Supporting Information - Royal Society of Chemistry

Supporting Information - Royal Society of Chemistry

Electronic Supplementary Material (ESI) for CrystEngComm.
This journal is © The Royal Society of Chemistry 2016
Supporting Information
Nanoporous Lanthanide Metal-Organic Frameworks as Efficient Heterogeneous
Catalysts for Henry Reaction
Anirban Karmakar,* Susanta Hazra, M. Fátima C. Guedes da Silva,* Anup Paul and Armando J.
L. Pombeiro*
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1049–001, Lisbon, Portugal. E-mail: [email protected]; [email protected];
[email protected]
A
B
C
D
E
Figure S1: Powder XRD curves of 1 (A), 2 (B), 3 (C), 4 (D) and 5 (E) [the red curve refers to experimental
curve and the black curve is theoretical one].
Figure S2: Plot of β-nitroalkanol yield vs. temperature for the Henry reaction of benzaldehyde and
nitroethane with framework 3 in water.
A
B
Figure S3: (A) FT-IR spectra of framework 3. The red and black curves were taken, respectively, before
and after the Henry reaction. (B) PXRD diffractograms of 3 before (red line) and after (blue line) the
Henry reaction of benzaldehyde with nitroethane.
A
C
B
D
E
Figure S4: Thermogravimetric curves for 1 (A), 2 (B), 3 (C), 4 (D) and 5 (E)
Table S1: Crystal data and structure refinement details for framework 1-5
Identification name
1
2
3
4
5
C36H35CeN4O13
871.80
triclinic
P-1
Formulae
C31H43LaN6O14
C29H36CeN5O13
C23H24N5O13Sm
Mol. wt.
862.62
802.75
728.82
Crystal system
Cubic
cubic
cubic
Space group
Ia-3
Ia-3
Ia-3
C36H35LaN4O13
870.59
triclinic
P-1
Temperature /K
Wavelength /Å
150(2)
0.71073
150(2)
0.71073
150(2)
0.71073
296(2)
0.71073
296(2)
0.71073
a /Å
27.0059(7)
b /Å
27.0059(7)
c /Å
27.0059(7)
α/°
90
β/°
90
γ/°
90
19695.9(15)
26.921(2)
26.921(2)
26.921(2)
90
90
90
19511(5)
24
24
1.745
26.681(3)
26.681(3)
26.681(3)
90
90
90
18993(7)
24
1.529
1.921
8712
36111
2872
25.307
9.8229(2)
11.4914(2)
16.3886(3)
94.801(5)
103.133(4)
97.661(5)
1772.97(7)
2
1.631
1.279
880
33303
6403
25.35
9.8826(2)
11.5594(3)
16.3655(4)
94.2570(10)
103.9510(10)
97.860(2)
1786.14(7)
2
1.621
1.348
882
20289
6244
25.350
V/
Å3
Z
F(000)
10560
Refl. collected
50931
Refl. unique
3126
Max. 2θ/°
25.648
1.640
1.473
9768
111230
3000
25.401
Ranges (h, k, l)
-25 <= h <=32
-26 <= k <=32
-32 <= l <= 21
-32 <= h <=31
-31 <= k <=32
-32 <= l <= 32
-31 <= h <=31
-23 <= k <=32
-27 <= l <= 21
-11 <= h <=11
-13 <= k <=13
-19 <= l <= 19
-11 <= h <=11
-13 <= k <=13
-19 <= l <= 19
Complete to 2θ (%)
99.9
Refl. with I > 2σ(I)
2390
99.9
2559
99.2
1951
99.0
5681
96.4
5630
Density/Mgm-3
Abs. Coeff.
/mm-1
1.384
Data/
Restraints/Parameters
3126/106/190
3000/106/188
2872/105/188
g. o. f (F2)
1.049
R1 [I > 2s(I)]
0.0648
wR2 [I > 2s(I)]
0.1907
R1 [all data]
0.0844
wR2 [all data]
0.2230
1.073
0.0496
0.1343
0.0588
0.1456
1.025
0.0452
0.1152
0.0741
0.1283
6403/ 20/492
6244/38/492
1.059
0.0533
0.1563
0.0613
0.1605
1.086
0.0503
0.1472
0.0559
0.1508
Table S2: Hydrogen bond geometry (Å, °) in frameworks 4 and 5
Compound
D-H---A
H∙∙∙A (Å)
D∙∙∙A (Å)
<D−H∙∙∙A(°)
4
N1-H1∙∙∙O3
2.04
2.671(8)
144
N2-H2∙∙∙O13
1.96
2.638(8)
145
O12-H12∙∙∙O2
1.64
2.428(7)
162
O30-H30A∙∙∙O14
1.95
2.797(7)
175
O30-H30C∙∙∙O15
2.19
2.988(8)
156
5
N1-H1∙∙∙O3
N2-H2∙∙∙O13
O30-H30A∙∙∙O14
O30-H30B∙∙∙O15
1.96
1.89
1.96
2.25
2.673(8)
2.647(7)
2.838(7)
3.062(8)
149
144
168
151
1
Table S3: Selected bond distances (Å) and angles (°) for compounds 1-5
La1-O1 2.685(5); La1-O2 2.665(5); La2-O2 2.512(5); La2-O3 2.549(5); La2-O4 2.567(5).
2
<O2-La1-O2 64.39(17); <O2-La1-O2 115.61(17); <O2-La1-O2 180.00(19); <O2-La1-O2
64.39(17); <O2-La1-O1 131.28(15); <O2-La1-O1 68.65(16); <O2-La1-O1 111.35(16); <O2La1-O1 105.93(16); <O2-La1-O1 74.07(16;) <O2-La1-O1 48.72(15); <O1-La1-O1 114.38(9);
<O1-La1-O1 65.62(9); <O1-La1-O1 180.00(8); <O2-La2-O2 68.82(18); <O2-La2-O3
136.41(17); <O2-La2-O3 76.90(17); <O2-La2-O3 74.26(17); <O3-La2-O3 119.02(4); <O2La2-O4 125.34(17); <O2-La2-O4 152.17(17); <O2-La2-O4 92.92(16); <O3-La2-O4 77.99(17);
<O3-La2-O4 129.47(18); <O3-La2-O4 51.21(17); <O4-La2-O4 80.50(18).
Ce1-O1 2.670(4); Ce1-O2 2.662(4); Ce2-O2 2.499(4); Ce2-O4 2.534(4); Ce2-O3 2.543(4).
<O2-Ce1-O2 115.63(13); <O2-Ce1-O2 64.37(13); <O2-Ce1-O2 180.00(17); <O2-Ce1-O1
131.34(12); <O2-Ce1-O1 111.40(12); <O2-Ce1-O1 68.60(12); <O2-Ce1-O1 48.66(12); <O2Ce1-O1 74.48(13); <O2- Ce1-O1 105.52(13); <O1-Ce1-O1 114.52(7); <O1-Ce1-O1 65.48(7);
<O1-Ce1-O1 180.00(19); <O2-Ce2-O2 69.11(14); <O2-Ce2-O4 136.53(14); <O2-Ce2-O4
76.92(14); <O2-Ce2-O4 73.99(13); <O4-Ce2-O4 119.04(4); <O2-Ce2-O3 125.08(14); <O2Ce2-O3 152.78(14); <O2-Ce2-O3 93.20(13); <O4-Ce2-O3 78.38(15); <O4-Ce2-O3
129.06(15); <O4-Ce2-O3 51.16(14); <O4-Ce2-O3 51.16(14); <O3-Ce2-O3 79.97(16).
3
4
5
Sm1-O1 2.605(4); Sm1-O2 2.617(4); Sm2-O2 2.433(4); Sm2-O3 2.477(4); Sm2-O4 2.477(5)
<O1-Sm1-O1 65.21(8); <O1-Sm1-O1 114.79(8); <O1-Sm1-O1 180.0; <O1-Sm1-O2
49.73(14); <O1-Sm1 -O2 67.83(14); <O1-Sm1-O2 112.17(14); <O1-Sm1-O2 106.23(14);
<O1-Sm1-O2 73.77(14); <O1-Sm1-O2 130.27(14); <O2-Sm1-O2 180.0; <O2-Sm1-O2
115.55(15); <O2-Sm1-O2 64.45(15); <O1-Sm1-O2 67.83(14); <O2-Sm2-O2 70.00(16); <O2Sm2-O4 125.17(15); <O2-Sm2-O4 153.12(15); <O2-Sm2-O4 93.31(15); <O4-Sm2-O4
78.98(17); <O2-Sm2-O3 77.48(15); <O2-Sm2-O3 72.61(15); <O2-Sm2-O3 136.76(15); <O4Sm2-O3 129.15(16); <O4-Sm2-O3 52.64(15); <O4-Sm2-O3 77.45(16); <O3-Sm2-O3
119.11(4).
La1-O1 2.545(7); La1-O3 2.686(8); La1-O4 2.522(8); La1-O11 2.519(8); La1-O13 2.669(8);
La1-O14 2.608(7); La1-O30 2.568(8); La1-O40 2.519(9); La1-O50 2.477(9).
<O50-La1-O40 142.2(3); <O50-La1-O11 69.9(3); <O40-La1-O11 139.5(3); <O50-La1-O4
99.8(3); <O40-La1-O4 72.9(3); <O11-La1-O4 137.5(3); <O50-La1-O1 135.8(3); <O40-La1-O1
80.4(3); <O11-La1-O1 81.5(3); <O4-La1-O1 79.1(3); <O50-La1-O30 71.6(3); <O40-La1-O30
71.1(3); <O11-La1-O30 135.9(3); <O4-La1-O30 69.8(3); <O1-La1-O30 142.5(3); <O50-La1O14 75.8(3); <O40-La1-O14 87.3(3); <O11-La1-O14 77.8(3); <O4-La1-O14 141.4(3); <O1La1-O14 130.7(2); <O30-La1-O14 72.6(3); <O50-La1-O13 116.3(3); <O40-La1-O13 72.4(3);
<O11-La1-O13 69.3(3); <O4-La1-O13 142.5(3); <O1-La1-O13 81.6(2); <O30-La1-O13
111.1(3); <O14-La1-O13 49.3(2); <O50-La1-O3 76.1(3); <O40-La1-O3 118.5(3); <O11-La1O3 88.0(3); <O4-La1-O3 49.9(3); <O1-La1-O3 69.7(3); <O30-La1-O3 102.9(3); <O14-La1-O3
151.5(3); <O13-La1-O3 145.9(2).
Ce1-O1 2.511(9); Ce1-O3 2.497(9); Ce1-O4 2.677(10); Ce1-O11 2.503(9); Ce1-O13
2.580(8); Ce1-O14 2.655(9); Ce1-O30 2.565(10); Ce1-O40 2.494(10); Ce1-O50 2.467(10).
<O50-Ce1-O40 141.5(4); <O50-Ce1-O3 99.6(4); <O40-Ce1-O3 72.4(4); <O50-Ce1-O11
69.8(3); <O40-Ce1-O11 140.3(3); <O3-Ce1-O11 137.8(3); <O50-Ce1-O1 135.5(4); <O40Ce1-O1 81.1(4); <O3-Ce1-O1 78.8(3); <O11-Ce1-O1 81.8(3); <O50-Ce1-O30 71.5(4); <O40Ce1-O30 70.4(4); <O3-Ce1-O30 70.0(3); <O11-Ce1-O30 135.4(3); <O1-Ce1-O30 142.6(3);
<O50-Ce1-O13 77.1(3); <O40-Ce1-O13 86.6(3); <O3-Ce1-O13 141.8(3); <O11-Ce1-O13
77.6(3); <O1-Ce1-O13 130.0(3); <O30-Ce1-O13 73.0(3); <O50-Ce1-O14 117.2(3); <O40Ce1-O14 73.0(3); <O3-Ce1-O14 142.0(4); <O11-Ce1-O14 69.1(3); <O1-Ce1-O14 80.9(3);
<O30-Ce1-O14 111.8(3); <O13-Ce1-O14 49.3(3); <O50-Ce1-O4 76.1(3); <O40-Ce1-O4
118.2(3); <O3-Ce1-O4 49.9(3); <O11-Ce1-O4 88.1(3); <O1-Ce1-O4 69.3(3); <O30-Ce1-O4
103.2(3); <O13-Ce1-O4 152.6(3); <O14-Ce1-O4 144.9(3).