244
B. Ivanova, M. Spiteller / Polyhedron 30 (2011) 241–245
ꢀ
form orthorhombic Pnma complex and triclinic P1 complex salt
by the interaction with the ZnII-ion, respectively.
Acknowledgements
The authors are grateful to thank the Alexander von Humboldt
Foundation for the Fellowships, the DAAD for a grant within the
priority program ‘‘Stability Pact South-Eastern Europe’’ and the
DFG for grant SP 255/21-1.
Appendix A. Supplementary data
Fig. 3. UV–vis–NIR spectra of MA (red line), complexes (1) (black line) and (2) (blue
line). (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
CCDC 771414, 771415, 795569 and 795570 contain the supple-
mentary crystallographic data for AgI-complexes with DL-mandelic
and squaric acid, respectively. These data can be obtained free of
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
terminal ligand and is joined bidentatelly by O-atoms (Fig. 1). In
(4), the ligand acts bidentatelly by the N-heterocyclic and O-atoms.
Similar to (3), the interaction of the 3PyA with ZnII, leads to forma-
tion of the mononuclear complex (5). The ligand is joined by the
References
N
py-heterocyclic atom. Terminal Cl-ligands are found. The geome-
try of the ZnIICl2N2 chromophor is a distorted Td (Table 2). The (6)
[1] Y. Sun, J. Riggs, Int. Rev. Phys. Chem. 18 (1999) 43.
[2] S. Marder, J. Sohn, G. Strucky, Materials for Nonlinear Optics, Chemical
Perspectives, American Chemical Society, Washington, DC, 1991.
[3] H. Xu, Y. Song, X. Meng, H. Hou, M. Tang, Y. Fan, Chem. Phys. 359 (2009) 101.
[4] F. Würthner, G. Archetti, R. Schmidt, H. Kuball, Angew. Chem., Int. Ed. 47
(2008) 4529.
[5] G. Dalton, M. Cifuentes, S. Petrie, R. Stranger, M. Humphrey, M. Samoc, J. Am.
Chem. Soc. 129 (2007) 11882.
[6] H. Xu, Y. Song, X. Meng, H. Hou, M. Tang, Y. Fan, Angew. Chem., Int. Ed. 47
(2008) 4538.
[7] B. Coe, Jon A. McCleverty, T.J. Meyer (Eds.), Comprehensive Coordination
Chemistry II, vol. 9, Elsevier, Pergamon, Oxford, 2004, p. 621.
[8] B. Coe, Acc. Chem. Res. 39 (2006) 383.
[9] H. Hou, Y. Wei, Y. Song, L. Mi, M. Tang, L. Li, Y. Fan, Angew. Chem., Int. Ed. 44
(2005) 6067.
[10] Y. Niu, H. Zheng, H. Hou, X. Xin, Coord. Chem. Rev. 248 (2004) 169.
[11] J. Perry, K. Mansour, S. Marder, K. Perry, D. Alvarez, I. Choong, Opt. Lett. 19
(1994) 625.
[12] C. Zhang, Y. Song, B. Fung, Z. Xue, X. Xin, Chem. Commun. (2001) 843.
[13] J. Wu, Y. Song, E. Zhang, H. Hou, Y. Fan, Y. Zhu, Chem. Eur. J. 12 (2006) 5823.
[14] D. Dini, M. Hanack, H. Egelhaaf, J. Sancho-García, J. Cornil, J. Phys. Chem. B 109
(2005) 5425.
[15] X. Meng, Y. Liu, H. Hou, Y. Fan, Y. Zhu, Novel ZnII, Inorg. Chim. Acta 358 (2005)
3024.
[16] H. Han, Y. Song, H. Hou, Y. Fan, Y. Zhu, Dalton Trans. (2006) 1972.
[17] H. Zhang, D. Zelmon, L. Deng, H. Liu, B. Teo, J. Am. Chem. Soc. 123 (2001)
11300.
[18] C. Liu, X. Wang, Q. Gong, K. Tang, X. Jin, H. Yan, P. Cui, Adv. Mater. 13 (2001)
1687.
[19] R. Philip, G.R. Kumar, Phys. Rev. B 62 (2000) 13160.
[20] B. Koleva, T. Kolev, R. Seidel, M. Spiteller, H. Mayer-Figge, W. Sheldrick, J. Phys.
Chem. 113A (2009) 3088.
2ꢀ
contains 2A8H cations, ZnCl4 anion and solvent water, joined by
NH ꢁ ꢁ ꢁ Cl (3.285, 3.298 Å), OH ꢁ ꢁ ꢁ O (2.795, 2.786 Å) and NH ꢁ ꢁ ꢁ O
(2.855 Å), interactions (Fig. 1).
The MA shows the IR-bands at: 3450 (
m
OH, theor. 3560), within
C@O, theor.
3400–2300 region ( OH, COOH, theor. 3600), 1729 (
m
m
1728), 1495, 1445 (in-plane (i.p.) modes of the benzene ring);
759 (theor. 760), 730 (theor. 728) and 690 cmꢀ1 (theor. 688)
(out-of-plane (o.p.) bending vibrations), respectively. The (1) is
characterized with new bands at 1556 and 1397 cmꢀ1
, of
as
m
and msCOOꢀ vibrations (theor. 1690, 1515 cmꢀ1), indicating a
COOꢀ
bidentate manner of coordination [7], in accordance with the crys-
tallographic data. The (2) shows the typical for the Sq2ꢀ complexes
IR-bands about 1800, 1550 and 700 cmꢀ1 [7,30,38–41].
The complexation of AgI and ZnII with 3PyA leads to a higher fre-
quency shifting of the
m
C@O and i.p. vibrations as well as to a split-
ting of the o.p. modes (800–690 cmꢀ1). The
m
,
msNH and dNH
as
NH2
2
2
(3500–3000 and 1630 cmꢀ1) peaks of 2A8H in both complexes
(4) and (6) are weakly effected. The new bands in (6) at 3555
and 3483 cmꢀ1 belong to mOH vibration of the solvent molecules
(Fig. 2).
The electronic absorption spectra of (1) and (2) (Fig. 3), indicate
a transmission within the 207–1100 (1), and 367–1100 nm (2)
regions, respectively. The bands about 250 nm in (2) correspond
*
to perturbed n ?
p
transition of C@O (em = 1007 l molꢀ1 cmꢀ1
)
[23]. The electronic absorption spectra of (3)–(6) show a batho-
[21] B. Ivanova, M. Spiteller, J. Phys. Chem. A 114 (2010) 5099.
[22] M. Spassova, T. Kolev, I. Kanev, D. Jacquemin, B. Champagne, Theochem 528
(2000) 151.
[23] B.B. Ivanova, M. Spiteller, Cryst. Growth Des. 10 (2010) 2470.
[25] B. Ivanova, M. Spiteller, Spectrochim. Acta A, 2010, doi:10.1016/
*
chromic shifting of heterocyclics bands. The n ?
p
transition
of C@O in 3PyA (em = 915 l molꢀ1 cmꢀ1) is also perturbed about
3 nm.
[26] WO/1991/016657-Non-linear Optical Device, United States Patent 5352388.
[27] A. Weiss, E. Riegler, C. Robl, Z. Naturforsch. B: Chem. Sci. 41 (1986) 1329.
[28] S. Neeraj, M. Noy, C. Rao, A. Cheetham, Solid State Sci. 4 (2002) 1231.
[29] C. Robl, W. Kuhs, J. Solid State Chem. 75 (1988) 15.
[30] C. Robl, A. Weiss, Z. Anorg. Allg. Chem. 546 (1987) 161.
[31] L. Farrugia, J. Appl. Cryst. 30 (1997) 565.
[32] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
[33] R. Blessing, Acta Crystallogr., Sect. A 51 (1995) 33.
[34] A.L. Spek, J. Appl. Cryst. 36 (2003) 7.
[35] M. Frisch, G. Trucks, H. Schlegel, G. Scuseria, M. Robb, J. Cheeseman, V.
Zakrzewski, J. Montgomery Jr., R. Stratmann, J. Burant, S. Dapprich, J. Millam, A.
Daniels, K. Kudin, M. Strain, Ö. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi,
B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, S. Ochterski, G. Petersson, P.
Ayala, Q. Cui, K. Morokuma, P. Salvador, J. Dannenberg, D. Malick, A. Rabuck, K.
Raghavachari, J. Foresman, J. Cioslowski, J. Ortiz, A. Baboul, B. Stefanov, G. Liu,
A. Liashenko, P. Piskorz, I. Komáromi, R. Gomperts, R. Martin, D. Fox, T. Keith,
M. Al-Laham, C. Peng, A. Nanayakkara, M. Challacombe, P. Gill, B. Johnson, W.
4. Conclusions
Interaction of AgI with MA and H2Sq leads to formation of
AgI-complexes, crystalizing in P21/n and C2/c space groups. The
geometry of AgIO4AgI chromophor in the first case has unusual
for AgI-complexes distorted square pyramidal geometry, with OA-
gIO, OAgIAgI angles within 64.5(1)–135.1(6)° range. In the corre-
sponding squarate complex, each AgI-ion is five-coordinated,
forming square-pyramidal AgIO5 chromophor (AgI–O distances
within 2.317–2.613 Å and O–AgI–O angles within 82.9(3)–
92.2(9)° ranges). The AgI-complexes with 3PyA and 2A8H
crystalized non-centrosymmetrically in the C2 and Cc space
groups, indication NLO properties in the bulk. The same ligands