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Synthesis and structure of Mn(II) and Zn(II) complexes containing 1,10-phenanthroline unit
Journal of Molecular Structure 605 (2002) 117±122
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Synthesis and structure of Mn(II) and Zn(II) complexes containing 1,10-phenanthroline unit Tian-Fu Liu, Hua-Kuan Lin*, Shou-Rong Zhu, Zhong-Ming Wang, Hong-gen Wang, Hong-Wei Sun, Xue-Bing Leng, Yun-Ti Chen Department of Chemistry, Nankai University, Tianjin 300071, People's Republic of China Received 5 April 2001; accepted 8 June 2001
Abstract The Mn(II) and Zn(II) complexes of N,N 0 -diisopropyl-1,10-phenanthroline-2,9-dimethanamine have been synthesised, and the structure of the two complexes have been studied by X-ray crystallography. q 2002 Elsevier Science B.V. All rights reserved. Keywords: X-ray crystallography; Mn(II) and Zn(II) complexes; 1,10-phenanthroline unit
1. Introduction 1,10-phenanthroline and its derivatives have been extensively used as ligands in both analytical and preparative coordination chemistry [1]. This heteroaromatic moiety can provide a further binding site for metal cations. It is rigid, and provides two aromatic nitrogens whose unshared electron pairs are beautifully placed to act co-operatively in binding cations [2,3]. The p-electron de®ciency makes phenanthroline an excellent p-acceptor. Phenanthroline derivatives containing amine groups are potential ligands containing both soft and hard sites. Most of the works on phenanthroline derivatives have been prompted by the intense current interest in their catalytic, redox, and photoredox properties, biological activity, complexation activity and their novel supermolecular chemistry [4±9]. In order to extend the range of available chelating * Corresponding author. Fax: 186-22-23502458. E-mail address: [email protected] (H.-K. Lin).
heteroatomic phenanthroline-based ligand, we have reported the synthesised N,N 0 -diisopropyl-1,10phenanthroline-2,9-dimethanamine [10] and studied the acid catalysed dissociation of copper(II) complexes of the ligand [11]. In this paper, we report the synthesis and structure of Mn(II) and Zn(II) complexes of the ligand. 2. Experimental N,N 0 -diisopropyl-1,10-phenanthroline-2,9dimethanamine(L) was prepared as described previously [10]. All other chemicals were of GR Grade. 2.1. Instruments Elemental analyses were performed on a Perkin Elmer 240C elemental analyser. IR spectra were obtained as KBr discs on a Nicolet 170 SX FT-IR spectrophotometer.
0022-2860/02/$ - see front matter q 2002 Elsevier Science B.V. All rights reserved. PII: S 0022-286 0(01)00745-1
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T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Table 1 Crystal data and structure re®nement for a and b a C20H29Cl3MnN4O
b C40H54Cl8N8OZn3
Formula weight Temperature Wavelength Crystal system, space group Unit cell dimensions
502.76 298(2) K Ê 0.71073 A Monoclinic, P21 =n Ê a 14:436 3 A Ê b 10:802 2 A b 105:305 48 Ê c 16:675 3 A
1142.62 298(2) K Ê 0.71073 A Monoclinic, P21 =c Ê a 19:233 5 A Ê b 10:785 3 A b 94:170 58 Ê c 26:941 7 A
Volume Z, calculated density Absorption coef®cient F(000) Crystal size u range for data collection Limiting indices Re¯ections collected/unique Completeness to u 25:02 Absorption correction Maximum and minimum transmission Re®nement method Data/restraints/parameters Goodness-of-®t on F 2 Final R indices [I . 2s (I)] R indices (all data) Largest difference peak and hole
Ê3 2508.1(9) A 4, 1.331 Mg/m 3 0.863 mm 21 1044 0:30 £ 0:25 £ 0:20 mm 1.66±25.028 212 # h # 17; 212 # k # 12; 218 # l # 19 10230/4423 R int 0:0391 99.9% None 0.8463 and 0.7817
Ê 3 5574(2) A 4, 1.362 Mg/m 3 1.700 mm 21 2336 0:25 £ 0:15 £ 0:10 mm 2.42±25.038 222 # h # 22; 29 # k # 12; 230 # l # 32 22427/9734 R int 0:0617 98.9% None 0.8484 and 0.6759
Full-matrix least-squares on F 2 4423/0/265 1.085 R1 0:0521; wR2 0:1530 R1 0:0904; wR2 0:1839 Ê 23 0.757 and 20.387 e A
Full-matrix least-squares on F 2 9734/6/546 0.974 R1 0:0632; wR2 0:1503 R1 0:1330; wR2 0:1821 Ê 23 0.662 and 20.43 e A
Empirical formula
3. Synthesis
3.2. [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O
3.1. [HMnLCl2]´Cl´H2O
A solution of ZnCl2´4H2O (0.01 mmol) in water (5 cm 3) was slowly added to aqueous solution (5 cm3) containing L´3HCl (0.01 mmol). The pH was adjusted to 6 with 0.01 mol dm 23 NaOH, and the resulting solution was stirred for 1 h at room temperature. White crystals of the complex suitable for X-ray analysis were obtained by slow evaporation at room temperature. Yield: 7.3 mg (64%). Calculated for C40H54Cl8N8OZn3: C, 42.0; H, 4.7; N, 9.8%; found: C, 41.7; H, 4.5; N, 9.6. IR (KBr pellet cm21) 3535, 2985, 2832, 1607, 1569, 1538, 1505, 1465, 1443, 1431, 1352, 1148, 871, 635, 585.
A solution of MnCl2´4H2O (0.01 mmol) in water (5 cm 3) was slowly added to aqueous solution (5 cm 3) containing L´3HCl (0.01 mmol). The pH was adjusted to 6 with 0.01 mol dm 23 NaOH, and the resulting solution was stirred for 1 h at room temperature. Pale-yellow crystals of the complex suitable for X-ray analysis were obtained by slow evaporation at room temperature. Yield: 2.7 mg (53%). Calculated for C20H29Cl3MnN4O: C, 47.7; H, 5.7; N, 12.7%; found: C, 47.3; H, 5.9; N, 12.5%. IR (KBr pellet cm 21) 3404, 2975, 2680, 2426, 1619, 1593, 1569, 1504, 1471, 1426, 1375, 1144, 866, 651, 580.
4. X-ray crystallography Data sets for complexes [HMnLCl2]´HCl´H2O (a)
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
119
Table 2 Ê ) and angles (8) for a Bond lengths (A Mn(1)±N(3) Mn(1)±N(2) Mn(1)±Cl(1) N(3)±Mn(1)±Cl(1) N(4)±Mn(1)±Cl(1) N(3)±Mn(1)±Cl(2) N(3)±Mn(1)±N(4) Cl(2)±Mn(1)±N(2)
2.172(3) 2.396(4) 2.3508(14) 118.49(10) 103.43(11) 124.84(10) 74.31(14) 95.04(9)
Mn(1)±N(4) Mn(1)±Cl(2)
2.320(4) 2.3640(14)
N(3)±Mn(1)±N(2) N(4)±Mn(1)±N(2) Cl(1)±Mn(1)±N(2) N(4)±Mn(1)±Cl(2) Cl(1)±Mn(1)±Cl(2)
and [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O (b) were measured on a Bruker SMART 1000X diffractometer using graphite monochromated MoKa radiation l at 298(2) K. The structures were solved 0:71037 A using direct methods in shelxs-97 and re®ned using a full-matrix least-square procedure on F 2 in shelxl97. The details of the structure analysis are given in Table 1. The selected bond lengths and angles are presented in Table 2 for a and Table 3 for b, respectively. A total of 10230 Rint 0:0391 of a independent re¯ections collected by u 2 2v scan technique in the range 1:66 # u # 25:028 from which 4423 I . 2s I re¯ections and 22427 R int 0:0617 of b independent re¯ections collected by u 2 2v scan
72.01(13) 145.56(13) 98.72(9) 98.26(11) 116.39(6)
technique in the range 2:42 # u # 25:038 from which 9734 I . 2s I re¯ections were collected. (a) [HMnLCl2]´Cl´H2O: Crystals of this compound belong to the monoclinic family, space group P2 1 =n Z 4; and lattice constants a 14:436 3; b Ê , b 105:305 48. The 10:802 2; c 16:675 3 A ®nal agreement factors for 265 re®ned parameters, where ,R1 0:0521 (for 4423 re¯ections with I . 2s I and wR2 0:1839 (for all data). (b) [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O: Crystals of this compound belong to the monoclinic family, space group P2 1 =c Z 4; and lattice constants a Ê, 19:233 5; b 10:785 3; c 26:941 7 A b 94:170 58. Doubtful positions introduced with population parameters 0.5 were found in the ethylenic
Table 3 Ê ) and angles (8) for b. Bond lengths (A Zn(1)±N(3) Zn(1)±N(4) Zn(1)±Cl(1) Zn(1)±Cl(2) Zn(1)±N(2) N(3)±Zn(1)±N(4) N(3)±Zn(1)±Cl(1) N(4)±Zn(1)±Cl(1) N(3)±Zn(1)±Cl(2) N(4)±Zn(1)±Cl(2) Cl(1)±Zn(1)±Cl(2) N(3)±Zn(1)±N(2) N(4)±Zn(1)±N(2) Cl(1)±Zn(1)±N(2) Cl(2)±Zn(1)±N(2) Zn(3)±Cl(5) Zn(3)±Cl(6) Cl(5)±Zn(3)±Cl(6) Cl(5)±Zn(3)±Cl(7) Cl(6)±Zn(3)±Cl(7)
2.040(5) 2.182(6) 2.2296(18) 2.2641(19) 2.512(6) 80.1(2) 126.09(15) 102.37(17) 114.01(14) 104.38(16) 117.12(8) 72.7(2) 151.94(19) 88.58(13) 92.97(13) 2.257(3) 2.279(3) 113.05(9) 110.41(11) 104.02(11)
Zn(2)±N(6) Zn(2)±N(5) Zn(2)±Cl(3) Zn(2)±Cl(4) Zn(2)±N(7) N(6)±Zn(2)±N(5) N(6)±Zn(2)±Cl(3) N(5)±Zn(2)±Cl(3) N(6)±Zn(2)±Cl(4) N(5)±Zn(2)±Cl(4) Cl(3)±Zn(2)±Cl(4) N(6)±Zn(2)±N(7) N(5)±Zn(2)±N(7) Cl(3)±Zn(2)±N(7) Cl(4)±Zn(2)±N(7) Zn(3)±Cl(7) Zn(3)±Cl(8) Cl(5)±Zn(3)±Cl(8) Cl(6)±Zn(3)±Cl(8) Cl(7)±Zn(3)±Cl(8)
2.048(5) 2.194(7) 2.258(2) 2.263(2) 2.395(5) 78.0(2) 117.77(14) 100.0(2) 119.18(14) 100.8(2) 122.12(9) 74.63(19) 152.6(2) 92.43(14) 92.90(13) 2.280(2) 2.283(2) 106.64(10) 111.54(12) 111.27(8)
120
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 1. An ORTEP drawing of the [HMnLCl2]´Cl.
chains of the N-isopropyl for N(8), N(9), C(36), C(37), C(38), C(39), C(40) and C(41). All of the non-hydrogen atoms were anisotropically re®ned, except the carbon atoms and the nitrogen atoms in doubtful positions (N(8), N(9), C(36), C(37), C(38), C(39), C(40), and C(41)). The hydrogen atoms were introduced in calculated positions and their coordination re®ned in agreement with those of the linked atoms. The ®nal agreement factors for 546 re®ned parameters, where R1 0:0632 (for 9734 re¯ections with I . 2s I and wR2 0:1821 (for all data).
ions. It shows rather unsaturated co-ordination spheres. The co-ordination geometry can be described as a distorted trigonal bipyramidal arrangement. The N(2) and N(4) atoms are in `axial' [N(4)±Mn(1)±N(2) 145.56(13)8] and other atoms N(3), Cl(1), and Cl(2) in `equatorial' [N(3)±Mn(1)±Cl(1) 118.49(10)8 and N(3)±Mn(1)±Cl(2) 124.84(10)8]. The observed average Mn±N distances from 2.172(3) to Ê indicated that both the benzylic amine 2.396(4) A groups and heteroaromatic ones are very weakly bound to the metal. The uncoordinated nitrogen N(1) is protonated between Cl(3) and H 1 exist Ê. hydrogen bond, the distance being 2.31 A
5. Results and discussion
5.2. Crystal structure of b
5.1. Crystal structure of a
The crystal structure consists of [HZn(1)LCl2] 1 and [HZn(2)LCl2] 1 complex cations, [Zn(3)Cl4] 22 anions and water molecules. An ORTEP drawing of the complex is shown in Fig. 2. The Zn(1) and Zn(2) ions are ®ve-coordinated by the three nitrogen atoms of the ligands and two chloride ions. It also shows rather unsaturated co-ordination spheres. The
The crystal structure consists of [HMnLCl2] 1 complex cations, chloride anions and water molecules. An ORTEP drawing of the complex is shown in Fig. 1. The Mn(II) ion is ®ve-coordinated by the three nitrogen atoms of the ligand and two chloride
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 2. An ORTEP drawing of (a) [HZn(1)LCl2] 1 and (b) [HZn(2)LCl2] 1.
121
122
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 3. Packing diagram for complex b.
co-ordination geometry can be described as a distorted trigonal bipyramidal arrangement. The coordination environment (Fig. 3) of Zn(1) and Zn(2) are similar to that of Mn(1) of a. The Zn(1)±N and Ê , which Zn(2)±N distances are from 2.040 to 2.512 A is shorter than that of Mn±N. It indicates that the bond between Zn(1)±N and Zn(2)±N are stronger than Mn±N. But, the distance between Zn(1) and N(2) is Ê , which are more weakly coordinated. 2.512(6) A [ZnCl4] 22 anions are slight distorted tetrahedrons. It is to be noted that the ligand rigidity, imposed by the large heteroaromatic moiety, does not allow the simultaneous co-ordination of both benzylic nitrogens and heteroaromatic ones to the same metal ion [12]. Acknowledgements The support of the National Science Foundation of China (Project 29971018) and the National Key Laboratory of the Coordination Chemistry of Nanjing University is gratefully acknowledged.
References [1] J. Reedijk, in: G. Wilkinson, R.D. Gillard, J.A. McCleaverty (Eds.), Comprehensive Coordination Chemistry, vol. 2, Pergamon, Oxford, UK, 1987. [2] C. Bazzicalupi, A. Bencini, V. Fusi, C. Giorgi, P. Paoletti, B. Valtancoli, J. Chem. Soc., Dalton Trans. (1999) 393. [3] P.G. Sammes, G. Yahioglu, Chem. Rev. (1994) 328. [4] C.E.A. Palmer, D.R. McMillin, C. Kimaier, D. Holten, Inorg. Chem. 26 (1987) 3167. [5] S. Sakaki, G. Koga, K. Ohkubo, Inorg. Chem. 25 (1986) 2330. [6] P.G. Sammes, G. Uahioglu, Chem. Soc. Rev. 23 (1994) 327. [7] D.M. Walla, Q.Y. Zheng, K. Schilling, J. Am. Chem. Soc. 114 (1992) 6259. [8] S.S. Zhu, T.M. Swager, J. Am. Chem. Soc. 119 (1997) 12568. [9] D.J. CaÂrdenas, P. GavinÄa, J.-P. Sauvage, J. Am. Chem. Soc. 119 (1997) 2656. [10] G. Zhao, H. Sun, H. Lin, S. Zhu, X. Su, R. Chen, J. Bioinorg. Chem. 72 (1998) 173. [11] H. Sun, H. Lin, Z. Zhou, G. Zhao, S. Zhu, X. Su, R. Chen, Trans. Metal Chem. 25 (2000) 247. [12] C. Bazzicalupi, A. Benicini, S. Ciattini, C. Giorgi, A. Masotti, P. Paoletti, B. Valtancoli, N. Navon, D. Meyerstein, J. Chem. Soc., Dalton Trans. (2000) 2383.
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Synthesis and structure of Mn(II) and Zn(II) complexes containing 1,10-phenanthroline unit Tian-Fu Liu, Hua-Kuan Lin*, Shou-Rong Zhu, Zhong-Ming Wang, Hong-gen Wang, Hong-Wei Sun, Xue-Bing Leng, Yun-Ti Chen Department of Chemistry, Nankai University, Tianjin 300071, People's Republic of China Received 5 April 2001; accepted 8 June 2001
Abstract The Mn(II) and Zn(II) complexes of N,N 0 -diisopropyl-1,10-phenanthroline-2,9-dimethanamine have been synthesised, and the structure of the two complexes have been studied by X-ray crystallography. q 2002 Elsevier Science B.V. All rights reserved. Keywords: X-ray crystallography; Mn(II) and Zn(II) complexes; 1,10-phenanthroline unit
1. Introduction 1,10-phenanthroline and its derivatives have been extensively used as ligands in both analytical and preparative coordination chemistry [1]. This heteroaromatic moiety can provide a further binding site for metal cations. It is rigid, and provides two aromatic nitrogens whose unshared electron pairs are beautifully placed to act co-operatively in binding cations [2,3]. The p-electron de®ciency makes phenanthroline an excellent p-acceptor. Phenanthroline derivatives containing amine groups are potential ligands containing both soft and hard sites. Most of the works on phenanthroline derivatives have been prompted by the intense current interest in their catalytic, redox, and photoredox properties, biological activity, complexation activity and their novel supermolecular chemistry [4±9]. In order to extend the range of available chelating * Corresponding author. Fax: 186-22-23502458. E-mail address: [email protected] (H.-K. Lin).
heteroatomic phenanthroline-based ligand, we have reported the synthesised N,N 0 -diisopropyl-1,10phenanthroline-2,9-dimethanamine [10] and studied the acid catalysed dissociation of copper(II) complexes of the ligand [11]. In this paper, we report the synthesis and structure of Mn(II) and Zn(II) complexes of the ligand. 2. Experimental N,N 0 -diisopropyl-1,10-phenanthroline-2,9dimethanamine(L) was prepared as described previously [10]. All other chemicals were of GR Grade. 2.1. Instruments Elemental analyses were performed on a Perkin Elmer 240C elemental analyser. IR spectra were obtained as KBr discs on a Nicolet 170 SX FT-IR spectrophotometer.
0022-2860/02/$ - see front matter q 2002 Elsevier Science B.V. All rights reserved. PII: S 0022-286 0(01)00745-1
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T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Table 1 Crystal data and structure re®nement for a and b a C20H29Cl3MnN4O
b C40H54Cl8N8OZn3
Formula weight Temperature Wavelength Crystal system, space group Unit cell dimensions
502.76 298(2) K Ê 0.71073 A Monoclinic, P21 =n Ê a 14:436 3 A Ê b 10:802 2 A b 105:305 48 Ê c 16:675 3 A
1142.62 298(2) K Ê 0.71073 A Monoclinic, P21 =c Ê a 19:233 5 A Ê b 10:785 3 A b 94:170 58 Ê c 26:941 7 A
Volume Z, calculated density Absorption coef®cient F(000) Crystal size u range for data collection Limiting indices Re¯ections collected/unique Completeness to u 25:02 Absorption correction Maximum and minimum transmission Re®nement method Data/restraints/parameters Goodness-of-®t on F 2 Final R indices [I . 2s (I)] R indices (all data) Largest difference peak and hole
Ê3 2508.1(9) A 4, 1.331 Mg/m 3 0.863 mm 21 1044 0:30 £ 0:25 £ 0:20 mm 1.66±25.028 212 # h # 17; 212 # k # 12; 218 # l # 19 10230/4423 R int 0:0391 99.9% None 0.8463 and 0.7817
Ê 3 5574(2) A 4, 1.362 Mg/m 3 1.700 mm 21 2336 0:25 £ 0:15 £ 0:10 mm 2.42±25.038 222 # h # 22; 29 # k # 12; 230 # l # 32 22427/9734 R int 0:0617 98.9% None 0.8484 and 0.6759
Full-matrix least-squares on F 2 4423/0/265 1.085 R1 0:0521; wR2 0:1530 R1 0:0904; wR2 0:1839 Ê 23 0.757 and 20.387 e A
Full-matrix least-squares on F 2 9734/6/546 0.974 R1 0:0632; wR2 0:1503 R1 0:1330; wR2 0:1821 Ê 23 0.662 and 20.43 e A
Empirical formula
3. Synthesis
3.2. [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O
3.1. [HMnLCl2]´Cl´H2O
A solution of ZnCl2´4H2O (0.01 mmol) in water (5 cm 3) was slowly added to aqueous solution (5 cm3) containing L´3HCl (0.01 mmol). The pH was adjusted to 6 with 0.01 mol dm 23 NaOH, and the resulting solution was stirred for 1 h at room temperature. White crystals of the complex suitable for X-ray analysis were obtained by slow evaporation at room temperature. Yield: 7.3 mg (64%). Calculated for C40H54Cl8N8OZn3: C, 42.0; H, 4.7; N, 9.8%; found: C, 41.7; H, 4.5; N, 9.6. IR (KBr pellet cm21) 3535, 2985, 2832, 1607, 1569, 1538, 1505, 1465, 1443, 1431, 1352, 1148, 871, 635, 585.
A solution of MnCl2´4H2O (0.01 mmol) in water (5 cm 3) was slowly added to aqueous solution (5 cm 3) containing L´3HCl (0.01 mmol). The pH was adjusted to 6 with 0.01 mol dm 23 NaOH, and the resulting solution was stirred for 1 h at room temperature. Pale-yellow crystals of the complex suitable for X-ray analysis were obtained by slow evaporation at room temperature. Yield: 2.7 mg (53%). Calculated for C20H29Cl3MnN4O: C, 47.7; H, 5.7; N, 12.7%; found: C, 47.3; H, 5.9; N, 12.5%. IR (KBr pellet cm 21) 3404, 2975, 2680, 2426, 1619, 1593, 1569, 1504, 1471, 1426, 1375, 1144, 866, 651, 580.
4. X-ray crystallography Data sets for complexes [HMnLCl2]´HCl´H2O (a)
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
119
Table 2 Ê ) and angles (8) for a Bond lengths (A Mn(1)±N(3) Mn(1)±N(2) Mn(1)±Cl(1) N(3)±Mn(1)±Cl(1) N(4)±Mn(1)±Cl(1) N(3)±Mn(1)±Cl(2) N(3)±Mn(1)±N(4) Cl(2)±Mn(1)±N(2)
2.172(3) 2.396(4) 2.3508(14) 118.49(10) 103.43(11) 124.84(10) 74.31(14) 95.04(9)
Mn(1)±N(4) Mn(1)±Cl(2)
2.320(4) 2.3640(14)
N(3)±Mn(1)±N(2) N(4)±Mn(1)±N(2) Cl(1)±Mn(1)±N(2) N(4)±Mn(1)±Cl(2) Cl(1)±Mn(1)±Cl(2)
and [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O (b) were measured on a Bruker SMART 1000X diffractometer using graphite monochromated MoKa radiation l at 298(2) K. The structures were solved 0:71037 A using direct methods in shelxs-97 and re®ned using a full-matrix least-square procedure on F 2 in shelxl97. The details of the structure analysis are given in Table 1. The selected bond lengths and angles are presented in Table 2 for a and Table 3 for b, respectively. A total of 10230 Rint 0:0391 of a independent re¯ections collected by u 2 2v scan technique in the range 1:66 # u # 25:028 from which 4423 I . 2s I re¯ections and 22427 R int 0:0617 of b independent re¯ections collected by u 2 2v scan
72.01(13) 145.56(13) 98.72(9) 98.26(11) 116.39(6)
technique in the range 2:42 # u # 25:038 from which 9734 I . 2s I re¯ections were collected. (a) [HMnLCl2]´Cl´H2O: Crystals of this compound belong to the monoclinic family, space group P2 1 =n Z 4; and lattice constants a 14:436 3; b Ê , b 105:305 48. The 10:802 2; c 16:675 3 A ®nal agreement factors for 265 re®ned parameters, where ,R1 0:0521 (for 4423 re¯ections with I . 2s I and wR2 0:1839 (for all data). (b) [H2Zn2L2Cl4]´[ZnCl4]´Cl2´H2O: Crystals of this compound belong to the monoclinic family, space group P2 1 =c Z 4; and lattice constants a Ê, 19:233 5; b 10:785 3; c 26:941 7 A b 94:170 58. Doubtful positions introduced with population parameters 0.5 were found in the ethylenic
Table 3 Ê ) and angles (8) for b. Bond lengths (A Zn(1)±N(3) Zn(1)±N(4) Zn(1)±Cl(1) Zn(1)±Cl(2) Zn(1)±N(2) N(3)±Zn(1)±N(4) N(3)±Zn(1)±Cl(1) N(4)±Zn(1)±Cl(1) N(3)±Zn(1)±Cl(2) N(4)±Zn(1)±Cl(2) Cl(1)±Zn(1)±Cl(2) N(3)±Zn(1)±N(2) N(4)±Zn(1)±N(2) Cl(1)±Zn(1)±N(2) Cl(2)±Zn(1)±N(2) Zn(3)±Cl(5) Zn(3)±Cl(6) Cl(5)±Zn(3)±Cl(6) Cl(5)±Zn(3)±Cl(7) Cl(6)±Zn(3)±Cl(7)
2.040(5) 2.182(6) 2.2296(18) 2.2641(19) 2.512(6) 80.1(2) 126.09(15) 102.37(17) 114.01(14) 104.38(16) 117.12(8) 72.7(2) 151.94(19) 88.58(13) 92.97(13) 2.257(3) 2.279(3) 113.05(9) 110.41(11) 104.02(11)
Zn(2)±N(6) Zn(2)±N(5) Zn(2)±Cl(3) Zn(2)±Cl(4) Zn(2)±N(7) N(6)±Zn(2)±N(5) N(6)±Zn(2)±Cl(3) N(5)±Zn(2)±Cl(3) N(6)±Zn(2)±Cl(4) N(5)±Zn(2)±Cl(4) Cl(3)±Zn(2)±Cl(4) N(6)±Zn(2)±N(7) N(5)±Zn(2)±N(7) Cl(3)±Zn(2)±N(7) Cl(4)±Zn(2)±N(7) Zn(3)±Cl(7) Zn(3)±Cl(8) Cl(5)±Zn(3)±Cl(8) Cl(6)±Zn(3)±Cl(8) Cl(7)±Zn(3)±Cl(8)
2.048(5) 2.194(7) 2.258(2) 2.263(2) 2.395(5) 78.0(2) 117.77(14) 100.0(2) 119.18(14) 100.8(2) 122.12(9) 74.63(19) 152.6(2) 92.43(14) 92.90(13) 2.280(2) 2.283(2) 106.64(10) 111.54(12) 111.27(8)
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T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 1. An ORTEP drawing of the [HMnLCl2]´Cl.
chains of the N-isopropyl for N(8), N(9), C(36), C(37), C(38), C(39), C(40) and C(41). All of the non-hydrogen atoms were anisotropically re®ned, except the carbon atoms and the nitrogen atoms in doubtful positions (N(8), N(9), C(36), C(37), C(38), C(39), C(40), and C(41)). The hydrogen atoms were introduced in calculated positions and their coordination re®ned in agreement with those of the linked atoms. The ®nal agreement factors for 546 re®ned parameters, where R1 0:0632 (for 9734 re¯ections with I . 2s I and wR2 0:1821 (for all data).
ions. It shows rather unsaturated co-ordination spheres. The co-ordination geometry can be described as a distorted trigonal bipyramidal arrangement. The N(2) and N(4) atoms are in `axial' [N(4)±Mn(1)±N(2) 145.56(13)8] and other atoms N(3), Cl(1), and Cl(2) in `equatorial' [N(3)±Mn(1)±Cl(1) 118.49(10)8 and N(3)±Mn(1)±Cl(2) 124.84(10)8]. The observed average Mn±N distances from 2.172(3) to Ê indicated that both the benzylic amine 2.396(4) A groups and heteroaromatic ones are very weakly bound to the metal. The uncoordinated nitrogen N(1) is protonated between Cl(3) and H 1 exist Ê. hydrogen bond, the distance being 2.31 A
5. Results and discussion
5.2. Crystal structure of b
5.1. Crystal structure of a
The crystal structure consists of [HZn(1)LCl2] 1 and [HZn(2)LCl2] 1 complex cations, [Zn(3)Cl4] 22 anions and water molecules. An ORTEP drawing of the complex is shown in Fig. 2. The Zn(1) and Zn(2) ions are ®ve-coordinated by the three nitrogen atoms of the ligands and two chloride ions. It also shows rather unsaturated co-ordination spheres. The
The crystal structure consists of [HMnLCl2] 1 complex cations, chloride anions and water molecules. An ORTEP drawing of the complex is shown in Fig. 1. The Mn(II) ion is ®ve-coordinated by the three nitrogen atoms of the ligand and two chloride
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 2. An ORTEP drawing of (a) [HZn(1)LCl2] 1 and (b) [HZn(2)LCl2] 1.
121
122
T.-F. Liu et al. / Journal of Molecular Structure 605 (2002) 117±122
Fig. 3. Packing diagram for complex b.
co-ordination geometry can be described as a distorted trigonal bipyramidal arrangement. The coordination environment (Fig. 3) of Zn(1) and Zn(2) are similar to that of Mn(1) of a. The Zn(1)±N and Ê , which Zn(2)±N distances are from 2.040 to 2.512 A is shorter than that of Mn±N. It indicates that the bond between Zn(1)±N and Zn(2)±N are stronger than Mn±N. But, the distance between Zn(1) and N(2) is Ê , which are more weakly coordinated. 2.512(6) A [ZnCl4] 22 anions are slight distorted tetrahedrons. It is to be noted that the ligand rigidity, imposed by the large heteroaromatic moiety, does not allow the simultaneous co-ordination of both benzylic nitrogens and heteroaromatic ones to the same metal ion [12]. Acknowledgements The support of the National Science Foundation of China (Project 29971018) and the National Key Laboratory of the Coordination Chemistry of Nanjing University is gratefully acknowledged.
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