Synthesis and crystal structure of (<em>E</em>)-2-({2-[azaniumylidene(methylsulfanyl)methyl]hydrazinylidene}methyl)benzene-1,4-diol hydrogen sulfate
Chemical context
Thiosemicarbazones and their complexes are well known for their pharmacological properties, as antimicrobial (Plech et al., 2011 ▸; Pandeya et al., 1999 ▸; Küçükgüzel et al., 2006 ▸), anti-inflammatory (Palaska et al., 2002 ▸) and antiumoural (de Oliveira et al., 2015 ▸) agents. Complexes of thiosemicarbazones are studied in the literature as drug candidates, biomarkers and biocatalysts (Hayne et al., 2014 ▸; Lim et al., 2010 ▸). It is believed that the biological activity of these compounds has a strong relationship with the nature of the aldehydes and ketones from which those thiosemicarbazones were obtained (Teoh et al., 1999 ▸), and also on the substituents attached at the NH2 N atom (Beraldo & Gambino, 2004 ▸). An interesting attribute of thiosemicarbazones is their ability to exhibit thione–thiol tautomerism and they can also exist as E and Z isomers. Thiosemicarbazones have an excellent capacity to complex transition metals, acting as chelating agents; this process usually takes place via dissociation of the acidic proton (Pal et al., 2002 ▸). The crystal structure of the title molecular salt was determined in order to investigate its biological and catalytic activities.
Structural commentary
The molecular structure of the title molecular salt is illustrated in Fig. 1 ▸. It comprises two entities, i.e. a thiosemicarbazone cation and a hydrogen sulfate anion. The cation is essentially planar and shows an E conformation with regard to the C6—N5 bond, the maximum deviation from the mean plane through the 15 non-H atoms being 0.1 (2) Å for atom C6. This planarity is due to electron delocalization along the cation backbone, which is further stabilized by an intramolecular O13—H13⋯N5 hydrogen bond (Zhu et al., 2004 ▸). The bond lengths and angles resemble those observed for similar thiosemicarbazone derivatives (Gangadharan et al., 2015 ▸; Joseph et al., 2004 ▸; Nehar et al., 2016 ▸; Houari et al., 2013 ▸). The anion (hydrogen sulfate) is disordered, split over two sets of siteswith relative occupancies of 0.501 (6) and 0.499 (6), and labelled with A and B suffixes.
Supramolecular features
In the crystal, the three-dimensional structure is established through an extensive network of O—H⋯O and N—H⋯O hydrogen bonds. Also within this network exists a weak C—H⋯O intermolecular hydrogen bond (Table 1 ▸ and Fig. 2 ▸). The crystal packing is shown in Fig. 2 ▸.
Table 1
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
---|---|---|---|---|
C10—H10⋯O12A | 0.95 | 2.60 | 3.541 (10) | 170 |
N3—H3A⋯O12A | 0.89 (2) | 1.85 (2) | 2.738 (12) | 178 (3) |
N3—H3A⋯O12B | 0.89 (2) | 1.98 (2) | 2.841 (11) | 163 (3) |
N3—H3B⋯O14 | 0.86 (2) | 2.05 (2) | 2.874 (3) | 160 (3) |
N4—H4⋯O13A | 0.86 (3) | 2.00 (3) | 2.849 (5) | 167 (3) |
N4—H4⋯O13B | 0.86 (3) | 2.00 (3) | 2.841 (5) | 164 (3) |
O13—H13⋯N5 | 0.78 (3) | 2.03 (3) | 2.685 (3) | 142 (3) |
O14—H14⋯O11A | 0.83 (4) | 1.90 (4) | 2.716 (16) | 167 (3) |
O14—H14⋯O11B | 0.83 (4) | 1.82 (4) | 2.62 (2) | 162 (3) |
O14A—H14A⋯O11A | 0.84 | 2.28 | 3.123 (17) | 180 |
O14B—H14B⋯S2B | 0.84 | 2.73 | 3.490 (9) | 152 |
O14B—H14B⋯O13B | 0.84 | 1.73 | 2.567 (7) | 180 |
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .
Database survey
A search in the Cambridge Structural Database (CSD, Version 5.4, May 2019 update; Groom et al., 2016 ▸) for the S-methyl(methylidene)thiosemicarbazidium cation yielded three results, viz. S-methyl-N-(pyrrolyl-2-methylene)isothiosemicarbazidium iodide monohydrate (CSD refcode JIHZUV; Bourosh et al., 1990 ▸), 8-quinolinealdehyde S-methylthiosemicarbazone hydrochloride dihydrate (RUJXOK; Botoshansky et al., 2009 ▸) and ((E)-{2-[(E)-(4-hydroxynaphthalen-1-yl)methylidene]hydrazin-1-yl}(methylsulfanyl)methylidene)azanium hydrogen sulfate monohydrate. The three-dimensional coordinates for the first structure are unavailable. A comparison of the structures reveals that the cation in the RUJXOK structure is less planar than the cation in ESOTIR, the latter being more similar to the cation of the title compound. However, for structures RUJXOK and ESOTIR, the bond lengths and angles are similar to those of the title molecular salt.
Synthesis and crystallization
An equimolar amount of thiosemicarbazide (10 mmol, 0.91 g) and 2,5-dihydroxybenzaldehyde (10 mmol, 1.38 g) were dissolved in a methanol–water solution in the presence of sulfuric acid. The mixture was then refluxed for 3 h. The solution was filtered and left to evaporate at room temperature. After slow evaporation, brown crystals suitable for X-ray diffraction analysis were obtained.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The hydrogen sulfate anion is disordered and had to be modelled as two conformations A and B, with relative occupancies of 0.501 (6) and 0.499 (6), respectively. H atoms were located in difference Fourier maps, but were subsequently included in calculated positions and treated as riding on their parent atoms with constrained thermal parameters: Uiso(H) = 1.5Ueq(C) and C—H = 0.98 Å for methyl H atoms, and Uiso(H) = 1.2Ueq(C,N) and C—H = 0.95 Å or N—H = 0.88 Å otherwise.
Table 2
Crystal data | |
Chemical formula | C9H12N3O2S·HSO4 |
Mr | 323.34 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 4.9411 (8), 16.139 (2), 16.426 (3) |
β (°) | 100.440 (7) |
V (Å) | 1288.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
μ (mm) | 0.44 |
Crystal size (mm) | 0.38 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2015 ▸) |
Tmin, Tmax | 0.838, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7962, 2846, 2014 |
Rint | 0.045 |
(sin θ/λ)max (Å) | 0.644 |
Refinement | |
R[F > 2σ(F)], wR(F), S | 0.050, 0.147, 1.03 |
No. of reflections | 2846 |
No. of parameters | 243 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å) | 0.36, −0.46 |
Abstract
The title molecular salt, C9H12N3O2S·HSO4, was obtained through the protonation of the azomethine N atom in a sulfuric acid medium. The crystal comprises two entities, a thiosemicarbazide cation and a hydrogen sulfate anion. The cation is essentially planar and is further stabilized by a strong intramolecular O—H⋯N hydrogen bond. In the crystal, a three-dimensional network is established through O—H⋯O and N—H⋯O hydrogen bonds. A weak intermolecular C—H⋯O hydrogen bond is also observed. The hydrogen sulfate anion exhibits disorder over two sets of sites and was modelled with refined occupancies of 0.501 (6) and 0.499 (6).
Crystal structure: contains datablock(s) global. DOI: 10.1107/S2056989019014233/lh5926sup1.cif
CCDC references: 1960006, 1960006
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are grateful for the support provided by the Algerian Ministry for Education and Research.
supplementary crystallographic information
Crystal data
C9H12N3O2S·HSO4− | F(000) = 672 |
Mr = 323.34 | Dx = 1.667 Mg m3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9411 (8) Å | Cell parameters from 2859 reflections |
b = 16.139 (2) Å | θ = 2.5–27.0° |
c = 16.426 (3) Å | µ = 0.44 mm1 |
β = 100.440 (7)° | T = 150 K |
V = 1288.2 (3) Å3 | Prism, colourless |
Z = 4 | 0.38 × 0.15 × 0.12 mm |
Data collection
Bruker APEXII diffractometer | 2846 independent reflections |
Radiation source: fine-focus sealed tube | 2014 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
CCD rotation images, thin slices scans | θmax = 27.3°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2014) | h = −6→4 |
Tmin = 0.838, Tmax = 0.948 | k = −19→20 |
7962 measured reflections | l = −21→19 |
Refinement
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F > 2σ(F)] = 0.050 | Hydrogen site location: mixed |
wR(F) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ(Fo) + (0.086P)] where P = (Fo + 2Fc)/3 |
2846 reflections | (Δ/σ)max < 0.001 |
243 parameters | Δρmax = 0.36 e Å3 |
8 restraints | Δρmin = −0.46 e Å3 |
Special details
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. |
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F, conventional R-factors R are based on F, with F set to zero for negative F. The threshold expression of F > 2sigma(F) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å)
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.99180 (14) | 0.09724 (4) | 0.39012 (4) | 0.0247 (2) | |
C1 | 1.1843 (6) | 0.05832 (18) | 0.31564 (19) | 0.0283 (7) | |
H1A | 1.103765 | 0.079127 | 0.260512 | 0.042* | |
H1B | 1.178644 | −0.002377 | 0.315474 | 0.042* | |
H1C | 1.375761 | 0.076956 | 0.330229 | 0.042* | |
C2 | 1.0137 (5) | 0.20289 (18) | 0.37549 (16) | 0.0196 (6) | |
N3 | 1.1584 (4) | 0.23722 (15) | 0.32555 (15) | 0.0212 (5) | |
H3A | 1.163 (6) | 0.2922 (11) | 0.3217 (18) | 0.025* | |
H3B | 1.253 (5) | 0.2090 (17) | 0.2961 (16) | 0.025* | |
N4 | 0.8734 (5) | 0.25101 (15) | 0.41903 (15) | 0.0221 (5) | |
H4 | 0.897 (6) | 0.304 (2) | 0.4220 (19) | 0.027* | |
N5 | 0.7288 (4) | 0.21422 (15) | 0.47329 (14) | 0.0209 (5) | |
C6 | 0.6012 (5) | 0.26348 (17) | 0.51479 (17) | 0.0207 (6) | |
H6 | 0.611234 | 0.321565 | 0.506437 | 0.025* | |
C7 | 0.4421 (5) | 0.23214 (17) | 0.57410 (16) | 0.0179 (6) | |
C8 | 0.4293 (5) | 0.14784 (17) | 0.59347 (17) | 0.0204 (6) | |
C9 | 0.2738 (5) | 0.12280 (18) | 0.65151 (18) | 0.0239 (6) | |
H9 | 0.265269 | 0.065663 | 0.664710 | 0.029* | |
C10 | 0.1324 (5) | 0.17925 (17) | 0.69007 (17) | 0.0225 (6) | |
H10 | 0.025988 | 0.161037 | 0.729373 | 0.027* | |
C11 | 0.1446 (5) | 0.26363 (17) | 0.67161 (17) | 0.0199 (6) | |
C12 | 0.2983 (5) | 0.28879 (17) | 0.61429 (16) | 0.0209 (6) | |
H12 | 0.306923 | 0.346085 | 0.601728 | 0.025* | |
O13 | 0.5640 (4) | 0.08764 (12) | 0.55849 (13) | 0.0270 (5) | |
H13 | 0.648 (7) | 0.106 (2) | 0.527 (2) | 0.032* | |
O14 | 0.0054 (4) | 0.31741 (13) | 0.71335 (13) | 0.0279 (5) | |
H14 | 0.001 (6) | 0.366 (2) | 0.697 (2) | 0.034* | |
S2A | 0.8844 (12) | 0.5353 (4) | 0.6254 (4) | 0.0254 (10) | 0.501 (6) |
O11A | 1.081 (3) | 0.4743 (10) | 0.6620 (9) | 0.031 (3) | 0.501 (6) |
O12A | 0.810 (2) | 0.5938 (7) | 0.6848 (5) | 0.030 (2) | 0.501 (6) |
O13A | 0.9688 (11) | 0.5797 (2) | 0.5572 (3) | 0.0297 (14) | 0.501 (6) |
O14A | 0.6216 (9) | 0.4839 (3) | 0.5891 (3) | 0.0302 (13) | 0.501 (6) |
H14A | 0.476218 | 0.481337 | 0.608697 | 0.045* | 0.501 (6) |
S2B | 0.9553 (12) | 0.5327 (5) | 0.6250 (5) | 0.0292 (12) | 0.499 (6) |
O11B | 1.084 (4) | 0.4751 (12) | 0.6870 (8) | 0.038 (3) | 0.499 (6) |
O12B | 0.767 (2) | 0.5891 (7) | 0.6534 (6) | 0.038 (2) | 0.499 (6) |
O13B | 1.1639 (10) | 0.5733 (3) | 0.5857 (3) | 0.0294 (13) | 0.499 (6) |
O14B | 0.7723 (10) | 0.4819 (4) | 0.5562 (3) | 0.0506 (17) | 0.499 (6) |
H14B | 0.793868 | 0.463761 | 0.509852 | 0.076* | 0.499 (6) |
Atomic displacement parameters (Å)
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0307 (4) | 0.0178 (4) | 0.0285 (4) | −0.0005 (3) | 0.0136 (3) | 0.0018 (3) |
C1 | 0.0313 (14) | 0.0220 (15) | 0.0354 (18) | 0.0012 (12) | 0.0162 (13) | 0.0003 (13) |
C2 | 0.0205 (11) | 0.0207 (14) | 0.0172 (14) | −0.0001 (11) | 0.0027 (11) | −0.0014 (11) |
N3 | 0.0252 (11) | 0.0175 (12) | 0.0236 (13) | 0.0011 (10) | 0.0114 (10) | 0.0049 (10) |
N4 | 0.0285 (11) | 0.0178 (12) | 0.0228 (13) | −0.0013 (10) | 0.0121 (10) | 0.0013 (10) |
N5 | 0.0226 (10) | 0.0229 (12) | 0.0188 (12) | −0.0018 (9) | 0.0079 (9) | 0.0010 (10) |
C6 | 0.0230 (11) | 0.0178 (14) | 0.0220 (15) | −0.0004 (11) | 0.0057 (11) | 0.0001 (11) |
C7 | 0.0197 (11) | 0.0182 (13) | 0.0162 (14) | −0.0007 (10) | 0.0040 (10) | −0.0011 (11) |
C8 | 0.0214 (11) | 0.0185 (14) | 0.0211 (15) | −0.0003 (10) | 0.0035 (11) | −0.0024 (11) |
C9 | 0.0285 (13) | 0.0185 (14) | 0.0252 (15) | −0.0032 (12) | 0.0063 (12) | 0.0006 (12) |
C10 | 0.0249 (12) | 0.0238 (15) | 0.0201 (15) | −0.0030 (11) | 0.0075 (11) | 0.0009 (12) |
C11 | 0.0214 (11) | 0.0191 (14) | 0.0202 (14) | 0.0002 (11) | 0.0064 (11) | −0.0040 (11) |
C12 | 0.0244 (12) | 0.0172 (14) | 0.0213 (15) | −0.0008 (11) | 0.0043 (11) | 0.0002 (11) |
O13 | 0.0342 (11) | 0.0182 (10) | 0.0329 (13) | 0.0024 (9) | 0.0175 (9) | −0.0009 (9) |
O14 | 0.0363 (10) | 0.0186 (10) | 0.0336 (12) | 0.0014 (9) | 0.0186 (9) | −0.0015 (9) |
S2A | 0.038 (3) | 0.0164 (14) | 0.0231 (13) | −0.0028 (16) | 0.0076 (16) | 0.0061 (9) |
O11A | 0.028 (3) | 0.020 (3) | 0.043 (8) | 0.003 (3) | 0.007 (5) | 0.010 (5) |
O12A | 0.040 (4) | 0.026 (3) | 0.026 (4) | −0.010 (3) | 0.009 (3) | −0.005 (3) |
O13A | 0.050 (3) | 0.018 (2) | 0.026 (3) | −0.004 (2) | 0.021 (2) | 0.0035 (18) |
O14A | 0.031 (2) | 0.025 (2) | 0.038 (3) | −0.0049 (18) | 0.016 (2) | −0.0021 (19) |
S2B | 0.037 (3) | 0.0182 (14) | 0.0338 (15) | −0.0054 (16) | 0.0117 (17) | −0.0075 (10) |
O11B | 0.051 (4) | 0.030 (4) | 0.035 (7) | −0.001 (3) | 0.014 (5) | 0.007 (5) |
O12B | 0.038 (4) | 0.017 (3) | 0.062 (7) | 0.005 (3) | 0.021 (5) | −0.011 (5) |
O13B | 0.030 (3) | 0.025 (2) | 0.036 (3) | 0.0028 (19) | 0.014 (2) | 0.008 (2) |
O14B | 0.042 (3) | 0.068 (4) | 0.044 (3) | −0.018 (3) | 0.012 (3) | −0.029 (3) |
Geometric parameters (Å, º)
S1—C2 | 1.728 (3) | C9—H9 | 0.9500 |
S1—C1 | 1.794 (3) | C10—C11 | 1.399 (4) |
C1—H1A | 0.9800 | C10—H10 | 0.9500 |
C1—H1B | 0.9800 | C11—O14 | 1.367 (3) |
C1—H1C | 0.9800 | C11—C12 | 1.374 (3) |
C2—N3 | 1.305 (3) | C12—H12 | 0.9500 |
C2—N4 | 1.332 (3) | O13—H13 | 0.78 (3) |
N3—H3A | 0.890 (18) | O14—H14 | 0.83 (4) |
N3—H3B | 0.861 (17) | S2A—O11A | 1.435 (8) |
N4—N5 | 1.374 (3) | S2A—O12A | 1.452 (7) |
N4—H4 | 0.86 (3) | S2A—O13A | 1.453 (6) |
N5—C6 | 1.285 (3) | S2A—O14A | 1.564 (8) |
C6—C7 | 1.449 (3) | O14A—H14A | 0.8399 |
C6—H6 | 0.9500 | S2B—O12B | 1.437 (7) |
C7—C12 | 1.395 (4) | S2B—O11B | 1.439 (8) |
C7—C8 | 1.401 (4) | S2B—O13B | 1.467 (6) |
C8—O13 | 1.362 (3) | S2B—O14B | 1.549 (9) |
C8—C9 | 1.388 (4) | O14B—H14B | 0.8401 |
C9—C10 | 1.371 (4) | ||
C2—S1—C1 | 101.32 (13) | C10—C9—H9 | 119.5 |
S1—C1—H1A | 109.5 | C8—C9—H9 | 119.5 |
S1—C1—H1B | 109.5 | C9—C10—C11 | 120.1 (2) |
H1A—C1—H1B | 109.5 | C9—C10—H10 | 120.0 |
S1—C1—H1C | 109.5 | C11—C10—H10 | 120.0 |
H1A—C1—H1C | 109.5 | O14—C11—C12 | 123.2 (3) |
H1B—C1—H1C | 109.5 | O14—C11—C10 | 117.6 (2) |
N3—C2—N4 | 119.2 (3) | C12—C11—C10 | 119.2 (2) |
N3—C2—S1 | 124.2 (2) | C11—C12—C7 | 121.5 (3) |
N4—C2—S1 | 116.7 (2) | C11—C12—H12 | 119.2 |
C2—N3—H3A | 119.5 (19) | C7—C12—H12 | 119.2 |
C2—N3—H3B | 123 (2) | C8—O13—H13 | 112 (2) |
H3A—N3—H3B | 118 (3) | C11—O14—H14 | 115 (2) |
C2—N4—N5 | 118.6 (2) | O11A—S2A—O12A | 113.5 (9) |
C2—N4—H4 | 122 (2) | O11A—S2A—O13A | 113.2 (7) |
N5—N4—H4 | 118 (2) | O12A—S2A—O13A | 109.8 (7) |
C6—N5—N4 | 116.1 (2) | O11A—S2A—O14A | 104.4 (10) |
N5—C6—C7 | 121.3 (3) | O12A—S2A—O14A | 107.9 (5) |
N5—C6—H6 | 119.4 | O13A—S2A—O14A | 107.6 (5) |
C7—C6—H6 | 119.4 | S2A—O14A—H14A | 126.1 |
C12—C7—C8 | 118.7 (2) | O12B—S2B—O11B | 114.1 (9) |
C12—C7—C6 | 118.3 (2) | O12B—S2B—O13B | 114.0 (7) |
C8—C7—C6 | 123.0 (2) | O11B—S2B—O13B | 110.1 (9) |
O13—C8—C9 | 117.1 (2) | O12B—S2B—O14B | 104.2 (6) |
O13—C8—C7 | 123.4 (2) | O11B—S2B—O14B | 107.4 (11) |
C9—C8—C7 | 119.5 (2) | O13B—S2B—O14B | 106.2 (5) |
C10—C9—C8 | 121.0 (3) | S2B—O14B—H14B | 133.8 |
C1—S1—C2—N3 | −4.6 (3) | C6—C7—C8—C9 | 179.5 (2) |
C1—S1—C2—N4 | 175.8 (2) | O13—C8—C9—C10 | 179.7 (2) |
N3—C2—N4—N5 | −178.0 (2) | C7—C8—C9—C10 | 0.1 (4) |
S1—C2—N4—N5 | 1.6 (3) | C8—C9—C10—C11 | −0.4 (4) |
C2—N4—N5—C6 | 178.8 (2) | C9—C10—C11—O14 | −178.4 (2) |
N4—N5—C6—C7 | −179.8 (2) | C9—C10—C11—C12 | 0.3 (4) |
N5—C6—C7—C12 | −177.1 (2) | O14—C11—C12—C7 | 178.7 (2) |
N5—C6—C7—C8 | 3.7 (4) | C10—C11—C12—C7 | 0.1 (4) |
C12—C7—C8—O13 | −179.3 (2) | C8—C7—C12—C11 | −0.4 (4) |
C6—C7—C8—O13 | −0.1 (4) | C6—C7—C12—C11 | −179.6 (2) |
C12—C7—C8—C9 | 0.3 (4) |
Hydrogen-bond geometry (Å, º)
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O12Ai | 0.95 | 2.60 | 3.541 (10) | 170 |
N3—H3A···O12Aii | 0.89 (2) | 1.85 (2) | 2.738 (12) | 178 (3) |
N3—H3A···O12Bii | 0.89 (2) | 1.98 (2) | 2.841 (11) | 163 (3) |
N3—H3B···O14iii | 0.86 (2) | 2.05 (2) | 2.874 (3) | 160 (3) |
N4—H4···O13Aii | 0.86 (3) | 2.00 (3) | 2.849 (5) | 167 (3) |
N4—H4···O13Bii | 0.86 (3) | 2.00 (3) | 2.841 (5) | 164 (3) |
O13—H13···N5 | 0.78 (3) | 2.03 (3) | 2.685 (3) | 142 (3) |
O14—H14···O11Aiv | 0.83 (4) | 1.90 (4) | 2.716 (16) | 167 (3) |
O14—H14···O11Biv | 0.83 (4) | 1.82 (4) | 2.62 (2) | 162 (3) |
O14A—H14A···O11Aiv | 0.84 | 2.28 | 3.123 (17) | 180 |
O14B—H14B···S2Bii | 0.84 | 2.73 | 3.490 (9) | 152 |
O14B—H14B···O13Bii | 0.84 | 1.73 | 2.567 (7) | 180 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) x+3/2, −y+1/2, z−1/2; (iv) x−1, y, z.