The crystal structures of the antimicrobial drug tinidazole [
TNZ; systematic name: 1-(2-ethylsulfonylethyl)-2-methyl-5-nitroimidazole, C
8H
13N
3O
4S] and the 1:1 cocrystal of
TNZ with the naturally occurring compound vanillic acid (
VA; systematic name: 4-hydroxy-3-methoxybenzoic acid, C
8H
8O
4), namely, the
TNZ–
VA cocrystal, were determined by single-crystal X-ray analysis at 100 K. The supramolecular structure of the
TNZ–
VA cocrystal is composed of a carboxylic acid dimer and an O—H
N(heterocycle) synthon in the form of layers made up of O—H
N and O—H
O hydrogen bonds. The layers are joined
via C—H
O hydrogen bonds, π–π stacking and C—H
π interactions. The energy framework analysis, together with interaction energy calculations using the DLPNO-CCSD(T) method, indicates that the
TNZ–
VA cocrystal inherits strong interactions from the
TNZ and
VA crystals, which accounts for the enhanced thermal stability and reduced dissolution rate. To the best of our knowledge, this is the first example of a cocrystal containing
TNZ.
Supporting information
CCDC references: 1976901; 1964729
For both structures, data collection: APEX3 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).
1-(2-Ethylsulfonylethyl)-2-methyl-5-nitroimidazole (TNZ)
top
Crystal data top
C8H13N3O4S | Dx = 1.523 Mg m−3 |
Mr = 247.27 | Melting point: 399 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8658 (7) Å | Cell parameters from 5399 reflections |
b = 5.4786 (3) Å | θ = 2.3–27.7° |
c = 16.7291 (9) Å | µ = 0.30 mm−1 |
β = 97.296 (2)° | T = 100 K |
V = 1078.72 (10) Å3 | Prism, colorless |
Z = 4 | 0.23 × 0.20 × 0.18 mm |
F(000) = 520 | |
Data collection top
Bruker APEX II CCD area detector diffractometer | 2491 independent reflections |
Radiation source: fine-focus sealed tube | 2233 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
phi and ω scans | θmax = 27.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015) | h = −15→15 |
Tmin = 0.678, Tmax = 0.746 | k = −7→5 |
9021 measured reflections | l = −21→21 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0346P)2 + 0.605P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2491 reflections | Δρmax = 0.43 e Å−3 |
147 parameters | Δρmin = −0.36 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.18385 (11) | 0.6154 (3) | 0.37337 (8) | 0.0164 (3) | |
C2 | 0.08810 (12) | 0.3127 (3) | 0.41070 (9) | 0.0206 (3) | |
H2 | 0.040670 | 0.172723 | 0.409400 | 0.025* | |
C3 | 0.13837 (11) | 0.4256 (3) | 0.47923 (8) | 0.0181 (3) | |
C4 | 0.23880 (12) | 0.7875 (3) | 0.32185 (8) | 0.0213 (3) | |
H4A | 0.320832 | 0.757079 | 0.328146 | 0.032* | |
H4B | 0.224598 | 0.955544 | 0.337991 | 0.032* | |
H4C | 0.207265 | 0.763610 | 0.265355 | 0.032* | |
C5 | 0.27293 (11) | 0.7923 (2) | 0.50549 (8) | 0.0161 (3) | |
H5A | 0.235540 | 0.843307 | 0.552434 | 0.019* | |
H5B | 0.286552 | 0.939841 | 0.473906 | 0.019* | |
C6 | 0.38598 (11) | 0.6673 (2) | 0.53444 (8) | 0.0146 (3) | |
H6A | 0.428646 | 0.643197 | 0.487893 | 0.018* | |
H6B | 0.370681 | 0.504307 | 0.556254 | 0.018* | |
C7 | 0.41331 (13) | 0.7879 (3) | 0.70109 (8) | 0.0215 (3) | |
H7A | 0.451262 | 0.899037 | 0.742774 | 0.026* | |
H7B | 0.331581 | 0.830563 | 0.692789 | 0.026* | |
C8 | 0.42595 (14) | 0.5268 (3) | 0.73203 (9) | 0.0274 (3) | |
H8A | 0.382826 | 0.416677 | 0.693351 | 0.041* | |
H8B | 0.396798 | 0.515085 | 0.784141 | 0.041* | |
H8C | 0.506375 | 0.480516 | 0.738516 | 0.041* | |
N1 | 0.19924 (9) | 0.6225 (2) | 0.45531 (6) | 0.0150 (2) | |
N2 | 0.11645 (10) | 0.4317 (2) | 0.34507 (7) | 0.0200 (3) | |
N3 | 0.12955 (10) | 0.3601 (2) | 0.55971 (7) | 0.0218 (3) | |
O1 | 0.07275 (11) | 0.1769 (2) | 0.57015 (7) | 0.0340 (3) | |
O2 | 0.17735 (10) | 0.4849 (2) | 0.61553 (6) | 0.0335 (3) | |
O3 | 0.45683 (9) | 1.09379 (19) | 0.58949 (6) | 0.0240 (2) | |
O4 | 0.58437 (8) | 0.7360 (2) | 0.61700 (6) | 0.0240 (2) | |
S1 | 0.47108 (3) | 0.83740 (6) | 0.60972 (2) | 0.01619 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0154 (6) | 0.0183 (7) | 0.0151 (6) | 0.0021 (5) | 0.0000 (5) | −0.0005 (5) |
C2 | 0.0187 (6) | 0.0200 (7) | 0.0229 (7) | −0.0032 (5) | 0.0019 (5) | −0.0002 (6) |
C3 | 0.0166 (6) | 0.0187 (7) | 0.0189 (6) | 0.0002 (5) | 0.0020 (5) | 0.0023 (5) |
C4 | 0.0251 (7) | 0.0215 (7) | 0.0173 (7) | −0.0036 (6) | 0.0027 (5) | 0.0010 (5) |
C5 | 0.0166 (6) | 0.0152 (6) | 0.0159 (6) | 0.0008 (5) | −0.0005 (5) | −0.0025 (5) |
C6 | 0.0150 (6) | 0.0142 (6) | 0.0141 (6) | 0.0005 (5) | −0.0003 (5) | −0.0024 (5) |
C7 | 0.0270 (7) | 0.0237 (7) | 0.0135 (6) | 0.0011 (6) | 0.0014 (5) | −0.0031 (5) |
C8 | 0.0368 (9) | 0.0280 (8) | 0.0169 (7) | 0.0001 (7) | 0.0013 (6) | 0.0029 (6) |
N1 | 0.0133 (5) | 0.0165 (6) | 0.0147 (5) | 0.0001 (4) | −0.0001 (4) | 0.0003 (4) |
N2 | 0.0193 (6) | 0.0212 (6) | 0.0189 (6) | −0.0019 (5) | 0.0004 (4) | −0.0014 (5) |
N3 | 0.0181 (6) | 0.0271 (7) | 0.0202 (6) | 0.0008 (5) | 0.0028 (5) | 0.0041 (5) |
O1 | 0.0429 (7) | 0.0295 (6) | 0.0311 (6) | −0.0101 (5) | 0.0104 (5) | 0.0083 (5) |
O2 | 0.0313 (6) | 0.0517 (8) | 0.0171 (5) | −0.0129 (6) | 0.0015 (4) | 0.0011 (5) |
O3 | 0.0324 (6) | 0.0156 (5) | 0.0233 (5) | −0.0031 (4) | 0.0010 (4) | −0.0012 (4) |
O4 | 0.0165 (5) | 0.0299 (6) | 0.0242 (5) | −0.0009 (4) | −0.0023 (4) | −0.0039 (4) |
S1 | 0.01731 (17) | 0.01577 (18) | 0.01475 (16) | −0.00152 (13) | −0.00083 (12) | −0.00202 (12) |
Geometric parameters (Å, º) top
C1—N2 | 1.3345 (18) | C6—S1 | 1.7753 (13) |
C1—N1 | 1.3603 (17) | C6—H6A | 0.9900 |
C1—C4 | 1.4830 (19) | C6—H6B | 0.9900 |
C2—N2 | 1.3553 (19) | C7—C8 | 1.522 (2) |
C2—C3 | 1.370 (2) | C7—S1 | 1.7736 (14) |
C2—H2 | 0.9500 | C7—H7A | 0.9900 |
C3—N1 | 1.3853 (18) | C7—H7B | 0.9900 |
C3—N3 | 1.4101 (18) | C8—H8A | 0.9800 |
C4—H4A | 0.9800 | C8—H8B | 0.9800 |
C4—H4B | 0.9800 | C8—H8C | 0.9800 |
C4—H4C | 0.9800 | N3—O1 | 1.2337 (17) |
C5—N1 | 1.4658 (17) | N3—O2 | 1.2355 (17) |
C5—C6 | 1.5292 (18) | O3—S1 | 1.4497 (11) |
C5—H5A | 0.9900 | O4—S1 | 1.4452 (10) |
C5—H5B | 0.9900 | | |
| | | |
N2—C1—N1 | 112.12 (12) | H6A—C6—H6B | 107.8 |
N2—C1—C4 | 124.15 (12) | C8—C7—S1 | 113.86 (10) |
N1—C1—C4 | 123.71 (12) | C8—C7—H7A | 108.8 |
N2—C2—C3 | 109.53 (13) | S1—C7—H7A | 108.8 |
N2—C2—H2 | 125.2 | C8—C7—H7B | 108.8 |
C3—C2—H2 | 125.2 | S1—C7—H7B | 108.8 |
C2—C3—N1 | 107.29 (12) | H7A—C7—H7B | 107.7 |
C2—C3—N3 | 127.36 (13) | C7—C8—H8A | 109.5 |
N1—C3—N3 | 125.35 (12) | C7—C8—H8B | 109.5 |
C1—C4—H4A | 109.5 | H8A—C8—H8B | 109.5 |
C1—C4—H4B | 109.5 | C7—C8—H8C | 109.5 |
H4A—C4—H4B | 109.5 | H8A—C8—H8C | 109.5 |
C1—C4—H4C | 109.5 | H8B—C8—H8C | 109.5 |
H4A—C4—H4C | 109.5 | C1—N1—C3 | 105.11 (11) |
H4B—C4—H4C | 109.5 | C1—N1—C5 | 126.09 (11) |
N1—C5—C6 | 109.41 (11) | C3—N1—C5 | 128.61 (11) |
N1—C5—H5A | 109.8 | C1—N2—C2 | 105.94 (12) |
C6—C5—H5A | 109.8 | O1—N3—O2 | 123.35 (13) |
N1—C5—H5B | 109.8 | O1—N3—C3 | 116.76 (13) |
C6—C5—H5B | 109.8 | O2—N3—C3 | 119.89 (13) |
H5A—C5—H5B | 108.2 | O4—S1—O3 | 118.14 (7) |
C5—C6—S1 | 112.74 (9) | O4—S1—C7 | 109.02 (7) |
C5—C6—H6A | 109.0 | O3—S1—C7 | 107.63 (7) |
S1—C6—H6A | 109.0 | O4—S1—C6 | 107.29 (6) |
C5—C6—H6B | 109.0 | O3—S1—C6 | 107.70 (6) |
S1—C6—H6B | 109.0 | C7—S1—C6 | 106.49 (7) |
| | | |
N2—C2—C3—N1 | 0.51 (16) | N1—C1—N2—C2 | −0.82 (16) |
N2—C2—C3—N3 | 179.45 (13) | C4—C1—N2—C2 | 177.31 (13) |
N1—C5—C6—S1 | −169.50 (9) | C3—C2—N2—C1 | 0.17 (16) |
N2—C1—N1—C3 | 1.12 (15) | C2—C3—N3—O1 | 2.1 (2) |
C4—C1—N1—C3 | −177.02 (13) | N1—C3—N3—O1 | −179.15 (13) |
N2—C1—N1—C5 | 176.50 (12) | C2—C3—N3—O2 | −177.75 (14) |
C4—C1—N1—C5 | −1.6 (2) | N1—C3—N3—O2 | 1.0 (2) |
C2—C3—N1—C1 | −0.96 (15) | C8—C7—S1—O4 | −48.58 (13) |
N3—C3—N1—C1 | −179.93 (13) | C8—C7—S1—O3 | −177.85 (11) |
C2—C3—N1—C5 | −176.18 (12) | C8—C7—S1—C6 | 66.88 (12) |
N3—C3—N1—C5 | 4.9 (2) | C5—C6—S1—O4 | −165.64 (9) |
C6—C5—N1—C1 | −98.36 (15) | C5—C6—S1—O3 | −37.48 (11) |
C6—C5—N1—C3 | 75.93 (16) | C5—C6—S1—C7 | 77.74 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2 | 0.98 | 2.64 | 3.331 (2) | 128 |
C2—H2···O1i | 0.95 | 2.39 | 3.3311 (19) | 171 |
C6—H6A···O3ii | 0.99 | 2.46 | 3.2362 (17) | 135 |
C6—H6B···O3iii | 0.99 | 2.50 | 3.3511 (17) | 143 |
C8—H8A···O3iii | 0.98 | 2.70 | 3.4161 (19) | 130 |
C7—H7A···N2iv | 0.99 | 2.60 | 3.5353 (19) | 157 |
C8—H8B···O1v | 0.98 | 2.58 | 3.4082 (19) | 143 |
C6—H6A···O4vi | 0.99 | 2.71 | 3.4133 (17) | 128 |
C5—H5A···O1vii | 0.99 | 2.70 | 3.4500 (18) | 133 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x, y−1, z; (iv) x+1/2, −y+3/2, z+1/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z. |
1-(2-Ethylsulfonylethyl)-2-methyl-5-nitroimidazole;
4-hydroxy-3-methoxybenzoic acid (TNZ-VA)
top
Crystal data top
C8H13N3O4S·C8H8O4 | F(000) = 872 |
Mr = 415.42 | Dx = 1.498 Mg m−3 |
Triclinic, P1 | Melting point: 404 K |
a = 11.1206 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.6519 (6) Å | Cell parameters from 9002 reflections |
c = 13.6042 (6) Å | θ = 2.4–27.5° |
α = 98.078 (1)° | µ = 0.23 mm−1 |
β = 97.793 (1)° | T = 100 K |
γ = 99.780 (1)° | Prism, yellow |
V = 1842.42 (15) Å3 | 0.57 × 0.35 × 0.25 mm |
Z = 4 | |
Data collection top
Bruker APEXII CCD area detector diffractometer | 8425 independent reflections |
Radiation source: fine-focus sealed tube | 7034 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
phi and ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015) | h = −14→14 |
Tmin = 0.678, Tmax = 0.746 | k = −14→16 |
16552 measured reflections | l = −16→17 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0476P)2 + 0.7942P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
8425 reflections | Δρmax = 0.39 e Å−3 |
511 parameters | Δρmin = −0.48 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.46056 (14) | 0.86128 (12) | 0.26200 (12) | 0.0181 (3) | |
C2 | −0.36794 (14) | 0.80378 (13) | 0.27192 (12) | 0.0196 (3) | |
H2 | −0.303525 | 0.815954 | 0.328133 | 0.024* | |
C3 | −0.48290 (14) | 0.73672 (13) | 0.12877 (12) | 0.0188 (3) | |
C4 | −0.52869 (16) | 0.67038 (14) | 0.02743 (13) | 0.0255 (4) | |
H4A | −0.519630 | 0.716963 | −0.023929 | 0.038* | |
H4B | −0.616105 | 0.637473 | 0.022657 | 0.038* | |
H4C | −0.480551 | 0.612898 | 0.016672 | 0.038* | |
C5 | −0.64659 (13) | 0.85083 (12) | 0.12261 (12) | 0.0172 (3) | |
H5A | −0.696638 | 0.872518 | 0.174146 | 0.021* | |
H5B | −0.697934 | 0.789346 | 0.073279 | 0.021* | |
C6 | −0.60737 (13) | 0.94607 (12) | 0.06971 (11) | 0.0165 (3) | |
H6A | −0.575349 | 0.918946 | 0.008476 | 0.020* | |
H6B | −0.538864 | 0.998278 | 0.114686 | 0.020* | |
C7 | −0.73585 (17) | 1.10524 (15) | 0.14532 (13) | 0.0283 (4) | |
H7A | −0.755094 | 1.063089 | 0.199162 | 0.034* | |
H7B | −0.655148 | 1.155129 | 0.169154 | 0.034* | |
C8 | −0.83651 (19) | 1.17061 (17) | 0.12190 (17) | 0.0411 (5) | |
H8A | −0.815246 | 1.214412 | 0.070539 | 0.062* | |
H8B | −0.843111 | 1.218652 | 0.183242 | 0.062* | |
H8C | −0.915777 | 1.120736 | 0.096896 | 0.062* | |
N1 | −0.53583 (11) | 0.81701 (10) | 0.17062 (10) | 0.0163 (3) | |
N2 | −0.38173 (12) | 0.72649 (11) | 0.18929 (10) | 0.0201 (3) | |
N3 | −0.47884 (12) | 0.94978 (11) | 0.33122 (10) | 0.0210 (3) | |
O1 | −0.39776 (11) | 0.98249 (10) | 0.40576 (9) | 0.0293 (3) | |
O2 | −0.57235 (11) | 0.98869 (10) | 0.31472 (9) | 0.0278 (3) | |
O3 | −0.84376 (10) | 0.93943 (9) | 0.00736 (9) | 0.0272 (3) | |
O4 | −0.68905 (12) | 1.07976 (11) | −0.03874 (10) | 0.0326 (3) | |
S1 | −0.72785 (3) | 1.01561 (3) | 0.03492 (3) | 0.01782 (10) | |
C9 | 0.01626 (14) | 0.47902 (12) | 0.29301 (12) | 0.0176 (3) | |
C10 | −0.01500 (14) | 0.43286 (12) | 0.19089 (12) | 0.0178 (3) | |
H10 | 0.026078 | 0.378217 | 0.163946 | 0.021* | |
C11 | −0.10512 (14) | 0.46637 (12) | 0.12932 (12) | 0.0180 (3) | |
C12 | −0.16802 (14) | 0.54533 (13) | 0.17106 (12) | 0.0201 (3) | |
C13 | −0.13652 (15) | 0.58994 (13) | 0.27226 (12) | 0.0224 (3) | |
H13 | −0.179388 | 0.642736 | 0.300050 | 0.027* | |
C14 | −0.04333 (14) | 0.55866 (13) | 0.33361 (12) | 0.0198 (3) | |
H14 | −0.020594 | 0.591259 | 0.402434 | 0.024* | |
C15 | 0.11253 (14) | 0.43973 (13) | 0.35574 (12) | 0.0196 (3) | |
C16 | −0.07432 (15) | 0.35336 (13) | −0.01673 (12) | 0.0213 (3) | |
H16A | 0.014440 | 0.384254 | −0.003279 | 0.032* | |
H16B | −0.102977 | 0.337225 | −0.089567 | 0.032* | |
H16C | −0.089379 | 0.286175 | 0.011607 | 0.032* | |
O5 | 0.15118 (11) | 0.35713 (10) | 0.32573 (9) | 0.0287 (3) | |
O6 | 0.15317 (11) | 0.49796 (10) | 0.44539 (8) | 0.0255 (3) | |
H6 | 0.218012 | 0.476315 | 0.474978 | 0.038* | |
O7 | −0.14007 (10) | 0.42987 (9) | 0.02857 (8) | 0.0210 (2) | |
O8 | −0.25695 (11) | 0.57457 (10) | 0.10785 (9) | 0.0292 (3) | |
H8 | −0.294480 | 0.621059 | 0.139295 | 0.044* | |
C17 | 0.94304 (16) | −0.07560 (14) | 0.59092 (13) | 0.0244 (4) | |
C18 | 0.85017 (16) | −0.01837 (15) | 0.59093 (14) | 0.0287 (4) | |
H18 | 0.776949 | −0.033059 | 0.542351 | 0.034* | |
C19 | 0.98849 (15) | 0.05546 (13) | 0.72037 (13) | 0.0218 (3) | |
C20 | 1.05196 (17) | 0.12934 (15) | 0.81456 (14) | 0.0297 (4) | |
H20A | 1.020283 | 0.197275 | 0.819536 | 0.044* | |
H20B | 1.141145 | 0.145242 | 0.813689 | 0.044* | |
H20C | 1.036305 | 0.094225 | 0.872592 | 0.044* | |
C21 | 1.15235 (14) | −0.05841 (13) | 0.70510 (13) | 0.0219 (3) | |
H21A | 1.208835 | 0.004903 | 0.748481 | 0.026* | |
H21B | 1.189875 | −0.078320 | 0.644839 | 0.026* | |
C22 | 1.13687 (14) | −0.15361 (13) | 0.76226 (12) | 0.0187 (3) | |
H22A | 1.073486 | −0.214209 | 0.721798 | 0.022* | |
H22B | 1.107962 | −0.131091 | 0.826266 | 0.022* | |
C23 | 1.27814 (15) | −0.30524 (13) | 0.68857 (12) | 0.0224 (3) | |
H23A | 1.204977 | −0.363532 | 0.684181 | 0.027* | |
H23B | 1.273367 | −0.277331 | 0.623995 | 0.027* | |
C24 | 1.39617 (18) | −0.35043 (16) | 0.70807 (15) | 0.0340 (4) | |
H24A | 1.468193 | −0.292072 | 0.713354 | 0.051* | |
H24B | 1.397172 | −0.408358 | 0.652373 | 0.051* | |
H24C | 1.399039 | −0.379924 | 0.771038 | 0.051* | |
N4 | 1.03218 (12) | −0.02863 (11) | 0.67403 (10) | 0.0204 (3) | |
N5 | 0.87873 (13) | 0.06310 (12) | 0.67142 (11) | 0.0261 (3) | |
N6 | 0.95208 (15) | −0.16613 (13) | 0.51980 (11) | 0.0317 (4) | |
O9 | 0.87115 (15) | −0.19110 (14) | 0.44492 (11) | 0.0552 (5) | |
O10 | 1.03764 (14) | −0.21426 (12) | 0.53472 (11) | 0.0448 (4) | |
O11 | 1.27991 (11) | −0.24272 (10) | 0.88032 (9) | 0.0270 (3) | |
O12 | 1.37899 (10) | −0.11068 (9) | 0.78510 (10) | 0.0280 (3) | |
S2 | 1.27955 (3) | −0.19896 (3) | 0.78827 (3) | 0.01716 (9) | |
C25 | 0.50219 (14) | 0.32744 (13) | 0.55299 (12) | 0.0195 (3) | |
C26 | 0.55642 (14) | 0.39283 (13) | 0.64589 (12) | 0.0189 (3) | |
H26 | 0.522721 | 0.453611 | 0.670389 | 0.023* | |
C27 | 0.65868 (14) | 0.36881 (12) | 0.70163 (12) | 0.0185 (3) | |
C28 | 0.70904 (14) | 0.27939 (13) | 0.66395 (12) | 0.0180 (3) | |
C29 | 0.65570 (15) | 0.21639 (13) | 0.57145 (12) | 0.0202 (3) | |
H29 | 0.690715 | 0.156907 | 0.545781 | 0.024* | |
C30 | 0.55186 (15) | 0.23925 (13) | 0.51603 (12) | 0.0210 (3) | |
H30 | 0.515016 | 0.194962 | 0.453315 | 0.025* | |
C31 | 0.38976 (15) | 0.35374 (13) | 0.49928 (12) | 0.0224 (3) | |
C32 | 0.66986 (16) | 0.51617 (14) | 0.83451 (13) | 0.0270 (4) | |
H32A | 0.680275 | 0.571157 | 0.790708 | 0.040* | |
H32B | 0.715997 | 0.546457 | 0.902031 | 0.040* | |
H32C | 0.581919 | 0.494700 | 0.838347 | 0.040* | |
O13 | 0.34422 (12) | 0.29145 (10) | 0.41124 (9) | 0.0306 (3) | |
H13A | 0.279267 | 0.318603 | 0.384668 | 0.046* | |
O14 | 0.34167 (12) | 0.42777 (11) | 0.53397 (9) | 0.0328 (3) | |
O15 | 0.71543 (11) | 0.42347 (9) | 0.79447 (9) | 0.0242 (3) | |
O16 | 0.80696 (10) | 0.25822 (9) | 0.72288 (8) | 0.0226 (2) | |
H16 | 0.831837 | 0.197997 | 0.697200 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0164 (7) | 0.0188 (7) | 0.0173 (7) | 0.0013 (6) | −0.0003 (6) | 0.0027 (6) |
C2 | 0.0182 (7) | 0.0213 (8) | 0.0189 (7) | 0.0043 (6) | −0.0012 (6) | 0.0051 (6) |
C3 | 0.0191 (7) | 0.0191 (7) | 0.0189 (7) | 0.0054 (6) | 0.0015 (6) | 0.0049 (6) |
C4 | 0.0292 (9) | 0.0252 (8) | 0.0207 (8) | 0.0107 (7) | −0.0036 (7) | −0.0002 (7) |
C5 | 0.0121 (6) | 0.0191 (7) | 0.0206 (7) | 0.0043 (6) | −0.0006 (6) | 0.0058 (6) |
C6 | 0.0128 (6) | 0.0189 (7) | 0.0180 (7) | 0.0042 (6) | 0.0008 (6) | 0.0034 (6) |
C7 | 0.0298 (9) | 0.0274 (9) | 0.0246 (9) | 0.0096 (7) | 0.0011 (7) | −0.0080 (7) |
C8 | 0.0375 (11) | 0.0366 (11) | 0.0460 (12) | 0.0203 (9) | 0.0002 (9) | −0.0140 (9) |
N1 | 0.0146 (6) | 0.0176 (6) | 0.0164 (6) | 0.0038 (5) | −0.0003 (5) | 0.0038 (5) |
N2 | 0.0202 (6) | 0.0213 (7) | 0.0185 (6) | 0.0060 (5) | −0.0014 (5) | 0.0047 (5) |
N3 | 0.0228 (7) | 0.0203 (7) | 0.0200 (7) | 0.0046 (5) | 0.0031 (5) | 0.0029 (5) |
O1 | 0.0299 (6) | 0.0308 (7) | 0.0214 (6) | 0.0042 (5) | −0.0046 (5) | −0.0048 (5) |
O2 | 0.0258 (6) | 0.0288 (6) | 0.0298 (6) | 0.0120 (5) | 0.0039 (5) | 0.0012 (5) |
O3 | 0.0175 (5) | 0.0254 (6) | 0.0343 (7) | 0.0068 (5) | −0.0045 (5) | −0.0044 (5) |
O4 | 0.0369 (7) | 0.0386 (7) | 0.0329 (7) | 0.0200 (6) | 0.0117 (6) | 0.0203 (6) |
S1 | 0.01769 (18) | 0.01863 (19) | 0.01722 (19) | 0.00720 (14) | 0.00008 (14) | 0.00144 (14) |
C9 | 0.0158 (7) | 0.0174 (7) | 0.0184 (7) | 0.0025 (6) | 0.0000 (6) | 0.0026 (6) |
C10 | 0.0167 (7) | 0.0169 (7) | 0.0197 (8) | 0.0046 (6) | 0.0020 (6) | 0.0020 (6) |
C11 | 0.0183 (7) | 0.0172 (7) | 0.0171 (7) | 0.0028 (6) | 0.0004 (6) | 0.0012 (6) |
C12 | 0.0192 (7) | 0.0199 (8) | 0.0210 (8) | 0.0068 (6) | −0.0005 (6) | 0.0032 (6) |
C13 | 0.0239 (8) | 0.0210 (8) | 0.0225 (8) | 0.0096 (6) | 0.0018 (6) | 0.0003 (6) |
C14 | 0.0207 (7) | 0.0208 (8) | 0.0164 (7) | 0.0044 (6) | 0.0005 (6) | −0.0002 (6) |
C15 | 0.0183 (7) | 0.0218 (8) | 0.0174 (7) | 0.0032 (6) | 0.0008 (6) | 0.0020 (6) |
C16 | 0.0228 (8) | 0.0213 (8) | 0.0185 (8) | 0.0053 (6) | 0.0026 (6) | −0.0014 (6) |
O5 | 0.0311 (6) | 0.0300 (7) | 0.0228 (6) | 0.0164 (5) | −0.0073 (5) | −0.0040 (5) |
O6 | 0.0249 (6) | 0.0306 (6) | 0.0189 (6) | 0.0130 (5) | −0.0058 (5) | −0.0031 (5) |
O7 | 0.0236 (6) | 0.0232 (6) | 0.0152 (5) | 0.0084 (5) | −0.0019 (4) | 0.0002 (4) |
O8 | 0.0323 (7) | 0.0338 (7) | 0.0217 (6) | 0.0213 (5) | −0.0063 (5) | −0.0021 (5) |
C17 | 0.0249 (8) | 0.0266 (9) | 0.0204 (8) | 0.0092 (7) | −0.0033 (7) | 0.0008 (7) |
C18 | 0.0266 (9) | 0.0312 (9) | 0.0264 (9) | 0.0116 (7) | −0.0063 (7) | 0.0009 (7) |
C19 | 0.0214 (8) | 0.0208 (8) | 0.0244 (8) | 0.0080 (6) | 0.0011 (6) | 0.0050 (7) |
C20 | 0.0270 (9) | 0.0272 (9) | 0.0315 (10) | 0.0092 (7) | −0.0036 (7) | −0.0030 (8) |
C21 | 0.0167 (7) | 0.0218 (8) | 0.0283 (9) | 0.0074 (6) | 0.0005 (6) | 0.0065 (7) |
C22 | 0.0148 (7) | 0.0210 (8) | 0.0204 (8) | 0.0053 (6) | 0.0003 (6) | 0.0040 (6) |
C23 | 0.0227 (8) | 0.0218 (8) | 0.0201 (8) | 0.0050 (6) | 0.0012 (6) | −0.0039 (6) |
C24 | 0.0344 (10) | 0.0325 (10) | 0.0347 (10) | 0.0177 (8) | 0.0032 (8) | −0.0070 (8) |
N4 | 0.0183 (6) | 0.0210 (7) | 0.0215 (7) | 0.0075 (5) | −0.0019 (5) | 0.0026 (5) |
N5 | 0.0238 (7) | 0.0267 (7) | 0.0276 (8) | 0.0119 (6) | −0.0025 (6) | 0.0022 (6) |
N6 | 0.0347 (8) | 0.0355 (9) | 0.0232 (7) | 0.0154 (7) | −0.0049 (6) | −0.0025 (7) |
O9 | 0.0505 (9) | 0.0680 (11) | 0.0361 (8) | 0.0292 (8) | −0.0209 (7) | −0.0233 (8) |
O10 | 0.0528 (9) | 0.0478 (9) | 0.0327 (8) | 0.0337 (7) | −0.0094 (7) | −0.0101 (7) |
O11 | 0.0317 (6) | 0.0328 (7) | 0.0186 (6) | 0.0145 (5) | −0.0004 (5) | 0.0056 (5) |
O12 | 0.0187 (6) | 0.0204 (6) | 0.0406 (7) | 0.0014 (5) | −0.0038 (5) | 0.0024 (5) |
S2 | 0.01659 (18) | 0.01639 (18) | 0.01694 (18) | 0.00511 (14) | −0.00258 (14) | 0.00034 (14) |
C25 | 0.0218 (8) | 0.0205 (8) | 0.0171 (7) | 0.0076 (6) | 0.0012 (6) | 0.0038 (6) |
C26 | 0.0202 (7) | 0.0173 (7) | 0.0201 (8) | 0.0066 (6) | 0.0021 (6) | 0.0032 (6) |
C27 | 0.0188 (7) | 0.0180 (7) | 0.0178 (7) | 0.0026 (6) | 0.0017 (6) | 0.0028 (6) |
C28 | 0.0164 (7) | 0.0212 (8) | 0.0182 (7) | 0.0053 (6) | 0.0033 (6) | 0.0070 (6) |
C29 | 0.0238 (8) | 0.0212 (8) | 0.0185 (7) | 0.0105 (6) | 0.0057 (6) | 0.0038 (6) |
C30 | 0.0244 (8) | 0.0233 (8) | 0.0156 (7) | 0.0074 (6) | 0.0018 (6) | 0.0023 (6) |
C31 | 0.0256 (8) | 0.0229 (8) | 0.0185 (8) | 0.0084 (6) | −0.0006 (6) | 0.0020 (6) |
C32 | 0.0294 (9) | 0.0227 (8) | 0.0258 (9) | 0.0068 (7) | 0.0000 (7) | −0.0040 (7) |
O13 | 0.0322 (7) | 0.0367 (7) | 0.0213 (6) | 0.0194 (6) | −0.0076 (5) | −0.0051 (5) |
O14 | 0.0341 (7) | 0.0365 (7) | 0.0256 (6) | 0.0216 (6) | −0.0094 (5) | −0.0064 (5) |
O15 | 0.0238 (6) | 0.0242 (6) | 0.0214 (6) | 0.0084 (5) | −0.0045 (5) | −0.0035 (5) |
O16 | 0.0209 (6) | 0.0256 (6) | 0.0221 (6) | 0.0110 (5) | −0.0016 (5) | 0.0033 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.361 (2) | C17—C18 | 1.358 (2) |
C1—N1 | 1.3865 (19) | C17—N4 | 1.386 (2) |
C1—N3 | 1.419 (2) | C17—N6 | 1.419 (2) |
C2—N2 | 1.355 (2) | C18—N5 | 1.356 (2) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—N2 | 1.3374 (19) | C19—N5 | 1.334 (2) |
C3—N1 | 1.3542 (19) | C19—N4 | 1.355 (2) |
C3—C4 | 1.484 (2) | C19—C20 | 1.486 (2) |
C4—H4A | 0.9800 | C20—H20A | 0.9800 |
C4—H4B | 0.9800 | C20—H20B | 0.9800 |
C4—H4C | 0.9800 | C20—H20C | 0.9800 |
C5—N1 | 1.4719 (18) | C21—N4 | 1.4728 (19) |
C5—C6 | 1.520 (2) | C21—C22 | 1.521 (2) |
C5—H5A | 0.9900 | C21—H21A | 0.9900 |
C5—H5B | 0.9900 | C21—H21B | 0.9900 |
C6—S1 | 1.7716 (15) | C22—S2 | 1.7850 (15) |
C6—H6A | 0.9900 | C22—H22A | 0.9900 |
C6—H6B | 0.9900 | C22—H22B | 0.9900 |
C7—C8 | 1.527 (2) | C23—C24 | 1.524 (2) |
C7—S1 | 1.7724 (17) | C23—S2 | 1.7671 (16) |
C7—H7A | 0.9900 | C23—H23A | 0.9900 |
C7—H7B | 0.9900 | C23—H23B | 0.9900 |
C8—H8A | 0.9800 | C24—H24A | 0.9800 |
C8—H8B | 0.9800 | C24—H24B | 0.9800 |
C8—H8C | 0.9800 | C24—H24C | 0.9800 |
N3—O2 | 1.2311 (18) | N6—O10 | 1.2234 (19) |
N3—O1 | 1.2329 (17) | N6—O9 | 1.2295 (19) |
O3—S1 | 1.4410 (12) | O11—S2 | 1.4385 (12) |
O4—S1 | 1.4408 (13) | O12—S2 | 1.4418 (12) |
C9—C14 | 1.389 (2) | C25—C30 | 1.389 (2) |
C9—C10 | 1.401 (2) | C25—C26 | 1.406 (2) |
C9—C15 | 1.474 (2) | C25—C31 | 1.473 (2) |
C10—C11 | 1.379 (2) | C26—C27 | 1.382 (2) |
C10—H10 | 0.9500 | C26—H26 | 0.9500 |
C11—O7 | 1.3636 (18) | C27—O15 | 1.3645 (18) |
C11—C12 | 1.412 (2) | C27—C28 | 1.409 (2) |
C12—O8 | 1.3555 (18) | C28—O16 | 1.3502 (18) |
C12—C13 | 1.386 (2) | C28—C29 | 1.388 (2) |
C13—C14 | 1.387 (2) | C29—C30 | 1.387 (2) |
C13—H13 | 0.9500 | C29—H29 | 0.9500 |
C14—H14 | 0.9500 | C30—H30 | 0.9500 |
C15—O5 | 1.2344 (19) | C31—O14 | 1.225 (2) |
C15—O6 | 1.3113 (19) | C31—O13 | 1.3217 (19) |
C16—O7 | 1.4306 (18) | C32—O15 | 1.4235 (19) |
C16—H16A | 0.9800 | C32—H32A | 0.9800 |
C16—H16B | 0.9800 | C32—H32B | 0.9800 |
C16—H16C | 0.9800 | C32—H32C | 0.9800 |
O6—H6 | 0.8811 | O13—H13A | 0.9048 |
O8—H8 | 0.8742 | O16—H16 | 0.8956 |
| | | |
C2—C1—N1 | 107.11 (13) | C18—C17—N4 | 107.55 (15) |
C2—C1—N3 | 127.29 (14) | C18—C17—N6 | 127.90 (15) |
N1—C1—N3 | 125.59 (13) | N4—C17—N6 | 124.54 (14) |
N2—C2—C1 | 109.55 (13) | N5—C18—C17 | 109.08 (15) |
N2—C2—H2 | 125.2 | N5—C18—H18 | 125.5 |
C1—C2—H2 | 125.2 | C17—C18—H18 | 125.5 |
N2—C3—N1 | 111.38 (13) | N5—C19—N4 | 111.28 (14) |
N2—C3—C4 | 124.02 (14) | N5—C19—C20 | 123.58 (15) |
N1—C3—C4 | 124.57 (14) | N4—C19—C20 | 125.14 (14) |
C3—C4—H4A | 109.5 | C19—C20—H20A | 109.5 |
C3—C4—H4B | 109.5 | C19—C20—H20B | 109.5 |
H4A—C4—H4B | 109.5 | H20A—C20—H20B | 109.5 |
C3—C4—H4C | 109.5 | C19—C20—H20C | 109.5 |
H4A—C4—H4C | 109.5 | H20A—C20—H20C | 109.5 |
H4B—C4—H4C | 109.5 | H20B—C20—H20C | 109.5 |
N1—C5—C6 | 109.35 (12) | N4—C21—C22 | 110.82 (13) |
N1—C5—H5A | 109.8 | N4—C21—H21A | 109.5 |
C6—C5—H5A | 109.8 | C22—C21—H21A | 109.5 |
N1—C5—H5B | 109.8 | N4—C21—H21B | 109.5 |
C6—C5—H5B | 109.8 | C22—C21—H21B | 109.5 |
H5A—C5—H5B | 108.3 | H21A—C21—H21B | 108.1 |
C5—C6—S1 | 113.92 (10) | C21—C22—S2 | 110.80 (11) |
C5—C6—H6A | 108.8 | C21—C22—H22A | 109.5 |
S1—C6—H6A | 108.8 | S2—C22—H22A | 109.5 |
C5—C6—H6B | 108.8 | C21—C22—H22B | 109.5 |
S1—C6—H6B | 108.8 | S2—C22—H22B | 109.5 |
H6A—C6—H6B | 107.7 | H22A—C22—H22B | 108.1 |
C8—C7—S1 | 109.14 (13) | C24—C23—S2 | 108.84 (11) |
C8—C7—H7A | 109.9 | C24—C23—H23A | 109.9 |
S1—C7—H7A | 109.9 | S2—C23—H23A | 109.9 |
C8—C7—H7B | 109.9 | C24—C23—H23B | 109.9 |
S1—C7—H7B | 109.9 | S2—C23—H23B | 109.9 |
H7A—C7—H7B | 108.3 | H23A—C23—H23B | 108.3 |
C7—C8—H8A | 109.5 | C23—C24—H24A | 109.5 |
C7—C8—H8B | 109.5 | C23—C24—H24B | 109.5 |
H8A—C8—H8B | 109.5 | H24A—C24—H24B | 109.5 |
C7—C8—H8C | 109.5 | C23—C24—H24C | 109.5 |
H8A—C8—H8C | 109.5 | H24A—C24—H24C | 109.5 |
H8B—C8—H8C | 109.5 | H24B—C24—H24C | 109.5 |
C3—N1—C1 | 105.70 (12) | C19—N4—C17 | 105.48 (13) |
C3—N1—C5 | 125.06 (13) | C19—N4—C21 | 125.99 (13) |
C1—N1—C5 | 129.15 (13) | C17—N4—C21 | 128.48 (14) |
C3—N2—C2 | 106.23 (13) | C19—N5—C18 | 106.61 (14) |
O2—N3—O1 | 124.08 (14) | O10—N6—O9 | 123.71 (15) |
O2—N3—C1 | 119.59 (13) | O10—N6—C17 | 119.87 (14) |
O1—N3—C1 | 116.33 (13) | O9—N6—C17 | 116.42 (15) |
O4—S1—O3 | 117.56 (8) | O11—S2—O12 | 117.34 (8) |
O4—S1—C6 | 107.18 (7) | O11—S2—C23 | 108.82 (8) |
O3—S1—C6 | 109.72 (7) | O12—S2—C23 | 108.23 (8) |
O4—S1—C7 | 108.38 (9) | O11—S2—C22 | 107.58 (7) |
O3—S1—C7 | 107.94 (8) | O12—S2—C22 | 108.17 (7) |
C6—S1—C7 | 105.41 (8) | C23—S2—C22 | 106.16 (8) |
C14—C9—C10 | 120.52 (14) | C30—C25—C26 | 120.32 (14) |
C14—C9—C15 | 121.30 (14) | C30—C25—C31 | 121.99 (14) |
C10—C9—C15 | 118.17 (14) | C26—C25—C31 | 117.65 (14) |
C11—C10—C9 | 120.32 (14) | C27—C26—C25 | 120.07 (14) |
C11—C10—H10 | 119.8 | C27—C26—H26 | 120.0 |
C9—C10—H10 | 119.8 | C25—C26—H26 | 120.0 |
O7—C11—C10 | 125.34 (14) | O15—C27—C26 | 125.13 (14) |
O7—C11—C12 | 115.45 (13) | O15—C27—C28 | 115.31 (13) |
C10—C11—C12 | 119.21 (14) | C26—C27—C28 | 119.52 (14) |
O8—C12—C13 | 123.13 (14) | O16—C28—C29 | 123.28 (14) |
O8—C12—C11 | 117.04 (14) | O16—C28—C27 | 116.85 (14) |
C13—C12—C11 | 119.82 (14) | C29—C28—C27 | 119.85 (14) |
C12—C13—C14 | 121.00 (15) | C30—C29—C28 | 120.78 (14) |
C12—C13—H13 | 119.5 | C30—C29—H29 | 119.6 |
C14—C13—H13 | 119.5 | C28—C29—H29 | 119.6 |
C13—C14—C9 | 119.08 (14) | C29—C30—C25 | 119.45 (15) |
C13—C14—H14 | 120.5 | C29—C30—H30 | 120.3 |
C9—C14—H14 | 120.5 | C25—C30—H30 | 120.3 |
O5—C15—O6 | 122.59 (14) | O14—C31—O13 | 122.42 (15) |
O5—C15—C9 | 121.99 (14) | O14—C31—C25 | 122.36 (15) |
O6—C15—C9 | 115.42 (13) | O13—C31—C25 | 115.21 (14) |
O7—C16—H16A | 109.5 | O15—C32—H32A | 109.5 |
O7—C16—H16B | 109.5 | O15—C32—H32B | 109.5 |
H16A—C16—H16B | 109.5 | H32A—C32—H32B | 109.5 |
O7—C16—H16C | 109.5 | O15—C32—H32C | 109.5 |
H16A—C16—H16C | 109.5 | H32A—C32—H32C | 109.5 |
H16B—C16—H16C | 109.5 | H32B—C32—H32C | 109.5 |
C15—O6—H6 | 110.6 | C31—O13—H13A | 106.3 |
C11—O7—C16 | 116.75 (12) | C27—O15—C32 | 117.33 (12) |
C12—O8—H8 | 112.1 | C28—O16—H16 | 113.0 |
| | | |
N1—C1—C2—N2 | 0.99 (18) | N4—C17—C18—N5 | 0.1 (2) |
N3—C1—C2—N2 | −179.26 (15) | N6—C17—C18—N5 | −178.96 (18) |
N1—C5—C6—S1 | −165.63 (10) | N4—C21—C22—S2 | 173.86 (11) |
N2—C3—N1—C1 | 1.63 (18) | N5—C19—N4—C17 | 0.1 (2) |
C4—C3—N1—C1 | −176.71 (15) | C20—C19—N4—C17 | 179.02 (17) |
N2—C3—N1—C5 | 178.45 (13) | N5—C19—N4—C21 | 177.60 (15) |
C4—C3—N1—C5 | 0.1 (2) | C20—C19—N4—C21 | −3.5 (3) |
C2—C1—N1—C3 | −1.56 (17) | C18—C17—N4—C19 | −0.1 (2) |
N3—C1—N1—C3 | 178.68 (15) | N6—C17—N4—C19 | 179.01 (17) |
C2—C1—N1—C5 | −178.21 (14) | C18—C17—N4—C21 | −177.57 (16) |
N3—C1—N1—C5 | 2.0 (3) | N6—C17—N4—C21 | 1.6 (3) |
C6—C5—N1—C3 | −94.54 (17) | C22—C21—N4—C19 | 100.69 (18) |
C6—C5—N1—C1 | 81.51 (19) | C22—C21—N4—C17 | −82.4 (2) |
N1—C3—N2—C2 | −1.04 (18) | N4—C19—N5—C18 | 0.0 (2) |
C4—C3—N2—C2 | 177.31 (16) | C20—C19—N5—C18 | −178.95 (17) |
C1—C2—N2—C3 | 0.00 (19) | C17—C18—N5—C19 | −0.1 (2) |
C2—C1—N3—O2 | −174.86 (16) | C18—C17—N6—O10 | −174.3 (2) |
N1—C1—N3—O2 | 4.8 (2) | N4—C17—N6—O10 | 6.8 (3) |
C2—C1—N3—O1 | 4.8 (2) | C18—C17—N6—O9 | 6.1 (3) |
N1—C1—N3—O1 | −175.50 (15) | N4—C17—N6—O9 | −172.85 (19) |
C5—C6—S1—O4 | −163.08 (11) | C24—C23—S2—O11 | −62.57 (15) |
C5—C6—S1—O3 | −34.38 (13) | C24—C23—S2—O12 | 65.97 (15) |
C5—C6—S1—C7 | 81.61 (13) | C24—C23—S2—C22 | −178.11 (13) |
C8—C7—S1—O4 | 64.52 (16) | C21—C22—S2—O11 | 150.14 (11) |
C8—C7—S1—O3 | −63.80 (16) | C21—C22—S2—O12 | 22.48 (14) |
C8—C7—S1—C6 | 179.01 (14) | C21—C22—S2—C23 | −93.49 (13) |
C14—C9—C10—C11 | 0.3 (2) | C30—C25—C26—C27 | −0.8 (2) |
C15—C9—C10—C11 | 179.54 (15) | C31—C25—C26—C27 | 177.05 (15) |
C9—C10—C11—O7 | 177.72 (14) | C25—C26—C27—O15 | −176.95 (15) |
C9—C10—C11—C12 | −1.9 (2) | C25—C26—C27—C28 | 0.9 (2) |
O7—C11—C12—O8 | 1.2 (2) | O15—C27—C28—O16 | −0.3 (2) |
C10—C11—C12—O8 | −179.13 (15) | C26—C27—C28—O16 | −178.35 (14) |
O7—C11—C12—C13 | −178.05 (14) | O15—C27—C28—C29 | 178.07 (14) |
C10—C11—C12—C13 | 1.6 (2) | C26—C27—C28—C29 | 0.0 (2) |
O8—C12—C13—C14 | −178.90 (16) | O16—C28—C29—C30 | 177.21 (15) |
C11—C12—C13—C14 | 0.3 (3) | C27—C28—C29—C30 | −1.0 (2) |
C12—C13—C14—C9 | −1.9 (3) | C28—C29—C30—C25 | 1.1 (3) |
C10—C9—C14—C13 | 1.6 (2) | C26—C25—C30—C29 | −0.2 (2) |
C15—C9—C14—C13 | −177.60 (15) | C31—C25—C30—C29 | −177.97 (16) |
C14—C9—C15—O5 | 167.39 (16) | C30—C25—C31—O14 | 176.00 (17) |
C10—C9—C15—O5 | −11.9 (2) | C26—C25—C31—O14 | −1.8 (3) |
C14—C9—C15—O6 | −12.1 (2) | C30—C25—C31—O13 | −3.7 (2) |
C10—C9—C15—O6 | 168.64 (14) | C26—C25—C31—O13 | 178.44 (15) |
C10—C11—O7—C16 | −2.3 (2) | C26—C27—O15—C32 | −3.7 (2) |
C12—C11—O7—C16 | 177.37 (14) | C28—C27—O15—C32 | 178.38 (14) |
Intermolecular interaction energy values for the TNZ crystal topR is the distance (Å) between molecular centroids
(mean atomic position).
Each line corresponds to different intermolecular interactions. |
Symmerty code | R | Eele | Epol | Edis | Erep | Etot |
-x, -y, -z | 6.68 | -49.4 | -12.9 | -33.7 | 37.3 | -68.1 |
-x, -y, -z | 5.43 | -16.7 | -9.4 | -34.2 | 24.0 | -39.6 |
x, y, z | 5.48 | -11.3 | -5.7 | -33.4 | 22.8 | -31.1 |
-x, -y, -z | 7.00 | -5.5 | -1.9 | -31.4 | 18.2 | -23.4 |
x + 1/2, -y + 1/2, z + 1/2 | 9.72 | -11.0 | -2.8 | -14.9 | 13.2 | -18.5 |
-x + 1/2, y + 1/2, -z + 1/2 | 7.82 | -6.5 | -2.0 | -12.4 | 8.1 | -14.1 |
-x, -y, -z | 9.69 | -13.6 | -1.9 | -7.9 | 17.2 | -12.0 |
-x + 1/2, y + 1/2, -z + 1/2 | 9.91 | -1.0 | -1.3 | -9.6 | 5.5 | -7.0 |
x + 1/2, -y + 1/2, z + 1/2 | 10.46 | -0.8 | -0.5 | -6.3 | 3.0 | -4.9 |
Geometric parameters of π–π stacking interactions in the TNZ–VA cocrystal topCg1, Cg2, Cg3 and Cg4 are the centroids of the
N1/C1/C2/N2/C3, N4/C17/C18/N5/C19, C9–C14 and C25–C30, respectively.
Cg···Cg, α and β denote the centroid–centroid separation,
the dihedral angle between the ring planes and the offset angle, respectively. |
First ring | Second ring | Cg···Cg (Å) | α (°) | β (°) |
Cg1 | Cg4iii | 3.5159 (10) | 4.41 (9) | 22.4 |
Cg2 | Cg2ix | 4.4661 (11) | 0 | 37.9 |
Cg3 | Cg4iv | 5.3651 (10) | 14.85 (8) | 45.4 |
Cg1 | Cg2iv | 5.7685 (10) | 7.89 (10) | 54.0 |
Symmetry codes: (iii) -x, -y + 1, -z + 1;
(iv) -x + 1, -y + 1, -z + 1;
(ix) -x + 2, -y, -z + 1. |
Energies (kJ mol-1) of interactions calculated using the
CrystalExplorer and DLPNO-CCSD(T) methods topInteraction types | CrystalExplorer | `DLPNO-CCSD(T)/NormalPNO/cc-pVTZ' |
Carboxylic acid dimer | -73.8 | -81.24 |
C—H···O hydrogen bonds | -62.8 | -60.59 |
O—H···N(heterocycle) synthon | -45.2 | -43.12 |
π–π stacking | -41.9 | -52.79 |
C—H···O hydrogen bonds | -40.8 | -47.54 |
C—H···π | -38.7 | -46.54 |
C—H···O hydrogen bonds | -34.0 | -35.65 |