Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis
2.2. Spectroscopic Analysis
2.3. Thermal Analyses of the Complexes
2.4. Molecular Structure of the Mercury Complex
3. Experimental Section
3.1. Materials and Methods
3.2. Synthesis of the Ligand: Sodium N-Methyl-N-phenyldithiocarbamate, Na[C6H5(CH3)NCS2]
3.3. Preparation of Complexes
3.3.1. Bis-(N-methyl-N-phenyldithiocarbamato)zinc(II): ZnL2 (1)
- 1H NMR (DMSO) δ = 7.46 – 7.19 (m, 10H, –C6H5), 3.64 (s, 6H, –CH3).
- 13C NMR (DMSO) δ 147.17, 129.55, 127.81, 126.31(−C6H5), 47.24(−CH3), 190.51(−CS2).
- Selected IR, υ (cm−1): 1491 (C=N), 1261 (C2-N), 969 (C=S). Anal. Calc. for C16H16N2S4Zn (429.94): C, 44.70; H, 3.75; N, 6.52; S, 29.83. Found: C, 44.69; H, 3.80; N, 6.90; S, 29.59.
- The product was recrystallized in dichloromethane.
3.3.2. Bis-(N-methyl-N-phenyldithiocarbamato)cadmium(II): CdL2 (2)
- Complex was obtained as white solid. Yield: 0.559 g (93.95 %), M.p. 296–298 °C.
- 1H NMR (DMSO) δ = 7.46–7.19 (m, 10H, −C6H5), 3.64 (s, 6H, −CH3).
- 13C NMR (DMSO) δ 148.55, 129.39, 128.79, 126.44 (−C6H5), 45.40 (−CH3), 202.10 (−CS2).
- Selected IR, υ (cm−1): 1490 (C=N), 1255 (C2-N), 963 (C=S). Anal. Calc. for C16H16N2S4Cd (476.97): C, 40.29; H, 3.38; N, 5.87; S, 26.89. Found: C, 39.96; H, 3.36; N, 6.05; S, 27.31
3.3.3. Bis(μ-N-methyl-N-phenyldithiocarbamato-S:S’)bis-[(N-methyl-N-henyldithiocarbamato) Mercury(II)]: Hg2L4 (3)
- Complex was obtained as yellow solid. Yield: 0.600 g (84.51%), M.p. 235–236 °C.
- 1H NMR (CHCl3) δ = 7.53–7.29 (m, 20H, −C6H5), 3.82 (s, 12H, −CH3).
- 13C NMR (CHCl3) δ 129.65, 128.35, 125.38 (−C6H5), 48.78 (−CH3), 201.20 (−CS2).
- Selected IR, υ (cm−1): 1491 (C=N), 1255 (C2-N), 959 (C=S). Anal. Calc. for C32H32N4S8Hg2 (565.15): C, 34.00; H, 2.85; N, 4.96; S, 22.69. Found: C, 34.02; H, 2.95; N, 5.04; S, 22.81.
- The product was recrystallized from a dichloromethane/ethyl acetate (3:1 v/v) mixture to afford yellow crystals suitable for X-ray crystallography.
3.4. Thermal Studies
3.5. Crystal Structure Determination
4. Conclusions
Supplementary Material
CCDC 762809 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK; Fax: (+44)-1223-336-033 or E-Mail: [email protected].Acknowledgments
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Complex | Decomposition temperature | DTG max. value | Decomposition reaction | Mass changes expet. found | |
---|---|---|---|---|---|
Zn(S2CNmeC6H5)2 | 219–375 | 310 | Zn(S2CNmeC6H5)2→ZnS ZnS→ZnO | 3.05 | 3.60 |
450–683 | 2.61 | 2.67 | |||
Cd(S2CNmeC6H5)2 | 270–372 | 324 | Cd(S2CNmeC6H5)2→CdS CdS→CdO | 2.92 | 3.25 |
430–640 | 2.59 | 2.65 | |||
Hg(S2CNmeC6H5)2 | 168–361 | 299 | Hg(S2CNmeC6H5)2→HgS Volatilization | 4.16 | 2.50 |
361–585 | - | - |
Compound | [(C6H5)(CH3)NCS2]4Hg2 |
Empirical formula | C32H32Hg2N4S8 |
Formula weight | 1130.28 |
Temperature | 100(2) K |
Wavelength | 1.54178 |
Crystal system | Monoclinic |
Space group | P21/C |
Unit cell dimensions | |
a (Å) | 12.7168(10) |
b (Å) | 6.5198(6) |
c (Å) | 22.2612(19) |
β (°) | 98.341(3) |
γ (°) | 90 |
Volume (A3) | 1826.2(3) |
Z | 2 |
Dcalc Mg/m3 | 2.056 Mg/m3 |
Absorption coefficient (mm−1) | 19.379 |
F(000) | 1080 |
Crystal size (mm) | 0.27 × 0.18 ×0.17 |
Theta range (°) | 3.51 to 69.82 |
Limiting indices | −15 ≤ h ≤ 15, −7 ≤ k ≤ 7, −27 < +1 ≤ 26 |
Reflections collected | 27791 |
Independent reflection | 3412 [R(int) =0.0343] |
Refinement method | Full-matrix least-squares on F2 |
Completeness to θ = 67.00 | 99.8 % |
Data/restraints/parameters/ | 3412/0/210 |
Goodness-of-fit on F2 | 1.022 |
Final R indices [I > 2sigma(I)] | R1 = 0.0262, wR2 = 0.0716 |
R indices (all data) | R1 = 0.0265, wR2 = 0.0718 |
Largest diff. Peak and hole e. Å−3 | 1.836 and −1.181 |
Bond length (Å) | Bond Angle (°) | ||
---|---|---|---|
Hg(1)—S(3) | 2.4114(9) | S(3)—Hg(1)—S(1) | 146.42(3) |
Hg(1)—S(1) | 2.4810(9) | S(3)—Hg(1)—S(4)#1 | 102.35(3) |
Hg(1)—S(4)#1 | 2.6955(9) | S(1)—Hg(1)—S(4)#1 | 107.67(3) |
Hg(1)—S(2) | 2.7327(9) | S(3)—Hg(1)—S(2) | 122.15(3) |
S(1)—C(1) | 1.7404(4) | S(1)—Hg(1)—S(1) | 69.91(3) |
S(3)—C(9) | 1.702(4) | S(4)#1—Hg(1)—S(2) | 95.46(3) |
S(4)—C(9) | 1.732(4) | C(1)—S(1)—Hg(1) | 88.17(13) |
S(4)—Hg(1)#1 | 1.716(4) | C(1)—S(2)—Hg(1) | 80.98(13) |
N(1)—C(1) | 1.347(5) | C(9)—S(3)—Hg(1) | 99.34(13) |
N(1)—C(3) | 1.444(5) | C(9)—S(4)—Hg(1)#1 | 95.89(13) |
N(1)—C(2) | 1.469(5) | S(2)—C(1)—S(1) | 120.9(2) |
N(2)—C(9) | 1.332(5) | N(1)—C(1)—S(2) | 121.7(3) |
N(2)—C(11) | 1.454(5) | N(1)—C(1)—S(1) | 117.4(3) |
N(2)—C(10) | 1.462(5) | N(2)—C(9)—S(4) | 122.0(3) |
N(2)—C(9)—S(3) | 116.2(3) | ||
S(4)—C(9)—S(3) | 121.8(2) |
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Onwudiwe, D.C.; Ajibade, P.A. Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2. Int. J. Mol. Sci. 2011, 12, 1964-1978. https://doi.org/10.3390/ijms12031964
Onwudiwe DC, Ajibade PA. Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2. International Journal of Molecular Sciences. 2011; 12(3):1964-1978. https://doi.org/10.3390/ijms12031964
Chicago/Turabian StyleOnwudiwe, Damian C., and Peter A. Ajibade. 2011. "Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2" International Journal of Molecular Sciences 12, no. 3: 1964-1978. https://doi.org/10.3390/ijms12031964