Journal of Molecular Structure 475 (1999) 93103

Structure and conformation of (dibenzyldiaza-18-crown-6)-Nd(III) and Eu(III) thiocyanates: infrared spectroscopic and X-ray crystallographic studies
Muhammad Idiris Saleh a,*, Abdussalam Salhin a, Bahruddin Saad a, Hoong-Kun Fun b
b

School of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia Received 13 October 1997; revised 18 May 1998; accepted 18 May 1998

Abstract Dibenzyldiaza-18-crown-6 was utilised as a host to accommodate Nd(III) and Eu(III) metal ions together with thiocyanate as counter ion. The crystalline complexes formed were studied for their absorption in the infrared region and their crystalline structure by X-ray diffraction. The coordination of the metal ions to the counter ion and also to the donor atoms of the crown ether was clearly seen from the shift of the absorption band of the pure compound by up to nearly 15 cm 1. From these absorption it was found that each lanthanide ion was coordinated to six donor atoms (2 N and 4 O) from crown ether and three donor atoms, N from NCS . This nine coordination number complex was found to have the stoichiometry of 1:1:3 (crown ether:lanthanide; NCS ). This ratio was further conrmed by X-ray crystallographic method. The lanthanide thiocyanate salts existed as an isolated (separate) entity in the center of the macrocyclic cavity. The three N atoms surrounded the Ln cation in a nearly planar trigonal arrangement with Ln ion being slightly out of plane. The trigonal plane was perpendicular to and bisects the plane of the macrocycle. 1999 Elsevier Science B.V. All rights reserved. Keywords: X-ray crystallography; IR; Dibenzyldiaza-18-crown-6; Neodymium/Europium thiocyanate; Macrocycle

1. Introduction Interest in studying the cation-binding properties of crown ethers as host with guests of cations as well as anions seem never ending since the rst discovery of the crown ethers by Pedersen [1]. Crown ethers with nitrogen atoms incorporated in the ether link were of immense interest to several authors [28] as they offer a new dimension to both cation and anion complexation chemistry [8], due to the possession of both oxygen and nitrogen donor atoms. They are able
* Corresponding author.

to ligate a wider variety of cations than either the purely oxygen-containing or nitrogen-containing crowns. Due to the strong interaction between metal ions and the cyclic polyether complexing agents, it is often possible to isolate crystalline salts which contain the complexed cation as an integral part of the crystal. Several crystal structures of such complexes have been determined [1,9,10], and offered useful information about the structure of the complex and its interaction with the ions involved as well as the type of solvent for crystallization. This includes the crystal structure studies of barium ions with cryptands

0022-2860/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 00 22 - 28 6 0( 9 8) 0 04 8 9- X

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[10] and alkali metal ion complexes with benzo-15crown-5, dibenzo-18-crown-6 and dibenzo-30-crown10 [9]. Such an ability to isolate the cation from its counterion provides a real new dimension to metal solution chemistry [11]. Crown ethers and their derivatives are interesting ligands for the investigation of the coordination properties of lanthanide metal ions. Their ability to form stable complexes with Ln serves as a springboard to explore the coordination chemistry of these metal ions [12,13]. Synthesis of macrocyclic complexes of Ln in identical ligand frameworks is essential to understand the inuence of the structure and dynamics of the aza ligand framework on the stability as well as other physicochemical properties of these metal ions. The bonding in these complexes largely involves ion dipole interaction [13,14]. It was also well established that lanthanide elements were highly coordinated metal ions, and hence they might be expected to form stronger complexes with crown ethers. In addition, crown ethers containing mixed donor atoms such as aza-crown ethers have been synthesized both in solution and crystalline forms [12,1418]. Complexes of diaza-18-crown-6 (DA18C6) with both trivalent and divalent lanthanide-silylamides, Ln[DA18C6][N(SiMe 3) 2], Ln = Y, Ce[15], and diaza-15-crown-5 (DA15C5) with lanthanide (III) in anhydrous methanol and propylene carbonate using potentiometric methods have been reported [19]. Ternary complexes of lanthanide (III) elements (Eu, Yb, Lu) using thenoyltriuoroacetone (TTA) as extractant, [Ln(L)TTA], L = [diaza-15-crown-5]-diacetic acid (DAPDA) and mixed binary Ln(TTA) 3 and ternary [Ln(DAPDA)] complexes (Ln = Yb and Lu) have also been reported using solvent extraction techniques [20,21]. The dominant ratio of combination of these elements with 18-membered crown ethers and their derivatives was 1:1 [12,14].

In an earlier report [22] we recently investigated the molecular structure and conformation of (dibenzyldiaza-18-crown-6)-lanthanum (III) complex ([DD18C6]-La(III)). It is interesting to note that the use of conformational analysis by PM3-calculation showed that the bond distances of the ligand (DD18C6) are in agreement with X-raygenerated bond distances for the [DD18C6]La(III) complex, but the bond angles and the torsion angles differ, reecting the open structure of the free diazacrown compared with the highly constrained structure of the ligating atoms encircling the lanthanum ion. The same crown ether that will be complexed with Nd(III) and Eu(III) metal ions will be reported in the present work in order to observe any signicant trends by increasing the atomic number of the lanthanides. As will be seen later, differences in bond angles and torsion angles have been observed. As observed in the previous work [22], the cavity size of the studied ligand changes minimally across the opposite-facing oxygen atoms but decreases markedly across nitrogen upon coordination, demonstrating the highly exible nature of the diazacrown ethers.

2. Experimental 2.1. Preparation of the complexes To a solution of dibenzyldiaza-18-crown-6 (0.089 g, 0.01 mmol) in 20 ml warm mixture of acetonitrile and methanol (1:1), the respective lanthanide (III) nitrate (0.01 mmol) hexahydrate was added, followed by the addition of excess amount (1.0 g, 0.5 mmol) of potassium thiocyanate in 20 ml warm mixture of acetonitrile and methanol. The resulting solution was ltered immediately and on cooling yielded small shiny crystals (pale violet for Nd 3+ and yellowish for

Table 1 Some of the characteristics of the DD18C6 complexes with lanthanide (III) elements Complex C1 C2 C3 Formula La(SCN) 3C 26H 38N 2O 4 Nd(SCN) 3C 26H 38N 2O 4 Eu(SCN) 3C 26H 38N 2O 4 Calc mass(g/mol) 755.74 761.07 768.79 Melting point(C) 293 332 304 Colour White Pink Yellowish Yield (%) 18 10 13 Period of crystallization 7 days 7 days 7 days

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Eu 3+). Table 1 shows some of the characteristics of these products. 2.2. Infrared spectroscopy studies IR-spectra were recorded on a Perkin Elmer system 200-FTIR spectrophotometer in the range of 4000 450 cm 1 by the KBr pellet method [23]. 2.3. X-ray crystallography studies The X-ray crystallographic data were obtained from Siemens P4 diffractometer with graphite ) radiation. monochromated MoKa (l = 0.71073 A Data collection: XSCANS [24]. Cell renement: XSCANS. Data reduction: XSCANS. Program(s) used to rene the structure: SHELXL93. Molecular graphics: SHELXTL/PC. Software used to prepare the material for publication: SHELXL93. Geometrical calculation: PARST. 2.4. Thermogravimetric studies Thermogravimetric analyses were recorded on a Perkin Elmer TGA-7 series thermal analyzer (under nitrogen atmosphere). Melting points of the resulted complexes were recorded on a Gallenkamp melting point apparatus.

3. Results and discussion 3.1. FTIR studies The absorption of the complexes in the infrared region showed some characteristic bands of the ligand framework, thus bond formation between lanthanide (III) and DD18C6 is evidenced from the IR-spectra recorded. The ligand vibrational modes undergo substantial shifts and splittings upon complexation. These shifts, dened as n(sample) n(ligand) [25] were highly dependent on both the ligand and the kind of anion. A comparison between the IR spectra of the crown ether DD18C6 and its complexes with lanthanide metal ions (Fig. 1) offered evidence for the complexation of Ln(NCS) 3 with the crown ether. Upon complexation, several bands from the IR spectrum of the free ligand have been shifted and new bands were clearly observed on the IR spectra of the complexes. The IR-bands that undergo signicant changes upon complexation of the ligand with lanthanide metal ions is shown in Table 2. The absorption bands at 949, 950 and 951 cm 1 for the studied complexes (C1C3) are due to the presence of the coordinated thiocyanate groups [28,30,31]. The absorption bands at 496, 497 and 495 cm 1 correspond to out of the plane bending, containing the (NCS) groups [28,30,31]. These observed

Table 2 Characteristic IR absorptions (cm 1) of the lanthanide (III) thiocynate complexes of DD18C6 Complex Assignments Macrocycle n(OH) L (C1) (C2) (C3) 3446 b,s 3446 b 3446 b 3446 b n(CH) 3085 sh,s 30262853 sh 30252853 sh 30812853 sh d(CH) 1495/1375 s 14771345 s 1475/1440 s 1475/1342 s n(COC) 11181025 vs,b 11041026 s,sp 11071027 s,sp 11081028 s,sp n(CNC) 12511212 s 12551200 m,sp 1256200 m,sp 12561200 m,sp d(CH) (ring) 749702 vs,sp 734708 m,sp 734708 m,sp 735708 s,sp Coordinated thiocynate n(CyC)(ring) n(CN) 1602 m,sp 1635 vw 1635 vw 1601 vw 2044 vs 2050 vs 2048 vs n(CS) 949 m 950 m 951 m n(NCS) 496 vw 497 vw 495 vw

L = DD18C6, (C1 = La(NCS) 3 L, C2 = Nd(NCS) 3L and C3 = Eu(NCS) 3L), b = broad, m = medium, s = strong, w = weak, vw = very weak, sh = shoulder, sp = sharp, vs = very strong [2531].

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vibration frequencies of the lanthanide thiocyanate complexes are consistent with N-bonded NCS-anion [31]. The absorption bands occurring in the 749 and 1602 cm 1 in the free ligand are characteristics of

vibrational n(CH) and n(CyC) groups [32,33], respectively, indicating the presence of the benzyl groups (side-arm of the ligand). Upon complexation, these bands, however, are shifted by 15 cm 1 for La and

Fig. 1. IR-spectra (KBr pellets) of the 1:1 complex of [dibenzyldiaza-18-crown-6]-Ln(NCS) 3. Ln = La, Nd, Eu.

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Nd, and 14 cm 1 for Eu as a clear evidence for the change in the position of the benzyl groups which were attached to the main plane of the DD18C6 ligand after complexation with lanthanide thiocynate. From the above observations (Table 2), it can be deduced that the coordination number of each lanthanide ion in its complex with DD18C6 is 9. Each lanthanide ion is coordinated to 6 donor atoms (2 nitrogen + 4 oxygen) on the DD18C6 cavity and to 3 monodentate (NCS) groups. Therefore, the suggested combination ratio between DD18C6, Ln and (NCS) anion is 1:1:3 (ligand: Ln: (NCS) ). This coordination number (9), is considered quite common among molecular complexes of lanthanide ions [34]. 3.2. Thermal analysis Thermogravimetric analysis shows that the lanthanide (III) complexes of DD18C6 exhibit high thermal stability. The thermal behaviour of these complexes are shown in Fig. 2. A single step decomposition of the ligand begins at around 200C, and maximum loss of weight of the ligand was recorded at about 340C, corresponding to the decomposition and combustion of the ligand. A further loss of 3.93% mass residue of the ligand

remaining occurs at 410C. Complete decomposition of the ligand was expected because of the organic nature of the compound [35]. The thermal analysis of the resulted complexes (C1C3) exhibited several decomposition steps, i.e., four for lanthanum, two for both neodymium and europium and three for dysprosmium complexes. Complexes lost most of their weight during the 330400C range, which included the decomposition range of the ligand (200358C) itself. These ndings indicated that the ligand remained intact with the metal ion up to this range of temperature, followed by the decomposition of the complex as well as the ligand itself. About 68.74%, 69.96% and 70.67% weight of the C1C3 complexes, respectively, were lost, corresponding to the loss of the thiocynate groups as well as two molecules of the diethanolamine derivative RN(CH 2CH 2OH) 2 compound (used as starting material for some of the aza-crown ether preparations [36]). These results seem to indicate that the decomposition of these complexes is highly dependent upon the type of the lanthanide element, even though, all of these complexes exhibited the same stoichiometry (i.e., 1:1; metal:ligand) as reected in the single crystal X-ray studies (Table 3).

Fig. 2a. Thermogram of the pure ligand DD18C6. Heating rate, 20C/min; sample weight, 3.95 mg; atmosphere, nitrogen.

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Fig. 2b. The thermogram of Ln(SCN) 3. DD18C6 complexes (a = La, b = Nd, c = Eu). Heating rate, 20C/min; sample weight, 4.91 mg each; in nitrogen atmosphere.

M. I. Saleh et al./Journal of Molecular Structure 475 (1999) 93103 Table 3 Crystal data and structure renement for Ln(SCN) 3. DD18C6(Ln = La, Nd and Eu) complexes Parameter Lanthanide metal ion La(Compound C1)* Empirical formula Temperature Wavelength Crystal system Space group Unit cell dimensions La(NCS) 3C 26H 38N 2O 4 293K 0.71073 A Monoclinic P2 1/c , a = 90 a = 15.5855(8) A , b = 94.188(4) b = 9.6801(5) A , g = 90 c = 21.8962(10) A 3 3294.6(3) A 4 1.524 mg m 3 1.527 mm 1 1536 0.14 0.43 0.50 mm 3 1.31 to 24.98 18 h 0, 11 k 0, 25 I 26 6027 5798 [R (int) = 0.0260] Full-matrix least-squares on F 2 5798/0/379 0.816 R 1 = 0.0403, wR 2 = 0.1057 R 1 = 0.0487, wR 2 = 0.1125 3 1.424 and 1.710e A Nd(Compound C2) Nd(NCS) 3C 26H 38N 2O 4 293K 0.71073 A Monoclinic P2 1/c , a = 90 a = 15.5610(4) A , b = 94.081(31) b = 9.6730(3) A , g = 90 c = 21.8770(10) A 3 3234.7(5) A 4 1.542 mg m 3 1.816 mm 1 1548 0.16 0.22 0.30 mm 3 1.86 to 27.56 1 h 20, 1 k 12, 28 I 28 9247 7466 [R (int) = 0.1088] Full-matrix least-squares on F 2 7466/0/369 0.876 R 1 = 0.0669, wR 2 = 0.1609 R 1 = 0.1424, wR 2 = 0.1902 3 1.968 and 1.469e A Eu(Compound C3) Eu(NCS) 3C 26H 38N 2O 4 293(2)K 0.71073 A Monoclinic P2 1/c , a = 90 a = 15.5220(10) A , b = 94.150(10) b = 9.6530(10) A , g = 90 c = 21.931(2) A 3 3277.4(5) A 4 1.558 mg m 3 2.146 mm 1 1560 0.22 0.40 0.94 mm 3 1.86 to 27.50 1 h 20, 1 k 12, 28 I 28 9323 7522 [R (int) = 0.0273] Full-matrix least-squares on F 2 7522/0/379 0.925 R 1 = 0.0327, wR 2 = 0.0743 R 1 = 0.0534, wR 2 = 0.0799 3 0.842 and 0.881e A

99

Volume Z Density (calculated) Absorption coefcient F(000) Crystal size v range for data collection Index ranges Reections collected Independent reections Renement method Data/restraints/parameters Goodness-of-t on F 2 Final R indices [l 2j(l)] R indices (all data) Largest diff. peak and hole *Reported in Ref. [22].

3.3. Structural studies The complexation reaction of crown ethers with lanthanide salts promotes interaction of the metal ion with the crown ether in solution [37]. However, these complexes are often very difcult to crystallize, as evidenced by the relatively few crystalline structures, determined in this system [14,15,38,39]. Single crystal diffraction studies showed that DD18C6 complexes with Ln(NCN) 3 are monoclinic (Table 3) with space group P2 1/c. The molecular geometry and the atomic labeling scheme for the three Ln(NCS) 3DD18C6 complexes are illustrated in Fig. 3 , Fig. 4, respectively. The atomic coordinates and selected bond distances and angles are given in Table 4Table 6. Bond distances and angles within each complex (Tables 5 and 6) are comparable to values that have been found in [DD18C6]La(NCS) 3 [22] and other aza-crown ether structures [15,40].

Fig. 3. The molecular structure of Nd(SCN) 3. DD18C6 complex showing Nd 3+ coordinations.

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The lanthanide thiocyanate salts existed as an isolated (individual) entity in the center of the hole of the macrocycle. The three thiocyanate nitrogen atoms surrounded the Ln cation (Ln = Nd, Eu) in a nearly

planar trigonal arrangement with the Ln ion being slightly out-of-plane (some of 358.5 and 358.6 for NLnN angle around Nd and Eu, respectively) and with an equal distribution NLnN bond angles

Table 4 Atomic coordination ( 10 4) of the dibenzyldiaza-18-crown-6 (DD18C6) complexes with lanthanide thiocynates (Nd, Eu) Atom Complex [Ln(SCN) 3DD18C6] Nd X Ln S(1) S(2) S(3) O(1) O(2) O(3) O(4) N(1) N(2) N(3) N(4) N(5) 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) C(26) C(27) C(28) C(29) 2260(1) 5434(2) 268(2) 1909(3) 1284(4) 706(4) 2674(4) 3193(4) 3707(6) 1183(6) 2303(6) 3064(5) 1896(5) 4848(7) 5195(8) 4977(10) 4449(8) 4092(7) 4280(6) 3845(7) 2441(6) 1574(7) 363(6) 121(7) 516(7) 937(6) 2281(6) 2104(6) 1414(7) 1222(7) 1745(9) 2425(8) 2606(8) 2241(7) 2158(8) 2859(8) 3519(7) 3734(6) 3278(6) 4440(7) 577(6) 2144(6) Y 2924(1) 2823(1) 6344(4) 2099(4) 3191(8) 1907(7) 4053(7) 5099(7) 2079(7) 4784(11) 659(10) 3430(8) 1380(9) 3691(14) 3785(17) 2785(22) 1720(17) 1655(13) 2612(11) 2531(11) 3098(13) 3711(14) 3046(14) 1790(12) 839(11) 1280(11) 38(11) 1018(10) 1947(11) 2877(13) 2892(13) 2037(14) 1100(13) 2101(12) 3643(12) 5485(11) 5689(12) 5406(11) 4939(10) 2380(11) 5461(11) 501(12) Z 3389(1) 3531(2) 3987(2) 2735(3) 2544(3) 3534(3) 4388(3) 3310(3) 3602(4) 3714(4) 2884(4) 2242(4) 4439(4) 1293(6) 710(6) 283(7) 450(7) 1038(6) 1484(5) 2121(5) 1787(4) 1939(5) 2633(5) 3002(6) 3977(5) 4552(5) 4391(5) 4920(5) 4901(6) 5376(5) 5856(5) 5886(5) 5412(6) 4973(4) 4945(4) 4354(5) 3837(5) 2778(4) 2230(5) 3589(5) 3821(5) 2793(5) Eu X 2241(1) 5411(1) 260(1) 1946(1) 1272(2) 690(2) 2659(2) 3160(2) 3660(2) 1201(2) 2262(2) 3049(2) 1888(2) 4836(3) 5183(3) 4994(4) 4464(4) 4089(3) 4263(3) 3843(3) 2433(3) 1560(3) 346(2) 199(3) 515(2) 937(2) 2284(3) 2106(2) 1418(3) 1241(3) 1759(3) 2455(3) 2630(3) 2235(3) 2148(3) 2842(3) 3496(3) 3717(3) 3266(3) 4392(3) 595(3) 2153(3) Y 2946(1) 2756(2) 6347(1) 2056(1) 3224(3) 1946(3) 4060(3) 5095(3) 2127(4) 4785(4) 700(3) 3404(3) 1386(3) 3632(5) 3825(7) 2786(8) 1706(7) 1612(6) 2589(4) 2520(4) 3076(5) 3694(5) 3089(5) 1810(5) 869(4) 1285(4) 36(4) 1016(4) 1923(4) 2858(4) 2902(5) 2009(5) 1075(4) 2111(4) 3664(4) 5507(4) 5710(4) 5378(4) 4897(4) 3271(4) 5451(4) 721(4) Z 3386(1) 3540(1) 3990(1) 2692(1) 2526(1) 3540(1) 4377(1) 3291(1) 3602(2) 3686(2) 2905(2) 2249(1) 4439(1) 1307(2) 712(2) 294(2) 454(2) 1053(2) 1478(2) 2129(2) 1782(2) 1935(2) 2642(2) 3012(2) 3977(2) 4544(2) 4373(2) 4907(2) 4903(2) 5372(2) 5858(2) 5866(2) 5389(2) 4964(2) 4921(2) 4345(2) 3819(2) 2752(2) 2217(2) 3584(2) 3811(2) 2793(2)

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(Table 6). The trigonal plane is perpendicular to, and bisects the plane of macrocyclic, indicating the presence of C 2 symmetry [22]. However, as in the case of the [DD18C6]La(NCS) 3 complex, the bonding around Nd 3+ and Eu 3+ is also made up of a primary coordination of the three thiocyanate N atoms and a secondary coordination of the two N atoms and four O atoms of the macrocyle. A nonahedral environment was also observed in each of the studied complexes. The primary bond distances LnN (LnyNd, Eu)

for Nd range from 2.4492.522 and 2.4112.457 A and Eu, respectively, while the secondary LnN bond distances are considerably longer, ranging from 2.767 for Nd and Eu, respectively, 2.769 and 2.7462.777 A and 2.7872.814 A for the compared to 2.5192.577 A primary and secondary bonds in the [DD18CB]La(NCS) 3 complex [22], respectively. However, the primary distance of each thiocyanate group (LnN1, LnN2 and LnN3) decreased as the ionic radius of the lanthanide metal ions (La, Nd, Eu)

Table 5 Comparison of selected angles () of DD18C6 complexes with Ln (La, Nd and Eu) Bond Angle () La* N(3)LnN(1) N(3)LnN(2) N(1)LnN(2) N(3)LnO(1) N(1)LnO(1) N(2)LnO(1) N(3)LnO(4) N(1)LnO(4) N(2)LnO(4) O(1)LnO(4) N(3)LnO(3) N(1)LnO(3) N(2)LnO(3) O(1)LnO(3) O(4)LnO(3) N(3)LnO(2) N(1)LnO(2) N(2)LnO(2) O(1)LnO(2) O(4)LnO(2) O(3)LnO(2) N(3)LnN(4) N(1)LnN(4) N(2)LnN(4) O(1)LnN(4) O(4)LnN(4) O(3)LnN(4) O(2)LnN(4) N(3)LnN(5) N(1)LnN(5) N(2)LnN(5) O(1)LnN(5) O(4)LnN(5) O(3)LnN(5) O(2)LnN(5) N(4)LnN(5) *Reported in Ref. [22]. 78.4(1) 139.8(1) 140.5(1) 74.5(1) 141.9(1) 73.9(1) 134.4(1) 76.5(1) 77.8(1) 104.4(1) 139.8(1) 71.1(1) 70.5(1) 143.8(1) 61.2(9) 74.3(1) 134.7(1) 68.9(1) 62.3(8) 146.2(9) 109.8(9) 76.4(1) 84.4(1) 110.1(1) 63.9(9) 63.5(9) 124.5(9) 122.2(9) 85.4(1) 79.0(1) 92.3(1) 125.5(9) 124.3(9) 63.4(9) 63.9(9) 157.5(1) Nd 78.2(3) 139.4(3) 140.9(3) 75.4(3) 140.9(3) 73.9(3) 135.1(3) 76.3(3) 78.2(3) 103.4(2) 139.8(3) 72.0(3) 70.0(3) 143.2(2) 62.1(2) 73.3(3) 134.5(3) 69.1(3) 62.2(2) 146.7(2) 110.0(2) 75.6(3) 82.7(3) 112.2(3) 63.2(2) 65.0(2) 125.1(2) 122.1(2) 83.8(3) 78.4(3) 93.2(3) 125.9(2) 125.5(2) 64.4(2) 64.1(2) 154.5(2) Eu 78.9(12) 139.0(12) 140.7(11) 75.9(11) 141.8(10) 72.9(11) 135.7(10) 76.5(10) 77.5(10) 102.5(9) 139.1(10) 71.3(10) 70.8(10) 143.0(9) 63.0(8) 72.9(10) 134.7(10) 69.4(10) 62.4(8) 146.4(8) 109.7(8) 75.9(10) 82.4(10) 112.0(11) 63.8(9) 64.7(8) 125.4(8) 122.5(9) 82.6(10) 77.7(10) 94.8(11) 126.1(9) 126.3(8) 64.4(8) 64.2(8) 153.2(9)

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decreased. These observations are in agreement with the decrease in the angle (N4LnN5) on the complexes (La = 157.5, Nd = 154.5 and Eu = 153). The secondary LnO bond distances range from 2.577 to 2.645 for the [22], 2.546 to 2.602 and 2.511 to 2.593 A three complexes, respectively, and are much longer, compared with primary bonds, found in lanthanide oxy ) [22]. As reported earlier [22], halides (average 2.40 A these changes in the bond distances reected the weaker electronic interactions between the Ln(NCS) 3 moiety and the macrocycle, arising from stearic requirements. Similar observations have been made for the primary and secondary bond distances for similar complexes such as lanthanide silylamides [15] and lanthanide nitrate [41]. In contrast to these elongations, these bands were found to be shorter than that in the La(NO 3) 3Cis-Syn-Cis-isomer of similar ligand (dicyclohexano-18-crown-6), with LaO distances of 2.61 [42]. The thiocyanate ions are bent with the to 2.92 A LnNC bond angles ranging from 166.9 to 144.0 and 166 to 146.3 for Nd and Eu, respectively, compared to 139.8 to 166.7 for the [DD18C6]La(NCS) 3 complex [22]. The three thiocyanate groups are positioned as reported previously [22]. These ndings, therefore, predicted that as the ionic radius of the lanthanide metal ion decrease, the nitrogen donor atoms became closer to the metal ion, and the metal ion gets deeper into the cavity of the ligand. This phenomenon indicated that the smaller the Ln

Fig. 4. The molecular structure of Eu(SCN) 3. DD18C6 complex showing Eu 3+ coordinations.

metal ion, the better t in the cavity of the macrocycle and the more difcult for the anion to accompany the metal ion. In addition, the coordinating ability of the anion of the lanthanide salt can dramatically alter the stoichiometry of the complexes isolated by crystallization [42]. However, this factor may affect the stability of the complex. 4. Conclusion Differences in the IR spectra of the dibenzyldiaza18-crown-6 and its complexes with lanthanide metal

Table 6 ) for the Ln(SCN) 3DD18C6 complexes (Ln = La, Nd, Eu) Selected distances (A Bond Complex La* Ligand LnO(1) LnO(2) LnO(3) LnO(4) LNN(4) LNN(5) Thiocynate LnN(1) LnN(2) LnN(3) 2.578(3) 2.616(3) 2.645(3) 2.577(3) 2.787(3) 2.814(3) Nd 2.546(1) 2.602(2) 2.571(3) 2.550(4) 2.769(8) 2.767(8) Eu 2.511(3) 2.593(2) 2.551(2) 2.518(2) 2.746(3) 2.777(3)

2.548(4) 2.577(4) 2.519(4)

2.466(1) 2.522(2) 2.449(3)

2.418(3) 2.457(4) 2.411(3)

Estimated standard deviation in parentheses. *Ref. [22].

M. I. Saleh et al./Journal of Molecular Structure 475 (1999) 93103

103

ions offered clear evidence for the 1:1 complex of these elements with aza-crown ethers. The resulting complexes were found to be thermally stable. Crystal structure investigations showed that the complexes were monoclinic. The bond distances and angles observed were typical for such complexes. Thus, the smaller the ionic radii of the Ln ion, the better they are tted in the cavity of the crown ether, the less stable complex formed. The coordination number of the lanthanide metal ion in the studied complexes was found to be 9. Acknowledgements The authors would like to thank the Malaysian Government and Universiti Sains Malaysia for the research grant R&D no. 190-9609-3403. References
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