A zeolite family with chiral and achiral structures built from the same building layer

Transcription

1 Supplementary information: A zeolite family with chiral and achiral structures built from the same building layer Liqiu Tang 1, Lei Shi 1,2, Charlotte Bonneau 1,2, Junliang Sun 1,2, Huijuan Yue 1,2, Arto Ojuva 1, Bao-Line Lee 1, Mikael Kritikos 1,2, Robert G. Bell 3, Zoltán Bacsik 4, Janos Mink 4,5 and Xiaodong Zou 1,2 * 1 Structural Chemistry, Stockholm University, SE Stockholm, Sweden. 2 Berzelii Centre EXSELENT on Porous Materials, Stockholm University, SE Stockholm, Sweden 3 Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK 4 Chemical Research Centre of the Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest, Hungary 5 Research Institute of Chemical and Process Engineering, University of Pannonia, P. O. Box 158, H-8201 Veszprém, Hungary Contents Table 1 Crystal data and details of structure determination. Table 2 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-15. Table 3 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-32a. Table 4 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-32b. Table 5 Atomic coordinates of the hypothetical polymorph C. Table 6 Coordination sequences of the T-atoms in SU-15. Table 7 Coordination sequences of the T-atoms in SU-32. Table 8 Coordination sequences of the T-atoms in the hypothetical polymorph C. Figure 1 The framework of SU-15 viewed along the [1 0 1] direction. Figure 2 Tiling pictures of SU-32. Figure 3 Energy of formation as the function of x = Ge/(Ge+Si) for SU-15 and SU-32. Figure 4 Scanning electron microscopy images of SU-15 and SU-32. Figure 5 Experimental and calculated XRPD patterns of SU-15 and SU-32. Figure 6 In situ X-ray powder diffraction of a mixture of SU-15 and SU-32. Figure 7 IR Spectra of an SU-15 crystal measured before and after calcination. Figure 8 IR Spectra of an SU-32 crystal measured before and after calcination. 1

2 Table 1 Crystal data and details of structure determination. SU-15* SU-32a SU-32b Chemical Formula H 3 N[CH(CH 3 ) 2 ] 2 [Ge 5.90 Si 4.10 O 20 ] F H 3 N[CH(CH 3 ) 2 ] [Ge 5.28 Si 4.72 O 20 ] F H 3 N[CH(CH 3 )] [Ge 5.45 Si 4.55 O 20 ] F Crystal system monoclinic hexagonal hexagonal Space group C2/c P P Unit cell (Å) a = (4) b = (3) c = (2) β = (3) º a = (3) c = (7) a = (17) c = (6) V(Å 3 ) (9) (16) (11) Z D(calc) (g/cm 3 ) Radiation (Å) MoKα: MoKα: MoKα: F(000) Crystal size(mm) Temperature (K) 298(3) 298(3) 298(3) θ min, max(deg) 1.93, , , 29.7 Dataset (h; k; l) -25~24 ; -14~15 ; -10~ 12-15~14 ; -15~15 ; -22~37-15~8 ; -15~15 ; -36~38 Tot.,Uniq.Data, R int 9730, 2442, , 2694, , 2603, Obs.I > 2.0σ Nref, Npar 2442, , , 164 R1, wr2, GooF , , , , , , Flack parameters -0.03(4) 0.02(5) T min, T max 0.34, , , Min., Max. Resd. Dens. (e/å 3 ) , , , * The data was collected from a pseudo-merohedrally twinned crystal, and the structure was solved through a HKLF 5 format data with BASF = The R int is calculated for the space group P1. 2

3 Table 2 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-15. Atoms x y z U eq /U iso (Å 2 ) Occupancy* T (3) (5) (7) (3) 0.267/ 0.733(9) T (3) (5) (7) (3) 0.249/0.751(9) T (4) (5) (8) (3) 0.360/0.640(9) T (4) (6) (9) (3) 0.407/ 0.593(9) T (4) (8) (2) (4) 0.780/0.220(6) O (2) (3) (5) (11) 1.0 O (2) (4) (5) (12) 1.0 O (2) (4) (5) (12) 1.0 O (2) (3) (7) (11) 1.0 O (2) (3) (5) (11) 1.0 O (2) (3) (6) (11) 1.0 O (3) 1.0 O (2) (3) (7) (10) 1.0 O (2) (3) (5) (10) 1.0 O (8) (3) 1.0 O (17) (3) (9) (9) 1.0 F (3) 1.0 N (8) (13) (17) 0.003(3) 0.25 N1' (8) (13) (17) 0.005(3) 0.25 C (8) (14) 0.054(2) 0.050(4) 0.5 C (7) (11) 0.095(2) 0.036(3) 0.5 C (10) (17) 0.010(2) 0.054(5) 0.5 * Occupancies for T: Si/Ge ratio 3

4 Table 3 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-32a. Atoms x y z U eq /U iso (Å 2 ) Occupancy* T (9) (9) (3) (4) 0.321/ 0.679(9) T (10) (10) (3) (4) 0.361/ 0.639(8) T (11) (10) (3) (4) 0.431/ 0.569(8) T (10) (10) (3) (4) 0.448/ 0.552(8) T (15) (14) (5) (6) 0.825/ 0.175(7) O (8) (2) 1.0 O (5) (6) (19) (14) 1.0 O (5) (5) (16) (16) 1.0 O (4) (4) (2) 1.0 O (5) (5) (17) (16) 1.0 O (8) (4) (3) 1.0 O (6) (7) (2) 0.067(2) 1.0 O (6) (8) (2) 0.066(2) 1.0 O (7) (6) (3) 0.078(3) 1.0 O (7) (7) (19) 0.085(3) 1.0 O (8) (6) (3) 0.090(3) 1.0 O (4) (4) (4) 1.0 F (12) (6) (4) 1.0 N (4) 0.575(3) (7) 0.183(14) 0.5 C (3) 0.429(2) (7) 0.095(9) 0.5 C (3) 0.551(2) (7) 0.108(10) 0.5 C (3) 0.611(2) (7) 0.089(9) 0.5 * Occupancies for T: Si/Ge ratio 4

5 Table 4 Atomic coordinates and equivalent isotropic (for T, O and F atoms) and isotropic (for N and C atoms) displacement parameters for SU-32b. Atoms x y z U eq /U iso (Å 2 ) Occupancy* T (9) (9) (4) (4) 0.333/0.667(11) T (9) (10) (4) (4) 0.355/0.645(11) T (11) (10) (4) (4) 0.437/0.563(10) T (10) (10) (4) (4) 0.441/0.559(10) T (15) (14) (6) (6) 0.844/0.156(8) O (9) (3) 1.0 O (6) (6) (2) (15) 1.0 O (6) (6) (2) (17) 1.0 O (5) (5) (3) 1.0 O (5) (5) (4) 1.0 O (6) (6) (2) (16) 1.0 O (8) (7) (3) 0.068(3) 1.0 O (7) (9) (3) 0.063(3) 1.0 O (11) (8) (3) 0.075(3) 1.0 O (7) (8) (3) 0.059(3) 1.0 O (8) (8) (4) 0.087(4) 1.0 O (10) (5) (4) 1.0 F (7) (7) (5) 1.0 N (2) 0.954(2) (7) 0.104(10) 0.5 C (3) 1.046(3) (8) 0.084(9) 0.5 C (3) 1.023(4) (9) 0.113(13) 0.5 C (2) 1.020(3) (9) 0.081(9) 0.5 * Occupancies for T: Si/Ge ratio 5

6 Table 5 Atomic coordinates of the hypothetical polymorph C * Atoms x y z Si Si Si Si Si Si Si Si Si Si O O O O O O O O O O O O O O O O O O O O O O * Space group of C2/c with a = Å, b = Å, c = Å and β = º 6

7 Table 6 Coordination sequences of the T-atoms in SU-15 T(1) T(2) T(3) T(4) T(5) Table 7 Coordination sequences of the T-atoms in SU-32 T(1) T(2) T(3) T(4) T(5) Table 8 Coordination sequences of the T-atoms in the hypothetical polymorph C T(1) T(2) T(3) T(4) T(5) T(6) T(7) T(8) T(9) T(10)

8 Figure 1 The framework of SU-15 viewed along the [1 0 1] direction showing the 9-rings channels, which intersect with the 12-ring channels to form a two-dimensional channel system. a b Figure 2 Tiling pictures of SU-32. a, The two different tiles in SU-32: a cube corresponding to the D4R (in purple) and a low symmetry tile corresponding to the cage (in grey). b, The helical channels of the two enantiomorphs represented as tile pictures. 8

9 25.00 Polymorph A (SU-32) Energy of formation (kj mol -1 TO2) T5 T3 T4 T1 T Ge content x (Ge x Si 1-x O 2 ) a Polymorph B (SU-15) Energy of formation (kj mol -1 TO2) T5 T3 T4 T1 T Ge content x (Ge x Si 1-x O 2 ) b Figure 3 Energy of formation as the function of x = Ge/(Ge+Si). a, Polymorph A (SU-32) and b, Polymorph B (SU-15). The potential given by Sastre & Gale 31 was used. The energy variations within the same Ge/(Ge+Si) are due to different locations of Ge and Si in different T sites in the structure. For x = 0.2, the Ge substituted site for each energy is marked. The energy of formation is calculated with respect to a mixture of silica quartz and germania quartz, i.e. for the equation x GeO 2 (α-quartz) + (1-x) SiO 2 (α-quartz) Ge x Si 1-x O 2 (zeolite) 9

10 a b Figure 4 Scanning electron microscopy images. a, SU-15 and b, SU-32. Figure 5 Experimental and calculated XRPD patterns of SU-15 and SU-32. a, SU-15 and b, SU-32. Experimental and calculated XRPD patterns are in red and black, respectively. The peaks marked by * are from GeO 2 in the samples. A trace amount of SU-32 is seen in the SU-15 sample in a. 10

11 Figure 6 In situ X-ray powder diffraction of a mixture of SU-15 and SU-32. A calculated X-ray powder pattern is shown at bottom in black for comparison with 85% of SU-15 and 15% of SU

12 .4 -NH 3 + -NH 3 + C-H inorganic a.3 Absorbance.2 C-H b.1 -NH Wavenumber / cm -1 Figure 7 IR Spectra of an SU-15 crystal measured a, before and b, after calcination at 300 ºC for 3 hours. Peaks corresponding to the C-H and amine features ( cm -1 ) disappeared indicating the removal of the templates. The characteristic broad bands of the inorganic framework remain at the same position. -NH C-H -NH 3 + inorganic a Absorbance.05 C=O b Wavenumber / cm -1 Figure 8 Spectra of an SU-32 crystal measured (a) before and (b) after calcination at 400 ºC for 2 hour. The removing of C-H and amine features and appearing new carbonyl bands are evidently seen. The characteristic broad bands of the inorganic framework remain at the same position. 12