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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 12| December 2015| Pages m234-m235
https://doi.org/10.1107/S2056989015021428

Crystal structure of cis-bis­­{4-phenyl-1-[(3R)-1,7,7-tri­methyl-2-oxobi­cyclo­[2.2.1]heptan-3-yl­idene]thio­semicarbazidato-κ3O,N1,S}cadmium(II) with an unknown solvent mol­ecule

Vanessa Senna Nogueira,a Leandro Bresolin,a* Christian Näther,b Inke Jessb and Adriano Bof de Oliveirac

aEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande–RS, Brazil, bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, D-24118 Kiel, Germany, and cDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão–SE, Brazil
*Correspondence e-mail: leandro_bresolin@yahoo.com.br

Edited by H. Ishida, Okayama University, Japan (Received 27 October 2015; accepted 11 November 2015; online 21 November 2015)

The reaction between the racemic mixture of the camphor-4-phenyl­thio­semicarbazone derivative and cadmium acetate dihydrate yielded the title compound, [Cd(C17H20N3OS)2]. The CdII ion is six-coordinated in a distorted octa­hedral environment by two deprotonated thio­semicarbazone ligands acting as an O,N,S-donor in a tridentate chelating mode, forming five-membered chelate rings. In the crystal, the mol­ecules are connected via pairs of N—H⋯S and C—H⋯S inter­actions, building centrosymmetric dimers. One of the ligands is disordered in the campher unit over two sets of sites with site-occupancy factors of 0.7 and 0.3. The structure contains additional solvent mol­ecules, which are disordered and for which no reasonable split model was found. Therefore, the data were corrected for disordered solvent using the SQUEEZE routine [Spek (2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). Acta Cryst. C71, 9–18] in PLATON. Since the disordered solvents were removed by data processing, and the number of solvent entities was a suggestion only, they were not considered in the chemical formula and subsequent chemical or crystal information.

CCDC reference: 1436346

Similar articles

1. Related literature

For one of the first reports of the synthesis of thio­semicarbazone derivatives, see: Freund & Schander (1902[Freund, M. & Schander, A. (1902). Ber. Dtsch. Chem. Ges. 35, 2602-2606.]). For one example of camphor oxidation to 1,2-diketone, see: Młochowski & Wójtowicz-Młochowska (2015[Młochowski, J. & Wójtowicz-Młochowska, H. (2015). Molecules, 20, 10205-10243.]). For the synthesis and crystal structure of an octa­hedral CdII complex with a thio­semicarbazone derivative, see: Fonseca et al. (2012[Fonseca, A. de S., Gervini, V. C., Bresolin, L., Locatelli, A. & Oliveira, A. B. de (2012). Acta Cryst. E68, m635-m636.]). For a review on the coordination chemistry of thio­semicarbazone derivatives, see: Lobana et al. (2009[Lobana, T. S., Sharma, R., Bawa, G. & Khanna, S. (2009). Coord. Chem. Rev. 253, 977-1055.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Cd(C17H20N3OS)2]

  • Mr = 741.24

  • Triclinic, [P \overline 1]

  • a = 10.3613 (3) Å

  • b = 12.3817 (4) Å

  • c = 16.5366 (6) Å

  • α = 68.727 (3)°

  • β = 72.094 (3)°

  • γ = 89.892 (3)°

  • V = 1866.74 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.73 mm−1

  • T = 170 K

  • 0.18 × 0.14 × 0.08 mm

2.2. Data collection

  • Stoe IPDS-1 diffractometer

  • Absorption correction: numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.831, Tmax = 0.957

  • 27175 measured reflections

  • 8157 independent reflections

  • 7089 reflections with I > 2σ(I)

  • Rint = 0.029

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.103

  • S = 1.04

  • 8157 reflections

  • 439 parameters

  • 20 restraints

  • H-atom parameters constrained

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.77 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N21—H21⋯S21i 0.88 2.58 3.363 (3) 148
C23—H23⋯S21i 0.95 2.97 3.629 (4) 128
Symmetry code: (i) -x+2, -y+2, -z.

Data collection: X-AREA (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and enCIFer (Allen et al., 2004[Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.]).

Supporting information

CCDC reference: 1436346

Crystal structure: contains datablocks I, General. DOI: https://doi.org/10.1107/S2056989015021428/is5430sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015021428/is5430Isup2.hkl

checkCIF report


Structural commentary top

Our ongoing research deals with the synthesis and crystal structure analysis of thio­semicarbazone derivatives from natural products with an supra­molecular approach. Herein we report the synthesis and the crystal structure of a new CdII complex with the R,S-camphor-4-phenyl­thio­semicarbazone, a derivative from a racemic mixture of camphor. In the title compound the molecular structure matches the asymmetric unit and the metal ion is six-coordinated in a distorted o­cta­hedral environment by two thio­semicarbazonate ligands (Fig. 1). The ligands are ONS-donors and build a chelate coordination mode, where each ligand forms two five-membered rings. The maximum deviation from the mean plane of the Cd1/S1/C1/N2/N3/C8/C9/O1 chelating group amounts to 0.0811 (11) Å for S1 and for the Cd1/S21/C21/N22/N23/C28/C29/O21 chelating group amounts to 0.0801 (26) Å for C29, with the dihedral angle between the two chelate entities being measured as 73.16 (5)°. The two ligands are deprotonated and the negative charge is delocalized over the C—N—N—C—S fragment as suggested by their inter­mediate bond distances. The imine and thio­amide C—N distances indicate considerable double bond character, while the C—S distance is consistent with increased single bond character. This change on the bond character is a key feature to distinguish neutral/free or deprotonated/coordinated thio­semicarbazones. For the title compound, these distances are C8—N3 = 1.280 (3) Å, N2—N3 = 1.362 (3) Å, N2—C1 = 1.319 (3) Å and C1—S1 = 1.734 (3) Å for one ligand and C28—N23 = 1.278 (4) Å, N22—N23 = 1.367 (3) Å, N22—C21 = 1.313 (4) Å and C21—S21 = 1.743 (3) Å for the another one. The bond distances and the meridional coordination geometry agree with a similar CdII thio­semicarbazonate o­cta­hedral complex (Fonseca et al., 2012) and are supported by literature data (Lobana et al., 2009). The camphor molecule has two chiral carbon atoms and a racemic mixture was used in the synthesis.

From the two crystallographically independent ligands in the asymmetric unit, one is disordered in the campher unit with S. O. F. = 0.7:0.3 (Fig. 2). The complex molecules are connected into centrosymmetric dimers via pairs of N—H···S and C—H···S inter­molecurar inter­actions. The dimers are stacked along the crystallographic a-direction (Fig. 3 and Table 1).

Synthesis and crystallization top

Starting materials were commercially available and were used without further purification. An R,S-camphor racemic mixture was oxidized with SeO2 to the respective 1,2-diketone (Młochowski & Wójtowicz-Młochowska, 2015). The synthesis of the R,S-camphor-4-phenyl­thio­semicarbazone derivative was adapted from a procedure reported previously (Freund & Schander, 1902). The ligand (2 mmol) was dissolved in ethanol (20 mL) and deprotonated with 1 mL of a 1 M KOH aqueous solution. Stirring was maintained for 40 min, while the reaction mixture turns yellow. A solution of cadmium acetate dihydrate (1 mmol) also in ethanol (20 mL) was added under continuous stirring and under slight warming to 333 K. After 3 h a yellow solid was formed. This solid was filtered-off, washed with small portions of cool ethanol and dried at room conditions. A bulk, rough material was observed and it was impossible to isolate enough qu­anti­ties of the title compound for complementar analysis or for yield calculation. Colourless crystals of the complex, suitable for X-ray analysis, were obtained by recrystallization from an ethanol solution.

Refinement top

All non-hydrogen atoms except the disordered C atoms of lower occupancy were refined anisotropic. The C—H and N—H H atoms were positioned with idealized geometry and were refined isotropic with Uiso(H) = 1.2 Ueq(C,N) (1.5 for methyl H atoms) using a riding model.

The campher unit in one of the two independent ligands is disordered. This part was refined using a split model with S. O. F. = 0.7:0.3 and with similarity restraints (SAME). The site occupation factors were selected in order that the disordered atoms exhibits similar isotropic displacement parameters based on the isotropic refinement. If the isotropic displacement parameters are fixed and the S. O. F. is refined, similar values are obtained. Finally, the disordered atoms of higher occupancy were refined anisotropic.

The refined structure contained additional disordered solvate molecules. Because no reasonable split model was found, the data were corrected for disordered solvent using the SQUEEZE option in PLATON (Spek, 2015). The void volume and void count electrons amount to 234 Å3 and 55 e-·Å-3. The void electrons count of 55 can be assigned to two solvent ethanol molecules (52 electrons in total). Ethanol was the synthesis solvent. Since the disordered solvents were removed by data processing, and the estimated number of two ethanol molecules was a suggestion only, they were not considered in the chemical formula and subsequent chemical or crystal informations.

Related literature top

For one of the first reports of the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902). For one example of camphor oxidation to 1,2-diketone, see: Młochowski & Wójtowicz-Młochowska (2015). For the synthesis and crystal structure of an octahedral CdII complex with a thiosemicarbazone derivative, see: Fonseca et al. (2012). For a review on the coordination chemistry of thiosemicarbazone derivatives, see: Lobana et al. (2009).

Structure description top

Our ongoing research deals with the synthesis and crystal structure analysis of thio­semicarbazone derivatives from natural products with an supra­molecular approach. Herein we report the synthesis and the crystal structure of a new CdII complex with the R,S-camphor-4-phenyl­thio­semicarbazone, a derivative from a racemic mixture of camphor. In the title compound the molecular structure matches the asymmetric unit and the metal ion is six-coordinated in a distorted o­cta­hedral environment by two thio­semicarbazonate ligands (Fig. 1). The ligands are ONS-donors and build a chelate coordination mode, where each ligand forms two five-membered rings. The maximum deviation from the mean plane of the Cd1/S1/C1/N2/N3/C8/C9/O1 chelating group amounts to 0.0811 (11) Å for S1 and for the Cd1/S21/C21/N22/N23/C28/C29/O21 chelating group amounts to 0.0801 (26) Å for C29, with the dihedral angle between the two chelate entities being measured as 73.16 (5)°. The two ligands are deprotonated and the negative charge is delocalized over the C—N—N—C—S fragment as suggested by their inter­mediate bond distances. The imine and thio­amide C—N distances indicate considerable double bond character, while the C—S distance is consistent with increased single bond character. This change on the bond character is a key feature to distinguish neutral/free or deprotonated/coordinated thio­semicarbazones. For the title compound, these distances are C8—N3 = 1.280 (3) Å, N2—N3 = 1.362 (3) Å, N2—C1 = 1.319 (3) Å and C1—S1 = 1.734 (3) Å for one ligand and C28—N23 = 1.278 (4) Å, N22—N23 = 1.367 (3) Å, N22—C21 = 1.313 (4) Å and C21—S21 = 1.743 (3) Å for the another one. The bond distances and the meridional coordination geometry agree with a similar CdII thio­semicarbazonate o­cta­hedral complex (Fonseca et al., 2012) and are supported by literature data (Lobana et al., 2009). The camphor molecule has two chiral carbon atoms and a racemic mixture was used in the synthesis.

From the two crystallographically independent ligands in the asymmetric unit, one is disordered in the campher unit with S. O. F. = 0.7:0.3 (Fig. 2). The complex molecules are connected into centrosymmetric dimers via pairs of N—H···S and C—H···S inter­molecurar inter­actions. The dimers are stacked along the crystallographic a-direction (Fig. 3 and Table 1).

For one of the first reports of the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902). For one example of camphor oxidation to 1,2-diketone, see: Młochowski & Wójtowicz-Młochowska (2015). For the synthesis and crystal structure of an octahedral CdII complex with a thiosemicarbazone derivative, see: Fonseca et al. (2012). For a review on the coordination chemistry of thiosemicarbazone derivatives, see: Lobana et al. (2009).

Synthesis and crystallization top

Starting materials were commercially available and were used without further purification. An R,S-camphor racemic mixture was oxidized with SeO2 to the respective 1,2-diketone (Młochowski & Wójtowicz-Młochowska, 2015). The synthesis of the R,S-camphor-4-phenyl­thio­semicarbazone derivative was adapted from a procedure reported previously (Freund & Schander, 1902). The ligand (2 mmol) was dissolved in ethanol (20 mL) and deprotonated with 1 mL of a 1 M KOH aqueous solution. Stirring was maintained for 40 min, while the reaction mixture turns yellow. A solution of cadmium acetate dihydrate (1 mmol) also in ethanol (20 mL) was added under continuous stirring and under slight warming to 333 K. After 3 h a yellow solid was formed. This solid was filtered-off, washed with small portions of cool ethanol and dried at room conditions. A bulk, rough material was observed and it was impossible to isolate enough qu­anti­ties of the title compound for complementar analysis or for yield calculation. Colourless crystals of the complex, suitable for X-ray analysis, were obtained by recrystallization from an ethanol solution.

Refinement details top

All non-hydrogen atoms except the disordered C atoms of lower occupancy were refined anisotropic. The C—H and N—H H atoms were positioned with idealized geometry and were refined isotropic with Uiso(H) = 1.2 Ueq(C,N) (1.5 for methyl H atoms) using a riding model.

The campher unit in one of the two independent ligands is disordered. This part was refined using a split model with S. O. F. = 0.7:0.3 and with similarity restraints (SAME). The site occupation factors were selected in order that the disordered atoms exhibits similar isotropic displacement parameters based on the isotropic refinement. If the isotropic displacement parameters are fixed and the S. O. F. is refined, similar values are obtained. Finally, the disordered atoms of higher occupancy were refined anisotropic.

The refined structure contained additional disordered solvate molecules. Because no reasonable split model was found, the data were corrected for disordered solvent using the SQUEEZE option in PLATON (Spek, 2015). The void volume and void count electrons amount to 234 Å3 and 55 e-·Å-3. The void electrons count of 55 can be assigned to two solvent ethanol molecules (52 electrons in total). Ethanol was the synthesis solvent. Since the disordered solvents were removed by data processing, and the estimated number of two ethanol molecules was a suggestion only, they were not considered in the chemical formula and subsequent chemical or crystal informations.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level. Disorder is shown with full and open bonds.
[Figure 2] Fig. 2. (a) Isotropic representation of the title compound with the disordered R-camphor entity. This ligand is labelled with C32, C33 and C34. (b) Isotropic representation of the title compound with the disordered S-camphor entity. This ligand is labelled with C32', C33' and C34'. The figure is valid for the asymmetric unit only and simplified for clarity.
[Figure 3] Fig. 3. A packing diagram of the title compound viewed along the crystallographic a-axis, showing the N—H··· S hydrogen bonds (dashed lines). The C—H···S interactions are not shown for clarity. The disordered atoms are not shown. .
cis-Bis{4-phenyl-1-[(3R)-1,7,7-trimethyl-2-oxobicyclo[2.2.1]heptan-3-ylidene]thiosemicarbazidato-κ3O,N1,S}cadmium(II) top
Crystal data top
[Cd(C17H20N3OS)2]V = 1866.74 (12) Å3
Mr = 741.24Z = 2
Triclinic, P1F(000) = 764
a = 10.3613 (3) ÅDx = 1.319 Mg m−3
b = 12.3817 (4) ÅMo Kα radiation, λ = 0.71073 Å
c = 16.5366 (6) ŵ = 0.73 mm−1
α = 68.727 (3)°T = 170 K
β = 72.094 (3)°Block, colourless
γ = 89.892 (3)°0.18 × 0.14 × 0.08 mm
Data collection top
Stoe IPDS-1
diffractometer		7089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube, Stoe IPDS-1Rint = 0.029
φ scansθmax = 27.0°, θmin = 1.4°
Absorption correction: numerical
(X-RED32 and X-SHAPE; Stoe & Cie, 2008)		h = −13→13
Tmin = 0.831, Tmax = 0.957k = −15→15
27175 measured reflectionsl = −21→21
8157 independent reflections
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)] = 0.038H-atom parameters constrained
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0619P)2 + 0.5654P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.018
8157 reflectionsΔρmax = 0.52 e Å−3
439 parametersΔρmin = −0.77 e Å−3
20 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0021 (6)
Crystal data top
[Cd(C17H20N3OS)2]γ = 89.892 (3)°
Mr = 741.24V = 1866.74 (12) Å3
Triclinic, P1Z = 2
a = 10.3613 (3) ÅMo Kα radiation
b = 12.3817 (4) ŵ = 0.73 mm−1
c = 16.5366 (6) ÅT = 170 K
α = 68.727 (3)°0.18 × 0.14 × 0.08 mm
β = 72.094 (3)°
Data collection top
Stoe IPDS-1
diffractometer		8157 independent reflections
Absorption correction: numerical
(X-RED32 and X-SHAPE; Stoe & Cie, 2008)		7089 reflections with I > 2σ(I)
Tmin = 0.831, Tmax = 0.957Rint = 0.029
27175 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03820 restraints
wR(F2) = 0.103H-atom parameters constrained
S = 1.04Δρmax = 0.52 e Å−3
8157 reflectionsΔρmin = −0.77 e Å−3
439 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd10.63629 (2)0.72196 (2)0.19359 (2)0.05151 (8)
S10.73767 (8)0.53984 (6)0.18346 (6)0.06243 (19)
O10.42054 (19)0.82822 (16)0.20261 (16)0.0612 (5)
N10.6277 (3)0.37580 (19)0.15356 (18)0.0580 (6)
H10.70550.35100.15890.070*
N20.4807 (2)0.51031 (18)0.17160 (17)0.0540 (5)
N30.4666 (2)0.61471 (18)0.18144 (16)0.0497 (5)
C10.6024 (3)0.4765 (2)0.16824 (19)0.0523 (6)
C20.5488 (3)0.3049 (2)0.1312 (2)0.0537 (6)
C30.5770 (3)0.1895 (2)0.1500 (2)0.0576 (6)
H30.64050.16060.18130.069*
C40.5128 (3)0.1175 (3)0.1231 (3)0.0676 (8)
H40.53290.03930.13570.081*
C50.4201 (3)0.1579 (3)0.0783 (3)0.0709 (8)
H50.37670.10820.05960.085*
C60.3904 (4)0.2709 (3)0.0608 (3)0.0706 (8)
H60.32530.29840.03070.085*
C70.4542 (3)0.3452 (3)0.0866 (2)0.0648 (7)
H70.43340.42320.07370.078*
C80.3484 (3)0.6498 (2)0.1934 (2)0.0527 (6)
C90.3312 (3)0.7644 (2)0.2025 (2)0.0552 (6)
C100.1844 (3)0.7820 (3)0.2097 (2)0.0646 (7)
C110.1820 (4)0.8005 (3)0.1098 (3)0.0748 (9)
H11A0.09540.82850.10180.090*
H11B0.25930.85820.06200.090*
C120.1945 (4)0.6810 (4)0.1038 (3)0.0788 (9)
H12A0.27540.68370.05170.095*
H12B0.11160.65140.09670.095*
C130.2109 (3)0.6035 (3)0.1985 (2)0.0639 (7)
H130.19400.51710.21690.077*
C140.1155 (3)0.6547 (3)0.2631 (3)0.0679 (8)
C150.1274 (4)0.6047 (4)0.3600 (2)0.0842 (10)
H15A0.22360.61370.35550.126*
H15B0.07500.64690.39660.126*
H15C0.09120.52170.38960.126*
C16−0.0346 (3)0.6409 (4)0.2700 (3)0.0880 (11)
H16A−0.08890.67550.31220.132*
H16B−0.04320.68060.20910.132*
H16C−0.06800.55770.29310.132*
C170.1301 (3)0.8764 (3)0.2432 (3)0.0763 (9)
H17A0.03470.88090.24550.114*
H17B0.13540.85830.30480.114*
H17C0.18490.95150.20120.114*
S210.80796 (7)0.89648 (6)0.07495 (5)0.05587 (16)
O210.4762 (2)0.62965 (17)0.36571 (15)0.0656 (5)
N210.9069 (2)1.0676 (2)0.10330 (18)0.0576 (5)
H210.95521.08020.04600.069*
N220.7536 (2)0.9355 (2)0.23571 (18)0.0559 (5)
N230.6675 (2)0.83345 (19)0.27396 (17)0.0541 (5)
C210.8192 (3)0.9663 (2)0.1475 (2)0.0533 (6)
C220.9341 (3)1.1559 (3)0.1333 (2)0.0608 (7)
C231.0073 (3)1.2596 (3)0.0638 (3)0.0693 (8)
H231.03651.26590.00180.083*
C241.0382 (4)1.3540 (3)0.0841 (4)0.0852 (12)
H241.08861.42420.03620.102*
C250.9959 (4)1.3452 (4)0.1731 (4)0.0950 (14)
H251.01561.40970.18740.114*
C260.9245 (4)1.2426 (4)0.2422 (4)0.1024 (16)
H260.89591.23710.30410.123*
C270.8932 (3)1.1461 (4)0.2232 (3)0.0841 (11)
H270.84471.07550.27140.101*
C280.5920 (3)0.8037 (2)0.3577 (2)0.0616 (7)
C290.4897 (4)0.6983 (3)0.4008 (2)0.0657 (7)
C300.3914 (5)0.7073 (4)0.4896 (3)0.0636 (10)0.7
C310.3272 (7)0.8220 (6)0.4572 (4)0.091 (2)0.7
H31A0.28610.82170.41060.109*0.7
H31B0.25410.82790.51000.109*0.7
C320.4329 (7)0.9221 (5)0.4177 (4)0.0885 (16)0.7
H32A0.41310.97310.45330.106*0.7
H32B0.44280.96880.35280.106*0.7
C330.5647 (8)0.8600 (4)0.4263 (4)0.0668 (18)0.7
H330.64390.91030.42190.080*0.7
C340.5009 (6)0.7574 (5)0.5187 (4)0.0837 (15)0.7
C350.6079 (9)0.6655 (6)0.5374 (6)0.0905 (19)0.7
H35A0.64580.64470.48370.136*0.7
H35B0.68210.70050.54860.136*0.7
H35C0.56140.59510.59130.136*0.7
C360.4387 (7)0.7926 (5)0.6011 (4)0.0886 (17)0.7
H36A0.40060.72230.65700.133*0.7
H36B0.50990.83700.60830.133*0.7
H36C0.36600.84120.59080.133*0.7
C370.2956 (15)0.5992 (10)0.5560 (9)0.090 (4)0.7
H37A0.23830.61400.60940.135*0.7
H37B0.23750.57790.52590.135*0.7
H37C0.34850.53510.57610.135*0.7
C30'0.4475 (12)0.6790 (9)0.5002 (8)0.066 (3)*0.3
C31'0.5572 (17)0.6658 (16)0.5409 (15)0.094 (7)*0.3
H31C0.60260.59670.53660.112*0.3
H31D0.51820.65390.60660.112*0.3
C32'0.6593 (13)0.7734 (11)0.4905 (9)0.083 (3)*0.3
H32C0.74650.75790.45290.100*0.3
H32D0.67750.80550.53330.100*0.3
C33'0.5827 (19)0.857 (2)0.4286 (17)0.146 (14)*0.3
H33'0.61110.94330.40520.176*0.3
C34'0.4308 (12)0.8135 (10)0.4799 (8)0.076 (3)*0.3
C35'0.3305 (15)0.8611 (14)0.4200 (11)0.082 (4)*0.3
H35D0.23580.82850.45840.122*0.3
H35E0.33870.94660.39790.122*0.3
H35F0.35620.83720.36740.122*0.3
C36'0.372 (3)0.842 (2)0.5673 (14)0.162 (9)*0.3
H36D0.27430.81130.59650.243*0.3
H36E0.42070.80560.61050.243*0.3
H36F0.38210.92670.55020.243*0.3
C37'0.313 (3)0.598 (3)0.553 (3)0.105 (12)*0.3
H37D0.25120.61760.51700.157*0.3
H37E0.33130.51660.56490.157*0.3
H37F0.27080.60640.61190.157*0.3
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.04595 (11)0.03978 (11)0.07460 (14)0.00295 (7)−0.02207 (9)−0.02640 (9)
S10.0592 (4)0.0487 (4)0.0981 (5)0.0148 (3)−0.0396 (4)−0.0376 (4)
O10.0486 (10)0.0435 (10)0.0958 (15)0.0036 (7)−0.0252 (10)−0.0300 (10)
N10.0618 (13)0.0424 (11)0.0850 (16)0.0137 (10)−0.0352 (12)−0.0322 (11)
N20.0561 (12)0.0380 (10)0.0741 (14)0.0058 (9)−0.0255 (11)−0.0249 (10)
N30.0477 (11)0.0392 (10)0.0663 (13)0.0036 (8)−0.0225 (10)−0.0215 (9)
C10.0587 (14)0.0373 (12)0.0648 (15)0.0055 (10)−0.0254 (12)−0.0195 (11)
C20.0571 (14)0.0411 (13)0.0662 (16)0.0043 (10)−0.0202 (12)−0.0244 (12)
C30.0570 (15)0.0406 (13)0.0762 (18)0.0060 (11)−0.0214 (13)−0.0238 (12)
C40.0634 (17)0.0457 (15)0.096 (2)0.0032 (12)−0.0216 (16)−0.0333 (15)
C50.0663 (18)0.0607 (18)0.097 (2)0.0000 (14)−0.0265 (17)−0.0431 (17)
C60.0709 (19)0.0677 (19)0.091 (2)0.0112 (15)−0.0385 (17)−0.0405 (17)
C70.0753 (19)0.0495 (15)0.083 (2)0.0152 (13)−0.0383 (16)−0.0303 (14)
C80.0455 (13)0.0448 (13)0.0712 (16)0.0021 (10)−0.0221 (12)−0.0233 (12)
C90.0456 (13)0.0438 (13)0.0770 (17)0.0032 (10)−0.0207 (12)−0.0232 (12)
C100.0458 (14)0.0570 (16)0.094 (2)0.0066 (12)−0.0229 (14)−0.0315 (16)
C110.0594 (17)0.079 (2)0.081 (2)0.0105 (15)−0.0315 (16)−0.0179 (17)
C120.0640 (19)0.100 (3)0.086 (2)0.0117 (18)−0.0366 (17)−0.040 (2)
C130.0504 (14)0.0573 (16)0.092 (2)0.0010 (12)−0.0253 (14)−0.0355 (15)
C140.0498 (15)0.0633 (18)0.089 (2)−0.0008 (13)−0.0205 (15)−0.0284 (16)
C150.067 (2)0.098 (3)0.071 (2)−0.0088 (18)−0.0145 (16)−0.0210 (19)
C160.0473 (16)0.091 (3)0.123 (3)−0.0046 (16)−0.0214 (18)−0.043 (2)
C170.0560 (16)0.068 (2)0.111 (3)0.0188 (14)−0.0273 (17)−0.0414 (19)
S210.0521 (3)0.0459 (3)0.0736 (4)−0.0015 (3)−0.0189 (3)−0.0286 (3)
O210.0807 (14)0.0451 (10)0.0729 (13)−0.0001 (9)−0.0272 (11)−0.0230 (9)
N210.0493 (11)0.0479 (12)0.0795 (15)−0.0034 (9)−0.0151 (11)−0.0337 (11)
N220.0496 (11)0.0464 (12)0.0762 (15)0.0013 (9)−0.0206 (11)−0.0285 (11)
N230.0523 (12)0.0435 (11)0.0723 (15)0.0055 (9)−0.0233 (11)−0.0261 (10)
C210.0419 (12)0.0455 (13)0.0802 (18)0.0071 (10)−0.0238 (12)−0.0295 (13)
C220.0412 (12)0.0559 (15)0.102 (2)0.0079 (11)−0.0258 (14)−0.0462 (16)
C230.0588 (16)0.0474 (15)0.116 (3)0.0086 (12)−0.0411 (17)−0.0369 (16)
C240.071 (2)0.0524 (17)0.162 (4)0.0172 (15)−0.061 (2)−0.055 (2)
C250.0628 (19)0.084 (3)0.187 (5)0.0211 (18)−0.054 (3)−0.096 (3)
C260.064 (2)0.129 (4)0.155 (4)0.000 (2)−0.024 (2)−0.109 (4)
C270.0594 (18)0.097 (3)0.113 (3)−0.0099 (17)−0.0136 (18)−0.071 (2)
C280.0721 (18)0.0455 (14)0.0690 (18)0.0020 (12)−0.0210 (15)−0.0255 (13)
C290.085 (2)0.0455 (15)0.0646 (17)−0.0009 (13)−0.0239 (15)−0.0195 (13)
C300.070 (3)0.056 (2)0.065 (3)0.001 (2)−0.023 (2)−0.023 (2)
C310.118 (5)0.080 (4)0.061 (3)0.037 (4)−0.020 (3)−0.020 (3)
C320.121 (5)0.066 (3)0.089 (4)0.025 (3)−0.041 (3)−0.036 (3)
C330.096 (4)0.042 (2)0.060 (3)−0.014 (2)−0.014 (2)−0.0268 (19)
C340.109 (4)0.075 (3)0.074 (3)−0.001 (3)−0.031 (3)−0.036 (3)
C350.098 (5)0.083 (4)0.101 (5)0.021 (4)−0.052 (4)−0.032 (3)
C360.121 (5)0.077 (3)0.068 (3)−0.006 (3)−0.020 (3)−0.037 (3)
C370.119 (8)0.061 (4)0.066 (4)−0.030 (4)−0.002 (4)−0.023 (3)
Geometric parameters (Å, º) top
Cd1—N32.306 (2)C22—C231.394 (5)
Cd1—N232.318 (2)C23—C241.390 (4)
Cd1—S12.5245 (7)C23—H230.9500
Cd1—S212.5445 (7)C24—C251.362 (7)
Cd1—O12.5839 (19)C24—H240.9500
Cd1—O212.627 (2)C25—C261.377 (7)
S1—C11.734 (3)C25—H250.9500
O1—C91.219 (3)C26—C271.403 (5)
N1—C11.364 (3)C26—H260.9500
N1—C21.414 (3)C27—H270.9500
N1—H10.8800C28—C291.484 (4)
N2—C11.319 (3)C28—C331.492 (6)
N2—N31.362 (3)C28—C33'1.52 (3)
N3—C81.280 (3)C29—C30'1.491 (12)
C2—C71.390 (4)C29—C301.550 (6)
C2—C31.398 (4)C30—C371.500 (7)
C3—C41.381 (4)C30—C311.553 (7)
C3—H30.9500C30—C341.569 (7)
C4—C51.375 (5)C31—C321.463 (9)
C4—H40.9500C31—H31A0.9900
C5—C61.377 (5)C31—H31B0.9900
C5—H50.9500C32—C331.585 (11)
C6—C71.387 (4)C32—H32A0.9900
C6—H60.9500C32—H32B0.9900
C7—H70.9500C33—C341.536 (7)
C8—C91.485 (4)C33—H331.0000
C8—C131.503 (4)C34—C361.535 (7)
C9—C101.511 (4)C34—C351.603 (9)
C10—C171.506 (4)C35—H35A0.9800
C10—C141.542 (4)C35—H35B0.9800
C10—C111.591 (5)C35—H35C0.9800
C11—C121.521 (5)C36—H36A0.9800
C11—H11A0.9900C36—H36B0.9800
C11—H11B0.9900C36—H36C0.9800
C12—C131.574 (5)C37—H37A0.9800
C12—H12A0.9900C37—H37B0.9800
C12—H12B0.9900C37—H37C0.9800
C13—C141.536 (5)C30'—C31'1.469 (15)
C13—H131.0000C30'—C37'1.529 (16)
C14—C161.531 (4)C30'—C34'1.595 (13)
C14—C151.537 (5)C31'—C32'1.499 (17)
C15—H15A0.9800C31'—H31C0.9900
C15—H15B0.9800C31'—H31D0.9900
C15—H15C0.9800C32'—C33'1.58 (2)
C16—H16A0.9800C32'—H32C0.9900
C16—H16B0.9800C32'—H32D0.9900
C16—H16C0.9800C33'—C34'1.530 (16)
C17—H17A0.9800C33'—H33'1.0000
C17—H17B0.9800C34'—C36'1.553 (15)
C17—H17C0.9800C34'—C35'1.619 (14)
S21—C211.743 (3)C35'—H35D0.9800
O21—C291.219 (4)C35'—H35E0.9800
N21—C211.365 (3)C35'—H35F0.9800
N21—C221.415 (3)C36'—H36D0.9800
N21—H210.8800C36'—H36E0.9800
N22—C211.313 (4)C36'—H36F0.9800
N22—N231.367 (3)C37'—H37D0.9800
N23—C281.278 (4)C37'—H37E0.9800
C22—C271.373 (5)C37'—H37F0.9800
N3—Cd1—N23141.00 (8)C25—C24—H24120.2
N3—Cd1—S175.51 (5)C23—C24—H24120.2
N23—Cd1—S1129.89 (6)C24—C25—C26119.8 (3)
N3—Cd1—S21131.35 (6)C24—C25—H25120.1
N23—Cd1—S2174.79 (6)C26—C25—H25120.1
S1—Cd1—S21107.49 (3)C25—C26—C27121.4 (4)
N3—Cd1—O169.93 (7)C25—C26—H26119.3
N23—Cd1—O179.45 (7)C27—C26—H26119.3
S1—Cd1—O1145.35 (4)C22—C27—C26118.6 (4)
S21—Cd1—O197.17 (5)C22—C27—H27120.7
N3—Cd1—O2179.09 (7)C26—C27—H27120.7
N23—Cd1—O2169.40 (7)N23—C28—C29119.2 (3)
S1—Cd1—O2197.73 (5)N23—C28—C33134.7 (3)
S21—Cd1—O21144.07 (5)C29—C28—C33105.5 (3)
O1—Cd1—O2173.80 (7)N23—C28—C33'132.2 (7)
C1—S1—Cd197.71 (9)C29—C28—C33'108.6 (7)
C9—O1—Cd1107.48 (17)O21—C29—C28125.9 (3)
C1—N1—C2130.3 (2)O21—C29—C30'128.8 (5)
C1—N1—H1114.8C28—C29—C30'102.4 (5)
C2—N1—H1114.8O21—C29—C30127.9 (3)
C1—N2—N3113.5 (2)C28—C29—C30105.5 (3)
C8—N3—N2118.0 (2)C37—C30—C29115.9 (6)
C8—N3—Cd1117.85 (17)C37—C30—C31117.2 (8)
N2—N3—Cd1123.77 (16)C29—C30—C31105.7 (4)
N2—C1—N1117.3 (2)C37—C30—C34120.1 (7)
N2—C1—S1129.2 (2)C29—C30—C3497.8 (4)
N1—C1—S1113.5 (2)C31—C30—C3496.8 (4)
C7—C2—C3119.2 (3)C32—C31—C30109.5 (5)
C7—C2—N1124.1 (2)C32—C31—H31A109.8
C3—C2—N1116.6 (3)C30—C31—H31A109.8
C4—C3—C2120.1 (3)C32—C31—H31B109.8
C4—C3—H3119.9C30—C31—H31B109.8
C2—C3—H3119.9H31A—C31—H31B108.2
C5—C4—C3120.5 (3)C31—C32—C33101.7 (4)
C5—C4—H4119.7C31—C32—H32A111.4
C3—C4—H4119.7C33—C32—H32A111.4
C4—C5—C6119.6 (3)C31—C32—H32B111.4
C4—C5—H5120.2C33—C32—H32B111.4
C6—C5—H5120.2H32A—C32—H32B109.3
C5—C6—C7121.0 (3)C28—C33—C34103.4 (3)
C5—C6—H6119.5C28—C33—C32104.1 (5)
C7—C6—H6119.5C34—C33—C3299.7 (5)
C6—C7—C2119.5 (3)C28—C33—H33115.8
C6—C7—H7120.2C34—C33—H33115.8
C2—C7—H7120.2C32—C33—H33115.8
N3—C8—C9118.9 (2)C36—C34—C33114.8 (4)
N3—C8—C13135.2 (2)C36—C34—C30113.5 (5)
C9—C8—C13105.8 (2)C33—C34—C3095.9 (4)
O1—C9—C8125.3 (2)C36—C34—C35111.4 (5)
O1—C9—C10129.5 (3)C33—C34—C35110.7 (6)
C8—C9—C10105.2 (2)C30—C34—C35109.6 (5)
C17—C10—C9115.7 (3)C34—C35—H35A109.5
C17—C10—C14120.2 (3)C34—C35—H35B109.5
C9—C10—C14100.2 (2)H35A—C35—H35B109.5
C17—C10—C11114.9 (3)C34—C35—H35C109.5
C9—C10—C11103.0 (3)H35A—C35—H35C109.5
C14—C10—C11100.1 (3)H35B—C35—H35C109.5
C12—C11—C10105.2 (3)C34—C36—H36A109.5
C12—C11—H11A110.7C34—C36—H36B109.5
C10—C11—H11A110.7H36A—C36—H36B109.5
C12—C11—H11B110.7C34—C36—H36C109.5
C10—C11—H11B110.7H36A—C36—H36C109.5
H11A—C11—H11B108.8H36B—C36—H36C109.5
C11—C12—C13103.0 (3)C30—C37—H37A109.5
C11—C12—H12A111.2C30—C37—H37B109.5
C13—C12—H12A111.2H37A—C37—H37B109.5
C11—C12—H12B111.2C30—C37—H37C109.5
C13—C12—H12B111.2H37A—C37—H37C109.5
H12A—C12—H12B109.1H37B—C37—H37C109.5
C8—C13—C14100.9 (2)C31'—C30'—C29116.5 (12)
C8—C13—C12104.5 (3)C31'—C30'—C37'120 (2)
C14—C13—C12101.1 (3)C29—C30'—C37'110.4 (19)
C8—C13—H13116.0C31'—C30'—C34'100.2 (11)
C14—C13—H13116.0C29—C30'—C34'92.6 (7)
C12—C13—H13116.0C37'—C30'—C34'113.9 (18)
C16—C14—C13114.2 (3)C30'—C31'—C32'109.4 (13)
C16—C14—C15109.6 (3)C30'—C31'—H31C109.8
C13—C14—C15111.9 (3)C32'—C31'—H31C109.8
C16—C14—C10112.9 (3)C30'—C31'—H31D109.8
C13—C14—C1096.3 (2)C32'—C31'—H31D109.8
C15—C14—C10111.6 (3)H31C—C31'—H31D108.2
C14—C15—H15A109.5C31'—C32'—C33'101.2 (11)
C14—C15—H15B109.5C31'—C32'—H32C111.5
H15A—C15—H15B109.5C33'—C32'—H32C111.5
C14—C15—H15C109.5C31'—C32'—H32D111.5
H15A—C15—H15C109.5C33'—C32'—H32D111.5
H15B—C15—H15C109.5H32C—C32'—H32D109.4
C14—C16—H16A109.5C28—C33'—C34'94.1 (14)
C14—C16—H16B109.5C28—C33'—C32'101.9 (17)
H16A—C16—H16B109.5C34'—C33'—C32'105.0 (13)
C14—C16—H16C109.5C28—C33'—H33'117.5
H16A—C16—H16C109.5C34'—C33'—H33'117.5
H16B—C16—H16C109.5C32'—C33'—H33'117.5
C10—C17—H17A109.5C33'—C34'—C36'114.0 (15)
C10—C17—H17B109.5C33'—C34'—C30'95.3 (12)
H17A—C17—H17B109.5C36'—C34'—C30'114.4 (12)
C10—C17—H17C109.5C33'—C34'—C35'115.3 (12)
H17A—C17—H17C109.5C36'—C34'—C35'105.7 (12)
H17B—C17—H17C109.5C30'—C34'—C35'112.3 (10)
C21—S21—Cd198.24 (10)C34'—C35'—H35D109.5
C29—O21—Cd1106.48 (19)C34'—C35'—H35E109.5
C21—N21—C22131.4 (3)H35D—C35'—H35E109.5
C21—N21—H21114.3C34'—C35'—H35F109.5
C22—N21—H21114.3H35D—C35'—H35F109.5
C21—N22—N23113.8 (2)H35E—C35'—H35F109.5
C28—N23—N22116.9 (2)C34'—C36'—H36D109.5
C28—N23—Cd1118.48 (18)C34'—C36'—H36E109.5
N22—N23—Cd1124.37 (18)H36D—C36'—H36E109.5
N22—C21—N21117.9 (2)C34'—C36'—H36F109.5
N22—C21—S21128.8 (2)H36D—C36'—H36F109.5
N21—C21—S21113.3 (2)H36E—C36'—H36F109.5
C27—C22—C23119.6 (3)C30'—C37'—H37D109.5
C27—C22—N21125.1 (3)C30'—C37'—H37E109.5
C23—C22—N21115.3 (3)H37D—C37'—H37E109.5
C24—C23—C22120.9 (4)C30'—C37'—H37F109.5
C24—C23—H23119.5H37D—C37'—H37F109.5
C22—C23—H23119.5H37E—C37'—H37F109.5
C25—C24—C23119.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···S21i0.882.583.363 (3)148
C23—H23···S21i0.952.973.629 (4)128
Symmetry code: (i) −x+2, −y+2, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···S21i0.882.583.363 (3)148
C23—H23···S21i0.952.973.629 (4)128
Symmetry code: (i) −x+2, −y+2, −z.
 

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany, and thank Professor Dr Wolfgang Bensch, University of Kiel, for access to his experimental facilities.

References

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ISSN: 2056-9890
Volume 71| Part 12| December 2015| Pages m234-m235
https://doi.org/10.1107/S2056989015021428
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