Synthesis and crystal structures of dioxomolybdenum(VI) complexes with ONS-donor ligands

Article abstract of DOI:10.1007/s10870-011-0160-1

Three dioxomolybdenum complexes namely dioxo(5-chlorosalicylaldehyde thiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C1), dioxo(5- chlorosalicylaldehyde 2-ethylthiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C2) and dioxo(5-chlorosalicylalde

Full text of DOI:10.1007/s10870-011-0160-1

J Chem Crystallogr (2011) 41:1700–1706
DOI 10.1007/s10870-011-0160-1
ORIGINAL PAPER
Synthesis and Crystal Structures of Dioxomolybdenum(VI)
Complexes with ONS-Donor Ligands
•
Ngui Khiong Ngan Chee Seng Wong
•
Kong Mun Lo
Received: 13 May 2011 / Accepted: 29 June 2011 / Published online: 14 July 2011
Ó Springer Science+Business Media, LLC 2011
Abstract Three dioxomolybdenum complexes namely
dioxo(5-chlorosalicylaldehyde thiosemicarbazonato) dime
thylsulfoxide molybdenum(VI) (C1), dioxo(5-chlorosali-
cylaldehyde 2-ethylthiosemicarbazonato) dimethylsulfox-
ide molybdenum(VI) (C2) and dioxo(5-chlorosalicylal
dehyde N-phenylthiosemicarbazonato) dimethylsulfoxide
molybdenum(VI) (C3) were prepared. The compounds
all crystallize in the triclinic space group P-1 with a =
are linked by N–HÁÁÁN intermolecular hydrogen bonding,
forming polymeric chains that run parallel to the bc plane.
On the other hand, C2 is a discrete molecule while the
molecules of C3 associate via weak N–HÁÁÁO hydrogen
bonding interaction to form a polymeric chain that runs
along the a-axis.
Keywords Dioxomolybdenum(VI) complexes Á
Schiff base Á Hydrogen bond Á ONS donor atoms
˚
˚
˚
7.3184(3) A, b = 7.5035(3) A, c = 14.9713(6) A, a =
85.005(2)°, b = 85.616(2)°, c = 66.987(2)° for C1,
˚
˚
˚
a = 8.2339(1) A, b = 10.1739(1) A, c = 10.4017(1) A,
a = 78.486(1)°, b = 89.312(1)°, c = 81.730(1)° for C2,
Introduction
˚
˚
˚
a = 7.0591(1) A, b = 9.5603(1) A, c = 14.5762(2) A,
a = 76.280(1)°, b = 81.351(1)°, c = 81.985(1)° for C3.
In general, the overall geometry of these complexes can be
regarded as a distorted octahedron with the tridentate thi-
Dioxomolybdenum(VI) complexes with thiosemicarbazo-
nato ligands have been investigated owing to their new
chemical features for potential biological activities such as
antitumor [1], antifungal [2] and antiviral [3] properties.
The first study on the use of thiosemicarbazone ligands
[(salicylaldehyde thiosemicarbazone (TSCsal) and salicyl-
aldehyde 4-phenylthisemicarbazone (4-PhTSCsal)] in the
modeling of molybdoenzyme binding site was carried out
by Saktiprosad Ghosh [4]. Thereafter, a flurry of literatures
on the structures and biological properties of the oxomo-
lybdenum(VI) complexes with ONS donor systems have
been reported [5–10].
osemicarbazonato ligands (L2-) bonded to the MoO2
2?
core, with the imine nitrogen, phenoxyl oxygen, sulfur
atom and one of the terminal oxygen atoms of the dioxo-
molybdenum occupying the equatorial position. The sixth
coordination site is occupied by the dimethylsulfoxide
(DMSO) solvent molecules. The adjacent molecules of C1
Thiosemicarbohydrazone ligand has several potential
donor sites which allow it to bind to the metal through sulfur
atom, hydrazinic nitrogen atom and phenolic oxygen atom.
The chemistry of thiosemicarbazones (mixed hard-soft
nitrogen-sulfur chelating ligands) and the compounds formed
with Mo moiety of higher oxidation states therefore is of
current interest. Although the thiosemicarbazone, obtained by
the condensation process with o-hydroxyl carbonyl com-
pounds, shows antibacterial activity, but the metal complexes
often manifest effect of a larger order of magnitude compared
N. K. Ngan (&) Á C. S. Wong Á K. M. Lo
Chemistry Department, University of Malaya, Lembah Pantai,
50603 Kuala Lumpur, Malaysia
e-mail: nicky_ngan@hotmail.com
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J Chem Crystallogr (2011) 41:1700–1706
1701
to the corresponding ligand [11]. In this context, molybdenum
(VI) complexes of this type of ligands constitute an important
class of compounds. As part of our studies on molybdenum
(VI) complexes with oxygen, nitrogen, and/or sulfur donor
ligands, we describe here the synthesis and structures of
MoO2L(DMSO) complexes, where L is 5-chlorosalicylalde-
hyde thiosemicarbazide (L1), 5-chlorosalicylaldehyde 2-eth-
ylthiosemicarbazide (L2) and 5-chlorosalicylaldehyde
N-phenylthiosemicarbazide (L3) ligands.
(m,OH),1601(m,C=N), 1269(s, C=S),;1HNMR(DMSO-d6,
ppm): 11.39 (1H,OH), 10.33 (1H, N–NH), 8.62 (1H, HC=N);
13C NMR (DMSO-d6, ppm): 158.25 (C=N), 181.11 (C=S).
5-Chlorosalicylaldehyde N-phenylthiosemicarbazone (L3)
m.p.: 145–147 °C (0.19 g, 73%) Calcd. for C14H12ClN3OS1:
C, 54.90; H, 3.92; N, 13.73%; Found: C, 54.33; H, 4.02; N,
13.52%; IR(KBr) (mmax/cm-1): 3365 (m, NH), 3137
(m, OH), 1614 (m, C=N), 1327 (s, C=S),; 1H NMR (DMSO-
d6, ppm): 12.41 (1H, OH), 11.05 (1H, N–NH), 8.57 (1H,
HC=N); 13C NMR (DMSO-d6, ppm): 160.55 (C=N), 183.26
(C=S).
Experimental
General Procedures
Synthesis of Complexes
All the reagents and solvents employed were procured
commercially and used without subsequent purification.
The starting complex, bis(acetylacetato) dioxomolybde-
num(VI), [MoO2 (acac)2] was prepared as described in the
literatures [12, 13].
Dioxo(5-chlorosalicylaldehyde-
thiosemicarbazinato)dimethylsulfoxide
Molybdenum(VI)(C1)
1H and 13C NMR spectra were measured in DMSO-d6 on a
JEOL Lambda and a ECA 400 MHz NMR spectrometers. IR
spectra were measured in Nujol mulls in the range of
4000–400 cm-1 by using a Perkin-Elmer 2000 FTIR instru-
ment. Elemental analysis was performed by the in-house
microanalytical laboratory using a Perkin-Elmer 2400 Series
II CHNS/O System. Single-crystal X-ray data collection was
carriedoutat100 KonaBrukerSmartApexIIdiffractometer.
A solution of L1 (0.231 g, 1.00 mmol), which was dis-
solved in 20.0 mL of ethanol was added to a solution of
MoO2(acac)2 in 20.0 mL methanol. A reddish precipitate
formed immediately DMSO was added dropwise until the
precipitate was completely dissolved in the solution. The
reaction mixture was then refluxed for 2 h and was allowed
to stand at room temperature. Reddish crystals were formed
after slow evaporation for 3 days. The products was fil-
tered, washed with ethanol and dried in air.
Synthesis of Ligands
m.p.: 208–210 °C (0.15 g, 46%) Calcd. for
C10H12ClMoN3O4S2: C, 27.71; H, 2.78; N, 9.59%; Found:
C, 28.00; H, 2.51; N, 9.47%; IR(KBr) (mmax/cm-1): 1587
5-Chlorosalicylaldehyde thiosemicarbazone (L1)
1
(s, C=N), 924, 895 (s,Mo=O). H NMR (DMSO-d6, ppm):
5-Chlorosalicylaldehyde (0.156 g, 1.00 mmol) was dis-
solved in 20 mL methanol. The solution was then added to a
20.0 mL thiosemicarbazide (0.091 g, 1.00 mmol) solution.
The reaction mixture was refluxed for 1 h. A precipitate was
formed when the solution was allowed to cool at room
temperature overnight. The yellow precipitate was filtered,
washed with methanol and dried in air. m.p.: 138–140 °C
(0.25 g, 82%) Calcd. for C8H8ClN3OS1: C, 41.56; H,3.90;
N, 18.19%; Found: C, 41.02; H, 4.02; N, 18.41%; IR(KBr)
(mmax/cm-1): 3411 (m, NH), 3245 (m, OH), 1613 (m, C=N),
1271 (s, C=S),; 1H NMR (DMSO-d6, ppm): 11.76 (1H, OH),
10.25 (1H, N–NH), 8.73 (1H, HC=N); 13C NMR (DMSO-d6,
ppm): 159.89 (C=N), 178.51 (C=S).
8.39 (1H, HC=N). 13C NMR (DMSO-d6, ppm): 166.65 (C=N).
Similar procedure was applied to the preparation of C2
and C3.
Dioxo(5-chlorosalicylaldehyde
2-Ethylthiosemicarbazinato)dimethylsulfoxide
Molybdenum(VI) (C2)
m.p.: 200–202 °C (0.17 g, 45%) Calcd. for C12H17ClMo-
N3O4S2: C, 31.17; H, 3.68; N, 9.09%; Found: C, 30.79; H,
3.56; N, 9.17%; %; IR(KBr) (mmax/cm-1): 1588 (s, C=N),
1
939, 905 (s,Mo=O). H NMR (DMSO-d6, ppm): 8.39 (1H,
HC=N). 13C NMR (DMSO-d6, ppm): 166.65 (C=N).
Similar procedure was applied to the preparation of L2
and L3.
Dioxo(5-chlorosalicylaldehyde N-
phenylthiosemicarbazinato)dimethylsulfoxide
molybdenum(VI) (C3)
5-Chlorosalicylaldehyde 2-ethylthiosemicarbazone (L2)
m.p.: 112–114 °C (0.22 g, 79%) Calcd. for C10H12ClN3OS1:
C, 46.51; H, 4.65; N, 16.28%; Found: C, 46.11; H, 4.82; N,
16.41%; IR(KBr) (mmax/cm-1): 3301 (m, NH), 3128
m.p.: 240–242 °C (0.21 g, 51%) Calcd. for C16H16ClMo-
N3O4S2: C, 37.64; H, 3.14; N, 8.24%; Found: C, 37.49; H,
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J Chem Crystallogr (2011) 41:1700–1706
3.36; N, 8.17%; IR(KBr) (mmax/cm-1): 1594 (s, C=N), 929,
889 (s,Mo=O). 1H NMR (DMSO-d6, ppm): 9.73 (1H, NH,)
8.73 (1H, HC=N). 13C NMR (DMSO-d6, ppm): 161.65
(C=N).
CH3
S
O
O
CH3
O
Mo
O
X-Ray Structural Analysis
S
C
Crystallographic data are given in Table 1. The X-ray data
N
R
for C1, C2 and C3 were collected on a Bruker Smart Apex
˚
Cl
C
H
N
N
H
II diffractometer using Mo–Ka (k = 0.71073 A) radiation
at 100(2) K. Data reduction and cell refinement was per-
Chart 1 Structural diagram of [MoO2L(DMSO)], L1: R = H, L2:
R = CH2CH3 and L3 = C6H5
formed using SAINT (Bruker 2008) [14]. The data sets
Table 1 Crystallographic data
Compounds
C1
C2
C3
for C1, C2 and C3
Chemical formula
Mr
C10H12ClMoN3O4S2
433.76
C12H16ClMoN3O4S2
461.81
C16H16ClMoN3O4S2
509.85
Crystal colour, habit
Crystal size (mm)
Crystal system
Space group
Red, block
0.40 9 0.30 9 0.20
Triclinic
Red, block
0.10 9 0.10 9 0.10
Triclinic
Red, block
0.40 9 0.30 9 0.20
Triclinic
P-1
P-1
P-1
Unit cell dimension
˚
a(A)
7.3148(3)
7.5035(3)
14.9713(6)
85.005(2)
85.616(2)
66.987(2)
752.65(5)
2
8.23390(10)
10.17390(10)
10.40170(10)
78.4860(10)
89.3120(10)
81.7320(10)
844.825(15)
2
7.05910(10)
9.56030(10)
14.5762(2)
76.2800(10)
81.3510(10)
81.9850(10)
939.24(2)
2
˚
b(A)
˚
c(A)
a(°)
b(°)
c(°)
3
˚
V(A )
Z
T(K)
Dcalc (gcm-3
296(2)
100(2)
100(2)
)
1.914
1.815
1.803
l(Mo–Ka) mm-1
Absorption correction
Tmin
1.343
1.202
1.116
Multi-scan
0.7620
Multi-scan
0.887
Multi-scan
0.6730
Tmax
0.8937
0.887
0.7457
F(0 0 0)
432
464
584
Total data
5693
5984
8954
Unique data
2925
3305
4298
Rint
0.0154
0.0144
0.0134
Observed data [I [ 2r(I)]
Number of parameter
R indices [I [ 2r(I)]
2806
3092
4199
197
211
246
R1 = 0.0291
wR2 = 0.1260
R = 0.0303
wR2 = 0.1286
1.174
R1 = 0.0213
wR2 = 0.0591
R1 = 0.0233
wR2 = 0.0602
1.035
R1 = 0.0201
wR2 = 0.0602
R1 = 0.206
wR2 = 0.0607
1.116
R indices[all data]
S
-3
˚
Dqmax(e A
)
0.955
0.623
0.360
-3
)
˚
Dqmin(e A
-0.927
825059
-0.465
-0.729
CCDC number
825057
825058
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J Chem Crystallogr (2011) 41:1700–1706
1703
Fig. 1 Molecular structure of C1 with numbering scheme.
Displacement ellipsoids are drawn at the 50%-level
were corrected for absorption effects based on multiple
scans. The structures were solved and refined using
SHELXS97 (Sheldrick, 2008) [15]. The molecular graphic
were drawn using the XSeed program [16].
Fig. 3 Molecular structure of C1 with numbering scheme. Dis-
placement ellipsoids are drawn at the 50%-level
stoichiometric amount of L1, L2, and L3, respectively in
ethanol. In the presence of DMSO, the reactions yielded red
mononuclear [MoO2L(DMSO)] complexes shown in
Chart 1. The IR spectra of the dioxomolybdenum(VI)
complexes show two strong absorption bands in the region
Result and Discussion
The dioxomolybdenum(VI) complexes, C1, C2, and C3
were obtained by the reaction of [MoO2(acac)2] with a
Fig. 2 Molecular structure
of C2 with numbering scheme.
Displacement ellipsoids are
drawn at the 50%-level
123

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J Chem Crystallogr (2011) 41:1700–1706
1
˚
The H NMR spectra of the ligands exhibits a phenolic
(OH) proton resonance at 11.76, 11.39, and 12.45 ppm,
respectively. Upon coordination to the Mo atom, the signal
for the OH disappeared, indicating the deprotonation of
phenolic OH in order to coordinate with the dioxomolyb-
denum(VI) cation. The 13C NMR spectra of the three
ligands, L1, L2 and L3 exhibit C–S chemical shift at
178.51, 181.11 and 183.26 ppm, respectively.
Table 2 Selected bond distances (A) and angles (°) for C1, C2 and
C3
C1
C2
C3
Bond distances
Mo–O1
1.954(2)
1.9507(16)
1.7115(17)
1.7021(17)
2.2628(19)
2.2897(19)
2.4156(6)
1.287(3)
1.9260(14)
1.7176(14)
1.6966(14)
2.3366(15)
2.2699(16)
2.4458(5)
1.297(3)
Mo–O2
1.711(2)
1.695(2)
2.312(2)
2.284(3)
2.4372(8)
1.295(4)
1.749(3)
1.309(4)
1.395(3)
Mo–O3
Mo–O4
Mo–N1
Molecular Structures of C1, C2, and C3
Mo–S1
C7–N1
The molecular structures of C1, C2, and C3 shows that the
Schiff base behave as a tridentate ligand, and reacted with
the dioxomolybdenum anion to give a six coordinated
molybdenum(VI) structure. As shown in the Figs. 1, 2 and
3, the imine nitrogen, one of the phenoxyl oxygen and the
sulfur atom are involved in the coordination with molyb-
denum atom. The overall geometry can be regarded as a
distorted octahedron, with the equatorial plane formed by
the imine nitrogen, phenoxyl oxygen, sulfur atom and one
of the terminal oxygen atoms of the dioxomolybdenum.
The other terminal oxygen and the oxygen atom from the
solvent occupy the apical position. In this case, the ligand
which coordinates to Mo atom formed six- and five-
member chelate rings around the cis-MoO2 centre.
C8–S1
1.759(2)
1.760(2)
C8–N2
1.307(3)
1.296(3)
N1–N2
1.397(2)
1.393(3)
Bond angles
O2–Mo–O3
O2–Mo–O1
O3–Mo–O1
O2–Mo–S1
O3–Mo–S1
O1–Mo–S1
O2–Mo–N1
O3–Mo–N1
O1–Mo–N1
S1–Mo–N1
O2–Mo–O4
O3–Mo–O4
O1–Mo–O4
105.53(11)
96.74(10)
107.63(10)
89.50(8)
105.17(9)
96.79(7)
106.43(7)
88.48(6)
99.81(6)
153.91(5)
160.19(7)
89.84(8)
84.05(6)
76.05(5)
88.60(7)
165.64(7)
74.96(6)
106.34(7)
99.00(7)
105.50(6)
90.23(5)
96.72(5)
153.51(5)
159.33(6)
90.49(6)
83.00(6)
75.66(4)
85.53(6)
168.13(6)
77.25(6)
100.40(8)
151.51(7)
159.40(10)
91.10(10)
81.76(9)
75.36(6)
The selected bond distances and angles are summarized
in Table 2. The Mo=O bond lengths and the O=M=O
angles have values which are in the expected range for cis-
dioxomolybdenum(VI) complexes [19–22]. The bond dis-
tance between the Mo and the oxygen atom from DMSO
85.20(9)
168.94(9)
77.07(8)
between 890 and 930 cm-1, which is indicative of sym-
metrical and anti-symmetrical stretching vibration of the two
doubly-bonded oxygen atoms at the molybdenum core
which are cis to each other [17, 18]. The IR spectra of the
ligands exhibit a few ligand bands at the region
3100–3200 cm-1 [t(OH)], 3400–3300 cm-1 [t(NH)],
1200–1400 cm-1 [t(C=S)]. Upon coordinating with
MoO22?, these absorption bands vanished as were observed
in the spectra of the complexes.
[2.312(2) A (C1), 2.2628(19) A (C2), 2.3366(15) A (C3)]
˚
˚
˚
2?
suggested that DMSO binds firmly to the MoO2 moiety
Tables 3 and 4.
The equatorial bases formed by S1, O2, O1 and N1 in
the complexes are non planar. The Mo atom of C1 and C2
˚
are shifted 0.2507 and 0.2359 A, respectively out from the
basal plane towards the solvent oxygen donor atom, O4,
˚
while the Mo atom of C3 show a 0.2466 A displacement
towards the apical oxo-oxygen atom, O3.
Table 3 Hydrogen bonds for C1
D–HÁÁÁA
d(D–H)
˚
d(HÁÁÁA)
d(DÁÁÁA)
\(DHA)
(o)
Symmetry operation
˚
˚
A
A
A
N(3)–H(2)ÁÁÁN(2)
N(3)–H(1)ÁÁÁO(4)
0.77
2.25
3.000(4)
2.897(3)
163.5
-x ? 2, -y, -z ? 1
0.83(4)
2.08(4)
167(4)
-x ? 2, -y ? 1, -z ? 1
Table 4 Hydrogen bonds for C3
D–HÁÁÁA
d(D–H)
˚
d(HÁÁÁA)
d(DÁÁÁA)
\(DHA)
(°)
Symmetry operation
˚
˚
A
A
A
N(3)–H(3)ÁÁÁO(4)
0.88
2.41
3.231(2)
154.9
x - 1, y, z
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J Chem Crystallogr (2011) 41:1700–1706
1705
˚
d(DÁÁÁA) of 3.23 A. As a result, the molecules forms infi-
nite chain that runs along the a-axis.
Conclusions
Three new dioxomolybdenum(VI) complexes with
5-chlorosalicylaldehyde thiosemicarbazate, 5-chlorosali-
cylaldehyde 2-ethylthiosemicabazate and 5-chlorosalicyl-
aldehyde N-phenylthiosemicarbazate tridentate ligands
have been prepared and characterized. The octahedral
coordination of each of the molybdenum atom is completed
by DMSO molecule. C1 and C3 molecules formed poly-
meric chains, respectively, through hydrogen bonds inter-
action, while C2 molecule exists as discrete molecule.
Fig. 4 C1 molecules are linked into a layer by N3–H2ÁÁÁN2 and
N3–H1ÁÁÁO4 hydrogen bonds
Supplementary Material
CCDC 825057, CCDC 825058 and CCDC 825059 contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_resquest/cif.
Acknowledgment We wish to thank the University of Malaya
(PS378/2010B and RG020/09AFR) for supporting this study.
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˚
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J Chem Crystallogr (2011) 41:1700–1706
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