

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989016002371/is5440sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989016002371/is5440Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989016002371/is5440Isup3.cml |
CCDC reference: 1452193
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.093
- Data-to-parameter ratio = 18.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for C14 -- C15 .. 7.0 s.u. PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ... 10 Report PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 Report PLAT977_ALERT_2_C Check the Negative Difference Density on H24 -0.33 eA-3
Alert level G PLAT005_ALERT_5_G No Embedded Refinement Details found in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT008_ALERT_5_G No _iucr_refine_reflections_details in the CIF Please Do ! PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 16 Note PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density 14 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 5 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
\ There has been immense interest in nitrogen–sulfur donor ligands since the report on S-benzyldithiocarbazate (SBDTC) (Ali & Tarafder, 1977). Since then, a number of Schiff bases have been derived from SBDTC (Crouse et al., 2004; Howlader et al., 2015). The versatile coordination chemistry and increasingly important biological properties of ligands derived from SBDTC have also received much attention (Zangrando et al., 2015). In a continuation of our research, the title compound (systematic name: 2-[1-(2-{(benzylsulfanyl)[((benzylsulfanyl){2-[1-(2-hydroxyphenyl)ethylidene]\ hydrazin-1-ylidene}methyl)disulfanyl]methylidene}hydrazin-1-ylidene)ethyl]\ phenol) was prepared from SBDTC.
In the title compound, the arrangement of the two Schiff base moieties (Fig. 1) is almost orthogonal with respect to the S2—S3 thioether bond (Fig. 2). The S2—S3 bond distance of 2.0373 (4) Å lies within a range of S—S single-bond lengths (2.03–2.36 Å) (Knop et al., 1988). In each of the Schiff base moieties, the benzene ring and the dithiocarbazate fragment are arranged trans across the C═N bond (C7═N1 and C25═N4). The (iminoethyl)phenol fragments (C1–C8/O1/N1 and C25–C32/O2/N4) are essentially planar with maximum deviations of 0.0559 (12) Å for N1 and 0.0200 (11) Å for N4 and make dihedral angles of 18.17 (4) and 17.49 (4)° with the N2/S1/S2/C9 and N3/S3/S4/C17 planes, respectively. The C—S distances (C9—S1, C9—S2, C10—S1, C17—S4, C17—S3 and C18—S4) of 1.7461 (12)–1.8220 (13) Å are comparable to the values of most similar dithiocarbazate derivatives (Zangrando et al., 2015; Crouse et al., 2004). The C—N distances (C7—N1, C9—N2, C25—N4 and C17—N3) of 1.2789 (15)–1.2983 (15) Å indicate double-bond character (Tarafder et al., 2008) but these values are slightly shorter than the C═N bond of the S-2-picolyl dithiocarbazate Schiff base of 2-acetyl pyrrole (Crouse et al., 2004). The bond angles S1—C9—S2 [117.77 (6)°], S2—C9—N2 [120.78 (9)°], S3—C17—S4 [118.82 (7)°] and S3—C17—N3 [120.15 (12)°] also agree with those observed in trans-cis S-benzyl dithiocarbazate (Tarafder et al., 2008). Intramolecular O—H···N and O—H···S hydrogen bonds are observed (Table 1).
Pairs of intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into inversion dimers. C—H···π interactions are also observed in the crystal, which link the dimers into a column along the b axis (Fig. 3)
A search of the CSD (Version 5.36; Groom & Allen 2014) gave three structures (VAHYAE: Dunstan et al., 1998; FIVQAD Liu et al., 2005; CUHHET: How et al., 2009) closely related to the title compound. S-benzyl-β-N-(2-hydroxyphenylethylidene)dithiocarbazate was prepared by Pramanik et al. (2007) and its crystal structure was reported by Biswal et al. (2015).
The ligand precursor, S-benzyl dithiocarbazate (SBDTC), was prepared according to the literature method (Ali & Tarafder, 1977). The title compound was prepared as follows: to the ligand precursor, SBDTC (0.99 g, 5 mmol) dissolved in ethanol (40 ml) was added 2-hydroxy acetophenone (0.68 g, 5 mmol) and the aliquot was heated under reflux for an 1 h. The resultant yellow solution was cooled to room temperature. The light-yellow precipitate which had had formed was filtered off, washed with hot ethanol and dried under vacuum over anhydrous CaCl2 (yield: 1.23 g, 73.65%). The prepared compound (0.17 g) was dissolved in acetonitrile (20 ml) on warming and mixed with ethanol (10 ml). Light yellow platelet single crystals of the title compound (m.p. 386–387 K) suitable for X-ray study were obtained after 17 days along with colorless needle-shaped crystalline solids (m.p. 413–418 K).
\ There has been immense interest in nitrogen–sulfur donor ligands since the report on S-benzyldithiocarbazate (SBDTC) (Ali & Tarafder, 1977). Since then, a number of Schiff bases have been derived from SBDTC (Crouse et al., 2004; Howlader et al., 2015). The versatile coordination chemistry and increasingly important biological properties of ligands derived from SBDTC have also received much attention (Zangrando et al., 2015). In a continuation of our research, the title compound (systematic name: 2-[1-(2-{(benzylsulfanyl)[((benzylsulfanyl){2-[1-(2-hydroxyphenyl)ethylidene]\ hydrazin-1-ylidene}methyl)disulfanyl]methylidene}hydrazin-1-ylidene)ethyl]\ phenol) was prepared from SBDTC.
In the title compound, the arrangement of the two Schiff base moieties (Fig. 1) is almost orthogonal with respect to the S2—S3 thioether bond (Fig. 2). The S2—S3 bond distance of 2.0373 (4) Å lies within a range of S—S single-bond lengths (2.03–2.36 Å) (Knop et al., 1988). In each of the Schiff base moieties, the benzene ring and the dithiocarbazate fragment are arranged trans across the C═N bond (C7═N1 and C25═N4). The (iminoethyl)phenol fragments (C1–C8/O1/N1 and C25–C32/O2/N4) are essentially planar with maximum deviations of 0.0559 (12) Å for N1 and 0.0200 (11) Å for N4 and make dihedral angles of 18.17 (4) and 17.49 (4)° with the N2/S1/S2/C9 and N3/S3/S4/C17 planes, respectively. The C—S distances (C9—S1, C9—S2, C10—S1, C17—S4, C17—S3 and C18—S4) of 1.7461 (12)–1.8220 (13) Å are comparable to the values of most similar dithiocarbazate derivatives (Zangrando et al., 2015; Crouse et al., 2004). The C—N distances (C7—N1, C9—N2, C25—N4 and C17—N3) of 1.2789 (15)–1.2983 (15) Å indicate double-bond character (Tarafder et al., 2008) but these values are slightly shorter than the C═N bond of the S-2-picolyl dithiocarbazate Schiff base of 2-acetyl pyrrole (Crouse et al., 2004). The bond angles S1—C9—S2 [117.77 (6)°], S2—C9—N2 [120.78 (9)°], S3—C17—S4 [118.82 (7)°] and S3—C17—N3 [120.15 (12)°] also agree with those observed in trans-cis S-benzyl dithiocarbazate (Tarafder et al., 2008). Intramolecular O—H···N and O—H···S hydrogen bonds are observed (Table 1).
Pairs of intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into inversion dimers. C—H···π interactions are also observed in the crystal, which link the dimers into a column along the b axis (Fig. 3)
A search of the CSD (Version 5.36; Groom & Allen 2014) gave three structures (VAHYAE: Dunstan et al., 1998; FIVQAD Liu et al., 2005; CUHHET: How et al., 2009) closely related to the title compound. S-benzyl-β-N-(2-hydroxyphenylethylidene)dithiocarbazate was prepared by Pramanik et al. (2007) and its crystal structure was reported by Biswal et al. (2015).
The ligand precursor, S-benzyl dithiocarbazate (SBDTC), was prepared according to the literature method (Ali & Tarafder, 1977). The title compound was prepared as follows: to the ligand precursor, SBDTC (0.99 g, 5 mmol) dissolved in ethanol (40 ml) was added 2-hydroxy acetophenone (0.68 g, 5 mmol) and the aliquot was heated under reflux for an 1 h. The resultant yellow solution was cooled to room temperature. The light-yellow precipitate which had had formed was filtered off, washed with hot ethanol and dried under vacuum over anhydrous CaCl2 (yield: 1.23 g, 73.65%). The prepared compound (0.17 g) was dissolved in acetonitrile (20 ml) on warming and mixed with ethanol (10 ml). Light yellow platelet single crystals of the title compound (m.p. 386–387 K) suitable for X-ray study were obtained after 17 days along with colorless needle-shaped crystalline solids (m.p. 413–418 K).
Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were positioned geometrically (C—H = 0.95–0.98 Å and O—H = 0.84 Å) and treated as riding with Uiso(H) = 1.2Ueq(C,O).
Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).
C32H30N4O2S4 | Z = 2 |
Mr = 630.85 | F(000) = 660.00 |
Triclinic, P1 | Dx = 1.351 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 10.5556 (3) Å | Cell parameters from 14309 reflections |
b = 11.0236 (3) Å | θ = 3.0–27.5° |
c = 15.5261 (5) Å | µ = 0.34 mm−1 |
α = 75.9922 (8)° | T = 173 K |
β = 71.9673 (7)° | Chunk, yellow |
γ = 65.5889 (7)° | 0.41 × 0.33 × 0.20 mm |
V = 1550.67 (8) Å3 |
Rigaku R-AXIS RAPID diffractometer | 6443 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.000 pixels mm-1 | Rint = 0.024 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −13→11 |
Tmin = 0.842, Tmax = 0.935 | k = −14→14 |
15605 measured reflections | l = −20→20 |
7075 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.2991P] where P = (Fo2 + 2Fc2)/3 |
7075 reflections | (Δ/σ)max < 0.001 |
383 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C32H30N4O2S4 | γ = 65.5889 (7)° |
Mr = 630.85 | V = 1550.67 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.5556 (3) Å | Mo Kα radiation |
b = 11.0236 (3) Å | µ = 0.34 mm−1 |
c = 15.5261 (5) Å | T = 173 K |
α = 75.9922 (8)° | 0.41 × 0.33 × 0.20 mm |
β = 71.9673 (7)° |
Rigaku R-AXIS RAPID diffractometer | 7075 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 6443 reflections with F2 > 2.0σ(F2) |
Tmin = 0.842, Tmax = 0.935 | Rint = 0.024 |
15605 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.39 e Å−3 |
7075 reflections | Δρmin = −0.35 e Å−3 |
383 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are stimated using the full convariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; corrections between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.09853 (4) | 0.18474 (3) | 0.26158 (2) | 0.04004 (9) | |
S2 | 0.33374 (3) | 0.22999 (3) | 0.10197 (2) | 0.03546 (9) | |
S3 | 0.43320 (3) | 0.06584 (3) | 0.18428 (2) | 0.03183 (8) | |
S4 | 0.33603 (3) | −0.04421 (3) | 0.06498 (2) | 0.03407 (9) | |
O1 | 0.34089 (12) | 0.48991 (10) | −0.06903 (8) | 0.0512 (3) | |
O2 | 0.65619 (13) | −0.09530 (10) | 0.33489 (8) | 0.0490 (3) | |
N1 | 0.12722 (11) | 0.47399 (10) | 0.06318 (7) | 0.0301 (2) | |
N2 | 0.06147 (11) | 0.40274 (11) | 0.13886 (7) | 0.0328 (3) | |
N3 | 0.48465 (11) | −0.19327 (10) | 0.18757 (7) | 0.0314 (2) | |
N4 | 0.55167 (11) | −0.19781 (10) | 0.25420 (7) | 0.0296 (2) | |
C1 | 0.26385 (16) | 0.62281 (13) | −0.08014 (9) | 0.0363 (3) | |
C2 | 0.32953 (18) | 0.70237 (15) | −0.14798 (10) | 0.0444 (4) | |
C3 | 0.2587 (2) | 0.83934 (16) | −0.16257 (11) | 0.0504 (4) | |
C4 | 0.1229 (2) | 0.89887 (16) | −0.11067 (14) | 0.0588 (5) | |
C5 | 0.05661 (18) | 0.82114 (14) | −0.04409 (12) | 0.0492 (4) | |
C6 | 0.12461 (14) | 0.68087 (12) | −0.02668 (9) | 0.0332 (3) | |
C7 | 0.05349 (13) | 0.60139 (12) | 0.04772 (9) | 0.0317 (3) | |
C8 | −0.09410 (15) | 0.66931 (15) | 0.10333 (11) | 0.0444 (4) | |
C9 | 0.15035 (13) | 0.28791 (12) | 0.16418 (8) | 0.0309 (3) | |
C10 | −0.08614 (15) | 0.29472 (15) | 0.30185 (10) | 0.0452 (4) | |
C11 | −0.14947 (14) | 0.22557 (13) | 0.39113 (9) | 0.0363 (3) | |
C12 | −0.25928 (15) | 0.18530 (16) | 0.39580 (10) | 0.0431 (3) | |
C13 | −0.32091 (17) | 0.12327 (17) | 0.47688 (12) | 0.0530 (4) | |
C14 | −0.27240 (19) | 0.09964 (17) | 0.55326 (11) | 0.0567 (5) | |
C15 | −0.1638 (3) | 0.1396 (2) | 0.55012 (11) | 0.0635 (5) | |
C16 | −0.10211 (19) | 0.20308 (18) | 0.46934 (11) | 0.0522 (4) | |
C17 | 0.42626 (12) | −0.07400 (12) | 0.14963 (8) | 0.0278 (3) | |
C18 | 0.34252 (15) | −0.21244 (14) | 0.06891 (9) | 0.0367 (3) | |
C19 | 0.24950 (14) | −0.26450 (14) | 0.15237 (8) | 0.0335 (3) | |
C20 | 0.27934 (16) | −0.40188 (15) | 0.16988 (10) | 0.0409 (3) | |
C21 | 0.19396 (18) | −0.45535 (16) | 0.24294 (10) | 0.0466 (4) | |
C22 | 0.07643 (17) | −0.37179 (17) | 0.29866 (10) | 0.0465 (4) | |
C23 | 0.04675 (16) | −0.23501 (17) | 0.28200 (11) | 0.0469 (4) | |
C24 | 0.13335 (15) | −0.18127 (15) | 0.20996 (10) | 0.0399 (3) | |
C25 | 0.58044 (12) | −0.30944 (12) | 0.30954 (8) | 0.0286 (3) | |
C26 | 0.54341 (18) | −0.42358 (14) | 0.30248 (11) | 0.0450 (4) | |
C27 | 0.64827 (12) | −0.31886 (12) | 0.38200 (8) | 0.0292 (3) | |
C28 | 0.68143 (14) | −0.21190 (13) | 0.39196 (9) | 0.0333 (3) | |
C29 | 0.74129 (15) | −0.22298 (15) | 0.46335 (10) | 0.0412 (3) | |
C30 | 0.77032 (17) | −0.33862 (17) | 0.52459 (10) | 0.0459 (4) | |
C31 | 0.73998 (18) | −0.44566 (17) | 0.51615 (11) | 0.0493 (4) | |
C32 | 0.67943 (16) | −0.43490 (14) | 0.44601 (10) | 0.0398 (3) | |
H1 | 0.2919 | 0.4508 | −0.0280 | 0.0614* | |
H2 | 0.6198 | −0.0986 | 0.2949 | 0.0587* | |
H3 | 0.4231 | 0.6618 | −0.1840 | 0.0533* | |
H4 | 0.3036 | 0.8930 | −0.2086 | 0.0604* | |
H5 | 0.0748 | 0.9935 | −0.1206 | 0.0705* | |
H6 | −0.0373 | 0.8636 | −0.0092 | 0.0591* | |
H7 | −0.1566 | 0.7271 | 0.0624 | 0.0533* | |
H8 | −0.0898 | 0.7239 | 0.1429 | 0.0533* | |
H9 | −0.1324 | 0.6012 | 0.1411 | 0.0533* | |
H10 | −0.0891 | 0.3817 | 0.3111 | 0.0542* | |
H11 | −0.1417 | 0.3122 | 0.2562 | 0.0542* | |
H12 | −0.2931 | 0.2003 | 0.3427 | 0.0517* | |
H13 | −0.3972 | 0.0972 | 0.4792 | 0.0635* | |
H14 | −0.3136 | 0.0557 | 0.6085 | 0.0680* | |
H15 | −0.1304 | 0.1237 | 0.6036 | 0.0762* | |
H16 | −0.0274 | 0.2310 | 0.4678 | 0.0626* | |
H17 | 0.3147 | −0.2148 | 0.0142 | 0.0440* | |
H18 | 0.4430 | −0.2752 | 0.0644 | 0.0440* | |
H19 | 0.3590 | −0.4600 | 0.1315 | 0.0491* | |
H20 | 0.2164 | −0.5497 | 0.2547 | 0.0560* | |
H21 | 0.0168 | −0.4080 | 0.3479 | 0.0558* | |
H22 | −0.0337 | −0.1771 | 0.3202 | 0.0563* | |
H23 | 0.1131 | −0.0873 | 0.2000 | 0.0479* | |
H24 | 0.4454 | −0.4115 | 0.3380 | 0.0539* | |
H25 | 0.6101 | −0.5085 | 0.3265 | 0.0539* | |
H26 | 0.5506 | −0.4253 | 0.2383 | 0.0539* | |
H27 | 0.7622 | −0.1501 | 0.4697 | 0.0495* | |
H28 | 0.8113 | −0.3452 | 0.5728 | 0.0551* | |
H29 | 0.7606 | −0.5257 | 0.5582 | 0.0592* | |
H30 | 0.6583 | −0.5083 | 0.4410 | 0.0478* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03573 (18) | 0.03325 (17) | 0.03854 (18) | −0.01161 (13) | −0.00120 (13) | 0.00559 (13) |
S2 | 0.02997 (16) | 0.02973 (16) | 0.03605 (17) | −0.00918 (12) | −0.00505 (12) | 0.00752 (12) |
S3 | 0.03227 (16) | 0.02733 (15) | 0.03573 (16) | −0.01093 (12) | −0.01294 (12) | 0.00250 (11) |
S4 | 0.03448 (17) | 0.03974 (17) | 0.02849 (15) | −0.01494 (13) | −0.01321 (12) | 0.00453 (12) |
O1 | 0.0525 (7) | 0.0291 (5) | 0.0504 (6) | −0.0123 (5) | 0.0081 (5) | 0.0011 (5) |
O2 | 0.0697 (8) | 0.0361 (5) | 0.0575 (7) | −0.0282 (5) | −0.0396 (6) | 0.0129 (5) |
N1 | 0.0316 (5) | 0.0271 (5) | 0.0319 (5) | −0.0112 (4) | −0.0111 (4) | 0.0013 (4) |
N2 | 0.0318 (6) | 0.0308 (5) | 0.0336 (6) | −0.0120 (5) | −0.0077 (5) | 0.0005 (4) |
N3 | 0.0327 (6) | 0.0298 (5) | 0.0317 (5) | −0.0097 (4) | −0.0127 (4) | −0.0005 (4) |
N4 | 0.0297 (5) | 0.0275 (5) | 0.0304 (5) | −0.0085 (4) | −0.0112 (4) | −0.0005 (4) |
C1 | 0.0509 (8) | 0.0292 (6) | 0.0328 (6) | −0.0177 (6) | −0.0165 (6) | 0.0027 (5) |
C2 | 0.0642 (10) | 0.0437 (8) | 0.0342 (7) | −0.0305 (7) | −0.0161 (7) | 0.0045 (6) |
C3 | 0.0827 (12) | 0.0453 (8) | 0.0449 (8) | −0.0409 (9) | −0.0389 (8) | 0.0184 (7) |
C4 | 0.0758 (12) | 0.0299 (7) | 0.0794 (12) | −0.0194 (8) | −0.0495 (11) | 0.0180 (8) |
C5 | 0.0497 (9) | 0.0294 (7) | 0.0694 (11) | −0.0078 (6) | −0.0339 (8) | 0.0059 (7) |
C6 | 0.0416 (7) | 0.0270 (6) | 0.0373 (7) | −0.0125 (5) | −0.0242 (6) | 0.0035 (5) |
C7 | 0.0326 (6) | 0.0291 (6) | 0.0365 (6) | −0.0085 (5) | −0.0180 (5) | −0.0023 (5) |
C8 | 0.0361 (7) | 0.0366 (7) | 0.0529 (9) | −0.0028 (6) | −0.0143 (6) | −0.0065 (6) |
C9 | 0.0308 (6) | 0.0300 (6) | 0.0314 (6) | −0.0132 (5) | −0.0062 (5) | −0.0009 (5) |
C10 | 0.0330 (7) | 0.0435 (8) | 0.0435 (8) | −0.0098 (6) | −0.0025 (6) | 0.0054 (6) |
C11 | 0.0338 (7) | 0.0347 (7) | 0.0335 (7) | −0.0099 (6) | −0.0024 (5) | −0.0040 (5) |
C12 | 0.0388 (8) | 0.0491 (8) | 0.0399 (7) | −0.0165 (7) | −0.0046 (6) | −0.0088 (6) |
C13 | 0.0425 (8) | 0.0479 (9) | 0.0595 (10) | −0.0204 (7) | 0.0064 (7) | −0.0085 (8) |
C14 | 0.0595 (10) | 0.0454 (9) | 0.0407 (8) | −0.0146 (8) | 0.0136 (7) | −0.0042 (7) |
C15 | 0.0872 (14) | 0.0642 (11) | 0.0331 (8) | −0.0215 (10) | −0.0174 (8) | −0.0033 (8) |
C16 | 0.0597 (10) | 0.0561 (10) | 0.0486 (9) | −0.0271 (8) | −0.0195 (8) | −0.0013 (7) |
C17 | 0.0252 (6) | 0.0313 (6) | 0.0255 (5) | −0.0109 (5) | −0.0057 (5) | −0.0006 (5) |
C18 | 0.0411 (7) | 0.0453 (8) | 0.0290 (6) | −0.0198 (6) | −0.0093 (5) | −0.0061 (6) |
C19 | 0.0356 (7) | 0.0425 (7) | 0.0296 (6) | −0.0183 (6) | −0.0147 (5) | −0.0012 (5) |
C20 | 0.0491 (8) | 0.0422 (8) | 0.0361 (7) | −0.0167 (7) | −0.0166 (6) | −0.0047 (6) |
C21 | 0.0651 (10) | 0.0441 (8) | 0.0427 (8) | −0.0284 (8) | −0.0250 (7) | 0.0045 (6) |
C22 | 0.0517 (9) | 0.0599 (10) | 0.0384 (7) | −0.0335 (8) | −0.0164 (7) | 0.0063 (7) |
C23 | 0.0386 (8) | 0.0572 (9) | 0.0447 (8) | −0.0220 (7) | −0.0045 (6) | −0.0052 (7) |
C24 | 0.0372 (7) | 0.0418 (8) | 0.0418 (7) | −0.0171 (6) | −0.0098 (6) | −0.0022 (6) |
C25 | 0.0258 (6) | 0.0252 (6) | 0.0307 (6) | −0.0063 (5) | −0.0072 (5) | −0.0014 (5) |
C26 | 0.0611 (9) | 0.0325 (7) | 0.0517 (9) | −0.0217 (7) | −0.0298 (8) | 0.0059 (6) |
C27 | 0.0256 (6) | 0.0287 (6) | 0.0295 (6) | −0.0074 (5) | −0.0073 (5) | −0.0008 (5) |
C28 | 0.0323 (6) | 0.0310 (6) | 0.0360 (7) | −0.0112 (5) | −0.0117 (5) | 0.0006 (5) |
C29 | 0.0438 (8) | 0.0448 (8) | 0.0416 (7) | −0.0195 (7) | −0.0160 (6) | −0.0033 (6) |
C30 | 0.0499 (9) | 0.0573 (9) | 0.0357 (7) | −0.0226 (7) | −0.0200 (6) | 0.0029 (7) |
C31 | 0.0614 (10) | 0.0489 (9) | 0.0411 (8) | −0.0243 (8) | −0.0264 (7) | 0.0142 (7) |
C32 | 0.0475 (8) | 0.0344 (7) | 0.0398 (7) | −0.0175 (6) | −0.0182 (6) | 0.0059 (6) |
S1—C9 | 1.7461 (12) | C25—C27 | 1.473 (2) |
S1—C10 | 1.8220 (13) | C27—C28 | 1.414 (3) |
S2—S3 | 2.0373 (4) | C27—C32 | 1.4041 (18) |
S2—C9 | 1.7909 (12) | C28—C29 | 1.395 (3) |
S3—C17 | 1.7862 (16) | C29—C30 | 1.376 (2) |
S4—C17 | 1.7464 (15) | C30—C31 | 1.388 (4) |
S4—C18 | 1.8139 (18) | C31—C32 | 1.384 (3) |
O1—C1 | 1.3480 (16) | O1—H1 | 0.840 |
O2—C28 | 1.3491 (16) | O2—H2 | 0.840 |
N1—N2 | 1.4065 (15) | C2—H3 | 0.950 |
N1—C7 | 1.2980 (15) | C3—H4 | 0.950 |
N2—C9 | 1.2818 (15) | C4—H5 | 0.950 |
N3—N4 | 1.4043 (19) | C5—H6 | 0.950 |
N3—C17 | 1.2789 (15) | C8—H7 | 0.980 |
N4—C25 | 1.2983 (15) | C8—H8 | 0.980 |
C1—C2 | 1.401 (3) | C8—H9 | 0.980 |
C1—C6 | 1.4082 (18) | C10—H10 | 0.990 |
C2—C3 | 1.377 (2) | C10—H11 | 0.990 |
C3—C4 | 1.377 (3) | C12—H12 | 0.950 |
C4—C5 | 1.383 (3) | C13—H13 | 0.950 |
C5—C6 | 1.4070 (18) | C14—H14 | 0.950 |
C6—C7 | 1.4773 (19) | C15—H15 | 0.950 |
C7—C8 | 1.4997 (17) | C16—H16 | 0.950 |
C10—C11 | 1.5117 (19) | C18—H17 | 0.990 |
C11—C12 | 1.380 (3) | C18—H18 | 0.990 |
C11—C16 | 1.383 (3) | C20—H19 | 0.950 |
C12—C13 | 1.385 (3) | C21—H20 | 0.950 |
C13—C14 | 1.361 (3) | C22—H21 | 0.950 |
C14—C15 | 1.373 (4) | C23—H22 | 0.950 |
C15—C16 | 1.390 (3) | C24—H23 | 0.950 |
C18—C19 | 1.5135 (19) | C26—H24 | 0.980 |
C19—C20 | 1.388 (3) | C26—H25 | 0.980 |
C19—C24 | 1.3904 (18) | C26—H26 | 0.980 |
C20—C21 | 1.389 (3) | C29—H27 | 0.950 |
C21—C22 | 1.383 (2) | C30—H28 | 0.950 |
C22—C23 | 1.382 (3) | C31—H29 | 0.950 |
C23—C24 | 1.390 (3) | C32—H30 | 0.950 |
C25—C26 | 1.499 (3) | ||
C9—S1—C10 | 99.56 (6) | C28—O2—H2 | 109.466 |
S3—S2—C9 | 104.38 (4) | C1—C2—H3 | 119.943 |
S2—S3—C17 | 105.39 (5) | C3—C2—H3 | 119.937 |
C17—S4—C18 | 99.70 (7) | C2—C3—H4 | 119.877 |
N2—N1—C7 | 115.35 (9) | C4—C3—H4 | 119.879 |
N1—N2—C9 | 112.35 (10) | C3—C4—H5 | 119.948 |
N4—N3—C17 | 113.08 (13) | C5—C4—H5 | 119.947 |
N3—N4—C25 | 114.85 (13) | C4—C5—H6 | 119.129 |
O1—C1—C2 | 116.61 (12) | C6—C5—H6 | 119.136 |
O1—C1—C6 | 122.57 (13) | C7—C8—H7 | 109.476 |
C2—C1—C6 | 120.82 (12) | C7—C8—H8 | 109.462 |
C1—C2—C3 | 120.12 (14) | C7—C8—H9 | 109.472 |
C2—C3—C4 | 120.24 (16) | H7—C8—H8 | 109.476 |
C3—C4—C5 | 120.10 (14) | H7—C8—H9 | 109.473 |
C4—C5—C6 | 121.73 (14) | H8—C8—H9 | 109.468 |
C1—C6—C5 | 116.97 (13) | S1—C10—H10 | 110.101 |
C1—C6—C7 | 122.56 (11) | S1—C10—H11 | 110.109 |
C5—C6—C7 | 120.41 (11) | C11—C10—H10 | 110.096 |
N1—C7—C6 | 116.53 (10) | C11—C10—H11 | 110.108 |
N1—C7—C8 | 123.33 (12) | H10—C10—H11 | 108.444 |
C6—C7—C8 | 120.10 (11) | C11—C12—H12 | 119.542 |
S1—C9—S2 | 117.77 (6) | C13—C12—H12 | 119.538 |
S1—C9—N2 | 121.43 (9) | C12—C13—H13 | 119.911 |
S2—C9—N2 | 120.78 (9) | C14—C13—H13 | 119.899 |
S1—C10—C11 | 107.98 (9) | C13—C14—H14 | 120.123 |
C10—C11—C12 | 119.49 (15) | C15—C14—H14 | 120.120 |
C10—C11—C16 | 121.90 (17) | C14—C15—H15 | 119.748 |
C12—C11—C16 | 118.60 (14) | C16—C15—H15 | 119.742 |
C11—C12—C13 | 120.92 (17) | C11—C16—H16 | 119.988 |
C12—C13—C14 | 120.2 (2) | C15—C16—H16 | 120.002 |
C13—C14—C15 | 119.76 (16) | S4—C18—H17 | 108.133 |
C14—C15—C16 | 120.5 (2) | S4—C18—H18 | 108.131 |
C11—C16—C15 | 120.0 (3) | C19—C18—H17 | 108.132 |
S3—C17—S4 | 118.82 (7) | C19—C18—H18 | 108.138 |
S3—C17—N3 | 120.15 (12) | H17—C18—H18 | 107.308 |
S4—C17—N3 | 121.03 (13) | C19—C20—H19 | 119.639 |
S4—C18—C19 | 116.64 (10) | C21—C20—H19 | 119.640 |
C18—C19—C20 | 117.90 (11) | C20—C21—H20 | 119.866 |
C18—C19—C24 | 123.27 (13) | C22—C21—H20 | 119.868 |
C20—C19—C24 | 118.79 (13) | C21—C22—H21 | 120.357 |
C19—C20—C21 | 120.72 (13) | C23—C22—H21 | 120.354 |
C20—C21—C22 | 120.27 (16) | C22—C23—H22 | 119.677 |
C21—C22—C23 | 119.29 (15) | C24—C23—H22 | 119.671 |
C22—C23—C24 | 120.65 (13) | C19—C24—H23 | 119.868 |
C19—C24—C23 | 120.25 (15) | C23—C24—H23 | 119.878 |
N4—C25—C26 | 122.05 (14) | C25—C26—H24 | 109.480 |
N4—C25—C27 | 117.20 (14) | C25—C26—H25 | 109.474 |
C26—C25—C27 | 120.73 (11) | C25—C26—H26 | 109.469 |
C25—C27—C28 | 122.18 (11) | H24—C26—H25 | 109.472 |
C25—C27—C32 | 120.68 (15) | H24—C26—H26 | 109.464 |
C28—C27—C32 | 117.12 (15) | H25—C26—H26 | 109.468 |
O2—C28—C27 | 122.60 (15) | C28—C29—H27 | 119.731 |
O2—C28—C29 | 116.91 (16) | C30—C29—H27 | 119.725 |
C27—C28—C29 | 120.48 (12) | C29—C30—H28 | 119.862 |
C28—C29—C30 | 120.54 (18) | C31—C30—H28 | 119.853 |
C29—C30—C31 | 120.28 (18) | C30—C31—H29 | 120.257 |
C30—C31—C32 | 119.47 (15) | C32—C31—H29 | 120.269 |
C27—C32—C31 | 122.09 (17) | C27—C32—H30 | 118.957 |
C1—O1—H1 | 109.472 | C31—C32—H30 | 118.953 |
C9—S1—C10—C11 | −176.67 (11) | S1—C10—C11—C12 | −114.03 (11) |
C10—S1—C9—S2 | 175.25 (11) | S1—C10—C11—C16 | 67.04 (15) |
C10—S1—C9—N2 | −3.17 (15) | C10—C11—C12—C13 | −179.14 (11) |
S3—S2—C9—S1 | −9.83 (11) | C10—C11—C16—C15 | 179.74 (11) |
S3—S2—C9—N2 | 168.60 (11) | C12—C11—C16—C15 | 0.8 (2) |
C9—S2—S3—C17 | 91.54 (6) | C16—C11—C12—C13 | −0.2 (2) |
S2—S3—C17—S4 | −3.18 (7) | C11—C12—C13—C14 | −0.8 (3) |
S2—S3—C17—N3 | 177.93 (7) | C12—C13—C14—C15 | 1.1 (3) |
C17—S4—C18—C19 | 70.94 (11) | C13—C14—C15—C16 | −0.5 (3) |
C18—S4—C17—S3 | −172.82 (7) | C14—C15—C16—C11 | −0.5 (3) |
C18—S4—C17—N3 | 6.06 (10) | S4—C18—C19—C20 | −162.98 (10) |
N2—N1—C7—C6 | 175.20 (12) | S4—C18—C19—C24 | 19.4 (2) |
N2—N1—C7—C8 | −2.3 (3) | C18—C19—C20—C21 | −177.02 (14) |
C7—N1—N2—C9 | −164.04 (13) | C18—C19—C24—C23 | 175.75 (14) |
N1—N2—C9—S1 | 175.36 (12) | C20—C19—C24—C23 | −1.9 (3) |
N1—N2—C9—S2 | −3.0 (2) | C24—C19—C20—C21 | 0.7 (3) |
N4—N3—C17—S3 | −0.88 (13) | C19—C20—C21—C22 | 0.9 (3) |
N4—N3—C17—S4 | −179.74 (8) | C20—C21—C22—C23 | −1.4 (3) |
C17—N3—N4—C25 | 163.60 (9) | C21—C22—C23—C24 | 0.2 (3) |
N3—N4—C25—C26 | −0.41 (14) | C22—C23—C24—C19 | 1.4 (3) |
N3—N4—C25—C27 | −178.84 (8) | N4—C25—C27—C28 | 0.01 (14) |
O1—C1—C2—C3 | −178.99 (16) | N4—C25—C27—C32 | 178.36 (9) |
O1—C1—C6—C5 | 178.96 (15) | C26—C25—C27—C28 | −178.44 (10) |
O1—C1—C6—C7 | 1.9 (3) | C26—C25—C27—C32 | −0.09 (15) |
C2—C1—C6—C5 | −0.7 (3) | C25—C27—C28—O2 | −1.44 (16) |
C2—C1—C6—C7 | −177.74 (16) | C25—C27—C28—C29 | 177.84 (9) |
C6—C1—C2—C3 | 0.7 (3) | C25—C27—C32—C31 | −178.45 (9) |
C1—C2—C3—C4 | −0.1 (3) | C28—C27—C32—C31 | −0.02 (17) |
C2—C3—C4—C5 | −0.5 (4) | C32—C27—C28—O2 | −179.85 (10) |
C3—C4—C5—C6 | 0.5 (4) | C32—C27—C28—C29 | −0.57 (16) |
C4—C5—C6—C1 | 0.1 (3) | O2—C28—C29—C30 | 179.98 (10) |
C4—C5—C6—C7 | 177.23 (19) | C27—C28—C29—C30 | 0.67 (17) |
C1—C6—C7—N1 | 1.4 (3) | C28—C29—C30—C31 | −0.16 (19) |
C1—C6—C7—C8 | 178.99 (15) | C29—C30—C31—C32 | −0.4 (2) |
C5—C6—C7—N1 | −175.60 (16) | C30—C31—C32—C27 | 0.5 (2) |
C5—C6—C7—C8 | 2.0 (3) |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.84 | 1.84 | 2.5725 (15) | 145 |
O2—H2···N4 | 0.84 | 1.84 | 2.576 (3) | 146 |
O1—H1···S2 | 0.84 | 2.73 | 3.4112 (12) | 139 |
O2—H2···S3 | 0.84 | 2.78 | 3.4792 (14) | 141 |
C18—H18···O1i | 0.99 | 2.52 | 3.4750 (19) | 161 |
C18—H17···Cg1ii | 0.99 | 2.54 | 3.5123 (17) | 165 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z. |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.84 | 1.84 | 2.5725 (15) | 145 |
O2—H2···N4 | 0.84 | 1.84 | 2.576 (3) | 146 |
O1—H1···S2 | 0.84 | 2.73 | 3.4112 (12) | 139 |
O2—H2···S3 | 0.84 | 2.78 | 3.4792 (14) | 141 |
C18—H18···O1i | 0.99 | 2.52 | 3.4750 (19) | 161 |
C18—H17···Cg1ii | 0.99 | 2.54 | 3.5123 (17) | 165 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C32H30N4O2S4 |
Mr | 630.85 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 10.5556 (3), 11.0236 (3), 15.5261 (5) |
α, β, γ (°) | 75.9922 (8), 71.9673 (7), 65.5889 (7) |
V (Å3) | 1550.67 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.41 × 0.33 × 0.20 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.842, 0.935 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 15605, 7075, 6443 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.093, 1.09 |
No. of reflections | 7075 |
No. of parameters | 383 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.35 |
Computer programs: RAPID-AUTO (Rigaku, 2001), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010).