КООРДИНАЦИОННАЯ ХИМИЯ, 2015, том 41, № 4, с. 220-227
УДК 541.49
HYDROTHERMAL SYNTHESES, CRYSTAL STRUCTURES, AND MAGNETIC PROPERTIES OF THREE MANGANESE(II) COMPLEXES BASED ON 4-SUBSTITUTED 2,2':6',2M-TERPYRIDINE LIGANDS © 2015 W. W. Fu*, M. S. Chen, W. Li, Y. Liu, F. X. Zhang, and D. Z. Kuang
Key Laboratory of Functional Organometallic Materials of Hunan Province College, Department of Chemistry and Materials Science, Hengyang Normal University, Hengyang, 421008P.R. China *E-mail: w.w.fu@hotmail.com Received September 11, 2014
Three manganese coordination compounds, [Mn(Meophtpy)2] ■ 2ClO4 (Meophtpy = 4'-(4-methoxylphe-nyl)-2,2':6',2''-terpyridine) (I), [Mn(Ftpy)2](ClO4)2 (Ftpy = 4'-(2-furyl)-2,2':6',2''-terpyridine) (II) and [Mn(m-ClPhtpy)2] ■ 2ClO4 (m-ClPhtpy = 4'-(3-chlorophenyl)-2,2':6',2''-terpyridine) (III), have been synthesized by hydrothermal methods and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 945032 (I), 945033 (II), 945034 (III)). In most cases, the face-to-face interactions between pyridyl rings or phenyl rings facilitate the construction of 3D network in the crystal for all three complexes. The magnetic properties of three complexes have been investigated.
DOI: 10.7868/S0132344X15040027
INTRODUCTION
Coordination compounds based on 2,2':6',2''-terpy-ridine have been widely investigated for their diverse structures and potential applications in luminescence, magnetism, catalysis, biology and nonlinear optical properties [1—7]. Among these explorations, one of the most used strategy is to fine tune these properties by adjusting the substitution group on 4' position of 2,2':6',2''-terpyridine [1, 8—11]. Manganese(II) complexes have been well researched for magnetic properties [12—14]. Although many 2,2':6',2''-terpyridine coordinated manganese compounds have been researched [15—18], only a few of them have been investigated for their magnetic properties [4, 19, 20]. In order to test the influence of different substitutes on the crystal packing and magnetic properties, in this paper, three new manganese(II) complexes based on different 4'-substituted 2,2':6',2''-terpyridines have been synthesized and their magnetic properties have been studied. To the best of our knowledge, compounds constructed of 4'-(2-furyl)-2,2':6',2''-terpyridine (Ftpy) and 4'-(3-chlorophenyl) - 2, 2': 6', 2'' - terpyridine (m -ClPhtpy) were first been reported.
EXPERIMENTAL
Materials and methods. All reagents and solvents were commercially available and used as received. Elemental analyses were carried out on EA1110 CHNS-0 CE elemental analyzer. Fourier-transform infrared spectra (FT—IR) were recorded on a Shi-
madzu Prestige-21 FT—IR spectrometer using dry KBr pellets from 400—4000 cm-1. The temperature-dependent magnetic susceptibilities were measured with crystalline samples on a Quantum Design MPMS XL-5 Squid magnetometer in a magnetic field of1000 Oe from 2 to 300 K. Power X-ray diffraction (PXRD) measurements were performed on a Bruker D8 dif-fractometer operated at 40 kV and 40 mA using Cu^a radiation (X = 1.5418 A).
Synthesis of [Mn(Meophtpy)2] • 2ClO4 (I). Meophtpy (0.034 g, 0.1 mmol), MnSO4 ■ H2O (0.0085 g, 0.05 mmol) and NaClO4 (0.012 g, 0.1 mmol) were mixed in water (5 mL) and ethanol (5 mL) and sealed in a 16 mL Teflon-lined stainless steel vessel. After heating at 160°C for 72 h, the temperature was gradually dropped to room temperature. Brown block crystals were obtained, washed with water and dried in air.
For C44H34N6O10Cl2Mn
anal. calcd., %: Found, %:
C, 56.67; C, 56.53;
H, 3.67; H, 3.71;
N, 9.01. N, 8.95.
IR (KBr; v, cm-1): 3080 m, 2938 m, 2843 m, 2017 w, 1601 v.s, 1572 s, 1547 s, 1518 s, 1477 s, 1431 s, 1406 s, 1244 s, 1184 s, 1090 v.s, 1014 s, 885 m, 829 s, 791 s, 748 m, 729 m, 688 m, 658 m, 638 m, 623 s, 577 m, 523 m, 407 m.
Table 1. Crystal data and structure refinement parameters for I—IIII—IIIa
Parameter Value
I II III
Formula mass 932.61 870.50 941.44
Crystal system Monoclinic Triclinic Orthorhombic
Space group P2x/c P1 Pcca
a, A 18.1425(13) 10.4081(7) 24.6383(14)
b, A 15.2934(11) 11.3866(8) 10.8645(6)
c, A 16.2992(11) 16.0693(11) 14.9919(8)
a, deg 90 97.6000(10) 90
ß, deg 113.3580(10) 102.8290(10) 90
Y, deg 90 93.2150(10) 90
V, A3 4151.8(5) 1833.4(2) 4013.1(4)
Z 4 2 4
Pcalcd g/cm3 1.492 1.577 1.558
p., mm-1 0.515 0.579 0.659
F(000) 1916 890 1916
6, deg 1.81-25.01 1.31-28.32 1.65-25.01
Reflections collected/independed 23072/7318 13231/8973 43923/3536
Rint 0.0469 0.0144 0.0763
GOOF on F2 1.105 1.069 1.071
Parameters refined 564 523 296
R, wR2 (I> 2a(T))* 0.0509, 0.1663 0.0363, 0.0932 0.0518, 0.1255
R, wR2 (all data)* 0.0571, 0.1731 0.0457, 0.0976 0.0594, 0.1337
Largest diff. peak and hole, e/A3 1.557 and -1.016 0.482 and -0.604 0.656 and -0.524
* R = E(|[F0| - /CiiWoi, wR = [Sw(|ij|2 - FClV/EwF2)]1/2.
Synthesis of [Mn(Ftpy)2] • 2ClO4 (II) was similar to that of I except that Ftpy (0.030 g, 0.1 mmol) was used instead of Meophtpy.
For C38H28N6OnCl2Mn
anal. calcd., %: C, 52.43; H, 3.24; N, 9.65. Found: %: C, 52.04; H, 3.30; N, 9.57.
IR (KBr; v, cm-1): 3588 s, 3526 s, 3109 m, 3074 m, 1614 v.s, 1600 v.s, 1570 s, 1545 s, 187 s, 1475 s, 1458 s, 1431 s, 1383 m, 1304 w, 1252 m, 1230 m, 1090 v.s, 1014 v.s, 928 m, 883 m, 833 m, 793 s, 758 m, 744 s, 729 s, 685 m, 623 s, 584 m, 474 m, 447 m, 407 m.
Synthesis of [Mn(m-ClPhtpy)2] • 2ClO4 (III) was
similar to that of I except that m-ClPhtpy (0.034 g, 0.1 mmol) was used instead of Meophtpy.
For C42H28N6O8Cl4Mn
anal. calcd., %: C, 53.58; H, 3.00; N, 8.93. Found,%: C, 53.44; H, 2.97; N, 8.89.
IR (KBr; v, cm-1): 3073 m, 1612 v.s, 1600 v.s, 1570 m, 1547 s, 1474 s, 1435 m, 1418 m, 1398 s, 1362 w, 1300 w, 1248 m, 1163 m, 1090 v.s, 1014 s, 868 m, 781 s, 744 m, 723 m, 685 m, 658 m, 623 s, 523 m, 409 m.
X-ray crystallography. Crystals of I—III were mounted on a Bruker SMART APEX II CCD diffrac-tometer with graphite monochromated Mo^a radiation (X = 0.71073 A) at 123 K. Empirical absorption corrections were applied by using the SADABS program. The structures were solved by direct methods and refined by full-matrix least squares on F2 via SHELXL-97 program [21]. All non-hydrogen atoms were refined anisotropically and the hydrogen atoms were generated geometrically. Crystallographic data and structural refinement parameters for compounds I—III are listed in Table 1. Selected bond lengths and angles are presented in Table 2.
Supplementary material has been deposited with the Cambridge Crystallographic Data Centre (CCDC nos. 945032 (I), 945 033 (II), 945 034 (III);
Table 2. Selected bond lengths and angles for I—III*
Bond d, A Bond d, A Bond d, A
I II III
Mn(1)-N(1) 2.206(2) Mn(1)-N(4) 2.1864(14) Mn(1)-N(1) 2.189(2)
Mn(1)—N(4) 2.209(2) Mn(1)-N(1) 2.1914(14) Mn(1)-N(2) 2.231(3)
Mn(1)-N(2) 2.240(2) Mn(1)-N(3) 2.2242(14) Mn(1)-N(3) 2.238(3)
Mn(1)-N(6) 2.242(2) Mn(1)-N(6) 2.2340(15)
Mn(1)-N(3) 2.242(2) Mn(1)-N(2) 2.2530(14)
Mn(1)-N(5) 2.270(2) Mn(1)-N(5) 2.2844(14)
Angle ro, deg Angle ro, deg Angle ro, deg
I II III
N(1)Mn(1)N(4) 167.12(8) N(4)Mn(1)N(1) 165.09(5) N(1)Mn(1)N(1)' 167.70(13)
N(1)Mn(1)N(2) 71.78(8) N(4)Mn(1)N(3) 116.99(5) N(1)Mn(1)N(2)' 115.93(9)
N(4)Mn(1)N(2) 110.49(8) N(1)Mn(1)N(3) 72.86(5) N(1)Mn(1)N(2) 72.49(9)
N(1)Mn(1)N(6) 120.69(9) N(4)Mn(1)N(6) 72.80(5) N(2)Mn(1)N(2) 100.92(15)
N(4)Mn(1)N(6) 72.03(9) N(1)Mn(1)N(6) 119.03(5) N(1)Mn(1)N(3) 72.33(9)
N(2)Mn(1)N(6) 97.01(8) N(3)Mn(1)N(6) 95.04(5) N(1)Mn(1)N(3) 99.25(9)
N(1)Mn(1)N(3) 72.20(8) N(4)Mn(1)N(2) 99.02(5) N(2)Mn(1)N(3) 91.84(10)
N(4)Mn(1)N(3) 106.30(7) N(1)Mn(1)N(2) 72.23(5) N(2)Mn(1)N(3) 144.71(9)
N(2)Mn(1)N(3) 143.20(8) N(3)Mn(1)N(2) 143.95(5) N(3)Mn(1)N(3) 96.43(14)
N(6)Mn(1)N(3) 94.83(8) N(6)Mn(1)N(2) 94.07(5)
N(1)Mn(1)N(5) 95.38(8) N(4)Mn(1)N(5) 72.41(5)
N(4)Mn(1)N(5) 71.87(8) N(1)Mn(1)N(5) 95.52(5)
N(2)Mn(1)N(5) 95.59(8) N(3)Mn(1)N(5) 99.51(5)
N(6)Mn(1)N(5) 143.90(9) N(6)Mn(1)N(5) 145.18(5)
N(3)Mn(1)N(5) 95.00(8) N(2)Mn(1)N(5) 92.47(5)
* Symmetry codes: 1 -x + 1/2, —y, z.
deposit@ccdc.cam.ac.uk or http://www.ccdc.cam. ac.uk).
RESULTS AND DISCUSSION
The asymmetric unit of I contains one Mn2+ cation, two Meophtpy ligands and two perchlorate anions. The manganese(II) ion is coordinated by six N atoms from two Meophtpy ligands. The distances between Mn and N from central pyridines (Mn—N(1) and Mn—N(4)) are 2.206(2) and 2.209(2) A which are slightly shorter than that between Mn and N from outer pyridines (Mn—N(2), Mn-N(6), Mn-N(3), and Mn-N(5) 2.240(2), 2.242(2), 2.242(2), and 2.270(2) A). Three transoid angles are: N(1)MnN(4) 167.12(8)°, N(2)MnN(3) 143.20(8)°, and N(5)MnN(6) 143.90(9)°, and the other twelve cisoid angles are ranging from 71.78(8)° to 120.69(9)°. Both the differences of bond lengths and bond angles show a distorted octahedral geometry in I which are common for terpyridine coordinated compounds [22, 23]. The angles between phe-
nyl ring and terpyridine ring are 19.6° and 7.9°. The angle between two terpyridine rings is 73.1° which are deviated from right angle.
Eleven hydrogen bonds all with C-H-O type link the individual components in I into three dimensional network which have been shown in Fig. 1b and Table 3. Except for O(8), all O atoms on perchlorate anions are acceptors with hydrogen on C as donors. The O(3) atom is triple acceptor linked with hydrogens H(8), H(16) and H(44C) which are attached to C(8), C(16), and C(44). The O(4) and O(7) atoms are double acceptors with hydrogen H(7), H(32), and H(10), H(22A) which are attached to C(7), C(32), and C(10), C(22), respectively. The most shortest hydrogen bonds (H-O) are 2.33 A for C(7)-H(7)---O(4)1 and C(35)-H(35)---O(10)v1. The other moderate hydrogen bonds are 2.39 A for C(32)-H(32)-O(4)v, 2.41 A for C(10)-H(10)--O(7)11, and 2.46 A for C(22)-H(22A)-"O(7)m (symmetry codes are shown in
Table 3). All the other hydrogen bond lengths are longer than 2.51 A, and
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