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Acta Cryst. (2008). E64, o2305    [ doi:10.1107/S1600536808035964 ]

4-(4-Chlorophenyl)-1-(2-hydroxy-2,2-diphenylacetyl)thiosemicarbazide

K. A. Abu-Safieh, M. A. Khanfar, K. Eichele and B. F. Ali

Abstract top

The asymmetric unit of the title compound, C21H18ClN3O2S, contains two molecules in which the bond lengths and angles are almost identical. Intramolecular N-H...S hydrogen bonds result in the formation of two five-membered rings. In the crystal structure, intermolecular N-H...O hydrogen bonds link the molecules into centrosymmetric dimers; these dimers are linked via intermolecular O-H...S hydrogen bonds, leading to infinite corrugated layers parallel to the bc plane through R22(16) ring motifs.

Comment top

Thiosemicarbazides have received special interest for their potential biological activities (Kucukguzel et al., 2006; Singh et al., 2005). They have also received considerable attention because of the possibility of their use as intermediates in the synthesis of many biologically active heterocyclic compounds such as 1,2,4-triazole derivatives (Ergenç et al., 1992), 1,3,4-thiadiazoles (Jalilian et al., 2000) and many others. As ligands, thiosemicarbazides are useful bidentate ligands (S- and N- donors) for transition metal ions and their complexes possess many biological activities (Shen et al., 1998). The title compound was synthesized as an intermediate for biologically active 1,2,4-triazole derivative (Ergenç et al., 1992). We report herein its crystal structure.

The asymmetric unit of the title compound contains two independent thiosemicarbazide molecules (Fig 1), where the bond lengths and angles are almost identical (Table 1). In both molecules, the linking C-N-N-C-N units are delocalized and flattened. The C-S and C-O bonds both show the double bond character, while the C-N and N-N bonds in the linking units imply significant electron delocalization. As a result of conjugation, O2-C14 [1.241 (2) Å] and O5-C35 [1.242 (2) Å] bonds are longer than the normal value of 1.20 Å (John, 1998), while N1-C14 [1.323 (2) Å] and N4-C35 [1.327 (2) Å] bonds are in accordance with the C-N double bond length (1.32 A°; John, 1998) and shorter than the C-N single bond length (1.475 A°; John, 1998). The sum of the bond angles around N1, N2, N3, C14, C15 and N4, N5, N6, C35, C36 atoms are about 360°, which implies sp2 hybridization for these atoms. The thiourea group is approximately planar. The intramolecular N-H···S hydrogen bonds (Table 2) result in the formation of two five-membered rings (S1/N1/N2/C15/H1N) and (S2/N4/N5/C36/H4N).

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers (Fig. 2), in which they are also linked to the other dimers via intermolecular O-H···S hydrogen bonds (Table 2) leading to infinite corrugated layers parallel to the bc plane through R22(16) ring motifs (Bernstein et al., 1995).

Related literature top

For a related structure, see: Ergenç et al. (1992). For general background, see: Jalilian et al. (2000); John (1998); Kucukguzel et al. (2006); Shen et al. (1998); Singh et al. (2005). For ring motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized according to the literature method (Ergenç et al., 1992) by the reaction of equimolar amounts of 2-hydroxy-2,2-diphenyl- acetohydrazide, (1), and 1-chloro-4-isothiocyanatobenzene, (2), (Fig. 3). Crystals suitable for X-ray analysis were obtained by recrystallization from a methanol solution at room temperature.

Refinement top

H1N, H2N, H3N, H4N, H5N and H6N atoms (for NH) were located in difference syntheses and refined isotropically [N-H = 0.81 (2)-0.90 (2) Å and Uiso(H) = 0.032 (5)-0.046 (7) Å2]. The remaining H atoms were positioned geometrically, with O-H = 0.84 Å (for OH) and C-H = 0.95 Å for aromatic H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,O).

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines [symmetry codes: (i) x, 3/2 - y, z + 1/2; (ii) x, y, z + 1]. H atoms not involved in hydrogen bonding are omitted for clarity.
[Figure 3] Fig. 3. A schematic representation of the reaction that afforded the title compound.
4-(4-Chlorophenyl)-1-(2-hydroxy-2,2-diphenylacetyl)thiosemicarbazide top
Crystal data top
C21H18ClN3O2SF(000) = 1712
Mr = 411.89Dx = 1.389 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 51 reflections
a = 14.1039 (19) Åθ = 4.9–12.6°
b = 18.1566 (19) ŵ = 0.32 mm−1
c = 16.9108 (19) ÅT = 173 K
β = 114.509 (10)°Prism, colorless
V = 3940.3 (9) Å30.9 × 0.4 × 0.4 mm
Z = 8
Data collection top
Bruker P4
diffractometer		6867 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
graphiteθmax = 27.5°, θmin = 2.2°
ω scansh = −18→1
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		k = −23→23
Tmin = 0.837, Tmax = 0.879l = −20→21
20863 measured reflections2 standard reflections every 98 reflections
9027 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0394P)2 + 1.5051P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
9027 reflectionsΔρmax = 0.91 e Å−3
532 parametersΔρmin = −0.82 e Å−3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (2)
Crystal data top
C21H18ClN3O2SV = 3940.3 (9) Å3
Mr = 411.89Z = 8
Monoclinic, P21/cMo Kα radiation
a = 14.1039 (19) ŵ = 0.32 mm−1
b = 18.1566 (19) ÅT = 173 K
c = 16.9108 (19) Å0.9 × 0.4 × 0.4 mm
β = 114.509 (10)°
Data collection top
Bruker P4
diffractometer		6867 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		Rint = 0.029
Tmin = 0.837, Tmax = 0.879θmax = 27.5°
20863 measured reflections2 standard reflections every 98 reflections
9027 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102Δρmax = 0.91 e Å−3
S = 1.02Δρmin = −0.82 e Å−3
9027 reflectionsAbsolute structure: ?
532 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl1−0.35372 (4)0.47876 (3)0.91532 (4)0.04719 (14)
S10.10518 (4)0.53220 (3)0.84004 (3)0.03220 (11)
O10.40810 (11)0.59866 (7)0.86727 (8)0.0351 (3)
H1O0.41360.59830.81970.053*
O20.34635 (10)0.74781 (7)0.97416 (9)0.0372 (3)
N10.26430 (12)0.64596 (9)0.90301 (10)0.0316 (3)
H1N0.2627 (16)0.6047 (12)0.8741 (14)0.041 (6)*
N20.18196 (12)0.65529 (9)0.92635 (11)0.0327 (4)
H2N0.1839 (18)0.6904 (13)0.9562 (15)0.046 (7)*
N30.03119 (11)0.62184 (8)0.93040 (10)0.0280 (3)
H3N0.0423 (15)0.6629 (11)0.9608 (13)0.032 (5)*
C10.53250 (13)0.66591 (9)0.98982 (11)0.0265 (4)
C20.59828 (14)0.72619 (10)1.02190 (12)0.0322 (4)
H20.58200.77140.99080.039*
C30.68734 (15)0.72099 (12)1.09875 (13)0.0384 (4)
H30.73140.76271.12020.046*
C40.71225 (16)0.65547 (12)1.14417 (13)0.0428 (5)
H4A0.77420.65161.19610.051*
C50.64697 (17)0.59559 (12)1.11394 (14)0.0436 (5)
H50.66350.55071.14570.052*
C60.55727 (15)0.60058 (10)1.03742 (13)0.0349 (4)
H60.51240.55921.01730.042*
C70.43300 (14)0.67069 (9)0.90531 (11)0.0281 (4)
C80.44508 (14)0.72594 (10)0.84178 (11)0.0305 (4)
C90.38732 (17)0.79023 (13)0.81501 (14)0.0450 (5)
H90.33580.80150.83560.054*
C100.4044 (2)0.83823 (15)0.75830 (17)0.0616 (7)
H100.36510.88240.74090.074*
C110.47860 (19)0.82192 (15)0.72685 (15)0.0557 (6)
H110.48970.85460.68760.067*
C120.53596 (16)0.75824 (13)0.75273 (13)0.0441 (5)
H120.58660.74690.73110.053*
C130.52029 (15)0.71046 (11)0.81031 (12)0.0355 (4)
H130.56100.66690.82850.043*
C140.34396 (13)0.69218 (10)0.93070 (11)0.0277 (4)
C150.10457 (13)0.60501 (9)0.90104 (11)0.0263 (4)
C16−0.06058 (13)0.58394 (9)0.92138 (11)0.0263 (4)
C17−0.08058 (14)0.50973 (10)0.90017 (11)0.0284 (4)
H17−0.03260.48090.88720.034*
C18−0.17141 (14)0.47832 (10)0.89816 (11)0.0305 (4)
H18−0.18580.42790.88310.037*
C19−0.24083 (13)0.51957 (11)0.91782 (12)0.0317 (4)
C20−0.22088 (15)0.59270 (11)0.94035 (14)0.0413 (5)
H20−0.26800.62090.95510.050*
C21−0.13118 (15)0.62458 (11)0.94123 (14)0.0391 (5)
H21−0.11780.67520.95570.047*
Cl20.85383 (5)1.00209 (4)0.11087 (5)0.06182 (19)
S20.40487 (4)0.95519 (3)0.18449 (3)0.03181 (11)
O40.09276 (10)0.90499 (7)0.15471 (8)0.0336 (3)
H4O0.08160.90660.19980.050*
O50.13097 (10)0.75772 (7)0.03205 (8)0.0342 (3)
N40.22880 (12)0.85044 (9)0.11506 (11)0.0325 (3)
H4N0.2363 (17)0.8894 (12)0.1476 (14)0.045 (6)*
N50.31033 (12)0.83735 (9)0.09191 (11)0.0362 (4)
H5N0.2991 (17)0.8017 (13)0.0518 (14)0.046 (6)*
N60.45659 (12)0.86864 (9)0.07879 (11)0.0350 (4)
H6N0.4369 (17)0.8333 (12)0.0391 (14)0.043 (6)*
C22−0.04212 (14)0.84829 (9)0.02956 (11)0.0277 (4)
C23−0.04205 (16)0.90432 (10)−0.02701 (12)0.0353 (4)
H230.01920.9327−0.01410.042*
C24−0.13058 (17)0.91890 (11)−0.10186 (13)0.0418 (5)
H24−0.12980.9574−0.13960.050*
C25−0.22013 (16)0.87771 (11)−0.12200 (13)0.0406 (5)
H25−0.28070.8877−0.17340.049*
C26−0.22073 (16)0.82195 (11)−0.06669 (13)0.0391 (4)
H26−0.28190.7933−0.08030.047*
C27−0.13221 (14)0.80740 (10)0.00893 (12)0.0319 (4)
H27−0.13360.76910.04670.038*
C280.05769 (14)0.83534 (9)0.11184 (11)0.0272 (4)
C290.04543 (14)0.77964 (10)0.17447 (11)0.0306 (4)
C300.10095 (18)0.71399 (13)0.19657 (15)0.0487 (5)
H300.14750.70190.17090.058*
C310.0892 (2)0.66601 (15)0.25556 (18)0.0653 (7)
H310.12750.62130.27000.078*
C320.0225 (2)0.68284 (15)0.29325 (15)0.0581 (7)
H320.01460.64970.33360.070*
C33−0.03331 (17)0.74784 (13)0.27265 (13)0.0466 (5)
H33−0.07920.75960.29900.056*
C34−0.02215 (15)0.79620 (11)0.21312 (12)0.0364 (4)
H34−0.06090.84080.19880.044*
C350.14256 (14)0.81022 (10)0.08231 (11)0.0285 (4)
C360.39154 (14)0.88456 (10)0.11629 (11)0.0293 (4)
C370.55058 (14)0.90486 (10)0.08987 (11)0.0290 (4)
C380.62840 (16)0.92071 (13)0.17052 (13)0.0420 (5)
H380.61830.91070.22160.050*
C390.72165 (16)0.95127 (13)0.17680 (14)0.0473 (5)
H390.77540.96230.23220.057*
C400.73569 (15)0.96547 (11)0.10254 (13)0.0366 (4)
C410.65866 (14)0.95032 (10)0.02156 (12)0.0322 (4)
H410.66910.9603−0.02940.039*
C420.56583 (14)0.92029 (10)0.01565 (11)0.0298 (4)
H420.51190.9101−0.03990.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0334 (3)0.0594 (3)0.0571 (3)−0.0161 (2)0.0271 (2)−0.0117 (3)
S10.0354 (2)0.0322 (2)0.0347 (2)−0.00651 (19)0.0203 (2)−0.00557 (18)
O10.0414 (8)0.0347 (7)0.0386 (7)−0.0121 (6)0.0261 (6)−0.0140 (6)
O20.0322 (7)0.0400 (7)0.0472 (8)−0.0083 (6)0.0245 (6)−0.0162 (6)
N10.0269 (8)0.0357 (9)0.0384 (8)−0.0060 (7)0.0196 (7)−0.0086 (7)
N20.0273 (8)0.0342 (9)0.0427 (9)−0.0073 (7)0.0206 (7)−0.0112 (7)
N30.0254 (8)0.0269 (8)0.0341 (8)−0.0040 (6)0.0149 (6)−0.0040 (6)
C10.0246 (8)0.0295 (9)0.0313 (9)−0.0011 (7)0.0174 (7)−0.0044 (7)
C20.0311 (10)0.0328 (9)0.0347 (9)−0.0040 (8)0.0158 (8)−0.0008 (8)
C30.0307 (10)0.0471 (12)0.0375 (10)−0.0097 (9)0.0143 (9)−0.0054 (9)
C40.0317 (10)0.0582 (13)0.0359 (10)0.0033 (10)0.0113 (9)0.0056 (9)
C50.0469 (12)0.0416 (11)0.0457 (12)0.0109 (10)0.0228 (10)0.0114 (9)
C60.0383 (11)0.0307 (9)0.0421 (10)−0.0011 (8)0.0232 (9)−0.0011 (8)
C70.0285 (9)0.0286 (9)0.0319 (9)−0.0054 (7)0.0173 (8)−0.0073 (7)
C80.0263 (9)0.0387 (10)0.0259 (8)−0.0073 (8)0.0102 (7)−0.0034 (7)
C90.0371 (11)0.0558 (13)0.0453 (12)0.0071 (10)0.0204 (10)0.0132 (10)
C100.0548 (15)0.0659 (16)0.0648 (16)0.0168 (13)0.0255 (13)0.0318 (13)
C110.0503 (14)0.0730 (17)0.0456 (13)−0.0039 (12)0.0216 (11)0.0225 (12)
C120.0372 (11)0.0629 (14)0.0365 (10)−0.0121 (10)0.0197 (9)−0.0011 (10)
C130.0334 (10)0.0429 (11)0.0352 (10)−0.0065 (9)0.0193 (8)−0.0045 (8)
C140.0246 (9)0.0323 (9)0.0285 (9)−0.0037 (7)0.0133 (7)−0.0026 (7)
C150.0245 (8)0.0294 (9)0.0245 (8)−0.0020 (7)0.0098 (7)0.0023 (7)
C160.0234 (8)0.0302 (9)0.0257 (8)−0.0016 (7)0.0107 (7)0.0027 (7)
C170.0249 (8)0.0298 (9)0.0310 (9)−0.0018 (7)0.0121 (7)−0.0002 (7)
C180.0281 (9)0.0328 (9)0.0297 (9)−0.0061 (7)0.0110 (7)−0.0015 (7)
C190.0235 (9)0.0410 (10)0.0316 (9)−0.0059 (8)0.0124 (7)0.0008 (8)
C200.0324 (10)0.0395 (11)0.0607 (13)0.0004 (9)0.0279 (10)−0.0055 (10)
C210.0349 (10)0.0312 (10)0.0577 (13)−0.0028 (8)0.0256 (10)−0.0059 (9)
Cl20.0482 (3)0.0682 (4)0.0875 (4)−0.0305 (3)0.0465 (3)−0.0349 (3)
S20.0382 (3)0.0311 (2)0.0292 (2)−0.0051 (2)0.01702 (19)−0.00241 (18)
O40.0416 (8)0.0312 (7)0.0379 (7)−0.0097 (6)0.0262 (6)−0.0099 (5)
O50.0321 (7)0.0342 (7)0.0421 (7)−0.0038 (6)0.0213 (6)−0.0107 (6)
N40.0285 (8)0.0358 (9)0.0408 (9)−0.0061 (7)0.0220 (7)−0.0108 (7)
N50.0286 (8)0.0410 (9)0.0469 (10)−0.0097 (7)0.0236 (8)−0.0147 (8)
N60.0321 (8)0.0409 (9)0.0383 (9)−0.0131 (7)0.0209 (7)−0.0153 (7)
C220.0308 (9)0.0255 (8)0.0333 (9)0.0023 (7)0.0198 (8)−0.0028 (7)
C230.0417 (11)0.0321 (10)0.0403 (10)−0.0023 (8)0.0254 (9)−0.0006 (8)
C240.0561 (13)0.0348 (10)0.0388 (11)0.0084 (10)0.0240 (10)0.0056 (8)
C250.0405 (11)0.0437 (11)0.0367 (10)0.0119 (9)0.0151 (9)0.0004 (9)
C260.0325 (10)0.0427 (11)0.0410 (11)0.0001 (9)0.0142 (9)−0.0042 (9)
C270.0342 (10)0.0309 (9)0.0346 (9)−0.0002 (8)0.0181 (8)−0.0008 (8)
C280.0300 (9)0.0256 (8)0.0320 (9)−0.0041 (7)0.0187 (8)−0.0048 (7)
C290.0290 (9)0.0344 (10)0.0292 (9)−0.0082 (8)0.0128 (8)−0.0026 (7)
C300.0503 (13)0.0486 (13)0.0564 (13)0.0089 (11)0.0312 (11)0.0164 (10)
C310.0720 (18)0.0561 (15)0.0774 (18)0.0105 (13)0.0405 (15)0.0305 (13)
C320.0647 (16)0.0634 (16)0.0495 (13)−0.0112 (13)0.0269 (12)0.0180 (12)
C330.0462 (12)0.0634 (15)0.0388 (11)−0.0239 (11)0.0263 (10)−0.0105 (10)
C340.0359 (10)0.0413 (11)0.0362 (10)−0.0119 (9)0.0191 (9)−0.0072 (8)
C350.0280 (9)0.0307 (9)0.0305 (9)−0.0016 (7)0.0158 (8)0.0004 (7)
C360.0277 (9)0.0332 (9)0.0281 (9)−0.0036 (7)0.0127 (7)0.0005 (7)
C370.0275 (9)0.0297 (9)0.0328 (9)−0.0052 (7)0.0156 (7)−0.0037 (7)
C380.0361 (11)0.0634 (14)0.0296 (9)−0.0134 (10)0.0168 (8)−0.0048 (9)
C390.0356 (11)0.0711 (15)0.0358 (10)−0.0169 (11)0.0155 (9)−0.0188 (10)
C400.0312 (10)0.0364 (10)0.0499 (11)−0.0102 (8)0.0246 (9)−0.0121 (9)
C410.0377 (10)0.0293 (9)0.0376 (10)0.0009 (8)0.0234 (8)0.0019 (7)
C420.0298 (9)0.0333 (9)0.0261 (8)0.0015 (8)0.0114 (7)−0.0005 (7)
Geometric parameters (Å, °) top
Cl1—C191.7407 (18)Cl2—C401.7445 (19)
S1—C151.6791 (18)S2—C361.6824 (19)
O1—C71.435 (2)O4—C281.439 (2)
O1—H1O0.8400O4—H4O0.8400
O2—C141.241 (2)O5—C351.242 (2)
N1—C141.323 (2)N4—C351.327 (2)
N1—N21.383 (2)N4—N51.380 (2)
N1—H1N0.89 (2)N4—H4N0.88 (2)
N2—C151.349 (2)N5—C361.351 (2)
N2—H2N0.81 (2)N5—H5N0.90 (2)
N3—C151.355 (2)N6—C361.345 (2)
N3—C161.417 (2)N6—C371.421 (2)
N3—H3N0.88 (2)N6—H6N0.89 (2)
C1—C21.391 (2)C22—C271.385 (2)
C1—C61.394 (3)C22—C231.397 (3)
C1—C71.535 (2)C22—C281.532 (3)
C2—C31.386 (3)C23—C241.386 (3)
C2—H20.9500C23—H230.9500
C3—C41.380 (3)C24—C251.383 (3)
C3—H30.9500C24—H240.9500
C4—C51.379 (3)C25—C261.381 (3)
C4—H4A0.9500C25—H250.9500
C5—C61.387 (3)C26—C271.392 (3)
C5—H50.9500C26—H260.9500
C6—H60.9500C27—H270.9500
C7—C81.530 (2)C28—C291.525 (2)
C7—C141.537 (2)C28—C351.545 (2)
C8—C91.387 (3)C29—C301.390 (3)
C8—C131.398 (3)C29—C341.394 (3)
C9—C101.389 (3)C30—C311.385 (3)
C9—H90.9500C30—H300.9500
C10—C111.389 (3)C31—C321.372 (4)
C10—H100.9500C31—H310.9500
C11—C121.374 (3)C32—C331.380 (3)
C11—H110.9500C32—H320.9500
C12—C131.389 (3)C33—C341.393 (3)
C12—H120.9500C33—H330.9500
C13—H130.9500C34—H340.9500
C16—C211.388 (2)C37—C381.380 (3)
C16—C171.393 (2)C37—C421.387 (2)
C17—C181.390 (2)C38—C391.390 (3)
C17—H170.9500C38—H380.9500
C18—C191.379 (3)C39—C401.375 (3)
C18—H180.9500C39—H390.9500
C19—C201.378 (3)C40—C411.377 (3)
C20—C211.386 (3)C41—C421.383 (2)
C20—H200.9500C41—H410.9500
C21—H210.9500C42—H420.9500
C7—O1—H1O109.5C28—O4—H4O109.5
C14—N1—N2120.78 (16)C35—N4—N5120.94 (16)
C14—N1—H1N123.6 (14)C35—N4—H4N123.9 (15)
N2—N1—H1N115.2 (14)N5—N4—H4N114.8 (15)
C15—N2—N1119.41 (16)C36—N5—N4120.32 (16)
C15—N2—H2N123.1 (17)C36—N5—H5N123.2 (15)
N1—N2—H2N117.5 (17)N4—N5—H5N115.4 (15)
C15—N3—C16130.79 (15)C36—N6—C37128.29 (16)
C15—N3—H3N115.2 (13)C36—N6—H6N116.9 (14)
C16—N3—H3N114.0 (13)C37—N6—H6N114.7 (14)
C2—C1—C6118.51 (17)C27—C22—C23118.62 (17)
C2—C1—C7121.52 (16)C27—C22—C28123.20 (16)
C6—C1—C7119.94 (16)C23—C22—C28118.18 (16)
C3—C2—C1120.69 (18)C24—C23—C22120.55 (18)
C3—C2—H2119.7C24—C23—H23119.7
C1—C2—H2119.7C22—C23—H23119.7
C4—C3—C2120.20 (19)C25—C24—C23120.42 (19)
C4—C3—H3119.9C25—C24—H24119.8
C2—C3—H3119.9C23—C24—H24119.8
C5—C4—C3119.79 (19)C26—C25—C24119.42 (19)
C5—C4—H4A120.1C26—C25—H25120.3
C3—C4—H4A120.1C24—C25—H25120.3
C4—C5—C6120.30 (19)C25—C26—C27120.40 (19)
C4—C5—H5119.9C25—C26—H26119.8
C6—C5—H5119.9C27—C26—H26119.8
C5—C6—C1120.49 (18)C22—C27—C26120.58 (18)
C5—C6—H6119.8C22—C27—H27119.7
C1—C6—H6119.8C26—C27—H27119.7
O1—C7—C8111.13 (14)O4—C28—C29110.30 (14)
O1—C7—C1108.97 (14)O4—C28—C22108.47 (14)
C8—C7—C1111.45 (14)C29—C28—C22113.96 (14)
O1—C7—C14106.27 (13)O4—C28—C35105.77 (13)
C8—C7—C14111.82 (15)C29—C28—C35110.80 (14)
C1—C7—C14106.96 (13)C22—C28—C35107.16 (13)
C9—C8—C13118.70 (18)C30—C29—C34118.53 (18)
C9—C8—C7124.01 (17)C30—C29—C28122.81 (17)
C13—C8—C7117.28 (17)C34—C29—C28118.63 (17)
C8—C9—C10120.5 (2)C31—C30—C29120.7 (2)
C8—C9—H9119.8C31—C30—H30119.6
C10—C9—H9119.8C29—C30—H30119.6
C9—C10—C11120.3 (2)C32—C31—C30120.3 (2)
C9—C10—H10119.8C32—C31—H31119.9
C11—C10—H10119.8C30—C31—H31119.9
C12—C11—C10119.7 (2)C31—C32—C33120.1 (2)
C12—C11—H11120.2C31—C32—H32119.9
C10—C11—H11120.2C33—C32—H32119.9
C11—C12—C13120.3 (2)C32—C33—C34119.9 (2)
C11—C12—H12119.8C32—C33—H33120.1
C13—C12—H12119.8C34—C33—H33120.1
C12—C13—C8120.5 (2)C33—C34—C29120.5 (2)
C12—C13—H13119.7C33—C34—H34119.8
C8—C13—H13119.7C29—C34—H34119.8
O2—C14—N1122.43 (16)O5—C35—N4123.06 (16)
O2—C14—C7123.19 (15)O5—C35—C28123.25 (15)
N1—C14—C7114.37 (15)N4—C35—C28113.68 (15)
N2—C15—N3111.80 (15)N6—C36—N5112.18 (16)
N2—C15—S1121.19 (13)N6—C36—S2125.65 (14)
N3—C15—S1127.00 (13)N5—C36—S2122.17 (14)
C21—C16—C17119.19 (16)C38—C37—C42119.58 (17)
C21—C16—N3115.52 (15)C38—C37—N6122.87 (16)
C17—C16—N3125.15 (16)C42—C37—N6117.42 (16)
C18—C17—C16119.30 (17)C37—C38—C39119.87 (18)
C18—C17—H17120.3C37—C38—H38120.1
C16—C17—H17120.3C39—C38—H38120.1
C19—C18—C17120.72 (17)C40—C39—C38119.69 (18)
C19—C18—H18119.6C40—C39—H39120.2
C17—C18—H18119.6C38—C39—H39120.2
C20—C19—C18120.42 (17)C39—C40—C41121.18 (17)
C20—C19—Cl1119.79 (15)C39—C40—Cl2119.50 (16)
C18—C19—Cl1119.79 (14)C41—C40—Cl2119.31 (15)
C19—C20—C21119.10 (18)C40—C41—C42118.90 (17)
C19—C20—H20120.4C40—C41—H41120.5
C21—C20—H20120.4C42—C41—H41120.5
C20—C21—C16121.25 (18)C41—C42—C37120.77 (17)
C20—C21—H21119.4C41—C42—H42119.6
C16—C21—H21119.4C37—C42—H42119.6
C14—N1—N2—C15−176.39 (17)C35—N4—N5—C36171.09 (17)
C6—C1—C2—C31.0 (3)C27—C22—C23—C240.4 (3)
C7—C1—C2—C3179.43 (16)C28—C22—C23—C24−179.29 (16)
C1—C2—C3—C40.5 (3)C22—C23—C24—C25−0.5 (3)
C2—C3—C4—C5−1.5 (3)C23—C24—C25—C260.2 (3)
C3—C4—C5—C61.0 (3)C24—C25—C26—C270.3 (3)
C4—C5—C6—C10.5 (3)C23—C22—C27—C260.0 (3)
C2—C1—C6—C5−1.5 (3)C28—C22—C27—C26179.73 (16)
C7—C1—C6—C5−179.97 (17)C25—C26—C27—C22−0.4 (3)
C2—C1—C7—O1153.48 (15)C27—C22—C28—O4−130.14 (17)
C6—C1—C7—O1−28.1 (2)C23—C22—C28—O449.6 (2)
C2—C1—C7—C830.5 (2)C27—C22—C28—C29−6.9 (2)
C6—C1—C7—C8−151.15 (16)C23—C22—C28—C29172.85 (15)
C2—C1—C7—C14−92.03 (19)C27—C22—C28—C35116.09 (18)
C6—C1—C7—C1486.35 (19)C23—C22—C28—C35−64.21 (19)
O1—C7—C8—C9122.7 (2)O4—C28—C29—C30−119.9 (2)
C1—C7—C8—C9−115.6 (2)C22—C28—C29—C30117.8 (2)
C14—C7—C8—C94.1 (2)C35—C28—C29—C30−3.1 (2)
O1—C7—C8—C13−58.3 (2)O4—C28—C29—C3458.3 (2)
C1—C7—C8—C1363.5 (2)C22—C28—C29—C34−64.0 (2)
C14—C7—C8—C13−176.87 (15)C35—C28—C29—C34175.04 (15)
C13—C8—C9—C10−0.2 (3)C34—C29—C30—C310.1 (3)
C7—C8—C9—C10178.8 (2)C28—C29—C30—C31178.3 (2)
C8—C9—C10—C110.8 (4)C29—C30—C31—C32−0.1 (4)
C9—C10—C11—C12−0.6 (4)C30—C31—C32—C33−0.1 (4)
C10—C11—C12—C13−0.3 (4)C31—C32—C33—C340.3 (4)
C11—C12—C13—C80.9 (3)C32—C33—C34—C29−0.4 (3)
C9—C8—C13—C12−0.6 (3)C30—C29—C34—C330.1 (3)
C7—C8—C13—C12−179.73 (17)C28—C29—C34—C33−178.10 (17)
N2—N1—C14—O2−4.2 (3)N5—N4—C35—O52.4 (3)
N2—N1—C14—C7175.22 (16)N5—N4—C35—C28−176.98 (16)
O1—C7—C14—O2171.68 (16)O4—C28—C35—O5−169.03 (16)
C8—C7—C14—O2−66.9 (2)C29—C28—C35—O571.4 (2)
C1—C7—C14—O255.4 (2)C22—C28—C35—O5−53.4 (2)
O1—C7—C14—N1−7.7 (2)O4—C28—C35—N410.4 (2)
C8—C7—C14—N1113.68 (17)C29—C28—C35—N4−109.15 (17)
C1—C7—C14—N1−124.05 (16)C22—C28—C35—N4125.97 (16)
N1—N2—C15—N3179.07 (15)C37—N6—C36—N5−178.74 (18)
N1—N2—C15—S1−1.2 (2)C37—N6—C36—S22.3 (3)
C16—N3—C15—N2−178.13 (16)N4—N5—C36—N6−171.84 (17)
C16—N3—C15—S12.2 (3)N4—N5—C36—S27.1 (3)
C15—N3—C16—C21−165.17 (18)C36—N6—C37—C3849.5 (3)
C15—N3—C16—C1719.2 (3)C36—N6—C37—C42−134.7 (2)
C21—C16—C17—C180.9 (3)C42—C37—C38—C39−0.6 (3)
N3—C16—C17—C18176.41 (16)N6—C37—C38—C39175.2 (2)
C16—C17—C18—C19−0.7 (3)C37—C38—C39—C400.0 (3)
C17—C18—C19—C20−0.4 (3)C38—C39—C40—C410.3 (3)
C17—C18—C19—Cl1−179.70 (14)C38—C39—C40—Cl2−178.71 (18)
C18—C19—C20—C211.3 (3)C39—C40—C41—C420.0 (3)
Cl1—C19—C20—C21−179.38 (16)Cl2—C40—C41—C42179.06 (14)
C19—C20—C21—C16−1.1 (3)C40—C41—C42—C37−0.7 (3)
C17—C16—C21—C200.0 (3)C38—C37—C42—C411.0 (3)
N3—C16—C21—C20−175.90 (19)N6—C37—C42—C41−175.05 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···S2i0.842.443.2242 (13)156
N1—H1N···S10.89 (2)2.44 (2)2.9075 (16)113.5 (17)
N2—H2N···O5ii0.81 (2)2.12 (2)2.870 (2)155 (2)
N3—H3N···O5ii0.88 (2)2.17 (2)3.003 (2)156.1 (18)
O4—H4O···S1iii0.842.513.2707 (13)151
N4—H4N···S20.88 (2)2.50 (2)2.9569 (16)113.5 (17)
N5—H5N···O2iv0.90 (2)1.96 (2)2.776 (2)149 (2)
N6—H6N···O2iv0.89 (2)2.02 (2)2.842 (2)154 (2)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y, z+1; (iii) x, −y+3/2, z−1/2; (iv) x, y, z−1.
Table 1
Selected geometric parameters (Å, °) top
S1—C151.6791 (18)S2—C361.6824 (19)
O1—C71.435 (2)O4—C281.439 (2)
O2—C141.241 (2)O5—C351.242 (2)
N1—C141.323 (2)N4—C351.327 (2)
N1—N21.383 (2)N4—N51.380 (2)
N2—C151.349 (2)N5—C361.351 (2)
N3—C151.355 (2)N6—C361.345 (2)
C14—N1—N2120.78 (16)C35—N4—H4N123.9 (15)
C14—N1—H1N123.6 (14)N5—N4—H4N114.8 (15)
N2—N1—H1N115.2 (14)N6—C36—N5112.18 (16)
N2—C15—S1121.19 (13)N6—C36—S2125.65 (14)
N3—C15—S1127.00 (13)N5—C36—S2122.17 (14)
C35—N4—N5120.94 (16)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···S2i0.842.443.2242 (13)156
N1—H1N···S10.89 (2)2.44 (2)2.9075 (16)113.5 (17)
N2—H2N···O5ii0.81 (2)2.12 (2)2.870 (2)155 (2)
N3—H3N···O5ii0.88 (2)2.17 (2)3.003 (2)156.1 (18)
O4—H4O···S1iii0.842.513.2707 (13)151
N4—H4N···S20.88 (2)2.50 (2)2.9569 (16)113.5 (17)
N5—H5N···O2iv0.90 (2)1.96 (2)2.776 (2)149 (2)
N6—H6N···O2iv0.89 (2)2.02 (2)2.842 (2)154 (2)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y, z+1; (iii) x, −y+3/2, z−1/2; (iv) x, y, z−1.
Acknowledgements top

The Deanship of Scientific Research at the Hashemite University and Al al-Bayt University are thanked for financial support. We also thank the DFG (Bonn, Germany) for financial support.

references
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