δρmax = 0.40 e Å−3 |
202 parameters | Δρmin = −0.33 e Å−3 |
0 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: 0.026 (7) |
C14H11N5O·2H2O | V = 1462.9 (3) Å3 |
Mr = 301.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.395 (3) Å | µ = 0.10 mm−1 |
b = 3.9517 (5) Å | T = 120 K |
c = 23.270 (3) Å | 0.56 × 0.23 × 0.08 mm |
β = 124.890 (9)° |
Rigaku R-AXIS conversion diffractometer | 3341 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 2189 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.992 | Rint = 0.053 |
12564 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.248 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.40 e Å−3 |
3341 reflections | Δρmin = −0.33 e Å−3 |
202 parameters |
Experimental. Compound (IIc): 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 8.84 (1H, s, H3), 8.70 (2H, s, H5 and H6), 7.80 (1H, s, N═CH), 7.61 (2H, J = 8.0 Hz, H2' and H6'), 7.47 (2H, J = 8.0 Hz, H3' and H5'), 3.63 (3H, s, NCH3); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 157.8, 150.0, 145.2, 144.9, 143.9, 138.7, 138.3, 132.7, 127.7, 118.5, 113.5, 28.9; IR (KBr, ν, cm-1): 2232 (CN), 1683 (C═O), 1608 (–N═C–CH3). LC/MS: m/z [M + H]+: 266. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.39035 (9) | 1.2988 (4) | 0.41661 (8) | 0.0470 (5) | |
N1 | 0.30755 (10) | 0.9113 (5) | 0.49844 (9) | 0.0357 (5) | |
N2 | 0.36554 (10) | 1.0804 (5) | 0.49269 (9) | 0.0370 (5) | |
N21 | 0.23766 (11) | 0.9867 (5) | 0.30927 (9) | 0.0394 (5) | |
N24 | 0.10404 (12) | 1.2139 (6) | 0.31377 (10) | 0.0483 (6) | |
N141 | 0.04799 (12) | 0.0201 (5) | 0.60153 (9) | 0.0466 (5) | |
C1 | 0.32763 (13) | 0.8270 (6) | 0.55927 (11) | 0.0373 (5) | |
H1 | 0.3823 | 0.8754 | 0.5996 | 0.045* | |
C2 | 0.34103 (13) | 1.1709 (6) | 0.42715 (11) | 0.0368 (5) | |
C11 | 0.26632 (12) | 0.6565 (6) | 0.56652 (10) | 0.0351 (5) | |
C12 | 0.29262 (13) | 0.5177 (6) | 0.63124 (10) | 0.0390 (6) | |
H12 | 0.3499 | 0.5367 | 0.6695 | 0.047* | |
C13 | 0.23719 (13) | 0.3541 (6) | 0.64061 (11) | 0.0387 (5) | |
H13 | 0.2560 | 0.2609 | 0.6849 | 0.046* | |
C14 | 0.15273 (13) | 0.3263 (6) | 0.58410 (11) | 0.0361 (5) | |
C15 | 0.12524 (13) | 0.4653 (6) | 0.51940 (10) | 0.0373 (5) | |
H15 | 0.0679 | 0.4462 | 0.4812 | 0.045* | |
C16 | 0.18116 (13) | 0.6307 (6) | 0.51062 (11) | 0.0363 (5) | |
H16 | 0.1620 | 0.7278 | 0.4665 | 0.044* | |
C22 | 0.25017 (12) | 1.1206 (6) | 0.36732 (11) | 0.0356 (5) | |
C23 | 0.18423 (13) | 1.2354 (6) | 0.36886 (12) | 0.0419 (6) | |
H23 | 0.1962 | 1.3342 | 0.4109 | 0.050* | |
C25 | 0.09194 (14) | 1.0692 (7) | 0.25688 (12) | 0.0494 (7) | |
H25 | 0.0361 | 1.0421 | 0.2166 | 0.059* | |
C26 | 0.15733 (14) | 0.9580 (6) | 0.25457 (11) | 0.0449 (6) | |
H26 | 0.1452 | 0.8571 | 0.2127 | 0.054* | |
C27 | 0.45005 (13) | 1.1569 (6) | 0.55350 (11) | 0.0431 (6) | |
H27A | 0.4802 | 1.2881 | 0.5387 | 0.065* | |
H27B | 0.4803 | 0.9453 | 0.5753 | 0.065* | |
H27C | 0.4465 | 1.2886 | 0.5874 | 0.065* | |
C141 | 0.09456 (13) | 0.1544 (6) | 0.59335 (11) | 0.0394 (6) | |
O1W | 0.35816 (10) | 0.6041 (5) | 0.29459 (8) | 0.0515 (5) | |
H1WA | 0.3690 | 0.4650 | 0.3345 | 0.077* | |
H1WB | 0.3254 | 0.7863 | 0.2941 | 0.077* | |
O2W | 0.49138 (13) | 0.6383 (11) | 0.28335 (12) | 0.1346 (15) | |
H2WA | 0.4499 | 0.6147 | 0.2904 | 0.202* | |
H2WB | 0.4701 | 0.4964 | 0.2503 | 0.202* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0315 (8) | 0.0599 (11) | 0.0496 (10) | −0.0051 (7) | 0.0231 (7) | 0.0029 (8) |
N1 | 0.0289 (9) | 0.0376 (10) | 0.0404 (10) | 0.0008 (7) | 0.0198 (8) | −0.0030 (8) |
N2 | 0.0265 (8) | 0.0419 (11) | 0.0408 (10) | −0.0033 (7) | 0.0183 (8) | −0.0033 (8) |
N21 | 0.0369 (10) | 0.0420 (11) | 0.0404 (10) | −0.0028 (8) | 0.0228 (8) | −0.0017 (8) |
N24 | 0.0318 (10) | 0.0682 (14) | 0.0425 (10) | 0.0048 (9) | 0.0199 (8) | 0.0063 (9) |
N141 | 0.0374 (11) | 0.0518 (13) | 0.0448 (11) | −0.0006 (9) | 0.0202 (9) | 0.0032 (9) |
C1 | 0.0308 (10) | 0.0417 (13) | 0.0352 (10) | 0.0033 (9) | 0.0164 (9) | −0.0032 (9) |
C2 | 0.0300 (10) | 0.0381 (12) | 0.0431 (11) | 0.0016 (8) | 0.0213 (9) | −0.0012 (9) |
C11 | 0.0312 (10) | 0.0376 (12) | 0.0365 (11) | 0.0061 (8) | 0.0195 (9) | −0.0015 (9) |
C12 | 0.0290 (10) | 0.0466 (14) | 0.0359 (11) | 0.0051 (9) | 0.0154 (9) | −0.0014 (9) |
C13 | 0.0355 (11) | 0.0404 (12) | 0.0362 (11) | 0.0033 (9) | 0.0182 (9) | 0.0005 (9) |
C14 | 0.0335 (10) | 0.0354 (12) | 0.0389 (11) | 0.0028 (8) | 0.0205 (9) | −0.0018 (9) |
C15 | 0.0316 (10) | 0.0406 (13) | 0.0373 (11) | 0.0046 (9) | 0.0183 (9) | −0.0010 (9) |
C16 | 0.0325 (10) | 0.0386 (12) | 0.0346 (10) | 0.0025 (9) | 0.0173 (9) | −0.0013 (9) |
C22 | 0.0316 (10) | 0.0355 (11) | 0.0389 (11) | −0.0009 (8) | 0.0198 (9) | 0.0005 (9) |
C23 | 0.0335 (11) | 0.0523 (14) | 0.0416 (11) | 0.0052 (9) | 0.0225 (10) | 0.0026 (10) |
C25 | 0.0316 (11) | 0.0669 (17) | 0.0418 (12) | −0.0029 (10) | 0.0165 (10) | 0.0054 (11) |
C26 | 0.0431 (13) | 0.0505 (15) | 0.0389 (11) | −0.0080 (10) | 0.0222 (10) | −0.0049 (10) |
C27 | 0.0286 (10) | 0.0492 (14) | 0.0446 (12) | −0.0037 (9) | 0.0169 (10) | −0.0042 (10) |
C141 | 0.0355 (11) | 0.0395 (12) | 0.0364 (11) | 0.0056 (9) | 0.0166 (9) | 0.0006 (9) |
O1W | 0.0424 (9) | 0.0672 (12) | 0.0487 (9) | 0.0053 (8) | 0.0283 (8) | 0.0012 (8) |
O2W | 0.0439 (12) | 0.301 (5) | 0.0627 (14) | 0.0041 (18) | 0.0324 (11) | 0.0090 (19) |
O2—C2 | 1.224 (3) | C13—H13 | 0.9500 |
N1—C1 | 1.279 (3) | C14—C15 | 1.391 (3) |
N1—N2 | 1.379 (2) | C14—C141 | 1.435 (3) |
N2—C2 | 1.360 (3) | C15—C16 | 1.378 (3) |
N2—C27 | 1.458 (3) | C15—H15 | 0.9500 |
N21—C22 | 1.337 (3) | C16—H16 | 0.9500 |
N21—C26 | 1.339 (3) | C22—C23 | 1.377 (3) |
N24—C25 | 1.334 (3) | C23—H23 | 0.9500 |
N24—C23 | 1.337 (3) | C25—C26 | 1.372 (3) |
N141—C141 | 1.154 (3) | C25—H25 | 0.9500 |
C1—C11 | 1.458 (3) | C26—H26 | 0.9500 |
C1—H1 | 0.9500 | C27—H27A | 0.9800 |
C2—C22 | 1.509 (3) | C27—H27B | 0.9800 |
C11—C12 | 1.396 (3) | C27—H27C | 0.9800 |
C11—C16 | 1.404 (3) | O1W—H1WA | 0.9935 |
C12—C13 | 1.375 (3) | O1W—H1WB | 0.9568 |
C12—H12 | 0.9500 | O2W—H2WA | 0.9136 |
C13—C14 | 1.400 (3) | O2W—H2WB | 0.8438 |
C1—N1—N2 | 118.99 (18) | C14—C15—H15 | 120.0 |
C2—N2—N1 | 117.06 (16) | C15—C16—C11 | 120.37 (19) |
C2—N2—C27 | 120.75 (18) | C15—C16—H16 | 119.8 |
N1—N2—C27 | 122.18 (17) | C11—C16—H16 | 119.8 |
C22—N21—C26 | 115.71 (19) | N21—C22—C23 | 121.49 (19) |
C25—N24—C23 | 115.25 (19) | N21—C22—C2 | 115.18 (18) |
N1—C1—C11 | 119.76 (19) | C23—C22—C2 | 122.99 (19) |
N1—C1—H1 | 120.1 | N24—C23—C22 | 122.8 (2) |
C11—C1—H1 | 120.1 | N24—C23—H23 | 118.6 |
O2—C2—N2 | 121.41 (19) | C22—C23—H23 | 118.6 |
O2—C2—C22 | 120.23 (18) | N24—C25—C26 | 122.3 (2) |
N2—C2—C22 | 118.33 (18) | N24—C25—H25 | 118.9 |
C12—C11—C16 | 118.7 (2) | C26—C25—H25 | 118.9 |
C12—C11—C1 | 119.17 (18) | N21—C26—C25 | 122.3 (2) |
C16—C11—C1 | 122.09 (18) | N21—C26—H26 | 118.8 |
C13—C12—C11 | 121.29 (19) | C25—C26—H26 | 118.8 |
C13—C12—H12 | 119.4 | N2—C27—H27A | 109.5 |
C11—C12—H12 | 119.4 | N2—C27—H27B | 109.5 |
C12—C13—C14 | 119.28 (19) | H27A—C27—H27B | 109.5 |
C12—C13—H13 | 120.4 | N2—C27—H27C | 109.5 |
C14—C13—H13 | 120.4 | H27A—C27—H27C | 109.5 |
C15—C14—C13 | 120.2 (2) | H27B—C27—H27C | 109.5 |
C15—C14—C141 | 120.13 (18) | N141—C141—C14 | 178.9 (2) |
C13—C14—C141 | 119.63 (18) | H1WA—O1W—H1WB | 102.2 |
C16—C15—C14 | 120.06 (19) | H2WA—O2W—H2WB | 94.2 |
C16—C15—H15 | 120.0 | ||
C1—N1—N2—C2 | −178.76 (19) | C14—C15—C16—C11 | 0.8 (3) |
C1—N1—N2—C27 | 2.0 (3) | C12—C11—C16—C15 | −1.3 (3) |
N2—N1—C1—C11 | 178.30 (18) | C1—C11—C16—C15 | 179.5 (2) |
N1—N2—C2—O2 | −174.4 (2) | C26—N21—C22—C23 | −3.0 (3) |
C27—N2—C2—O2 | 4.8 (3) | C26—N21—C22—C2 | −176.47 (19) |
N1—N2—C2—C22 | 7.5 (3) | O2—C2—C22—N21 | 46.1 (3) |
C27—N2—C2—C22 | −173.25 (19) | N2—C2—C22—N21 | −135.8 (2) |
N1—C1—C11—C12 | 169.8 (2) | O2—C2—C22—C23 | −127.3 (2) |
N1—C1—C11—C16 | −11.0 (3) | N2—C2—C22—C23 | 50.8 (3) |
C16—C11—C12—C13 | 0.9 (3) | C25—N24—C23—C22 | 0.7 (4) |
C1—C11—C12—C13 | −179.9 (2) | N21—C22—C23—N24 | 1.6 (4) |
C11—C12—C13—C14 | 0.0 (3) | C2—C22—C23—N24 | 174.6 (2) |
C12—C13—C14—C15 | −0.5 (3) | C23—N24—C25—C26 | −1.6 (4) |
C12—C13—C14—C141 | 179.7 (2) | C22—N21—C26—C25 | 2.1 (3) |
C13—C14—C15—C16 | 0.1 (3) | N24—C25—C26—N21 | 0.1 (4) |
C141—C14—C15—C16 | 179.93 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···N21 | 0.96 | 2.08 | 2.963 (2) | 153 |
O2W—H2WA···O1W | 0.91 | 1.84 | 2.745 (3) | 172 |
O1W—H1WA···O2i | 0.99 | 1.83 | 2.807 (2) | 167 |
O2W—H2WB···O2Wii | 0.84 | 1.96 | 2.649 (3) | 138 |
C13—H13···O1Wiii | 0.95 | 2.59 | 3.465 (3) | 152 |
C26—H26···N141iv | 0.95 | 2.62 | 3.480 (3) | 150 |
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. |
C13H11N5O3 | F(000) = 592 |
Mr = 285.27 | Dx = 1.502 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 14894 reflections |
a = 3.7974 (2) Å | θ = 2.9–27.5° |
b = 33.3126 (17) Å | µ = 0.11 mm−1 |
c = 10.0959 (5) Å | T = 120 K |
β = 99.027 (2)° | Lath, yellow |
V = 1261.33 (11) Å3 | 0.40 × 0.10 × 0.02 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 2168 independent reflections |
Radiation source: fine-focus sealed tube | 1563 reflections with I > 2σ(I) |
Vertically mounted graphite crystal monochromator | Rint = 0.071 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
CCD scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −39→39 |
Tmin = 0.957, Tmax = 0.998 | l = −11→11 |
11176 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.080 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.196 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0855P)2 + 1.4865P] where P = (Fo2 + 2Fc2)/3 |
2168 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C13H11N5O3 | V = 1261.33 (11) Å3 |
Mr = 285.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.7974 (2) Å | µ = 0.11 mm−1 |
b = 33.3126 (17) Å | T = 120 K |
c = 10.0959 (5) Å | 0.40 × 0.10 × 0.02 mm |
β = 99.027 (2)° |
Nonius KappaCCD area-detector diffractometer | 2168 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1563 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.998 | Rint = 0.071 |
11176 measured reflections |
R[F2 > 2σ(F2)] = 0.080 | 0 restraints |
wR(F2) = 0.196 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.32 e Å−3 |
2168 reflections | Δρmin = −0.32 e Å−3 |
191 parameters |
Experimental. Compound (IId): 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 8.84 (1H, s, H3), 8.69 (2H, m, H5 and H6), 8.39 (1H, s, N═CH), 8.02(1H, d, N═CH), 7.57–7.48 (3H, m), 3.65 (3H, s, NCH3); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 167.8, 150.0, 148.4, 145.1, 144.8, 143.9, 136.8, 133.6, 130.4, 128.8, 128.3, 125.0, 29.1; IR (KBr, ν, cm-1): 1672 (C═O), 1597 (–N═C–CH3). LC/MS: m/z [M + Na]-: 281. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.3911 (7) | 0.65099 (7) | 0.7717 (2) | 0.0403 (7) | |
O121 | 1.0540 (8) | 0.51292 (8) | 0.3594 (3) | 0.0452 (8) | |
O122 | 0.7448 (8) | 0.49513 (8) | 0.1686 (3) | 0.0519 (8) | |
N1 | 0.6819 (7) | 0.62022 (8) | 0.4785 (3) | 0.0265 (7) | |
N2 | 0.5626 (7) | 0.61611 (8) | 0.5997 (3) | 0.0273 (7) | |
N12 | 0.9002 (8) | 0.52058 (9) | 0.2455 (3) | 0.0350 (8) | |
C1 | 0.7285 (8) | 0.58864 (10) | 0.4111 (3) | 0.0255 (8) | |
H1 | 0.6922 | 0.5626 | 0.4452 | 0.031* | |
C2 | 0.4829 (9) | 0.65095 (10) | 0.6602 (3) | 0.0289 (8) | |
C11 | 0.8402 (8) | 0.59398 (10) | 0.2788 (3) | 0.0248 (8) | |
C12 | 0.9069 (8) | 0.56205 (10) | 0.1962 (3) | 0.0263 (8) | |
C13 | 0.9867 (9) | 0.56702 (11) | 0.0685 (3) | 0.0320 (9) | |
H13 | 1.0223 | 0.5443 | 0.0152 | 0.038* | |
C14 | 1.0141 (9) | 0.60516 (11) | 0.0193 (3) | 0.0325 (8) | |
H14 | 1.0737 | 0.6092 | −0.0676 | 0.039* | |
C15 | 0.9528 (10) | 0.63778 (11) | 0.0990 (4) | 0.0347 (9) | |
H15 | 0.9742 | 0.6643 | 0.0663 | 0.042* | |
C16 | 0.8617 (9) | 0.63219 (10) | 0.2247 (4) | 0.0312 (8) | |
H16 | 0.8125 | 0.6549 | 0.2755 | 0.037* | |
N21 | 0.3203 (8) | 0.69483 (10) | 0.4634 (3) | 0.0375 (8) | |
C22 | 0.5046 (9) | 0.69004 (10) | 0.5885 (3) | 0.0268 (8) | |
C23 | 0.6829 (9) | 0.72100 (10) | 0.6577 (3) | 0.0283 (8) | |
H23 | 0.8081 | 0.7163 | 0.7454 | 0.034* | |
N24 | 0.6860 (9) | 0.75790 (10) | 0.6050 (3) | 0.0455 (9) | |
C25 | 0.4941 (11) | 0.76297 (12) | 0.4819 (4) | 0.0408 (10) | |
H25 | 0.4794 | 0.7890 | 0.4430 | 0.049* | |
C26 | 0.3203 (10) | 0.73189 (12) | 0.4112 (4) | 0.0351 (9) | |
H26 | 0.1969 | 0.7366 | 0.3232 | 0.042* | |
C27 | 0.5144 (9) | 0.57723 (10) | 0.6605 (3) | 0.0316 (8) | |
H27A | 0.4352 | 0.5812 | 0.7474 | 0.047* | |
H27B | 0.7410 | 0.5626 | 0.6735 | 0.047* | |
H27C | 0.3345 | 0.5617 | 0.6015 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0600 (18) | 0.0346 (16) | 0.0289 (15) | 0.0014 (12) | 0.0152 (13) | −0.0012 (12) |
O121 | 0.0686 (19) | 0.0348 (16) | 0.0322 (15) | 0.0115 (13) | 0.0081 (13) | 0.0045 (12) |
O122 | 0.087 (2) | 0.0298 (16) | 0.0413 (17) | −0.0150 (15) | 0.0180 (16) | −0.0102 (13) |
N1 | 0.0307 (15) | 0.0264 (16) | 0.0218 (15) | −0.0015 (12) | 0.0021 (12) | −0.0032 (12) |
N2 | 0.0364 (16) | 0.0253 (16) | 0.0211 (15) | −0.0010 (12) | 0.0070 (12) | 0.0011 (12) |
N12 | 0.0507 (19) | 0.0271 (17) | 0.0290 (17) | 0.0007 (14) | 0.0119 (15) | −0.0038 (14) |
C1 | 0.0280 (17) | 0.0245 (18) | 0.0235 (18) | 0.0007 (14) | 0.0021 (14) | −0.0002 (14) |
C2 | 0.0341 (19) | 0.031 (2) | 0.0216 (18) | 0.0004 (15) | 0.0036 (15) | −0.0010 (15) |
C11 | 0.0257 (16) | 0.0269 (19) | 0.0208 (17) | −0.0004 (13) | 0.0009 (13) | −0.0016 (14) |
C12 | 0.0288 (18) | 0.0238 (19) | 0.0261 (18) | −0.0013 (14) | 0.0035 (14) | −0.0015 (14) |
C13 | 0.039 (2) | 0.033 (2) | 0.0239 (18) | 0.0020 (16) | 0.0033 (15) | −0.0058 (15) |
C14 | 0.0332 (19) | 0.039 (2) | 0.0265 (18) | 0.0000 (16) | 0.0078 (15) | 0.0029 (16) |
C15 | 0.044 (2) | 0.027 (2) | 0.034 (2) | −0.0013 (16) | 0.0066 (17) | 0.0057 (16) |
C16 | 0.038 (2) | 0.0241 (19) | 0.032 (2) | 0.0019 (15) | 0.0067 (16) | −0.0013 (15) |
N21 | 0.0359 (17) | 0.045 (2) | 0.0310 (17) | −0.0018 (14) | 0.0032 (13) | −0.0005 (15) |
C22 | 0.0289 (17) | 0.0293 (19) | 0.0225 (17) | 0.0014 (14) | 0.0053 (14) | −0.0022 (14) |
C23 | 0.0356 (19) | 0.0279 (19) | 0.0209 (17) | 0.0000 (15) | 0.0024 (14) | −0.0012 (15) |
N24 | 0.060 (2) | 0.037 (2) | 0.041 (2) | −0.0051 (16) | 0.0131 (17) | −0.0024 (16) |
C25 | 0.052 (2) | 0.032 (2) | 0.041 (2) | 0.0042 (18) | 0.0155 (19) | 0.0076 (18) |
C26 | 0.036 (2) | 0.043 (2) | 0.0254 (19) | 0.0013 (16) | 0.0036 (16) | 0.0092 (17) |
C27 | 0.039 (2) | 0.028 (2) | 0.0283 (19) | 0.0007 (16) | 0.0073 (15) | 0.0017 (15) |
O2—C2 | 1.230 (4) | C14—H14 | 0.9500 |
O121—N12 | 1.232 (4) | C15—C16 | 1.379 (5) |
O122—N12 | 1.235 (4) | C15—H15 | 0.9500 |
N1—C1 | 1.280 (4) | C16—H16 | 0.9500 |
N1—N2 | 1.377 (4) | N21—C26 | 1.343 (5) |
N2—C2 | 1.367 (4) | N21—C22 | 1.353 (4) |
N2—C27 | 1.457 (4) | C22—C23 | 1.365 (5) |
N12—C12 | 1.470 (4) | C23—N24 | 1.340 (5) |
C1—C11 | 1.474 (5) | C23—H23 | 0.9500 |
C1—H1 | 0.9500 | N24—C25 | 1.350 (5) |
C2—C22 | 1.498 (5) | C25—C26 | 1.367 (5) |
C11—C16 | 1.393 (5) | C25—H25 | 0.9500 |
C11—C12 | 1.399 (4) | C26—H26 | 0.9500 |
C12—C13 | 1.380 (5) | C27—H27A | 0.9800 |
C13—C14 | 1.374 (5) | C27—H27B | 0.9800 |
C13—H13 | 0.9500 | C27—H27C | 0.9800 |
C14—C15 | 1.393 (5) | ||
C1—N1—N2 | 118.9 (3) | C16—C15—H15 | 119.5 |
C2—N2—N1 | 116.0 (3) | C14—C15—H15 | 119.5 |
C2—N2—C27 | 121.0 (3) | C15—C16—C11 | 121.5 (3) |
N1—N2—C27 | 122.9 (3) | C15—C16—H16 | 119.2 |
O121—N12—O122 | 123.7 (3) | C11—C16—H16 | 119.2 |
O121—N12—C12 | 118.7 (3) | C26—N21—C22 | 116.3 (3) |
O122—N12—C12 | 117.7 (3) | N21—C22—C23 | 122.1 (3) |
N1—C1—C11 | 117.8 (3) | N21—C22—C2 | 119.6 (3) |
N1—C1—H1 | 121.1 | C23—C22—C2 | 118.0 (3) |
C11—C1—H1 | 121.1 | N24—C23—C22 | 121.7 (3) |
O2—C2—N2 | 121.6 (3) | N24—C23—H23 | 119.2 |
O2—C2—C22 | 119.1 (3) | C22—C23—H23 | 119.2 |
N2—C2—C22 | 119.3 (3) | C23—N24—C25 | 116.3 (3) |
C16—C11—C12 | 115.7 (3) | N24—C25—C26 | 122.2 (4) |
C16—C11—C1 | 120.6 (3) | N24—C25—H25 | 118.9 |
C12—C11—C1 | 123.6 (3) | C26—C25—H25 | 118.9 |
C13—C12—C11 | 123.5 (3) | N21—C26—C25 | 121.4 (3) |
C13—C12—N12 | 116.5 (3) | N21—C26—H26 | 119.3 |
C11—C12—N12 | 119.9 (3) | C25—C26—H26 | 119.3 |
C14—C13—C12 | 119.3 (3) | N2—C27—H27A | 109.5 |
C14—C13—H13 | 120.4 | N2—C27—H27B | 109.5 |
C12—C13—H13 | 120.4 | H27A—C27—H27B | 109.5 |
C13—C14—C15 | 118.9 (3) | N2—C27—H27C | 109.5 |
C13—C14—H14 | 120.6 | H27A—C27—H27C | 109.5 |
C15—C14—H14 | 120.6 | H27B—C27—H27C | 109.5 |
C16—C15—C14 | 121.0 (3) | ||
C1—N1—N2—C2 | −173.5 (3) | N12—C12—C13—C14 | −176.9 (3) |
C1—N1—N2—C27 | 5.2 (4) | C12—C13—C14—C15 | −1.3 (5) |
N2—N1—C1—C11 | 177.2 (3) | C13—C14—C15—C16 | −0.8 (5) |
N1—N2—C2—O2 | −176.3 (3) | C14—C15—C16—C11 | 2.4 (5) |
C27—N2—C2—O2 | 5.0 (5) | C12—C11—C16—C15 | −1.7 (5) |
N1—N2—C2—C22 | 4.2 (4) | C1—C11—C16—C15 | −177.6 (3) |
C27—N2—C2—C22 | −174.5 (3) | C26—N21—C22—C23 | −0.4 (5) |
N1—C1—C11—C16 | −5.8 (5) | C26—N21—C22—C2 | 172.9 (3) |
N1—C1—C11—C12 | 178.7 (3) | O2—C2—C22—N21 | −124.9 (4) |
C16—C11—C12—C13 | −0.5 (5) | N2—C2—C22—N21 | 54.6 (4) |
C1—C11—C12—C13 | 175.2 (3) | O2—C2—C22—C23 | 48.7 (5) |
C16—C11—C12—N12 | 178.4 (3) | N2—C2—C22—C23 | −131.8 (3) |
C1—C11—C12—N12 | −5.9 (5) | N21—C22—C23—N24 | −0.2 (5) |
O121—N12—C12—C13 | 133.6 (3) | C2—C22—C23—N24 | −173.6 (3) |
O122—N12—C12—C13 | −45.1 (4) | C22—C23—N24—C25 | 2.0 (5) |
O121—N12—C12—C11 | −45.3 (4) | C23—N24—C25—C26 | −3.2 (6) |
O122—N12—C12—C11 | 135.9 (3) | C22—N21—C26—C25 | −0.8 (5) |
C11—C12—C13—C14 | 2.0 (5) | N24—C25—C26—N21 | 2.7 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O122i | 0.95 | 2.54 | 3.439 (5) | 157 |
C14—H14···O2ii | 0.95 | 2.58 | 3.428 (4) | 150 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z−1. |
C13H11N5O3 | F(000) = 1184 |
Mr = 285.27 | Dx = 1.442 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -C 2yc | Cell parameters from 3733 reflections |
a = 17.510 (2) Å | θ = 3.1–27.4° |
b = 10.5421 (11) Å | µ = 0.11 mm−1 |
c = 14.9638 (14) Å | T = 120 K |
β = 107.887 (8)° | Prism, orange |
V = 2628.7 (5) Å3 | 0.42 × 0.24 × 0.16 mm |
Z = 8 |
Rigaku R-AXIS conversion diffractometer | 3000 independent reflections |
Radiation source: Sealed tube | 2610 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
profile data from ω scans | h = −22→22 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −13→13 |
Tmin = 0.956, Tmax = 0.983 | l = −19→18 |
7284 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0773P)2 + 2.8776P] where P = (Fo2 + 2Fc2)/3 |
3000 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C13H11N5O3 | V = 2628.7 (5) Å3 |
Mr = 285.27 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.510 (2) Å | µ = 0.11 mm−1 |
b = 10.5421 (11) Å | T = 120 K |
c = 14.9638 (14) Å | 0.42 × 0.24 × 0.16 mm |
β = 107.887 (8)° |
Rigaku R-AXIS conversion diffractometer | 3000 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 2610 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.983 | Rint = 0.042 |
7284 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.31 e Å−3 |
3000 reflections | Δρmin = −0.26 e Å−3 |
191 parameters |
Experimental. Compound (IIe): 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 8.85 (1H, s, H3), 8.70 (2H, m, H5 and H6), 8.17 (2H, d, J = 8.0Hz, H3' and H5'), 7.84 (1H, s, N═CH), 7.52 (2H, d, J = 8.0Hz, H2' and H6'), 3.64 (3H, s, NCH3); 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 167.7, 149.8, 148.4, 145.2, 144.8, 143.8, 139.9, 138.1, 128.8, 127.8, 124.2, 28.9. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.57061 (8) | 0.47908 (13) | 0.45169 (10) | 0.0343 (3) | |
O141 | 0.86046 (10) | −0.34850 (14) | 0.71616 (12) | 0.0430 (4) | |
O142 | 0.95959 (9) | −0.26236 (14) | 0.82272 (11) | 0.0400 (4) | |
N1 | 0.69672 (9) | 0.24637 (14) | 0.58377 (11) | 0.0289 (4) | |
N2 | 0.67240 (9) | 0.36628 (15) | 0.55006 (11) | 0.0288 (4) | |
N14 | 0.89617 (10) | −0.25541 (15) | 0.75878 (12) | 0.0330 (4) | |
N21 | 0.57793 (10) | 0.16583 (15) | 0.41024 (12) | 0.0331 (4) | |
N24 | 0.42373 (10) | 0.15461 (17) | 0.43127 (13) | 0.0374 (4) | |
C1 | 0.76619 (11) | 0.23431 (18) | 0.64385 (13) | 0.0293 (4) | |
H1 | 0.7979 | 0.3071 | 0.6677 | 0.035* | |
C2 | 0.59832 (11) | 0.37657 (17) | 0.48461 (13) | 0.0284 (4) | |
C11 | 0.79675 (11) | 0.10698 (18) | 0.67581 (13) | 0.0291 (4) | |
C12 | 0.75341 (11) | −0.00272 (18) | 0.63833 (13) | 0.0296 (4) | |
H12 | 0.7015 | 0.0047 | 0.5939 | 0.035* | |
C13 | 0.78555 (12) | −0.12142 (19) | 0.66549 (14) | 0.0319 (4) | |
H13 | 0.7566 | −0.1960 | 0.6398 | 0.038* | |
C14 | 0.86118 (11) | −0.12919 (18) | 0.73113 (13) | 0.0294 (4) | |
C15 | 0.90534 (11) | −0.02318 (19) | 0.77173 (13) | 0.0303 (4) | |
H15 | 0.9563 | −0.0314 | 0.8178 | 0.036* | |
C16 | 0.87229 (11) | 0.09528 (19) | 0.74256 (14) | 0.0306 (4) | |
H16 | 0.9015 | 0.1695 | 0.7684 | 0.037* | |
C22 | 0.54957 (11) | 0.25722 (17) | 0.45338 (12) | 0.0282 (4) | |
C23 | 0.47319 (11) | 0.25233 (18) | 0.46330 (14) | 0.0320 (4) | |
H23 | 0.4557 | 0.3204 | 0.4937 | 0.038* | |
C25 | 0.45238 (13) | 0.0629 (2) | 0.38884 (16) | 0.0393 (5) | |
H25 | 0.4195 | −0.0088 | 0.3651 | 0.047* | |
C26 | 0.52813 (12) | 0.06823 (19) | 0.37812 (15) | 0.0362 (4) | |
H26 | 0.5453 | 0.0005 | 0.3470 | 0.043* | |
C27 | 0.72305 (12) | 0.47763 (18) | 0.58082 (14) | 0.0319 (4) | |
H27A | 0.6958 | 0.5526 | 0.5469 | 0.048* | |
H27B | 0.7741 | 0.4652 | 0.5678 | 0.048* | |
H27C | 0.7333 | 0.4900 | 0.6484 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0341 (7) | 0.0258 (7) | 0.0408 (8) | 0.0033 (5) | 0.0084 (6) | −0.0002 (6) |
O141 | 0.0461 (9) | 0.0295 (7) | 0.0499 (9) | 0.0008 (6) | 0.0097 (7) | −0.0035 (7) |
O142 | 0.0357 (8) | 0.0374 (8) | 0.0425 (8) | 0.0062 (6) | 0.0054 (6) | 0.0064 (6) |
N1 | 0.0289 (8) | 0.0252 (8) | 0.0337 (8) | 0.0017 (6) | 0.0115 (6) | 0.0012 (6) |
N2 | 0.0281 (8) | 0.0237 (8) | 0.0340 (8) | −0.0004 (6) | 0.0088 (6) | −0.0011 (6) |
N14 | 0.0337 (8) | 0.0294 (9) | 0.0370 (9) | 0.0028 (7) | 0.0127 (7) | 0.0021 (7) |
N21 | 0.0332 (8) | 0.0292 (8) | 0.0372 (9) | −0.0006 (6) | 0.0114 (7) | −0.0054 (7) |
N24 | 0.0305 (8) | 0.0345 (9) | 0.0467 (10) | −0.0022 (7) | 0.0110 (7) | −0.0065 (7) |
C1 | 0.0283 (9) | 0.0291 (9) | 0.0319 (9) | −0.0019 (7) | 0.0112 (7) | −0.0006 (7) |
C2 | 0.0302 (9) | 0.0255 (9) | 0.0309 (9) | 0.0013 (7) | 0.0113 (7) | −0.0025 (7) |
C11 | 0.0282 (9) | 0.0315 (9) | 0.0299 (9) | 0.0003 (7) | 0.0124 (7) | 0.0001 (7) |
C12 | 0.0245 (8) | 0.0326 (10) | 0.0305 (9) | −0.0012 (7) | 0.0068 (7) | −0.0005 (7) |
C13 | 0.0310 (9) | 0.0311 (10) | 0.0346 (9) | −0.0022 (7) | 0.0118 (8) | −0.0022 (8) |
C14 | 0.0303 (9) | 0.0290 (9) | 0.0307 (9) | 0.0015 (7) | 0.0119 (7) | 0.0016 (7) |
C15 | 0.0264 (9) | 0.0335 (10) | 0.0298 (9) | −0.0002 (7) | 0.0071 (7) | 0.0008 (7) |
C16 | 0.0293 (9) | 0.0289 (9) | 0.0330 (9) | −0.0034 (7) | 0.0087 (7) | −0.0021 (7) |
C22 | 0.0288 (9) | 0.0257 (9) | 0.0275 (8) | 0.0019 (7) | 0.0050 (7) | 0.0004 (7) |
C23 | 0.0289 (9) | 0.0280 (9) | 0.0373 (10) | 0.0030 (7) | 0.0076 (7) | −0.0042 (7) |
C25 | 0.0351 (10) | 0.0329 (10) | 0.0475 (12) | −0.0044 (8) | 0.0095 (9) | −0.0077 (9) |
C26 | 0.0373 (10) | 0.0290 (10) | 0.0427 (11) | −0.0002 (8) | 0.0128 (8) | −0.0089 (8) |
C27 | 0.0325 (9) | 0.0273 (9) | 0.0354 (10) | −0.0030 (7) | 0.0096 (8) | −0.0012 (8) |
O2—C2 | 1.224 (2) | C12—C13 | 1.381 (3) |
O141—N14 | 1.231 (2) | C12—H12 | 0.9500 |
O142—N14 | 1.225 (2) | C13—C14 | 1.388 (3) |
N1—C1 | 1.278 (3) | C13—H13 | 0.9500 |
N1—N2 | 1.379 (2) | C14—C15 | 1.388 (3) |
N2—C2 | 1.369 (2) | C15—C16 | 1.389 (3) |
N2—C27 | 1.458 (2) | C15—H15 | 0.9500 |
N14—C14 | 1.470 (2) | C16—H16 | 0.9500 |
N21—C22 | 1.337 (2) | C22—C23 | 1.391 (3) |
N21—C26 | 1.339 (3) | C23—H23 | 0.9500 |
N24—C25 | 1.336 (3) | C25—C26 | 1.385 (3) |
N24—C23 | 1.336 (3) | C25—H25 | 0.9500 |
C1—C11 | 1.470 (3) | C26—H26 | 0.9500 |
C1—H1 | 0.9500 | C27—H27A | 0.9800 |
C2—C22 | 1.512 (3) | C27—H27B | 0.9800 |
C11—C16 | 1.397 (3) | C27—H27C | 0.9800 |
C11—C12 | 1.402 (3) | ||
C1—N1—N2 | 117.97 (16) | C15—C14—N14 | 118.52 (17) |
C2—N2—N1 | 116.92 (15) | C14—C15—C16 | 117.64 (17) |
C2—N2—C27 | 120.87 (15) | C14—C15—H15 | 121.2 |
N1—N2—C27 | 122.20 (15) | C16—C15—H15 | 121.2 |
O142—N14—O141 | 123.44 (17) | C15—C16—C11 | 121.04 (18) |
O142—N14—C14 | 118.25 (16) | C15—C16—H16 | 119.5 |
O141—N14—C14 | 118.30 (16) | C11—C16—H16 | 119.5 |
C22—N21—C26 | 115.43 (17) | N21—C22—C23 | 122.45 (17) |
C25—N24—C23 | 115.58 (17) | N21—C22—C2 | 119.39 (16) |
N1—C1—C11 | 119.52 (17) | C23—C22—C2 | 117.89 (16) |
N1—C1—H1 | 120.2 | N24—C23—C22 | 121.90 (17) |
C11—C1—H1 | 120.2 | N24—C23—H23 | 119.0 |
O2—C2—N2 | 121.95 (17) | C22—C23—H23 | 119.0 |
O2—C2—C22 | 119.60 (17) | N24—C25—C26 | 122.57 (19) |
N2—C2—C22 | 118.44 (16) | N24—C25—H25 | 118.7 |
C16—C11—C12 | 119.38 (17) | C26—C25—H25 | 118.7 |
C16—C11—C1 | 118.91 (17) | N21—C26—C25 | 122.05 (18) |
C12—C11—C1 | 121.66 (17) | N21—C26—H26 | 119.0 |
C13—C12—C11 | 120.53 (17) | C25—C26—H26 | 119.0 |
C13—C12—H12 | 119.7 | N2—C27—H27A | 109.5 |
C11—C12—H12 | 119.7 | N2—C27—H27B | 109.5 |
C12—C13—C14 | 118.41 (18) | H27A—C27—H27B | 109.5 |
C12—C13—H13 | 120.8 | N2—C27—H27C | 109.5 |
C14—C13—H13 | 120.8 | H27A—C27—H27C | 109.5 |
C13—C14—C15 | 122.98 (18) | H27B—C27—H27C | 109.5 |
C13—C14—N14 | 118.50 (17) | ||
C1—N1—N2—C2 | 178.94 (16) | C13—C14—C15—C16 | −1.8 (3) |
C1—N1—N2—C27 | −0.1 (3) | N14—C14—C15—C16 | 178.07 (16) |
N2—N1—C1—C11 | −175.23 (15) | C14—C15—C16—C11 | 1.0 (3) |
N1—N2—C2—O2 | 178.58 (16) | C12—C11—C16—C15 | 0.5 (3) |
C27—N2—C2—O2 | −2.4 (3) | C1—C11—C16—C15 | −176.98 (17) |
N1—N2—C2—C22 | −0.8 (2) | C26—N21—C22—C23 | −0.8 (3) |
C27—N2—C2—C22 | 178.22 (15) | C26—N21—C22—C2 | −174.73 (17) |
N1—C1—C11—C16 | −179.05 (17) | O2—C2—C22—N21 | 118.3 (2) |
N1—C1—C11—C12 | 3.5 (3) | N2—C2—C22—N21 | −62.3 (2) |
C16—C11—C12—C13 | −1.3 (3) | O2—C2—C22—C23 | −55.9 (2) |
C1—C11—C12—C13 | 176.12 (17) | N2—C2—C22—C23 | 123.49 (19) |
C11—C12—C13—C14 | 0.6 (3) | C25—N24—C23—C22 | −0.4 (3) |
C12—C13—C14—C15 | 1.0 (3) | N21—C22—C23—N24 | 0.9 (3) |
C12—C13—C14—N14 | −178.83 (16) | C2—C22—C23—N24 | 174.98 (18) |
O142—N14—C14—C13 | −173.56 (17) | C23—N24—C25—C26 | −0.3 (3) |
O141—N14—C14—C13 | 6.8 (3) | C22—N21—C26—C25 | 0.2 (3) |
O142—N14—C14—C15 | 6.6 (3) | N24—C25—C26—N21 | 0.4 (4) |
O141—N14—C14—C15 | −173.05 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O2i | 0.95 | 2.42 | 3.325 (2) | 159 |
C23—H23···O2ii | 0.95 | 2.36 | 3.290 (2) | 166 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
(IIa) | (IIb) | (IIc) | (IId) | |
Crystal data | ||||
Chemical formula | C13H12N4O | C14H14N4O2 | C14H11N5O·2H2O | C13H11N5O3 |
Mr | 240.27 | 270.29 | 301.31 | 285.27 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 100 | 120 | 120 |
a, b, c (Å) | 7.4961 (3), 7.6923 (3), 10.8821 (7) | 4.032 (5), 10.628 (15), 15.034 (19) | 19.395 (3), 3.9517 (5), 23.270 (3) | 3.7974 (2), 33.3126 (17), 10.0959 (5) |
α, β, γ (°) | 73.421 (5), 84.844 (6), 88.530 (6) | 94.08 (3), 90.36 (3), 92.07 (3) | 90, 124.890 (9), 90 | 90, 99.027 (2), 90 |
V (Å3) | 598.97 (5) | 642.2 (15) | 1462.9 (3) | 1261.33 (11) |
Z | 2 | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 | 0.10 | 0.11 |
Crystal size (mm) | 0.56 × 0.43 × 0.23 | 0.18 × 0.13 × 0.12 | 0.56 × 0.23 × 0.08 | 0.40 × 0.10 × 0.02 |
Data collection | ||||
Diffractometer | Rigaku R-AXIS conversion diffractometer | Rigaku Saturn724+ diffractometer | Rigaku R-AXIS conversion diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.952, 0.980 | 0.983, 0.988 | 0.946, 0.992 | 0.957, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7672, 2712, 2270 | 4990, 2246, 1859 | 12564, 3341, 2189 | 11176, 2168, 1563 |
Rint | 0.016 | 0.033 | 0.053 | 0.071 |
(sin θ/λ)max (Å−1) | 0.649 | 0.595 | 0.650 | 0.595 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.119, 1.17 | 0.055, 0.159, 1.10 | 0.063, 0.248, 1.23 | 0.080, 0.196, 1.10 |
No. of reflections | 2712 | 2246 | 3341 | 2168 |
No. of parameters | 164 | 185 | 202 | 191 |
No. of restraints | 0 | 6 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.21 | 0.18, −0.26 | 0.40, −0.33 | 0.32, −0.32 |
(IIe) | |
Crystal data | |
Chemical formula | C13H11N5O3 |
Mr | 285.27 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 17.510 (2), 10.5421 (11), 14.9638 (14) |
α, β, γ (°) | 90, 107.887 (8), 90 |
V (Å3) | 2628.7 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.42 × 0.24 × 0.16 |
Data collection | |
Diffractometer | Rigaku R-AXIS conversion diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) |
Tmin, Tmax | 0.956, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7284, 3000, 2610 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.169, 1.08 |
No. of reflections | 3000 |
No. of parameters | 191 |
No. of restraints | 0 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: CrystalClear-SM Expert (Rigaku, 2011), COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C25—H25···O2i | 0.95 | 2.59 | 3.1823 (16) | 121 |
Symmetry code: (i) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···N21i | 0.95 | 2.61 | 3.514 (8) | 159 |
Symmetry code: (i) x−1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···N21 | 0.96 | 2.08 | 2.963 (2) | 153 |
O2W—H2WA···O1W | 0.91 | 1.84 | 2.745 (3) | 172 |
O1W—H1WA···O2i | 0.99 | 1.83 | 2.807 (2) | 167 |
O2W—H2WB···O2Wii | 0.84 | 1.96 | 2.649 (3) | 138 |
C13—H13···O1Wiii | 0.95 | 2.59 | 3.465 (3) | 152 |
C26—H26···N141iv | 0.95 | 2.62 | 3.480 (3) | 150 |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O122i | 0.95 | 2.54 | 3.439 (5) | 157 |
C14—H14···O2ii | 0.95 | 2.58 | 3.428 (4) | 150 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O2i | 0.95 | 2.42 | 3.325 (2) | 159 |
C23—H23···O2ii | 0.95 | 2.36 | 3.290 (2) | 166 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
θ is the dihedral angle between pyrazine ring and the phenyl ring, ϕ1 and ϕ2 are the torsion angles N21—C22—C2—N2 and N1—C1—C11—C12, respectively, and ϕ3 is the angular deviation of atom C2 from the mean plane of the pyrazine ring. In (Ib), the molecule sits on a mirror plane. |
Compound | R1 | θ | ϕ1 | ϕ2 | ϕ3 |
(IIa) | H | 77.46 (6) | 72.83 (14) | 175.16 (10) | 6.77 (8) |
(IIb) | oOCH3 (major) | 58.1 (3) | -128.9 (4) | 168.73 (18) | 3.2 (3) |
oOCH3 (minor) | 69.5 (3) | 67.1 (6) | n/a | '4.1 (3) | |
(IIc) | [pCN].2H2O | 55.43 (12) | -135.8 (2) | 169.8 (2) | 4.06 (14) |
(IId) | oNO2 | 48.51(17 | 54.6 (5) | 178.7 (3) | 6.3 (2) |
(IIe) | pNO2 | 55.39 (9) | -62.3 (2) | 3.5 (3) | 4.59 (13) |
(Ib) | oOCH3 | 0.0 | 0.0 | 0.0 | 0.0 |
(Ic) | (pCN | 5.82 (7) | -3.76 (18) | 176.21 (17) | 1.56 (9) |
(Id) | (oNO2 | 0.54 (5) | -12.72 (15) | -169.90 (10) | 1.49 (7) |
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Pyrazine derivatives exhibit a wide range of biological activities. Recent studies have revealed that pyrazine-2-carbohydrazides, (I) (see scheme; Vergara et al., 2009; Lima et al., 2011), have moderate antituberculosis properties. Crystal structures of various of the pyrazine-2-carbohydrazides have been reported (Baddeley et al., 2009; Howie et al., 2010a,b,c; Howie, de Souza et al., 2010; de Souza et al., 2011). In continuation of these studies, the synthesis and antituberculosis activities of a series of methylated pyrazine-2-carbohydrazide derivatives, (II) (see scheme), have been studied. It is worth noting that methylation of (I) occurred at the imine N atom rather than at the pyridine N atom. However, none of the compounds (II) were found to exhibit antituberculosis properties (de Souza, 2013).
A recently reported study of mono- and diesters of 3-(pyrazin-2-ylcarbonyl)dithiocarbazic acid suggested that the planarity of pyrazinyl derivatives may be a prerequisite for tubercolostatic activity (Szczesio et al., 2011; Orlewska et al., 2001). This prompted crystal structure determinations of the five title methylated pyrazine-2-carbohydrazide derivatives, namely N'-benzylidene-N-methylpyrazine-2-carbohydrazide, (IIa) (Fig. 1), N'-(2-methoxybenzylidene)-N-methylpyrazine-2-carbohydrazide, (IIb) (Fig. 2), N'-(4-cyanobenzylidene)-N-methylpyrazine-2-carbohydrazide dihydrate, (IIc) (Fig. 3), N'-(2-nitrobenzylidene)-N-methylpyrazine-2-carbohydrazide, (IId) (Fig. 4), and N'-(4-nitrobenzylidene)-N-methylpyrazine-2-carbohydrazide, (IIe) (Fig. 5). A comparative analysis of the structures of these inactive compounds on the one hand with, on the other, those of moderately active N'-benzylidenepyrazine-2-carbohydrazide, (Ib) (de Souza et al., 2011), N'-(4-methoxybenzylidene)methylpyrazine-2-carbohydrazide, (Ic) (Howie et al., 2010a), and N'-(2-nitrobenzylidene)pyrazine-2-carbohydrazide, (Id) (Howie et al., 2010a), will be a useful contribution to the understanding of the correlation between structure and activity.
As will be shown, derivatives (IIa)–(IIe) are not planar, unlike the analogous compounds (Ib)–(Id). A search of the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002) (see Supplementary materials, 27 structures), revealed that pyrazine-2-carbohydrazides of type (I) exhibit a preference for conformations having the carbonyl group trans to the H—N(pyrazinamide), shown as conformation E1 in Fig. 6. Furthermore, a short intramolecular pyrazine–hydrazide ortho-N···H—N' contact is observed for the majority of these structures [see, for example, Baddeley et al. (2009), Howie et al., 2010a,b,c; Howie, de Souza et al. (2010) and de Souza et al. (2011)]. These two effects constrain the relative positions of the pyrazinyl N atoms with respect to the hydrazinyl group. Hyperconjugation from the heteroaryl ring to the benzene ring via the hydrazinyl unit has been suggested as the main contributor to the near planarity of type (I) compounds and this is reinforced by the intramolecular N—H···N hydrogen bond (Szczesio et al., 2011). However, this planarity can be dramatically influenced by the nature and position of the substituents on the benzene ring (see Supplementary materials).
As expected, the substitution of a methyl group on N2 in the pyrazine-2-carbohydrazide system induces significant structural change. The major changes are in the relative positions of the pyrazine ring and carbonyl groups and the nonplanarity of the methylated compounds. The methyl group precludes the formation of the intramolecular hydrogen bond observed in the compounds of type (I) and imposes steric hindrance near the pyrazine ring, with the result that the conformation of compounds of type (II) is E(2) (Fig. 6), in contrast with the E(1) conformation assumed by the nonmethylated compounds (I). The overall planarity is lost, probably due to the loss of hyperconjugation within the C(O)NMeN═C group. The deviations from planarity of (IIa)–(IIe) arise fundamentally from the rotation of the pyrazine ring about the C(py)—C(═O) axis (py is pyrazine). Various torsion and other angles determined for (I) and (II) are listed in Table 1. The molecule of (Ib) (de Souza et al., 2011) is planar and lies on a crystallographic mirror plane, while that of (Ic) (Howie et al., 2010a) is nearly so [θ = 5.82 (7)°]. In contrast, θ values for (II) are in the range 55–78° (Table 1). The rotation of the pyrazine ring about the C22—C2 axis is the main contributor to the nonplanarity of the methylated compounds, since the benzene rings are largely coplanar with the CNNC spacer group. Compound (IIa) exhibits the largest dihedral angle and the greatest deviation of atom C2 from the mean plane through the pyrazine ring. The angle the pyrazine ring makes with the C22—C2 bond is probably due to the participation of atom C25 as a donor in an intermolecular hydrogen bond.
Compound (IIb) exhibits conformational disorder. The pyrazine ring is rotated anticlockwise by 71.10 (3)° for the major component and clockwise by 67.14 (3)° for the minor one. It is interesting to note that atom N21 of the major component participates as an acceptor in a weak N···H—C intermolecular interaction, while the equivalent interaction is absent in the minor component.
Compound (IIc) crystallizes as a dihydrate. The asymmetric unit was selected such that the three molecules form a hydrogen-bonded unit. The water molecules are involved in hydrogen-bonded chains with atoms N21.
In compound (IId), the plane of the benzene ring is practically coplanar with the plane of the CNNC spacer group, the dihedral angle being 5.3 (3)°. The dihedral angle between the plane of the CNNC spacer group and the mean plane of the pyrazine ring is 53.0 (2)°, a clockwise rotation around the C2—C22 axis. The nitro group is twisted out of the plane of the benzene ring by 45.8 (4)°. In spite of this, there is a short contact between atoms O121 and H1 of 2.40Å, with an angle at atom H1 of 112°. The twist of this nitro group may result as a compromise between this weak intramolecular interaction and a weak intermolecuar interaction involving atom O122 of the nitro group.
In isomeric compound (IIe), the dihedral angle between the benzene-ring mean plane and the CNNC spacer group is 8.26 (17)°, and the dihedral angle between the CNNC spacer group and the mean plane of the pyrazine ring is 59.65 (17)°, again a clockwise rotation around the C2—C22 axis. In contrast with (IId), the nitro substituent is twisted out of the plane of the benzene ring plane by only 7.1 (2)°.
Only in hydrated (IIc) are strong hydrogen bonds present. For the other compounds studied here, the intermolecular arrangements are formed by weak C—H..O/N hydrogen bonds and π–π stacking interactions.
For compound (IIa), a weak C25–H25···O2(x, y - 1, z) hydrogen bond links the molecules into a C(7) chain (Bernstein et al., 1995), which runs parallel to the b axis (Table 2 and Fig. 7). There is a π–π short contact between the pyrazine rings, lying across the centre of symmetry at (1/2, 1/2, 1/2); the centroid-to-centroid distance is 3.6631 (7) Å, the perpendicular distance between the rings is 3.6415 (5) Å and the slippage is 0.395 Å.
In compound (IIb), the intermolecular short contacts (Table 3) involve atom C13 as a donor and atom N21 of the major disordered pyrazine ring as an acceptor. There are no similar contacts for the minor component. This suggests that this interaction does not play any significant part in the supramolecular structure of this compound. The other short intermolecular contacts involve the methyl H atoms (Table 3). There is a π–π short contact between the pyrazine rings, which stack above each other with unit translation along the a axis; for the major component, the centroid-to-centroid distance is 4.032 (7) Å, the perpendicular distance between the rings is 3.600 (3) Å and the slippage is 1.816 Å, while for minor component, the centroid-to-centroid distance is 4.033 (8) Å, the perpendicular distance between the rings is 3.164 (4) Å and the slippage is 2.500 Å. The benzene rings also stack above each other with unit translation along the a axis; the centroid-to-centroid distance is 4.032 (6) Å, the perpendicular distance between the rings is 3.4489 (9) Å and the slippage is 2.088 Å.
For compound (IIc), water molecule O1W links the molecules into a C22(7) chain via O1W—H1WB···N21 (within the defined asymmetric unit) and O1W—H1WA···O2(x, y - 1,z) hydrogen bonds. This chain runs parallel to the b axis. The O2W water molecules are linked into a C2 chain by an O2—H2WB···O2W(-x + 1, y - 1/2, -z + 1/2) hydrogen bond. This chain of water molecules links two antiparallel chains together to form a ribbon which runs parallel to the b axis (Table 4 and Fig. 8). These chains are linked into a three-dimensional structure by weak C13—H13···O1W(x, -y + 1/2, z + 1/2) and C26—H26···N141(x, -y + 1/2, -z + 1/2) hydrogen bonds (Table 4). There is a π–π short contact between the pyrazine rings, which stack above each other along the b axis; the centroid-to-centroid distance between these pyrazine rings is 3.9517 (15) Å, the perpendicular distance between the rings is 3.5627 (10) Å and the slippage is 1.710 Å. The benzene rings also stack above each other with unit translation along the a axis; the centroid-to-centroid distance is 3.9516 (15) Å, the perpendicular distance between the rings is 3.4128 (10) Å and the slippage is 2.088 Å.
For compound (IId), a weak C14—H14···O2(x + 1, y, z - 1) hydrogen bond links the molecules into a C(10) chain, which is formed by unit translations along the a and c axes; this chain and a centrosymetrically antiparallel chain are linked by a C13—H13···O122(-x + 2, -y + 1, -z) hydrogen bond and its centrosymetrically related bond, so forming an R22(14) ring, linking the molecules into ribbons which lie parallel to (101) (Fig. 9 and Table 5). There is a π–π short contact between the pyrazine rings, which stack above each other along the a axis; the centroid-to-centroid distance is 3.797 (2) Å, the perpendicular distance between the rings is 3.3838 (15) Å and the slippage is 1.723 Å. The benzene rings also stack above each other with unit translation along the a axis; the centroid-to-centroid distance is 3.797 (2) Å, the perpendicular distance between the rings is 3.5009 (14) Å and the slippage is 2.471 Å,
For compound (IIe), a C15—H15···O2(x - 1/2, -y + 1/2, z + 1/2) hydrogen bond links the molecules into a C(9) chain. The molecules are linked across a centre of symmetry at (1/2, 1/2, 1/2) by a C23—H23···O2 hydrogen bond. These two interactions combine the molecules into a double-sided sheet which runs parallel to the (101) plane (Fig. 10 and Table 6). The pyrazine rings stack above each other across a centre of symmetry at (1/2, 0, 1/2); the centroid-to-centroid distance is 4.1331 (7) Å, the perpendicular distance between the rings is 3.4738 (11) Å and the slippage is 2.240 Å.
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