





Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015007227/hb7402sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989015007227/hb7402Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015007227/hb7402Isup3.cml |
CCDC reference: 1059141
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.091
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 -- C1 .. 5.7 su
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 2 Note C H4 O PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ... 4 Report
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Concerning our on-going research on the supramolecular chemistry of thiosemicarbazone derivatives from natural products, we report herein the synthesis and structure of the 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone methanol monosolvate, a thiosemicarbazone derivative from vanillin. The thiosemicarbazone group of the title compound doesn't match the ideal planarity and the maximum deviation from the mean plane of the non-H atoms concerning the thiosemicarbazone group amounts to 0.4659 (14) Å for C15 and the dihedral angle between the two aromatic rings amounts to 9.83 (8)° (Fig. 1). In the crystal, molecules are linked into dimers via pairs of N1—H14···S1 hydrogen bonds. The dimers are linked into a three dimensional hydrogen bonded network through the methanol molecules by the O1—H15···O3, O3—H19···O2 and O3—H19···O1 hydrogen interactions (Fig. 2). In addition, one intermolecular N3—H13···N2 hydrogen interaction is also observed (Table 1).
The crystal structure of the solvate free 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone is already published (Oliveira et al., 2014) and the molecules are linked by N—H···S hydrogen interactions into dimers. Additionally, the dimers are linked by N—H···O and O—H···S hydrogen interactions building a three-dimensional hydrogen-bonded network.
In the actual structure, the presence of the methanol solvate molecules maintains the dimensionality of the network. As the outstanding feature, a bifurcated hydrogen bond is observed. The atom H19 of the hydroxy group of the methanol solvate builds a bifurcated hydrogen bond with the O1 and O2 atoms of the ortho-hydroxy-methoxy entity of the thiosemicarbazone derivative. The H19···O2 and H19···O1 distances amount to 2.26 (2) Å and 2.46 (2) Å (Fig. 1). As the difference between the lengths of the two hydrogen interactions is about 0.2 Å, the bifurcation is considered symmetric. Due to the hydrogen-bond interactions promoted by the solvate molecule, the supramolecularity of the structure modifies the arrangement molecules but the three-dimensional H-bonded network is preserved (Fig. 2).
Starting materials were commercially available and were used without further purification. The synthesis of the title compound, 4-hydroxy-3-methoxybenzaldehyde-4-methylthiosemicarbazone, was adapted from a previously procedure (Freund & Schander, 1902 and Oliveira et al., 2014). Colourless blocks were obtained unexpectedly from a mixture containing uranyl acetate dihydrate and the title compound in methanol by the slow evaporation of the solvent.
Concerning our on-going research on the supramolecular chemistry of thiosemicarbazone derivatives from natural products, we report herein the synthesis and structure of the 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone methanol monosolvate, a thiosemicarbazone derivative from vanillin. The thiosemicarbazone group of the title compound doesn't match the ideal planarity and the maximum deviation from the mean plane of the non-H atoms concerning the thiosemicarbazone group amounts to 0.4659 (14) Å for C15 and the dihedral angle between the two aromatic rings amounts to 9.83 (8)° (Fig. 1). In the crystal, molecules are linked into dimers via pairs of N1—H14···S1 hydrogen bonds. The dimers are linked into a three dimensional hydrogen bonded network through the methanol molecules by the O1—H15···O3, O3—H19···O2 and O3—H19···O1 hydrogen interactions (Fig. 2). In addition, one intermolecular N3—H13···N2 hydrogen interaction is also observed (Table 1).
The crystal structure of the solvate free 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone is already published (Oliveira et al., 2014) and the molecules are linked by N—H···S hydrogen interactions into dimers. Additionally, the dimers are linked by N—H···O and O—H···S hydrogen interactions building a three-dimensional hydrogen-bonded network.
In the actual structure, the presence of the methanol solvate molecules maintains the dimensionality of the network. As the outstanding feature, a bifurcated hydrogen bond is observed. The atom H19 of the hydroxy group of the methanol solvate builds a bifurcated hydrogen bond with the O1 and O2 atoms of the ortho-hydroxy-methoxy entity of the thiosemicarbazone derivative. The H19···O2 and H19···O1 distances amount to 2.26 (2) Å and 2.46 (2) Å (Fig. 1). As the difference between the lengths of the two hydrogen interactions is about 0.2 Å, the bifurcation is considered symmetric. Due to the hydrogen-bond interactions promoted by the solvate molecule, the supramolecularity of the structure modifies the arrangement molecules but the three-dimensional H-bonded network is preserved (Fig. 2).
For one of the first reports of thiosemicarbazone derivatives synthesis, see: Freund & Schander (1902). For the report concerning the synthesis and crystal structure of 4-hydroxy-3-methoxybenzaldehyde 4-phenylthiosemicarbazone, see: Oliveira et al. (2014).
Starting materials were commercially available and were used without further purification. The synthesis of the title compound, 4-hydroxy-3-methoxybenzaldehyde-4-methylthiosemicarbazone, was adapted from a previously procedure (Freund & Schander, 1902 and Oliveira et al., 2014). Colourless blocks were obtained unexpectedly from a mixture containing uranyl acetate dihydrate and the title compound in methanol by the slow evaporation of the solvent.
Crystal data, data collection and structure refinement details are summarized in the Experimental part. All hydrogen atoms were localized in a difference density Fourier map. Their positions and isotropic displacement parameters were refined.
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).
C15H15N3O2S·CH4O | F(000) = 704 |
Mr = 333.40 | Dx = 1.370 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 32712 reflections |
a = 11.1833 (2) Å | θ = 2.9–27.5° |
b = 8.4207 (2) Å | µ = 0.22 mm−1 |
c = 17.2521 (4) Å | T = 123 K |
β = 95.752 (1)° | Block, colorless |
V = 1616.47 (6) Å3 | 0.29 × 0.15 × 0.09 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3692 independent reflections |
Radiation source: fine-focus sealed tube, Nonius KappaCCD | 2926 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
CCD rotation images, thick slices scans | h = −14→14 |
Absorption correction: multi-scan (Blessing, 1995) | k = −10→10 |
Tmin = 0.924, Tmax = 0.983 | l = −22→22 |
46461 measured reflections |
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.091 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.4527P] where P = (Fo2 + 2Fc2)/3 |
3692 reflections | (Δ/σ)max < 0.001 |
284 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C15H15N3O2S·CH4O | V = 1616.47 (6) Å3 |
Mr = 333.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1833 (2) Å | µ = 0.22 mm−1 |
b = 8.4207 (2) Å | T = 123 K |
c = 17.2521 (4) Å | 0.29 × 0.15 × 0.09 mm |
β = 95.752 (1)° |
Nonius KappaCCD diffractometer | 3692 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2926 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.983 | Rint = 0.053 |
46461 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.21 e Å−3 |
3692 reflections | Δρmin = −0.32 e Å−3 |
284 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.61038 (3) | 0.16794 (5) | 0.57257 (2) | 0.03151 (12) | |
O1 | −0.20192 (9) | 0.56394 (12) | 0.31751 (6) | 0.0250 (2) | |
O2 | −0.03515 (8) | 0.71233 (11) | 0.40440 (6) | 0.0228 (2) | |
O3 | −0.17481 (9) | 0.93717 (13) | 0.30693 (6) | 0.0267 (2) | |
N1 | 0.39757 (10) | 0.21003 (14) | 0.49762 (7) | 0.0211 (2) | |
N2 | 0.29562 (10) | 0.29685 (13) | 0.47526 (7) | 0.0200 (2) | |
N3 | 0.44949 (11) | 0.40722 (14) | 0.58388 (7) | 0.0239 (3) | |
C1 | 0.48140 (12) | 0.26955 (16) | 0.55234 (8) | 0.0207 (3) | |
C2 | 0.21931 (12) | 0.23390 (16) | 0.42367 (8) | 0.0203 (3) | |
C4 | 0.02092 (12) | 0.24228 (16) | 0.34674 (8) | 0.0223 (3) | |
C5 | −0.08460 (12) | 0.32173 (16) | 0.32039 (8) | 0.0223 (3) | |
C3 | 0.10997 (11) | 0.31895 (15) | 0.39506 (8) | 0.0191 (3) | |
C6 | −0.10163 (11) | 0.47803 (16) | 0.34134 (8) | 0.0197 (3) | |
C7 | −0.01078 (12) | 0.55645 (15) | 0.38947 (8) | 0.0192 (3) | |
C8 | 0.09313 (12) | 0.47800 (16) | 0.41617 (8) | 0.0191 (3) | |
C9 | 0.51071 (12) | 0.51201 (16) | 0.63818 (8) | 0.0212 (3) | |
C10 | 0.61312 (13) | 0.47347 (18) | 0.68703 (8) | 0.0254 (3) | |
C11 | 0.66528 (13) | 0.58702 (18) | 0.73831 (8) | 0.0266 (3) | |
C12 | 0.61602 (13) | 0.73693 (18) | 0.74239 (9) | 0.0261 (3) | |
C13 | 0.51291 (13) | 0.77472 (18) | 0.69408 (9) | 0.0276 (3) | |
C14 | 0.46044 (13) | 0.66315 (17) | 0.64255 (9) | 0.0247 (3) | |
C15 | 0.05810 (13) | 0.80047 (18) | 0.44801 (9) | 0.0254 (3) | |
C16 | −0.24398 (16) | 0.9612 (2) | 0.37071 (10) | 0.0355 (4) | |
H1 | 0.2343 (13) | 0.1272 (19) | 0.4021 (8) | 0.021 (4)* | |
H2 | 0.0297 (14) | 0.131 (2) | 0.3319 (9) | 0.028 (4)* | |
H3 | −0.1460 (14) | 0.269 (2) | 0.2890 (9) | 0.028 (4)* | |
H4 | 0.1569 (14) | 0.5318 (19) | 0.4486 (9) | 0.026 (4)* | |
H5 | 0.6477 (14) | 0.370 (2) | 0.6856 (9) | 0.030 (4)* | |
H6 | 0.7391 (15) | 0.5623 (19) | 0.7720 (9) | 0.032 (4)* | |
H7 | 0.6504 (15) | 0.818 (2) | 0.7786 (10) | 0.031 (4)* | |
H8 | 0.4727 (15) | 0.883 (2) | 0.6956 (9) | 0.032 (4)* | |
H9 | 0.3903 (15) | 0.688 (2) | 0.6076 (10) | 0.031 (4)* | |
H10 | 0.0725 (14) | 0.757 (2) | 0.5024 (10) | 0.029 (4)* | |
H11 | 0.1347 (15) | 0.7966 (19) | 0.4238 (9) | 0.027 (4)* | |
H12 | 0.0276 (15) | 0.910 (2) | 0.4506 (9) | 0.033 (4)* | |
H13 | 0.3793 (16) | 0.438 (2) | 0.5638 (9) | 0.030 (4)* | |
H14 | 0.4096 (15) | 0.115 (2) | 0.4769 (10) | 0.035 (5)* | |
H15 | −0.2449 (17) | 0.513 (2) | 0.2819 (11) | 0.049 (6)* | |
H16 | −0.2038 (19) | 0.922 (3) | 0.4223 (14) | 0.067 (6)* | |
H17 | −0.321 (2) | 0.914 (3) | 0.3632 (12) | 0.064 (7)* | |
H18 | −0.2597 (19) | 1.079 (3) | 0.3773 (12) | 0.061 (6)* | |
H19 | −0.1477 (18) | 0.846 (3) | 0.3092 (12) | 0.052 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02158 (19) | 0.0286 (2) | 0.0418 (2) | 0.00936 (14) | −0.00942 (15) | −0.01015 (16) |
O1 | 0.0196 (5) | 0.0227 (5) | 0.0306 (6) | 0.0036 (4) | −0.0071 (4) | −0.0031 (4) |
O2 | 0.0194 (5) | 0.0176 (5) | 0.0300 (5) | 0.0020 (4) | −0.0043 (4) | −0.0050 (4) |
O3 | 0.0264 (5) | 0.0231 (5) | 0.0297 (6) | 0.0045 (4) | −0.0013 (4) | 0.0023 (4) |
N1 | 0.0179 (6) | 0.0204 (6) | 0.0242 (6) | 0.0045 (4) | −0.0020 (4) | −0.0017 (5) |
N2 | 0.0173 (5) | 0.0205 (6) | 0.0220 (6) | 0.0043 (4) | 0.0000 (4) | 0.0018 (5) |
N3 | 0.0180 (6) | 0.0229 (6) | 0.0291 (6) | 0.0048 (5) | −0.0061 (5) | −0.0042 (5) |
C1 | 0.0190 (6) | 0.0214 (7) | 0.0214 (7) | 0.0008 (5) | 0.0008 (5) | 0.0011 (5) |
C2 | 0.0209 (7) | 0.0190 (7) | 0.0208 (7) | 0.0014 (5) | 0.0006 (5) | −0.0001 (5) |
C4 | 0.0239 (7) | 0.0177 (7) | 0.0245 (7) | 0.0011 (5) | −0.0010 (6) | −0.0016 (5) |
C5 | 0.0212 (7) | 0.0202 (7) | 0.0240 (7) | −0.0013 (5) | −0.0043 (5) | −0.0015 (5) |
C3 | 0.0184 (6) | 0.0199 (7) | 0.0187 (6) | 0.0013 (5) | 0.0005 (5) | 0.0011 (5) |
C6 | 0.0171 (6) | 0.0210 (7) | 0.0206 (7) | 0.0019 (5) | −0.0006 (5) | 0.0022 (5) |
C7 | 0.0208 (6) | 0.0158 (6) | 0.0207 (7) | 0.0002 (5) | 0.0018 (5) | 0.0000 (5) |
C8 | 0.0177 (6) | 0.0200 (7) | 0.0191 (6) | −0.0003 (5) | −0.0005 (5) | −0.0005 (5) |
C9 | 0.0199 (7) | 0.0220 (7) | 0.0216 (7) | −0.0013 (5) | 0.0019 (5) | −0.0001 (5) |
C10 | 0.0244 (7) | 0.0237 (7) | 0.0271 (7) | 0.0033 (6) | −0.0029 (6) | −0.0011 (6) |
C11 | 0.0235 (7) | 0.0300 (8) | 0.0251 (7) | −0.0009 (6) | −0.0028 (6) | −0.0010 (6) |
C12 | 0.0264 (7) | 0.0269 (7) | 0.0255 (7) | −0.0059 (6) | 0.0042 (6) | −0.0050 (6) |
C13 | 0.0277 (7) | 0.0238 (7) | 0.0314 (8) | 0.0022 (6) | 0.0038 (6) | −0.0026 (6) |
C14 | 0.0218 (7) | 0.0251 (7) | 0.0268 (7) | 0.0038 (6) | 0.0007 (6) | −0.0019 (6) |
C15 | 0.0228 (7) | 0.0218 (7) | 0.0305 (8) | −0.0009 (6) | −0.0025 (6) | −0.0068 (6) |
C16 | 0.0295 (9) | 0.0420 (10) | 0.0355 (9) | 0.0070 (7) | 0.0059 (7) | 0.0097 (7) |
S1—C1 | 1.6832 (13) | C3—C8 | 1.4055 (18) |
O1—C6 | 1.3630 (15) | C6—C7 | 1.4102 (18) |
O1—H15 | 0.86 (2) | C7—C8 | 1.3753 (18) |
O2—C7 | 1.3703 (15) | C8—H4 | 0.973 (16) |
O2—C15 | 1.4308 (16) | C9—C10 | 1.3906 (19) |
O3—C16 | 1.421 (2) | C9—C14 | 1.3964 (19) |
O3—H19 | 0.83 (2) | C10—C11 | 1.391 (2) |
N1—C1 | 1.3579 (17) | C10—H5 | 0.952 (17) |
N1—N2 | 1.3766 (15) | C11—C12 | 1.382 (2) |
N1—H14 | 0.896 (19) | C11—H6 | 0.983 (17) |
N2—C2 | 1.2843 (17) | C12—C13 | 1.390 (2) |
N3—C1 | 1.3440 (18) | C12—H7 | 0.975 (17) |
N3—C9 | 1.4130 (17) | C13—C14 | 1.383 (2) |
N3—H13 | 0.866 (18) | C13—H8 | 1.020 (17) |
C2—C3 | 1.4597 (18) | C14—H9 | 0.964 (17) |
C2—H1 | 0.993 (16) | C15—H10 | 1.004 (17) |
C4—C3 | 1.3918 (18) | C15—H11 | 0.991 (17) |
C4—C5 | 1.3925 (19) | C15—H12 | 0.983 (18) |
C4—H2 | 0.975 (17) | C16—H16 | 1.01 (2) |
C5—C6 | 1.3831 (19) | C16—H17 | 0.95 (2) |
C5—H3 | 0.941 (16) | C16—H18 | 1.01 (2) |
C6—O1—H15 | 109.5 (13) | C7—C8—H4 | 121.0 (9) |
C7—O2—C15 | 116.58 (10) | C3—C8—H4 | 118.9 (9) |
C16—O3—H19 | 108.7 (15) | C10—C9—C14 | 119.45 (13) |
C1—N1—N2 | 119.57 (11) | C10—C9—N3 | 124.81 (13) |
C1—N1—H14 | 119.2 (11) | C14—C9—N3 | 115.72 (12) |
N2—N1—H14 | 121.2 (11) | C11—C10—C9 | 119.51 (14) |
C2—N2—N1 | 116.69 (11) | C11—C10—H5 | 119.9 (10) |
C1—N3—C9 | 132.57 (12) | C9—C10—H5 | 120.6 (10) |
C1—N3—H13 | 111.3 (11) | C12—C11—C10 | 121.10 (14) |
C9—N3—H13 | 116.0 (11) | C12—C11—H6 | 118.6 (10) |
N3—C1—N1 | 114.01 (12) | C10—C11—H6 | 120.3 (10) |
N3—C1—S1 | 127.69 (10) | C11—C12—C13 | 119.31 (14) |
N1—C1—S1 | 118.30 (10) | C11—C12—H7 | 122.3 (10) |
N2—C2—C3 | 120.52 (12) | C13—C12—H7 | 118.4 (10) |
N2—C2—H1 | 120.5 (8) | C14—C13—C12 | 120.19 (14) |
C3—C2—H1 | 118.9 (8) | C14—C13—H8 | 117.8 (9) |
C3—C4—C5 | 120.31 (13) | C12—C13—H8 | 122.0 (9) |
C3—C4—H2 | 121.1 (9) | C13—C14—C9 | 120.44 (13) |
C5—C4—H2 | 118.6 (9) | C13—C14—H9 | 121.3 (10) |
C6—C5—C4 | 120.41 (12) | C9—C14—H9 | 118.3 (10) |
C6—C5—H3 | 119.0 (10) | O2—C15—H10 | 110.1 (9) |
C4—C5—H3 | 120.5 (10) | O2—C15—H11 | 112.1 (9) |
C4—C3—C8 | 119.39 (12) | H10—C15—H11 | 108.6 (13) |
C4—C3—C2 | 119.98 (12) | O2—C15—H12 | 105.8 (10) |
C8—C3—C2 | 120.62 (12) | H10—C15—H12 | 108.6 (14) |
O1—C6—C5 | 123.84 (12) | H11—C15—H12 | 111.6 (14) |
O1—C6—C7 | 116.85 (12) | O3—C16—H16 | 114.0 (13) |
C5—C6—C7 | 119.30 (12) | O3—C16—H17 | 113.2 (13) |
O2—C7—C8 | 125.07 (12) | H16—C16—H17 | 107.7 (18) |
O2—C7—C6 | 114.46 (11) | O3—C16—H18 | 109.9 (12) |
C8—C7—C6 | 120.46 (12) | H16—C16—H18 | 106.6 (18) |
C7—C8—C3 | 120.10 (12) | H17—C16—H18 | 104.8 (18) |
C1—N1—N2—N2 | 0.00 (10) | O2—O2—C7—C6 | 0.0 (4) |
C1—N1—N2—C2 | −179.57 (12) | C15—O2—C7—C6 | −175.37 (12) |
N2—N1—N2—C2 | 0 (33) | O1—C6—C7—O2 | −1.49 (17) |
C9—N3—C1—N1 | −175.91 (13) | O1—C6—C7—O2 | −1.49 (17) |
C9—N3—C1—S1 | 3.6 (2) | C5—C6—C7—O2 | 177.86 (12) |
N2—N1—C1—N3 | 4.88 (18) | O1—C6—C7—O2 | −1.49 (17) |
N2—N1—C1—N3 | 4.88 (18) | O1—C6—C7—O2 | −1.49 (17) |
N2—N1—C1—S1 | −174.68 (10) | C5—C6—C7—O2 | 177.86 (12) |
N2—N1—C1—S1 | −174.68 (10) | O1—C6—C7—C8 | 179.85 (12) |
N1—N2—C2—N2 | 0 (78) | O1—C6—C7—C8 | 179.85 (12) |
N2—N2—C2—C3 | 0.00 (13) | C5—C6—C7—C8 | −0.8 (2) |
N1—N2—C2—C3 | −178.52 (11) | O2—C7—C8—C3 | −177.97 (12) |
C3—C4—C5—C6 | 0.6 (2) | O2—C7—C8—C3 | −177.97 (12) |
C5—C4—C3—C8 | −0.9 (2) | C6—C7—C8—C3 | 0.5 (2) |
C5—C4—C3—C2 | 178.81 (13) | C4—C3—C8—C7 | 0.3 (2) |
N2—C2—C3—C4 | −171.87 (13) | C2—C3—C8—C7 | −179.37 (12) |
N2—C2—C3—C4 | −171.87 (13) | C1—N3—C9—C10 | −17.0 (2) |
N2—C2—C3—C8 | 7.8 (2) | C1—N3—C9—C14 | 164.40 (15) |
N2—C2—C3—C8 | 7.8 (2) | C14—C9—C10—C11 | −1.3 (2) |
O1—O1—C6—C5 | 0.00 (5) | N3—C9—C10—C11 | −179.84 (13) |
O1—O1—C6—C7 | 0.00 (7) | C9—C10—C11—C12 | 1.0 (2) |
C4—C5—C6—O1 | 179.54 (13) | C10—C11—C12—C13 | −0.3 (2) |
C4—C5—C6—O1 | 179.54 (13) | C11—C12—C13—C14 | 0.0 (2) |
C4—C5—C6—C7 | 0.2 (2) | C12—C13—C14—C9 | −0.4 (2) |
C15—O2—C7—O2 | 0 (24) | C10—C9—C14—C13 | 1.0 (2) |
O2—O2—C7—C8 | 0.0 (4) | N3—C9—C14—C13 | 179.68 (13) |
C15—O2—C7—C8 | 3.22 (19) | C7—O2—C15—O2 | 0 (76) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H13···N2 | 0.866 (18) | 2.082 (17) | 2.5865 (16) | 116.4 (14) |
N1—H14···S1i | 0.896 (19) | 2.530 (19) | 3.4033 (13) | 165.2 (15) |
O1—H15···O3ii | 0.86 (2) | 1.81 (2) | 2.6562 (14) | 167.7 (19) |
O3—H19···O2 | 0.83 (2) | 2.26 (2) | 2.8853 (14) | 132.1 (18) |
O3—H19···O1 | 0.83 (2) | 2.46 (2) | 3.1645 (15) | 144.2 (18) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H13···N2 | 0.866 (18) | 2.082 (17) | 2.5865 (16) | 116.4 (14) |
N1—H14···S1i | 0.896 (19) | 2.530 (19) | 3.4033 (13) | 165.2 (15) |
O1—H15···O3ii | 0.86 (2) | 1.81 (2) | 2.6562 (14) | 167.7 (19) |
O3—H19···O2 | 0.83 (2) | 2.26 (2) | 2.8853 (14) | 132.1 (18) |
O3—H19···O1 | 0.83 (2) | 2.46 (2) | 3.1645 (15) | 144.2 (18) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1/2, y−1/2, −z+1/2. |