Spontaneous Resolution upon Crystallization and Preferential Induction of Chirality in a Discrete Tetrahedral Zinc(II) Complex Comprised of Achiral Precursors

Article abstract of DOI:10.1021/acs.inorgchem.9b01934

A pair of enantiomeric tetrahedral complexes (Λ-[Zn(L)₂] and Δ-[Zn(L)₂]) comprised of the achiral ligand methyl-3-hydroxy-3-phenyl-2-propenedithioate (L) have been synthesized by spontaneous resolution. Two chiral inducers, viz., d-(

Full text of DOI:10.1021/acs.inorgchem.9b01934

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Spontaneous Resolution upon Crystallization and Preferential
Induction of Chirality in a Discrete Tetrahedral Zinc(II) Complex
Comprised of Achiral Precursors
Chote Lal Yadav, Gunjan Rajput,* Kamal Kumar Bisht, Michael G. B. Drew,§
†
,‡
‡
,
†
and Nanhai Singh*
†
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India
Department of Chemistry, Ram Chandra Uniyal Government Post Graduate College, Uttarkashi 249193, India
Department of Chemistry, University of Reading, Whiteknights Campus, Reading RG6 6AD, U.K.
‡
§
*
S Supporting Information
ABSTRACT: A pair of enantiomeric tetrahedral complexes
Λ-[Zn(L) ] and Δ-[Zn(L) ]) comprised of the achiral ligand
(
2
2
methyl-3-hydroxy-3-phenyl-2-propenedithioate (L) have been
synthesized by spontaneous resolution. Two chiral inducers,
viz., D-(−)- and L-(+)-tartaric and mandelic acids, have been
employed to achieve bulk homochirality and extend the
generality of the present work. The work highlights the
achievement of bulk homochirality using readily available
chiral inducers in the synthesis of a spontaneously resolving
chiral tetrahedral zinc(II) complex using achiral starting
materials. These findings are established by 30 sets of single-
crystal X-ray diffraction data with refined Flack parameters
and circular dichroism spectroscopy.
INTRODUCTION
of Enamullah and Janiack first reported spontaneous resolution
in the case of a discrete four-coordinated complex, [Rh(N-
■
Chirality is an eminent attribute of life for the vital biological
systems involving homochiral molecules, including D-saccha-
rides, D-nucleotides, and L-amino acids. The discovery of the
polarization of light by Biot, the recognition of the
spontaneous resolution of tartrates by Pasteur, and the
contribution of Werner to chiral octahedral complexes in the
9th century have laid the foundation of today’s flourishing
4
phenylglycinato)(η -cycloocta-1,5-diene)], which contained
40,41
1
,2
the prochiral ligand N-phenylglycine.
Chirality in the
2
complex arises from the nitrogen atom becoming the
stereogenic center upon metal coordination.
3
4
The process of spontaneous resolution often suffers from the
limitation of unpredictable handedness of the final product,
1
22,23
5
which diminishes its relevance for practical use.
This issue,
research in the field of chirality. With the advances made in
the field of chiral compounds, the demand for chiral substances
in the pharmaceutical and chemical industries has seen a
in principle, can be resolved by employing an enantiopure
additive or solvent as a “chirality inducer”, which promotes the
preferential formation of a specific enantiomer over another.
We are unaware of any instance where chirality induction is
employed to synthesize a preferentially chiral discrete
tetrahedral complex from achiral units. Nevertheless, the use
of chirality inducers is reported in the construction of some
5
−10
continuous rise.
Thus, the synthesis of enantiopure
substances through economically viable methods has been an
area of active research for several decades.
11−21
In this connection, the spontaneous resolution upon
crystallization of achiral precursors has the potential to evolve
42
2
2−25
octahedral complexes, metal−organic polymeric architec-
tures such as coordination polymers, metal−organic frame-
works (MOFs), and covalent organic frameworks from achiral
as a useful method.
As discussed by Bernal in a series of
reviews, the spontaneous resolution of discrete six-coordinated
cobalt(III) complexes comprised of achiral ligands was first
recognized by Werner in the late 19th century.
43−54
2
5−27
building blocks.
Helical motifs with unique handedness
are often realized in such examples, which are sustained by
supramolecular interactions, including hydrogen bonds and
π−π interactions, as well as the structural robustness of the
frameworks. Such studies are continuously populating a library
Subsequently, a few more six-coordinated discrete complexes
were reported to undergo spontaneous resolution upon
2
8−32
crystallization.
Lennartson and Håkansson and others
have even reported conglomerate crystallization in the case of
3
3−35
36,37
38
five,
eight,
and nine -coordinated discrete com-
39
plexes, although four -coordinated discrete chiral complexes
containing achiral constituents are scarce. The research group
Received: July 1, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b01934
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Article
of enantiopure molecules, including camphoric acid, mandelic
acid, cinchona alkaloids, ionic liquids, proline, 1-phenylethyl-
amine, propane-1,2-diol, and camphorsulfonic acid, which may
Scheme 2. Synthesis of a Discrete Chiral Complex from
Achiral Precursors
19
be considered as potential chiral inducers.
We have extensively explored β-oxodithioester, including
dithiocarbamate ligands, to stabilize their transition-metal
55−58
complexes and organometallic systems.
In the present
context, an achiral β-oxodithioester ligand has been used to
prepare new chiral discrete tetrahedral complexes exploiting
the phenomenon of spontaneous resolution and chirality
induction in a synergistic approach. Therefore, by applying
chirality induction in the process of spontaneous resolution, we
have successfully crystallized homochiral crystals of discrete
tetrahedral complexes comprised of an achiral β-oxodithioester
ligand with control over the preferential handedness (Scheme
Hence, it was concluded that the phenomenon of
spontaneous resolution is operational in the studied reaction.
This result propelled us to employ a chiral inducer in order to
get bulk homochirality in the product. To generalize the scope
of this study, we used two chiral inducers, viz., L-(+)- and D-
1
). To extend the generality of the phenomenon of chiral
Scheme 1. Synthesis of Discrete Chiral Complexes from
Achiral Precursors: (1) Rare Event of Spontaneous
Resolution (SR) Leading to a Mechanical Mixture of
Enantiomorphs; (2) Control over the Bulk Chirality of a
Spontaneously Resolving System Using Chirality Induction
(
−)-tartaric and mandelic acids (Schemes 2 and S1). Owing to
their good solubility in the solvent system in question and
economic viability, they were an ideal choice for a chiral
inducer. The addition of a chiral influencer resulted in the
formation of bulk homochiral products. The D-(−) and L-(+)
isomers of each of the chirality inducer molecules yielded bulk
(
CI) (Present Study)
Λ and Δ isomers of [Zn(L) ], respectively.
2
A complexation process similar to that discussed for batch
A was adopted to produce batches 1B, 1C, 1D, 1E, 1F, and
G, with the only difference being the addition of 0.5 mmol of
1
1
D-(−)-tartaric acid for batch 1B, L-(+)-tartaric acid for batch
1
C, D-(−)-mandelic acid for batch 1D, L-(+)- mandelic acid
for batch 1E, (±)-tartaric acid for batch 1F, and (±)-mandelic
acid for batch 1G. All of the batches were characterized
through NMR, UV, powder X-ray diffraction (PXRD), and CD
spectroscopy. Solids precipitated through batches 1A−1E were
recrystallized by slow evaporation of their DMF solutions.
Their solid-state structures were confirmed by SCXRD
crystallography. The PXRD patterns recorded for the
precipitated as well as recrystallized forms of samples 1A−1E
corroborate well with the PXRD pattern simulated from the
single-crystal data. This suggests that precipitated products and
their respective recrystallized forms are identical with each
other (Figure S1). The physical forms of the crystals in all
cases are indistinguishable.
induction in the synthesized zinc(II) complex, two different
chiral inducers, viz., (+)- and (−)-tartaric and mandelic acid
enantiomers, have been employed. To the best of our
knowledge, this is the first report of the preparation of discrete
chiral tetrahedral zinc(II) complexes by means of imposing
chirality induction in the process of spontaneous resolution.
General Procedures and Spectroscopy. In the IR
spectra, complex 1 displays bands at 1597, 1565, and 1028−
RESULTS AND DISCUSSION
In the present study, we first obtained an enantiomeric pair
−1
■
1029 cm
for the νCO, νCC, and νC−S vibrations,
respectively, diagnostic of the coordinated β-oxodithioester
5
5,56
1
(
Λ-1 and Δ-1) of the tetrahedral zinc(II) complex [Zn(L) ]
ligand.
In the H NMR spectra of the ligand L, the −OH
2
by reacting an achiral β-oxodithioester ligand, methyl-3-
hydroxy-3-phenyl-2-propenedithioate (L), and Zn(NO ) ·
protons at 15.08 ppm are absent in complexes 1A−1G because
of keto−enol tautomerism. The positions of the vinylic proton
in the free ligands at 6.94 ppm and the complex at 6.99−7.02
3
2
6
H O in a 2:1 ratio in a water−methanol solvent, followed
2
1
3
1
by the harvesting of pale-yellow needle-shaped crystals from a
dimethylformamide (DMF) solution. Circular dichroism (CD)
spectroscopy and single-crystal X-ray diffraction (SCXRD)
studies established that the reaction involves a spontaneous
resolution process and yields a conglomerate product, i.e., a
mechanical mixture of enantiomers Λ-1 and Δ-1 (Scheme 2).
Four samples from this batch, called 1A, were selected at
random and studied by X-ray crystallography (Table S1), and
it was established that there were two samples of each type,
ppm remain almost unchanged. The C{ H} NMR
resonances observed at 169.29 ppm for the −C−OH carbon
in the free ligands are not observed in the complexes because
of stabilization of the keto form. The vinylic carbon of the
ligands showed a chemical shift in the 107.93 ppm range, while
the corresponding vinylic carbon in the complexes at 108.78−
108.97 ppm displays a downfield shift in the range 1−2 ppm.
The −CS carbon located at 217.33 ppm in the free ligand is
upfield-shifted at 190.43−190.60 ppm in the complexes
indicating metal−ligand bonding. The −C−OH carbon
observed at 169.29 ppm in the ligand is located at 184.02−
1
A1 and 1A2 having the Λ-1 structure and 1A3 and 1A4
having the Δ-1 structure.
B
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1
84.32 ppm in the complex showing −CO oxygen
analysis. The FTIR spectrum of the recovered precipitate did
not show bands corresponding to DMSO coordination, which
rules out the occurrence of solvent−complex 1 coordination
(Figure S9). The recovered precipitate was further charac-
terized by PXRD (Figure S10). The signal-to-noise ratio
(SNR) and root-mean-square noise levels for the discussed CD
data sets are provided in Table S8. Solid-state CD spectra
(Figure S7) also exhibited mirror-related features for bulk
samples from 1B−1E. Dichroic signals in the range 377−401
nm were observed in the solid state.
5
5,56
coordination.
This indicates that the keto form of the β-
oxodithioester ligand is stabilized in these complexes, as
confirmed by the crystal structures vide infra, instead of the
more stable enolate form reported in the transition-metal
5
5,56
complex.
Optical Properties. Absorption and Emission Spectra.
The UV−vis absorption spectrum of complex 1 in a dimethyl
sulfoxide (DMSO) solution exhibited a prominent absorption
peak at 388 nm (inset Figure 1), whereas that in the solid state
Crystallography. Crystal Structure of 1. In order to verify
the results obtained using CD spectroscopy, eight crystals each
from batches 1B and 1C and five crystals each from batches
1
D and 1E were randomly picked and analyzed by the SCXRD
technique (Tables S2−S5). In fact, seven out of eight crystals
from batch 1B and four out five crystals from batch 1D showed
a Λ configuration, and the remaining one was an Δ isomer,
whereas all eight crystals from batch 1C and four crystals from
batch 1E showed a Δ configuration. The remaining single
crystal from batch 1E showed a Λ configuration. Overall, 30
crystal data sets with refined Flack parameter values in
corroboration with the solution and solid-state CD spectra of
the bulk products establish that the desired enantiomorph of
the title complex can be predominantly synthesized by
employing a suitable enantiomer of L-(+)- and D-(−)-tartaric
or mandelic acid as the chirality inducer. However, it should be
noted that several samples showed inversion twinning,
although this was not extensive because when all samples
were considered, the maximum value of the Flack parameter
was only 0.12(4). A reaction in the absence of a chirality
inducer results in a racemic mixture in solution and a
conglomerate in the solid state. The bulk purity of the powder
samples was established by the PXRD data, as presented in
Figure S1. The crystallization experiments in the presence of L-
(+)- and D-(−)-tartaric and mandelic acids were repeated and
found to be reproducible, as is evident from their CD and
PXRD analyses.
Figure 1. 200 pts Savitzky−Golay-filtered CD spectra of complex 1
−
4
obtained from batches 1A−1C in a 1.0 × 10 M DMSO solution
(
the solution-phase absorption spectrum is given in the inset).
appeared at 377 nm (inset in Figure S7) along with a broad
shoulder at ∼450 nm. In the emission spectra, complex 1
showed bands at 490 and 510 nm upon excitation at λ = 387
nm in the solid state (Figure S2), whereas emission bands at
4
42 and 465 nm were observed upon excitation at λ = 400 nm
−
4
in a 1.0 × 10 M DMSO solution, suggestive of an intraligand
energy-transfer process (Figure S3).
CD. As discussed above, our study of batch 1A, which was
obtained in the absence of a chirality-inducing agent, presented
negligible dichroic signals in the solution and solid-state CD
spectra of the bulk product from 1A, which showed that it
contained both isomers (Figure 1). Thus, the bulk product is
likely to be a racemic mixture in solution and a conglomerate
in the solid phase.
The CD spectra in a DMSO solution (Figures 1 and S4 and
S5) for 1B and 1C showed opposite dichroic signals in the
wavelength range 377−401 nm, which correspond to the
absorption maxima of the complex at 388 nm. Opposite CD
signals for 1B and 1C (Figure 1) indicate their enantiomorphic
nature, as revealed by single-crystal analyses. Similar mirror-
related CD spectra were also observed for batches 1D and 1E
The mononuclear enantiomorphic complexes Λ-1 and Δ-1
crystallize in the chiral space group C2, with an asymmetric
unit comprised of half an atom of zinc residing in a special
position with C2 symmetry and a complete β-oxodithioester
moiety. The geometry about the metal center is distorted
tetrahedral having O S coordination from the two chelating β-
2 2
oxodithioester ligands, as presented in Figure 2a. Here we
discuss dimensions from the 1A1 and 1A3 crystals as typical
representatives of the Λ-1 and Δ-1 structures, respectively.
The dihedral angles θ (Figure 2b) between planes confining
the two chelate rings around the metal center are 85.93(9)°
and 85.93(5)° in Λ-1 and Δ-1, respectively. The θ values upon
division by 90° provide τtet‑sq indices of ca. 0.955 in both cases,
(Figures S4 and S5). It is noteworthy that the nature of the CD
spectra remains the same for a given batch irrespective of its
precipitated or recrystallized form.
60,61
As observed for batch 1A, the solution-phase CD spectra of
the precipitates obtained from batches 1F and 1G also did not
exhibit significant dichroic signals (Figure S6). This obviously
suggests that the racemic forms of the chiral inducers could not
impart an enantiomeric preference to the final outcome of the
reaction because of compensation of their chirality, thus
reiterating the vital role played by enantiopure chiral inducers
in the adoption of a preferential homochirality in the bulk
products. The possibilities of coordination between DMSO
and complex 1 in the experimental solutions were explored by
indicative of a slight distortion in the tetrahedral geometry
of the complexes (Figure 2). The Zn−O and Zn−S distances
for Λ-1 are 1.961(4) and 2.276(15) Å, whereas those for Δ-1
are 1.960(2) and 2.2787(7) Å, respectively. The angles O11−
Zn−S15 and O11−Zn−S15$1 in complex Λ-1 are
101.34(12)° and 110.11(12)°, respectively, while those in
complex Δ-1 are 101.21(6)° and 110.21(6)°, respectively.
In the crystal lattice, each discrete [Zn(L) ] moiety is
2
anchored to four crystallographically and stereochemically
identical neighboring complexes via intermolecular C−H···O
hydrogen-bonding interactions sustained between the coordi-
nated oxygen and methyl hydrogen atoms, as presented in
59
Fourier transform infrared (FTIR) spectroscopy. Complex 1
was recovered as a precipitate from its DMSO solution by
using methanol as an antisolvent and subjected to FTIR
1
1
Figure 3a [Λ-1, C17···O11 (x − / , y − / , z) = 3.436(8) Å,
2
2
C
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Figure 2. (a) ORTEP drawings of Λ-1 and Δ-1 with an atom-
numbering scheme and 60% probability for thermal ellipsoids. (b)
Dihedral angle defined by two planes confining the chelate rings
around the central metal in Λ-1. (c) Depiction of the chirality
descriptors Λ and Δ for a tetrahedral ZnO S coordination
2
2
environment.
H17B···O11 = 2.49 Å; ∠C17−H17B···O11 = 163.3°; Δ-1,
1
1
C17···O11 ( / + x, / + y, z) = 3.470(4) Å, H17B···O11 =
2
2
2
.55 Å; ∠C17−H17B···O11 = 161.1°]. These intermolecular
hydrogen-bonding interactions form a 2D supramolecular
62
network with sql topology in the ab plane (Figures 3b and
S8). Moreover, the chelate rings of the studied complexes can
be interpreted as a segment of a helix or a screw along the 2-
fold rotational axis (Figure 3c). Such helical segments of
adjacent discrete complexes lying along the a axis mutually
complement each other by means of the aforementioned
intermolecular C17−H···O11 hydrogen-bonding interactions
to complete the homohelices running down the b axis, as
presented in Figures 3b,c and 4. Thus, M homohelices are
Figure 3. (a) Intermolecular C−H···O hydrogen-bonding interactions
anchor each Λ-[Zn(L) ] moiety to four surrounding homochiral
2
complexes. (b) Realization of M homohelices running along the b axis
in the 2D supramolecular hydrogen-bonded network of Λ-1. (c)
Schematic depiction of the mirror symmetric relationship of 2D
networks realized in the structures of Λ-1 and Δ-1.
realized in the hydrogen-bonded 2D networks of Λ-[Zn(L) ],
2
while the Δ enantiomer reveals P homohelices. The pitches of
these homohelices are 4.8371(7) and 4.8573(3) Å for Λ-1 and
Δ-1, respectively (Figures 3c). Therefore, the homochirality of
complexes Λ-1 and Δ-1 can be concomitantly ascribed to the
chiral configuration at the metal center and the realization of
supramolecular homohelices in stabilization of the crystal
lattice by C17−H···O11 hydrogen bonds and other weak
interactions (Figure 4). Representative crystal data and
refinement parameters and details of the bond distances and
hydrogen-bonding parameters for both enantiomers of batches
Pale-yellow needle-shaped crystals were obtained by slow evaporation
of the compound in a DMF solution within 2 weeks.
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
g, 88%. Mp: 200−205 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.55; H, 3.88; S, 26.21. IR
−
1
1
(
(
KBr, cm ): 1597 (νC−O), 1522 (ν
), 1028 (ν ). H NMR
CC
CS
500 MHz, DMSO-d ): δ 2.52 (s, 3H, −SCH ), 6.99 (s, 1H, 
6
3
1
3
1
CHC(S)−), 7.45−7.90 (m, 5H, C H ). C{ H} NMR (125 MHz,
6
5
DMSO-d ): δ 16.83 (−SCH ), 108.78 (CHC(S)−), 127.50,
6
3
1
28.66, 131.91, 139.99 (−C H ), 184.02 (CO−), 190.43 (−C
6
5
1
B−1E are presented in Tables S2−S7.
−1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
max
3
(
3.22 × 10 ). UV−vis (Nujol; λmax, nm): 377, 445.
EXPERIMENTAL SECTION
■
Batch 1B: Synthesis of Complex 1 as an Enantio-Rich Λ
The general details pertaining to the materials and methods and
instrumentation used are provided in the Supporting Information.
The syntheses of a protonated ligand and its potassium salt is similar
Enantiomer. To synthesize complex 1 as an enantio-rich Λ
enantiomer, 5 mL of a methanolic solution of D-(−)-tartaric acid
(0.075 g, 0.5 mmol) was added to a methanolic solution of the
55,56
to those in our previous work.
The relevant synthetic details and
potassium salt of the ligand KL (0.248 g, 1 mmol) and Zn(NO
3 2
) ·
characterization data are provided in sections S1−S3.
Synthesis and Characterization of Complex 1. Batch 1A:
Synthesis of Complex 1 as a Racemic Mixture/Conglomerate. To
6H O (0.148 g, 0.5 mmol), followed by the case of batch 1A. The
2
resulting reaction mixture was allowed to stir for 4 h. The yellow solid
thus obtained was filtered off, washed with methanol, and allowed to
dry in open air. Pale-yellow needle-shaped crystals were obtained by
slow evaporation of the DMF solution of compound within 2 weeks.
1
5 mL of a stirred methanol solution of potassium salt of the ligand
KL (0.248 g, 1 mmol) was added gradually 10 mL of a methanol−
water (80:20) solution of Zn(NO ) ·6H O (0.148 g, 0.5 mmol), and
Characterization Data. Empirical formula: [Zn(L) ].Yield: 0.43 g,
3
2
2
2
the resulting solution was further stirred for 4 h. The yellow solid thus
88%. Mp: 198−201 °C. Anal. Calcd for C H O S Zn (483.95): C,
2
0
18
2 4
formed was filtered off, washed with methanol, and dried in open air.
49.63; H, 3.75; S, 26.50. Found: C, 49.50; H, 3.90; S, 26.32. IR (KBr,
D
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−
1
), 1028 (ν ).1H NMR (500
3
(
KBr, cm ): 1597 (νC−O), 1520 (ν
CC
CS
MHz DMSO-d ): δ 2.53 (s, 3H, −SCH ), 6.99 (s, 1H, CHC(S)−),
6
1
3
1
7
1
1
[
1
.45−7.91 (m, 5H, C H ). C{ H} NMR (125 MHz, DMSO-d ): δ
6
5
6
6.79 (−SCH ), 108.78 (CHC(S)−), 127.48, 128.63, 131.87,
3
39.98 (-C H ), 184.00 (CO−), 190.43 (−CS). UV−vis
6
5
−
1
−1
4
DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310 (3.22 ×
max
3
0 ). UV−vis (Nujol; λmax, nm): 377, 445.
Batch 1E: Synthesis of Complex 1 as an Enantio-Rich Δ
Enantiomer. The synthesis procedure followed for batch 1E is the
same as that for batch 1B, with the only difference being that L-
(
(
+)-mandelic acid (0.076 g, 0.5 mmol) was used instead of D-
−)-tartaric acid.
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
g, 88%. Mp: 198−203 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.60; H, 3.86; S, 26.35. IR
−
1
1
(
KBr, cm ): 1597 (νC−O), 1531 (ν
), 1028 (ν ). H NMR (500
CC
CS
MHz, DMSO-d ): δ 2.55 (s, 3H, −SCH ), 7.02 (s, 1H, 
6
3
1
3
1
CHC(S)−), 7.48−7.93 (m, 5H, C H ). C{ H} NMR (125 MHz,
6
5
DMSO-d ): δ 17.11 (−SCH ), 109.10 (CHC(S)−), 127.80,
6
3
1
28.94, 132.19, 140.30 (−C H ), 184.32 (CO−), 190.76 (−C
6
5
−1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
max
3
(
3.22 × 10 ). UV−vis (Nujol; λmax, nm): 377, 445.
Batch 1F: Synthesis of 1 in the Presence of (±)-Tartaric Acid. A
total of 5 mL of a methanolic solution of (±)-tartaric acid (0.075 g,
0
.5 mmol) was added to the methanolic solution of the potassium salt
of the ligand KL (0.248 g, 1 mmol) and Zn(NO ) ·6H O (0.148 g,
3
2
2
0
.5 mmol). The resulting reaction mixture was allowed to stir for 4 h.
The yellow solid thus obtained was filtered off, washed with methanol,
and allowed to dry in open air.
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
g, 88%. Mp: 197−201 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
Figure 4. Hydrogen-bonding interactions in the crystal lattice of the
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.53; H, 3.87; S, 26.22. IR
enantiomorph Δ-[Zn(L) ] resulting in a 2D supramolecular square-
−1
1
2
(KBr, cm ): 1596 (νC−O), 1523 (ν
), 1029 (ν ). H NMR
CC
CS
lattice network in which the formation of P homohelices running
(
500 MHz, DMSO-d ): δ 2.55 (s, 3H, −SCH ), 7.02 (s, 1H, 
6
3
along the b axis is clearly evident. Notably, each discrete Δ-[Zn(L) ]
13
1
2
CHC(S)−), 7.48−7.94 (m, 5H, C H ). C{ H} NMR (125 MHz,
6 5
complex is anchored to four surrounding Δ-[Zn(L) ] complexes in
2
DMSO-d ): δ 17.36 (−SCH ), 109.33 (CHC(S)−), 128.03,
1
6 5
6
3
the crystal lattice via C−H···O hydrogen-bonding interactions. The
dimensions in the sample Δ-1 (=1A3) are C17−H···O11 = 2.55 Å,
29.19, 132.42, 140.53 (−C H ), 184.55 (CO−), 190.98 (−C
−
1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
max
3
∠C17−H17B···O11 = 161.1°, and C17···O11 = 3.470(4) Å.
(
3.22 × 10 ). UV−vis (Nujol; λmax, nm): 377, 445.
Batch 1G: Synthesis of 1 in the Presence of (±)-Mandelic Acid.
The synthesis was carried out following a procedure similar to that of
−
1
1
cm ): 1597 (νC−O), 1522 (ν
), 1028 (ν ). H NMR (500
CC
CS
1
F except that (±)-mandelic acid (0.076 g, 0.5 mmol) was used
MHz, DMSO-d ): δ 2.52 (s, 3H, −SCH ), 6.99 (s, 1H, 
6
3
instead of (±)-tartaric acid.
1
3
1
CHC(S)−), 7.45−7.91 (m, 5H, C H ). C{ H} NMR (125 MHz,
6
5
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
DMSO-d ): δ 16.83 (−SCH ), 108.80 (CHC(S)−), 127.50,
6
3
g, 88%. Mp: 198−202 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
1
28.66, 131.91, 139.99 (−C H ), 184.02 (CO−), 190.44 (−C
6
5
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.56; H, 3.84; S, 26.30. IR
−
1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
−1
1
max
(
(
KBr, cm ): 1597 (νC−O), 1523 (ν
), 1028 (ν ). H NMR
3
CC
CS
(
3.22 × 10 ), UV−vis (Nujol; λmax, nm): 377, 445.
500 MHz, DMSO-d ): δ 2.55 (s, 3H, −SCH ), 7.02 (s, 1H, 
6
3
Batch 1C: Synthesis of Complex 1 as an Enantio-Rich Δ
13
1
CHC(S)−), 7.48−7.94 (m, 5H, C H ). C{ H} NMR (125 MHz,
6
5
Enantiomer. The synthesis procedure followed for batch 1C is the
same as that for batch 1B, with the only difference being that L-
DMSO-d ): δ 17.36 (−SCH ), 109.34 (CHC(S)−), 128.03,
6
3
1
29.19, 132.43, 140.52 (−C H ), 184.56 (CO−), 190.98 (−C
6
5
(
(
+)-tartaric acid (0.075 g, 0.5 mmol) was used instead of D-
−
1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
max
−)-tartaric acid.
3
(
3.22 × 10 ). UV−vis (Nujol; λmax, nm): 377, 445.
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
g, 88%. Mp: 199−204 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.52; H, 3.85; S, 26.28. IR
CONCLUSION
■
−
1
1
(
KBr, cm ): 1597 (νC−O), 1523 (ν
), 1029 (ν ). H NMR (500
CC
CS
In summary, a spontaneously resolving discrete complex,
MHz, DMSO-d ): δ 2.55 (s, 3H, −SCH ), 7.02 (s, 1H, 
6
3
1
3
1
[Zn(L) ] (1), has been synthesized. The chirality of the
CHC(S)−), 7.48−7.93 (m, 5H, C H ). C{ H} NMR (125 MHz,
2
6
5
DMSO-d ): δ 17.00 (−SCH ), 108.97 (CHC(S)−), 127.68,
complex originates from asymmetric tetrahedral ZnO2S
coordination, which extends into the crystal lattice via C−
2
6
3
1
28.83, 132.08, 140.17 (−C H ), 184.32 (CO−), 190.60 (−C
6
5
−
1
−1
4
S). UV−vis [DMSO; λ , nm (ε, M cm )]: 388 (1.0 × 10 ), 310
H···O hydrogen-bonding interactions and manifests in the
prominent supramolecular homohelices. It may be suggested
here that the preferential chiral orientation around the metal
center can be attributed to hydrogen-bonding interactions
between the chiral inducer molecule and 1A in sync with the
phenomenon of spontaneous resolution. We have further
demonstrated that the bulk chirality of the otherwise racemic 1
can be governed by employing a suitable enantiomer of the
chirality inducer molecule. The D-(−) enantiomer of tartaric
max
3
(
3.22 × 10 ). UV−vis (Nujol; λmax, nm): 377, 445.
Batch 1D: Synthesis of Complex 1 as an Enantio-Rich Λ
Enantiomer. The synthesis procedure followed for batch 1D is the
same as that for batch 1B, with the only difference being that D-
(
−)-mandelic acid (0.076 g, 0.5 mmol) was used instead of D-
(−)-tartaric acid.
Characterization Data. Empirical formula: [Zn(L) ]. Yield: 0.43
2
g, 88%. Mp: 198−202 °C. Anal. Calcd for C H O S Zn (483.95):
2
0
18
2 4
C, 49.63; H, 3.75; S, 26.50. Found: C, 49.58; H, 3.83; S, 26.20. IR
E
DOI: 10.1021/acs.inorgchem.9b01934
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
acid predominantly induces the formation of Λ-1, whereas its
L-(+) enantiomer induces the formation of Δ-1. Repetition of
the results with L-(+) and D-(−)-mandelic acid in line with
those obtained with L-(+) and D-(−)-tartaric acid expands the
generality of the present work. These findings were
unambiguously established by 30 SCXRD data sets with
refined Flack parameters and CD spectroscopy. Our results
demonstrate the applicability of chirality induction, which is
prevalent in organic chemistry and recently in MOF chemistry,
to tetrahedral inorganic discrete complexes. The results have
offered a new and potential methodology to synthesize bulk
enantiopure zinc(II) complexes starting from achiral sub-
stances. In order to further generalize the discussed method-
ology, we are currently exploring different achiral metal
complexes and chiral substances as chirality inducer agents
to maneuver the handedness of spontaneously resolving
discrete complex systems.
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ASSOCIATED CONTENT
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(
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b01934.
(
(
General methods, synthesis protocols, crystal data,
supporting crystallographic figures, PXRD, photolumi-
nescence and CD plots, IR spectra, SNR values, and
details of selected bond lengths and angles for Λ-1 and
Δ-1 (PDF)
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octahedral stereogenic-at-metal complexes featuring chiral ligands.
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Corresponding Authors
E-mail: gunjan.raajput@gmail.com or gunjanrajput777@
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E-mail: nsinghbhu@gmail.com or nsingh@bhu.ac.in.
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ORCID
Metal−Organic Frameworks. Comprehensive Supramolecular Chemistry
Kamal Kumar Bisht: 0000-0003-0987-6765
Nanhai Singh: 0000-0003-1535-5018
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