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Two new 1,2,4-triazine-containing sulfonamide derivatives, namely, 4-bromo-
N-(5,6-diphenyl-2
H-1,2,4-triazin-3-ylidene)benzenesulfonamide, C
21H
15BrN
4O
4S,
3a, and methyl 2-{[(5,6-diphenyl-1,2,4-triazin-3-yl)sulfamoyl]methyl}benzoate, C
24H
20N
4O
4S,
3b, which crystallize in the different sulfonimide and sulfonamide tautomeric forms, respectively, were synthesized and characterized by spectroscopic, X-ray diffraction and theoretical calculation methods. Both molecules adopt a very similar conformation of the common part of the structure and the differences occur within the substituents on the sulfonamide group. The amino groups characteristic for the existing tautomeric forms are involved in strong intermolecular N—H
N and N—H
O hydrogen bonds in
3a and
3b, respectively. The Hirshfeld surface analysis showed that H
H contacts constitute a high percentage of the intermolecular interactions. Theoretical calculations at the
ab initio DFT/B3LYP/6-311++G(d,p) level showed that the two tautomeric forms observed for
3a and
3b can co-exist in chloroform, ethanol and water solutions, with a distinct predominance of the sulfonamide form; the participation of the sulfonimide form increases with increasing solvent polarity.
Supporting information
CCDC references: 2194382; 2194383
For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and WinGX (Farrugia, 2012).
4-Bromo-
N-(5,6-diphenyl-2
H-1,2,4-triazin-3-ylidene)benzenesulfonamide (3a)
top
Crystal data top
C21H15BrN4O2S | Z = 2 |
Mr = 467.34 | F(000) = 472 |
Triclinic, P1 | Dx = 1.589 Mg m−3 |
a = 5.781 (2) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 12.717 (2) Å | Cell parameters from 1543 reflections |
c = 14.655 (3) Å | θ = 3.8–74.9° |
α = 67.751 (18)° | µ = 4.09 mm−1 |
β = 78.78 (3)° | T = 120 K |
γ = 82.94 (2)° | Needle, yellow |
V = 976.7 (5) Å3 | 0.25 × 0.10 × 0.05 mm |
Data collection top
Agilent SuperNova Single Source diffractometer with an Atlas detector | 3828 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 2377 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.061 |
Detector resolution: 5.2763 pixels mm-1 | θmax = 80.3°, θmin = 3.3° |
ω scans | h = −7→5 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −15→15 |
Tmin = 0.589, Tmax = 1.000 | l = −18→17 |
6490 measured reflections | |
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)] = 0.079 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.251 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0949P)2 + 2.6148P] where P = (Fo2 + 2Fc2)/3 |
3828 reflections | (Δ/σ)max < 0.001 |
275 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C3 | 0.8158 (12) | 0.4867 (4) | 0.8997 (4) | 0.0338 (13) | |
C5 | 1.0892 (11) | 0.3917 (5) | 0.8175 (4) | 0.0341 (13) | |
C6 | 0.9554 (11) | 0.2917 (5) | 0.8682 (4) | 0.0334 (13) | |
C51 | 1.3032 (12) | 0.3995 (5) | 0.7422 (5) | 0.0379 (13) | |
C52 | 1.4683 (12) | 0.4794 (5) | 0.7265 (5) | 0.0411 (14) | |
H52 | 1.4412 | 0.5260 | 0.7638 | 0.062* | |
C53 | 1.6713 (14) | 0.4895 (6) | 0.6561 (6) | 0.0546 (18) | |
H53 | 1.7842 | 0.5395 | 0.6487 | 0.082* | |
C54 | 1.7041 (14) | 0.4237 (7) | 0.5964 (6) | 0.061 (2) | |
H54 | 1.8388 | 0.4304 | 0.5485 | 0.091* | |
C55 | 1.5355 (14) | 0.3483 (6) | 0.6086 (6) | 0.0522 (18) | |
H55 | 1.5562 | 0.3061 | 0.5675 | 0.078* | |
C56 | 1.3386 (12) | 0.3355 (5) | 0.6809 (5) | 0.0414 (14) | |
H56 | 1.2283 | 0.2840 | 0.6890 | 0.062* | |
C61 | 1.0298 (11) | 0.1768 (4) | 0.8656 (4) | 0.0326 (12) | |
C62 | 1.2389 (12) | 0.1228 (5) | 0.8983 (4) | 0.0364 (13) | |
H62 | 1.3356 | 0.1595 | 0.9192 | 0.055* | |
C63 | 1.3023 (12) | 0.0127 (5) | 0.8993 (4) | 0.0365 (13) | |
H63 | 1.4413 | −0.0242 | 0.9214 | 0.055* | |
C64 | 1.1595 (12) | −0.0408 (5) | 0.8678 (5) | 0.0423 (15) | |
H64 | 1.2015 | −0.1145 | 0.8698 | 0.063* | |
C65 | 0.9543 (11) | 0.0134 (5) | 0.8332 (5) | 0.0368 (13) | |
H65 | 0.8603 | −0.0228 | 0.8104 | 0.055* | |
C66 | 0.8903 (12) | 0.1218 (5) | 0.8328 (5) | 0.0372 (13) | |
H66 | 0.7515 | 0.1583 | 0.8101 | 0.056* | |
C81 | 0.8559 (12) | 0.7498 (5) | 0.7498 (4) | 0.0374 (13) | |
C82 | 0.6485 (15) | 0.8025 (9) | 0.7173 (6) | 0.072 (3) | |
H82 | 0.5157 | 0.8087 | 0.7627 | 0.108* | |
C83 | 0.6411 (19) | 0.8462 (11) | 0.6155 (8) | 0.092 (4) | |
H83 | 0.5009 | 0.8800 | 0.5927 | 0.138* | |
C84 | 0.8372 (18) | 0.8401 (7) | 0.5487 (5) | 0.059 (2) | |
C85 | 1.0393 (18) | 0.7889 (6) | 0.5817 (6) | 0.067 (3) | |
H85 | 1.1736 | 0.7848 | 0.5362 | 0.100* | |
C86 | 1.0478 (15) | 0.7428 (6) | 0.6822 (6) | 0.062 (2) | |
H86 | 1.1872 | 0.7062 | 0.7043 | 0.093* | |
N1 | 0.7504 (10) | 0.2960 (4) | 0.9250 (3) | 0.0356 (12) | |
N2 | 0.6833 (10) | 0.3961 (4) | 0.9355 (4) | 0.0365 (12) | |
H2 | 0.587 (15) | 0.400 (7) | 0.974 (6) | 0.055* | |
N4 | 1.0171 (10) | 0.4866 (4) | 0.8345 (4) | 0.0364 (11) | |
N7 | 0.7303 (10) | 0.5754 (4) | 0.9250 (4) | 0.0374 (12) | |
O1 | 1.1136 (9) | 0.6745 (4) | 0.8896 (4) | 0.0514 (12) | |
O2 | 0.7214 (10) | 0.7651 (4) | 0.9239 (4) | 0.0515 (13) | |
S8 | 0.8673 (3) | 0.69186 (12) | 0.87965 (11) | 0.0406 (4) | |
Br1A | 0.879 (3) | 0.8881 (9) | 0.4094 (4) | 0.061 (2) | 0.47 (4) |
Br1B | 0.780 (4) | 0.9120 (11) | 0.4108 (5) | 0.079 (3) | 0.53 (4) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C3 | 0.048 (4) | 0.017 (2) | 0.037 (3) | 0.006 (2) | −0.012 (3) | −0.011 (2) |
C5 | 0.046 (4) | 0.022 (3) | 0.035 (3) | −0.002 (2) | −0.007 (2) | −0.011 (2) |
C6 | 0.048 (4) | 0.023 (3) | 0.032 (3) | −0.001 (2) | −0.006 (2) | −0.015 (2) |
C51 | 0.044 (4) | 0.028 (3) | 0.040 (3) | −0.003 (3) | −0.008 (3) | −0.009 (2) |
C52 | 0.048 (4) | 0.027 (3) | 0.046 (3) | 0.000 (3) | −0.013 (3) | −0.008 (2) |
C53 | 0.049 (4) | 0.044 (4) | 0.060 (4) | −0.008 (3) | −0.010 (3) | −0.004 (3) |
C54 | 0.048 (5) | 0.052 (4) | 0.062 (5) | −0.002 (3) | 0.012 (4) | −0.010 (4) |
C55 | 0.056 (5) | 0.045 (4) | 0.052 (4) | −0.005 (3) | 0.008 (3) | −0.020 (3) |
C56 | 0.047 (4) | 0.029 (3) | 0.048 (3) | −0.004 (3) | 0.000 (3) | −0.017 (3) |
C61 | 0.047 (4) | 0.019 (2) | 0.033 (3) | 0.000 (2) | −0.002 (2) | −0.013 (2) |
C62 | 0.044 (4) | 0.027 (3) | 0.039 (3) | 0.007 (2) | −0.008 (3) | −0.016 (2) |
C63 | 0.048 (4) | 0.023 (3) | 0.038 (3) | 0.004 (2) | −0.003 (3) | −0.014 (2) |
C64 | 0.053 (4) | 0.028 (3) | 0.043 (3) | −0.001 (3) | 0.008 (3) | −0.017 (2) |
C65 | 0.041 (4) | 0.033 (3) | 0.040 (3) | −0.005 (3) | −0.004 (3) | −0.017 (2) |
C66 | 0.042 (4) | 0.028 (3) | 0.044 (3) | 0.003 (2) | −0.003 (3) | −0.020 (2) |
C81 | 0.049 (4) | 0.031 (3) | 0.033 (3) | −0.005 (3) | 0.000 (3) | −0.015 (2) |
C82 | 0.045 (5) | 0.099 (7) | 0.048 (4) | 0.008 (4) | 0.002 (3) | −0.009 (4) |
C83 | 0.063 (7) | 0.126 (10) | 0.062 (6) | −0.010 (6) | −0.017 (5) | −0.002 (6) |
C84 | 0.102 (7) | 0.045 (4) | 0.030 (3) | −0.030 (4) | −0.005 (4) | −0.008 (3) |
C85 | 0.091 (7) | 0.040 (4) | 0.051 (4) | 0.002 (4) | 0.024 (4) | −0.017 (3) |
C86 | 0.062 (5) | 0.037 (4) | 0.063 (5) | 0.007 (3) | 0.017 (4) | −0.009 (3) |
N1 | 0.057 (3) | 0.020 (2) | 0.031 (2) | 0.008 (2) | −0.006 (2) | −0.0141 (18) |
N2 | 0.050 (3) | 0.025 (2) | 0.036 (3) | 0.001 (2) | 0.001 (2) | −0.017 (2) |
N4 | 0.049 (3) | 0.022 (2) | 0.040 (3) | 0.002 (2) | −0.006 (2) | −0.0140 (19) |
N7 | 0.053 (3) | 0.022 (2) | 0.042 (3) | −0.002 (2) | −0.002 (2) | −0.018 (2) |
O1 | 0.061 (3) | 0.035 (2) | 0.070 (3) | −0.001 (2) | −0.032 (3) | −0.023 (2) |
O2 | 0.082 (4) | 0.027 (2) | 0.048 (3) | −0.008 (2) | 0.011 (2) | −0.0251 (19) |
S8 | 0.0618 (11) | 0.0247 (7) | 0.0400 (8) | −0.0034 (6) | −0.0078 (7) | −0.0169 (6) |
Br1A | 0.095 (5) | 0.049 (2) | 0.0379 (11) | −0.004 (2) | −0.0069 (15) | −0.0163 (11) |
Br1B | 0.127 (7) | 0.062 (2) | 0.0464 (11) | −0.009 (4) | −0.022 (2) | −0.0139 (13) |
Geometric parameters (Å, º) top
C3—N7 | 1.328 (7) | C63—H63 | 0.9300 |
C3—N2 | 1.340 (8) | C64—C65 | 1.381 (10) |
C3—N4 | 1.354 (8) | C64—H64 | 0.9300 |
C5—N4 | 1.326 (7) | C65—C66 | 1.381 (8) |
C5—C6 | 1.439 (8) | C65—H65 | 0.9300 |
C5—C51 | 1.474 (9) | C66—H66 | 0.9300 |
C6—N1 | 1.317 (8) | C81—C86 | 1.354 (9) |
C6—C61 | 1.485 (7) | C81—C82 | 1.377 (11) |
C51—C56 | 1.397 (8) | C81—S8 | 1.772 (6) |
C51—C52 | 1.404 (9) | C82—C83 | 1.388 (13) |
C52—C53 | 1.388 (10) | C82—H82 | 0.9300 |
C52—H52 | 0.9300 | C83—C84 | 1.361 (14) |
C53—C54 | 1.396 (12) | C83—H83 | 0.9300 |
C53—H53 | 0.9300 | C84—C85 | 1.348 (13) |
C54—C55 | 1.391 (11) | C84—Br1A | 1.870 (9) |
C54—H54 | 0.9300 | C84—Br1B | 1.954 (9) |
C55—C56 | 1.374 (9) | C85—C86 | 1.372 (12) |
C55—H55 | 0.9300 | C85—H85 | 0.9300 |
C56—H56 | 0.9300 | C86—H86 | 0.9300 |
C61—C66 | 1.384 (9) | N1—N2 | 1.341 (6) |
C61—C62 | 1.391 (9) | N2—H2 | 0.72 (8) |
C62—C63 | 1.397 (7) | N7—S8 | 1.612 (5) |
C62—H62 | 0.9300 | O1—S8 | 1.441 (5) |
C63—C64 | 1.372 (9) | O2—S8 | 1.432 (4) |
| | | |
N7—C3—N2 | 117.0 (6) | C66—C65—C64 | 119.2 (6) |
N7—C3—N4 | 123.9 (5) | C66—C65—H65 | 120.4 |
N2—C3—N4 | 118.9 (5) | C64—C65—H65 | 120.4 |
N4—C5—C6 | 120.0 (6) | C65—C66—C61 | 120.9 (6) |
N4—C5—C51 | 115.4 (5) | C65—C66—H66 | 119.5 |
C6—C5—C51 | 124.5 (5) | C61—C66—H66 | 119.5 |
N1—C6—C5 | 120.6 (5) | C86—C81—C82 | 119.5 (7) |
N1—C6—C61 | 113.8 (5) | C86—C81—S8 | 121.0 (6) |
C5—C6—C61 | 125.6 (5) | C82—C81—S8 | 119.4 (5) |
C56—C51—C52 | 118.8 (6) | C81—C82—C83 | 118.9 (8) |
C56—C51—C5 | 121.9 (6) | C81—C82—H82 | 120.6 |
C52—C51—C5 | 119.1 (6) | C83—C82—H82 | 120.6 |
C53—C52—C51 | 120.8 (6) | C84—C83—C82 | 120.6 (10) |
C53—C52—H52 | 119.6 | C84—C83—H83 | 119.7 |
C51—C52—H52 | 119.6 | C82—C83—H83 | 119.7 |
C52—C53—C54 | 119.3 (7) | C85—C84—C83 | 119.7 (8) |
C52—C53—H53 | 120.4 | C85—C84—Br1A | 110.0 (9) |
C54—C53—H53 | 120.4 | C83—C84—Br1A | 130.2 (10) |
C55—C54—C53 | 120.0 (7) | C85—C84—Br1B | 128.1 (10) |
C55—C54—H54 | 120.0 | C83—C84—Br1B | 112.1 (11) |
C53—C54—H54 | 120.0 | C84—C85—C86 | 120.3 (7) |
C56—C55—C54 | 120.5 (7) | C84—C85—H85 | 119.9 |
C56—C55—H55 | 119.7 | C86—C85—H85 | 119.9 |
C54—C55—H55 | 119.7 | C81—C86—C85 | 120.9 (8) |
C55—C56—C51 | 120.4 (6) | C81—C86—H86 | 119.6 |
C55—C56—H56 | 119.8 | C85—C86—H86 | 119.6 |
C51—C56—H56 | 119.8 | C6—N1—N2 | 116.0 (5) |
C66—C61—C62 | 119.6 (5) | C3—N2—N1 | 125.0 (6) |
C66—C61—C6 | 120.5 (6) | C3—N2—H2 | 112 (7) |
C62—C61—C6 | 119.8 (5) | N1—N2—H2 | 120 (7) |
C61—C62—C63 | 119.3 (6) | C5—N4—C3 | 118.4 (5) |
C61—C62—H62 | 120.3 | C3—N7—S8 | 120.8 (5) |
C63—C62—H62 | 120.3 | O2—S8—O1 | 118.1 (3) |
C64—C63—C62 | 120.0 (6) | O2—S8—N7 | 103.9 (3) |
C64—C63—H63 | 120.0 | O1—S8—N7 | 113.2 (3) |
C62—C63—H63 | 120.0 | O2—S8—C81 | 107.5 (3) |
C63—C64—C65 | 120.9 (6) | O1—S8—C81 | 106.7 (3) |
C63—C64—H64 | 119.5 | N7—S8—C81 | 106.8 (3) |
C65—C64—H64 | 119.5 | | |
| | | |
N4—C5—C6—N1 | 6.0 (9) | C81—C82—C83—C84 | −1.9 (18) |
C51—C5—C6—N1 | −171.4 (6) | C82—C83—C84—C85 | 1.4 (17) |
N4—C5—C6—C61 | −172.3 (6) | C82—C83—C84—Br1A | 178.6 (9) |
C51—C5—C6—C61 | 10.3 (10) | C82—C83—C84—Br1B | −178.2 (10) |
N4—C5—C51—C56 | −148.0 (6) | C83—C84—C85—C86 | 0.2 (14) |
C6—C5—C51—C56 | 29.5 (10) | Br1A—C84—C85—C86 | −177.5 (7) |
N4—C5—C51—C52 | 27.3 (9) | Br1B—C84—C85—C86 | 179.8 (7) |
C6—C5—C51—C52 | −155.2 (6) | C82—C81—C86—C85 | 1.0 (12) |
C56—C51—C52—C53 | −4.3 (10) | S8—C81—C86—C85 | −179.2 (6) |
C5—C51—C52—C53 | −179.8 (6) | C84—C85—C86—C81 | −1.4 (13) |
C51—C52—C53—C54 | 3.6 (11) | C5—C6—N1—N2 | −3.0 (8) |
C52—C53—C54—C55 | −0.6 (12) | C61—C6—N1—N2 | 175.5 (5) |
C53—C54—C55—C56 | −1.7 (13) | N7—C3—N2—N1 | −173.8 (6) |
C54—C55—C56—C51 | 1.0 (12) | N4—C3—N2—N1 | 11.3 (9) |
C52—C51—C56—C55 | 2.0 (10) | C6—N1—N2—C3 | −5.6 (9) |
C5—C51—C56—C55 | 177.3 (7) | C6—C5—N4—C3 | −0.4 (9) |
N1—C6—C61—C66 | 59.1 (8) | C51—C5—N4—C3 | 177.2 (5) |
C5—C6—C61—C66 | −122.5 (7) | N7—C3—N4—C5 | 177.9 (6) |
N1—C6—C61—C62 | −119.5 (6) | N2—C3—N4—C5 | −7.6 (9) |
C5—C6—C61—C62 | 58.9 (8) | N2—C3—N7—S8 | −175.7 (5) |
C66—C61—C62—C63 | −1.3 (9) | N4—C3—N7—S8 | −1.0 (9) |
C6—C61—C62—C63 | 177.4 (5) | C3—N7—S8—O2 | 179.8 (5) |
C61—C62—C63—C64 | 0.4 (9) | C3—N7—S8—O1 | −50.7 (6) |
C62—C63—C64—C65 | 1.1 (9) | C3—N7—S8—C81 | 66.4 (6) |
C63—C64—C65—C66 | −1.6 (9) | C86—C81—S8—O2 | 144.6 (6) |
C64—C65—C66—C61 | 0.6 (9) | C82—C81—S8—O2 | −35.5 (7) |
C62—C61—C66—C65 | 0.8 (9) | C86—C81—S8—O1 | 17.0 (6) |
C6—C61—C66—C65 | −177.8 (6) | C82—C81—S8—O1 | −163.1 (7) |
C86—C81—C82—C83 | 0.6 (15) | C86—C81—S8—N7 | −104.3 (6) |
S8—C81—C82—C83 | −179.2 (9) | C82—C81—S8—N7 | 75.5 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C86—H86···O1 | 0.93 | 2.55 | 2.917 (10) | 104 |
N2—H2···N7i | 0.72 (8) | 2.19 (9) | 2.911 (8) | 173 (9) |
C83—H83···Br1Bii | 0.93 | 2.92 | 3.63 (2) | 134 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z+1. |
Methyl 2-{[(5,6-diphenyl-1,2,4-triazin-3-yl)sulfamoyl]methyl}benzoate (3b)
top
Crystal data top
C24H20N4O4S | F(000) = 960 |
Mr = 460.50 | Dx = 1.402 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 10.919 (2) Å | Cell parameters from 3956 reflections |
b = 8.0871 (16) Å | θ = 4.6–75.6° |
c = 24.875 (5) Å | µ = 1.66 mm−1 |
β = 96.65 (3)° | T = 120 K |
V = 2181.9 (8) Å3 | Plate, yellow |
Z = 4 | 0.30 × 0.10 × 0.10 mm |
Data collection top
Agilent SuperNova Single Source diffractometer with an Atlas detector | 4438 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 3507 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.049 |
Detector resolution: 5.2763 pixels mm-1 | θmax = 76.5°, θmin = 3.6° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −8→10 |
Tmin = 0.782, Tmax = 1.000 | l = −31→31 |
8470 measured reflections | |
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)] = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.253 | w = 1/[σ2(Fo2) + (0.128P)2 + 2.0409P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max < 0.001 |
4438 reflections | Δρmax = 0.64 e Å−3 |
302 parameters | Δρmin = −1.16 e Å−3 |
18 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0015 (4) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C3 | 0.5856 (3) | 0.3397 (4) | 0.63161 (13) | 0.0288 (5) | |
C5 | 0.5785 (3) | 0.3612 (4) | 0.72213 (13) | 0.0277 (5) | |
C6 | 0.7094 (3) | 0.3482 (4) | 0.72907 (14) | 0.0270 (7) | |
C9 | 0.3271 (3) | 0.5231 (5) | 0.59242 (14) | 0.0313 (7) | |
H9A | 0.3491 | 0.5177 | 0.6313 | 0.047* | |
H9B | 0.3699 | 0.6167 | 0.5789 | 0.047* | |
C10 | 0.2111 (3) | 0.7638 (4) | 0.50776 (13) | 0.0317 (7) | |
C12 | 0.2140 (4) | 0.9891 (5) | 0.44913 (17) | 0.0437 (10) | |
H12A | 0.1599 | 1.0719 | 0.4319 | 0.066* | |
H12B | 0.2800 | 1.0417 | 0.4717 | 0.066* | |
H12C | 0.2473 | 0.9239 | 0.4220 | 0.066* | |
C51 | 0.4987 (3) | 0.3849 (4) | 0.76596 (13) | 0.0275 (7) | |
C52 | 0.3845 (4) | 0.3033 (5) | 0.76124 (15) | 0.0357 (8) | |
H52 | 0.3623 | 0.2328 | 0.7322 | 0.054* | |
C53 | 0.3049 (4) | 0.3280 (6) | 0.80003 (17) | 0.0434 (10) | |
H53 | 0.2306 | 0.2708 | 0.7977 | 0.065* | |
C54 | 0.3355 (4) | 0.4375 (6) | 0.84228 (16) | 0.0437 (10) | |
H54 | 0.2810 | 0.4554 | 0.8678 | 0.066* | |
C55 | 0.4468 (4) | 0.5200 (5) | 0.84652 (15) | 0.0409 (9) | |
H55 | 0.4672 | 0.5929 | 0.8750 | 0.061* | |
C56 | 0.5284 (4) | 0.4948 (5) | 0.80845 (15) | 0.0347 (8) | |
H56 | 0.6030 | 0.5515 | 0.8114 | 0.052* | |
C61 | 0.7902 (3) | 0.3471 (4) | 0.78100 (14) | 0.0269 (7) | |
C62 | 0.7635 (3) | 0.2545 (4) | 0.82579 (13) | 0.0294 (7) | |
H62 | 0.6918 | 0.1916 | 0.8237 | 0.044* | |
C63 | 0.8441 (4) | 0.2566 (5) | 0.87351 (14) | 0.0358 (8) | |
H63 | 0.8266 | 0.1933 | 0.9029 | 0.054* | |
C64 | 0.9502 (4) | 0.3522 (5) | 0.87750 (16) | 0.0366 (8) | |
H64 | 1.0025 | 0.3554 | 0.9098 | 0.055* | |
C65 | 0.9778 (3) | 0.4429 (5) | 0.83323 (16) | 0.0361 (8) | |
H65 | 1.0487 | 0.5074 | 0.8358 | 0.054* | |
C66 | 0.9003 (3) | 0.4378 (4) | 0.78517 (15) | 0.0328 (7) | |
H66 | 0.9214 | 0.4954 | 0.7552 | 0.049* | |
C91 | 0.1909 (3) | 0.5496 (4) | 0.58061 (13) | 0.0292 (7) | |
C92 | 0.1358 (3) | 0.6610 (4) | 0.54204 (14) | 0.0311 (7) | |
C93 | 0.0076 (4) | 0.6795 (5) | 0.53476 (17) | 0.0387 (9) | |
H93 | −0.0289 | 0.7537 | 0.5092 | 0.058* | |
C94 | −0.0648 (4) | 0.5872 (5) | 0.56568 (18) | 0.0435 (9) | |
H94 | −0.1501 | 0.5989 | 0.5605 | 0.065* | |
C95 | −0.0117 (4) | 0.4778 (5) | 0.60419 (17) | 0.0393 (9) | |
H95 | −0.0608 | 0.4162 | 0.6249 | 0.059* | |
C96 | 0.1151 (4) | 0.4607 (5) | 0.61166 (15) | 0.0373 (8) | |
H96 | 0.1507 | 0.3883 | 0.6380 | 0.056* | |
N1 | 0.7690 (3) | 0.3342 (4) | 0.68541 (12) | 0.0294 (6) | |
N2 | 0.7092 (3) | 0.3326 (4) | 0.63565 (12) | 0.0312 (7) | |
N4 | 0.5187 (3) | 0.3534 (4) | 0.67275 (11) | 0.0280 (5) | |
N7 | 0.5258 (3) | 0.3388 (4) | 0.57955 (11) | 0.0300 (5) | |
H7 | 0.574 (4) | 0.320 (6) | 0.553 (2) | 0.045* | |
O1 | 0.3236 (2) | 0.1997 (3) | 0.58655 (11) | 0.0370 (6) | |
O2 | 0.3626 (3) | 0.3521 (4) | 0.50456 (10) | 0.0386 (7) | |
O10 | 0.3196 (2) | 0.7421 (4) | 0.50363 (11) | 0.0386 (6) | |
O11 | 0.1456 (3) | 0.8832 (3) | 0.48194 (12) | 0.0413 (7) | |
S8 | 0.37658 (8) | 0.33808 (11) | 0.56239 (3) | 0.0303 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C3 | 0.0326 (10) | 0.0314 (10) | 0.0231 (10) | 0.0025 (8) | 0.0067 (9) | 0.0005 (8) |
C5 | 0.0343 (11) | 0.0256 (11) | 0.0237 (11) | 0.0008 (9) | 0.0061 (10) | 0.0001 (9) |
C6 | 0.0354 (17) | 0.0196 (14) | 0.0279 (16) | −0.0004 (12) | 0.0117 (13) | 0.0002 (11) |
C9 | 0.0347 (17) | 0.0321 (17) | 0.0268 (15) | −0.0030 (14) | 0.0022 (13) | −0.0003 (13) |
C10 | 0.0399 (18) | 0.0305 (17) | 0.0257 (15) | 0.0045 (15) | 0.0079 (13) | −0.0025 (13) |
C12 | 0.065 (3) | 0.0289 (18) | 0.039 (2) | 0.0013 (18) | 0.0127 (18) | 0.0037 (16) |
C51 | 0.0317 (16) | 0.0265 (15) | 0.0254 (15) | 0.0038 (13) | 0.0084 (12) | 0.0011 (12) |
C52 | 0.0380 (19) | 0.0368 (18) | 0.0333 (17) | −0.0025 (16) | 0.0080 (15) | −0.0022 (15) |
C53 | 0.041 (2) | 0.050 (2) | 0.043 (2) | −0.0018 (18) | 0.0226 (18) | −0.0023 (17) |
C54 | 0.045 (2) | 0.053 (2) | 0.0350 (19) | 0.0118 (19) | 0.0165 (16) | 0.0044 (17) |
C55 | 0.051 (2) | 0.040 (2) | 0.0324 (18) | 0.0123 (18) | 0.0098 (16) | −0.0068 (15) |
C56 | 0.0414 (19) | 0.0305 (17) | 0.0330 (17) | 0.0014 (15) | 0.0079 (15) | −0.0030 (14) |
C61 | 0.0316 (17) | 0.0214 (15) | 0.0285 (16) | 0.0025 (12) | 0.0068 (13) | −0.0023 (12) |
C62 | 0.0341 (17) | 0.0272 (16) | 0.0269 (15) | 0.0023 (14) | 0.0036 (13) | −0.0002 (12) |
C63 | 0.049 (2) | 0.0330 (18) | 0.0258 (16) | 0.0070 (16) | 0.0042 (15) | 0.0000 (13) |
C64 | 0.0399 (19) | 0.0347 (19) | 0.0334 (18) | 0.0083 (16) | −0.0041 (15) | −0.0067 (14) |
C65 | 0.0339 (18) | 0.0318 (18) | 0.0405 (19) | 0.0019 (15) | −0.0042 (15) | −0.0021 (15) |
C66 | 0.0357 (18) | 0.0272 (16) | 0.0359 (17) | 0.0033 (14) | 0.0058 (14) | 0.0015 (14) |
C91 | 0.0319 (16) | 0.0303 (16) | 0.0270 (15) | 0.0016 (14) | 0.0101 (13) | −0.0046 (13) |
C92 | 0.0344 (18) | 0.0293 (17) | 0.0320 (17) | 0.0018 (14) | 0.0135 (14) | −0.0048 (13) |
C93 | 0.039 (2) | 0.0352 (19) | 0.043 (2) | 0.0082 (16) | 0.0110 (16) | −0.0042 (16) |
C94 | 0.0368 (19) | 0.042 (2) | 0.055 (2) | 0.0007 (17) | 0.0168 (17) | −0.0087 (18) |
C95 | 0.0359 (19) | 0.0380 (19) | 0.048 (2) | −0.0018 (16) | 0.0204 (16) | −0.0038 (17) |
C96 | 0.046 (2) | 0.0319 (18) | 0.0366 (18) | 0.0013 (16) | 0.0165 (16) | 0.0013 (15) |
N1 | 0.0338 (15) | 0.0297 (14) | 0.0246 (13) | 0.0019 (11) | 0.0028 (11) | 0.0006 (11) |
N2 | 0.0337 (15) | 0.0329 (15) | 0.0279 (14) | 0.0024 (12) | 0.0077 (12) | −0.0017 (11) |
N4 | 0.0333 (10) | 0.0285 (10) | 0.0228 (9) | 0.0018 (8) | 0.0051 (8) | 0.0004 (7) |
N7 | 0.0327 (11) | 0.0357 (11) | 0.0219 (10) | 0.0033 (9) | 0.0045 (9) | 0.0007 (9) |
O1 | 0.0402 (14) | 0.0316 (13) | 0.0391 (14) | 0.0023 (11) | 0.0042 (11) | 0.0011 (11) |
O2 | 0.0453 (15) | 0.0470 (16) | 0.0231 (12) | 0.0057 (12) | 0.0027 (11) | −0.0033 (10) |
O10 | 0.0352 (13) | 0.0476 (16) | 0.0354 (13) | 0.0066 (12) | 0.0144 (11) | 0.0093 (12) |
O11 | 0.0489 (16) | 0.0319 (13) | 0.0445 (15) | 0.0081 (12) | 0.0109 (12) | 0.0083 (12) |
S8 | 0.0347 (5) | 0.0320 (5) | 0.0248 (4) | 0.0016 (3) | 0.0063 (3) | −0.0021 (3) |
Geometric parameters (Å, º) top
C3—N4 | 1.329 (4) | C55—H55 | 0.9300 |
C3—N2 | 1.342 (5) | C56—H56 | 0.9300 |
C3—N7 | 1.381 (4) | C61—C62 | 1.401 (5) |
C5—N4 | 1.324 (4) | C61—C66 | 1.401 (5) |
C5—C6 | 1.424 (5) | C62—C63 | 1.394 (5) |
C5—C51 | 1.484 (4) | C62—H62 | 0.9300 |
C6—N1 | 1.334 (4) | C63—C64 | 1.387 (6) |
C6—C61 | 1.478 (5) | C63—H63 | 0.9300 |
C9—C91 | 1.498 (5) | C64—C65 | 1.385 (6) |
C9—S8 | 1.784 (4) | C64—H64 | 0.9300 |
C9—H9A | 0.9700 | C65—C66 | 1.383 (5) |
C9—H9B | 0.9700 | C65—H65 | 0.9300 |
C10—O10 | 1.213 (4) | C66—H66 | 0.9300 |
C10—O11 | 1.323 (5) | C91—C96 | 1.395 (5) |
C10—C92 | 1.502 (5) | C91—C92 | 1.400 (5) |
C12—O11 | 1.448 (5) | C92—C93 | 1.398 (5) |
C12—H12A | 0.9600 | C93—C94 | 1.384 (6) |
C12—H12B | 0.9600 | C93—H93 | 0.9300 |
C12—H12C | 0.9600 | C94—C95 | 1.381 (6) |
C51—C56 | 1.390 (5) | C94—H94 | 0.9300 |
C51—C52 | 1.404 (5) | C95—C96 | 1.382 (6) |
C52—C53 | 1.386 (5) | C95—H95 | 0.9300 |
C52—H52 | 0.9300 | C96—H96 | 0.9300 |
C53—C54 | 1.385 (6) | N1—N2 | 1.331 (4) |
C53—H53 | 0.9300 | N7—S8 | 1.636 (3) |
C54—C55 | 1.379 (6) | N7—H7 | 0.90 (5) |
C54—H54 | 0.9300 | O1—S8 | 1.425 (3) |
C55—C56 | 1.389 (5) | O2—S8 | 1.434 (3) |
| | | |
N4—C3—N2 | 125.7 (3) | C63—C62—H62 | 119.9 |
N4—C3—N7 | 118.7 (3) | C61—C62—H62 | 119.9 |
N2—C3—N7 | 115.6 (3) | C64—C63—C62 | 120.5 (3) |
N4—C5—C6 | 119.3 (3) | C64—C63—H63 | 119.7 |
N4—C5—C51 | 114.8 (3) | C62—C63—H63 | 119.7 |
C6—C5—C51 | 125.9 (3) | C65—C64—C63 | 119.7 (4) |
N1—C6—C5 | 119.0 (3) | C65—C64—H64 | 120.2 |
N1—C6—C61 | 114.4 (3) | C63—C64—H64 | 120.2 |
C5—C6—C61 | 126.6 (3) | C66—C65—C64 | 120.3 (4) |
C91—C9—S8 | 112.3 (2) | C66—C65—H65 | 119.9 |
C91—C9—H9A | 109.1 | C64—C65—H65 | 119.9 |
S8—C9—H9A | 109.1 | C65—C66—C61 | 120.9 (3) |
C91—C9—H9B | 109.1 | C65—C66—H66 | 119.6 |
S8—C9—H9B | 109.1 | C61—C66—H66 | 119.6 |
H9A—C9—H9B | 107.9 | C96—C91—C92 | 118.3 (3) |
O10—C10—O11 | 122.9 (3) | C96—C91—C9 | 117.2 (3) |
O10—C10—C92 | 124.9 (3) | C92—C91—C9 | 124.4 (3) |
O11—C10—C92 | 112.2 (3) | C93—C92—C91 | 120.1 (3) |
O11—C12—H12A | 109.5 | C93—C92—C10 | 118.2 (3) |
O11—C12—H12B | 109.5 | C91—C92—C10 | 121.6 (3) |
H12A—C12—H12B | 109.5 | C94—C93—C92 | 119.9 (4) |
O11—C12—H12C | 109.5 | C94—C93—H93 | 120.1 |
H12A—C12—H12C | 109.5 | C92—C93—H93 | 120.1 |
H12B—C12—H12C | 109.5 | C95—C94—C93 | 120.6 (4) |
C56—C51—C52 | 119.4 (3) | C95—C94—H94 | 119.7 |
C56—C51—C5 | 122.4 (3) | C93—C94—H94 | 119.7 |
C52—C51—C5 | 118.0 (3) | C94—C95—C96 | 119.4 (4) |
C53—C52—C51 | 119.8 (4) | C94—C95—H95 | 120.3 |
C53—C52—H52 | 120.1 | C96—C95—H95 | 120.3 |
C51—C52—H52 | 120.1 | C95—C96—C91 | 121.6 (4) |
C54—C53—C52 | 120.3 (4) | C95—C96—H96 | 119.2 |
C54—C53—H53 | 119.8 | C91—C96—H96 | 119.2 |
C52—C53—H53 | 119.8 | N2—N1—C6 | 121.7 (3) |
C55—C54—C53 | 120.0 (3) | N1—N2—C3 | 116.7 (3) |
C55—C54—H54 | 120.0 | C5—N4—C3 | 117.5 (3) |
C53—C54—H54 | 120.0 | C3—N7—S8 | 126.4 (3) |
C54—C55—C56 | 120.4 (4) | C3—N7—H7 | 116 (3) |
C54—C55—H55 | 119.8 | S8—N7—H7 | 117 (3) |
C56—C55—H55 | 119.8 | C10—O11—C12 | 114.8 (3) |
C55—C56—C51 | 120.0 (4) | O1—S8—O2 | 118.97 (18) |
C55—C56—H56 | 120.0 | O1—S8—N7 | 109.51 (16) |
C51—C56—H56 | 120.0 | O2—S8—N7 | 104.40 (16) |
C62—C61—C66 | 118.5 (3) | O1—S8—C9 | 108.95 (17) |
C62—C61—C6 | 122.7 (3) | O2—S8—C9 | 110.58 (17) |
C66—C61—C6 | 118.8 (3) | N7—S8—C9 | 103.20 (16) |
C63—C62—C61 | 120.1 (3) | | |
| | | |
N4—C5—C6—N1 | 2.4 (5) | C96—C91—C92—C10 | 178.8 (3) |
C51—C5—C6—N1 | −177.1 (3) | C9—C91—C92—C10 | 1.1 (5) |
N4—C5—C6—C61 | −177.2 (3) | O10—C10—C92—C93 | −167.7 (4) |
C51—C5—C6—C61 | 3.3 (5) | O11—C10—C92—C93 | 12.3 (5) |
N4—C5—C51—C56 | −136.7 (4) | O10—C10—C92—C91 | 12.6 (6) |
C6—C5—C51—C56 | 42.8 (5) | O11—C10—C92—C91 | −167.4 (3) |
N4—C5—C51—C52 | 37.7 (5) | C91—C92—C93—C94 | −0.2 (6) |
C6—C5—C51—C52 | −142.8 (4) | C10—C92—C93—C94 | −179.9 (3) |
C56—C51—C52—C53 | −2.5 (6) | C92—C93—C94—C95 | 0.7 (6) |
C5—C51—C52—C53 | −177.1 (4) | C93—C94—C95—C96 | −0.1 (6) |
C51—C52—C53—C54 | 2.4 (7) | C94—C95—C96—C91 | −1.0 (6) |
C52—C53—C54—C55 | −1.3 (7) | C92—C91—C96—C95 | 1.5 (6) |
C53—C54—C55—C56 | 0.4 (6) | C9—C91—C96—C95 | 179.4 (3) |
C54—C55—C56—C51 | −0.5 (6) | C5—C6—N1—N2 | 0.1 (5) |
C52—C51—C56—C55 | 1.6 (6) | C61—C6—N1—N2 | 179.7 (3) |
C5—C51—C56—C55 | 175.9 (3) | C6—N1—N2—C3 | −2.3 (5) |
N1—C6—C61—C62 | −135.4 (3) | N4—C3—N2—N1 | 2.2 (5) |
C5—C6—C61—C62 | 44.2 (5) | N7—C3—N2—N1 | 179.6 (3) |
N1—C6—C61—C66 | 42.4 (4) | C6—C5—N4—C3 | −2.5 (5) |
C5—C6—C61—C66 | −138.0 (3) | C51—C5—N4—C3 | 177.1 (3) |
C66—C61—C62—C63 | 1.3 (5) | N2—C3—N4—C5 | 0.2 (5) |
C6—C61—C62—C63 | 179.1 (3) | N7—C3—N4—C5 | −177.1 (3) |
C61—C62—C63—C64 | 1.2 (5) | N4—C3—N7—S8 | −5.3 (5) |
C62—C63—C64—C65 | −1.7 (6) | N2—C3—N7—S8 | 177.1 (3) |
C63—C64—C65—C66 | −0.2 (6) | O10—C10—O11—C12 | −1.3 (5) |
C64—C65—C66—C61 | 2.7 (6) | C92—C10—O11—C12 | 178.6 (3) |
C62—C61—C66—C65 | −3.2 (5) | C3—N7—S8—O1 | −56.5 (3) |
C6—C61—C66—C65 | 178.9 (3) | C3—N7—S8—O2 | 175.0 (3) |
S8—C9—C91—C96 | 79.8 (3) | C3—N7—S8—C9 | 59.4 (3) |
S8—C9—C91—C92 | −102.5 (4) | C91—C9—S8—O1 | −64.9 (3) |
C96—C91—C92—C93 | −0.9 (5) | C91—C9—S8—O2 | 67.6 (3) |
C9—C91—C92—C93 | −178.6 (3) | C91—C9—S8—N7 | 178.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···N4 | 0.97 | 2.41 | 3.047 (4) | 123 |
C9—H9B···O10 | 0.97 | 2.14 | 2.825 (5) | 126 |
C93—H93···O11 | 0.93 | 2.34 | 2.678 (5) | 101 |
N7—H7···O10i | 0.90 (5) | 1.99 (5) | 2.893 (4) | 175 (4) |
C12—H12···N2i | 0.96 | 2.60 | 3.512 (5) | 159 |
C63—H63···O2ii | 0.93 | 2.54 | 3.360 (4) | 147 |
C95—H95···N1iii | 0.93 | 2.61 | 3.505 (5) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1, y, z. |
Selected bond lengths (Å) and torsion angles (°) topBond | 3a | 3b |
N1—N2 | 1.341 (6) | 1.340 (8) |
N2—C3 | 1.331 (4) | 1.342 (5) |
N4—C3 | 1.354 (8) | 1.329 (4) |
N4—C5 | 1.326 (7) | 1.439 (8) |
C5—C6 | 1.317 (8) | 1.328 (7) |
N1—C6 | 1.324 (4) | 1.424 (5) |
N7—C3 | 1.334 (4) | 1.381 (4) |
Torsion angle | | |
N2—C3—N7—S8 | -175.7 (5) | 177.1 (3) |
C3—N7—S8—C81 | 66.4 (6) | – |
N7—S8—C81—C82 | 75.5 (7) | – |
C3—N7—S8—C9 | – | 59.4 (3) |
N7—S8—C9—C91 | – | 178.8 (2) |
S8—C9—C91—C92 | – | -102.5 (4) |
O1—S8—N7—C3 | -50.7 (6) | -56.5 (3) |
O2—S8—C7—N3 | 179.8 (5) | 175.0 (3) |
N4—C5—C511—C52 | 27.3 (9) | 37.7 (5) |
N1—C6—C61—C62 | -119.5 (6) | -135.4 (3) |
C91—C92—C10—O11 | – | -167.4 (3) |
C92—C10—O11—C12 | – | 178.6 (3) |
C91—C92—C10—O10 | – | 12.6 (6) |
Relative energies ΔEZPE (kcal mol-1) and
tautomeric forms populations Pi (%) for 3a and 3b topCompound 3a | ΔEZPE (Pi) | | |
Tautomeric form | N2—H | N4—H | N7—H |
Gas phase | 4.83 (0.02) | 9.91 (0.00) | 0.00 (99.98) |
Chloroform, ε = 4.4113 | 1.45 (7.64) | 7.41 (0.00) | 0.00 (92.36) |
Ethanol, ε = 24.8520 | 0.25 (39.39) | 6.46 (0.00) | 0.00 (60.61) |
Water, ε = 78.3553 | 0.06 (47.31) | 6.27 (0.00) | 0.00 (52.69) |
| | | |
Compound 3b | ΔEZPE (Pi) | | |
Tautomeric form | N2—H | N4—H | N7—H |
Gas phase | 6.09 (0.00) | 10.54 (0.00) | 0.00 (100.00) |
Chloroform, ε = 4.4113 | 2.07 (2.77) | 7.84 (0.00) | 0.00 (97.23) |
Ethanol, ε = 24.8520 | 0.63 (25.39) | 6.71 (0.00) | 0.00 (74.61) |
Water, ε = 78.3553 | 0.37 (34.37) | 6.53 (0.00) | 0.00 (65.63) |
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