Yi et al.
59
Table 1. Structure determination summary for complex 1.
Empirical formula
Color and habit
Crystal size (mm)
Crystal system
Space group
a (A)
b (A)
c (A)
α (º)
β (º)
C26H32N2O10Zn
Yellow block
0.17×0.08×0.05
Triclinic
P1
7.8511(3)
8.9457(3)
10.5008(3)
74.749(3)
86.959(3)
70.118(4)
668.59(4)
1
γ (º)
V (Å3)
Z
Scheme 1. Reaction route.
Formula weight
d
Absorption coefficient(mm−1)
F(000)
Reflections measured
Index ranges of measured data
597.91
1.485
0.979
312
calcd. (gcm−3)
Elemental microanalyses of carbon, hydrogen, and nitro-
gen were performed on an Elementar Vario EL elemental
analyzer. 1H NMR spectra were measured on Bruker
Avance 400MHz instrument with dimethyl sulfoxide
(DMSO) as solvent. Photoluminescence measurements
were performed on a F97XP photoluminescence spectrom-
eter. Solid-state ultraviolet (UV)-vis reflectance spectros-
copy was carried out with a TU1901 UV-Vis spectrometer
equipped with an integrating sphere. A BaSO4 plate acted
as a 100% reflectance reference, on which the finely ground
powder was coated. TDDFT investigations were carried out
by means of the Gaussian 03 suite of program packages.
7434
−9<=h<=9,
−10<=k<=10,
−12<=l<=12
4174 (Rint=0.0198)
3972 (>2sigma(I))
0.910–0.952
Independent reflections
Observed reflection
Relative transmission factor
Parameter/restraints/data (obs.) 353/3/3972
Final R indices (obs.)
S
R1 =0.0354, wR2 =0.0909
1.115
0, 0
0.448, −0.542
Largest and mean Δ/σ
Δρ (max, min) (eÅ−3)
Preparation of HMCA
HMCA was prepared according to the following reaction
route (Scheme 1).
were mixed in a 25-mLTeflon-lined stainless steel autoclave.
The autoclave was heated to 200°C in an oven and kept there
for 3days and then allowed to cool. When the autoclave
reached room temperature, yellow block crystals were
obtained and used to collect the single-crystal X-ray data.
Yield 60% based on (CH3COO)2Zn·6H2O. IR peaks (KBr,
cm−1): 3434(s), 3338(vs), 3122(w), 2962(w), 2740(w), 2500
(s), 2018(w), 1656(m), 1608(s), 1580 (s), 1524(s), 1434(m),
1408(m), 1242(vs), 1158(m), 1019(s), 912(s), 870(s),
812(w), and 764(s); Anal. Calcd for C26H32N2O10Zn: C,
52.23; H, 5.39; N, 4.69; found: C, 52.32; H, 5.31; N, 4.68%.
Synthesis of isatin. Indigo (262g) and K2Cr2O7 (147g) were
added into H2O (500mL) and stirred. After cooling, K2Cr2O7
(147g), H2O (300mL) and dil. H2SO4 (500mL) were added and
kept stirring at 40°C and 45°C for 1.5h. Then, the mixture was
diluted with twice its volume of H2O, filtered off, dissolved with
a KOH solution, filtered again, acidified by HCl and refiltered.
Yield, 230g (⩾90%); m.p. 210°C; high-resolution mass spec-
trometry (HRMS) m/z electrospray ionization (ESI) calcd for
C8H5NO2 ([M+H]+)147.0320, found 147.0826.
Synthesis of HMCA. Isatin (1.0mol) and KOH (1.0mol) were
dissolved into a sufficient amount of water and filtered. The
filtrate and 1.0mol KOH were added into chloroacetone
(2.0mol), and hydrochloric acid was added dropwise to
adjust to pH=7, and the solution was then filtered. Yield
⩾95% and m.p. 225°C. IR peaks (KBr, cm−1): 3433(vs),
3125(w), 3043(w), 2869(w), 2499 (m), 2040(m), 1621(m),
1553 (s), 1500 (m), 1462(m), 1410(m), 1242(vs), 1160(m),
1014(w), 906(m), and 686(s); HRMS m/z (ESI) calcd for
C11H9NO3 ([M+H]+) 203.0582, found 203.0548; 1H NMR
(400MHz, DMSO) δ 9.15 (s, 1H), 7.93 (d, J=8.2Hz 1H),
7.64 (t, J=7.7Hz, 1H), 7.60–7.52 (m, 3H), 2.70 (s, 3H).
The melting points of isatin and HMCA are in reasona-
ble agreement with those reported in the literature.9
X-ray structural determination
The X-ray diffraction data were collected on a SuperNova
charge-coupled device (CCD) X-ray diffractometer with
a
carefully selected single crystal (dimensions of
0.17×0.08×0.05mm). The X-ray source was graphite
monochromated Mo-Kα radiation with λ=0.71073Å. The
reduction and empirical absorption correction of the diffraction
data were carried out with the CrystalClear software. The
crystal structure is solved by direct methods and the Siemens
SHELXTLTM V5 software10 and refined with a full-matrix
least-squares refinement on F2. All non-hydrogen atoms were
located on the difference Fourier maps with applied anisotropic
refinement. The hydrogen atoms were theoretically attached
to their parent atoms and included in the structural factor
calculations with assigned isotropic thermal parameters.11
Reflections measured were 7434; the final R=0.0354 for 353
parameters and 3972 observed reflections with I>2σ(I) and
wR=0.0909 (w=1/(σ2(Fo2)+(0.0536P)2+0.0977P), where
Preparation of complex 1
HMCA (1mmol, 203mg), (CH3COO)2Zn·6H2O (0.5mmol,
109mg), methanol (9.5mL) and distilled water (0.5mL)