research communications
N′-[(1E)-(5-Nitrofuran-2-yl)methylidene]thiophene-2-carbohydrazide: and Hirshfeld surface analysis
aFundaçaö Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, bDepartment of Chemistry, University of Aberdeen, Old Aberdeen, AB24 3UE, Scotland, cCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland, dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and eResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
In the title carbohydrazide, C10H7N3O4S, the dihedral angle between the terminal five-membered rings is 27.4 (2)°, with these lying to the same side of the plane through the central CN2C(=O) atoms (r.m.s. deviation = 0.0403 Å), leading to a curved molecule. The conformation about the C=N imine bond [1.281 (5) Å] is E, and the carbonyl O and amide H atoms are anti. In the crystal, N—H⋯O hydrogen bonds lead to supramolecular chains, generated by a 41 screw-axis along the c direction. A three-dimensional architecture is consolidated by thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions, as well as π–π interactions between the thienyl and furanyl rings [inter-centroid distance = 3.515 (2) Å]. These, and other, weak intermolecular interactions, e.g. nitro-N—O⋯π(thienyl), have been investigated by Hirshfeld surface analysis, which confirms the dominance of the conventional N—H⋯O hydrogen bonding to the overall molecular packing.
Keywords: crystal structure; carbohydrazide; hydrogen bonding; conformation; Hirshfeld surface analysis.
CCDC reference: 1486459
1. Chemical context
Thiophene and its derivatives have been well studied as materials, e.g. in applications in organic electronics and photonics (Perepichka & Perepichka, 2009) and in the medical area. In the latter context, the thiophene nucleus is present in many natural and synthetic products having a wide range of pharmacological activities, such as anti-viral (Chan et al., 2004), anti-cancer (Romagnoli et al., 2011), anti-bacterial (Sivadas et al., 2011; Jain et al., 2012), anti-fungal (Jain et al., 2012; Saeed et al., 2010), anti-inflammatory (Kumar et al., 2004) and anti-microbial and anti-tuberculosis (anti-TB) activities (Abdel-Aal et al., 2010). Our interests in the biological activities and structural chemistry of have led us to investigate thiophene and its derivatives as tuberculostatic agents. Thus, some of us have reported the anti-TB activities of acetamido derivatives, 2-(RR′NCOCH2)-thiophene (Lourenço et al., 2007; de Sousa, Ferreira et al., 2008; de Sousa, Lourenço et al., 2008), acetohydrazide derivatives 2-(ArCH=N–NRCOCH2)-thiophene, 1 (Cardoso et al., 2014; Cardoso et al., 2016a) and 2-(ArCH=N–NRCO)-thiophene, 2, R = H or Me (Cardoso et al., 2016a). Herein, we wish to report the of the title compound, (E)-N′-(5-nitrofuran-2-ylmethylene)thiophene-2-carbohydrazide, (I), Scheme 1, as well as an analysis of its Hirshfeld surface. Crystal structures of 1: Ar = 5-nitrothien-2-yl; R = H, Me (Cardoso et al., 2016b), 2: Ar = 5-nitrothien-2-yl; R = H Me (Cardoso et al., 2016b) and 1: Ar = 5-HOC6H4: R = H (Cardoso et al., 2014) have been previously published.
2. Structural commentary
In (I), Fig. 1, the conformation about the C6=N2 bond [1.281 (5) Å] is E. A 5-nitrofuran-2-yl ring is connected at the C6 atom. The furanyl ring is almost planar [r.m.s deviation = 0.006 Å] and the nitro group is almost co-planar with its attached ring as seen in the O3—N3—C10—O2 torsion angle of −1.7 (5)°. The thienyl ring is also planar within experimental error [r.m.s. deviation = 0.005 Å] and orientated so that the sulfur atom is syn to the carbonyl-O1 atom. Overall, the molecule is curved with the rings lying to the same side of the plane through the bridging CN2C(=O) atoms, r.m.s. deviation = 0.0403 Å, with twists noted in both the S1—C1—C5—O1 and N2—C6—C7—O2 torsion angles of −9.8 (5) and 5.4 (6)°, respectively; the dihedral angle between the five-membered rings is 27.4 (2)°.
3. Supramolecular features
The anti relationship between the carbonyl-O and amide-H atoms enables the formation of directional N—H⋯O hydrogen bonds leading to supramolecular chains, generated by a 41 screw-axis propagating along the c-axis direction, Fig. 2a and Table 1. The chains are connected into a three-dimensional architecture by thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions, involving the same nitro-O4 atom, Table 1. In addition, π–π interactions are formed between the two five-membered rings with the inter-centroid distance being 3.515 (2) Å, and the angle of inclination is 3.9 (2)° for (i) 1 − y, − x, − + z. A view of the unit-cell contents is shown in Fig. 2b.
4. Hirshfeld surface analysis
Crystal Explorer 3.1 (Wolff et al., 2012) was used to generate Hirshfeld surfaces mapped over dnorm, de, shape-index, curvedness and electrostatic potential. The latter were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) integrated into Crystal Explorer, wherein the experimental structure was used as the input geometry. In addition, the electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at Hartree–Fock level of theory over a range ±0.12 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (McKinnon et al., 2004) provides a useful summary of intermolecular contacts in the crystal.
Two views of Hirshfeld surfaces calculated for (I), mapped over dnorm in the −0.1 to 1.2 Å range are shown in Fig. 3. The bright-red spots near the amino-N—H and carbonyl-O atoms, labelled as `1' in Fig. 3, indicate their roles as respective donor and acceptor sites in the dominant N—H⋯O hydrogen bonding in the crystal. These also appear as blue and red regions, respectively, corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential in Fig. 4. The light-red spots labelled as `2' and `3' in Fig. 3, and light-blue and light-red regions in Fig. 4, represent the intermolecular thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions involving the nitro-O4 atom as described above in Supramolecular features. The immediate environment about the molecule within dnorm mapped Hirshfeld surface mediated by the above interactions is illustrated in Fig. 5.
The presence of a short intermolecular C⋯C contact between thienyl-C2 and furanyl-C10 atoms, Table 2, which fall within π–π contact between the thienyl and furanyl rings can also be viewed as faint-red spots near these atoms, labelled as `4' in Fig. 3. In the crystal, a comparatively weak N—O⋯π interaction (Spek, 2009) between the nitro—O4 atom and a symmetry-related thienyl ring [N3⋯Cg(S1,C1–C4) = 3.506 (4) Å, O4⋯Cg(S1,C1–C4) = 3.639 (4) Å and N3—O4⋯Cg = 74.0 (2)°] is also evident from the light-blue and red regions corresponding to their respective potentials on the Hirshfeld surface mapped over electrostatic potential in Fig. 4.
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The overall two-dimensional fingerprint plot is shown in Fig. 6a and those delineated into O⋯H/H⋯O, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C, C⋯C, C⋯O/O⋯C and S⋯H/H⋯S contacts (McKinnon et al., 2007) are illustrated in Fig. 6b–h, respectively; their relative contributions to the overall Hirshfeld surface are summarized in Table 3. In the fingerprint plot delineated into O⋯H/H⋯O contacts, which make the greatest contribution to the Hirshfeld surface, i.e. 36.4%, arises from the N—H⋯O hydrogen bond and is viewed as a pair of spikes with tips at de + di ∼2.1 Å in Fig. 6b. The C—H⋯O interactions, which are masked by the above interactions, appear as the groups of green points appearing in pairs in the plot. However, a forceps-like distribution of points in the fingerprint plot delineated into C⋯O/O⋯C contacts, Fig. 6g, with the tips at de + di ∼2.3 Å is indicative of C—H⋯O interactions. In the fingerprint plot corresponding to H⋯H contacts, which make the next most significant contribution to the surface, Fig. 6c, the points are scattered in the plot at (de, di) distances greater than their van der Waals separations with the comparatively low contribution, i.e. 13.6%, due to the relatively low hydrogen-atom content in the molecule. The absence of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C and the low contribution to the Hirshfeld surface, Fig. 6e and Table 3, clearly indicate the absence of C—H⋯π interactions in the crystal. However, a pair of thin edges with their ends at de + di ∼2.9 Å belong to short interatomic C⋯H contacts, Table 2. The lung-shaped distribution of points with the bending at at de + di ∼2.7 Å in the fingerprint plot corresponding to N⋯H/H⋯N contacts, Fig. 6e, with a 7.5% contribution to the Hirshfeld surface is the result of short interatomic N⋯H/H⋯N contacts, Table 2. The C⋯C contacts assigned to the short C2⋯C10 contact and π–π stacking interactions appear as the distribution of points around de = di ∼1.7 Å, Fig. 6f. The presence of π–π stacking interactions between the symmetry-related thienyl and furanyl rings is also indicated by the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with the shape-index property identified with arrows in the images of Fig. 7, and in the flat region on the Hirshfeld surface mapped over curvedness in Fig. 8. Finally, although the S⋯H/H⋯S contacts in the structure of (I) make a 8.9% contribution to the surface, and also show a nearly symmetrical distribution of points in the corresponding fingerprint plot, Fig. 6h, they do not have a significant influence on the molecular packing as they are separated at distances greater than the sum of their van der Waals radii.
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The final analysis based on the Hirshfeld surfaces is an evaluation of enrichment ratios (ER) (Jelsch et al., 2014); a list of the ER values is given in Table 4. The low content of hydrogen in the molecular structure of (I) yields a very low ER, 0.72, indicating no propensity to form intermolecular H⋯H contacts. The ER value of 1.55 from O⋯H/H⋯O contacts is in the expected 1.2–1.6 range and confirm their involvement in the N—H⋯O and C—H⋯O interactions. The presence of intermolecular C—H⋯O interactions is also confirmed through the ER value near to unity i.e. 0.99, corresponding to the C⋯O/O⋯C contacts. The high propensity to form π–π stacking interactions between the thienyl and furanyl rings is reflected from the high enrichment ratio 2.66 for C⋯C contacts. The ER value of 1.26 resulting from 6.75% of the surface occupied by nitrogen atoms and a 7.5% contribution to the Hirshfeld surface from N⋯H/H⋯N contacts is due to the presence of short N⋯H contacts in the structure, Table 2. The ER values < 1 related to other contacts and low % contribution to the surface indicate their low significance in the crystal.
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5. Database survey
A search of the crystallographic literature (Groom et al., 2016) reveals one closely related structure, namely the species with a methyl group rather than a nitro group, N′-[(5-methyl-2-furyl)methylene]thiophene-2-carbohydrazide [(II); Jiang, 2010].
The relative dispositions of the heteroatoms in the two structures are the same but, the twist in (II) is significantly less as seen in the dihedral angle of 10.2 (6)° between the five-membered rings. This is highlighted in the overlay diagram in Fig. 9. The molecular structure of the all thienyl analogue of (I) has been described recently (Cardoso et al., 2016b). There are two almost identical, near planar molecules in the and each adopts the conformation indicated in Scheme 2, which might be described as having the thienyl-S atoms syn. The intramolecular S⋯S separations of 3.770 (4) and 3.879 (4) Å, are beyond the sum of their van der Waals radii. The conformational differences found for the thienyl molecules is consistent with our NMR studies that indicate multiple conformations exist in solution for these compounds.
6. Synthesis and crystallization
The title compound was prepared following a procedure outlined in Fig. 10. Yellow rods of (I) were grown by slow evaporation of a methanol solution held at room temperature. Yellow solid; m.p.: 528–529 K. IR νmax (cm−1; KBr disc): 1629 (C=O); 3209 (N—H). 1H NMR (400 MHz; DMSO) δ: 12.26 (1H; NH), 8.10–7.96 (3H; m; H-4′; H-8′ and H-9′), 7.81 (1H; d; JHH = 3.9 Hz; H-5), 7.28 (1H; d; JHH = 3.9 Hz; H-4), 7.26-7.24 (1H; m; H-3). 13C NMR (100 MHz DMSO) δ: 161.6 (C=O), 157.9 (C-2), 151.6 (C-4′), 137.5 (C-5′), 135.2 (C-3), 132.7 (C-2) 131.4 (C-7′), 129.7 (C-8′), 128.2 (C-9′), 127.1 (C-9′). HRMS m/z: 288.0082 [M + Na]+; (calculated for [C10H7N3O4S+Na]+: 288.0055.
7. details
Crystal data, data collection and structure . The C-bound H atoms were geometrically placed (C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atom was located from a difference map and refined with (N—H = 0.88±0.01 Å), and with Uiso(H) = 1.2Ueq(C). The slightly elongated displacement ellipsoid for the C2 atom in the thienyl ring is likely due to unresolved disorder in the ring where the second, co-planar orientation related by 180° to that modelled is present. However, this was not modelled as the maximum residual electron density peak was only 0.46 e Å−3, 0.61 Å from the C2 atom. It is also noted that the relevant S—C and C—C bond lengths show the expected values.
details are summarized in Table 5Supporting information
CCDC reference: 1486459
https://doi.org/10.1107/S2056989016009968/hb7593sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016009968/hb7593Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016009968/hb7593Isup3.cml
Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell
CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C10H7N3O4S | Dx = 1.605 Mg m−3 |
Mr = 265.25 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41cd | Cell parameters from 9311 reflections |
a = 17.4072 (16) Å | θ = 3.3–27.5° |
c = 14.4881 (10) Å | µ = 0.31 mm−1 |
V = 4390.0 (9) Å3 | T = 100 K |
Z = 16 | Rod, yellow |
F(000) = 2176 | 0.13 × 0.03 × 0.02 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 2292 independent reflections |
Radiation source: Rotating Anode | 2081 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.061 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
profile data from ω–scans | h = −22→22 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −22→13 |
Tmin = 0.543, Tmax = 1.000 | l = −15→18 |
10325 measured reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters not defined? |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.066P)2 + 2.8065P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.113 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.46 e Å−3 |
2292 reflections | Δρmin = −0.31 e Å−3 |
166 parameters | Absolute structure: Flack x determined using 766 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al. 2013) |
2 restraints | Absolute structure parameter: −0.06 (6) |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.48085 (6) | 0.10242 (6) | 0.44233 (8) | 0.0259 (3) | |
O1 | 0.36361 (17) | 0.16769 (16) | 0.56218 (18) | 0.0200 (6) | |
O2 | 0.22698 (16) | 0.39128 (15) | 0.66600 (18) | 0.0161 (6) | |
O3 | 0.25495 (19) | 0.40880 (19) | 0.8415 (2) | 0.0265 (7) | |
O4 | 0.18400 (18) | 0.51202 (19) | 0.8477 (2) | 0.0266 (7) | |
N1 | 0.31555 (19) | 0.25578 (19) | 0.4618 (2) | 0.0165 (7) | |
H1N | 0.319 (3) | 0.278 (2) | 0.4082 (17) | 0.020* | |
N2 | 0.28004 (19) | 0.29467 (19) | 0.5325 (2) | 0.0171 (7) | |
N3 | 0.2125 (2) | 0.4568 (2) | 0.8067 (2) | 0.0196 (7) | |
C1 | 0.4111 (2) | 0.1666 (2) | 0.4094 (3) | 0.0162 (8) | |
C2 | 0.4137 (2) | 0.1857 (2) | 0.3137 (3) | 0.0206 (9) | |
H2 | 0.3797 | 0.2195 | 0.2824 | 0.025* | |
C3 | 0.4770 (2) | 0.1443 (2) | 0.2728 (3) | 0.0221 (9) | |
H3 | 0.4901 | 0.1482 | 0.2093 | 0.027* | |
C4 | 0.5164 (3) | 0.0990 (2) | 0.3336 (3) | 0.0251 (10) | |
H4 | 0.5595 | 0.0686 | 0.3166 | 0.030* | |
C5 | 0.3616 (2) | 0.1960 (2) | 0.4838 (3) | 0.0158 (8) | |
C6 | 0.2361 (2) | 0.3499 (2) | 0.5074 (3) | 0.0170 (8) | |
H6 | 0.2247 | 0.3576 | 0.4439 | 0.020* | |
C7 | 0.2040 (2) | 0.4004 (2) | 0.5764 (3) | 0.0166 (8) | |
C8 | 0.1580 (2) | 0.4633 (2) | 0.5673 (3) | 0.0183 (8) | |
H8 | 0.1351 | 0.4815 | 0.5120 | 0.022* | |
C9 | 0.1511 (2) | 0.4962 (2) | 0.6561 (3) | 0.0181 (8) | |
H9 | 0.1228 | 0.5406 | 0.6731 | 0.022* | |
C10 | 0.1940 (2) | 0.4502 (2) | 0.7116 (3) | 0.0160 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0246 (6) | 0.0270 (6) | 0.0260 (5) | 0.0060 (4) | 0.0037 (5) | 0.0022 (4) |
O1 | 0.0246 (16) | 0.0207 (15) | 0.0146 (14) | 0.0052 (11) | 0.0020 (11) | 0.0039 (11) |
O2 | 0.0182 (14) | 0.0169 (14) | 0.0132 (13) | 0.0042 (10) | −0.0002 (11) | −0.0039 (11) |
O3 | 0.0289 (17) | 0.0334 (18) | 0.0174 (15) | 0.0083 (13) | −0.0045 (13) | −0.0010 (13) |
O4 | 0.0333 (18) | 0.0288 (18) | 0.0179 (15) | 0.0057 (14) | 0.0017 (13) | −0.0096 (13) |
N1 | 0.0219 (17) | 0.0185 (17) | 0.0093 (15) | 0.0042 (13) | 0.0034 (13) | 0.0006 (13) |
N2 | 0.0183 (17) | 0.0187 (16) | 0.0142 (16) | −0.0004 (13) | −0.0009 (13) | −0.0027 (13) |
N3 | 0.0209 (17) | 0.0195 (18) | 0.0183 (17) | 0.0003 (13) | 0.0021 (14) | −0.0034 (13) |
C1 | 0.0161 (18) | 0.0135 (18) | 0.0191 (19) | −0.0022 (14) | 0.0016 (15) | −0.0006 (14) |
C2 | 0.020 (2) | 0.0125 (19) | 0.029 (2) | −0.0047 (14) | 0.0117 (17) | −0.0102 (16) |
C3 | 0.028 (2) | 0.019 (2) | 0.020 (2) | 0.0015 (16) | 0.0085 (17) | −0.0002 (16) |
C4 | 0.021 (2) | 0.027 (2) | 0.027 (2) | 0.0054 (17) | 0.0089 (18) | −0.0021 (18) |
C5 | 0.0177 (19) | 0.0146 (18) | 0.0151 (18) | −0.0033 (14) | −0.0004 (15) | −0.0007 (14) |
C6 | 0.0170 (19) | 0.019 (2) | 0.0150 (18) | 0.0014 (14) | 0.0004 (14) | −0.0017 (15) |
C7 | 0.0176 (19) | 0.023 (2) | 0.0096 (18) | −0.0021 (15) | −0.0001 (14) | 0.0016 (15) |
C8 | 0.018 (2) | 0.022 (2) | 0.0153 (19) | 0.0012 (14) | 0.0007 (15) | 0.0013 (16) |
C9 | 0.020 (2) | 0.0170 (19) | 0.0176 (19) | 0.0015 (15) | 0.0042 (15) | 0.0017 (15) |
C10 | 0.0156 (19) | 0.0174 (18) | 0.0150 (18) | −0.0003 (14) | 0.0021 (14) | −0.0013 (14) |
S1—C4 | 1.694 (5) | C1—C5 | 1.472 (5) |
S1—C1 | 1.718 (4) | C2—C3 | 1.444 (6) |
O1—C5 | 1.239 (5) | C2—H2 | 0.9500 |
O2—C10 | 1.349 (5) | C3—C4 | 1.367 (6) |
O2—C7 | 1.367 (5) | C3—H3 | 0.9500 |
O3—N3 | 1.225 (5) | C4—H4 | 0.9500 |
O4—N3 | 1.234 (4) | C6—C7 | 1.443 (5) |
N1—C5 | 1.351 (5) | C6—H6 | 0.9500 |
N1—N2 | 1.374 (5) | C7—C8 | 1.364 (6) |
N1—H1N | 0.870 (14) | C8—C9 | 1.413 (6) |
N2—C6 | 1.281 (5) | C8—H8 | 0.9500 |
N3—C10 | 1.419 (5) | C9—C10 | 1.358 (6) |
C1—C2 | 1.427 (6) | C9—H9 | 0.9500 |
C4—S1—C1 | 91.3 (2) | S1—C4—H4 | 123.4 |
C10—O2—C7 | 104.6 (3) | O1—C5—N1 | 122.6 (4) |
C5—N1—N2 | 118.1 (3) | O1—C5—C1 | 121.1 (4) |
C5—N1—H1N | 120 (3) | N1—C5—C1 | 116.3 (3) |
N2—N1—H1N | 119 (3) | N2—C6—C7 | 119.4 (3) |
C6—N2—N1 | 115.3 (3) | N2—C6—H6 | 120.3 |
O3—N3—O4 | 125.1 (4) | C7—C6—H6 | 120.3 |
O3—N3—C10 | 118.9 (3) | O2—C7—C8 | 110.9 (3) |
O4—N3—C10 | 116.0 (3) | O2—C7—C6 | 118.3 (3) |
C2—C1—C5 | 130.5 (4) | C8—C7—C6 | 130.5 (4) |
C2—C1—S1 | 113.5 (3) | C7—C8—C9 | 106.7 (4) |
C5—C1—S1 | 115.9 (3) | C7—C8—H8 | 126.7 |
C1—C2—C3 | 107.8 (4) | C9—C8—H8 | 126.7 |
C1—C2—H2 | 126.1 | C10—C9—C8 | 104.7 (4) |
C3—C2—H2 | 126.1 | C10—C9—H9 | 127.6 |
C4—C3—C2 | 114.0 (4) | C8—C9—H9 | 127.6 |
C4—C3—H3 | 123.0 | O2—C10—C9 | 113.1 (3) |
C2—C3—H3 | 123.0 | O2—C10—N3 | 116.1 (3) |
C3—C4—S1 | 113.3 (3) | C9—C10—N3 | 130.7 (4) |
C3—C4—H4 | 123.4 | ||
C5—N1—N2—C6 | −178.9 (3) | C10—O2—C7—C8 | −0.1 (4) |
C4—S1—C1—C2 | 0.7 (3) | C10—O2—C7—C6 | 174.1 (3) |
C4—S1—C1—C5 | −176.2 (3) | N2—C6—C7—O2 | 5.4 (6) |
C5—C1—C2—C3 | 175.6 (4) | N2—C6—C7—C8 | 178.2 (4) |
S1—C1—C2—C3 | −0.7 (4) | O2—C7—C8—C9 | −0.1 (4) |
C1—C2—C3—C4 | 0.4 (5) | C6—C7—C8—C9 | −173.3 (4) |
C2—C3—C4—S1 | 0.2 (5) | C7—C8—C9—C10 | 0.2 (4) |
C1—S1—C4—C3 | −0.5 (3) | C7—O2—C10—C9 | 0.2 (4) |
N2—N1—C5—O1 | 11.6 (5) | C7—O2—C10—N3 | −176.4 (3) |
N2—N1—C5—C1 | −167.3 (3) | C8—C9—C10—O2 | −0.3 (4) |
C2—C1—C5—O1 | 174.0 (4) | C8—C9—C10—N3 | 175.8 (4) |
S1—C1—C5—O1 | −9.8 (5) | O3—N3—C10—O2 | −1.7 (5) |
C2—C1—C5—N1 | −7.1 (6) | O4—N3—C10—O2 | 178.1 (3) |
S1—C1—C5—N1 | 169.1 (3) | O3—N3—C10—C9 | −177.6 (4) |
N1—N2—C6—C7 | −172.1 (3) | O4—N3—C10—C9 | 2.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.87 (3) | 2.05 (3) | 2.882 (4) | 159 (3) |
C4—H4···O4ii | 0.95 | 2.42 | 3.293 (6) | 152 |
C8—H8···O4iii | 0.95 | 2.53 | 3.242 (5) | 132 |
Symmetry codes: (i) −y+1/2, x, z−1/4; (ii) x+1/2, y−1/2, z−1/2; (iii) x, −y+1, z−1/2. |
Contact | Distance | Symmetry operation |
C2···C10 | 3.361 (5) | 1/2 - x, 1/2 -y, -1/2 + z |
C5···H2 | 2.89 | 1/2 - x, y, 1/4 + z |
N2···H6 | 2.72 | 1/2 - x, y, 1/4 + z |
N2···H1N | 2.69 (4) | 1/2 - x, y, 1/4 + z |
O1···H2 | 2.68 | 1/2 - x, y, 1/4 + z |
O1···H6 | 2.68 | 1/2 - x, y, 1/4 + z |
Contact | % |
H···H | 13.8 |
O···H/H···O | 36.4 |
C···H/H···C | 7.4 |
N···H/H···N | 7.5 |
C···C | 6.6 |
C···O/O···C | 8.3 |
S···H/H···S | 8.9 |
N···O/O···N | 3.1 |
S···O/O···S | 2.6 |
C···N/N···C | 2.1 |
O···O | 1.5 |
N···S/S···N | 0.6 |
S···S | 0.6 |
C···S/S···C | 0.5 |
N···N | 0.1 |
Contact | ER |
H···H | 0.72 |
O···H/H···O | 1.55 |
N···H/H···N | 1.26 |
C···C | 2.66 |
C···O/O···C | 0.99 |
C···H/H···C | 0.53 |
S···O/O···S | 0.71 |
N···O/O···N | 0.86 |
S···H/H···S | 0.64 |
Footnotes
‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.
Acknowledgements
The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CNPq (Brazil).
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