89
Z. Kristallogr. NCS 223 (2008) 89-91 / DOI 10.1524/ncrs.2008.0039
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of hippurato-bis(2,2"-bipyridine)copper(II) nitrate
tetrahydrate, [Cu(C9H8NO3)(C10H8N2)2][NO3] · 4H2O
Ying Chen, Zhi-Fu Liu, Shang-Chao Du and Han-Lie Hong*
China University of Geoscience, Faculty of Material Science and Chemical Engineering, Wuhan, Hubei 430074, P. R. China
Received September 18, 2007, accepted and available on-line February 17, 2008; CCDC no. 1267/2185
Source of material
An aqueous solution (5 ml) of Cu(NO3)2 · 6H2O (0.299 g, 1.0 mmol)
was slowly added to a stirred solution of 2,2)-bipyridine (0.324 g,
2 mmol) and hippuric acid (0.179 g, 1.0 mmol) in 20 ml ethanol.
The mixture was further stirred for ca. 30 min at room temperature, and the pH was adjusted to 6-7 with 1 M NaOH solution. The
mixture was further stirred for another 2 hours, filtered, and the
resulting filtrate was allowed to stand at room temperature. Blue
prismatic crystals were obtained by slow evaporation after one
week (yield 45 % based on the initial Cu(NO3)2 · 6H2O input).
%
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Abstract
C29H32CuN6O10, triclinic, P1 (no. 2), a = 10.631(2) Å,
b = 10.712(2) Å, c = 14.732(2) Å, 4 = 91.471(2)°,
3 = 106.048(2)°, 2 = 106.186(2)°, V = 1538.7 Å3, Z = 2,
Rgt(F) = 0.053, wRref(F2) = 0.124, T = 173 K.
_____________
#/ "
* Correspondence author (e-mail: [email protected])
Discussion
The crystal structure of the title compound is composed of
[Cu(C9H8NO3)(C10H8N2)2]+ complex cations, nitrate anions,
and lattice water molecules. The Cu atom is five-coordinated
by one oxygen atoms of the hippurato (O1), and four nitrogen
atoms of two 2,2)-bipyridine ligands, forming a distorted trigonal bipyramidal polyhedron with the axial apexes occupied
by pyridyl nitrogen atoms (N2 and N4), from two distinct 2,2)bipyridine ligands (figure, top). There is a dihedral angle of
80.70° between the two crystallographically independent 2,2)bipyridine ligands. The Cu—O1 bond distance is 2.039(2) Å,
which is similar to the Cu—O bond length (2.0639(2) Å) in the
monomeric bipyridine-hippurato-copper(II) perchlorate hydrate
[Cu(C9H8NO3)(C10H8N2)2]ClO4 · 2H2O [1]. The Cu—N1 bond
distance (2.133(2) Å) is longer than the other Cu—N lengths
(ranging from 1.970(3) Å to 2.076(3) Å). The axial angle of
N2–Cu1–N4 (172.38(1)°) is slightly deviated from the ideal
value. As a result, CuN4O2 chromophore exhibits a slightly distorted trigonal bipyramidal configuration.
There exist significantly fruitful hydrogen-bonding interactions
in the crystal structure. The uncoordinated carboxylato O2 and
the carbonyl O3 of the hippurato group act as hydrogen bonds acceptors binding hydrogen atoms from O1w and O2w (figure,
top), and the nitrate group serves as a multifunctional hydrogen
acceptor binding hydrogen atoms from lattice water molecules.
Along the [001] direction, the nitrate groups and water molecules
are interlinked by intermolecular hydrogen-bonding interactions
into one-dimensional chains, with R64(12), R44(12), and S12(3)
motifs [2] (figure, middle). The [Cu(C9H8NO3)(C10H8N2)2]+
complex cations reside on the outside linked by the hydrogen
bonds. The resulting chains are held together by '-' stacking interactions between the 2,2)-bipyridine rings forming the threedimensional supramolecular structure, where the distance between the centroids of the pyridyl rings are 3.621 Å and 3.657 Å
for the N4-pyridine rings and N1-pyridine rings, respectively
(figure, bottom). The intermolecular hydrogen-bonding interactions and '-' stacking interactions play important roles in the
supramolecular assembly and contribute to stabilize the crystal
structure.
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90
[Cu(C9H8NO3)(C10H8N2)2][NO3] · 4H2O
Table 1. Data collection and handling.
Table 2. Continued.
Crystal:
Atom
Site
x
y
z
Uiso
H(10)
H(11)
H(12)
H(13)
H(14)
H(17)
H(18)
H(19)
H(20)
H(22A)
H(22B)
H(25)
H(26)
H(27)
H(28)
H(29)
H(1A)
H(1B)
H(2A)
H(2B)
H(3A)
H(3B)
H(4A)
H(4B)
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
0.9824
1.2184
1.3822
1.3940
1.2337
1.0720
0.9025
0.7554
0.7831
0.5616
0.5380
0.4796
0.4225
0.4228
0.4854
0.5493
0.7799
0.8121
0.9144
0.7917
1.1354
0.9955
0.5003
0.4023
1.2644
1.2639
1.3360
1.1976
0.9890
0.8006
0.6009
0.5687
0.7350
0.9980
0.9323
1.2785
1.4601
1.6294
1.6190
1.4399
1.3350
1.2712
1.4951
1.4061
1.5256
1.4405
1.0617
0.9271
0.6819
0.8355
0.9813
1.0995
1.0717
1.0331
0.9787
0.8239
0.7276
0.5920
0.6844
0.8007
0.8437
0.7491
0.6098
0.5690
0.8963
0.8281
0.6745
0.6111
0.8331
0.8270
0.8898
0.8547
0.062
0.062
0.074
0.073
0.062
0.063
0.072
0.068
0.060
0.060
0.060
0.067
0.076
0.078
0.087
0.075
0.110
0.057
0.144
0.111
0.144
0.076
0.069
0.127
Wavelength:
*:
Diffractometer, scan mode:
2%max:
N(hkl)measured, N(hkl)unique:
Criterion for Iobs, N(hkl)gt:
N(param)refined:
Programs:
blue prism,
size 0.12 × 0.33 × 0.34 mm
Mo K4 radiation (0.71073 Å)
7.77 cm−1
Bruker SMART APEX II CCD, 6
56.96°
11297, 6985
Iobs > 2 #(Iobs), 4172
416
SHELXS-97 [3], SHELXL-97 [4]
Table 2. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
y
z
Uiso
H(1)
H(2)
H(3)
H(4)
H(5)
H(7)
H(8)
H(9)
2i
2i
2i
2i
2i
2i
2i
2i
1.0748
1.1939
1.2880
1.2646
0.4956
1.2308
1.1854
1.0607
0.7293
0.6348
0.7483
0.9560
1.1106
1.1466
1.3476
1.4065
0.7351
0.6580
0.5476
0.5196
0.7306
0.5010
0.4882
0.5799
0.055
0.062
0.068
0.059
0.058
0.059
0.068
0.067
Table 3. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
y
z
U11
U22
U33
U12
Cu(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
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)
C(21)
C(22)
C(23)
C(24)
C(25)
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
2i
0.99053(4)
0.7897(2)
0.8097(2)
0.6250(3)
0.7177(4)
0.6394(3)
0.6771(4)
1.0967(2)
1.0583(2)
1.1318(2)
0.9438(2)
0.5405(3)
0.6773(3)
1.1135(3)
1.1841(3)
1.2397(3)
1.2256(3)
1.1534(3)
1.1312(3)
1.1797(3)
1.1530(4)
1.0797(4)
1.0336(3)
1.2219(3)
1.3196(4)
1.3256(4)
1.2321(3)
1.1358(3)
1.0290(3)
1.0132(4)
0.9124(4)
0.8261(4)
0.8439(3)
0.7410(3)
0.5869(3)
0.5647(3)
0.5201(3)
0.4819(3)
0.99655(4)
0.9628(2)
1.1142(2)
1.2424(2)
1.3984(4)
1.1963(4)
1.2733(4)
0.8931(2)
1.1238(2)
1.0875(2)
0.8612(2)
1.1192(3)
1.2893(4)
0.7756(3)
0.7186(3)
0.7858(4)
0.9082(3)
0.9597(3)
1.0894(3)
1.1718(3)
1.2904(3)
1.3249(3)
1.2400(3)
1.2068(3)
1.2503(4)
1.1695(4)
1.0463(3)
1.0089(3)
0.8804(3)
0.7852(3)
0.6680(4)
0.6489(3)
0.7476(3)
1.0346(3)
1.0127(3)
1.2298(4)
1.3404(3)
1.3479(3)
0.73638(3)
0.6612(2)
0.7739(2)
0.5866(2)
1.0206(3)
0.9826(3)
1.1227(3)
0.6745(2)
0.6531(2)
0.8649(2)
0.8196(2)
0.6880(2)
1.0421(3)
0.6904(2)
0.6450(2)
0.5806(3)
0.5636(2)
0.6120(2)
0.5999(2)
0.5380(2)
0.5305(2)
0.5842(3)
0.6447(2)
0.8838(2)
0.9703(3)
1.0398(3)
1.0236(2)
0.9345(2)
0.9092(2)
0.9696(2)
0.9380(3)
0.8470(3)
0.7902(3)
0.7026(2)
0.6622(2)
0.6482(2)
0.6794(2)
0.7617(3)
0.0430(2)
0.046(1)
0.050(1)
0.094(2)
0.150(4)
0.090(2)
0.117(3)
0.040(1)
0.044(2)
0.039(1)
0.041(1)
0.044(2)
0.056(2)
0.048(2)
0.050(2)
0.050(2)
0.043(2)
0.033(2)
0.035(2)
0.046(2)
0.057(2)
0.059(2)
0.062(2)
0.051(2)
0.052(2)
0.050(2)
0.056(2)
0.040(2)
0.044(2)
0.057(2)
0.075(3)
0.059(2)
0.052(2)
0.045(2)
0.038(2)
0.040(2)
0.041(2)
0.055(2)
0.0436(3)
0.055(1)
0.063(2)
0.075(2)
0.094(3)
0.121(3)
0.187(4)
0.044(2)
0.040(2)
0.043(2)
0.040(2)
0.055(2)
0.083(3)
0.050(2)
0.052(2)
0.069(3)
0.064(2)
0.044(2)
0.047(2)
0.058(2)
0.055(2)
0.040(2)
0.044(2)
0.053(2)
0.065(3)
0.082(3)
0.062(2)
0.047(2)
0.045(2)
0.063(2)
0.058(2)
0.042(2)
0.046(2)
0.044(2)
0.055(2)
0.061(2)
0.052(2)
0.054(2)
0.0380(2)
0.048(1)
0.054(2)
0.072(2)
0.171(4)
0.143(3)
0.069(2)
0.035(2)
0.039(2)
0.040(2)
0.039(2)
0.054(2)
0.071(3)
0.043(2)
0.055(2)
0.056(2)
0.041(2)
0.033(2)
0.028(2)
0.039(2)
0.044(2)
0.058(2)
0.052(2)
0.049(2)
0.053(2)
0.043(2)
0.039(2)
0.037(2)
0.036(2)
0.043(2)
0.061(3)
0.074(3)
0.052(2)
0.044(2)
0.059(2)
0.045(2)
0.048(2)
0.065(2)
0.0133(2)
0.022(1)
0.020(1)
0.033(2)
0.017(3)
0.022(2)
0.038(3)
0.015(1)
0.013(1)
0.011(1)
0.012(1)
0.019(1)
0.015(2)
0.019(2)
0.022(2)
0.025(2)
0.012(2)
0.007(1)
0.003(1)
0.007(2)
−0.000(2)
0.007(2)
0.019(2)
0.006(2)
0.001(2)
0.017(2)
0.024(2)
0.018(2)
0.021(2)
0.027(2)
0.031(2)
0.015(2)
0.014(2)
0.017(2)
0.015(2)
0.016(2)
0.018(2)
0.019(2)
U13
0.0138(2)
0.016(1)
0.005(1)
0.054(2)
0.050(3)
0.025(2)
0.027(2)
0.012(1)
0.012(1)
0.015(1)
0.016(1)
0.024(1)
0.014(2)
0.013(2)
0.015(2)
0.018(2)
0.016(2)
0.005(1)
0.003(1)
0.013(2)
0.009(2)
0.007(2)
0.018(2)
0.020(2)
0.010(2)
0.005(2)
0.012(2)
0.013(2)
0.018(2)
0.017(2)
0.029(2)
0.027(2)
0.014(2)
0.017(2)
0.015(2)
0.013(2)
0.012(2)
0.025(2)
U23
0.0095(2)
0.006(1)
−0.007(1)
0.021(2)
0.055(3)
−0.042(3)
0.023(3)
0.008(1)
0.005(1)
0.008(1)
0.007(1)
0.014(1)
−0.002(2)
0.011(2)
0.002(2)
−0.009(2)
0.003(2)
0.001(1)
0.004(1)
0.015(2)
0.017(2)
0.012(2)
0.011(2)
0.006(2)
−0.002(2)
−0.003(2)
0.009(2)
0.003(2)
0.009(1)
0.018(2)
0.030(2)
0.017(2)
0.002(2)
0.015(2)
0.002(2)
0.007(2)
0.011(2)
0.015(2)
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91
[Cu(C9H8NO3)(C10H8N2)2][NO3] · 4H2O
Table 3. Continued.
Atom
Site
x
y
z
U11
U22
U33
U12
U13
C(26)
C(27)
C(28)
C(29)
O(1w)
O(2w)
O(3w)
O(4w)
2i
2i
2i
2i
2i
2i
2i
2i
0.4473(4)
0.4479(4)
0.4851(4)
0.5219(4)
0.8242(3)
0.8527(3)
1.0515(3)
0.4330(3)
1.4555(4)
1.5561(4)
1.5502(4)
1.4429(4)
1.3531(2)
1.4851(3)
1.4818(3)
1.0097(3)
0.7868(3)
0.7312(3)
0.6492(3)
0.6249(3)
0.8524(2)
0.6163(2)
0.7943(2)
0.8417(2)
0.058(2)
0.056(2)
0.083(3)
0.073(3)
0.086(2)
0.092(2)
0.098(2)
0.100(2)
0.065(3)
0.057(3)
0.072(3)
0.074(3)
0.049(2)
0.077(2)
0.094(2)
0.102(2)
0.073(3)
0.081(3)
0.067(3)
0.050(2)
0.077(2)
0.108(3)
0.083(2)
0.065(2)
0.016(2)
0.026(2)
0.040(2)
0.038(2)
0.018(1)
0.017(2)
0.004(2)
0.018(2)
0.033(2)
0.008(2)
0.012(2)
0.017(2)
0.020(2)
0.031(2)
0.032(2)
0.029(2)
U23
−0.002(2)
0.004(2)
0.024(2)
0.018(2)
0.006(1)
0.035(2)
−0.006(2)
0.021(2)
References
1. Chen, F.-P.; Wang, X.-W.; Hu, B.; Chen, Y.; Chen, J.-Z.: Bis(2,2-bipyridine--2N,N)) (hippurato--O)-copper(II) perchlorate dihydrate. Acta
Crystallogr. E62 (2006) m3044-m3046.
2. Bernstein, J.; Davis, R. E.; Shimoni, L.; Chang, N.-L.: Hydrogen bonding:
Functionality and graph set analysis in crystals. Angew. Chem., Int. Ed. 34
(1995) 1555-1573.
3. Sheldrick, G. M.: Phase annealing in SHELX-90: direct methods for
larger structures. Acta Crystallogr. A46 (1990) 467-473.
4. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal
Structures. University of Göttingen, Germany 1997.
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