Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The crystal structures of the anti­microbial drug tinidazole [TNZ; systematic name: 1-(2-ethyl­sulfonyl­eth­yl)-2-methyl-5-nitro­imidazole, C8H13N3O4S] and the 1:1 cocrystal of TNZ with the naturally occurring com­pound vanillic acid (VA; systematic name: 4-hy­droxy-3-meth­oxy­benzoic acid, C8H8O4), namely, the TNZVA cocrystal, were determined by single-crystal X-ray analysis at 100 K. The supra­molecular structure of the TNZVA 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 TNZVA 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620004180/dg3004sup1.cif
Contains datablocks TNZ, TNZ-VA, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229620004180/dg3004TNZsup2.hkl
Contains datablock TNZ

cdx

Chemdraw file https://doi.org/10.1107/S2053229620004180/dg3004TNZsup4.cdx
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229620004180/dg3004TNZ-VAsup3.hkl
Contains datablock TNZ-VA

cdx

Chemdraw file https://doi.org/10.1107/S2053229620004180/dg3004TNZ-VAsup5.cdx
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620004180/dg3004sup6.pdf
Tables of intermolecular interaction energies and complete hydrogen bonding

CCDC references: 1976901; 1964729

Computing details top

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
C8H13N3O4SDx = 1.523 Mg m3
Mr = 247.27Melting point: 399 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.8658 (7) ÅCell parameters from 5399 reflections
b = 5.4786 (3) Åθ = 2.3–27.7°
c = 16.7291 (9) ŵ = 0.30 mm1
β = 97.296 (2)°T = 100 K
V = 1078.72 (10) Å3Prism, colorless
Z = 40.23 × 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 tube2233 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
phi and ω scansθmax = 27.7°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS2016; Krause et al., 2015)
h = 1515
Tmin = 0.678, Tmax = 0.746k = 75
9021 measured reflectionsl = 2121
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-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 reflectionsΔρmax = 0.43 e Å3
147 parametersΔρmin = 0.36 e Å3
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
xyzUiso*/Ueq
C10.18385 (11)0.6154 (3)0.37337 (8)0.0164 (3)
C20.08810 (12)0.3127 (3)0.41070 (9)0.0206 (3)
H20.0406700.1727230.4094000.025*
C30.13837 (11)0.4256 (3)0.47923 (8)0.0181 (3)
C40.23880 (12)0.7875 (3)0.32185 (8)0.0213 (3)
H4A0.3208320.7570790.3281460.032*
H4B0.2245980.9555440.3379910.032*
H4C0.2072650.7636100.2653550.032*
C50.27293 (11)0.7923 (2)0.50549 (8)0.0161 (3)
H5A0.2355400.8433070.5524340.019*
H5B0.2865520.9398410.4739060.019*
C60.38598 (11)0.6673 (2)0.53444 (8)0.0146 (3)
H6A0.4286460.6431970.4878930.018*
H6B0.3706810.5043070.5562540.018*
C70.41331 (13)0.7879 (3)0.70109 (8)0.0215 (3)
H7A0.4512620.8990370.7427740.026*
H7B0.3315810.8305630.6927890.026*
C80.42595 (14)0.5268 (3)0.73203 (9)0.0274 (3)
H8A0.3828260.4166770.6933510.041*
H8B0.3967980.5150850.7841410.041*
H8C0.5063750.4805160.7385160.041*
N10.19924 (9)0.6225 (2)0.45531 (6)0.0150 (2)
N20.11645 (10)0.4317 (2)0.34507 (7)0.0200 (3)
N30.12955 (10)0.3601 (2)0.55971 (7)0.0218 (3)
O10.07275 (11)0.1769 (2)0.57015 (7)0.0340 (3)
O20.17735 (10)0.4849 (2)0.61553 (6)0.0335 (3)
O30.45683 (9)1.09379 (19)0.58949 (6)0.0240 (2)
O40.58437 (8)0.7360 (2)0.61700 (6)0.0240 (2)
S10.47108 (3)0.83740 (6)0.60972 (2)0.01619 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0154 (6)0.0183 (7)0.0151 (6)0.0021 (5)0.0000 (5)0.0005 (5)
C20.0187 (6)0.0200 (7)0.0229 (7)0.0032 (5)0.0019 (5)0.0002 (6)
C30.0166 (6)0.0187 (7)0.0189 (6)0.0002 (5)0.0020 (5)0.0023 (5)
C40.0251 (7)0.0215 (7)0.0173 (7)0.0036 (6)0.0027 (5)0.0010 (5)
C50.0166 (6)0.0152 (6)0.0159 (6)0.0008 (5)0.0005 (5)0.0025 (5)
C60.0150 (6)0.0142 (6)0.0141 (6)0.0005 (5)0.0003 (5)0.0024 (5)
C70.0270 (7)0.0237 (7)0.0135 (6)0.0011 (6)0.0014 (5)0.0031 (5)
C80.0368 (9)0.0280 (8)0.0169 (7)0.0001 (7)0.0013 (6)0.0029 (6)
N10.0133 (5)0.0165 (6)0.0147 (5)0.0001 (4)0.0001 (4)0.0003 (4)
N20.0193 (6)0.0212 (6)0.0189 (6)0.0019 (5)0.0004 (4)0.0014 (5)
N30.0181 (6)0.0271 (7)0.0202 (6)0.0008 (5)0.0028 (5)0.0041 (5)
O10.0429 (7)0.0295 (6)0.0311 (6)0.0101 (5)0.0104 (5)0.0083 (5)
O20.0313 (6)0.0517 (8)0.0171 (5)0.0129 (6)0.0015 (4)0.0011 (5)
O30.0324 (6)0.0156 (5)0.0233 (5)0.0031 (4)0.0010 (4)0.0012 (4)
O40.0165 (5)0.0299 (6)0.0242 (5)0.0009 (4)0.0023 (4)0.0039 (4)
S10.01731 (17)0.01577 (18)0.01475 (16)0.00152 (13)0.00083 (12)0.00202 (12)
Geometric parameters (Å, º) top
C1—N21.3345 (18)C6—S11.7753 (13)
C1—N11.3603 (17)C6—H6A0.9900
C1—C41.4830 (19)C6—H6B0.9900
C2—N21.3553 (19)C7—C81.522 (2)
C2—C31.370 (2)C7—S11.7736 (14)
C2—H20.9500C7—H7A0.9900
C3—N11.3853 (18)C7—H7B0.9900
C3—N31.4101 (18)C8—H8A0.9800
C4—H4A0.9800C8—H8B0.9800
C4—H4B0.9800C8—H8C0.9800
C4—H4C0.9800N3—O11.2337 (17)
C5—N11.4658 (17)N3—O21.2355 (17)
C5—C61.5292 (18)O3—S11.4497 (11)
C5—H5A0.9900O4—S11.4452 (10)
C5—H5B0.9900
N2—C1—N1112.12 (12)H6A—C6—H6B107.8
N2—C1—C4124.15 (12)C8—C7—S1113.86 (10)
N1—C1—C4123.71 (12)C8—C7—H7A108.8
N2—C2—C3109.53 (13)S1—C7—H7A108.8
N2—C2—H2125.2C8—C7—H7B108.8
C3—C2—H2125.2S1—C7—H7B108.8
C2—C3—N1107.29 (12)H7A—C7—H7B107.7
C2—C3—N3127.36 (13)C7—C8—H8A109.5
N1—C3—N3125.35 (12)C7—C8—H8B109.5
C1—C4—H4A109.5H8A—C8—H8B109.5
C1—C4—H4B109.5C7—C8—H8C109.5
H4A—C4—H4B109.5H8A—C8—H8C109.5
C1—C4—H4C109.5H8B—C8—H8C109.5
H4A—C4—H4C109.5C1—N1—C3105.11 (11)
H4B—C4—H4C109.5C1—N1—C5126.09 (11)
N1—C5—C6109.41 (11)C3—N1—C5128.61 (11)
N1—C5—H5A109.8C1—N2—C2105.94 (12)
C6—C5—H5A109.8O1—N3—O2123.35 (13)
N1—C5—H5B109.8O1—N3—C3116.76 (13)
C6—C5—H5B109.8O2—N3—C3119.89 (13)
H5A—C5—H5B108.2O4—S1—O3118.14 (7)
C5—C6—S1112.74 (9)O4—S1—C7109.02 (7)
C5—C6—H6A109.0O3—S1—C7107.63 (7)
S1—C6—H6A109.0O4—S1—C6107.29 (6)
C5—C6—H6B109.0O3—S1—C6107.70 (6)
S1—C6—H6B109.0C7—S1—C6106.49 (7)
N2—C2—C3—N10.51 (16)N1—C1—N2—C20.82 (16)
N2—C2—C3—N3179.45 (13)C4—C1—N2—C2177.31 (13)
N1—C5—C6—S1169.50 (9)C3—C2—N2—C10.17 (16)
N2—C1—N1—C31.12 (15)C2—C3—N3—O12.1 (2)
C4—C1—N1—C3177.02 (13)N1—C3—N3—O1179.15 (13)
N2—C1—N1—C5176.50 (12)C2—C3—N3—O2177.75 (14)
C4—C1—N1—C51.6 (2)N1—C3—N3—O21.0 (2)
C2—C3—N1—C10.96 (15)C8—C7—S1—O448.58 (13)
N3—C3—N1—C1179.93 (13)C8—C7—S1—O3177.85 (11)
C2—C3—N1—C5176.18 (12)C8—C7—S1—C666.88 (12)
N3—C3—N1—C54.9 (2)C5—C6—S1—O4165.64 (9)
C6—C5—N1—C198.36 (15)C5—C6—S1—O337.48 (11)
C6—C5—N1—C375.93 (16)C5—C6—S1—C777.74 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8A···O20.982.643.331 (2)128
C2—H2···O1i0.952.393.3311 (19)171
C6—H6A···O3ii0.992.463.2362 (17)135
C6—H6B···O3iii0.992.503.3511 (17)143
C8—H8A···O3iii0.982.703.4161 (19)130
C7—H7A···N2iv0.992.603.5353 (19)157
C8—H8B···O1v0.982.583.4082 (19)143
C6—H6A···O4vi0.992.713.4133 (17)128
C5—H5A···O1vii0.992.703.4500 (18)133
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+2, z+1; (iii) x, y1, 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·C8H8O4F(000) = 872
Mr = 415.42Dx = 1.498 Mg m3
Triclinic, P1Melting point: 404 K
a = 11.1206 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.6519 (6) ÅCell parameters from 9002 reflections
c = 13.6042 (6) Åθ = 2.4–27.5°
α = 98.078 (1)°µ = 0.23 mm1
β = 97.793 (1)°T = 100 K
γ = 99.780 (1)°Prism, yellow
V = 1842.42 (15) Å30.57 × 0.35 × 0.25 mm
Z = 4
Data collection top
Bruker APEXII CCD area detector
diffractometer
8425 independent reflections
Radiation source: fine-focus sealed tube7034 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
phi and ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS2016; Krause et al., 2015)
h = 1414
Tmin = 0.678, Tmax = 0.746k = 1416
16552 measured reflectionsl = 1617
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.039H-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 reflectionsΔρmax = 0.39 e Å3
511 parametersΔρmin = 0.48 e Å3
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
xyzUiso*/Ueq
C10.46056 (14)0.86128 (12)0.26200 (12)0.0181 (3)
C20.36794 (14)0.80378 (13)0.27192 (12)0.0196 (3)
H20.3035250.8159540.3281330.024*
C30.48290 (14)0.73672 (13)0.12877 (12)0.0188 (3)
C40.52869 (16)0.67038 (14)0.02743 (13)0.0255 (4)
H4A0.5196300.7169630.0239290.038*
H4B0.6161050.6374730.0226570.038*
H4C0.4805510.6128980.0166720.038*
C50.64659 (13)0.85083 (12)0.12261 (12)0.0172 (3)
H5A0.6966380.8725180.1741460.021*
H5B0.6979340.7893460.0732790.021*
C60.60737 (13)0.94607 (12)0.06971 (11)0.0165 (3)
H6A0.5753490.9189460.0084760.020*
H6B0.5388640.9982780.1146860.020*
C70.73585 (17)1.10524 (15)0.14532 (13)0.0283 (4)
H7A0.7550941.0630890.1991620.034*
H7B0.6551481.1551290.1691540.034*
C80.83651 (19)1.17061 (17)0.12190 (17)0.0411 (5)
H8A0.8152461.2144120.0705390.062*
H8B0.8431111.2186520.1832420.062*
H8C0.9157771.1207360.0968960.062*
N10.53583 (11)0.81701 (10)0.17062 (10)0.0163 (3)
N20.38173 (12)0.72649 (11)0.18929 (10)0.0201 (3)
N30.47884 (12)0.94978 (11)0.33122 (10)0.0210 (3)
O10.39776 (11)0.98249 (10)0.40576 (9)0.0293 (3)
O20.57235 (11)0.98869 (10)0.31472 (9)0.0278 (3)
O30.84376 (10)0.93943 (9)0.00736 (9)0.0272 (3)
O40.68905 (12)1.07976 (11)0.03874 (10)0.0326 (3)
S10.72785 (3)1.01561 (3)0.03492 (3)0.01782 (10)
C90.01626 (14)0.47902 (12)0.29301 (12)0.0176 (3)
C100.01500 (14)0.43286 (12)0.19089 (12)0.0178 (3)
H100.0260780.3782170.1639460.021*
C110.10512 (14)0.46637 (12)0.12932 (12)0.0180 (3)
C120.16802 (14)0.54533 (13)0.17106 (12)0.0201 (3)
C130.13652 (15)0.58994 (13)0.27226 (12)0.0224 (3)
H130.1793880.6427360.3000500.027*
C140.04333 (14)0.55866 (13)0.33361 (12)0.0198 (3)
H140.0205940.5912590.4024340.024*
C150.11253 (14)0.43973 (13)0.35574 (12)0.0196 (3)
C160.07432 (15)0.35336 (13)0.01673 (12)0.0213 (3)
H16A0.0144400.3842540.0032790.032*
H16B0.1029770.3372250.0895670.032*
H16C0.0893790.2861750.0116070.032*
O50.15118 (11)0.35713 (10)0.32573 (9)0.0287 (3)
O60.15317 (11)0.49796 (10)0.44539 (8)0.0255 (3)
H60.2180120.4763150.4749780.038*
O70.14007 (10)0.42987 (9)0.02857 (8)0.0210 (2)
O80.25695 (11)0.57457 (10)0.10785 (9)0.0292 (3)
H80.2944800.6210590.1392950.044*
C170.94304 (16)0.07560 (14)0.59092 (13)0.0244 (4)
C180.85017 (16)0.01837 (15)0.59093 (14)0.0287 (4)
H180.7769490.0330590.5423510.034*
C190.98849 (15)0.05546 (13)0.72037 (13)0.0218 (3)
C201.05196 (17)0.12934 (15)0.81456 (14)0.0297 (4)
H20A1.0202830.1972750.8195360.044*
H20B1.1411450.1452420.8136890.044*
H20C1.0363050.0942250.8725920.044*
C211.15235 (14)0.05841 (13)0.70510 (13)0.0219 (3)
H21A1.2088350.0049030.7484810.026*
H21B1.1898750.0783200.6448390.026*
C221.13687 (14)0.15361 (13)0.76226 (12)0.0187 (3)
H22A1.0734860.2142090.7217980.022*
H22B1.1079620.1310910.8262660.022*
C231.27814 (15)0.30524 (13)0.68857 (12)0.0224 (3)
H23A1.2049770.3635320.6841810.027*
H23B1.2733670.2773310.6239950.027*
C241.39617 (18)0.35043 (16)0.70807 (15)0.0340 (4)
H24A1.4681930.2920720.7133540.051*
H24B1.3971720.4083580.6523730.051*
H24C1.3990390.3799240.7710380.051*
N41.03218 (12)0.02863 (11)0.67403 (10)0.0204 (3)
N50.87873 (13)0.06310 (12)0.67142 (11)0.0261 (3)
N60.95208 (15)0.16613 (13)0.51980 (11)0.0317 (4)
O90.87115 (15)0.19110 (14)0.44492 (11)0.0552 (5)
O101.03764 (14)0.21426 (12)0.53472 (11)0.0448 (4)
O111.27991 (11)0.24272 (10)0.88032 (9)0.0270 (3)
O121.37899 (10)0.11068 (9)0.78510 (10)0.0280 (3)
S21.27955 (3)0.19896 (3)0.78827 (3)0.01716 (9)
C250.50219 (14)0.32744 (13)0.55299 (12)0.0195 (3)
C260.55642 (14)0.39283 (13)0.64589 (12)0.0189 (3)
H260.5227210.4536110.6703890.023*
C270.65868 (14)0.36881 (12)0.70163 (12)0.0185 (3)
C280.70904 (14)0.27939 (13)0.66395 (12)0.0180 (3)
C290.65570 (15)0.21639 (13)0.57145 (12)0.0202 (3)
H290.6907150.1569070.5457810.024*
C300.55186 (15)0.23925 (13)0.51603 (12)0.0210 (3)
H300.5150160.1949620.4533150.025*
C310.38976 (15)0.35374 (13)0.49928 (12)0.0224 (3)
C320.66986 (16)0.51617 (14)0.83451 (13)0.0270 (4)
H32A0.6802750.5711570.7907080.040*
H32B0.7159970.5464570.9020310.040*
H32C0.5819190.4947000.8383470.040*
O130.34422 (12)0.29145 (10)0.41124 (9)0.0306 (3)
H13A0.2792670.3186030.3846680.046*
O140.34167 (12)0.42777 (11)0.53397 (9)0.0328 (3)
O150.71543 (11)0.42347 (9)0.79447 (9)0.0242 (3)
O160.80696 (10)0.25822 (9)0.72288 (8)0.0226 (2)
H160.8318370.1979970.6972000.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0164 (7)0.0188 (7)0.0173 (7)0.0013 (6)0.0003 (6)0.0027 (6)
C20.0182 (7)0.0213 (8)0.0189 (7)0.0043 (6)0.0012 (6)0.0051 (6)
C30.0191 (7)0.0191 (7)0.0189 (7)0.0054 (6)0.0015 (6)0.0049 (6)
C40.0292 (9)0.0252 (8)0.0207 (8)0.0107 (7)0.0036 (7)0.0002 (7)
C50.0121 (6)0.0191 (7)0.0206 (7)0.0043 (6)0.0006 (6)0.0058 (6)
C60.0128 (6)0.0189 (7)0.0180 (7)0.0042 (6)0.0008 (6)0.0034 (6)
C70.0298 (9)0.0274 (9)0.0246 (9)0.0096 (7)0.0011 (7)0.0080 (7)
C80.0375 (11)0.0366 (11)0.0460 (12)0.0203 (9)0.0002 (9)0.0140 (9)
N10.0146 (6)0.0176 (6)0.0164 (6)0.0038 (5)0.0003 (5)0.0038 (5)
N20.0202 (6)0.0213 (7)0.0185 (6)0.0060 (5)0.0014 (5)0.0047 (5)
N30.0228 (7)0.0203 (7)0.0200 (7)0.0046 (5)0.0031 (5)0.0029 (5)
O10.0299 (6)0.0308 (7)0.0214 (6)0.0042 (5)0.0046 (5)0.0048 (5)
O20.0258 (6)0.0288 (6)0.0298 (6)0.0120 (5)0.0039 (5)0.0012 (5)
O30.0175 (5)0.0254 (6)0.0343 (7)0.0068 (5)0.0045 (5)0.0044 (5)
O40.0369 (7)0.0386 (7)0.0329 (7)0.0200 (6)0.0117 (6)0.0203 (6)
S10.01769 (18)0.01863 (19)0.01722 (19)0.00720 (14)0.00008 (14)0.00144 (14)
C90.0158 (7)0.0174 (7)0.0184 (7)0.0025 (6)0.0000 (6)0.0026 (6)
C100.0167 (7)0.0169 (7)0.0197 (8)0.0046 (6)0.0020 (6)0.0020 (6)
C110.0183 (7)0.0172 (7)0.0171 (7)0.0028 (6)0.0004 (6)0.0012 (6)
C120.0192 (7)0.0199 (8)0.0210 (8)0.0068 (6)0.0005 (6)0.0032 (6)
C130.0239 (8)0.0210 (8)0.0225 (8)0.0096 (6)0.0018 (6)0.0003 (6)
C140.0207 (7)0.0208 (8)0.0164 (7)0.0044 (6)0.0005 (6)0.0002 (6)
C150.0183 (7)0.0218 (8)0.0174 (7)0.0032 (6)0.0008 (6)0.0020 (6)
C160.0228 (8)0.0213 (8)0.0185 (8)0.0053 (6)0.0026 (6)0.0014 (6)
O50.0311 (6)0.0300 (7)0.0228 (6)0.0164 (5)0.0073 (5)0.0040 (5)
O60.0249 (6)0.0306 (6)0.0189 (6)0.0130 (5)0.0058 (5)0.0031 (5)
O70.0236 (6)0.0232 (6)0.0152 (5)0.0084 (5)0.0019 (4)0.0002 (4)
O80.0323 (7)0.0338 (7)0.0217 (6)0.0213 (5)0.0063 (5)0.0021 (5)
C170.0249 (8)0.0266 (9)0.0204 (8)0.0092 (7)0.0033 (7)0.0008 (7)
C180.0266 (9)0.0312 (9)0.0264 (9)0.0116 (7)0.0063 (7)0.0009 (7)
C190.0214 (8)0.0208 (8)0.0244 (8)0.0080 (6)0.0011 (6)0.0050 (7)
C200.0270 (9)0.0272 (9)0.0315 (10)0.0092 (7)0.0036 (7)0.0030 (8)
C210.0167 (7)0.0218 (8)0.0283 (9)0.0074 (6)0.0005 (6)0.0065 (7)
C220.0148 (7)0.0210 (8)0.0204 (8)0.0053 (6)0.0003 (6)0.0040 (6)
C230.0227 (8)0.0218 (8)0.0201 (8)0.0050 (6)0.0012 (6)0.0039 (6)
C240.0344 (10)0.0325 (10)0.0347 (10)0.0177 (8)0.0032 (8)0.0070 (8)
N40.0183 (6)0.0210 (7)0.0215 (7)0.0075 (5)0.0019 (5)0.0026 (5)
N50.0238 (7)0.0267 (7)0.0276 (8)0.0119 (6)0.0025 (6)0.0022 (6)
N60.0347 (8)0.0355 (9)0.0232 (7)0.0154 (7)0.0049 (6)0.0025 (7)
O90.0505 (9)0.0680 (11)0.0361 (8)0.0292 (8)0.0209 (7)0.0233 (8)
O100.0528 (9)0.0478 (9)0.0327 (8)0.0337 (7)0.0094 (7)0.0101 (7)
O110.0317 (6)0.0328 (7)0.0186 (6)0.0145 (5)0.0004 (5)0.0056 (5)
O120.0187 (6)0.0204 (6)0.0406 (7)0.0014 (5)0.0038 (5)0.0024 (5)
S20.01659 (18)0.01639 (18)0.01694 (18)0.00511 (14)0.00258 (14)0.00034 (14)
C250.0218 (8)0.0205 (8)0.0171 (7)0.0076 (6)0.0012 (6)0.0038 (6)
C260.0202 (7)0.0173 (7)0.0201 (8)0.0066 (6)0.0021 (6)0.0032 (6)
C270.0188 (7)0.0180 (7)0.0178 (7)0.0026 (6)0.0017 (6)0.0028 (6)
C280.0164 (7)0.0212 (8)0.0182 (7)0.0053 (6)0.0033 (6)0.0070 (6)
C290.0238 (8)0.0212 (8)0.0185 (7)0.0105 (6)0.0057 (6)0.0038 (6)
C300.0244 (8)0.0233 (8)0.0156 (7)0.0074 (6)0.0018 (6)0.0023 (6)
C310.0256 (8)0.0229 (8)0.0185 (8)0.0084 (6)0.0006 (6)0.0020 (6)
C320.0294 (9)0.0227 (8)0.0258 (9)0.0068 (7)0.0000 (7)0.0040 (7)
O130.0322 (7)0.0367 (7)0.0213 (6)0.0194 (6)0.0076 (5)0.0051 (5)
O140.0341 (7)0.0365 (7)0.0256 (6)0.0216 (6)0.0094 (5)0.0064 (5)
O150.0238 (6)0.0242 (6)0.0214 (6)0.0084 (5)0.0045 (5)0.0035 (5)
O160.0209 (6)0.0256 (6)0.0221 (6)0.0110 (5)0.0016 (5)0.0033 (5)
Geometric parameters (Å, º) top
C1—C21.361 (2)C17—C181.358 (2)
C1—N11.3865 (19)C17—N41.386 (2)
C1—N31.419 (2)C17—N61.419 (2)
C2—N21.355 (2)C18—N51.356 (2)
C2—H20.9500C18—H180.9500
C3—N21.3374 (19)C19—N51.334 (2)
C3—N11.3542 (19)C19—N41.355 (2)
C3—C41.484 (2)C19—C201.486 (2)
C4—H4A0.9800C20—H20A0.9800
C4—H4B0.9800C20—H20B0.9800
C4—H4C0.9800C20—H20C0.9800
C5—N11.4719 (18)C21—N41.4728 (19)
C5—C61.520 (2)C21—C221.521 (2)
C5—H5A0.9900C21—H21A0.9900
C5—H5B0.9900C21—H21B0.9900
C6—S11.7716 (15)C22—S21.7850 (15)
C6—H6A0.9900C22—H22A0.9900
C6—H6B0.9900C22—H22B0.9900
C7—C81.527 (2)C23—C241.524 (2)
C7—S11.7724 (17)C23—S21.7671 (16)
C7—H7A0.9900C23—H23A0.9900
C7—H7B0.9900C23—H23B0.9900
C8—H8A0.9800C24—H24A0.9800
C8—H8B0.9800C24—H24B0.9800
C8—H8C0.9800C24—H24C0.9800
N3—O21.2311 (18)N6—O101.2234 (19)
N3—O11.2329 (17)N6—O91.2295 (19)
O3—S11.4410 (12)O11—S21.4385 (12)
O4—S11.4408 (13)O12—S21.4418 (12)
C9—C141.389 (2)C25—C301.389 (2)
C9—C101.401 (2)C25—C261.406 (2)
C9—C151.474 (2)C25—C311.473 (2)
C10—C111.379 (2)C26—C271.382 (2)
C10—H100.9500C26—H260.9500
C11—O71.3636 (18)C27—O151.3645 (18)
C11—C121.412 (2)C27—C281.409 (2)
C12—O81.3555 (18)C28—O161.3502 (18)
C12—C131.386 (2)C28—C291.388 (2)
C13—C141.387 (2)C29—C301.387 (2)
C13—H130.9500C29—H290.9500
C14—H140.9500C30—H300.9500
C15—O51.2344 (19)C31—O141.225 (2)
C15—O61.3113 (19)C31—O131.3217 (19)
C16—O71.4306 (18)C32—O151.4235 (19)
C16—H16A0.9800C32—H32A0.9800
C16—H16B0.9800C32—H32B0.9800
C16—H16C0.9800C32—H32C0.9800
O6—H60.8811O13—H13A0.9048
O8—H80.8742O16—H160.8956
C2—C1—N1107.11 (13)C18—C17—N4107.55 (15)
C2—C1—N3127.29 (14)C18—C17—N6127.90 (15)
N1—C1—N3125.59 (13)N4—C17—N6124.54 (14)
N2—C2—C1109.55 (13)N5—C18—C17109.08 (15)
N2—C2—H2125.2N5—C18—H18125.5
C1—C2—H2125.2C17—C18—H18125.5
N2—C3—N1111.38 (13)N5—C19—N4111.28 (14)
N2—C3—C4124.02 (14)N5—C19—C20123.58 (15)
N1—C3—C4124.57 (14)N4—C19—C20125.14 (14)
C3—C4—H4A109.5C19—C20—H20A109.5
C3—C4—H4B109.5C19—C20—H20B109.5
H4A—C4—H4B109.5H20A—C20—H20B109.5
C3—C4—H4C109.5C19—C20—H20C109.5
H4A—C4—H4C109.5H20A—C20—H20C109.5
H4B—C4—H4C109.5H20B—C20—H20C109.5
N1—C5—C6109.35 (12)N4—C21—C22110.82 (13)
N1—C5—H5A109.8N4—C21—H21A109.5
C6—C5—H5A109.8C22—C21—H21A109.5
N1—C5—H5B109.8N4—C21—H21B109.5
C6—C5—H5B109.8C22—C21—H21B109.5
H5A—C5—H5B108.3H21A—C21—H21B108.1
C5—C6—S1113.92 (10)C21—C22—S2110.80 (11)
C5—C6—H6A108.8C21—C22—H22A109.5
S1—C6—H6A108.8S2—C22—H22A109.5
C5—C6—H6B108.8C21—C22—H22B109.5
S1—C6—H6B108.8S2—C22—H22B109.5
H6A—C6—H6B107.7H22A—C22—H22B108.1
C8—C7—S1109.14 (13)C24—C23—S2108.84 (11)
C8—C7—H7A109.9C24—C23—H23A109.9
S1—C7—H7A109.9S2—C23—H23A109.9
C8—C7—H7B109.9C24—C23—H23B109.9
S1—C7—H7B109.9S2—C23—H23B109.9
H7A—C7—H7B108.3H23A—C23—H23B108.3
C7—C8—H8A109.5C23—C24—H24A109.5
C7—C8—H8B109.5C23—C24—H24B109.5
H8A—C8—H8B109.5H24A—C24—H24B109.5
C7—C8—H8C109.5C23—C24—H24C109.5
H8A—C8—H8C109.5H24A—C24—H24C109.5
H8B—C8—H8C109.5H24B—C24—H24C109.5
C3—N1—C1105.70 (12)C19—N4—C17105.48 (13)
C3—N1—C5125.06 (13)C19—N4—C21125.99 (13)
C1—N1—C5129.15 (13)C17—N4—C21128.48 (14)
C3—N2—C2106.23 (13)C19—N5—C18106.61 (14)
O2—N3—O1124.08 (14)O10—N6—O9123.71 (15)
O2—N3—C1119.59 (13)O10—N6—C17119.87 (14)
O1—N3—C1116.33 (13)O9—N6—C17116.42 (15)
O4—S1—O3117.56 (8)O11—S2—O12117.34 (8)
O4—S1—C6107.18 (7)O11—S2—C23108.82 (8)
O3—S1—C6109.72 (7)O12—S2—C23108.23 (8)
O4—S1—C7108.38 (9)O11—S2—C22107.58 (7)
O3—S1—C7107.94 (8)O12—S2—C22108.17 (7)
C6—S1—C7105.41 (8)C23—S2—C22106.16 (8)
C14—C9—C10120.52 (14)C30—C25—C26120.32 (14)
C14—C9—C15121.30 (14)C30—C25—C31121.99 (14)
C10—C9—C15118.17 (14)C26—C25—C31117.65 (14)
C11—C10—C9120.32 (14)C27—C26—C25120.07 (14)
C11—C10—H10119.8C27—C26—H26120.0
C9—C10—H10119.8C25—C26—H26120.0
O7—C11—C10125.34 (14)O15—C27—C26125.13 (14)
O7—C11—C12115.45 (13)O15—C27—C28115.31 (13)
C10—C11—C12119.21 (14)C26—C27—C28119.52 (14)
O8—C12—C13123.13 (14)O16—C28—C29123.28 (14)
O8—C12—C11117.04 (14)O16—C28—C27116.85 (14)
C13—C12—C11119.82 (14)C29—C28—C27119.85 (14)
C12—C13—C14121.00 (15)C30—C29—C28120.78 (14)
C12—C13—H13119.5C30—C29—H29119.6
C14—C13—H13119.5C28—C29—H29119.6
C13—C14—C9119.08 (14)C29—C30—C25119.45 (15)
C13—C14—H14120.5C29—C30—H30120.3
C9—C14—H14120.5C25—C30—H30120.3
O5—C15—O6122.59 (14)O14—C31—O13122.42 (15)
O5—C15—C9121.99 (14)O14—C31—C25122.36 (15)
O6—C15—C9115.42 (13)O13—C31—C25115.21 (14)
O7—C16—H16A109.5O15—C32—H32A109.5
O7—C16—H16B109.5O15—C32—H32B109.5
H16A—C16—H16B109.5H32A—C32—H32B109.5
O7—C16—H16C109.5O15—C32—H32C109.5
H16A—C16—H16C109.5H32A—C32—H32C109.5
H16B—C16—H16C109.5H32B—C32—H32C109.5
C15—O6—H6110.6C31—O13—H13A106.3
C11—O7—C16116.75 (12)C27—O15—C32117.33 (12)
C12—O8—H8112.1C28—O16—H16113.0
N1—C1—C2—N20.99 (18)N4—C17—C18—N50.1 (2)
N3—C1—C2—N2179.26 (15)N6—C17—C18—N5178.96 (18)
N1—C5—C6—S1165.63 (10)N4—C21—C22—S2173.86 (11)
N2—C3—N1—C11.63 (18)N5—C19—N4—C170.1 (2)
C4—C3—N1—C1176.71 (15)C20—C19—N4—C17179.02 (17)
N2—C3—N1—C5178.45 (13)N5—C19—N4—C21177.60 (15)
C4—C3—N1—C50.1 (2)C20—C19—N4—C213.5 (3)
C2—C1—N1—C31.56 (17)C18—C17—N4—C190.1 (2)
N3—C1—N1—C3178.68 (15)N6—C17—N4—C19179.01 (17)
C2—C1—N1—C5178.21 (14)C18—C17—N4—C21177.57 (16)
N3—C1—N1—C52.0 (3)N6—C17—N4—C211.6 (3)
C6—C5—N1—C394.54 (17)C22—C21—N4—C19100.69 (18)
C6—C5—N1—C181.51 (19)C22—C21—N4—C1782.4 (2)
N1—C3—N2—C21.04 (18)N4—C19—N5—C180.0 (2)
C4—C3—N2—C2177.31 (16)C20—C19—N5—C18178.95 (17)
C1—C2—N2—C30.00 (19)C17—C18—N5—C190.1 (2)
C2—C1—N3—O2174.86 (16)C18—C17—N6—O10174.3 (2)
N1—C1—N3—O24.8 (2)N4—C17—N6—O106.8 (3)
C2—C1—N3—O14.8 (2)C18—C17—N6—O96.1 (3)
N1—C1—N3—O1175.50 (15)N4—C17—N6—O9172.85 (19)
C5—C6—S1—O4163.08 (11)C24—C23—S2—O1162.57 (15)
C5—C6—S1—O334.38 (13)C24—C23—S2—O1265.97 (15)
C5—C6—S1—C781.61 (13)C24—C23—S2—C22178.11 (13)
C8—C7—S1—O464.52 (16)C21—C22—S2—O11150.14 (11)
C8—C7—S1—O363.80 (16)C21—C22—S2—O1222.48 (14)
C8—C7—S1—C6179.01 (14)C21—C22—S2—C2393.49 (13)
C14—C9—C10—C110.3 (2)C30—C25—C26—C270.8 (2)
C15—C9—C10—C11179.54 (15)C31—C25—C26—C27177.05 (15)
C9—C10—C11—O7177.72 (14)C25—C26—C27—O15176.95 (15)
C9—C10—C11—C121.9 (2)C25—C26—C27—C280.9 (2)
O7—C11—C12—O81.2 (2)O15—C27—C28—O160.3 (2)
C10—C11—C12—O8179.13 (15)C26—C27—C28—O16178.35 (14)
O7—C11—C12—C13178.05 (14)O15—C27—C28—C29178.07 (14)
C10—C11—C12—C131.6 (2)C26—C27—C28—C290.0 (2)
O8—C12—C13—C14178.90 (16)O16—C28—C29—C30177.21 (15)
C11—C12—C13—C140.3 (3)C27—C28—C29—C301.0 (2)
C12—C13—C14—C91.9 (3)C28—C29—C30—C251.1 (3)
C10—C9—C14—C131.6 (2)C26—C25—C30—C290.2 (2)
C15—C9—C14—C13177.60 (15)C31—C25—C30—C29177.97 (16)
C14—C9—C15—O5167.39 (16)C30—C25—C31—O14176.00 (17)
C10—C9—C15—O511.9 (2)C26—C25—C31—O141.8 (3)
C14—C9—C15—O612.1 (2)C30—C25—C31—O133.7 (2)
C10—C9—C15—O6168.64 (14)C26—C25—C31—O13178.44 (15)
C10—C11—O7—C162.3 (2)C26—C27—O15—C323.7 (2)
C12—C11—O7—C16177.37 (14)C28—C27—O15—C32178.38 (14)
Intermolecular interaction energy values for the TNZ crystal top
R is the distance (Å) between molecular centroids (mean atomic position). Each line corresponds to different intermolecular interactions.
Symmerty codeREeleEpolEdisErepEtot
-x, -y, -z6.68-49.4-12.9-33.737.3-68.1
-x, -y, -z5.43-16.7-9.4-34.224.0-39.6
x, y, z5.48-11.3-5.7-33.422.8-31.1
-x, -y, -z7.00-5.5-1.9-31.418.2-23.4
x + 1/2, -y + 1/2, z + 1/29.72-11.0-2.8-14.913.2-18.5
-x + 1/2, y + 1/2, -z + 1/27.82-6.5-2.0-12.48.1-14.1
-x, -y, -z9.69-13.6-1.9-7.917.2-12.0
-x + 1/2, y + 1/2, -z + 1/29.91-1.0-1.3-9.65.5-7.0
x + 1/2, -y + 1/2, z + 1/210.46-0.8-0.5-6.33.0-4.9
Geometric parameters of ππ stacking interactions in the TNZ–VA cocrystal top
Cg1, 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 ringSecond ringCg···Cg (Å)α (°)β (°)
Cg1Cg4iii3.5159 (10)4.41 (9)22.4
Cg2Cg2ix4.4661 (11)037.9
Cg3Cg4iv5.3651 (10)14.85 (8)45.4
Cg1Cg2iv5.7685 (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 top
Interaction typesCrystalExplorer`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
ππ 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
 

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.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds