research communications
Crystal structures of three N-acylhydrazone isomers
aDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, Mangalore, India, bDepartment of Chemistry, Sri Dharmasthala Manjunatheshwara College (Autonomous), Ujire 574 240, India, cInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Str. 2, D-64287, Darmstadt, Germany, and dKarnataka State Higher Education Council, Y. Ramachandra Road, Gandhingar, Bengaluru-560009, India
*Correspondence e-mail: gowdabt@yahoo.com
The crystal structures of three isomers of (E)-4-chloro-N-{2-[2-(chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide, namely, (E)-4-chloro-N-{2-[2-(2-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (I), (E)-4-chloro-N-{2-[2-(3-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (II) and (E)-4-chloro-N-{2-[2-(4-chlorobenzylidene)hydrazinyl]-2-oxoethyl}benzenesulfonamide (III), with the general formula C15H13Cl2N3O3S are described, with the chloro group in ortho, meta and para positions in the benzylidene benzene ring. All the three isomeric compounds crystallize in the centrosymmetric triclinic P with one molecule each in the and two molecules in the The dihedral angles between the two phenyl rings are 11.09 (14), 53.79 (18) and 72.37 (11)° in (I), (II) and (III), respectively. The central part of the molecule (–C—N—N=C–) is almost linear with C—N—N—C torsion angles of 179.1 (2), −169.5 (3) and 178.5 (2)° for (I), (II) and (III), respectively. In all the three crystals, the molecules form inversion dimers with R22(8) ring motifs, which are further augmented by C—H⋯O interactions.
1. Chemical context
The properties of molecules in solution and the solid state are strongly influenced by weak non-covalent interactions. Weak molecular interactions are investigated routinely in the areas of molecular recognition (Brouwer et al., 1999), self-assembly (Seth et al., 2011), supramolecular chemistry and general host–guest interactions (Kim et al., 2000; Sharma et al., 2009). Analysis of intermolecular interactions and estimation of their energies provide greater insights into molecular conformations (Cao et al., 2020; Jablonski, 2020). The nature and site of substituents influence the extent of polarization of electron distribution in covalent compounds. In our previous work (Purandara et al., 2017a,b), the presence of the electron-withdrawing nitro group on the benzene ring was found to decrease the electronic density, rendering aromatic C—H protons acidic, whereas a methyl substituent did not activate aromatic protons for participation in intermolecular C—H⋯O interactions. In a continuation of these efforts to study the effect of substituents on weak molecular interactions, we report herein the synthesis, characterization and crystal structures of three isomeric molecules.
2. Structural commentary
All three isomers (I)–(III) (Figs. 1–3) crystallize in the centrosymmetric triclinic system with P and with one molecule in the and two molecules in the The conformation of both the sulfonamide and hydrazine N—H bonds are syn with respect to the C=O bonds in all the three compounds. Similarly, the imine C—H bond in the amide part is also syn with respect to the amide N—H bond. All four such bonds in the central part are syn to each other. The C8—O3 and C9—N3 bond lengths of 1.224 (3)–1.236 (3) Å and 1.271 (3)–1.275 (4) Å, respectively, are in the ranges of normal C=O and C=N bond lengths, indicating double-bond character and thus confirming the keto tautomeric form and are comparable with those in related N-acylhydrazone structures (Purandara et al., 2017). The delocalization of π-electron density over the C9/N3/N2/C8/O3 fragment is indicated by the shortening of the C8—N2 [1.337 (3)–1.342 (4) Å] distances compared to the normal C—N single bond length of 1.40 Å (Allen et al., 1987). The sulfonamide bonds are synclinal, anticlinal and antiperiplanar with the S1—N1—C7—C8 torsion angle being 83.6 (3), −107.2 (3) and 171.09 (18)°, in compounds (I), (II) and (III), respectively. The major twist in the molecule occurs about the S1—N1 bond [C1—S1—N1—C7 = 97.6 (2) (I), 65.6 (2) (II) and −80.1 (2)° (III)], giving the molecule an approximate overall L-shape. All the molecules adopt an E configuration around the C9=N3 bond as indicated by the N2—N3—C9—C10 torsion angles of 179.6 (2), 179.1 (3) and 180.0 (2)° for (I), (II) and (III), respectively. The central fragment of the molecule, (C9/N3/N2/C8/O3) is nearly coplanar with the phenyl ring (C10–C15), as indicated by the dihedral angles between their best planes of 4.2 (2) in (I), 11.9 (3) in (II) and 7.0 (3)° in (III). The dihedral angles between the two phenyl rings, C1–C6 and C10–·C15 are 11.1 (1), 53.8 (1) and 72.4 (1)° for (I), (II) and (III), respectively, indicating non-planarity of the three molecules. An intramolecular hydrogen bond, N1—H1N⋯O3, is observed in (II) and (III), generating an S(5) ring motif.
3. Supramolecular features
In the crystal of (I), the carbonyl oxygen (O3) shows bifurcated hydrogen bonding. In one part, the molecules are linked by a pair of N2—H2N⋯O3 hydrogen bonds involving the amide NH atom, forming inversion dimers with an (8) ring motif. In the other part, the molecules are linked by a pair of N1—H1N⋯O3 hydrogen bonds with the sulfonamide NH atom of another molecule, forming rings with an (10) graph-set motif, leading to a layered structure with the mean planes of the layers inclined to the ab plane by 16.1 (5)° (Table 1, Fig. 4). In the crystal of (II), the molecules are linked by two pairs of N—H⋯O hydrogen bonds (N1—H1N⋯O2 and N2—H2N⋯O3), involving both the sulfonyl and carbonyl O atoms with both sulfonamide and amide N—H bonds (N1—H1N and N2—H2N), forming inversion dimers with (8) ring motifs. These interactions are further strengthened by C—H⋯O hydrogen bonds. Thus, three-center N1—H1N/C6—H6⋯O1 hydrogen bonds result in molecular chains containing the R21(7) ring motif (Fig. 5). These rings are extended along the principal diagonal of the ac plane via C7—H7⋯O2 hydrogen bonds, forming (10) ring motifs, and by C15—H15⋯O2 interactions. In addition, the is reinforced by C—H⋯π(ring) interactions (Fig. 5), details of which are summarized in Table 2. In the crystal of (III), the molecules are also linked by two pairs of N—H⋯O hydrogen bonds (N1—H1N⋯O2 and N2—H2N⋯O3), forming inversion dimers with (8) ring motifs. These dimers are connected by intermolecular C15—H15⋯O1 interactions, forming ribbons two molecules wide and extending along the principal diagonal of the ab plane (Table 3, Fig. 6). The presence of the chlorine atom on the phenyl ring (C10–C15) of (I)–(III) makes the aromatic protons acidic, resulting in the formation of C—H⋯O hydrogen bonds with the sulfonyl O atom.
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4. Database survey
Comparison of structures (I)–(III) with those of related N-acylhydrazone derivatives (Purandara et al., 2017, 2018) shows that the site of substitution of an electron-withdrawing group on the aromatic ring plays a major role in stabilizing the crystal packing by linking the molecules through various weak interactions.
5. Synthesis and crystallization
General procedure for the synthesis of N-(4-chlorobenzenesulfonyl) glycine hydrazone derivatives (I)–(III)
A mixture of N-(4-chlorobenzenesulfonyl) glycinyl hydrazide (0.01 mol) and the appropriate chlorobenzaldehyde (0.01 mol) in anhydrous methanol (30 mL) and two drops of glacial acetic acid was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol. The purity of the compound was checked by TLC and characterized by its IR and NMR spectra. Single crystals suitable for the X-ray diffraction study were grown from DMF solution by slow evaporation of the solvent.
Compound (I): Prism-like yellow single crystals; m.p. 506–507 K; IR (KBr, γ, cm−1): 3190.3 (N—H), 1672.3 (C=O), 1608.6 (C=N), 1334.7 (S=O, asym) and 1159.2 cm−1 (S=O, sym); 1H NMR (400 MHz, DMSO-d6, δ ppm): 3.64, 4.14 (d, 2H), 7.36–7.45 (m, 2H, Ar-H), 7.47–7.50 (m, 1H, Ar-H), 7.61–7.67 (m, 2H, Ar-H), 7.83–7.95 (m, 3H, Ar-H), 8.12 (s, 1H), 8.13 (s, 1H), 11.64 (s, 1H). 13C NMR (400 MHz, DMSO-d6, δ ppm): 43.27, 44.49, 126.82, 127.53, 128.54, 129.11, 129.82, 131.25, 133.02, 137.24, 139.19, 139.81, 143.18, 164.23, 169.08.
Compound (II): Prism-like colourless single crystals; m.p. 469–470 K; IR (KBr, γ, cm−1): 3265.5 (N—-H), 1687.7 (C=O), 1589.3 (C=N), 1340.5 (S=O, asym) and 1168.9 cm−1 (S=O, sym); 1H NMR (400 MHz, DMSO-d6, δ ppm): 3.64, 4.11 (2d, 2H), 7.39–7.44 (m, 2H, Ar-H), 7.54–7.65 (m, 4H, Ar-H), 7.84–7.87 (m, 2H, Ar-H), 7.91, 8.15 (2s, 1H), 8.01, 8.21 (2t, 1H), 11.51, 11.54 (2s, 1H). 13C NMR (400 MHz, DMSO-d6, δ ppm): 43.24, 44.42, 125.52, 126.14, 128.44, 128.91, 129.47, 130.31, 133.70, 136.05, 137.34, 139.36, 142.18, 145.60, 164.17, 168.96.
Compound (III): Rod-like colourless single crystals; m.p. 473–475 K; IR (KBr, γ, cm−1): 3246.2 (N—H), 1685.8 (C=O), 1591.3 (C=N), 1344.4 (S=O, asym) and 1168.9 cm−1 (S=O, sym); 1H NMR (400 MHz, DMSO-d6, δ ppm): 3.62, 4.11 (2d, 2H), 7.48–7.51 (m, 2H, Ar-H), 7.63–7.71 (m, 4H, Ar-H), 7.81–7.85 (m, 2H, Ar-H), 7.92, 8.14 (2s, 1H), 8.01 (t, 1H), 11.49, 11.53 (2s, 1H). 13C NMR (400 MHz, DMSO-d6, δ ppm): 43.21, 128.50, 128.70, 128.86, 129.14, 132.87, 134.34, 137.20, 139.50, 142.53, 145.80, 164.07, 168.96.
6. details
Crystal data, data collection and structure . H atoms bonded to C were positioned with idealized geometry using a riding model with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene). The amino H atoms were refined with the N—H distances restrained to 0.86 (2) Å. All H atoms were assigned isotropic displacement parameters 1.2 × Ueq of the parent atom. In compound (III), the 3 reflection had a poor agreement with its calculated value and was omitted from the final refinement.
details are summarized in Table 4
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Supporting information
https://doi.org/10.1107/S2056989021006885/mw2177sup1.cif
contains datablocks I, II, III, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006885/mw2177Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIIsup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989021006885/mw2177Isup5.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989021006885/mw2177IIsup6.cml
For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell
CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015).C15H13Cl2N3O3S | Z = 2 |
Mr = 386.24 | F(000) = 396 |
Triclinic, P1 | Dx = 1.512 Mg m−3 |
a = 7.7426 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.429 (1) Å | Cell parameters from 2012 reflections |
c = 10.934 (1) Å | θ = 2.8–27.8° |
α = 85.51 (1)° | µ = 0.52 mm−1 |
β = 76.92 (1)° | T = 293 K |
γ = 81.04 (1)° | Prism, yellow |
V = 848.64 (14) Å3 | 0.48 × 0.36 × 0.10 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 2359 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.018 |
Rotation method data acquisition using ω scans. | θmax = 26.4°, θmin = 2.8° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −9→9 |
Tmin = 0.787, Tmax = 0.949 | k = −10→13 |
5699 measured reflections | l = −13→13 |
3417 independent reflections |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0321P)2 + 0.3938P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3417 reflections | Δρmax = 0.24 e Å−3 |
223 parameters | Δρmin = −0.29 e Å−3 |
Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 | ||
C1 | 0.1746 (3) | 0.6076 (2) | 0.8440 (2) | 0.0487 (6) | |
C2 | 0.1897 (4) | 0.7192 (3) | 0.8985 (3) | 0.0687 (8) | |
H2 | 0.3023 | 0.7399 | 0.8985 | 0.082* | |
C3 | 0.0378 (5) | 0.7997 (3) | 0.9529 (3) | 0.0852 (11) | |
H3 | 0.0473 | 0.8756 | 0.9888 | 0.102* | |
C4 | −0.1270 (5) | 0.7675 (4) | 0.9540 (3) | 0.0801 (11) | |
C5 | −0.1448 (4) | 0.6551 (4) | 0.9042 (3) | 0.0763 (10) | |
H5 | −0.2579 | 0.6330 | 0.9083 | 0.092* | |
C6 | 0.0079 (4) | 0.5742 (3) | 0.8473 (3) | 0.0595 (7) | |
H6 | −0.0022 | 0.4982 | 0.8118 | 0.071* | |
C7 | 0.5597 (3) | 0.6727 (2) | 0.6046 (3) | 0.0521 (7) | |
H7A | 0.5504 | 0.7198 | 0.6794 | 0.063* | |
H7B | 0.5376 | 0.7357 | 0.5378 | 0.063* | |
C8 | 0.7483 (3) | 0.6002 (2) | 0.5670 (2) | 0.0386 (5) | |
C9 | 0.9738 (3) | 0.8484 (2) | 0.6184 (2) | 0.0405 (6) | |
H9 | 1.0910 | 0.8074 | 0.5943 | 0.049* | |
C10 | 0.9368 (3) | 0.9816 (2) | 0.6622 (2) | 0.0381 (5) | |
C11 | 1.0705 (3) | 1.0515 (2) | 0.6753 (2) | 0.0430 (6) | |
C12 | 1.0322 (4) | 1.1777 (2) | 0.7149 (3) | 0.0545 (7) | |
H12 | 1.1239 | 1.2217 | 0.7240 | 0.065* | |
C13 | 0.8572 (4) | 1.2374 (3) | 0.7408 (3) | 0.0616 (8) | |
H13 | 0.8306 | 1.3224 | 0.7669 | 0.074* | |
C14 | 0.7213 (4) | 1.1717 (3) | 0.7281 (3) | 0.0614 (8) | |
H14 | 0.6032 | 1.2124 | 0.7452 | 0.074* | |
C15 | 0.7610 (3) | 1.0457 (2) | 0.6902 (3) | 0.0516 (7) | |
H15 | 0.6681 | 1.0019 | 0.6831 | 0.062* | |
N1 | 0.4241 (3) | 0.5872 (2) | 0.6292 (2) | 0.0526 (6) | |
H1N | 0.383 (3) | 0.569 (3) | 0.569 (2) | 0.063* | |
N2 | 0.8820 (3) | 0.66560 (18) | 0.5716 (2) | 0.0420 (5) | |
H2N | 0.990 (2) | 0.631 (2) | 0.544 (2) | 0.050* | |
N3 | 0.8430 (2) | 0.79018 (18) | 0.61392 (19) | 0.0411 (5) | |
O1 | 0.5090 (3) | 0.5131 (2) | 0.8282 (2) | 0.0751 (6) | |
O2 | 0.3180 (3) | 0.39150 (17) | 0.7388 (2) | 0.0732 (6) | |
O3 | 0.7778 (2) | 0.48784 (15) | 0.53116 (17) | 0.0483 (4) | |
Cl1 | −0.31736 (16) | 0.87209 (13) | 1.01893 (11) | 0.1407 (6) | |
Cl2 | 1.29502 (9) | 0.98193 (7) | 0.63926 (8) | 0.0690 (3) | |
S1 | 0.36939 (9) | 0.51159 (7) | 0.76264 (7) | 0.0529 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0476 (15) | 0.0454 (15) | 0.0497 (16) | −0.0040 (12) | −0.0062 (12) | 0.0005 (12) |
C2 | 0.0685 (19) | 0.062 (2) | 0.071 (2) | −0.0128 (16) | −0.0002 (16) | −0.0158 (17) |
C3 | 0.105 (3) | 0.062 (2) | 0.071 (2) | 0.004 (2) | 0.011 (2) | −0.0138 (18) |
C4 | 0.079 (2) | 0.077 (2) | 0.056 (2) | 0.026 (2) | 0.0122 (17) | 0.0121 (18) |
C5 | 0.0474 (17) | 0.105 (3) | 0.064 (2) | 0.0034 (18) | −0.0040 (15) | 0.019 (2) |
C6 | 0.0504 (16) | 0.0663 (19) | 0.0597 (18) | −0.0082 (14) | −0.0104 (14) | 0.0043 (15) |
C7 | 0.0380 (13) | 0.0404 (15) | 0.0759 (19) | −0.0050 (11) | −0.0040 (13) | −0.0151 (13) |
C8 | 0.0374 (12) | 0.0324 (13) | 0.0450 (14) | −0.0041 (10) | −0.0076 (11) | −0.0029 (11) |
C9 | 0.0360 (12) | 0.0333 (13) | 0.0513 (15) | −0.0035 (10) | −0.0079 (11) | −0.0032 (11) |
C10 | 0.0392 (12) | 0.0289 (12) | 0.0452 (14) | −0.0035 (10) | −0.0077 (11) | −0.0018 (11) |
C11 | 0.0402 (13) | 0.0371 (13) | 0.0525 (16) | −0.0063 (10) | −0.0113 (11) | −0.0021 (12) |
C12 | 0.0604 (17) | 0.0397 (15) | 0.0690 (19) | −0.0164 (13) | −0.0179 (14) | −0.0070 (14) |
C13 | 0.075 (2) | 0.0322 (14) | 0.077 (2) | −0.0029 (14) | −0.0153 (16) | −0.0124 (14) |
C14 | 0.0508 (16) | 0.0414 (16) | 0.086 (2) | 0.0051 (13) | −0.0068 (15) | −0.0124 (15) |
C15 | 0.0414 (14) | 0.0391 (14) | 0.0737 (19) | −0.0058 (11) | −0.0096 (13) | −0.0072 (13) |
N1 | 0.0412 (12) | 0.0617 (15) | 0.0576 (15) | −0.0181 (11) | −0.0039 (10) | −0.0171 (12) |
N2 | 0.0340 (10) | 0.0305 (11) | 0.0600 (14) | −0.0033 (9) | −0.0053 (10) | −0.0093 (10) |
N3 | 0.0405 (11) | 0.0298 (10) | 0.0529 (13) | −0.0052 (9) | −0.0086 (9) | −0.0057 (9) |
O1 | 0.0577 (12) | 0.0822 (15) | 0.0895 (16) | 0.0029 (11) | −0.0313 (11) | −0.0095 (13) |
O2 | 0.0696 (13) | 0.0384 (11) | 0.1099 (18) | −0.0079 (10) | −0.0132 (12) | −0.0116 (11) |
O3 | 0.0393 (9) | 0.0342 (9) | 0.0725 (12) | −0.0030 (7) | −0.0115 (8) | −0.0153 (9) |
Cl1 | 0.1177 (9) | 0.1400 (10) | 0.1047 (8) | 0.0695 (8) | 0.0332 (7) | 0.0151 (7) |
Cl2 | 0.0391 (4) | 0.0617 (5) | 0.1092 (7) | −0.0066 (3) | −0.0181 (4) | −0.0182 (4) |
S1 | 0.0428 (4) | 0.0433 (4) | 0.0722 (5) | −0.0029 (3) | −0.0113 (3) | −0.0093 (3) |
C1—C2 | 1.380 (4) | C9—C10 | 1.469 (3) |
C1—C6 | 1.381 (4) | C9—H9 | 0.9300 |
C1—S1 | 1.769 (3) | C10—C11 | 1.394 (3) |
C2—C3 | 1.377 (4) | C10—C15 | 1.398 (3) |
C2—H2 | 0.9300 | C11—C12 | 1.385 (3) |
C3—C4 | 1.367 (5) | C11—Cl2 | 1.745 (2) |
C3—H3 | 0.9300 | C12—C13 | 1.376 (4) |
C4—C5 | 1.369 (5) | C12—H12 | 0.9300 |
C4—Cl1 | 1.736 (3) | C13—C14 | 1.379 (4) |
C5—C6 | 1.391 (4) | C13—H13 | 0.9300 |
C5—H5 | 0.9300 | C14—C15 | 1.377 (3) |
C6—H6 | 0.9300 | C14—H14 | 0.9300 |
C7—N1 | 1.447 (3) | C15—H15 | 0.9300 |
C7—C8 | 1.518 (3) | N1—S1 | 1.604 (2) |
C7—H7A | 0.9700 | N1—H1N | 0.841 (16) |
C7—H7B | 0.9700 | N2—N3 | 1.379 (3) |
C8—O3 | 1.236 (3) | N2—H2N | 0.852 (16) |
C8—N2 | 1.337 (3) | O1—S1 | 1.4283 (19) |
C9—N3 | 1.271 (3) | O2—S1 | 1.4312 (19) |
C2—C1—C6 | 120.3 (3) | C11—C10—C9 | 123.2 (2) |
C2—C1—S1 | 119.8 (2) | C15—C10—C9 | 120.2 (2) |
C6—C1—S1 | 119.8 (2) | C12—C11—C10 | 122.1 (2) |
C3—C2—C1 | 119.9 (3) | C12—C11—Cl2 | 117.61 (19) |
C3—C2—H2 | 120.1 | C10—C11—Cl2 | 120.32 (18) |
C1—C2—H2 | 120.1 | C13—C12—C11 | 119.4 (2) |
C4—C3—C2 | 119.6 (3) | C13—C12—H12 | 120.3 |
C4—C3—H3 | 120.2 | C11—C12—H12 | 120.3 |
C2—C3—H3 | 120.2 | C12—C13—C14 | 120.2 (2) |
C3—C4—C5 | 121.4 (3) | C12—C13—H13 | 119.9 |
C3—C4—Cl1 | 119.1 (3) | C14—C13—H13 | 119.9 |
C5—C4—Cl1 | 119.5 (3) | C15—C14—C13 | 119.7 (3) |
C4—C5—C6 | 119.4 (3) | C15—C14—H14 | 120.1 |
C4—C5—H5 | 120.3 | C13—C14—H14 | 120.1 |
C6—C5—H5 | 120.3 | C14—C15—C10 | 121.9 (2) |
C1—C6—C5 | 119.4 (3) | C14—C15—H15 | 119.0 |
C1—C6—H6 | 120.3 | C10—C15—H15 | 119.0 |
C5—C6—H6 | 120.3 | C7—N1—S1 | 122.21 (19) |
N1—C7—C8 | 112.8 (2) | C7—N1—H1N | 119 (2) |
N1—C7—H7A | 109.0 | S1—N1—H1N | 119 (2) |
C8—C7—H7A | 109.0 | C8—N2—N3 | 119.52 (19) |
N1—C7—H7B | 109.0 | C8—N2—H2N | 119.0 (17) |
C8—C7—H7B | 109.0 | N3—N2—H2N | 121.4 (17) |
H7A—C7—H7B | 107.8 | C9—N3—N2 | 117.61 (19) |
O3—C8—N2 | 121.5 (2) | O1—S1—O2 | 120.84 (13) |
O3—C8—C7 | 122.1 (2) | O1—S1—N1 | 107.43 (13) |
N2—C8—C7 | 116.5 (2) | O2—S1—N1 | 107.08 (12) |
N3—C9—C10 | 119.0 (2) | O1—S1—C1 | 107.99 (13) |
N3—C9—H9 | 120.5 | O2—S1—C1 | 107.31 (12) |
C10—C9—H9 | 120.5 | N1—S1—C1 | 105.16 (12) |
C11—C10—C15 | 116.6 (2) | ||
C6—C1—C2—C3 | −2.1 (4) | C11—C12—C13—C14 | 0.5 (4) |
S1—C1—C2—C3 | 174.7 (2) | C12—C13—C14—C15 | 0.4 (5) |
C1—C2—C3—C4 | 0.9 (5) | C13—C14—C15—C10 | −0.8 (4) |
C2—C3—C4—C5 | 1.3 (5) | C11—C10—C15—C14 | 0.4 (4) |
C2—C3—C4—Cl1 | −178.2 (2) | C9—C10—C15—C14 | −178.1 (3) |
C3—C4—C5—C6 | −2.3 (5) | C8—C7—N1—S1 | 83.6 (3) |
Cl1—C4—C5—C6 | 177.2 (2) | O3—C8—N2—N3 | −179.0 (2) |
C2—C1—C6—C5 | 1.1 (4) | C7—C8—N2—N3 | 2.6 (3) |
S1—C1—C6—C5 | −175.7 (2) | C10—C9—N3—N2 | 179.6 (2) |
C4—C5—C6—C1 | 1.1 (4) | C8—N2—N3—C9 | 179.1 (2) |
N1—C7—C8—O3 | 17.0 (4) | C7—N1—S1—O1 | −17.3 (2) |
N1—C7—C8—N2 | −164.6 (2) | C7—N1—S1—O2 | −148.5 (2) |
N3—C9—C10—C11 | 177.3 (2) | C7—N1—S1—C1 | 97.6 (2) |
N3—C9—C10—C15 | −4.3 (4) | C2—C1—S1—O1 | 36.9 (3) |
C15—C10—C11—C12 | 0.5 (4) | C6—C1—S1—O1 | −146.3 (2) |
C9—C10—C11—C12 | 179.0 (2) | C2—C1—S1—O2 | 168.7 (2) |
C15—C10—C11—Cl2 | −178.54 (19) | C6—C1—S1—O2 | −14.6 (3) |
C9—C10—C11—Cl2 | 0.0 (3) | C2—C1—S1—N1 | −77.6 (2) |
C10—C11—C12—C13 | −0.9 (4) | C6—C1—S1—N1 | 99.2 (2) |
Cl2—C11—C12—C13 | 178.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O3i | 0.84 (2) | 2.01 (2) | 2.823 (3) | 162 (3) |
N2—H2N···O3ii | 0.85 (2) | 2.06 (2) | 2.897 (2) | 167 (2) |
C12—H12···O2iii | 0.93 | 2.53 | 3.439 (3) | 166 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x+1, y+1, z. |
C15H13Cl2N3O3S | Z = 2 |
Mr = 386.24 | F(000) = 396 |
Triclinic, P1 | Dx = 1.539 Mg m−3 |
a = 9.491 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.976 (1) Å | Cell parameters from 2850 reflections |
c = 10.446 (1) Å | θ = 2.6–27.9° |
α = 67.22 (1)° | µ = 0.53 mm−1 |
β = 66.80 (1)° | T = 293 K |
γ = 86.32 (1)° | Prism, colourless |
V = 833.59 (17) Å3 | 0.36 × 0.14 × 0.08 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 2688 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Rotation method data acquisition using ω scans. | θmax = 26.4°, θmin = 2.6° |
Absorption correction: multi-scan (CrysAlis RED, Oxford Diffraction, 2009) | h = −11→11 |
Tmin = 0.831, Tmax = 0.959 | k = −12→12 |
5759 measured reflections | l = −13→12 |
3354 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: mixed |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.22 | w = 1/[σ2(Fo2) + (0.0148P)2 + 1.1114P] where P = (Fo2 + 2Fc2)/3 |
3354 reflections | (Δ/σ)max = 0.002 |
223 parameters | Δρmax = 0.27 e Å−3 |
2 restraints | Δρmin = −0.39 e Å−3 |
Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 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 > 2sigma(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 | ||
C1 | 0.2520 (3) | −0.1930 (3) | 1.0295 (3) | 0.0312 (6) | |
C2 | 0.1178 (3) | −0.2828 (3) | 1.0900 (4) | 0.0408 (7) | |
H2 | 0.0241 | −0.2549 | 1.1415 | 0.049* | |
C3 | 0.1226 (4) | −0.4145 (4) | 1.0739 (4) | 0.0458 (8) | |
H3 | 0.0329 | −0.4769 | 1.1166 | 0.055* | |
C4 | 0.2616 (4) | −0.4519 (3) | 0.9939 (4) | 0.0392 (7) | |
C5 | 0.3966 (4) | −0.3626 (3) | 0.9327 (4) | 0.0393 (7) | |
H5 | 0.4898 | −0.3896 | 0.8789 | 0.047* | |
C6 | 0.3924 (3) | −0.2326 (3) | 0.9519 (3) | 0.0356 (7) | |
H6 | 0.4828 | −0.1724 | 0.9131 | 0.043* | |
C7 | 0.2808 (3) | 0.1427 (3) | 0.7715 (3) | 0.0356 (7) | |
H7A | 0.2814 | 0.2480 | 0.7273 | 0.043* | |
H7B | 0.1751 | 0.0995 | 0.8162 | 0.043* | |
C8 | 0.3771 (3) | 0.0903 (3) | 0.6490 (3) | 0.0351 (7) | |
C9 | 0.1510 (4) | 0.1675 (4) | 0.4412 (3) | 0.0414 (7) | |
H9 | 0.2108 | 0.1262 | 0.3740 | 0.050* | |
C10 | 0.0084 (4) | 0.2250 (3) | 0.4311 (3) | 0.0400 (7) | |
C11 | −0.0769 (4) | 0.3041 (4) | 0.5152 (4) | 0.0469 (8) | |
H11 | −0.0426 | 0.3245 | 0.5783 | 0.056* | |
C12 | −0.2121 (4) | 0.3515 (4) | 0.5037 (4) | 0.0540 (9) | |
C13 | −0.2654 (4) | 0.3247 (4) | 0.4096 (5) | 0.0600 (10) | |
H13 | −0.3566 | 0.3589 | 0.4022 | 0.072* | |
C14 | −0.1815 (5) | 0.2467 (4) | 0.3273 (5) | 0.0603 (10) | |
H14 | −0.2165 | 0.2274 | 0.2640 | 0.072* | |
C15 | −0.0459 (4) | 0.1966 (4) | 0.3371 (4) | 0.0497 (8) | |
H15 | 0.0097 | 0.1435 | 0.2808 | 0.060* | |
Cl1 | 0.26935 (11) | −0.61454 (10) | 0.96808 (12) | 0.0584 (3) | |
Cl2 | −0.32203 (15) | 0.44557 (16) | 0.61290 (17) | 0.0976 (5) | |
N1 | 0.3402 (3) | 0.1031 (3) | 0.8891 (3) | 0.0318 (5) | |
H1N | 0.436 (2) | 0.101 (3) | 0.860 (3) | 0.038* | |
N2 | 0.3309 (3) | 0.1124 (3) | 0.5371 (3) | 0.0436 (7) | |
H2N | 0.378 (4) | 0.072 (4) | 0.474 (3) | 0.052* | |
N3 | 0.1952 (3) | 0.1727 (3) | 0.5398 (3) | 0.0394 (6) | |
O1 | 0.3340 (2) | −0.0350 (2) | 1.1413 (2) | 0.0411 (5) | |
O2 | 0.0898 (2) | 0.0034 (2) | 1.1055 (2) | 0.0408 (5) | |
O3 | 0.4936 (2) | 0.0311 (3) | 0.6515 (2) | 0.0475 (6) | |
S1 | 0.24739 (8) | −0.02589 (8) | 1.05320 (8) | 0.03071 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0333 (15) | 0.0300 (15) | 0.0385 (16) | 0.0073 (12) | −0.0189 (13) | −0.0176 (13) |
C2 | 0.0280 (16) | 0.0415 (18) | 0.057 (2) | 0.0072 (13) | −0.0145 (15) | −0.0268 (16) |
C3 | 0.0347 (17) | 0.0386 (18) | 0.069 (2) | 0.0006 (14) | −0.0209 (17) | −0.0261 (17) |
C4 | 0.0461 (19) | 0.0299 (16) | 0.0530 (19) | 0.0096 (14) | −0.0279 (16) | −0.0204 (15) |
C5 | 0.0347 (17) | 0.0377 (17) | 0.0496 (19) | 0.0124 (13) | −0.0173 (15) | −0.0224 (15) |
C6 | 0.0291 (15) | 0.0343 (16) | 0.0469 (18) | 0.0061 (12) | −0.0159 (14) | −0.0192 (14) |
C7 | 0.0354 (16) | 0.0374 (17) | 0.0375 (16) | 0.0116 (13) | −0.0156 (14) | −0.0185 (14) |
C8 | 0.0341 (16) | 0.0371 (17) | 0.0339 (16) | 0.0086 (13) | −0.0129 (13) | −0.0153 (14) |
C9 | 0.0435 (18) | 0.050 (2) | 0.0326 (16) | 0.0112 (15) | −0.0145 (14) | −0.0195 (15) |
C10 | 0.0422 (18) | 0.0414 (18) | 0.0329 (16) | 0.0052 (14) | −0.0150 (14) | −0.0113 (14) |
C11 | 0.047 (2) | 0.054 (2) | 0.0451 (19) | 0.0126 (16) | −0.0246 (16) | −0.0199 (17) |
C12 | 0.048 (2) | 0.052 (2) | 0.052 (2) | 0.0109 (17) | −0.0181 (18) | −0.0131 (18) |
C13 | 0.044 (2) | 0.060 (2) | 0.067 (3) | 0.0048 (18) | −0.031 (2) | −0.006 (2) |
C14 | 0.065 (3) | 0.060 (2) | 0.062 (2) | −0.004 (2) | −0.042 (2) | −0.011 (2) |
C15 | 0.062 (2) | 0.047 (2) | 0.0440 (19) | 0.0028 (17) | −0.0269 (18) | −0.0156 (16) |
Cl1 | 0.0641 (6) | 0.0405 (5) | 0.0897 (7) | 0.0132 (4) | −0.0367 (5) | −0.0401 (5) |
Cl2 | 0.0847 (9) | 0.1137 (11) | 0.1072 (10) | 0.0590 (8) | −0.0404 (8) | −0.0618 (9) |
N1 | 0.0274 (12) | 0.0354 (13) | 0.0368 (14) | 0.0033 (11) | −0.0109 (11) | −0.0205 (11) |
N2 | 0.0416 (16) | 0.0597 (18) | 0.0408 (15) | 0.0224 (13) | −0.0198 (13) | −0.0303 (14) |
N3 | 0.0378 (14) | 0.0457 (16) | 0.0368 (14) | 0.0134 (12) | −0.0165 (12) | −0.0183 (12) |
O1 | 0.0400 (12) | 0.0535 (14) | 0.0406 (12) | 0.0020 (10) | −0.0200 (10) | −0.0249 (11) |
O2 | 0.0309 (11) | 0.0474 (13) | 0.0512 (13) | 0.0071 (9) | −0.0115 (10) | −0.0320 (11) |
O3 | 0.0404 (13) | 0.0727 (16) | 0.0418 (13) | 0.0248 (12) | −0.0208 (11) | −0.0336 (12) |
S1 | 0.0279 (4) | 0.0352 (4) | 0.0363 (4) | 0.0050 (3) | −0.0127 (3) | −0.0219 (3) |
C1—C2 | 1.377 (4) | C9—C10 | 1.462 (4) |
C1—C6 | 1.385 (4) | C9—H9 | 0.9300 |
C1—S1 | 1.773 (3) | C10—C15 | 1.394 (4) |
C2—C3 | 1.384 (4) | C10—C11 | 1.394 (4) |
C2—H2 | 0.9300 | C11—C12 | 1.372 (5) |
C3—C4 | 1.374 (4) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—C13 | 1.381 (5) |
C4—C5 | 1.380 (4) | C12—Cl2 | 1.743 (4) |
C4—Cl1 | 1.737 (3) | C13—C14 | 1.370 (6) |
C5—C6 | 1.382 (4) | C13—H13 | 0.9300 |
C5—H5 | 0.9300 | C14—C15 | 1.378 (5) |
C6—H6 | 0.9300 | C14—H14 | 0.9300 |
C7—N1 | 1.457 (4) | C15—H15 | 0.9300 |
C7—C8 | 1.510 (4) | N1—S1 | 1.618 (3) |
C7—H7A | 0.9700 | N1—H1N | 0.841 (17) |
C7—H7B | 0.9700 | N2—N3 | 1.380 (3) |
C8—O3 | 1.224 (3) | N2—H2N | 0.863 (18) |
C8—N2 | 1.342 (4) | O1—S1 | 1.433 (2) |
C9—N3 | 1.275 (4) | O2—S1 | 1.430 (2) |
C2—C1—C6 | 120.8 (3) | C15—C10—C9 | 118.8 (3) |
C2—C1—S1 | 120.2 (2) | C11—C10—C9 | 122.2 (3) |
C6—C1—S1 | 119.0 (2) | C12—C11—C10 | 119.3 (3) |
C1—C2—C3 | 119.9 (3) | C12—C11—H11 | 120.4 |
C1—C2—H2 | 120.0 | C10—C11—H11 | 120.4 |
C3—C2—H2 | 120.0 | C11—C12—C13 | 121.9 (4) |
C4—C3—C2 | 119.1 (3) | C11—C12—Cl2 | 119.4 (3) |
C4—C3—H3 | 120.4 | C13—C12—Cl2 | 118.7 (3) |
C2—C3—H3 | 120.4 | C14—C13—C12 | 118.7 (3) |
C3—C4—C5 | 121.4 (3) | C14—C13—H13 | 120.6 |
C3—C4—Cl1 | 119.8 (2) | C12—C13—H13 | 120.6 |
C5—C4—Cl1 | 118.8 (2) | C13—C14—C15 | 120.9 (4) |
C4—C5—C6 | 119.5 (3) | C13—C14—H14 | 119.6 |
C4—C5—H5 | 120.3 | C15—C14—H14 | 119.6 |
C6—C5—H5 | 120.3 | C14—C15—C10 | 120.3 (4) |
C5—C6—C1 | 119.3 (3) | C14—C15—H15 | 119.9 |
C5—C6—H6 | 120.4 | C10—C15—H15 | 119.9 |
C1—C6—H6 | 120.4 | C7—N1—S1 | 119.9 (2) |
N1—C7—C8 | 111.0 (2) | C7—N1—H1N | 116 (2) |
N1—C7—H7A | 109.4 | S1—N1—H1N | 112 (2) |
C8—C7—H7A | 109.4 | C8—N2—N3 | 120.8 (2) |
N1—C7—H7B | 109.4 | C8—N2—H2N | 117 (2) |
C8—C7—H7B | 109.4 | N3—N2—H2N | 121 (2) |
H7A—C7—H7B | 108.0 | C9—N3—N2 | 115.1 (3) |
O3—C8—N2 | 121.4 (3) | O2—S1—O1 | 119.53 (13) |
O3—C8—C7 | 121.1 (3) | O2—S1—N1 | 107.80 (13) |
N2—C8—C7 | 117.5 (3) | O1—S1—N1 | 105.65 (13) |
N3—C9—C10 | 121.6 (3) | O2—S1—C1 | 107.23 (13) |
N3—C9—H9 | 119.2 | O1—S1—C1 | 107.84 (13) |
C10—C9—H9 | 119.2 | N1—S1—C1 | 108.40 (13) |
C15—C10—C11 | 119.0 (3) | ||
C6—C1—C2—C3 | 0.2 (5) | Cl2—C12—C13—C14 | −178.0 (3) |
S1—C1—C2—C3 | −178.6 (3) | C12—C13—C14—C15 | −0.4 (6) |
C1—C2—C3—C4 | −1.7 (5) | C13—C14—C15—C10 | −0.2 (6) |
C2—C3—C4—C5 | 1.5 (5) | C11—C10—C15—C14 | 0.3 (5) |
C2—C3—C4—Cl1 | −178.3 (3) | C9—C10—C15—C14 | 178.7 (3) |
C3—C4—C5—C6 | 0.0 (5) | C8—C7—N1—S1 | −107.2 (3) |
Cl1—C4—C5—C6 | 179.8 (2) | O3—C8—N2—N3 | 176.8 (3) |
C4—C5—C6—C1 | −1.4 (5) | C7—C8—N2—N3 | −3.8 (5) |
C2—C1—C6—C5 | 1.3 (5) | C10—C9—N3—N2 | 179.1 (3) |
S1—C1—C6—C5 | −179.8 (2) | C8—N2—N3—C9 | −169.5 (3) |
N1—C7—C8—O3 | −4.1 (4) | C7—N1—S1—O2 | −50.2 (2) |
N1—C7—C8—N2 | 176.5 (3) | C7—N1—S1—O1 | −179.0 (2) |
N3—C9—C10—C15 | −170.4 (3) | C7—N1—S1—C1 | 65.6 (2) |
N3—C9—C10—C11 | 8.0 (5) | C2—C1—S1—O2 | −13.7 (3) |
C15—C10—C11—C12 | 0.2 (5) | C6—C1—S1—O2 | 167.4 (2) |
C9—C10—C11—C12 | −178.2 (3) | C2—C1—S1—O1 | 116.3 (3) |
C10—C11—C12—C13 | −0.8 (6) | C6—C1—S1—O1 | −62.6 (3) |
C10—C11—C12—Cl2 | 178.1 (3) | C2—C1—S1—N1 | −129.8 (3) |
C11—C12—C13—C14 | 0.9 (6) | C6—C1—S1—N1 | 51.3 (3) |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.84 (2) | 2.23 (2) | 3.041 (3) | 161 (3) |
N2—H2N···O3ii | 0.86 (2) | 1.97 (2) | 2.828 (3) | 171 (3) |
C6—H6···O1i | 0.93 | 2.53 | 3.422 (4) | 161 |
C7—H7B···O2iii | 0.97 | 2.47 | 3.434 (4) | 172 |
C15—H15···O2iv | 0.93 | 2.58 | 3.474 (4) | 162 |
C14—H14···Cgv | 0.93 | 2.84 | 3.675 (5) | 150 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+2; (iv) x, y, z−1; (v) −x, −y, −z+1. |
C15H13Cl2N3O3S | Z = 2 |
Mr = 386.24 | F(000) = 396 |
Triclinic, P1 | Dx = 1.459 Mg m−3 |
a = 6.7234 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.281 (1) Å | Cell parameters from 1746 reflections |
c = 13.611 (2) Å | θ = 2.9–27.9° |
α = 74.98 (1)° | µ = 0.51 mm−1 |
β = 87.11 (1)° | T = 293 K |
γ = 75.34 (1)° | Rod, colourless |
V = 879.0 (2) Å3 | 0.46 × 0.42 × 0.20 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 2600 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Rotation method data acquisition using ω scans. | θmax = 26.4°, θmin = 2.9° |
Absorption correction: multi-scan (CrysAlis RED, Oxford Diffraction, 2009) | h = −8→8 |
Tmin = 0.801, Tmax = 0.906 | k = −12→12 |
5737 measured reflections | l = −13→16 |
3598 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: mixed |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0407P)2 + 0.5495P] where P = (Fo2 + 2Fc2)/3 |
3598 reflections | (Δ/σ)max < 0.001 |
223 parameters | Δρmax = 0.33 e Å−3 |
2 restraints | Δρmin = −0.30 e Å−3 |
Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 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 > 2sigma(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 | ||
Cl1 | −0.75370 (19) | 0.81534 (16) | 0.50474 (9) | 0.1284 (5) | |
Cl2 | 1.20248 (15) | 0.42711 (14) | 0.39838 (7) | 0.1119 (4) | |
S1 | −0.27969 (10) | 1.01993 (7) | 0.11321 (5) | 0.04891 (19) | |
O1 | −0.1031 (3) | 1.05461 (19) | 0.14290 (15) | 0.0609 (5) | |
O2 | −0.4241 (3) | 1.12132 (19) | 0.04119 (15) | 0.0628 (5) | |
O3 | −0.1441 (3) | 0.66440 (19) | 0.00307 (15) | 0.0601 (5) | |
N1 | −0.1982 (3) | 0.8899 (2) | 0.06592 (17) | 0.0518 (5) | |
H1N | −0.285 (4) | 0.868 (3) | 0.038 (2) | 0.062* | |
N2 | 0.1718 (3) | 0.5636 (2) | 0.07085 (17) | 0.0529 (5) | |
H2N | 0.179 (4) | 0.490 (2) | 0.050 (2) | 0.063* | |
N3 | 0.3257 (3) | 0.5661 (2) | 0.13326 (15) | 0.0490 (5) | |
C1 | −0.4154 (4) | 0.9674 (3) | 0.2247 (2) | 0.0487 (6) | |
C2 | −0.3286 (5) | 0.9436 (4) | 0.3189 (2) | 0.0707 (8) | |
H2 | −0.199533 | 0.958848 | 0.324412 | 0.085* | |
C3 | −0.4330 (5) | 0.8971 (4) | 0.4049 (2) | 0.0840 (10) | |
H3 | −0.374571 | 0.880441 | 0.468907 | 0.101* | |
C4 | −0.6231 (5) | 0.8754 (4) | 0.3961 (3) | 0.0767 (9) | |
C5 | −0.7090 (5) | 0.8990 (4) | 0.3026 (3) | 0.0909 (11) | |
H5 | −0.837854 | 0.883342 | 0.297257 | 0.109* | |
C6 | −0.6066 (5) | 0.9456 (4) | 0.2165 (2) | 0.0773 (9) | |
H6 | −0.666116 | 0.962570 | 0.152735 | 0.093* | |
C7 | −0.0149 (4) | 0.7821 (3) | 0.10526 (19) | 0.0471 (6) | |
H7A | −0.022691 | 0.748572 | 0.178490 | 0.057* | |
H7B | 0.105960 | 0.818535 | 0.089975 | 0.057* | |
C8 | −0.0016 (4) | 0.6659 (3) | 0.05555 (18) | 0.0466 (6) | |
C9 | 0.4825 (4) | 0.4633 (3) | 0.1450 (2) | 0.0521 (6) | |
H9 | 0.486624 | 0.393537 | 0.112435 | 0.063* | |
C10 | 0.6568 (4) | 0.4535 (3) | 0.20951 (19) | 0.0480 (6) | |
C11 | 0.6490 (4) | 0.5479 (3) | 0.2675 (2) | 0.0606 (7) | |
H11 | 0.530130 | 0.618121 | 0.266545 | 0.073* | |
C12 | 0.8152 (5) | 0.5385 (3) | 0.3263 (2) | 0.0682 (8) | |
H12 | 0.808568 | 0.601525 | 0.365387 | 0.082* | |
C13 | 0.9906 (4) | 0.4354 (4) | 0.3268 (2) | 0.0648 (8) | |
C14 | 1.0018 (4) | 0.3406 (3) | 0.2719 (2) | 0.0692 (8) | |
H14 | 1.120998 | 0.270324 | 0.273761 | 0.083* | |
C15 | 0.8334 (4) | 0.3497 (3) | 0.2128 (2) | 0.0596 (7) | |
H15 | 0.840415 | 0.284985 | 0.175185 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1225 (9) | 0.1721 (12) | 0.0862 (7) | −0.0563 (9) | 0.0375 (7) | −0.0130 (8) |
Cl2 | 0.0737 (6) | 0.1848 (12) | 0.0779 (6) | −0.0439 (7) | −0.0247 (5) | −0.0185 (7) |
S1 | 0.0460 (3) | 0.0478 (4) | 0.0565 (4) | −0.0123 (3) | −0.0034 (3) | −0.0181 (3) |
O1 | 0.0516 (10) | 0.0629 (12) | 0.0799 (13) | −0.0225 (9) | −0.0016 (9) | −0.0303 (10) |
O2 | 0.0616 (12) | 0.0518 (11) | 0.0695 (13) | −0.0097 (9) | −0.0111 (9) | −0.0076 (9) |
O3 | 0.0520 (10) | 0.0608 (11) | 0.0742 (13) | −0.0063 (9) | −0.0165 (9) | −0.0329 (10) |
N1 | 0.0454 (12) | 0.0572 (13) | 0.0591 (14) | −0.0092 (10) | −0.0070 (10) | −0.0277 (11) |
N2 | 0.0500 (12) | 0.0529 (13) | 0.0604 (14) | −0.0070 (10) | −0.0122 (10) | −0.0258 (11) |
N3 | 0.0473 (12) | 0.0524 (13) | 0.0495 (12) | −0.0115 (10) | −0.0077 (9) | −0.0161 (10) |
C1 | 0.0438 (13) | 0.0487 (14) | 0.0566 (15) | −0.0078 (11) | −0.0012 (11) | −0.0215 (12) |
C2 | 0.0552 (17) | 0.103 (3) | 0.0606 (18) | −0.0226 (16) | −0.0005 (14) | −0.0302 (18) |
C3 | 0.076 (2) | 0.119 (3) | 0.0541 (19) | −0.019 (2) | −0.0019 (16) | −0.0212 (19) |
C4 | 0.072 (2) | 0.090 (2) | 0.066 (2) | −0.0230 (18) | 0.0196 (16) | −0.0157 (18) |
C5 | 0.061 (2) | 0.139 (3) | 0.080 (2) | −0.044 (2) | 0.0082 (17) | −0.023 (2) |
C6 | 0.0577 (18) | 0.118 (3) | 0.0617 (19) | −0.0349 (18) | −0.0015 (15) | −0.0199 (19) |
C7 | 0.0455 (13) | 0.0516 (14) | 0.0475 (14) | −0.0129 (11) | −0.0030 (11) | −0.0169 (12) |
C8 | 0.0462 (13) | 0.0511 (14) | 0.0455 (14) | −0.0142 (11) | −0.0029 (11) | −0.0145 (11) |
C9 | 0.0533 (15) | 0.0527 (15) | 0.0548 (15) | −0.0139 (12) | −0.0041 (12) | −0.0200 (12) |
C10 | 0.0469 (13) | 0.0483 (14) | 0.0483 (14) | −0.0115 (11) | −0.0032 (11) | −0.0110 (11) |
C11 | 0.0581 (16) | 0.0583 (17) | 0.0647 (18) | −0.0068 (13) | −0.0100 (13) | −0.0200 (14) |
C12 | 0.075 (2) | 0.077 (2) | 0.0606 (18) | −0.0238 (17) | −0.0107 (15) | −0.0244 (16) |
C13 | 0.0557 (17) | 0.089 (2) | 0.0481 (16) | −0.0261 (16) | −0.0076 (13) | −0.0056 (15) |
C14 | 0.0499 (16) | 0.075 (2) | 0.0688 (19) | −0.0025 (14) | −0.0039 (14) | −0.0055 (16) |
C15 | 0.0584 (16) | 0.0557 (16) | 0.0644 (18) | −0.0101 (13) | −0.0019 (13) | −0.0183 (14) |
Cl1—C4 | 1.735 (3) | C4—C5 | 1.362 (5) |
Cl2—C13 | 1.738 (3) | C5—C6 | 1.368 (4) |
S1—O1 | 1.4275 (18) | C5—H5 | 0.9300 |
S1—O2 | 1.4297 (19) | C6—H6 | 0.9300 |
S1—N1 | 1.594 (2) | C7—C8 | 1.500 (3) |
S1—C1 | 1.764 (3) | C7—H7A | 0.9700 |
O3—C8 | 1.229 (3) | C7—H7B | 0.9700 |
N1—C7 | 1.450 (3) | C9—C10 | 1.467 (3) |
N1—H1N | 0.818 (17) | C9—H9 | 0.9300 |
N2—C8 | 1.341 (3) | C10—C15 | 1.375 (4) |
N2—N3 | 1.380 (3) | C10—C11 | 1.390 (4) |
N2—H2N | 0.861 (17) | C11—C12 | 1.377 (4) |
N3—C9 | 1.273 (3) | C11—H11 | 0.9300 |
C1—C2 | 1.373 (4) | C12—C13 | 1.371 (4) |
C1—C6 | 1.374 (4) | C12—H12 | 0.9300 |
C2—C3 | 1.375 (4) | C13—C14 | 1.360 (4) |
C2—H2 | 0.9300 | C14—C15 | 1.392 (4) |
C3—C4 | 1.369 (5) | C14—H14 | 0.9300 |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
O1—S1—O2 | 119.70 (12) | N1—C7—C8 | 107.76 (19) |
O1—S1—N1 | 107.02 (11) | N1—C7—H7A | 110.2 |
O2—S1—N1 | 106.60 (12) | C8—C7—H7A | 110.2 |
O1—S1—C1 | 107.38 (12) | N1—C7—H7B | 110.2 |
O2—S1—C1 | 107.41 (12) | C8—C7—H7B | 110.2 |
N1—S1—C1 | 108.32 (12) | H7A—C7—H7B | 108.5 |
C7—N1—S1 | 121.73 (16) | O3—C8—N2 | 121.3 (2) |
C7—N1—H1N | 117 (2) | O3—C8—C7 | 121.3 (2) |
S1—N1—H1N | 116 (2) | N2—C8—C7 | 117.4 (2) |
C8—N2—N3 | 119.7 (2) | N3—C9—C10 | 120.7 (2) |
C8—N2—H2N | 119.9 (19) | N3—C9—H9 | 119.7 |
N3—N2—H2N | 119.6 (19) | C10—C9—H9 | 119.7 |
C9—N3—N2 | 115.3 (2) | C15—C10—C11 | 118.6 (2) |
C2—C1—C6 | 120.1 (3) | C15—C10—C9 | 119.8 (2) |
C2—C1—S1 | 120.5 (2) | C11—C10—C9 | 121.6 (2) |
C6—C1—S1 | 119.3 (2) | C12—C11—C10 | 120.8 (3) |
C1—C2—C3 | 119.8 (3) | C12—C11—H11 | 119.6 |
C1—C2—H2 | 120.1 | C10—C11—H11 | 119.6 |
C3—C2—H2 | 120.1 | C13—C12—C11 | 119.3 (3) |
C4—C3—C2 | 119.7 (3) | C13—C12—H12 | 120.3 |
C4—C3—H3 | 120.1 | C11—C12—H12 | 120.3 |
C2—C3—H3 | 120.1 | C14—C13—C12 | 121.2 (3) |
C5—C4—C3 | 120.4 (3) | C14—C13—Cl2 | 119.7 (3) |
C5—C4—Cl1 | 119.9 (3) | C12—C13—Cl2 | 119.1 (2) |
C3—C4—Cl1 | 119.7 (3) | C13—C14—C15 | 119.5 (3) |
C4—C5—C6 | 120.3 (3) | C13—C14—H14 | 120.3 |
C4—C5—H5 | 119.8 | C15—C14—H14 | 120.3 |
C6—C5—H5 | 119.8 | C10—C15—C14 | 120.6 (3) |
C5—C6—C1 | 119.7 (3) | C10—C15—H15 | 119.7 |
C5—C6—H6 | 120.2 | C14—C15—H15 | 119.7 |
C1—C6—H6 | 120.2 | ||
O1—S1—N1—C7 | 35.4 (2) | S1—C1—C6—C5 | 177.1 (3) |
O2—S1—N1—C7 | 164.6 (2) | S1—N1—C7—C8 | 171.09 (18) |
C1—S1—N1—C7 | −80.1 (2) | N3—N2—C8—O3 | −177.6 (2) |
C8—N2—N3—C9 | 178.5 (2) | N3—N2—C8—C7 | 2.2 (4) |
O1—S1—C1—C2 | −10.8 (3) | N1—C7—C8—O3 | −9.0 (3) |
O2—S1—C1—C2 | −140.8 (2) | N1—C7—C8—N2 | 171.1 (2) |
N1—S1—C1—C2 | 104.5 (2) | N2—N3—C9—C10 | 180.0 (2) |
O1—S1—C1—C6 | 171.5 (2) | N3—C9—C10—C15 | −173.1 (3) |
O2—S1—C1—C6 | 41.5 (3) | N3—C9—C10—C11 | 6.4 (4) |
N1—S1—C1—C6 | −73.3 (3) | C15—C10—C11—C12 | 0.6 (4) |
C6—C1—C2—C3 | 0.4 (5) | C9—C10—C11—C12 | −179.0 (3) |
S1—C1—C2—C3 | −177.3 (3) | C10—C11—C12—C13 | 0.5 (5) |
C1—C2—C3—C4 | −0.2 (5) | C11—C12—C13—C14 | −1.4 (5) |
C2—C3—C4—C5 | 0.3 (6) | C11—C12—C13—Cl2 | 178.2 (2) |
C2—C3—C4—Cl1 | 179.5 (3) | C12—C13—C14—C15 | 1.1 (5) |
C3—C4—C5—C6 | −0.5 (6) | Cl2—C13—C14—C15 | −178.5 (2) |
Cl1—C4—C5—C6 | −179.7 (3) | C11—C10—C15—C14 | −0.9 (4) |
C4—C5—C6—C1 | 0.6 (6) | C9—C10—C15—C14 | 178.7 (3) |
C2—C1—C6—C5 | −0.6 (5) | C13—C14—C15—C10 | 0.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.82 (2) | 2.25 (2) | 3.032 (3) | 162 (3) |
N1—H1N···O3 | 0.82 (2) | 2.23 (3) | 2.609 (3) | 109 (2) |
N2—H2N···O3ii | 0.86 (2) | 1.98 (2) | 2.829 (3) | 170 (3) |
C15—H15···O1iii | 0.93 | 2.45 | 3.330 (3) | 157 |
Symmetry codes: (i) −x−1, −y+2, −z; (ii) −x, −y+1, −z; (iii) x+1, y−1, z. |
Acknowledgements
The authors thank the SAIF, Panjab University, for providing the NMR facility.
Funding information
BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under a UGC–BSR one-time grant to faculty.
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