S. Vijayapritha and P. Viswanathamurthi
Journal of Organometallic Chemistry 929 (2020) 121555
Table 2
˚
Selected bond length [A] and bond angle [°] for complex 3.
˚
Bond length (A)
Bond angle (°)
Ru(1)-N(3)
Ru(1)-N(1)
Ru(1)-Cl(1)
Ru(1)-C(20)
Ru(1)-C(21)
Ru(1)-C(22)
Ru(1)-C(23)
Ru(1)-C(24)
Ru(1)-C(25)
N(3)-C(12)
N(2)-C(12)
2.096(6)
2.105(6)
2.391(2)
2.239(8)
2.205(7)
2.171(9)
2.206(10)
2.143(9)
2.171(9)
1.300(10)
1.344(11)
N(3)-Ru(1)-N(1)
N(3)-Ru(1)-Cl(1)
N(1)-Ru(1)-Cl(1)
N(2)-N(1)-Ru(1)
N(3)-Ru(1)-C(24)
N(1)-Ru(1)-C(24)
N(3)-Ru(1)-C(22)
N(1)-Ru(1)-C(22)
C(24)-Ru(1)-C(22)
C(12)-N(2)-N(1)
C(13)-N(3)-Ru(1)
76.1(2)
87.77(19)
85.06(19)
116.0(5)
139.9(5)
92.5(3)
93.3(3)
134.7(4)
67.6(4)
109.9(6)
136.2(5)
H, 4.26; N, 13.29; S, 10.19%. IR (ATR, cm−1): 3630 (br, νOH), 3066
(w, νNH), 1582 + 1471 (s, νC=N + νC−N), 774 (s, νC-S). 1H NMR
(400 MHz, CDCl3, ppm): 10.65 (s, 1H, OH), 8.10 (s, 1H, −CH=N),
7.96−7.22 (m, 10H, Ar H), 4.35 (s, 1H, NH). 13C NMR (75.47
MHz, CDCl3, ppm): 168.46 (S-C=N), 156.27 (Ar-C), 148.44 (Ar-C),
142.49 (C=N), 132.63 (Ar-C), 129.28 (Ar-C), 128.52 (Ar-C), 128.15
(Ar-C), 126.03 (Ar-C), 125.85 (Ar-C), 123.95 (Ar-C), 122.13 (Ar-C),
121.12 (Ar-C), 108.61 (Ar-C), 105.68 (Ar-C). ESI mass (m/z) calcd. for
C18 H13N3OS, 319.38; Found, 320.39 [M+H]+.
Fig. 1. Perspective view (50 % probability ellipsoids) of complex 3.
Table 1
Crystal data and structure refinement parameters for complex 3.
Parameter
Complex 3
CCDC Number
1981468
Empirical formula
C28H26ClN3ORuS
Formula weight
589.10
Temperature
296(2) K
˚
Wavelength
0.71073 A
Hexagonal
P-61
Crystal system
Space group
2.3. Synthesis of new ruthenium complexes
Unit cell dimensions
˚
17.5528(6) A
˚
17.5528(6) A
a
All the complexes were synthesized by following general proce-
dure. The precursor [Ru(η6-p-cymene)Cl2]2 (0.1 mmol) was treated
with corresponding ligand (0.1 mmol) in ethanol (20 mL) for 24 h
under reflux. During the course of the reaction, the color changed
to orange. After completion of the reaction, a rotary evaporator
was used to remove the solvent and the resulting crude product
was dissolved in chloroform and then petroleum ether was added.
The suspension was filtered and the orange solid was thoroughly
washed with cold ethanol and diethyl ether.
b
˚
c
16.2430(5) A
α
β
γ
90°
90°
120°
˚
Volume
4334.0(3) A3
Z
6
Density (calculated)
Absorption coefficient
F(000)
1.354 Mg/m3
0.731 mm-1
1800
Crystal size
0.240×0.170×0.090 mm3
1.340 to 29.002°.
-23<=h<=17,
-23<=k<=23,
-21<=l<=22
27919
Theta range for data collection
Index ranges
2.3.1. Synthesis of [Ru(η6-p-cymene)(SAL-HBT)Cl] (1)
The ligand SAL-HBT was reacted with [Ru(η6-p-cymene)Cl2]2
for the synthesis of complex 1. Yield: 74%; Color: Orange; M.p.
175 °C. Anal. Calcd. for C25H27ON3RuSCl: C, 54.19; H, 4.91; N, 7.58
S, 5.79%. Found: C, 54.35; H, 5.08; N, 7.69; S, 5.92 %. IR (ATR,
cm−1): 3349 (br, νOH), 1569 + 1461 (m, νC=N + νC−N), 756 (s,
Reflections collected
Independent reflections
Completeness to theta = 25.242°
Absorption correction
7665 [R(int) = 0.0451]
99.8 %
None
ν
C-S). 1H NMR (400 MHz, CDCl3, ppm): 11.02 (s, 1H, OH), 8.53
Refinement method
Full-matrix least-squares on F2
7632 / 1 / 310
1.144
Data / restraints / parameters
Goodness-of-fit on F2
(s, 1H, −CH=N), 8.13-7.69 (m, 2H, Ar H), 7.51-6.97 (m, 6H, Ar H),
5.59 (d, J = 8 Hz, 1H, CH), 5.49 (d, J = 4 Hz, 1H, CH), 5.41 (d,
J = 4 Hz, 1H, CH), 5.35 (d, J = 4 Hz, 1H, CH), 2.53 (s, 3H, CH3),
2.39 (sep, 1H, CH), 1.08 (d, J = 4 Hz, 3H, CH3), 0.92 (d, J = 4 Hz,
3H, CH3). 13C NMR (75.47 MHz, CDCl3, ppm): 162.53 (C=N), 161.24
(S-C=N), 160.26 (Ar-C),147.33 (Ar-C), 146.87 (Ar-C), 136.29 (Ar-C),
133.60 (Ar-C), 131.78 (Ar-C), 129.69 (Ar-C), 128.01 (Ar-C), 127.42
(Ar-C), 124.22 (Ar-C), 122.92 (Ar-C), 121.07 (Ar-C), 119.37 (Ar-C),
117.67 (Ar-C), 117.07 (Ar-C), 35.07 (CH), 22.87 (CH3), 22.19 (CH3),
21.57 (CH3). ESI mass (m/z) calcd. for C15H13N3O2S, 539.06; Found,
540.04 [M+H]+.
Final R indices [I>2 sigma(I)
R indices (all data)
R1 = 0.0487, wR2 = 0.1143
R1 = 0.0846, wR2 = 0.1400
0.002(16)
Absolute structure parameter
Extinction coefficient
n/a
˚
0.844 and -0.605 e.A-3
Largest diff. peak and hole
(s, 1H, OH), 8.39 (s, 1H, −CH=N), 7.51−6.84 (m, 7H, Ar H), 4.51 (s,
1H, NH), 3.93 (s, 3H, −OCH3). 13C NMR (75.47 MHz, CDCl3, ppm):
167.12 (S-C=N), 153.34 (Ar-C), 151.01 (Ar-C), 148.42 (Ar-C), 146.78
(C=N), 126.37 (Ar-C), 125.11 (Ar-C), 124.12 (Ar-C), 122.05 (Ar-C),
120.83 (Ar-C), 119.46 (Ar-C), 117.50 (Ar-C), 56.35 (Ar-C). ESI mass
(m/z) calcd. for C15H13N3O2S, 299.35; Found, 300.38 [M+H]+.
2.3.2. Synthesis of [Ru(η6-p-cymene)(VAN-HBT)Cl] (2)
The ligand VAN-HBT was reacted with [Ru(η6-p-cymene)Cl2]2
for the synthesis of complex 2. Yield: 76%; Color: Orange; M.p. 155
°C. Anal. Calcd. for C26H29O2N3RuSCl: C, 53.46; H, 5.00; N, 7.19;
S, 5.49 %. Found: C, 53.62; H, 5.11; N, 7.33; S, 5.61 %. IR (ATR,
cm−1): 3635 (br, νOH); 1598 + 1460 (m, νC=N + νC−N); 760 (s,
2.2.3. Synthesis of (E)-1-((2-(benzo[d]thiazol-2-
yl)hydrazineylidene)methyl)naphthalen-2-ol
(NAP-HBT)
The reaction of 2-hydroxy-1-naphthaldehyde and 2-hydrazino
benzothiazole was carried out for the synthesis of the ligand
NAP-HBT. Yield: 84%; Color: Yellow; M.p. 230 °C. Anal. Calcd for
C18 H13ON3S: C, 67.69; H, 4.10; N, 13.16; S, 10.04%. Found: C, 67.81;
ν
C-S). 1H NMR (400 MHz, CDCl3, ppm): 11.73 (s, 1H, OH), 8.05 (s,
1H, −CH=N), 7.89-6.86 (m, 7H, Ar H), 5.48 (d, J = 8 Hz, 2H, CH),
5.35 (d, J = 4 Hz, 2H, CH), 3.96 (s, 3H, OCH3), 2.62 (s, 3H, CH3),
2.39 (Sep, 1H, CH), 1.29 (d, J = 8 Hz, 3H, CH3), 1.13 (d, J = 4 Hz,
3