Z. Kristallogr. NCS 228 (2013) 57-58 / DOI 10.1524/ncrs.2013.0035
57
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of quininium-trichloro-zinc(II), ZnCl3(C20H25N2O2),
C20H25Cl3N2O2Zn
Jaeun KangI, Hoseop YunII and Junghwan Do*, I
I
II
Department of Chemistry, Konkuk University, Seoul 147-701, Republic of Korea
Division of Energy Systems Reseach and Department of Chemistry, Ajou University, Suwon 441-749, Republic of Korea
Received August 30, 2012, accepted October 24, 2012, available online January 18, 2013, CCDC no. 1267/3895
Experimental details
All the hydrogen atoms associated with the quininium cation
were placed geometrically and refined as riding. The Flack parameter was 0.00(3).
Abstract
C20H25Cl3N2O2Zn, orthorhombic, P212121 (no. 19),
a = 7.673(2) Å, b = 11.485(2) Å, c = 24.655(5) Å,
V = 2172.6 Å3, Z = 4, Rgt(F) = 0.0487, wRref(F2) = 0.1381,
T = 296 K.
Table 1. Data collection and handling.
Crystal:
Wavelength:
$:
Diffractometer, scan mode:
2#max:
N(hkl)measured, N(hkl)unique:
Criterion for Iobs, N(hkl)gt:
N(param)refined:
Programs:
colourless rods, size 0.12#0.13#0.29 mm
Mo K! radiation (0.71073 Å)
15.18 cm"1
Bruker P4, "
54.92°
21164, 4937
Iobs > 2 !(Iobs), 2756
258
SHELX [7]
Source of material
The title complex was synthesized from a mixture of ZnCl2
(0.123g, 0.90mmol), quinine (0.097g, 0.30 mmol) and ethanol
(1.0 ml), which was sealed in a Pyrex tube and heated to 100 °C
for 68 h, then cooled to room temperature at 10 °C/h. The solid
products were recovered by vacuum filtration and washed with
distilled water. Colourless rod-like crystals were obtained with
unidentified yellow powder. The product was stable in air. The
yield of the compound was about 48 % based on zinc. EDS analysis confirmed the presence of Zn and Cl.
_____________
Discussion
Cinchona alkaloids have been intensively studied due to their usages in antimalarial treatments and asymmetric synthesis as powerful chiral auxiliaries [1]. There are more than 30 Cinchona
alkaloids extracted from the Cinchona tree, and among them the
most important molecules are quinine, quinidine, cinchonine,
cinchonidine, and their threo epimers. Depending on the absolute
configurations of the Cinchona alkaloids, the biological activities
in the antimalarial action are different. This implies that the reaction of Cinchona alkloids and a metal cation in a potential receptor possibly hematin may have a big impact on antimalarial
actions. To understand this clearly, structural studies are required
and several trichlorocobalt(II) complexes of quinine, cinchonine,
quinidine, cinchonidine, epiquinine, epiquinidine, and
epidihydrocinchonine have been reported [2-5]. The crystal
structure of the title compound comprise a discrete
noncentrosymmetric mononuclear ZnCl3(Hquinine) molecule.
One crystallographically unique Zn atom is coordinated by one
nitrogen atom (d(Zn–N) = 2.087(6) Å) in a protonated quininium
cation and three chlorine atoms (d(Cu–Cl) = 2.246(2) Å, 2.250(2)
Å, 2.272(2) Å) in a tetrahedral geometry. This compound is a so
called, "zwitterion", where the positive charge is localized at the
protonated nitrogen atom of quinuclidine moiety and the negative
charge in the vicinity of three chlorine atoms. The absolute configuration of the diasteroisomer, quinine is S and R for C12 and
C11, respectively. A bond valence sum (BVS) calculation of Zn
gives a value of +1.97, indicating an oxidation state of +2 [6]. The
ZnCl3(Hquinine) molecules are weakly hydrogen bonded to each
other through D–H···Cl (D = C, N, O) in a complex arrangement.
Table 2. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
H(2)
H(2A)
H(1)
H(2B)
H(4)
H(5)
H(7A)
H(7B)
H(7C)
H(8)
H(11)
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
x
"0.1216
0.1278
0.1465
0.2735
0.3907
0.3613
0.0790
0.2113
0.2688
0.1656
0.0243
y
z
Uiso
0.3564
0.6237
0.2305
0.1548
0.4566
0.6531
0.8265
0.9259
0.8231
0.6325
0.5201
0.3623
0.4329
0.3363
0.2589
0.1507
0.1550
0.2812
0.2668
0.3046
0.3055
0.3574
0.3(1)
0.06(3)
0.063
0.067
0.066
0.072
0.084
0.084
0.084
0.056
0.053
* Correspondence author (e-mail: [email protected])
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58
C20H25Cl3N2O2Zn
Table 2. continued.
Atom
Site
H(12)
H(13A)
H(13B)
H(14)
H(15A)
H(15B)
H(16A)
4a
4a
4a
4a
4a
4a
4a
Table 2. continued.
x
0.3206
0.4032
0.2210
0.2666
"0.0235
0.0128
"0.1007
y
z
Uiso
Atom
Site
0.5004
0.3510
0.2919
0.3048
0.3400
0.4034
0.5086
0.3913
0.4374
0.4282
0.5225
0.4914
0.5467
0.4585
0.053
0.061
0.061
0.060
0.073
0.073
0.077
H(16B)
H(17A)
H(17B)
H(18)
H(19)
H(20A)
H(20B)
4a
4a
4a
4a
4a
4a
4a
x
"0.0306
0.2731
0.4077
0.2831
0.5890
0.5541
0.7305
y
z
Uiso
0.5741
0.6517
0.6015
0.4972
0.4362
0.4847
0.4483
0.5102
0.5110
0.4691
0.5618
0.5041
0.6121
0.5810
0.077
0.076
0.076
0.063
0.086
0.104
0.104
Table 3. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
Zn(1)
Cl(1)
Cl(2)
Cl(3)
O(1)
O(2)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
x
0.3378(1)
0.5654(3)
0.0763(3)
0.3639(3)
0.2555(8)
"0.0475(7)
0.3046(8)
0.156(1)
0.184(1)
0.257(1)
0.291(1)
0.344(1)
0.328(1)
0.260(1)
0.199(1)
0.209(1)
0.2234(9)
0.167(1)
0.0812(9)
0.218(1)
0.279(1)
0.237(1)
0.044(1)
"0.001(1)
0.303(1)
0.334(1)
0.525(1)
0.612(1)
y
z
U11
U22
U33
0.21558(8)
0.2854(2)
0.2549(2)
0.0233(2)
0.7795(5)
0.3667(5)
0.3008(5)
0.5571(5)
0.2804(7)
0.2349(7)
0.4200(6)
0.4907(7)
0.6076(7)
0.6610(7)
0.8441(7)
0.5963(6)
0.4728(6)
0.3984(6)
0.4461(7)
0.4678(6)
0.3611(7)
0.3759(7)
0.4015(8)
0.5173(8)
0.5841(7)
0.4795(7)
0.4572(9)
0.4640(9)
0.14590(3)
0.09879(8)
0.10670(8)
0.16141(9)
0.2274(2)
0.3858(2)
0.2200(2)
0.4509(2)
0.3089(3)
0.2614(3)
0.2250(3)
0.1817(3)
0.1844(3)
0.2311(3)
0.2738(3)
0.2747(3)
0.2726(3)
0.3149(2)
0.3662(3)
0.4094(3)
0.4419(3)
0.5026(3)
0.5085(4)
0.4825(3)
0.4894(3)
0.5264(3)
0.5347(4)
0.5803(5)
0.0531(5)
0.063(1)
0.055(1)
0.056(1)
0.091(4)
0.055(3)
0.055(4)
0.096(6)
0.076(5)
0.078(6)
0.050(5)
0.078(6)
0.089(6)
0.050(5)
0.064(6)
0.068(6)
0.044(4)
0.047(4)
0.050(4)
0.052(5)
0.067(6)
0.067(5)
0.066(6)
0.071(6)
0.104(8)
0.066(5)
0.057(6)
0.073(7)
0.0433(5)
0.058(1)
0.048(1)
0.047(1)
0.038(3)
0.055(4)
0.042(4)
0.036(4)
0.040(4)
0.044(5)
0.037(4)
0.045(5)
0.048(5)
0.032(4)
0.049(5)
0.033(4)
0.038(4)
0.041(4)
0.041(4)
0.039(5)
0.047(5)
0.038(5)
0.060(6)
0.073(7)
0.051(5)
0.049(5)
0.082(8)
0.078(8)
0.0442(4)
0.053(1)
0.060(1)
0.075(1)
0.057(3)
0.054(3)
0.041(3)
0.040(3)
0.042(4)
0.045(4)
0.041(4)
0.043(4)
0.044(4)
0.058(5)
0.055(5)
0.038(4)
0.034(4)
0.033(3)
0.042(4)
0.040(4)
0.039(4)
0.044(4)
0.057(5)
0.048(5)
0.036(4)
0.044(4)
0.076(6)
0.108(8)
Acknowledgments. This paper was supported by Konkuk University in 2010.
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U12
"0.0007(5)
"0.003(1)
"0.0018(9)
0.002(1)
0.003(3)
"0.009(3)
"0.001(3)
0.008(4)
0.001(5)
0.004(4)
0.001(3)
"0.004(5)
0.008(5)
0.002(4)
0.011(4)
0.000(4)
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0.000(4)
0.002(4)
"0.002(4)
"0.001(5)
0.012(5)
"0.013(5)
0.004(5)
"0.006(5)
0.012(6)
U13
0.0016(5)
0.012(1)
"0.005(1)
"0.001(1)
0.004(3)
0.006(3)
"0.006(3)
"0.005(4)
0.009(4)
"0.005(4)
0.003(3)
0.009(5)
0.013(5)
"0.002(4)
0.001(4)
0.009(4)
"0.002(3)
0.004(4)
0.004(3)
0.001(3)
"0.006(4)
0.001(4)
0.002(5)
0.021(5)
"0.012(5)
0.002(5)
0.000(5)
"0.017(7)
U23
"0.0035(4)
"0.002(1)
0.0007(9)
0.004(1)
0.004(3)
0.007(3)
0.002(3)
0.001(3)
0.001(4)
0.002(4)
"0.002(3)
"0.001(3)
"0.002(4)
0.000(4)
"0.003(4)
0.001(3)
"0.003(3)
0.000(3)
0.005(3)
"0.005(3)
"0.002(4)
0.008(4)
0.013(5)
0.005(5)
"0.003(4)
"0.001(4)
"0.013(6)
"0.007(6)
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