Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106037668/my3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037668/my3010Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037668/my3010IIsup3.hkl |
CCDC references: 628524; 628525
For the preparation of (I), acyl hydrazone (0.005 mol) was added to a solution of hydrazine hydrate (0.01 mol) in 1-propanol (50 ml) and the mixture was refluxed for 24 h. On cooling, a precipitate was formed, and this product was filtered off and dried. The dry product was washed with benzene (20 ml). The insoluble part in benzene was recrystallized from 1-propanol to afford the pure compound. Recrystallization from ethyl acetate gave a white product (yield 87%). Single crystals of (I) were obtained from ethyl acetate at room temperature by slow evaporation (m.p. 488–489 K). IR (KBr, cm−1): 3245–3142 (vNH2), 1652 (VC=N); 1H NMR (DMSO-d6, p.p.m.): δ 2.38 (6H, CH3), 6.05 (s, 2H, NH2), [ar-H: 7.30 (d, 2H, J = 7.80 Hz), 7.92 (d, 2H, J = 7.80 Hz)]; 13C NMR (DMSO-d6, p.p.m.): δ 153.06 (triazole C3), 152.10 (triazole C5), [ar-C: 138.67, 128.81 (2 C), 127.57 (2 C), 124.71], 20.83 (ar-CH3), 9.80 (CH3). Elemental analysis, calculated for C10H12N4: C 63.81, H 6.43, N 29.76%; found: C 63.80, H 6.41, N 29.73%. For the preparation of compound (II), acyl hydrazone (0.005 mol) was added to a solution of hydrazine hydrate (0.01 mol) in 1- propanol (50 ml) and the mixture was refluxed for 24 h. On cooling, a precipitate was formed, and this product was filtered off and dried. The dry product was washed with benzene (20 ml). The insoluble part in benzene was recrystallized from 1-propanol to afford the pure compound. Recrystallization from ethyl acetate gave a white product (yield 75%). Single crystals of (II) were obtained from ethyl acetate at room temperature by slow evaporation (m.p. 467–468 K). IR (KBr, cm−1): 3255–3150 (vNH2), 1645 (vC=N); 1H NMR (DMSO-d6, p.p.m.): δ 2.40 (s, 3H, CH3), 6.06 (s, 2H, NH2), [ar-H: 7.40–7.70 (m, 3H), 8.00–8.20 (m, 2H)]; 13C NMR (DMSO-d6, p.p.m.): δ 53.86 (triazole C3), 152.33 (triazole C5), [ar-C: 129.00, 128.22 (2 C), 127.65 (2 C), 127.38], 9.73 (CH3). Elemental analysis, calculated for C9H10N4: C 62.05, H 5.79, N 32.16%; found: C 62.04, H 5.77, N 32.76%.
For both compounds, methyl H atoms were located in a difference Fourier synthesis and then refined as rigid rotating groups [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)]. Aromatic H atoms were placed geometrically and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. Atoms H4AA and H4AB bound to N4A were refined freely.
For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).
C10H12N4 | Dx = 1.182 Mg m−3 |
Mr = 188.24 | Melting point = 488–489 K |
Tetragonal, I41/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I4ad | Cell parameters from 7427 reflections |
a = 16.4033 (11) Å | θ = 1.8–27.9° |
c = 15.7192 (12) Å | µ = 0.08 mm−1 |
V = 4229.5 (5) Å3 | T = 296 K |
Z = 16 | Square prism, colorless |
F(000) = 1600 | 0.66 × 0.57 × 0.51 mm |
STOE IPDS-II diffractometer | 1511 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 26.0°, θmin = 1.8° |
Detector resolution: 6.67 pixels mm-1 | h = −19→9 |
ω scan | k = −20→19 |
7427 measured reflections | l = −18→19 |
2082 independent 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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.2861P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2082 reflections | Δρmax = 0.11 e Å−3 |
138 parameters | Δρmin = −0.11 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0019 (6) |
C10H12N4 | Z = 16 |
Mr = 188.24 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.08 mm−1 |
a = 16.4033 (11) Å | T = 296 K |
c = 15.7192 (12) Å | 0.66 × 0.57 × 0.51 mm |
V = 4229.5 (5) Å3 |
STOE IPDS-II diffractometer | 1511 reflections with I > 2σ(I) |
7427 measured reflections | Rint = 0.061 |
2082 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.11 e Å−3 |
2082 reflections | Δρmin = −0.11 e Å−3 |
138 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.33618 (10) | 1.10610 (9) | 0.74921 (8) | 0.0808 (5) | |
N2 | 0.33372 (10) | 1.14100 (9) | 0.82946 (9) | 0.0837 (5) | |
C3 | 0.38287 (10) | 1.09962 (9) | 0.87798 (9) | 0.0627 (4) | |
C3M | 0.39951 (12) | 1.11687 (11) | 0.96885 (10) | 0.0795 (5) | |
H3MA | 0.3733 | 1.1669 | 0.9848 | 0.119* | |
H3MB | 0.4572 | 1.1218 | 0.9774 | 0.119* | |
H3MC | 0.3787 | 1.0731 | 1.0031 | 0.119* | |
N4 | 0.41736 (7) | 1.03854 (7) | 0.83185 (6) | 0.0503 (3) | |
N4A | 0.46926 (8) | 0.97643 (8) | 0.86186 (7) | 0.0571 (3) | |
H4AB | 0.4381 (11) | 0.9481 (11) | 0.9056 (11) | 0.077 (5)* | |
H4AA | 0.5115 (12) | 1.0046 (11) | 0.8885 (11) | 0.080 (5)* | |
C5 | 0.38650 (9) | 1.04420 (8) | 0.75176 (8) | 0.0552 (4) | |
C1P | 0.40449 (9) | 0.99300 (8) | 0.67790 (8) | 0.0551 (4) | |
C2P | 0.34685 (11) | 0.98820 (10) | 0.61326 (9) | 0.0681 (4) | |
H2P | 0.2966 | 1.0138 | 0.6199 | 0.082* | |
C3P | 0.36338 (12) | 0.94590 (11) | 0.53944 (10) | 0.0745 (5) | |
H3P | 0.3241 | 0.9438 | 0.4968 | 0.089* | |
C4P | 0.43693 (12) | 0.90659 (10) | 0.52731 (10) | 0.0693 (5) | |
C5P | 0.49363 (11) | 0.91111 (10) | 0.59214 (10) | 0.0712 (5) | |
H5P | 0.5437 | 0.8853 | 0.5855 | 0.085* | |
C6P | 0.47794 (9) | 0.95301 (10) | 0.66656 (9) | 0.0640 (4) | |
H6P | 0.5170 | 0.9543 | 0.7094 | 0.077* | |
C4M | 0.45477 (15) | 0.86136 (13) | 0.44633 (11) | 0.0972 (7) | |
H4MA | 0.5124 | 0.8519 | 0.4419 | 0.146* | |
H4MB | 0.4368 | 0.8932 | 0.3986 | 0.146* | |
H4MC | 0.4266 | 0.8101 | 0.4467 | 0.146* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.1050 (11) | 0.0752 (9) | 0.0623 (8) | 0.0333 (8) | −0.0179 (7) | −0.0036 (7) |
N2 | 0.1115 (12) | 0.0745 (9) | 0.0649 (8) | 0.0339 (8) | −0.0160 (8) | −0.0096 (7) |
C3 | 0.0725 (10) | 0.0586 (9) | 0.0570 (8) | 0.0062 (8) | −0.0034 (7) | −0.0017 (7) |
C3M | 0.0995 (13) | 0.0794 (12) | 0.0598 (9) | 0.0104 (10) | −0.0058 (9) | −0.0101 (8) |
N4 | 0.0522 (6) | 0.0504 (6) | 0.0484 (6) | 0.0004 (5) | −0.0040 (5) | 0.0047 (5) |
N4A | 0.0558 (7) | 0.0609 (7) | 0.0546 (7) | 0.0057 (6) | −0.0065 (6) | 0.0103 (6) |
C5 | 0.0605 (8) | 0.0540 (8) | 0.0512 (8) | 0.0049 (7) | −0.0065 (6) | 0.0049 (6) |
C1P | 0.0627 (9) | 0.0538 (8) | 0.0487 (7) | −0.0003 (7) | −0.0051 (6) | 0.0073 (6) |
C2P | 0.0757 (10) | 0.0665 (9) | 0.0620 (9) | 0.0094 (8) | −0.0152 (8) | 0.0014 (7) |
C3P | 0.0935 (13) | 0.0721 (11) | 0.0580 (9) | −0.0021 (9) | −0.0206 (8) | −0.0006 (7) |
C4P | 0.0949 (13) | 0.0576 (9) | 0.0555 (8) | −0.0059 (9) | 0.0048 (8) | 0.0013 (7) |
C5P | 0.0750 (11) | 0.0721 (10) | 0.0664 (9) | 0.0078 (8) | 0.0074 (8) | −0.0013 (8) |
C6P | 0.0630 (9) | 0.0695 (9) | 0.0595 (8) | 0.0038 (7) | −0.0053 (7) | 0.0005 (7) |
C4M | 0.1394 (19) | 0.0825 (13) | 0.0697 (11) | −0.0080 (12) | 0.0113 (11) | −0.0126 (9) |
N1—N2 | 1.3859 (19) | C1P—C5 | 1.4629 (19) |
N1—C5 | 1.3091 (19) | C2P—C3P | 1.379 (2) |
N2—C3 | 1.301 (2) | C2P—H2P | 0.9300 |
C3—N4 | 1.3600 (18) | C3P—C4P | 1.381 (3) |
C3—C3M | 1.481 (2) | C3P—H3P | 0.9300 |
C3M—H3MA | 0.9600 | C4P—C5P | 1.382 (2) |
C3M—H3MB | 0.9600 | C4P—C4M | 1.502 (2) |
C3M—H3MC | 0.9600 | C5P—C6P | 1.381 (2) |
N4—N4A | 1.4090 (16) | C5P—H5P | 0.9300 |
N4A—H4AB | 0.975 (19) | C6P—H6P | 0.9300 |
N4A—H4AA | 0.932 (19) | C4M—H4MA | 0.9600 |
N4—C5 | 1.3602 (16) | C4M—H4MB | 0.9600 |
C1P—C6P | 1.383 (2) | C4M—H4MC | 0.9600 |
C1P—C2P | 1.390 (2) | ||
C3—N4—C5 | 106.76 (11) | C4P—C5P—H5P | 119.1 |
C3—N4—N4A | 127.27 (11) | C5P—C6P—C1P | 120.50 (14) |
C5—N4—N4A | 125.74 (11) | C5P—C6P—H6P | 119.8 |
C3—N2—N1 | 107.45 (13) | C1P—C6P—H6P | 119.8 |
C5—N1—N2 | 108.12 (12) | C4P—C4M—H4MA | 109.5 |
N4—N4A—H4AB | 105.3 (10) | C4P—C4M—H4MB | 109.5 |
N4—N4A—H4AA | 104.0 (11) | H4MA—C4M—H4MB | 109.5 |
H4AB—N4A—H4AA | 108.1 (14) | C4P—C4M—H4MC | 109.5 |
C6P—C1P—C2P | 118.11 (14) | H4MA—C4M—H4MC | 109.5 |
C6P—C1P—C5 | 123.38 (13) | H4MB—C4M—H4MC | 109.5 |
C2P—C1P—C5 | 118.39 (14) | N1—C5—N4 | 108.42 (12) |
C3P—C2P—C1P | 120.66 (16) | N1—C5—C1P | 123.24 (12) |
C3P—C2P—H2P | 119.7 | N4—C5—C1P | 128.34 (12) |
C1P—C2P—H2P | 119.7 | N2—C3—N4 | 109.25 (12) |
C2P—C3P—C4P | 121.52 (15) | N2—C3—C3M | 125.43 (14) |
C2P—C3P—H3P | 119.2 | N4—C3—C3M | 125.32 (14) |
C4P—C3P—H3P | 119.2 | C3—C3M—H3MA | 109.5 |
C3P—C4P—C5P | 117.46 (14) | C3—C3M—H3MB | 109.5 |
C3P—C4P—C4M | 121.18 (17) | H3MA—C3M—H3MB | 109.5 |
C5P—C4P—C4M | 121.36 (18) | C3—C3M—H3MC | 109.5 |
C6P—C5P—C4P | 121.74 (16) | H3MA—C3M—H3MC | 109.5 |
C6P—C5P—H5P | 119.1 | H3MB—C3M—H3MC | 109.5 |
C3—N2—N1—C5 | 0.4 (2) | N4A—N4—C5—N1 | 175.27 (14) |
C6P—C1P—C2P—C3P | −1.2 (2) | C3—N4—C5—C1P | 179.62 (15) |
C5—C1P—C2P—C3P | 174.99 (14) | N4A—N4—C5—C1P | −5.6 (2) |
C1P—C2P—C3P—C4P | 0.5 (3) | C6P—C1P—C5—N1 | 151.09 (17) |
C2P—C3P—C4P—C5P | 0.1 (2) | C2P—C1P—C5—N1 | −24.8 (2) |
C2P—C3P—C4P—C4M | −179.38 (17) | C6P—C1P—C5—N4 | −28.0 (2) |
C3P—C4P—C5P—C6P | 0.1 (2) | C2P—C1P—C5—N4 | 156.11 (15) |
C4M—C4P—C5P—C6P | 179.57 (16) | N1—N2—C3—N4 | −0.1 (2) |
C4P—C5P—C6P—C1P | −0.9 (3) | N1—N2—C3—C3M | 179.20 (17) |
C2P—C1P—C6P—C5P | 1.3 (2) | C5—N4—C3—N2 | −0.21 (18) |
C5—C1P—C6P—C5P | −174.59 (14) | N4A—N4—C3—N2 | −174.93 (14) |
N2—N1—C5—N4 | −0.5 (2) | C5—N4—C3—C3M | −179.50 (16) |
N2—N1—C5—C1P | −179.73 (14) | N4A—N4—C3—C3M | 5.8 (3) |
C3—N4—C5—N1 | 0.45 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AB···N1i | 0.975 (19) | 2.072 (19) | 3.0269 (19) | 166.2 (14) |
N4A—H4AA···N2ii | 0.932 (19) | 2.12 (2) | 3.033 (2) | 166.2 (15) |
Symmetry codes: (i) y−3/4, −x+5/4, z+1/4; (ii) −y+7/4, x+3/4, −z+7/4. |
C9H10N4 | Dx = 1.303 Mg m−3 |
Mr = 174.21 | Melting point = 467–468 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac2ab | Cell parameters from 4368 reflections |
a = 6.1062 (8) Å | θ = 2.8–27.9° |
b = 7.3981 (11) Å | µ = 0.09 mm−1 |
c = 19.653 (4) Å | T = 296 K |
V = 887.8 (3) Å3 | Prism, colorless |
Z = 4 | 0.62 × 0.52 × 0.40 mm |
F(000) = 368 |
STOE IPDS-II diffractometer | 1556 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.080 |
Graphite monochromator | θmax = 26.0°, θmin = 2.9° |
Detector resolution: 6.67 pixels mm-1 | h = −7→7 |
w scan | k = −9→8 |
4368 measured reflections | l = −17→24 |
1692 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0683P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.107 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.19 e Å−3 |
1692 reflections | Δρmin = −0.22 e Å−3 |
128 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.056 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 660 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0 (2) |
C9H10N4 | V = 887.8 (3) Å3 |
Mr = 174.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1062 (8) Å | µ = 0.09 mm−1 |
b = 7.3981 (11) Å | T = 296 K |
c = 19.653 (4) Å | 0.62 × 0.52 × 0.40 mm |
STOE IPDS-II diffractometer | 1556 reflections with I > 2σ(I) |
4368 measured reflections | Rint = 0.080 |
1692 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | Δρmax = 0.19 e Å−3 |
S = 1.04 | Δρmin = −0.22 e Å−3 |
1692 reflections | Absolute structure: Flack (1983), 660 Friedel pairs |
128 parameters | Absolute structure parameter: 0 (2) |
0 restraints |
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 | ||
N4 | 0.41918 (18) | 0.58192 (19) | 0.67928 (7) | 0.0341 (3) | |
N2 | 0.6840 (2) | 0.6841 (2) | 0.74308 (8) | 0.0444 (4) | |
N1 | 0.7641 (2) | 0.6558 (2) | 0.67741 (8) | 0.0402 (4) | |
N4A | 0.2212 (2) | 0.4999 (2) | 0.65931 (8) | 0.0432 (4) | |
H4AA | 0.205 (4) | 0.397 (4) | 0.6874 (15) | 0.068 (7)* | |
H4AB | 0.111 (3) | 0.584 (3) | 0.6635 (13) | 0.052 (6)* | |
C1P | 0.6165 (2) | 0.5460 (2) | 0.56770 (8) | 0.0338 (4) | |
C2P | 0.8001 (2) | 0.4531 (3) | 0.54390 (9) | 0.0425 (4) | |
H2P | 0.9107 | 0.4201 | 0.5740 | 0.051* | |
C3P | 0.8177 (3) | 0.4102 (3) | 0.47548 (10) | 0.0513 (5) | |
H3P | 0.9393 | 0.3468 | 0.4599 | 0.062* | |
C4P | 0.6560 (3) | 0.4609 (3) | 0.43047 (10) | 0.0532 (5) | |
H4P | 0.6689 | 0.4333 | 0.3845 | 0.064* | |
C5P | 0.4755 (3) | 0.5526 (3) | 0.45396 (10) | 0.0519 (5) | |
H5P | 0.3665 | 0.5867 | 0.4235 | 0.062* | |
C6P | 0.4534 (3) | 0.5947 (3) | 0.52204 (9) | 0.0429 (4) | |
H6P | 0.3295 | 0.6556 | 0.5373 | 0.052* | |
C5 | 0.6030 (2) | 0.5941 (2) | 0.64035 (8) | 0.0325 (4) | |
C3 | 0.4768 (3) | 0.6382 (2) | 0.74262 (10) | 0.0394 (4) | |
C3M | 0.3229 (4) | 0.6466 (3) | 0.80075 (11) | 0.0567 (5) | |
H3MA | 0.3968 | 0.6955 | 0.8397 | 0.085* | |
H3MB | 0.2710 | 0.5272 | 0.8111 | 0.085* | |
H3MC | 0.2011 | 0.7226 | 0.7891 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N4 | 0.0264 (5) | 0.0426 (7) | 0.0333 (7) | −0.0003 (5) | 0.0002 (5) | −0.0022 (6) |
N2 | 0.0403 (7) | 0.0538 (8) | 0.0391 (8) | −0.0053 (6) | −0.0025 (6) | −0.0064 (7) |
N1 | 0.0322 (6) | 0.0512 (8) | 0.0371 (7) | −0.0021 (5) | −0.0017 (5) | −0.0033 (6) |
N4A | 0.0248 (6) | 0.0588 (10) | 0.0460 (8) | −0.0038 (6) | −0.0037 (5) | −0.0027 (7) |
C1P | 0.0327 (7) | 0.0363 (8) | 0.0325 (8) | −0.0015 (6) | 0.0003 (6) | 0.0000 (6) |
C2P | 0.0370 (8) | 0.0506 (9) | 0.0399 (9) | 0.0060 (7) | −0.0025 (7) | −0.0030 (8) |
C3P | 0.0508 (9) | 0.0569 (11) | 0.0461 (10) | 0.0082 (8) | 0.0078 (8) | −0.0096 (9) |
C4P | 0.0695 (11) | 0.0561 (11) | 0.0338 (9) | 0.0006 (9) | 0.0019 (8) | −0.0070 (8) |
C5P | 0.0581 (10) | 0.0575 (11) | 0.0401 (9) | 0.0065 (9) | −0.0138 (8) | −0.0001 (9) |
C6P | 0.0415 (8) | 0.0470 (9) | 0.0403 (9) | 0.0094 (7) | −0.0048 (6) | −0.0003 (8) |
C5 | 0.0276 (6) | 0.0365 (8) | 0.0335 (8) | 0.0024 (6) | 0.0002 (6) | 0.0014 (6) |
C3 | 0.0371 (7) | 0.0416 (8) | 0.0395 (9) | 0.0000 (6) | 0.0012 (6) | −0.0043 (7) |
C3M | 0.0603 (10) | 0.0666 (13) | 0.0433 (10) | −0.0056 (9) | 0.0145 (8) | −0.0086 (9) |
N4—C3 | 1.359 (2) | C2P—H2P | 0.9300 |
N4—C5 | 1.3615 (19) | C3P—C4P | 1.378 (3) |
N4—N4A | 1.4081 (18) | C3P—H3P | 0.9300 |
N2—C3 | 1.310 (2) | C4P—C5P | 1.374 (3) |
N2—N1 | 1.396 (2) | C4P—H4P | 0.9300 |
N1—C5 | 1.306 (2) | C5P—C6P | 1.380 (3) |
N4A—H4AA | 0.95 (3) | C5P—H5P | 0.9300 |
N4A—H4AB | 0.92 (2) | C6P—H6P | 0.9300 |
C1P—C6P | 1.388 (2) | C3—C3M | 1.480 (3) |
C1P—C2P | 1.396 (2) | C3M—H3MA | 0.9600 |
C1P—C5 | 1.474 (2) | C3M—H3MB | 0.9600 |
C2P—C3P | 1.386 (3) | C3M—H3MC | 0.9600 |
C3—N4—C5 | 106.32 (13) | C3P—C4P—H4P | 120.2 |
C3—N4—N4A | 127.54 (14) | C4P—C5P—C6P | 121.02 (17) |
C5—N4—N4A | 125.43 (13) | C4P—C5P—H5P | 119.5 |
C3—N2—N1 | 107.04 (14) | C6P—C5P—H5P | 119.5 |
C5—N1—N2 | 107.71 (12) | C5P—C6P—C1P | 119.86 (16) |
N4—N4A—H4AA | 105.8 (16) | C5P—C6P—H6P | 120.1 |
N4—N4A—H4AB | 108.2 (14) | C1P—C6P—H6P | 120.1 |
H4AA—N4A—H4AB | 115 (2) | N1—C5—N4 | 109.31 (14) |
C6P—C1P—C2P | 119.17 (16) | N1—C5—C1P | 125.63 (13) |
C6P—C1P—C5 | 121.57 (14) | N4—C5—C1P | 125.06 (13) |
C2P—C1P—C5 | 119.24 (14) | N2—C3—N4 | 109.61 (16) |
C3P—C2P—C1P | 120.03 (16) | N2—C3—C3M | 126.64 (18) |
C3P—C2P—H2P | 120.0 | N4—C3—C3M | 123.75 (16) |
C1P—C2P—H2P | 120.0 | C3—C3M—H3MA | 109.5 |
C4P—C3P—C2P | 120.32 (17) | C3—C3M—H3MB | 109.5 |
C4P—C3P—H3P | 119.8 | H3MA—C3M—H3MB | 109.5 |
C2P—C3P—H3P | 119.8 | C3—C3M—H3MC | 109.5 |
C5P—C4P—C3P | 119.59 (17) | H3MA—C3M—H3MC | 109.5 |
C5P—C4P—H4P | 120.2 | H3MB—C3M—H3MC | 109.5 |
C3—N2—N1—C5 | −0.16 (19) | C3—N4—C5—C1P | 179.83 (15) |
C6P—C1P—C2P—C3P | −0.2 (3) | N4A—N4—C5—C1P | 8.9 (3) |
C5—C1P—C2P—C3P | −178.64 (17) | C6P—C1P—C5—N1 | −136.80 (19) |
C1P—C2P—C3P—C4P | 0.9 (3) | C2P—C1P—C5—N1 | 41.6 (2) |
C2P—C3P—C4P—C5P | −0.8 (3) | C6P—C1P—C5—N4 | 42.8 (2) |
C3P—C4P—C5P—C6P | 0.0 (3) | C2P—C1P—C5—N4 | −138.84 (17) |
C4P—C5P—C6P—C1P | 0.7 (3) | N1—N2—C3—N4 | −0.2 (2) |
C2P—C1P—C6P—C5P | −0.6 (3) | N1—N2—C3—C3M | −179.43 (19) |
C5—C1P—C6P—C5P | 177.79 (16) | C5—N4—C3—N2 | 0.5 (2) |
N2—N1—C5—N4 | 0.44 (19) | N4A—N4—C3—N2 | 171.16 (16) |
N2—N1—C5—C1P | −179.95 (15) | C5—N4—C3—C3M | 179.72 (18) |
C3—N4—C5—N1 | −0.56 (19) | N4A—N4—C3—C3M | −9.6 (3) |
N4A—N4—C5—N1 | −171.52 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AA···N2i | 0.95 (3) | 2.19 (3) | 3.078 (2) | 156 (2) |
N4A—H4AB···N1ii | 0.92 (2) | 2.20 (2) | 3.0411 (19) | 151.4 (18) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C10H12N4 | C9H10N4 |
Mr | 188.24 | 174.21 |
Crystal system, space group | Tetragonal, I41/a | Orthorhombic, P212121 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 16.4033 (11), 16.4033 (11), 15.7192 (12) | 6.1062 (8), 7.3981 (11), 19.653 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 4229.5 (5) | 887.8 (3) |
Z | 16 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.09 |
Crystal size (mm) | 0.66 × 0.57 × 0.51 | 0.62 × 0.52 × 0.40 |
Data collection | ||
Diffractometer | STOE IPDS-II diffractometer | STOE IPDS-II diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7427, 2082, 1511 | 4368, 1692, 1556 |
Rint | 0.061 | 0.080 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.01 | 0.040, 0.107, 1.04 |
No. of reflections | 2082 | 1692 |
No. of parameters | 138 | 128 |
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 |
Δρmax, Δρmin (e Å−3) | 0.11, −0.11 | 0.19, −0.22 |
Absolute structure | ? | Flack (1983), 660 Friedel pairs |
Absolute structure parameter | ? | 0 (2) |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).
N1—N2 | 1.3859 (19) | N4—N4A | 1.4090 (16) |
N1—C5 | 1.3091 (19) | C1P—C5 | 1.4629 (19) |
N2—C3 | 1.301 (2) | ||
C5—N4—N4A | 125.74 (11) | C5—N1—N2 | 108.12 (12) |
N4A—N4—C5—C1P | −5.6 (2) | C6P—C1P—C5—N4 | −28.0 (2) |
C6P—C1P—C5—N1 | 151.09 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AB···N1i | 0.975 (19) | 2.072 (19) | 3.0269 (19) | 166.2 (14) |
N4A—H4AA···N2ii | 0.932 (19) | 2.12 (2) | 3.033 (2) | 166.2 (15) |
Symmetry codes: (i) y−3/4, −x+5/4, z+1/4; (ii) −y+7/4, x+3/4, −z+7/4. |
N4—N4A | 1.4081 (18) | N1—C5 | 1.306 (2) |
N2—C3 | 1.310 (2) | C1P—C5 | 1.474 (2) |
N2—N1 | 1.396 (2) | ||
C5—N4—N4A | 125.43 (13) | C5—N1—N2 | 107.71 (12) |
C6P—C1P—C5—N1 | −136.80 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AA···N2i | 0.95 (3) | 2.19 (3) | 3.078 (2) | 156 (2) |
N4A—H4AB···N1ii | 0.92 (2) | 2.20 (2) | 3.0411 (19) | 151.4 (18) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z. |
1,2,4-Triazole and its derivatives belong to a class of exceptionally active compounds possessing a wide spectrum of biological properties, including anti-inflammatory, antifungal, antiviral (Mahomed et al., 1993; Massa et al., 1992; Mullican et al., 1993), analgesic, anticonvulsant and antidepressant activities (Bradbury & Rivett, 1991; Sughen & Yoloye, 1978; Kane et al., 1988). Some of these compounds are also known to exhibit anticancer activity, e.g. anastrozole, 2,2'-[5-(1H-1,2,4-triazol-1-ylmethyl)-1,3-phenylene]bis(2- methylpropiononitrile), and letrozole, 1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole (Bonte, 2000; Lønning, 1996, 2001). These are completely selective and well tolerated modern, orally active, non-steroidal aromatase inhibitors which are increasingly being used in the treatment of advanced breast cancer in postmenopausal women. Apart from their pharmacological significance, 1,2,4-triazole derivatives exhibit interesting chemical properties. The ability of triazoles to form a bridge between metal ions makes such ligands very important for magnetochemical applications. Some complexes containing substituted 1,2,4-triazole ligands have potential uses as optical sensors or molecular-based memory devices (Kahn & Martinez, 1998; Garcia et al., 1997). In spite of the chemical and medicinal importance of this class of compounds, relatively few crystal structure determinations of 1,2,4-triazole derivatives have been reported (Cambridge Structural Database, Version 5.27 of November 2005; Allen, 2002). In addition to the X-ray structure determination reported here, the title compound, (I), has also been characterized by IR, 1H NMR and 13C NMR spectroscopies and by elemental analysis.
Compound (I) consists of a 1,2,4-triazole ring with methyl, amino and p-tolyl substituents at the 3-, 4- and 5-positions, respectively (Fig. 1). Least-squares mean-plane calculations for the triazole (N1/N2/C3/N4/C5) and phenyl (C1P–C6P) ring planes show that these are approximately planar, with respective maximum deviations of 0.0027 (10) Å for C5 and 0.0066 (11) Å for C1P, the two atoms forming the external bond linking the two rings. The dihedral angle between the triazole and phenyl ring planes is 26.59 (9)°.
The N4—N4A bond length (Table 1) is similar to the corresponding distance in 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole [1.411 (4) Å; Guo & Du, 2002]. The C3═N2 and C5═N1 distances are in good agreement with those found for structures containing the 1,2,4-triazole ring (see, for example, Özbey et al., 2000; Zhu et al., 2000). The N1—N2 bond length is elongated to 1.3859 (19) Å. This value is comparable to those observed in 1-methyl-3,5-diphenyl-1H-1,2,4-triazole (Yazıcı et al., 2004).
Compound (II) consists of a 1,2,4-triazole ring with methyl, amino and phenyl ring substituents at the 3-, 4- and 5-positions, respectively (Fig. 2). The 1,2,4-triazole ring (A; N1/N2/C3/N4/C5) plane and the phenyl ring (Ph; C1P–C6P) plane are approximately planar, the maximum deviations from the least-squares planes being 0.0028 (10) Å for atom C5 and 0.0056 (15) Å for atom C3P. The dihedral angle between the planes of rings A and Ph is 137.66 (2)°. The N1—N2 bond length (Table 3) agrees with the corresponding distance in 3,6-bis(2-chlorophenyl)-1,4-dihydro-1,2,4,5-tetrazine [1.395 (3) Å; Zachara et al., 2004]. The benzene ring is twisted about the external bond to the 1,2,4-triazole ring a torsion angle of −136.80 (19)°.
Molecules are linked by intermolecular hydrogen bonding, and we employ graph-set notation (Bernstein et al., 1995) to describe the patterns of hydrogen bonding. In (I), the arrangement of the interactions (Fig. 3 and Table 2) can be described by the graph-set notation R44(20). The interlinking interactions are described by the notation R44(10). The combined effect of the linked R44(20) and R44(10) motifs is to generate a three dimensional network of molecules.
In (II), the one-dimensional assemblies formed by hydrogen bonding are enforced by weaker intermolecular interactions. N—H···N contacts are observed along the main chains, between the 4-amino-1,2,4-triazole rings of adjacent molecules. Amino atom N4A in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H4AB, to N1 in the molecule at (x − 1, y, z), while N4A at (x − 1, y, z), in turn, acts as a donor to N1 at (x − 2, y, z). In this manner, a C(5) (motif g) chain is formed, running along the a axis. The arrangement of N4A—H4AB···N1i, N4Aii—H4AAii···N2i, N4Aii—H4ABii···N1iii and N4Aiii—H4AAiii···N2 interactions [symmetry codes: (i) x − 1, y, z; (ii) −x, 1/2 + y, 3/2 − z; (iii) 1 − x, 1/2 + y, 3/2 − z] can be described by the graph-set notation R44(15). Amino atom N4A in the molecule at (1 − x, 1/2 + y, 3/2 − z) acts as a hydrogen-bond donor, via H4AA, to N2 in the molecule at (x, y, z), while N4A at (x, y, z), in turn, acts as a donor to N2 at (1 − x, y − 1/2, 3/2 − z). In this manner, a C(5) (motif f) chain is formed, running along the b axis (Fig. 4). The geometry of the hydrogen bonding is given in Table 4.
Compound (I) also contains two intermolecular C—H···π contacts from the 1,2,4-triazole ring to two different symmetry-related molecules (Fig. 5)·The first is from atom C2P in the tolyl ring of the reference molecule to the centroid (d) of the triazole ring related by the symmetry operation (1/4 − y, −1/4 + x, −1/4 + z) [C2P···d = 3.8088 (19) Å, H2P···d = 2.9639 Å, C2P—H2P···d = 152°]. The second C—H···π contact is between C5P in the tolyl ring to the centroid (e) of the symmetry-related tolyl ring at (−1/4 + y, 1/4 − x, 1/4 − z) [C5P···e = 3.7366 (19) Å, H5P···e = 2.8850 Å, C5P—H5P···e = 153°].
In compound (II), the interlinked C3Pi—H3Pi···Ph [C3Pi···Ph = 3.659 (2) Å, H3Pi···Ph = 2.9668 Å and C3Pi—H3Pi···Ph = 132.34°; symmetry code: (i) −1/2 + x, 3/2 − y, −z], C6P—H6P···Phii [C6P···Phii = 3.574 (2) Å, H6P···Phii = 2.8771 Å and C6P—H6P···Phii = 132.74°; symmetry code: (ii) 1/2 + x, 1/2 − y, −z], N4Aiii—H4AAiii···N2ii [symmetry code: (iii) 1/2 − x, 1 − y, z − 1/2] and N4Ai—H4AAi···N2iii interactions, which define an R44(21) ring pattern (Fig. 6).