Synthesis, spectroscopic studies, and single crystal X-ray diffraction analysis of a lead(II) based hybrid perovskite: Morpholinium trichloroplumbate(II)

Article abstract of DOI:10.1515/mgmc-2016-0005

Morpholinium trichloroplumbate(II), [cyclo-O(CH₂CH₂)₂NH]PbCl₃ (1), has been synthesized and characterized by elemental analysis, FTIR and ¹H and ¹³C NMR spectroscopy, thermogravimetric analysis (TGA), diffuse reflectance spectra, and single-crystal X-ray diffraction analysis. An FTIR spectrum showed a shift of 100 cm^-1 in the NH₂ stretching due to the protonated nitrogen of the morpholinium ion. ¹H NMR spectrum of the compound showed significant high-frequency shift of the resonance for the CH₂ protons due to the presence of cationic charge on the adjacent nitrogen and hydrogen bonded interactions. Contrary to ¹H NMR, the ¹³C NMR signals showed a lowering of 'δ' in the hybrid material. A diffuse reflectance spectrum (DRS) illustrated intense charge transfer in the compound. The observed band gap value for the compound is 3.23 eV based on the DRS data. TG-DT analysis showed the compound to be stable up to 241°C. Single crystal X-ray diffraction analysis of the hybrid material showed the Pb²⁺ ion being surrounded by six chloride anions in a distorted octahedral geometry. In addition to the six chloride anions, the oxygen atom of the morpholinium cation is also in short contact with the lead cation. Bond valence sum (BVS) calculation confirmed the formal oxidation state of lead to be +2. Continuous symmetry measure (CSM) calculations indicated the PbCl₆ to be a distorted octahedron with a magnitude of 5.246 clearly far away from the trigonal prismatic geometry.

Full text of DOI:10.1515/mgmc-2016-0005

Main Group Met. Chem. 2016; 39(5-6): 175–181
KSuyppnuktkhanenusRiasm,alsingpame*c, CtorrorasdocRoizzpolii,cThsantguardasiueRsaja,raamnandansd iMnangiklaendan Prabu
crystal X-ray diffraction analysis of a lead(II)
based hybrid perovskite: morpholinium
trichloroplumbate(II)
DOI 10.1515/mgmc-2016-0005
Introduction
Naturally occurring perovskites have been extensively
Received February 24, 2016; accepted July 11, 2016; previously
published online November 5, 2016
Abstract: Morpholinium trichloroplumbate(II), [cyclo- studied for their functional, structural, optical, electri-
O(CH2CH2)2NH]PbCl3 (1), has been synthesized and char- cal, and other properties (Mitzi et al., 2001; Mitzi et al.,
acterized by elemental analysis, FTIR and 1H and 13C NMR 2002; Stoumpos et al., 2013; Aharon et al., 2014; Dirin
spectroscopy, thermogravimetric analysis (TGA), diffuse et al., 2014; Lindblad et al., 2014). Variation in optical and
reflectance spectra, and single-crystal X-ray diffraction structural features of perovskites strongly depends on the
analysis. An FTIR spectrum showed a shift of 100 cm-1 in extended network of the MX6 octahedron (Owczarek et al.,
the NH2 stretching due to the protonated nitrogen of the 2013; Frost et al., 2014). Organic compounds offer a variety
1
morpholinium ion. H NMR spectrum of the compound of expedient properties such as mechanical plasticity,
showed significant high-frequency shift of the resonance ease of processing, diverse structures, and efficient lumi-
for the CH2 protons due to the presence of cationic charge nescence. As a contrast, inorganic materials show excel-
on the adjacent nitrogen and hydrogen bonded interac- lent electrical conductivity, tunable band gap, mechanical
1
tions. Contrary to H NMR, the 13C NMR signals showed firmness, and thermal stability. Inorganic-organic hybrids
a lowering of ‘δ’ in the hybrid material. A diffuse reflec- favorably combine the often dissimilar properties of
tance spectrum (DRS) illustrated intense charge transfer organic and inorganic components in one material. Inor-
in the compound. The observed band gap value for the ganic-organic hybrid materials of perovskite structure are
compound is 3.23 eV based on the DRS data. TG-DT analy- of the general formula, AMX3, where Aꢀ=ꢀorganic ammo-
sis showed the compound to be stable up to 241°C. Single nium moiety; Mꢀ=ꢀPb2+, Sn2+; and Xꢀ=ꢀCl-, Br-, and I- (Baikie
crystal X-ray diffraction analysis of the hybrid material et al., 2013; Ahmad et al., 2014; Dimesso et al., 2014;
showed the Pb2+ ion being surrounded by six chloride Lindblad et al., 2014; Egger and Kronik, 2014; Carrero
anions in a distorted octahedral geometry. In addition to et al., 2015; Shi et al., 2015; Yin et al., 2015). Organic-inor-
the six chloride anions, the oxygen atom of the morpho- ganic hybrids have generated substantial interest because
linium cation is also in short contact with the lead cation. of their ability to combine the desirable characteristics for
Bond valence sum (BVS) calculation confirmed the formal solar applications in a single molecular scale (Kieslich
oxidation state of lead to be +2. Continuous symmetry et al., 2015). In the last decade, organic-inorganic hybrid
measure (CSM) calculations indicated the PbCl6 to be a perovskites are the most extensively investigated crystal-
distorted octahedron with a magnitude of 5.246 clearly far line solids (Kagan et al., 1999; Mitzi, 1999). Generally, the
away from the trigonal prismatic geometry.
inorganic part of the hybrid materials consists of perovs-
kite-like layers of corner-shared octahedral units (Subbiah
et al., 2014). The research spurt in hybrids has reached
its zenith in the last 5 years with a phenomenal number
of publications (ꢀ>ꢀ1600) and patents (~400) worldwide
due to their use in harvesting solar energy. The hybrids
have pliable electrical mobility, band gap, and thermal
stability (Snaith, 2013; Yang et al., 2014; Muller, 2015).
In the present work, we report the synthesis of morpho-
linium trichloroplumbate(II), [cyclo-O(CH2CH2)2NH]PbCl3,
and characterize it by elemental analysis, IR and NMR
Keywords: band gap; BVS; CSM; DRS; hybrid perovskite;
lead(II); morpholinium.
*Corresponding author: Kuppukkannu Ramalingam, Department of
Chemistry, Annamalai University, Annamalai Nagar 608 002, Tamil
Nadu, India, e-mail: krauchem@yahoo.com
Corrado Rizzoli: Department of General and Inorganic Chemistry,
University of Parma, Parma, Italy
Thangarasu Rajaraman and Manikandan Prabu: Department of
Chemistry, Annamalai University, Annamalai Nagar, Tamil Nadu, India
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176ꢀ ꢀK. Ramalingam et al.: Synthesis and characterization of hybrid morpholinium trichloroplumbate(II)
spectroscopy, optical spectrum, thermal behavior, and (Figures S2, S3). The signals are listed in Table 1. It shows
single crystal X-ray diffraction analysis.
four α, α′-CH2 protons adjacent to nitrogen observed as a
triplet at δ 3.769–3.793 ppm and four β, β′-CH2 protons at
1
δ 3.074–3.099 ppm. The H NMR signals of the α, α′- and
Results and discussion
β, β′-CH2 protons of morpholine are observed at δ 3.669
and 2.860 ppm, respectively (SDBS). The shift of both the
Morpholinium trichloroplumbate(II), [cyclo-O(CH2CH2)2 signals to higher δ is due to two factors, viz., the presence
NH]PbCl3 (1) was synthesized by the reaction of lead dichlo- of a cationic charge on the adjacent nitrogen atom and
+
ride, PbCl2, with an equimolar amount of morpholinium hydrogen bond interactions. The NH2 proton signals are
chloride, [cyclo-O(CH2CH2)2NH]Cl in dimethyl formamide, observed as a broad singlet at 9.188 ppm, whereas the free
DMF, at 60°C. Analytical data, FTIR, and NMR spectro- amine signal is observed at 2.590 ppm. The signals for the
scopic analysis confirmed the identity of the compound.
α- and β-CH2 carbon atoms are observed at δ 63.18 and 42.9
ppm, respectively, whereas the corresponding signals for
morpholine are observed at 68.16 and 46.61 ppm.
Infrared spectroscopy
An FTIR spectrum of 1 is given in the supplementary mate-
rial (Figure S1). The NH2 stretching vibration of 1 was
observed at 3432 cm-1, and its deformation vibration was
observed at 1570 cm-1. In morpholine, the corresponding
vibrations were observed at 3334 and 1463 cm-1, respec-
tively (Jelev et al., 1999). As a result of protonation, the
stretching vibration shifted by approximately 100 cm-1 to
a higher wave number. The deformation vibration also
shifted to a lower wave number to the same extent. Com-
pound 1 showed symmetric stretching νCH2 vibrations at
3147 and 3072 cm-1, whereas morpholine showed the vibra-
tions at 2949 and 2939 cm-1 (Lan et al., 1990; Furic et al.,
1992). In addition, vibrations due to the C-O-C moiety are
observed at 1084 and 584 cm-1 in the compound, whereas
the two are observed at 1097 and 597 cm-1, respectively, in
morpholine. The observation clearly signifies the strong
bonding of oxygen to lead in compound 1, and hence, a
significant shift to lower wave number is observed.
Diffuse reflectance spectrum
DRS spectrum and a plot of hν versus (F(R) hν)2 for the
determination of band gap of the hybrid are included in the
supplementary material (Figures S4, S5). The strength of the
Pb-Cl bond determines the band gaps of this class of mate-
rials. The morpholinium cation is involved in strong inter-
action with the lead(II) ion. It donates one electron to the
hybrid perovskite material (Bernal and Yang, 2014). The Eg
value of morpholinium trichloroplumbate(II) is 3.23 eV.
Thermal analysis
Thermogravimetric and differential thermal analysis was
carried out in an atmosphere of nitrogen at a heating rate
of 20 K/min in the temperature range of 0–1200°C and is
shown in Figure 1. The TG-DT shows that the compound
is thermally stable up to 241°C. Above 241°C, the TG curve
shows a weight loss in two stages. In the first stage, a mol-
ecule of morpholinium chloride was lost between 296°C
1H and 13C NMR spectroscopy
1H and 13C NMR spectra of morpholinium trichlorido- and 361°C. The observed weight loss of 30.5% is in excel-
plumbate(II) are given in the supplementary material lent agreement with the expected weight loss of 30.8%
Table 1:ꢀIR, 1H, and 13C NMR spectral data for compound 1.
ꢁ
ꢂ
ꢂ
ꢂ
νNH
ꢁ
νCH2
ꢁ
νCN
ꢁ
δNH
ꢁ
νC-O-C
IR (cm-1)
1H NMR (ppm)
3432
ꢂ
3147, 3072ꢂ
1038
ꢂ
1570 ꢂ
1084, 584
+
α-C(H2) ꢂ(4H, t)
3.767–3.793ꢃ(3.669)
α-C(H2)
ꢂ
ꢂ
β-C(H2)ꢂ (4H, t)
ꢂ
NH2 (2H, b s)
ꢂ
9.188ꢃ(2.590)a
3.074–3.099ꢃ(2.860)
13C NMR (ppm) ꢂ
ꢂ
ꢂ
β-C(H2)
ꢂ
63.18ꢃ(68.16)
42.69ꢃ(46.61)
aMorpholine: NH.
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K. Ramalingam et al.: Synthesis and characterization of hybrid morpholinium trichloroplumbate(II)ꢃ
ꢃ177
100
80
60
40
20
0
0.0
TGA
-0.5
DTA
-1.0
[1]
-1.5
-2.0
-2.5
-3.0
-3.5
[1]
-4.0
200
400
600
800
1000
Temperature (°C)
Figure 1:ꢀTG-DT analysis of morpholinium trichloroplumbate(II).
during the decomposition. The remaining PbCl2 vaporized the ‘a’ axis of the unit cell, as shown Figure 3. The six-coor-
completely at 800°C.
dinate Pb atoms are triply bridged by three chloride anions
resulting in the effective charge balance. The triple bridg-
ing observed in this compound is feasible only when the
2+
Single crystal X-ray diffraction analysis
central atom is bulky enough (rPb ꢀ=ꢀ133 pm) as reported for
the bromide analogue (Kawasaki et al., 2012). Moreover,
Crystal data collection and structure refinement para- large variations are forced on X-Pb-X bond angles due to
meters are given in the online supplementary material. triple bridging in these types of hybrids, which are respon-
Selected bond parameters are given in Table 2. Molecular sible for the distortions of the PbX6 octahedron (Baikie
plot of the compound is shown in Figure 2. Morpholinium et al., 2013). Pb-Cl non-bonding distances along the ‘a’
trichloroplumbate(II) contains the lead ion in a distorted axis of the unit cell are 2.738, 2.840, 2.923, 2.937, 2.997, and
octahedral environment of six chloride ions. The Pb-Cl 3.102 Å, and the Cl-Pb-Cl angles along the linear chain
interatomic distances vary from 2.738(2) Å to 2.997(3) Å. are 160.02(5) and 168.28(5)°. The interatomic Pb-Pb non-
However, one of the Pb-Cl bond is quite long, 3.102(2) bonding distance along the chain is 3.918 Å. The morpho-
Å. The Cl-Pb-Cl bond angles vary to a large extent from linium cation is arranged parallel to the PbCl3 chain in the
81.31(8) to 90.02(8)°, and the associated bond parameters unit cell, and a short contact exists between Pb and O at
indicate a very large distortion in the PbCl6 octahedron. a distance of 3.122(3) Å, which is less than the sum of the
PbCl6 octahedra are linked as an infinite linear chain along van der Waals radiiꢀ=ꢀ3.42 Å. A neutron diffraction study on
Figure 2:ꢀMolecular plot of morpholinium trichloroplumbate(II)
showing short contact between Pb-O.
Figure 3:ꢀLinear PbCl6 chain extending along the ‘a’ axis.
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178ꢀ ꢀK. Ramalingam et al.: Synthesis and characterization of hybrid morpholinium trichloroplumbate(II)
the tribromo-substituted analogue showed a similar struc-
tural environment in the crystal structure (Kawasaki et al.,
Bond valence sum (BVS) calculation
2012). Interestingly, the bromide analogue crystallized in BVS calculations offer a reliable method of determin-
the space group: P212121 with very small increment in the ing the formal oxidation state of an atom in a com-
unit cell lengths in keeping with the relatively larger size pound from the structural data, particularly the bond
of the bromide ions in the place of chloride ions. The Pb-O lengths. For an ionic compound, the method depends
distance in the bromide analogue is 3.235(2) Å, which is on the Rij, the bond distance for the bond between the
significantly longer than the distance observed in the atoms i and j in a compound (Brown and Altermatt,
present chloride compound.
1985; Bresse and O’Keefe, 1991; Brown, 2002, 2009).
The molecule shows extensive hydrogen bonding, as In a compound, the oxidation state of a central atom i
shown in Table 3. Hydrogen atoms at the nitrogen atom bonded to j is equivalent to the bond valence, Sij, and
of morpholine and the hydrogen atom on the carbon the total valence of the central atom, which is its oxida-
atoms of morpholine are in hydrogen bonding interac- tion state, ΣSijꢀ=ꢀexp[(Ro-Rij)/b] (Brown and Altermatt,
tions with three chlorine atoms. All the hydrogen bonds 1985). Ro is the bond distance determined from a large
observed in the compound are significantly shorter than volume of X-ray structural data for predominantly ionic
the sum of the van der Waals radii of H and Cl of 2.85 Å, compounds, and Rij is the experimentally determined
and therefore, a set of strong hydrogen bonded interac- bond distance in this study. The constant b is assumed
tion is observed. The Pb-O and N-H-Cl/Br interactions to be 0.37. For compound 1, the BVS was calculated by
are responsible for the contribution of the organic part summing up the bond valence contributions from six
to the conducting property of the material.
Pb-Cl bonds, and it was found to be 2.166. However,
the BVS for PbCl6O, including the contribution from the
Pb-O short contact, was found to be 2.219. In the present
case, the BVS value clearly establishes the formal oxida-
tion state of lead as +2.0. Therefore, a considerable ionic
character to the predominantly covalent bonding in the
compound is clearly established (Summers et al., 1994)
Table 2:ꢀSelected bond lengths (Å) and bond angles (°) for 1.
Bond lengths
ꢃPb1-Cl1
ꢃPb1-Cl2
ꢃPb1-Cl3
ꢃPb1-Cl1ii
ꢃPb1-Cl2i
Bond angles
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
2.738 (2)ꢂ
2.840 (3)ꢂ
2.926 (2)ꢂ
3.102 (2)ꢂ
2.997 (3)ꢂ
Pb1-Cl3i
O1-C4
O1-C1
N1-C3
N1-C2
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
2.937 (2)
1.418 (13) besides proving the fact that the X-ray structure deter-
1.425 (14)
1.468 (15)
1.472 (14)
mined in this study is perfect.
Continuous symmetry measure (CSM)
ꢃCl1-Pb1-Cl2 ꢂ
ꢃCl1-Pb1-Cl3 ꢂ
ꢃCl2-Pb1-Cl3 ꢂ
ꢃCl1-Pb1-Cl3iꢂ
ꢃCl2-Pb1-Cl3iꢂ
ꢃCl3-Pb1-Cl3iꢂ
ꢃCl1-Pb1-Cl2iꢂ
ꢃCl2-Pb1-Cl2iꢂ
ꢃCl2i-Pb1-Cl3ꢂ
83.21 (8)ꢂ
81.31 (8)ꢂ
89.04 (8)ꢂ
79.01 (7)ꢂ
90.02 (8)ꢂ
160.28 (5)ꢂ
76.81 (7)ꢂ
160.02 (5)ꢂ
88.30 (7)ꢂ
Cl2i-Pb1-Cl3i ꢂ
Pb1-Cl2-Pb1iiꢂ
Pb1-Cl3-Pb1iiꢂ
C1-O1-C4
C2-N1-C3
O1-C1-C2
N1-C2-C1
N1-C3-C4
O1-C4-C3
85.89 (7)
84.30 (7)
83.88 (6)
108.7 (8)
111.7 (8)
110.4 (9)
109.6 (8)
109.9 (9)
CSM assesses the deviation of a given structure from
the desired ideal symmetry or from a reference shape
(Zabrodsky et al., 1992; Keinan and Avnir, 2000; Alvarez
et al., 2002; Ok et al., 2006). The descriptions such as
‘slightly distorted’ or ‘highly distorted’ relative to the
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
111.2 (9) reference polyhedron is highly qualitative in nature.
The extent of deviation of a structure from an ideal poly-
hedron can be quantified by symmetry measures. The
ideal geometries associated with hexa-coordinated atoms
are ideal octahedron (iOh) or ideal trigonal prism (itp).
The CSM value is to a scale of 0–100 with 0 correspond-
ing to an ideal octahedron and 100 to an ideal trigonal
Symmetry codes: iꢂ=ꢂ1/2+x, 1/2-y, 1ꢂ–ꢂz; iiꢂ=ꢂx+1/2, -y+1/2, -z+1.
Table 3:ꢀHydrogen bond distances (Å).
D-H···A
ꢁ
D-Hꢁ
H···Aꢁ
D···Aꢁ
D-H···A
prism for a six coordinated central atom. In the present
investigation, the coordination around lead has been
found to be in a distorted octahedron (dOh) environment
of six chloride ions. In the present case, the CSM of PbCl6
core is 5.246. The observed CSM value clearly indicates
the proximity of the compound to octahedral geometry
rather than trigonal prism.
N1-H1N···Cl3iiiꢂ
N1-H2N···Cl1ivꢂ
N1-H2N···Cl2v ꢂ
C4-H4B···Cl1ii ꢂ
0.89ꢂ
0.89ꢂ
0.89ꢂ
0.97ꢂ
2.49ꢂ
2.69ꢂ
2.79ꢂ
2.78ꢂ
3.270 (9)ꢂ
3.339 (9)ꢂ
3.431 (8)ꢂ
3.540 (11)ꢂ
1.46
1.31
1.30
1.36
Symmetry codes: iꢂ=ꢂ1/2+x, 1/2-y, 1ꢂ–ꢂz; iiꢂ=ꢂx+1/2, -y+1/2, -z+1;
iiiꢂ=ꢂ-x+1, y-1/2, -z+1/2; ivꢂ=ꢂ-x+1/2, -y+1, z-1/2; vꢂ=ꢂ-x+1, y+1/2, -z+1/2.
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ꢃ179
X-ray crystallography
Conclusions
Single crystal X-ray intensity data were collected at ambient tem-
perature (295 K) using graphite monochromated Mo-Kα radiation
(λꢀ=ꢀ0.71073 Å) on a Bruker SMART 1000 CCD diffractometer (USA).
Data were corrected for absorption using SADABS (Bruker, 2001).
The structures were solved by direct methods using SIR97 (Altomare
et al., 1999) and were refined by SHELX2014 (Sheldrick, 2015). The
non-hydrogen atoms were refined anisotropically, and all the hydro-
gen atoms were fixed geometrically. Molecular plots were obtained
with ORTEP-3 (Farrugia, 1999) program.
Morpholinium trichloroplumbate(II) is an organic-inor-
ganic hybrid perovskite material synthesized at 60°C in
DMF. An FTIR spectrum of the compound shows charac-
teristic shift of C-H and N-H stretching vibrations to lower
wave numbers on forming the hybrid material. The 1H NMR
signals of α, α′- and β, β′-CH2 protons of morpholine shifted
to higher ‘δ’ due to the presence of cationic charge on the
adjacent nitrogen atom and extensive hydrogen-bonded
+
interactions. The NH2 proton signals are observed as a
broad singlet at 9.188 ppm, compared to the free amine
Synthesis of morpholinium chloride
13
signal observed at 2.590 ppm. C NMR signals showed a
lowering of ‘δ’ in the hybrid material. DRS spectrum con-
firmed intense charge transfer being present in the com-
pound. The observed band gap value for the hybrid is
3.23 eV based on the DRS data, which indicated its suit-
ability as a semiconductor for various applications. TG-DT
analysis showed the compound to be stable up to 241°C
and established the correctness of proposed formula of
the compound. Single crystal X-ray diffraction analysis of
compound 1 shows the divalent lead ion to be in an envi-
ronment of six chloride ions resulting in a distorted octahe-
dral geometry. PbCl6 octahedra formed a rigid [MX6]∞ chain
along the unit cell ‘a’ axis, and the organic morpholinium
cation juxtapositioned itself in the lattice. In addition to the
six chloride ions, the oxygen atom of the morpholinium
cation is at a short distance of 3.122(3) Å, which is less than
the sum of the van der Waals radiiꢀ=ꢀ3.42 Å. BVS calculation
confirmed the formal oxidation state of lead to be +2. The
Pb-O and N-H-Cl/Br interactions are responsible for the
contribution of organic part to the conducting property of
the material. CSM calculations indicated the PbCl6 to be a
distorted octahedron with a magnitude of 5.246 clearly far
away from the trigonal prismatic geometry.
Morpholinium chloride, [cyclo-O(CH2CH2)2NH]Cl, was prepared by
passing HCl gas through morpholine (0.34 mL, 4 mm) in diethyl ether
(5 mL), and the resultant colorless solid was filtered through a filter
paper and dried over anhydrous calcium chloride (yield: 82%, m.p.:
174°C). Elemental analysis showed as follows: %Calcd. for C4H10ONCl:
C, 38.90; H, 8.16; N, 11.34; Foud C, 38.87; H, 8.14; N, 11.30.
Preparation of lead(II) chloride
Lead(II) nitrate (0.662 g, 2 mmol) was dissolved in water (30 mL). To
this solution, concentrated hydrochloric acid (35%, 5 mL) was added.
Amorphous colorless precipitate of lead(II) chloride was filtered from
the solution and was recrystallized from boiling water.
Preparation of morpholinium trichloridoplumbate(II)
Lead chloride (0.278 g, 1 mm) in DMF (5 mL) was mixed with morpho-
linium chloride (0.247 g) in DMF (5 mL) (1:2) and was stirred at 60°C
for 6 h. The resultant colorless solution was filtered and allowed to
stand for crystallization. Colorless crystals were formed on evapo-
ration of the solution after 2 weeks (yield: 76%; m.p.: 254–256°C).
Elemental analysis showed as follows: %Calcd. for C4H9ONPbCl3: C,
11.99; H, 2.26; N, 3.50. Found C, 12.02; H, 2.22; N, 3.48.
Experimental section
Supplementary crystallographic data
Reagents and equipment
CCDC 1055004 contains the supplementary crystallographic data for
compound (2). The data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/con-ts/ retrieving.html or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: +44 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
All reagents were acquired commercially and were used with-
out further purification. Morpholine (Merck, India), DMF (Merck,
India), and lead nitrate (Merck, India) were used in the synthetic
process. Avatar Nicolet 360 spectrophotometer (USA) was employed
1
to record IR spectrum. H and 13C NMR spectra were recorded on
Bruker AMX-400 spectrometer (USA). The elemental analysis was
performed on a Perkin Elmer 2100 series II CHN/S Analyzer (USA).
TGA analyses were performed on a NETZSCH-STA 449 F3 JUPITER
thermal analyzer (Germany). Optical diffuse reflectivity was meas-
ured using Varian 5000 UV-vis spectrophotometer (USA) from 200
to 2500 nm using barium sulfate as standard with 100% reflectance.
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180ꢀ ꢀK. Ramalingam et al.: Synthesis and characterization of hybrid morpholinium trichloroplumbate(II)
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