Buy article online - an online subscription or single-article purchase is required to access this article.
Methyl rearrangement in the solid state of 2,4-dimethoxy-6-(4-nitroanilino)-1,3,5-triazine reveals three different products: (II), C11H11N5O4·H2O, (III), C12H13N5O4, and (IV), C12H13N5O4. (II) crystallizes with a molecule of water and (IV) crystallizes in two polymorphic forms. The conformation of the molecules is expressed by the torsion about the bond joining the triazine and the aniline moieties. The two moieties are almost coplanar in (II) due to an intramolecular hydrogen bond between a triazine-N atom and a phenyl-H atom. The methyl groups of the triazine exert severe steric repulsion in the other two compounds, affecting not only the conformation but also the exocyclic bond angles.
Supporting information
CCDC references: 147644; 147645; 147646; 147647
The title compounds were obtained by heating 2-(4'-nitroanilino)-4,6-dimethyoxy-1,3,5-triazine to 493 K. Crystals of (II) and (IV) were obtained from MeOH solution, crystals of (III) from CHCl3 solution and crystals of (V) from MeOH/EtOH solution.
No attempt has been made to find the absolute structure of (II). Hydrogen atoms were treated by a mixture of independent (H atoms of the water molecule) and by constrained refinement. Crystals of (III) were unstable and poorly diffracted, therefore the data was not collected to completeness, and the Rint was greater than expected.
Data collection: Philips PW 1110/20 (Philips, 1973) for (II); COLLECT (Nonius, 1998) for (III), (IV), (V). Cell refinement: Philips PW 1110/20 for (II); DENZO (Otwinowski & Minor, 1997) for (III), (IV), (V). Data reduction: PROCN (Philips, 1973) for (II); DENZO for (III), (IV), (V). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) and TEXSAN (Molecular Structure Corporation, 1995) for (II); TEXSAN for (III), (IV), (V). For all compounds, software used to prepare material for publication: SHELXL97.
Crystal data top
C11H11N5O4·H2O | F(000) = 616 |
Mr = 295.26 | Dx = 1.470 Mg m−3 |
Orthorhombic, P_21_21_21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 18.170 (4) Å | θ = 3.2–19.7° |
b = 10.530 (3) Å | µ = 0.12 mm−1 |
c = 6.972 (2) Å | T = 293 K |
V = 1334.0 (6) Å3 | Prism, pale yellow |
Z = 4 | 0.80 × 0.50 × 0.40 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→21 |
ω/2θ scans | k = 0→12 |
1339 measured reflections | l = 0→8 |
1339 independent reflections | 3 standard reflections every 120 min reflections |
1152 reflections with I > 2σ(I) | intensity decay: 2.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0499P)2 + 0.9787P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.030 |
1339 reflections | Δρmax = 0.20 e Å−3 |
205 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.024 (3) |
Crystal data top
C11H11N5O4·H2O | V = 1334.0 (6) Å3 |
Mr = 295.26 | Z = 4 |
Orthorhombic, P_21_21_21 | Mo Kα radiation |
a = 18.170 (4) Å | µ = 0.12 mm−1 |
b = 10.530 (3) Å | T = 293 K |
c = 6.972 (2) Å | 0.80 × 0.50 × 0.40 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.000 |
1339 measured reflections | 3 standard reflections every 120 min reflections |
1339 independent reflections | intensity decay: 2.1% |
1152 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | Δρmax = 0.20 e Å−3 |
1339 reflections | Δρmin = −0.20 e Å−3 |
205 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.78975 (17) | 0.3631 (3) | 0.1258 (7) | 0.0577 (11) | |
O2 | 0.54559 (15) | 0.2910 (3) | 0.1905 (6) | 0.0533 (10) | |
O3 | 1.02148 (19) | −0.3010 (4) | 0.1898 (8) | 0.0930 (16) | |
O4 | 0.9512 (2) | −0.4611 (4) | 0.1494 (8) | 0.0876 (15) | |
O5 | 0.60984 (19) | −0.2423 (4) | 0.3599 (7) | 0.0629 (12) | |
N1 | 0.66752 (18) | 0.3310 (3) | 0.1619 (6) | 0.0372 (9) | |
N2 | 0.75229 (17) | 0.1604 (3) | 0.1721 (6) | 0.0348 (9) | |
N3 | 0.62488 (16) | 0.1245 (3) | 0.2113 (6) | 0.0335 (9) | |
N4 | 0.70773 (18) | −0.0424 (3) | 0.2157 (6) | 0.0353 (9) | |
N5 | 0.9609 (2) | −0.3478 (4) | 0.1737 (7) | 0.0580 (12) | |
C1 | 0.7403 (2) | 0.2863 (4) | 0.1523 (7) | 0.0384 (11) | |
C2 | 0.6969 (2) | 0.0845 (4) | 0.2002 (6) | 0.0296 (9) | |
C3 | 0.6085 (2) | 0.2528 (4) | 0.1892 (7) | 0.0348 (10) | |
C4 | 0.7747 (2) | −0.1104 (4) | 0.2001 (6) | 0.0318 (10) | |
C5 | 0.8446 (2) | −0.0583 (4) | 0.2259 (7) | 0.0372 (10) | |
H5 | 0.8502 | 0.0281 | 0.2501 | 0.045* | |
C6 | 0.9055 (2) | −0.1370 (4) | 0.2148 (7) | 0.0411 (11) | |
H6 | 0.9524 | −0.1035 | 0.2308 | 0.049* | |
C7 | 0.8966 (2) | −0.2643 (4) | 0.1804 (7) | 0.0385 (10) | |
C8 | 0.8276 (2) | −0.3176 (4) | 0.1545 (8) | 0.0433 (12) | |
H8 | 0.8224 | −0.4043 | 0.1324 | 0.052* | |
C9 | 0.7672 (2) | −0.2396 (4) | 0.1621 (7) | 0.0373 (10) | |
H9 | 0.7206 | −0.2735 | 0.1415 | 0.045* | |
C10 | 0.6534 (3) | 0.4680 (4) | 0.1406 (10) | 0.0593 (15) | |
H10A | 0.6794 | 0.4995 | 0.0306 | 0.089* | |
H10B | 0.6699 | 0.5118 | 0.2533 | 0.089* | |
H10C | 0.6015 | 0.4819 | 0.1238 | 0.089* | |
C11 | 0.5629 (2) | 0.0363 (4) | 0.2329 (9) | 0.0518 (14) | |
H11A | 0.5176 | 0.0834 | 0.2362 | 0.078* | |
H11B | 0.5683 | −0.0106 | 0.3501 | 0.078* | |
H11C | 0.5621 | −0.0215 | 0.1264 | 0.078* | |
H1N4 | 0.674 (2) | −0.089 (4) | 0.241 (7) | 0.037 (13)* | |
H1O5 | 0.621 (3) | −0.277 (6) | 0.463 (9) | 0.07 (2)* | |
H2O5 | 0.559 (5) | −0.243 (8) | 0.358 (12) | 0.16 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0364 (17) | 0.0297 (15) | 0.107 (3) | −0.0058 (14) | 0.008 (2) | −0.004 (2) |
O2 | 0.0268 (15) | 0.0418 (17) | 0.091 (3) | 0.0082 (13) | −0.0015 (17) | −0.003 (2) |
O3 | 0.040 (2) | 0.089 (3) | 0.150 (5) | 0.021 (2) | −0.013 (3) | −0.025 (4) |
O4 | 0.061 (2) | 0.049 (2) | 0.153 (4) | 0.0231 (19) | 0.012 (3) | −0.005 (3) |
O5 | 0.0311 (18) | 0.057 (2) | 0.100 (3) | 0.0003 (16) | 0.000 (2) | 0.019 (3) |
N1 | 0.0311 (18) | 0.0258 (17) | 0.055 (2) | 0.0055 (14) | 0.0010 (18) | −0.0007 (18) |
N2 | 0.0284 (17) | 0.0260 (16) | 0.050 (2) | −0.0006 (14) | 0.0022 (18) | −0.0006 (18) |
N3 | 0.0219 (15) | 0.0284 (17) | 0.050 (2) | −0.0025 (13) | −0.0016 (16) | −0.0004 (19) |
N4 | 0.0227 (16) | 0.0262 (17) | 0.057 (2) | 0.0005 (14) | 0.0027 (18) | 0.002 (2) |
N5 | 0.036 (2) | 0.065 (3) | 0.072 (3) | 0.020 (2) | 0.003 (2) | −0.002 (3) |
C1 | 0.033 (2) | 0.030 (2) | 0.052 (3) | −0.0016 (19) | 0.002 (2) | −0.006 (2) |
C2 | 0.0254 (17) | 0.0270 (19) | 0.037 (2) | −0.0002 (16) | 0.0032 (19) | −0.0017 (19) |
C3 | 0.032 (2) | 0.029 (2) | 0.044 (2) | 0.0021 (18) | 0.003 (2) | −0.004 (2) |
C4 | 0.0281 (19) | 0.031 (2) | 0.036 (2) | 0.0040 (17) | 0.0032 (19) | 0.004 (2) |
C5 | 0.032 (2) | 0.029 (2) | 0.051 (3) | −0.0024 (18) | −0.004 (2) | −0.002 (2) |
C6 | 0.027 (2) | 0.049 (3) | 0.047 (3) | −0.0002 (19) | −0.001 (2) | −0.003 (3) |
C7 | 0.030 (2) | 0.042 (2) | 0.043 (2) | 0.0116 (19) | 0.003 (2) | 0.003 (2) |
C8 | 0.042 (2) | 0.033 (2) | 0.055 (3) | 0.0043 (19) | 0.006 (2) | −0.002 (2) |
C9 | 0.029 (2) | 0.032 (2) | 0.051 (3) | −0.0019 (17) | 0.001 (2) | 0.001 (2) |
C10 | 0.047 (3) | 0.025 (2) | 0.105 (5) | 0.003 (2) | 0.005 (3) | −0.005 (3) |
C11 | 0.028 (2) | 0.037 (2) | 0.091 (4) | −0.0060 (18) | 0.000 (2) | 0.008 (3) |
Geometric parameters (Å, º) top
O1—C1 | 1.223 (5) | N5—C7 | 1.462 (5) |
O2—C3 | 1.212 (5) | C4—C9 | 1.393 (6) |
O3—N5 | 1.210 (6) | C4—C5 | 1.395 (6) |
O4—N5 | 1.218 (6) | C5—C6 | 1.385 (6) |
O5—H1O5 | 0.83 (6) | C5—H5 | 0.9300 |
O5—H2O5 | 0.93 (8) | C6—C7 | 1.372 (7) |
N1—C3 | 1.365 (5) | C6—H6 | 0.9300 |
N1—C1 | 1.404 (5) | C7—C8 | 1.386 (6) |
N1—C10 | 1.473 (5) | C8—C9 | 1.372 (6) |
N2—C2 | 1.300 (5) | C8—H8 | 0.9300 |
N2—C1 | 1.351 (5) | C9—H9 | 0.9300 |
N3—C2 | 1.377 (5) | C10—H10A | 0.9600 |
N3—C3 | 1.391 (5) | C10—H10B | 0.9600 |
N3—C11 | 1.468 (5) | C10—H10C | 0.9600 |
N4—C2 | 1.355 (5) | C11—H11A | 0.9600 |
N4—C4 | 1.416 (5) | C11—H11B | 0.9600 |
N4—H1N4 | 0.80 (4) | C11—H11C | 0.9600 |
| | | |
H1O5—O5—H2O5 | 104 (6) | C6—C5—H5 | 120.5 |
C3—N1—C1 | 122.9 (3) | C4—C5—H5 | 120.5 |
C3—N1—C10 | 117.9 (3) | C7—C6—C5 | 120.1 (4) |
C1—N1—C10 | 119.2 (4) | C7—C6—H6 | 120.0 |
C2—N2—C1 | 119.5 (3) | C5—C6—H6 | 120.0 |
C2—N3—C3 | 119.6 (3) | C6—C7—C8 | 121.7 (4) |
C2—N3—C11 | 122.8 (3) | C6—C7—N5 | 120.0 (4) |
C3—N3—C11 | 117.5 (3) | C8—C7—N5 | 118.4 (4) |
C2—N4—C4 | 128.2 (4) | C9—C8—C7 | 118.4 (4) |
C2—N4—H1N4 | 121 (3) | C9—C8—H8 | 120.8 |
C4—N4—H1N4 | 111 (3) | C7—C8—H8 | 120.8 |
O3—N5—O4 | 122.9 (4) | C8—C9—C4 | 121.0 (4) |
O3—N5—C7 | 118.6 (4) | C8—C9—H9 | 119.5 |
O4—N5—C7 | 118.5 (4) | C4—C9—H9 | 119.5 |
O1—C1—N2 | 123.0 (4) | N1—C10—H10A | 109.5 |
O1—C1—N1 | 118.5 (4) | N1—C10—H10B | 109.5 |
N2—C1—N1 | 118.4 (4) | H10A—C10—H10B | 109.5 |
N2—C2—N4 | 120.4 (4) | N1—C10—H10C | 109.5 |
N2—C2—N3 | 123.8 (3) | H10A—C10—H10C | 109.5 |
N4—C2—N3 | 115.8 (4) | H10B—C10—H10C | 109.5 |
O2—C3—N1 | 122.8 (4) | N3—C11—H11A | 109.5 |
O2—C3—N3 | 121.6 (4) | N3—C11—H11B | 109.5 |
N1—C3—N3 | 115.6 (3) | H11A—C11—H11B | 109.5 |
C9—C4—C5 | 119.8 (4) | N3—C11—H11C | 109.5 |
C9—C4—N4 | 115.2 (3) | H11A—C11—H11C | 109.5 |
C5—C4—N4 | 125.0 (3) | H11B—C11—H11C | 109.5 |
C6—C5—C4 | 119.0 (4) | | |
| | | |
C2—N2—C1—O1 | 179.9 (5) | C11—N3—C3—O2 | 1.1 (8) |
C2—N2—C1—N1 | −0.3 (7) | C2—N3—C3—N1 | −1.5 (7) |
C3—N1—C1—O1 | 179.4 (5) | C11—N3—C3—N1 | −177.5 (4) |
C10—N1—C1—O1 | −0.2 (8) | C2—N4—C4—C9 | −160.6 (5) |
C3—N1—C1—N2 | −0.4 (7) | C2—N4—C4—C5 | 21.5 (8) |
C10—N1—C1—N2 | −180.0 (5) | C9—C4—C5—C6 | −0.6 (7) |
C1—N2—C2—N4 | 178.4 (5) | N4—C4—C5—C6 | 177.2 (4) |
C1—N2—C2—N3 | 0.1 (7) | C4—C5—C6—C7 | −0.5 (7) |
C4—N4—C2—N2 | −1.8 (8) | C5—C6—C7—C8 | 0.5 (8) |
C4—N4—C2—N3 | 176.6 (4) | C5—C6—C7—N5 | −178.4 (5) |
C3—N3—C2—N2 | 0.9 (7) | O3—N5—C7—C6 | −3.5 (8) |
C11—N3—C2—N2 | 176.6 (5) | O4—N5—C7—C6 | 177.5 (6) |
C3—N3—C2—N4 | −177.5 (4) | O3—N5—C7—C8 | 177.5 (6) |
C11—N3—C2—N4 | −1.7 (7) | O4—N5—C7—C8 | −1.4 (8) |
C1—N1—C3—O2 | −177.2 (5) | C6—C7—C8—C9 | 0.6 (8) |
C10—N1—C3—O2 | 2.3 (7) | N5—C7—C8—C9 | 179.5 (5) |
C1—N1—C3—N3 | 1.3 (7) | C7—C8—C9—C4 | −1.7 (8) |
C10—N1—C3—N3 | −179.1 (5) | C5—C4—C9—C8 | 1.8 (8) |
C2—N3—C3—O2 | 177.1 (4) | N4—C4—C9—C8 | −176.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H1N4···O5 | 0.81 (5) | 2.16 (5) | 2.933 (5) | 162 (5) |
O5—H2O5···O2i | 0.92 (11) | 1.96 (11) | 2.867 (5) | 166 (10) |
O5—H1O5···O1ii | 0.83 (6) | 2.18 (6) | 2.895 (6) | 145 (5) |
O9—H9···O5 | 0.93 (5) | 2.55 (5) | 3.175 (6) | 125 (4) |
C5—H5···N2 | 0.93 (5) | 2.32 (4) | 2.874 (5) | 117 (4) |
C6—H6···O4iii | 0.93 (5) | 2.45 (5) | 3.333 (6) | 158 (4) |
C8—H8···O1iv | 0.93 (5) | 2.52 (5) | 3.438 (6) | 169 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+3/2, −y, z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) x, y−1, z. |
Crystal data top
C12H13N5O4 | F(000) = 608 |
Mr = 291.27 | Dx = 1.495 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 15151 reflections |
a = 11.3330 (12) Å | θ = 2.2–27.5° |
b = 16.0250 (14) Å | µ = 0.12 mm−1 |
c = 7.1620 (7) Å | T = 293 K |
β = 95.587 (5)° | Prism, pale yellow |
V = 1294.5 (2) Å3 | 0.40 × 0.18 × 0.10 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1216 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.115 |
Graphite monochromator | θmax = 27.6°, θmin = 2.2° |
phi scan | h = 0→14 |
16754 measured reflections | k = 0→20 |
2776 independent reflections | l = −9→9 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | All H-atom parameters refined |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.0927P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.73 | (Δ/σ)max < 0.001 |
2776 reflections | Δρmax = 0.19 e Å−3 |
243 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.040 (6) |
Crystal data top
C12H13N5O4 | V = 1294.5 (2) Å3 |
Mr = 291.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3330 (12) Å | µ = 0.12 mm−1 |
b = 16.0250 (14) Å | T = 293 K |
c = 7.1620 (7) Å | 0.40 × 0.18 × 0.10 mm |
β = 95.587 (5)° | |
Data collection top
Nonius KappaCCD diffractometer | 1216 reflections with I > 2σ(I) |
16754 measured reflections | Rint = 0.115 |
2776 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.141 | All H-atom parameters refined |
S = 0.73 | Δρmax = 0.19 e Å−3 |
2776 reflections | Δρmin = −0.20 e Å−3 |
243 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.08281 (17) | 0.37408 (11) | 0.7172 (3) | 0.0739 (6) | |
O2 | −0.11797 (15) | 0.13533 (12) | 0.5758 (3) | 0.0681 (6) | |
O3 | 0.36497 (18) | −0.12662 (12) | 0.1907 (3) | 0.0749 (6) | |
O4 | 0.4256 (2) | −0.20089 (12) | 0.4296 (3) | 0.0851 (7) | |
N1 | −0.02049 (17) | 0.25642 (12) | 0.6440 (3) | 0.0452 (5) | |
N2 | 0.17820 (17) | 0.25231 (12) | 0.7828 (3) | 0.0450 (5) | |
N3 | 0.07128 (16) | 0.12819 (11) | 0.7127 (3) | 0.0448 (5) | |
N4 | 0.27060 (17) | 0.12495 (12) | 0.8331 (3) | 0.0469 (5) | |
N5 | 0.38699 (19) | −0.13619 (14) | 0.3597 (4) | 0.0554 (6) | |
C1 | 0.0819 (2) | 0.29840 (15) | 0.7175 (3) | 0.0473 (6) | |
C2 | 0.1728 (2) | 0.17107 (14) | 0.7743 (3) | 0.0408 (6) | |
C3 | −0.0293 (2) | 0.17154 (15) | 0.6385 (3) | 0.0467 (6) | |
C4 | 0.3068 (2) | 0.05973 (14) | 0.7139 (3) | 0.0427 (6) | |
C5 | 0.2938 (2) | 0.07099 (15) | 0.5228 (4) | 0.0469 (6) | |
C6 | 0.3218 (2) | 0.00644 (15) | 0.4054 (4) | 0.0484 (7) | |
C7 | 0.3643 (2) | −0.06716 (14) | 0.4848 (3) | 0.0432 (6) | |
C8 | 0.3815 (2) | −0.07856 (16) | 0.6750 (4) | 0.0514 (7) | |
C9 | 0.3523 (2) | −0.01390 (16) | 0.7914 (4) | 0.0525 (7) | |
C10 | −0.1269 (3) | 0.3047 (2) | 0.5811 (5) | 0.0645 (9) | |
C11 | 0.0564 (3) | 0.03802 (17) | 0.7479 (5) | 0.0590 (8) | |
C12 | 0.3655 (3) | 0.1676 (2) | 0.9503 (5) | 0.0636 (9) | |
H5 | 0.266 (2) | 0.1269 (16) | 0.471 (3) | 0.057 (7)* | |
H6 | 0.310 (2) | 0.0144 (14) | 0.283 (4) | 0.053 (8)* | |
H8 | 0.411 (2) | −0.1327 (16) | 0.727 (3) | 0.062 (7)* | |
H9 | 0.358 (2) | −0.0271 (17) | 0.931 (4) | 0.081 (9)* | |
H101 | −0.100 (3) | 0.356 (2) | 0.510 (5) | 0.106 (11)* | |
H102 | −0.185 (5) | 0.273 (3) | 0.546 (7) | 0.18 (2)* | |
H103 | −0.150 (4) | 0.341 (3) | 0.668 (6) | 0.143 (18)* | |
H111 | −0.026 (3) | 0.0301 (18) | 0.771 (4) | 0.089 (10)* | |
H112 | 0.099 (3) | 0.026 (2) | 0.870 (5) | 0.106 (13)* | |
H113 | 0.085 (3) | 0.0064 (18) | 0.642 (5) | 0.089 (10)* | |
H121 | 0.398 (3) | 0.2053 (19) | 0.881 (5) | 0.088 (12)* | |
H122 | 0.425 (3) | 0.126 (2) | 0.997 (4) | 0.102 (11)* | |
H123 | 0.341 (3) | 0.194 (2) | 1.064 (6) | 0.131 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0752 (14) | 0.0388 (11) | 0.1032 (17) | 0.0023 (9) | −0.0141 (11) | −0.0062 (10) |
O2 | 0.0438 (11) | 0.0661 (12) | 0.0920 (16) | −0.0100 (10) | −0.0057 (10) | −0.0098 (10) |
O3 | 0.0897 (16) | 0.0787 (14) | 0.0561 (13) | 0.0127 (11) | 0.0054 (11) | −0.0114 (11) |
O4 | 0.1127 (18) | 0.0559 (13) | 0.0856 (16) | 0.0348 (12) | 0.0042 (13) | −0.0015 (11) |
N1 | 0.0404 (12) | 0.0439 (12) | 0.0505 (13) | 0.0058 (9) | 0.0003 (9) | −0.0035 (10) |
N2 | 0.0439 (12) | 0.0413 (11) | 0.0491 (12) | −0.0035 (9) | 0.0015 (9) | −0.0067 (9) |
N3 | 0.0397 (12) | 0.0392 (11) | 0.0555 (13) | −0.0039 (9) | 0.0042 (9) | −0.0027 (9) |
N4 | 0.0407 (12) | 0.0507 (12) | 0.0476 (12) | 0.0055 (10) | −0.0041 (9) | −0.0076 (10) |
N5 | 0.0525 (14) | 0.0497 (13) | 0.0642 (16) | 0.0067 (11) | 0.0061 (11) | −0.0057 (12) |
C1 | 0.0508 (16) | 0.0438 (15) | 0.0473 (15) | −0.0007 (12) | 0.0047 (12) | −0.0021 (12) |
C2 | 0.0385 (14) | 0.0453 (14) | 0.0385 (14) | −0.0021 (11) | 0.0029 (11) | −0.0043 (11) |
C3 | 0.0404 (15) | 0.0526 (15) | 0.0473 (15) | −0.0034 (12) | 0.0060 (12) | −0.0048 (12) |
C4 | 0.0397 (14) | 0.0423 (14) | 0.0457 (15) | 0.0023 (11) | 0.0019 (11) | −0.0021 (11) |
C5 | 0.0472 (15) | 0.0420 (14) | 0.0510 (16) | 0.0034 (12) | 0.0029 (12) | 0.0027 (12) |
C6 | 0.0503 (16) | 0.0519 (16) | 0.0427 (17) | 0.0027 (12) | 0.0039 (12) | 0.0015 (13) |
C7 | 0.0383 (14) | 0.0410 (13) | 0.0500 (15) | 0.0021 (10) | 0.0030 (11) | −0.0031 (11) |
C8 | 0.0456 (16) | 0.0482 (15) | 0.0596 (18) | 0.0082 (12) | 0.0001 (13) | 0.0060 (13) |
C9 | 0.0560 (17) | 0.0526 (16) | 0.0474 (16) | 0.0086 (12) | −0.0026 (13) | −0.0003 (13) |
C10 | 0.058 (2) | 0.0604 (19) | 0.073 (2) | 0.0151 (16) | −0.0050 (17) | 0.0042 (17) |
C11 | 0.057 (2) | 0.0439 (16) | 0.077 (2) | −0.0081 (13) | 0.0113 (17) | 0.0001 (15) |
C12 | 0.0498 (19) | 0.077 (2) | 0.061 (2) | 0.0046 (17) | −0.0120 (16) | −0.0182 (18) |
Geometric parameters (Å, º) top
O1—C1 | 1.213 (3) | C5—C6 | 1.389 (3) |
O2—C3 | 1.209 (3) | C5—H5 | 1.01 (2) |
O3—N5 | 1.222 (3) | C6—C7 | 1.376 (3) |
O4—N5 | 1.214 (3) | C6—H6 | 0.88 (2) |
N1—C3 | 1.364 (3) | C7—C8 | 1.369 (3) |
N1—C1 | 1.399 (3) | C8—C9 | 1.389 (3) |
N1—C10 | 1.467 (3) | C8—H8 | 0.99 (3) |
N2—C2 | 1.304 (3) | C9—H9 | 1.01 (3) |
N2—C1 | 1.362 (3) | C10—H101 | 1.04 (4) |
N3—C2 | 1.375 (3) | C10—H102 | 0.85 (5) |
N3—C3 | 1.395 (3) | C10—H103 | 0.90 (5) |
N3—C11 | 1.479 (3) | C11—H111 | 0.97 (3) |
N4—C2 | 1.364 (3) | C11—H112 | 0.98 (4) |
N4—C4 | 1.435 (3) | C11—H113 | 0.99 (3) |
N4—C12 | 1.467 (3) | C12—H121 | 0.89 (3) |
N5—C7 | 1.462 (3) | C12—H122 | 0.98 (3) |
C4—C5 | 1.374 (3) | C12—H123 | 0.98 (4) |
C4—C9 | 1.382 (3) | | |
| | | |
C3—N1—C1 | 123.1 (2) | C7—C6—H6 | 123.3 (16) |
C3—N1—C10 | 117.5 (2) | C5—C6—H6 | 118.1 (16) |
C1—N1—C10 | 119.3 (2) | C8—C7—C6 | 122.4 (2) |
C2—N2—C1 | 119.5 (2) | C8—C7—N5 | 119.5 (2) |
C2—N3—C3 | 120.0 (2) | C6—C7—N5 | 118.1 (2) |
C2—N3—C11 | 122.6 (2) | C7—C8—C9 | 118.5 (2) |
C3—N3—C11 | 116.7 (2) | C7—C8—H8 | 120.1 (14) |
C2—N4—C4 | 118.80 (19) | C9—C8—H8 | 121.3 (14) |
C2—N4—C12 | 116.9 (2) | C4—C9—C8 | 119.8 (3) |
C4—N4—C12 | 116.3 (2) | C4—C9—H9 | 123.9 (15) |
O4—N5—O3 | 123.1 (2) | C8—C9—H9 | 115.9 (15) |
O4—N5—C7 | 118.1 (2) | N1—C10—H101 | 107.2 (19) |
O3—N5—C7 | 118.8 (2) | N1—C10—H102 | 111 (3) |
O1—C1—N2 | 122.4 (2) | H101—C10—H102 | 127 (4) |
O1—C1—N1 | 119.1 (2) | N1—C10—H103 | 114 (3) |
N2—C1—N1 | 118.4 (2) | H101—C10—H103 | 87 (3) |
N2—C2—N4 | 119.5 (2) | H102—C10—H103 | 109 (4) |
N2—C2—N3 | 123.2 (2) | N3—C11—H111 | 106.5 (18) |
N4—C2—N3 | 117.2 (2) | N3—C11—H112 | 106.6 (19) |
O2—C3—N1 | 123.0 (2) | H111—C11—H112 | 103 (3) |
O2—C3—N3 | 121.4 (2) | N3—C11—H113 | 108.5 (17) |
N1—C3—N3 | 115.5 (2) | H111—C11—H113 | 117 (2) |
C5—C4—C9 | 120.8 (2) | H112—C11—H113 | 115 (3) |
C5—C4—N4 | 119.2 (2) | N4—C12—H121 | 109 (2) |
C9—C4—N4 | 120.0 (2) | N4—C12—H122 | 108.9 (19) |
C4—C5—C6 | 119.8 (2) | H121—C12—H122 | 110 (3) |
C4—C5—H5 | 118.9 (14) | N4—C12—H123 | 115 (2) |
C6—C5—H5 | 121.3 (14) | H121—C12—H123 | 110 (3) |
C7—C6—C5 | 118.6 (3) | H122—C12—H123 | 104 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 1.01 (2) | 2.62 (2) | 3.204 (3) | 117 (2) |
C5—H5···N3i | 1.01 (2) | 2.51 (2) | 3.500 (3) | 168 (2) |
C9—H9···O3ii | 1.02 (3) | 2.45 (3) | 3.374 (3) | 151 (2) |
C10—H101···O2iii | 0.97 (3) | 2.58 (3) | 3.087 (3) | 112 (2) |
C12—H123···N3iv | 0.98 (4) | 2.68 (4) | 3.579 (4) | 153 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1; (iii) −x, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2. |
(IV) 2-(4'-nitrophenylimino)-1,3,5-trimethyl-1,3,5-triazine-4,6,-dione
top
Crystal data top
C12H13N5O4 | Z = 2 |
Mr = 291.27 | F(000) = 304 |
Triclinic, P1 | Dx = 1.445 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71093 Å |
a = 8.253 (6) Å | Cell parameters from 25 reflections |
b = 8.493 (3) Å | θ = 2.5–16.6° |
c = 10.084 (2) Å | µ = 0.11 mm−1 |
α = 78.79° | T = 293 K |
β = 88.52° | Plate, pale yellow |
γ = 74.95° | 0.9 × 0.45 × 0.1 mm |
V = 669.3 (6) Å3 | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.068 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.1° |
Graphite monochromator | h = −9→9 |
ω/2θ scans | k = −9→10 |
2494 measured reflections | l = 0→11 |
2349 independent reflections | 3 standard reflections every 120 min min |
1806 reflections with I > 2σ(I) | intensity decay: 2.4% |
Refinement top
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)] = 0.048 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.144 | All H-atom parameters refined |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0885P)2 + 0.2017P] where P = (Fo2 + 2Fc2)/3 |
2349 reflections | (Δ/σ)max = 0.011 |
242 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C12H13N5O4 | γ = 74.95° |
Mr = 291.27 | V = 669.3 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.253 (6) Å | Mo Kα radiation |
b = 8.493 (3) Å | µ = 0.11 mm−1 |
c = 10.084 (2) Å | T = 293 K |
α = 78.79° | 0.9 × 0.45 × 0.1 mm |
β = 88.52° | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.068 |
2494 measured reflections | 3 standard reflections every 120 min min |
2349 independent reflections | intensity decay: 2.4% |
1806 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.144 | All H-atom parameters refined |
S = 0.91 | Δρmax = 0.24 e Å−3 |
2349 reflections | Δρmin = −0.25 e Å−3 |
242 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.2041 (2) | 0.03085 (18) | 0.10070 (18) | 0.0649 (5) | |
O2 | 0.28833 (19) | 0.54925 (18) | 0.04935 (16) | 0.0576 (4) | |
O3 | −0.6043 (3) | 0.0763 (3) | 0.6994 (2) | 0.0991 (7) | |
O4 | −0.7843 (2) | 0.1975 (3) | 0.5373 (2) | 0.0852 (6) | |
N1 | 0.2571 (2) | 0.2852 (2) | 0.08282 (17) | 0.0463 (4) | |
N2 | 0.0088 (2) | 0.23124 (19) | 0.18234 (17) | 0.0452 (4) | |
N3 | 0.0641 (2) | 0.49373 (19) | 0.16930 (16) | 0.0443 (4) | |
N4 | −0.1612 (2) | 0.4446 (2) | 0.29049 (18) | 0.0529 (5) | |
N5 | −0.6431 (3) | 0.1652 (3) | 0.5889 (2) | 0.0643 (6) | |
C1 | 0.1604 (3) | 0.1725 (2) | 0.1215 (2) | 0.0462 (5) | |
C2 | −0.0375 (2) | 0.3867 (2) | 0.22033 (19) | 0.0422 (5) | |
C3 | 0.2081 (2) | 0.4500 (2) | 0.09606 (19) | 0.0424 (5) | |
C4 | −0.2752 (3) | 0.3656 (3) | 0.3637 (2) | 0.0468 (5) | |
C5 | −0.2292 (3) | 0.2499 (3) | 0.4837 (2) | 0.0543 (6) | |
C6 | −0.3488 (3) | 0.1846 (3) | 0.5591 (2) | 0.0568 (6) | |
C7 | −0.5143 (3) | 0.2354 (3) | 0.5129 (2) | 0.0487 (5) | |
C8 | −0.5634 (3) | 0.3523 (3) | 0.3965 (2) | 0.0550 (6) | |
C9 | −0.4453 (3) | 0.4195 (3) | 0.3222 (2) | 0.0568 (6) | |
C10 | −0.1086 (4) | 0.1228 (3) | 0.1970 (3) | 0.0607 (6) | |
C11 | 0.0211 (4) | 0.6619 (3) | 0.2030 (3) | 0.0582 (6) | |
C12 | 0.4186 (3) | 0.2265 (3) | 0.0171 (3) | 0.0618 (6) | |
H5 | −0.116 (3) | 0.216 (3) | 0.512 (2) | 0.059 (6)* | |
H6 | −0.322 (3) | 0.109 (3) | 0.635 (3) | 0.066 (7)* | |
H8 | −0.678 (3) | 0.385 (3) | 0.368 (3) | 0.070 (7)* | |
H9 | −0.478 (3) | 0.505 (4) | 0.242 (3) | 0.076 (8)* | |
H101 | −0.088 (4) | 0.063 (4) | 0.123 (3) | 0.102 (10)* | |
H102 | −0.223 (4) | 0.194 (4) | 0.184 (3) | 0.082 (9)* | |
H103 | −0.093 (3) | 0.053 (4) | 0.282 (3) | 0.075 (8)* | |
H111 | −0.095 (4) | 0.723 (4) | 0.172 (3) | 0.094 (10)* | |
H112 | 0.094 (4) | 0.721 (4) | 0.163 (3) | 0.098 (10)* | |
H113 | 0.026 (4) | 0.641 (4) | 0.303 (4) | 0.099 (10)* | |
H121 | 0.487 (4) | 0.122 (5) | 0.071 (4) | 0.105 (11)* | |
H122 | 0.481 (4) | 0.308 (4) | 0.003 (3) | 0.098 (10)* | |
H123 | 0.401 (4) | 0.209 (4) | −0.069 (4) | 0.102 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0702 (10) | 0.0404 (8) | 0.0865 (12) | −0.0141 (7) | 0.0127 (9) | −0.0200 (8) |
O2 | 0.0582 (9) | 0.0497 (8) | 0.0684 (10) | −0.0242 (7) | 0.0111 (7) | −0.0074 (7) |
O3 | 0.1157 (17) | 0.1218 (18) | 0.0681 (13) | −0.0642 (15) | 0.0160 (12) | 0.0051 (12) |
O4 | 0.0597 (11) | 0.1067 (16) | 0.1006 (15) | −0.0372 (11) | 0.0201 (10) | −0.0286 (12) |
N1 | 0.0468 (9) | 0.0426 (9) | 0.0506 (10) | −0.0135 (7) | 0.0060 (7) | −0.0100 (7) |
N2 | 0.0515 (10) | 0.0400 (9) | 0.0501 (10) | −0.0203 (7) | 0.0073 (7) | −0.0120 (7) |
N3 | 0.0484 (9) | 0.0384 (9) | 0.0506 (10) | −0.0165 (7) | 0.0043 (7) | −0.0128 (7) |
N4 | 0.0543 (10) | 0.0546 (10) | 0.0574 (11) | −0.0213 (8) | 0.0132 (8) | −0.0205 (8) |
N5 | 0.0720 (14) | 0.0709 (13) | 0.0616 (13) | −0.0326 (11) | 0.0211 (11) | −0.0241 (11) |
C1 | 0.0504 (11) | 0.0403 (11) | 0.0488 (11) | −0.0134 (9) | 0.0012 (9) | −0.0083 (8) |
C2 | 0.0467 (10) | 0.0410 (10) | 0.0418 (10) | −0.0153 (8) | −0.0003 (8) | −0.0099 (8) |
C3 | 0.0441 (10) | 0.0403 (10) | 0.0426 (10) | −0.0127 (8) | −0.0039 (8) | −0.0046 (8) |
C4 | 0.0496 (11) | 0.0486 (11) | 0.0485 (11) | −0.0174 (9) | 0.0090 (9) | −0.0192 (9) |
C5 | 0.0450 (12) | 0.0606 (13) | 0.0568 (13) | −0.0120 (10) | −0.0030 (10) | −0.0119 (10) |
C6 | 0.0651 (14) | 0.0579 (13) | 0.0455 (12) | −0.0162 (11) | 0.0008 (10) | −0.0052 (10) |
C7 | 0.0516 (12) | 0.0544 (12) | 0.0467 (11) | −0.0204 (10) | 0.0111 (9) | −0.0178 (9) |
C8 | 0.0448 (12) | 0.0655 (14) | 0.0560 (13) | −0.0154 (10) | 0.0003 (10) | −0.0136 (11) |
C9 | 0.0552 (13) | 0.0636 (14) | 0.0501 (13) | −0.0174 (11) | −0.0016 (10) | −0.0044 (11) |
C10 | 0.0702 (17) | 0.0532 (14) | 0.0729 (17) | −0.0344 (13) | 0.0192 (13) | −0.0231 (13) |
C11 | 0.0668 (16) | 0.0454 (12) | 0.0710 (17) | −0.0219 (11) | 0.0083 (13) | −0.0228 (11) |
C12 | 0.0519 (13) | 0.0576 (15) | 0.0753 (18) | −0.0114 (11) | 0.0165 (12) | −0.0174 (13) |
Geometric parameters (Å, º) top
O1—C1 | 1.221 (2) | N3—C2 | 1.409 (3) |
O2—C3 | 1.221 (2) | N3—C11 | 1.483 (3) |
O3—N5 | 1.216 (3) | N4—C2 | 1.274 (3) |
O4—N5 | 1.231 (3) | N4—C4 | 1.406 (3) |
N1—C3 | 1.384 (3) | N5—C7 | 1.478 (3) |
N1—C1 | 1.393 (3) | C4—C5 | 1.394 (3) |
N1—C12 | 1.484 (3) | C4—C9 | 1.406 (3) |
N2—C1 | 1.395 (3) | C5—C6 | 1.393 (3) |
N2—C2 | 1.401 (2) | C6—C7 | 1.385 (3) |
N2—C10 | 1.487 (3) | C7—C8 | 1.375 (3) |
N3—C3 | 1.388 (3) | C8—C9 | 1.386 (3) |
| | | |
C3—N1—C1 | 124.02 (17) | N4—C2—N2 | 128.54 (18) |
C3—N1—C12 | 118.21 (17) | N4—C2—N3 | 116.58 (17) |
C1—N1—C12 | 117.69 (18) | N2—C2—N3 | 114.84 (16) |
C1—N2—C2 | 123.14 (16) | O2—C3—N1 | 122.25 (18) |
C1—N2—C10 | 115.77 (17) | O2—C3—N3 | 122.23 (18) |
C2—N2—C10 | 120.97 (17) | N1—C3—N3 | 115.50 (16) |
C3—N3—C2 | 124.68 (16) | C5—C4—N4 | 122.34 (19) |
C3—N3—C11 | 117.18 (17) | C5—C4—C9 | 118.84 (19) |
C2—N3—C11 | 118.02 (17) | N4—C4—C9 | 118.4 (2) |
C2—N4—C4 | 130.02 (18) | C6—C5—C4 | 120.6 (2) |
O3—N5—O4 | 122.8 (2) | C7—C6—C5 | 119.1 (2) |
O3—N5—C7 | 118.5 (2) | C8—C7—C6 | 121.3 (2) |
O4—N5—C7 | 118.7 (2) | C8—C7—N5 | 118.3 (2) |
O1—C1—N2 | 121.64 (18) | C6—C7—N5 | 120.3 (2) |
O1—C1—N1 | 121.83 (19) | C7—C8—C9 | 119.7 (2) |
N2—C1—N1 | 116.51 (17) | C8—C9—C4 | 120.3 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O4i | 0.94 (2) | 2.72 (3) | 3.624 (4) | 163 (2) |
C12—H121···O3ii | 0.98 (3) | 2.62 (4) | 3.529 (3) | 153 (3) |
C12—H122···O2iii | 0.95 (4) | 2.50 (4) | 3.426 (4) | 163 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z. |
(V) 2-(4'-nitrophenylimino)-1,3,5-trimethyl-1,3,5-triazine-4,6,-dione
top
Crystal data top
C12H13N5O4 | F(000) = 608 |
Mr = 291.27 | Dx = 1.473 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 4397 reflections |
a = 11.1270 (6) Å | θ = 1.0–25.4° |
b = 9.1950 (9) Å | µ = 0.11 mm−1 |
c = 13.0940 (11) Å | T = 293 K |
β = 101.264 (5)° | Cube, pale yellow |
V = 1313.88 (18) Å3 | 0.25 × 0.25 × 0.20 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1739 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 25.4°, θmin = 1.9° |
phi scan | h = 0→13 |
7133 measured reflections | k = 0→11 |
2404 independent reflections | l = −15→15 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | All H-atom parameters refined |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0636P)2 + 0.3001P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2404 reflections | Δρmax = 0.19 e Å−3 |
243 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.016 (4) |
Crystal data top
C12H13N5O4 | V = 1313.88 (18) Å3 |
Mr = 291.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1270 (6) Å | µ = 0.11 mm−1 |
b = 9.1950 (9) Å | T = 293 K |
c = 13.0940 (11) Å | 0.25 × 0.25 × 0.20 mm |
β = 101.264 (5)° | |
Data collection top
Nonius KappaCCD diffractometer | 1739 reflections with I > 2σ(I) |
7133 measured reflections | Rint = 0.035 |
2404 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.142 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.19 e Å−3 |
2404 reflections | Δρmin = −0.16 e Å−3 |
243 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.17723 (18) | 0.3667 (2) | 0.54611 (15) | 0.0837 (6) | |
O2 | 0.50592 (14) | 0.65544 (19) | 0.65163 (13) | 0.0662 (5) | |
O3 | 0.02820 (19) | 0.6423 (3) | −0.14645 (15) | 0.0953 (7) | |
O4 | 0.1423 (2) | 0.4526 (3) | −0.13815 (17) | 0.1060 (8) | |
N1 | 0.34684 (16) | 0.50221 (19) | 0.59971 (13) | 0.0499 (5) | |
N2 | 0.23395 (16) | 0.5199 (2) | 0.42872 (13) | 0.0520 (5) | |
N3 | 0.39908 (14) | 0.67631 (19) | 0.48649 (13) | 0.0460 (5) | |
N4 | 0.30495 (15) | 0.6909 (2) | 0.31697 (14) | 0.0530 (5) | |
N5 | 0.1031 (2) | 0.5582 (3) | −0.09866 (17) | 0.0699 (7) | |
C1 | 0.2480 (2) | 0.4572 (3) | 0.52613 (18) | 0.0550 (6) | |
C2 | 0.30940 (17) | 0.6280 (2) | 0.40360 (17) | 0.0446 (5) | |
C3 | 0.42251 (18) | 0.6142 (2) | 0.58353 (17) | 0.0479 (5) | |
C4 | 0.24684 (18) | 0.6488 (2) | 0.21708 (16) | 0.0475 (5) | |
C5 | 0.2826 (2) | 0.5246 (3) | 0.1702 (2) | 0.0612 (7) | |
C6 | 0.2346 (2) | 0.4938 (3) | 0.0680 (2) | 0.0627 (7) | |
C7 | 0.15078 (19) | 0.5877 (3) | 0.01162 (17) | 0.0522 (6) | |
C8 | 0.1117 (2) | 0.7097 (3) | 0.05584 (18) | 0.0546 (6) | |
C9 | 0.1611 (2) | 0.7414 (3) | 0.15849 (18) | 0.0529 (6) | |
C10 | 0.1216 (3) | 0.4781 (5) | 0.3542 (3) | 0.0846 (11) | |
C11 | 0.4765 (3) | 0.7988 (3) | 0.4680 (2) | 0.0615 (7) | |
C12 | 0.3638 (3) | 0.4393 (4) | 0.7049 (2) | 0.0715 (8) | |
H5 | 0.340 (3) | 0.462 (3) | 0.209 (2) | 0.082 (8)* | |
H6 | 0.256 (3) | 0.412 (3) | 0.033 (2) | 0.092 (10)* | |
H8 | 0.049 (2) | 0.768 (3) | 0.018 (2) | 0.071 (7)* | |
H9 | 0.136 (2) | 0.833 (3) | 0.1891 (19) | 0.065 (7)* | |
H101 | 0.062 (4) | 0.443 (5) | 0.391 (4) | 0.173 (19)* | |
H102 | 0.148 (3) | 0.409 (4) | 0.314 (3) | 0.109 (14)* | |
H103 | 0.093 (3) | 0.558 (4) | 0.313 (3) | 0.116 (13)* | |
H111 | 0.510 (3) | 0.782 (4) | 0.408 (3) | 0.112 (12)* | |
H112 | 0.539 (3) | 0.817 (4) | 0.536 (3) | 0.120 (11)* | |
H113 | 0.426 (3) | 0.888 (4) | 0.447 (3) | 0.114 (12)* | |
H121 | 0.298 (4) | 0.380 (5) | 0.707 (3) | 0.145 (16)* | |
H122 | 0.356 (4) | 0.520 (5) | 0.758 (3) | 0.150 (16)* | |
H123 | 0.438 (3) | 0.399 (4) | 0.723 (3) | 0.117 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0977 (14) | 0.0841 (14) | 0.0648 (12) | −0.0418 (11) | 0.0048 (10) | 0.0142 (10) |
O2 | 0.0609 (10) | 0.0734 (11) | 0.0533 (10) | −0.0043 (8) | −0.0162 (8) | −0.0060 (9) |
O3 | 0.0811 (13) | 0.148 (2) | 0.0479 (11) | −0.0086 (14) | −0.0085 (10) | 0.0071 (13) |
O4 | 0.137 (2) | 0.1195 (19) | 0.0654 (14) | −0.0160 (15) | 0.0293 (13) | −0.0373 (13) |
N1 | 0.0581 (10) | 0.0493 (10) | 0.0387 (10) | 0.0000 (8) | 0.0008 (8) | 0.0028 (8) |
N2 | 0.0525 (10) | 0.0593 (12) | 0.0403 (11) | −0.0169 (9) | −0.0005 (8) | 0.0007 (9) |
N3 | 0.0442 (9) | 0.0487 (10) | 0.0408 (10) | −0.0064 (8) | −0.0023 (7) | −0.0024 (8) |
N4 | 0.0531 (10) | 0.0596 (11) | 0.0424 (11) | −0.0093 (9) | −0.0001 (8) | 0.0041 (9) |
N5 | 0.0642 (13) | 0.1011 (18) | 0.0455 (13) | −0.0279 (13) | 0.0135 (11) | −0.0084 (13) |
C1 | 0.0626 (14) | 0.0551 (14) | 0.0447 (14) | −0.0097 (11) | 0.0040 (10) | 0.0008 (11) |
C2 | 0.0414 (10) | 0.0467 (12) | 0.0430 (13) | −0.0032 (9) | 0.0018 (9) | −0.0012 (10) |
C3 | 0.0470 (11) | 0.0474 (12) | 0.0444 (13) | 0.0060 (9) | −0.0032 (9) | −0.0048 (10) |
C4 | 0.0439 (10) | 0.0551 (13) | 0.0411 (12) | −0.0091 (9) | 0.0022 (9) | 0.0033 (10) |
C5 | 0.0575 (14) | 0.0559 (15) | 0.0631 (17) | 0.0026 (11) | −0.0058 (12) | −0.0005 (12) |
C6 | 0.0621 (15) | 0.0622 (15) | 0.0627 (17) | −0.0025 (12) | 0.0094 (12) | −0.0116 (13) |
C7 | 0.0479 (12) | 0.0715 (15) | 0.0367 (12) | −0.0140 (11) | 0.0070 (9) | −0.0023 (11) |
C8 | 0.0461 (12) | 0.0744 (16) | 0.0419 (13) | 0.0015 (11) | 0.0052 (10) | 0.0070 (12) |
C9 | 0.0518 (12) | 0.0599 (14) | 0.0464 (13) | 0.0043 (11) | 0.0081 (10) | 0.0009 (11) |
C10 | 0.077 (2) | 0.114 (3) | 0.0532 (18) | −0.050 (2) | −0.0122 (15) | 0.009 (2) |
C11 | 0.0600 (14) | 0.0588 (16) | 0.0627 (17) | −0.0197 (12) | 0.0043 (13) | −0.0025 (13) |
C12 | 0.085 (2) | 0.080 (2) | 0.0450 (15) | 0.0042 (17) | 0.0023 (14) | 0.0147 (15) |
Geometric parameters (Å, º) top
O1—C1 | 1.209 (3) | C5—C6 | 1.371 (4) |
O2—C3 | 1.215 (2) | C5—H5 | 0.93 (3) |
O3—N5 | 1.217 (3) | C6—C7 | 1.375 (4) |
O4—N5 | 1.220 (3) | C6—H6 | 0.94 (3) |
N1—C3 | 1.373 (3) | C7—C8 | 1.372 (3) |
N1—C1 | 1.377 (3) | C8—C9 | 1.380 (3) |
N1—C12 | 1.471 (3) | C8—H8 | 0.94 (3) |
N2—C1 | 1.381 (3) | C9—H9 | 1.00 (2) |
N2—C2 | 1.381 (3) | C10—H101 | 0.95 (5) |
N2—C10 | 1.478 (3) | C10—H102 | 0.91 (4) |
N3—C3 | 1.371 (3) | C10—H103 | 0.93 (4) |
N3—C2 | 1.396 (3) | C11—H111 | 0.95 (4) |
N3—C11 | 1.466 (3) | C11—H112 | 1.03 (4) |
N4—C2 | 1.265 (3) | C11—H113 | 1.00 (4) |
N4—C4 | 1.396 (3) | C12—H121 | 0.91 (4) |
N5—C7 | 1.463 (3) | C12—H122 | 1.03 (5) |
C4—C5 | 1.391 (3) | C12—H123 | 0.89 (4) |
C4—C9 | 1.392 (3) | | |
| | | |
C3—N1—C1 | 123.22 (18) | C5—C6—H6 | 123.6 (19) |
C3—N1—C12 | 118.0 (2) | C7—C6—H6 | 117.1 (19) |
C1—N1—C12 | 118.4 (2) | C8—C7—C6 | 121.6 (2) |
C1—N2—C2 | 123.78 (18) | C8—C7—N5 | 119.0 (2) |
C1—N2—C10 | 115.4 (2) | C6—C7—N5 | 119.3 (2) |
C2—N2—C10 | 120.3 (2) | C7—C8—C9 | 119.0 (2) |
C3—N3—C2 | 124.47 (18) | C7—C8—H8 | 120.2 (16) |
C3—N3—C11 | 117.49 (18) | C9—C8—H8 | 120.7 (16) |
C2—N3—C11 | 118.01 (19) | C8—C9—C4 | 120.5 (2) |
C2—N4—C4 | 130.05 (19) | C8—C9—H9 | 118.6 (14) |
O3—N5—O4 | 123.6 (2) | C4—C9—H9 | 120.9 (14) |
O3—N5—C7 | 118.0 (3) | N2—C10—H101 | 110 (3) |
O4—N5—C7 | 118.4 (3) | N2—C10—H102 | 104 (2) |
O1—C1—N1 | 121.4 (2) | H101—C10—H102 | 113 (4) |
O1—C1—N2 | 121.8 (2) | N2—C10—H103 | 109 (2) |
N1—C1—N2 | 116.87 (19) | H101—C10—H103 | 112 (4) |
N4—C2—N2 | 128.53 (19) | H102—C10—H103 | 109 (3) |
N4—C2—N3 | 116.64 (18) | N3—C11—H111 | 111 (2) |
N2—C2—N3 | 114.79 (18) | N3—C11—H112 | 107.3 (19) |
O2—C3—N3 | 122.0 (2) | H111—C11—H112 | 116 (3) |
O2—C3—N1 | 121.6 (2) | N3—C11—H113 | 111 (2) |
N3—C3—N1 | 116.37 (17) | H111—C11—H113 | 102 (3) |
C5—C4—C9 | 118.9 (2) | H112—C11—H113 | 110 (3) |
C5—C4—N4 | 121.4 (2) | N1—C12—H121 | 108 (3) |
C9—C4—N4 | 119.3 (2) | N1—C12—H122 | 110 (2) |
C6—C5—C4 | 120.7 (2) | H121—C12—H122 | 103 (3) |
C6—C5—H5 | 119.9 (18) | N1—C12—H123 | 111 (2) |
C4—C5—H5 | 119.5 (18) | H121—C12—H123 | 117 (3) |
C5—C6—C7 | 119.2 (3) | H122—C12—H123 | 108 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.93 (3) | 2.49 (3) | 3.402 (3) | 165 (2) |
C6—H6···O1ii | 0.94 (3) | 2.72 (3) | 3.377 (3) | 128 (2) |
C8—H8···O1iii | 0.94 (2) | 2.65 (2) | 3.539 (3) | 157 (2) |
C9—H9···O3iv | 1.00 (3) | 2.67 (3) | 3.366 (3) | 127 (2) |
C10—H102···O3v | 0.91 (4) | 2.68 (3) | 3.104 (4) | 109 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x, −y+1, −z. |
Experimental details
| (II) | (III) | (IV) | (V) |
Crystal data |
Chemical formula | C11H11N5O4·H2O | C12H13N5O4 | C12H13N5O4 | C12H13N5O4 |
Mr | 295.26 | 291.27 | 291.27 | 291.27 |
Crystal system, space group | Orthorhombic, P_21_21_21 | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 293 | 293 | 293 | 293 |
a, b, c (Å) | 18.170 (4), 10.530 (3), 6.972 (2) | 11.3330 (12), 16.0250 (14), 7.1620 (7) | 8.253 (6), 8.493 (3), 10.084 (2) | 11.1270 (6), 9.1950 (9), 13.0940 (11) |
α, β, γ (°) | 90, 90, 90 | 90, 95.587 (5), 90 | 78.79, 88.52, 74.95 | 90, 101.264 (5), 90 |
V (Å3) | 1334.0 (6) | 1294.5 (2) | 669.3 (6) | 1313.88 (18) |
Z | 4 | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.12 | 0.11 | 0.11 |
Crystal size (mm) | 0.80 × 0.50 × 0.40 | 0.40 × 0.18 × 0.10 | 0.9 × 0.45 × 0.1 | 0.25 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Philips PW 1100 diffractometer | Nonius KappaCCD diffractometer | Philips PW 1100 diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1339, 1339, 1152 | 16754, 2776, 1216 | 2494, 2349, 1806 | 7133, 2404, 1739 |
Rint | 0.000 | 0.115 | 0.068 | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 | 0.651 | 0.595 | 0.603 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.130, 1.19 | 0.048, 0.141, 0.73 | 0.048, 0.144, 0.91 | 0.050, 0.142, 1.05 |
No. of reflections | 1339 | 2776 | 2349 | 2404 |
No. of parameters | 205 | 243 | 242 | 243 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.20 | 0.19, −0.20 | 0.24, −0.25 | 0.19, −0.16 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H1N4···O5 | 0.81 (5) | 2.16 (5) | 2.933 (5) | 162 (5) |
O5—H2O5···O2i | 0.92 (11) | 1.96 (11) | 2.867 (5) | 166 (10) |
O5—H1O5···O1ii | 0.83 (6) | 2.18 (6) | 2.895 (6) | 145 (5) |
O9—H9···O5 | 0.93 (5) | 2.55 (5) | 3.175 (6) | 125 (4) |
C5—H5···N2 | 0.93 (5) | 2.32 (4) | 2.874 (5) | 117 (4) |
C6—H6···O4iii | 0.93 (5) | 2.45 (5) | 3.333 (6) | 158 (4) |
C8—H8···O1iv | 0.93 (5) | 2.52 (5) | 3.438 (6) | 169 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+3/2, −y, z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) x, y−1, z. |
Comparison of bond lengths and bond angles of the s-triazine moiety. top | (II) | (III) | (IV) | (V) |
O1-C1 | 1.223 (5) | 1.213 (3) | 1.221 (2) | 1.209 (3) |
O2-C3 | 1.212 (5) | 1.209 (3) | 1.221 (2) | 1.215 (2) |
N1-C3 | 1.365 (5) | 1.364 (3) | 1.384 (3) | 1.373 (3) |
N1-C1 | 1.404 (5) | 1.399 (3) | 1.393 (3) | 1.377 (3) |
N2-C2 | 1.300 (5) | 1.304 (3) | 1.401 (2) | 1.381 (3) |
N2-C1 | 1.351 (5) | 1.362 (3) | 1.395 (3) | 1.381 (3) |
N3-C2 | 1.377 (5) | 1.375 (3) | 1.409 (3) | 1.396 (3) |
N3-C3 | 1.391 (5) | 1.395 (3) | 1.388 (3) | 1.371 (3) |
N4-C2 | 1.355 (5) | 1.364 (3) | 1.274 (3) | 1.265 (3) |
N4-C4 | 1.416 (5) | 1.435 (3) | 1.406 (3) | 1.396 (3) |
C3-N1-C1 | 122.9 (3) | 123.1 (2) | 124.02 (17) | 123.22 (18) |
C2-N2-C1 | 119.5 (4) | 119.5 (2) | 123.14 (16) | 123.78 (18) |
C2-N3-C3 | 119.6 (3) | 120.0 (2) | 124.68 (16) | 124.47 (18) |
N2-C1-N1 | 118.4 (4) | 118.4 (2) | 116.51 (17) | 116.87 (19) |
N2-C2-N3 | 123.8 (3) | 123.2 (2) | 114.84 (16) | 114.79 (18) |
N1-C3-N3 | 115.6 (3) | 115.5 (2) | 115.50 (16) | 116.37 (17) |
C2-N4-C4 | 128.2 (4) | 118.8 (2) | 130.02 (18) | 130.05 (19) |
N2-C2-N4 | 120.4 (4) | 119.5 (2) | 128.54 (18) | 128.53 (19) |
N4-C2-N3 | 115.8 (4) | 117.2 (2) | 116.58 (17) | 116.64 (18) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 1.01 (2) | 2.62 (2) | 3.204 (3) | 117 (2) |
C5—H5···N3i | 1.01 (2) | 2.51 (2) | 3.500 (3) | 168 (2) |
C9—H9···O3ii | 1.02 (3) | 2.45 (3) | 3.374 (3) | 151 (2) |
C10—H101···O2iii | 0.97 (3) | 2.58 (3) | 3.087 (3) | 112 (2) |
C12—H123···N3iv | 0.98 (4) | 2.68 (4) | 3.579 (4) | 153 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1; (iii) −x, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O4i | 0.94 (2) | 2.72 (3) | 3.624 (4) | 163 (2) |
C12—H121···O3ii | 0.98 (3) | 2.62 (4) | 3.529 (3) | 153 (3) |
C12—H122···O2iii | 0.95 (4) | 2.50 (4) | 3.426 (4) | 163 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.93 (3) | 2.49 (3) | 3.402 (3) | 165 (2) |
C6—H6···O1ii | 0.94 (3) | 2.72 (3) | 3.377 (3) | 128 (2) |
C8—H8···O1iii | 0.94 (2) | 2.65 (2) | 3.539 (3) | 157 (2) |
C9—H9···O3iv | 1.00 (3) | 2.67 (3) | 3.366 (3) | 127 (2) |
C10—H102···O3v | 0.91 (4) | 2.68 (3) | 3.104 (4) | 109 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x, −y+1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Methoxy-s-triazines and their thio-analogues tend to undergo methyl rearrangement either in the liquid state or in the solid-tate (Paolini et al., 1968; Tosato, 1982, 1984; Kaftory & Handelsman-Benory, 1994; Handelsman-Benory et al., 1995, 2000; Greenberg et al., 2000). In the course of a study on the alkyl rearrangement of four derivatives of 2-anilino-4,6-dialkoxy-1,3,5-triazines, it was found that while three of the compounds undergo rearrangement in the liquid state, the fourth, (I), undergoes methyl rearrangement in the solid state (see scheme. The crystal structures and the thermal behaviours of these compounds are described elsewhere (Taycher et al., 2000). Based on the crystal structure of 2,4-dimethoxy-6-(4-nitroanilino)-1,3,5-triazine, it was concluded that the rearrangement is not topochemically controlled. As a result of the rearrangement, a mixture of products are produced, of which three were analyzed by 1H NMR and by single-crystal structure determination. One of the products, (II), crystallizes with a molecule of water, which is hydrogen bonded to the amino hydrogen atom. A second product (IV) crystallizes in two polymorphic forms. The crystal structures of all four compounds, (II)-(IV), are shown in Figures 1–4. \sch
Comparison of bond lengths and angles of the s-triazine moiety is given in Table 5. Some differences of bond angles should be noted. The endocyclic bond angles at the carbon atoms (C1, C2, C3) in the two polymorphs [(IV) and (V)] are significantly smaller than the endocyclic bond angles at the nitrogen atoms (N1, N2, N3); 114.8 (2)–116.9 (2)° compared with 123.1 (2)–124.7 (2)°. In compounds (II) and (III), however, only the N1—C3—N3 bond angle is significantly smaller [115.6 (3), 115.5 (2)°]. Similar differences between the endocyclic bond angles are found in all s-triazine moieties whenever the carbonyl carbon atom is bonded to two N—CH3 groups (Greenberg et al., 2000; Thaladi et al., 1998; Handelsman-Benory et al., 1995).
Selected intermolecular hydrogen-bond geometries are given in Tables 1–4. Weak C—H···O and C—H···N hydrogen bonds have only little effect on the conformation of the molecules but they determine the packing of molecules in the unit cell of each of the compounds. The intramolecular hydrogen bond in (II), N2···H5 [2.32 (4) Å], forces the triazine and the aniline moieties to be almost coplanar [the C2—N4—C4—C5 torsion angle is 21.5 (8)°]. The molecules pack in layers where the water molecules, through hydrogen bonds, form the glue between neighbour molecules in the layer.
Severe steric effect determines the conformation in regards with the torsion angles N2—C2—N4—C4, and C2—N4—C4—C5 and in regards with the external ring bond angles at C2. The only difference between compounds (II) and (III) is the substituent on N4, a hydrogen atom and a methyl group, respectively. The presence of the smaller H atom is not followed by a rotation of the aniline moiety about C2—N4, thus the produced torsion angle is only −1.8 (8)°, the torsion angle about N4—C4 bond is 21.5 (8)°. This conformation is also stabilized by the hydrogen bond discussed above. Replacing the hydrogen atom by a CH3 group causes an increase of the rotation of the aniline moiety, thus the torsion angle about C2—N4 bond increases to −131.2 (2)°, and the torsion about N4—C4 bond increases to 36.0 (3)°. As a result, the two moieties are perpendicular to each other and the close proximity of the two methyl groups C11 and C12 is avoided.
One of the two degrees of freedom available in (II) and (III) to overcome steric repulsion is lost in (IV) due to the replacement of the single to double bond of C2═N4. Partial relief of the steric repulsion is achieved by rotation of the phenyl ring about N4—C4 bond [71.1 (2) and −64.7 (2)° in polymorphs (IV) and (V), respectively], and also by a small rotation about the double bond [8.5 (2) and −18.3 (2)° in (IV) and (V), respectively] which indicates that there is some π-delocalization along the chain joining the triazine to the phenyl. Moreover, the N2—C2—N4 bond angle opens up to 128.5 (2)°, N3—C2—N4 bond angle closes to 116.6 (2)° in both polymorphs. Similar differences between the exocyclic bond angles is found to a lesser extent (124.8, 118.2°) in N-methylthio-N'-(2,6-dimethylphenyl)-2,6-dimethyl-1,4- quinonedi-imine (Klerks et al., 1981) and to a higher extent (134.1, 113.9°) when the N—CH3 is replaced by N—C-(CH3)2 (Al-Talib et al., 1985).