SCIENCE CHINA Chemistry • ARTICLES •
March 2014 Vol.57 No.3: 365–370 doi: 10.1007/s11426-013-5048-9
Thermal expansion behaviors of Mn(II)-pyridylbenzoate frameworks based on metal-carboxylate chains ZHOU HaoLong1, LI Mian2, LI Dan2, ZHANG JiePeng1* & CHEN XiaoMing1 1
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China 2 Department of Chemistry, Shantou University, Shantou 515063, China Received October 14, 2013; accepted December 3, 2013; published online January 9, 2014
Solvothermal reactions of MnCl2 with pyridylbenzoic acids gave three-dimensional metal-carboxylate frameworks (MCFs), named MCF-34, MCF-43, and MCF-44, based on one-dimensional Mn-carboxylate chains. The crystal structure, stability, porosity, and framework flexibility of the new compound MCF-44 were studied in detail and compared with its analogs. Depending on their shapes and the bridging angles of the ligands, these compounds possess different network connectivities and porosities. Considering the pyridylbenzote ligands and Mn(II) ions as, respectively, 3- and 6-connected nodes, they resemble either the anatase (ant) or rutile (rtl) polymorph of TiO2. Variable-temperature single-crystal X-ray diffraction studies revealed large thermal expansion coefficients for these compounds, which are probably related to the relatively flexible edge-sharing polyhedral structure of their Mn-carboxylate chains. Interestingly, the new compound MCF-44, with its highly porous rtl structure exhibits the largest thermal expansion coefficienct among the coordination polymers reported so far. coordination polymer, thermal expansion, framework flexibility, topology
1 Introduction Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) have attracted great interest for their potential applications to separation, catalysis, luminescence, sensors, etc. [1–8]. Recent research has shown that PCPs are very promising for designing thermoresponsive materials because of their flexible frameworks and adjustable pore metrics [9–20]. For examples, the porous silver(I) triazolate framework FMOF-1, [Ag(Tz)] (HTz = 3,5-bis(trifluoromethyl)-1,2,4-triazole), simultaneously exhibits both huge linear positive thermal expansion (PTE) ( = +230 × 106 K1) and negative thermal expansion (NTE) ( = –170 × 106 K1) [13]. The cubic porous copper(II) carboxylate framework HKUST-1, [Cu3(btc)2] (H3btc = 1,3,5-benzenetricarboxylic
*Corresponding author (email:
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acid), exhibits very rare isotropic NTE ( = 4.1 × 106 K1) property [14]. Because most solids display small PTE (0 < < +20 × 106 K1) [21], materials with these unusual thermal-expansion properties may be useful as thermalexpansion compensators or thermomechanical actuators [22–25]. Although understanding the structural origins or mechanisms is crucial obviously for tuning the thermal expansion behaviors of these materials, the design and construction of PCPs with exceptionally large thermal expansion coefficients remain an important challenge. We recently reported the design, synthesis, structure and exceptional thermal expansion properties of a flexible ultramicroporous metal-carboxylate framework [Mn(34-pba)2] (MCF-34, 1, 34-Hpba = 3-(pyridin-4-yl)benzoic acid) consisting of one-dimensional (1D) zigzag Mn-carboxylate chains [20]. In this framework, the ligand 34-Hpba, bearing a low rotational energy barrier between its pyridyl and phenyl rings, serves as a tripodal node to connect the octahedral chem.scichina.com
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metal ions to construct an ultramicropous network with a (3,6)-connected ant (anatase) topology (Figure 1). By virtue of the unique ligand and framework structures, MCF-34 exhibits constant/huge PTE ( = +224 × 106 K1) and NTE ( = 170 × 106 K1). In this context, it should be interesting to study the thermal expansion behaviors of similar framework structures consisting of similar metal ions and organic ligands. In this work, we used two similar pyridylbenzate ligands with different conformations to construct two similar (3,6)connected frameworks consisting of Mn-carboxylate chains. Variable-temperature single-crystal X-ray diffraction studies showed that the thermal expansion coefficients of these compounds are closely related to their framework topologies and porosities. In addition, not only constant and very large PTE/NTE properties ( = 381 × 106 K1 and 148 × 106 K1), as well as interesting framework flexibility were observed for the new porous metal-carboxylate framework.
2 Experimental 2.1
Materials and general methods
Commercially available reagents were used as received without further purification. The ligands 4-(pyridin-3-yl) benzoic acid (43-Hpba) and 4-(pyridin-4-yl)benzoic acid (44-Hpba) were synthesized according to Ref. [26]. Infrared (IR) spectra were recorded with a Bruker TENSOR 27
Figure 1
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Fourier Transform FT-IR Spectrophotometer (Bruker, Germany) on KBr pellets in the range of 4000–400 cm1. Elemental (C, H, and N) analyses (EA) were performed on a Perkin-Elmer 240 Elemental analyzer (PerkinElmer, Inc., USA). Thermogravimetry analyses were performed on a TA Q50 system (TA Instruments-Waters, LLC., USA) in flowing N2 with a heating rate of 10 °C min1. Powder X-ray diffraction measurements were performed on a Bruker D8 ADVANCE X-ray Diffractometer (Bruker, Germany) with Cu K radiation. The CO2 adsorption measurement was performed with an automatic volumetric adsorption apparatus (Belsorp-Max, Japan) at 195 K. 2.2
Synthesis
[Mn(43-pba)2] (2, MCF-43) 43-Hpba (0.40 g, 2.0 mmol) was dissolved in DMF (90 mL) using a 250-mL vial and then added to a DMF solution of MnCl2 (0.1 mol L1, 10 mL) and methanol (80 mL). The mixture was then sealed with a screw cap and heated to 90 °C for 72 h. Colorless needle-like crystals of 2 were filtered and washed by DMF (yield 720 mg, ~80%). EA calcd (%) for 2 (C24H16N2O4Mn): C 63.87, H 3.57, N 6.21; Found: C 63.47, H 3.691, N 6.01. IR 3419(w), 3097(w), 3069(w), 1654(s), 1601(s), 1555(m), 1471(m), 1383(s), 1336(m), 1196(w), 1135(w), 1029(w), 1006(w), 867(m), 841(m), 773(s), 705(m).
Self-assembly, structures and topologies of MCF-34, MCF-43, and MCF-44 from Mn2+ ions and pyridylbenzote ligands.
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[Mn(44-pba)2]·2.5DMF (3, MCF-44). This compound was prepared by a similar procedure as 2, except that 43-Hpba was replaced by 44-Hpba. Yellow needle-like crystals of 3 were filtered and washed by DMF (yield 570 mg, ~45%). EA calcd (%) for 3 (C31.5H33.5N4.5O6.5Mn): C 59.67, H 5.33, N 9.94; Found: C 56.80, H 5.30, N 8.79. IR 3346(m), 3251(m), 2925(m), 1654(m), 1611(s), 1594(s), 1562(s), 1381(s), 1189(w), 1095(w), 1033(w), 1006(w), 829(m), 775(s), 751(s). 2.3
Crystallography
Diffraction data were recorded on an Oxford Gemini S Ultra CCD Diffractometer (Agilent Technologies, USA) using mirror-monochromated Cu K radiation. A single crystal of 2 was mounted on the top of a glass fiber, while a single crystal of as-synthesized 3 (just removed from the DMF) was sealed in a glass capillary. The test temperature was controlled by dry N2 flow using a Cryo Stream 700 system (Agilent Technologies, USA), and corrected by a thermal couple at the crystal position. The variable temperature unit-cell parameters were obtained by indexing the diffraction spots that were obtained with a few diffraction images. The crystal structures were solved through the direct method and developed by the difference Fourier technique using the SHELXTL software package. Anisotropic thermal parameters were used to refine all non-hydrogen atoms of the frameworks. Hydrogen atoms were generated geometrically and refined in a riding model. The relatively large R-factor for the 144-K structure indicates that the guest molecules relocate to an arrangement that cannot be modeled well in the crystal structure. Actually, when the guest molecules were omitted by the SQUEEZE routine of Platon, the R-factor decreased drastically (Table 1 and Table S1, see the supporting information online).
3 Results and discussion 3.1
Syntheses and structures
[Mn(43-pba)2] (2) and [Mn(44-pba)2]·2.5DMF (3) were obtained in high yield and purity through solvothermal reactions similar to 1 [20]. Single-crystal X-ray diffraction revealed that 2 is a nonporous coordination framework [27] that can also be simplified as a (3,6)-connected ant topology if the 44-pba− ligands and Mn2+ ions are regarded as 3and 6-connected nodes, respectively, that are isoreticular with 1 [20]. However, 3 crystallizes in a monoclinic space group P21/c and consists of 1D Mn-carboxylate chains. The asymmetric unit of the host framework includes one Mn2+ ion (two independent atoms, each with half-occupancy), two 44-pba− ligands and 2.5 DMF guest molecules. Each Mn2+ ion is coordinated by two N atoms and four O atoms from six pba− ligands in a distorted octahedral geometry,
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Table 1
Crystal data and structural refinement results
Complex
3
3
Formula
C31.5H33.5N4.5O6.5Mn
C31.5H33.5N4.5O6.5Mn
Formula weight
670.61
670.61
Temperature (K)
144(2)
298(2)
Crystal system
Monoclinic
Monoclinic
Space group
P21/c
P21/c
a (Å)
9.7821(2)
9.8457(5)
b (Å)
19.9160(4)
19.4937(10)
c (Å)
16.1047(4)
16.7455(9)
(o)
93.581(2)
94.348(4)
V (Å3)
3131.40(12)
3204.7(3)
Z
4
4
Dc (g cm3)
1.345
1.314
Reflns coll.
9782
11032
Unique reflns
4606
4722
Rint
0.0326
0.0418
R1 [I > 2(I)]a)
0.1073
0.0695
wR2 [I > 2(I)]b)
0.3035
0.1826
R1 (all data)
0.1236
0.0852
wR2 (all data)
0.3216
0.1951
GOF
1.053
1.057
a) R1 = {Fo Fc}/Fo; b) wR2 = [w(Fo2 Fc2)2/w(Fo2)2]1/2.
and each 44-pba− is bound to three Mn2+ ions by two carboxylate oxygen and one pyridyl nitrogen donors. Therefore, the overall coordination framework of 3 can be also simplified as a (3,6)-connected topology similar to those of 1 and 2. However, detailed analysis showed that 3 possesses a rtl (rutile) topology. It should be noted that anatase and rutile are two typical polymorphic phases of TiO2 (Figure 1). By taking advantage of a recently proposed topological analysis approach [28], the 1D Mn-carboxylate chains in 1–3 can be treated as rod-like secondary building units (i.e.. rod SBUs). Based on these rod SBUs, 1/2 and 3 are simplified as two new (5,8)-connected nets with point symbols (34.43.52.6) (38.49.56.64.7) and (34.42.54)(38.48.56.65.7), respectively. For reference, these two new topologies have been registered in the RCSR database with codenames zhl and hlz, respectively. As shown in Figure 2, the rod SBUs of 1, 2, and 3 are all edge-sharing octahedra, which may produce notable framework flexibility because the commonly observed rod SBUs are all face-sharing octahedra [28, 29]. The variation of network connectivity among 1–3 can be attributed to the different bridging angles of the pyridylcarboxylate ligands, which for 34-pba− and 43-pba− are 120o, while for 44-pba− it is 180o. This difference is clearly demonstrated by the different coordination configuration of the MnN2O4 sphere, in which 1 and 2 adopt a cis conformation whereas 3 has a trans conformation. Similarly to 1 and 2, adjacent Mn2+ ions in 3 are bridged by exo-bidentate carboxylate groups to form a 1D Mn-carboxylate chain along the a-axis, and adjacent Mn-carboxylate chains are connected to each other through the pyridyl ends of the ligands and the residual
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Figure 2 Deconstruction of the 1D Mn-carboxylate chains in MCF-34 (a) and MCF-44 (b) into a rod of edge-sharing octahedra and their underlying nets of these rods, zhl (c) and hlz (d), linked by ditopic linkers.
coordination sites of Mn2+ ions, all of which create large 1D rhombic channels (cross-section size ~6.2 × 6.7 Å2, guestaccessible volume = 46.3%) parallel to the Mn-carboxylate chains. Although the pore size of 3 is quite large, 2.5 DMF molecules can be modeled in its crystal structure (1.5 are ordered and the remaining 1 is two-fold disordered). 3.2
Framework stability, flexibility, and porosity
The thermogravimetry curve of 3 showed a weight loss of 28.3% below 200 °C, which corresponded to the removal of DMF molecules (calcd. 28.8%), followed by a steady plateau until decomposition above 400 °C (Figure S1). Powder X-ray diffraction patterns of guest-free 3 (Figure S2) show that this is a new phase with a drastic contraction but poor crystallinity. The original crystallinity can be restored in DMF vapor, however, which indicates that the framework is distorted rather than collapsed. The CO2 sorption isotherm of guest-free 3 (Figure S3) was collected at 195 K to evaluate its porosity. The low CO2 uptake (24.7 cm3 g1) indicates that the vacant framework has a drastic contraction. 3.3
Thermal expansion properties
Some recent examples have revealed the role of framework composition (e.g., metal ion [15], ligand [18], and guest [9, 13, 19, 20]) on the magnitude of thermal-expansion coefficients. However, the underlying mechanics of thermal expansion remain poorly understood. Understanding the thermal expansion mechanisms of a series of structurally similar analogs should be highly desirable for rationally designing thermoresponsive materials. For comparision with com-
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pound 1, the thermal expansion behaviors of compounds 2 and 3 were studied with variable-temperature single-crystal X-ray diffraction experiments (Figure 3, Tables 2 and S2), and the thermal expansion coefficients of the principal axes (a′, b′, and c′) were calculated by using the PASCal program [30]. The unit-cell parameters of 2 and 3 changed linearly and reversibly against temperature. From 156 to 271 K, the unit-cell volume of 2 increased 0.8%, corresponding to a relatively large coefficient of thermal expansion +65(3) × 106 K1. Meanwhile, it’s a-, b-, and c-axes change +0.46%, +0.21%, and 0.05%, respectively, giving linear thermal expansion coefficients a′ = 49(5) × 106 K1,b′ = 20(4) × 106 K1 andc′ = 6(3) × 106 K1 (Table 2). Interestingly, compound 3 showed extremely large thermal expansion. Its unit-cell volume expanded 3.2% from 144 to 278 K, which corresponded to the volumetric thermal expansion coefficient of 259(20) × 106 K1. The unit-cell parameters b and c change 1.8% and 4.2%, respectively, which corresponded to exceptionally huge axial NTE (b′ = 148(12) × 106 K1) and PTE (c′ = 381(23) × 106 K1): this is one of the largest PTE/NTE of framework materials reported to date [13, 18–20]. To reveal the structural origin of the exceptionally large thermal expansion of 3, we compared its single-crystal structures measured at 144 and 298 K and found that the change were very small in coordination-bond lengths (< 0.014 Å) but very large in the angles (max = 1.2°) (Table S3). Consequently, the rhombus grids consisting of Mn vertexes and 44-pba− edges were distorted (Figure S4). The two interior angles of these rhombus grids, with their bisectors parallel to the b- and c-axes, changes of approximately 3.4° and 3.4°, respectively (Figure S4 and Table S4). These changes caused a typical lattice-fence effect on the bc-plane, which resulted in the large NTE/PTE of the b-/c-axes. Notably, the thermal expansion coefficients were 3 > 1 > 2 (Table 2), which are in accordance with their guestaccessible volumes. This indicated that the free space plays an important role in the expansion and contraction of the frameworks, processes that are necessary to accommodate a chemical or physical stimulus that results in the reversible movement of “soft” coordination bonds and flexible links [31]. Interestingly, the a′-axis thermal expansion of 2 was the largest among 1–3, although its volumetric coefficient was the smallest because of its nonporous framework. These abnormal thermal expansion behaviors are likely related to the rod of edge-sharing octahedra along the a-axis in 1–3. One structural requirement for framework flexibility is the existence of certain “weak points” in the local coordination networks [31]. Several frameworks based on zigzag ladder (which can also be viewed as edge-sharing square) SBUs showed such structural dynamics. Likewise, compared with those face-sharing octahedra, the relatively flexible edgesharing rods in the zhl and hlz nets provided such “weak points” leading to expansion and contraction under chemical
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Figure 3 Table 2
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Temperature dependence of the unit-cell parameters of 2 (left) and 3 (right). The error bars show the standard deviations. The thermal expansion coefficients of 1, 2 and 3
Compound
Accessible volume of solvent (%)
V × 106
1
19.7
2
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0.0
Component of principal axis along the crystallographic axes a b c 0.9833 0 0.1822 0 1 0 0 0.8607 0.5091
Principal axis
Direction
×106 (K1)
+110(1)
a' b' c'
~a b ~c
+2(1) +224(1) 107(1)
+65(3)
a' b' c'
~a b ~c
+49(5) +20(4) 6(3)
0.9983 0 0.3074
0 -1 0
0.0584 0 0.9516
This work
+261(15)
a' b' c'
~a b ~c
+28(3) 148(12) +381(23)
0.9546 0 0.6475
0 1 0
0.2978 0 0.7621
This work
1
(K )
Reference
[20]
3
46.3
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or physical stimuli. When temperature changes, 1 and 3 could expand and contract across the bc-plane or the cross sections of their channels, whereas the nonporous framework of 2 could deform only along the rod direction (i.e. the weak points). In addition, the thermal expansion coefficients of b- and c-axes of 3 were the opposite of those of 1 and 2, which may be ascribed to the different coordination configurations of the Mn(II) ions and framework topologies of 1/2 and 3.
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12
13
14
4 Conclusions 15
In summary, (3,6)-connected ant- and rtl-type metal carboxylate frameworks were synthesized by reacting MnCl2 with different pyridylcarboxylate ligands under solvothermal conditions. These metal carboxylate frameworks possess 1D Mn-carboxylate chains, which can be interpreted as flexible rods of edge-sharing octahedra. Besides framework stability, guest-induced framework breathing, and gas sorption properties, the thermal expansion behavior of the new compound MCF-44 was also studied in detail and compared with its structural analogs. Notably, MCF-44 exhibited exceptionally large thermal expansion coefficients, which we attributed to its relatively large pore volume and Mncarboxylate chains. This work was supported by the National Basic Research Progrem of China (2012CB821706) and the National Natural Science Foundation of China (21121061 and 21225105).
16
17 18
19 20
21 1 2 3
4
5 6
7 8
9
10
11
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SCIENCE CHINA Chemistry • SUPPORTING INFORMATION •
doi: 10.1007/s11426-013-5048-9
Thermal expansion behaviors of Mn(II)-pyridylbenzoate frameworks based on metal-carboxylate chains ZHOU HaoLong1, Li Mian2, LI Dan2, ZHANG JiePeng1* & CHEN XiaoMing1 1
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China 2 Department of Chemistry, Shantou University, Shantou 515063, China Received October 14, 2013; accepted December 3, 2013; published online January 9, 2014
Figure S1
Thermogravimetry curve for compound 3.
Figure S2
PXRD patterns for compound 3.
*Corresponding author (email:
[email protected]) © Science China Press and Springer-Verlag Berlin Heidelberg 2014
chem.scichina.com
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2
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Figure S3
Table S1
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Figure S4 Illustration of the “rhombus grid” showing the crystal structure transformation.
CO2 sorption isotherms for 3 after treatment at 300 °C.
Comparison of the crystal data and structural refinement results before and after the SQUEZZE treatment Complex
3
3-SQUEEZE
Formula
C31.5H33.5N4.5O6.5Mn
C24H16N2O4Mn
Formula weight
670.61
451.33
Temperature (K)
144(2)
144(2)
Crystal system
Monoclinic
Monoclinic
Space group
P21/c
P21/c
a (Å)
9.7821(2)
9.7821(2)
b (Å)
19.9160(4)
19.9160(4)
c (Å)
16.1047(4)
16.1047(4)
(°)
93.581(2)
93.581(2)
V (Å3)
3131.40(12)
3131.40(12)
Z
4
4
Dc (g cm3)
1.345
0.957
Reflns coll.
9782
9782
Unique reflns
4606
4606
Rint
0.0326
0.0313
R1 [I > 2σ(I)] a)
0.1073
0.0433
wR2 [I > 2σ(I)] b)
0.3035
0.1152
R1 (all data)
0.1236
0.0562
wR2 (all data)
0.3216
0.1214
GOF
1.053
1.038
a) R1 = {Fo Fc}/Fo; b) wR2 = [w(Fo2 Fc2)2/w(Fo2)2]1/2.
Table S2
Temperature-dependent unit-cell parameters of 2 and 3
Temperature-dependent unit-cell parameters of 3
Temperature-dependent unit-cell parameters of 3
T (K) 155.8 194.3 232.8 271.3 143.6 177.1 210.6 244.1 277.6
a (Å) 7.256(9) 7.281(9) 7.283(9) 7.290(10) 9.655(2) 9.678(2) 9.72(2) 9.727(2) 9.753(3)
b (Å) 11.883(13) 11.880(14) 11.896(14) 11.908(19) 19.693(5) 19.670(5) 19.440(5) 19.411(6) 19.334(6)
c (Å) 22.35(3) 22.34(4) 22.33(4) 22.34(6) 16.200(7) 16.262(6) 16.57(5) 16.756(7) 16.883(8)
(o) 106.24(15) 106.30(16) 106.22(16) 106.0(2) 91.36(4) 91.65(4) 92.6(2) 92.69(4) 93.04(4)
V (Å3) 1850(5) 1855(5) 1858(5) 1865(4) 3079(2) 3094(2) 3128(11) 3160(2) 3179(2)
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Table S3
Sci China Chem
Coordination bond lengths and angles of 3
144 K Mn1—N1 2.288(6) Mn1—O2 2.170(5) Mn1—O3 2.145(5) Mn2—N2 2.262(6) Mn2—O1 2.180(5) Mn2—O4 2.181(5) O3—Mn1—N1 85.50(18) O2a—Mn1—O3 94.74(18) O3—Mn1—O3b 180 O3—Mn1—N1b 94.50(18) O2c—Mn1—O3 85.26(18) O2a—Mn1—N1 85.24(17) O3b—Mn1—N1 94.50(18) N1—Mn1—N1b 180 O2c—Mn1—N1 94.76(17) O2a—Mn1—O3b 85.26(18) O2a—Mn1—N1b 94.76(17) O2a—Mn1—O2c 180 O3b—Mn1—N1b 85.50(18) O2c—Mn1—O3b 94.74(18) O2c—Mn1—N1b 85.24(17) O1d—Mn2—N2 84.77(18) O4e—Mn2—N2 87.40(17) O1f—Mn2—N2 95.23(18) N2—Mn2—N2g 180 O4c—Mn2—N2 92.60(17) O1d—Mn2—O4e 91.45(17) O1d—Mn2—O1f 180 O1d—Mn2—N2g 95.23(18) O1d—Mn2—O4c 88.55(17) O1f—Mn2—O4e 88.55(17) O4e—Mn2—N2g 92.60(17) O4e—Mn2—O4c 180 O1f—Mn2—N2g 84.77(18) O1f—Mn2—O4c 91.45(17) O4c—Mn2—N2g 87.40(17) Symmetry codes: a = 1x, 1/2+y, 1/2z; b = 1x, y, 1z; c = x, 1/2y, 1/2+z; d = 1+x, y, 1+z; e = 2x, 1/2+y, 3/2z; f = 2z. Table S4
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March (2014) Vol.57 No.3
298 K 2.292(3) 2.180(3) 2.150(3) 2.276(4) 2.180(3) 2.172(3) 86.67(12) 94.35(11) 180 93.33(12) 85.65(11) 85.83(12) 93.33(12) 180 94.17(12) 85.65(11) 94.17(12) 180 86.67(12) 94.35(11) 85.83(12) 85.50(13) 87.78(12) 94.51(13) 180 92.22(12) 91.18(12) 180 94.51(13) 88.82(12) 88.82(12) 92.22(12) 180 85.50(13) 91.18(12) 87.78(12) 1x, 1y, 1z; g = 2x, 1y,
The interior angles of the rhombus grids of 3 Temperature (K) Along b-axis Along c-axis
144 77.920 102.08
298 81.327 98.673
