Multifunctinality and Crystal Dynamics of Highly Stable Porous Metal-Organic Framework [Zn 4 O(NTB) 2 ]

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1 Supporting Information Multifunctinality and Crystal Dynamics of Highly Stable Porous Metal-Organic Framework [Zn 4 O(NTB) 2 ] Eun Young Lee, Seung Yeon Jang, and Myunghyun Paik Suh* School of Chemistry, Seoul National University, Seoul , Republic of Korea. S1

2 Figure S1. TGA/DSC trace for 1. S2

3 (a) (b) Figure S2. Photos for the crystal (a) [Zn 4 O(NTB) 2 ] 3DEF EtOH (1), and (b) [Zn 4 O(NTB) 2 ] (1 ) obtained by heating 1 at 400 C and 10-5 torr for 0.5 h. S3

4 Figure S3. An ORTEP drawing of resolvated crystal, [Zn 4 O(NTB) 2 ] xdef yetoh (1 ), with the atomic numbering scheme. Statistically disordered structure is separated into two independent structures. Thermal ellipsoids are drawn with 30% probability. Zn, yellow; O, red; N, blue; C, gray. S4

5 Table S1. Crystallographic data for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [squeezed data] formula C 59 H 63 N 5 O 17 Zn 4 crystal system cubic space group Ia-3 fw a, Å (5) V Å (4) Z 8 ρ calc, g/cm temperature 293(2) K λ, Å µ, mm GOF F(000) 5664 no. of data collcd 4234 no. of unique data 2201 no. of obsd data [I>2σ(I)] 1180 no. of variables 118 Crystal size 0.3 x 0.15 x 0.15 mm θ range for data collection 3.13 to º Limiting indices -29 h 29, -20 k 20, -20 l 20 Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Final R indices [I>2σ(I)] [a] R 1 = , [b] wr2 = R indices (all data) R [a] 1 = , wr [b] 2 = Largest diff. peak and hole and e Å -3 [a] R = Σ Fo - F c /Σ F o [b] wr(f 2 ) = [Σw(F o 2 - Fc 2 ) 2 /Σw(F o 2 ) 2 ] ½ where w = 1/[σ 2 (F o 2 ) + (0.1890P) 2 + (0.0000)P], P = (Fo 2 + 2F c 2 )/3 S5

6 Table S2. Fractional atomic coordinates and equivalent displacement parameters (Å 2 ) for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [squeezed data] atom x y z U eq * O (15) Zn (5) (5) (5) (5) Zn (5) (5) (5) (7) N (2) (2) (2) 0.080(3) O (3) (4) (4) 0.060(2) O (3) (5) (4) 0.071(3) O (3) (4) (4) 0.066(2) O (5) (4) (7) 0.104(4) C (3) (3) (3) (19) C (2) (2) (2) (17) C (4) (4) (5) 0.161(5) C (3) (3) (4) 0.127(4) C (3) (2) (3) (18) C (3) (3) (3) 0.091(2) C (3) (3) (3) 0.092(3) * U eq = (1/3) ΣiΣj U ij a* i a* jai aj S6

7 Table S3. Selected bond distances (Å) and angles ( ) for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [squeezed data] Zn1---Zn (2) Zn1---Zn1A 3.195(2) N1-C (5) Zn2-O (2) Zn2-O (7) Zn1-O (8) Zn1-O (9) Zn1-O (11) Zn1-O (10) C1-O2B 1.288(11) Zn2-Zn1-Zn1A 59.8(9) Zn1-Zn2-Zn1A 60.3(1) C5-N1-C5D (4) O1-Zn2-O (3) O4D-Zn2-O (3) O2-Zn1-O (3) O3-Zn1-O (3) O5-Zn1-O (4) O2-Zn1-O (3) O2-Zn1-O (4) O3-Zn1-O (6) Zn1-O1-Zn (3) Zn1E-O1-Zn (3) C1C-O2-Zn (6) C1B-O3-Zn (7) C1-O4-Zn (6) C1-O5-Zn (7) C1-O3C 1.254(12) O4-C (10) O5-C (11) C1-C (8) C2-C (9) C2-C (8) C3-C (10) C4-C (9) C5-C (8) C6-C (8) O2B-C1-O3C 130.8(8) O4-C1-O (8) O2B-C1-C (8) O3C-C1-C (8) O4-C1-C (6) O5-C1-C (8) C3-C2-C (5) C3-C2-C (6) C7-C2-C (5) C4-C3-C (7) C3-C4-C (7) C6-C5-C (5) C6-C5-N (5) C4-C5-N (5) C7-C6-C (6) C6-C7-C (6) Symmetry code: A: 0.5-z, 1-x, y-0.5, B: z, 0.5+x, 1-y, C: y-0.5, 1-z, x, D: y, z, x, E: z, x, y. S7

8 Table S4. Crystallographic data for [Zn 4 O(NTB) 2 ] (1 ) formula C 42 H 24 N 2 O 13 Zn 4 crystal system cubic space group Pa-3 fw a, Å (5) V Å (4) Z 8 ρ calc, g/cm temperature 293(2) K λ, Å µ, mm GOF F(000) 4112 no. of data collcd 6952 no. of unique data 4287 no. of obsd data [I>2σ(I)] 2367 no. of variables 184 Crystal size 0.3 x 0.15 x 0.15 mm θ range for data collection 1.57 to º Limiting indices -29 h 29, -20 k 20, -20 l 20 Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Final R indices [I>2σ(I)] R [a] [b] 1 = , wr 2 = R indices (all data) R [a] [b] 1 = , wr 2 = Largest diff. peak and hole and e Å -3 [a] R = Σ Fo - F c /Σ F o [b] wr(f 2 ) = [Σw(F o 2 - Fc 2 ) 2 /Σw(F o 2 ) 2 ] ½ where w = 1/[σ 2 (F o 2 ) + (0.1152P) 2 + (13.74)P], P = (Fo 2 + 2F c 2 )/3 S8

9 Table S5. Fractional atomic coordinates and equivalent displacement parameters (Å 2 ) for [Zn 4 O(NTB) 2 ] (1 ) atom x y z U eq * O (19) (19) (19) (17) Zn (3) (3) (3) (3) Zn (3) (3) (3) (4) N (13) (12) (12) 0.074(3) O (13) (12) (12) (15) O (13) (12) (12) (17) C (13) (12) (12) (18) C (13) (12) (12) (18) C (13) (12) (12) 0.073(2) C (4) (3) (3) 0.073(2) C (3) (3) (3) (19) C (4) (4) (4) 0.083(2) C (4) (4) (4) 0.080(2) N (3) (3) (3) 0.070(3) O (2) (2) (2) (13) O (3) (3) (4) 0.114(2) C (3) (3) (3) (18) C (3) (3) (3) 0.067(2) C (4) (3) (4) 0.080(2) C (3) (3) (4) 0.082(2) C (3) (3) (3) 0.067(2) C (4) (4) (5) 0.097(3) C (13) (12) (12) 0.097(3) * U eq = (1/3) Σ i Σ j U ij a * i a* j a i a j S9

10 Table S6. Selected bond distances (Å) and angles ( ) for [Zn 4 O(NTB) 2 ] (1 ) Zn1---Zn (2) Zn1---Zn1A 3.123(1) O1-Zn (3) O1-Zn (8) Zn1-O (6) Zn1-O (5) Zn1-O3B 1.943(5) Zn2-O (4) O2-C (9) O3-C (9) N1-C (7) C1-C (10) C2-C (10) C2-C (10) Zn2-Zn1-Zn1A 58.2(0) Zn1-Zn2-Zn1A 60.9(0) Zn1-O1-Zn1B 107.3(2) Zn1-O1-Zn (2) O5-Zn1-O (3) O5-Zn1-O (3) O2-Zn1-O (18) O5-Zn1-O3B 106.6(3) O2-Zn1-O3B 115.1(2) O1-Zn1-O3B 112.2(2) O1-Zn2-O (15) O4-Zn2-O4B (16) C1-O2-Zn (5) C1-O3-Zn1C 128.3(5) C5-N1-C5D 118.7(2) O3-C1-O (7) O3-C1-C (7) O2-C1-C (7) C7-C2-C (7) C7-C2-C (7) C3-C2-C (7) C4-C3-C (7) C3-C (10) C4-C (10) C5-C (11) C6-C (10) O4-C (8) O5-C (9) N2-C (7) C8-C (10) C9-C (11) C9-C (11) C10-C (10) C11-C (10) C12-C (11) C13-C (11) C5-C4-C (7) C4-C5-C (7) C4-C5-N (7) C6-C5-N (7) C7-C6-C (8) C6-C7-C (8) C8-O4-Zn (5) C8-O5-Zn (5) C12-N2-C12E (14) O4-C8-O (7) O4-C8-C (6) O5-C8-C (7) C10-C9-C (7) C10-C9-C (7) C14-C9-C (7) C11-C10-C (7) C10-C11-C (7) C13-C12-C (7) C13-C12-N (7) C11-C12-N (7) C14-C13-C (8) C13-C14-C (8) Symmetry code: A: 1-y, 0.5+z, 0.5-x, B: 0.5-z, 1-x, -0.5+y, C: 1-y, 0.5+z, 0.5-z, D: y, z, x, E: 0.5-y, 1-z, 0.5+x. S10

11 Table S7. Crystallographic data for [Zn 4 O(NTB) 2 ] xdef yetoh (1 ) crystal system cubic space group Ia-3 a, Å (4) V Å (3) temperature 293(2) K λ, Å GOF no. of data collcd 4164 no. of unique data 2165 no. of obsd data [I>2σ(I)] 1505 no. of variables 118 Crystal size 0.5 x 0.25 x 0.25 mm θ range for data collection 3.40 to º Limiting indices -29 h 29, -20 k 20, -20 l 20 Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Final R indices [I>2σ(I)] R [a] 1 = , wr [b] 2 = R indices (all data) R [a] 1 = , wr [b] 2 = Largest diff. peak and hole and e Å -3 [a] R = Σ Fo - F c /Σ F o [b] wr(f 2 ) = [Σw(F o 2 - F c 2 ) 2 /Σw(F o 2 ) 2 ]½ where w = 1/[σ 2 (F o 2 ) + (0.1616P) 2 + (21.90)P], P =(Fo 2 + 2Fc 2 )/3. S11

12 Table S8. Fractional atomic coordinates and equivalent displacement parameters (Å 2 ) for [Zn 4 O(NTB) 2 ] xdef yetoh (1 ) * atom x y z U eq O (15) Zn (4) (4) (4) (4) Zn (4) (4) (4) (5) N (3) (3) (3) 0.087(3) O (4) (5) (4) 0.073(2) O (4) (4) (4) 0.065(2) O (4) (4) (4) 0.064(2) O (5) (4) (5) 0.088(3) C (3) (2) (2) (13) C (2) (2) (2) (13) C (3) (3) (4) 0.100(3) C (3) (3) (4) 0.105(3) C (3) (3) (3) (18) C (3) (3) (3) 0.086(2) C (3) (3) (3) (19) * U eq = (1/3) Σ i Σ j U ij a * i a* j a i a j S12

13 Table S9. Selected bond distances (Å) and angles ( ) for [Zn 4 O(NTB) 2 ] xdef yetoh (1 ) Zn1---Zn (2) Zn1---Zn1A 3.164(2) N1-C (5) Zn2-O (2) Zn2-O (8) Zn1-O (8) Zn1-O (7) Zn1-O (1) Zn1-O (9) C1-O2B 1.224(10) Zn2-Zn1-Zn1A 60.04(2) Zn1-Zn2-Zn1A 59.93(4) C5-N1-C5D (5) O1-Zn2-O (3) O4D-Zn2-O (3) O2-Zn1-O (3) O3-Zn1-O (3) O5-Zn1-O (3) O2-Zn1-O (4) O2-Zn1-O (5) O3-Zn1-O (5) Zn1-O1-Zn (3) Zn1E-O1-Zn (3) C1C-O2-Zn (6) C1B-O3-Zn (6) C1-O4-Zn (6) C1-O5-Zn (6) C1-O3C 1.245(10) O4-C (10) O5-C (10) C1-C (7) C2-C (8) C2-C (8) C3-C (9) C4-C (8) C5-C (9) C6-C (8) O2B-C1-O3C 129.6(7) O4-C1-O (6) O2B-C1-C (7) O3C-C1-C (6) O4-C1-C (6) O5-C1-C (5) C3-C2-C (5) C3-C2-C (5) C7-C2-C (5) C4-C3-C (6) C3-C4-C (6) C6-C5-C (5) C6-C5-N (6) C4-C5-N (6) C7-C6-C (6) C6-C7-C (5) Symmetry code: A: 0.5-z, 1-x, y-0.5, B: z, 0.5+x, 1-y, C: y-0.5, 1-z, x, D: y, z, x, E: z, x, y. S13

14 Table S10. Crystallographic data for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [raw data] formula C 59 H 63 N 5 O 17 Zn 4 crystal system cubic space group Ia-3 fw a, Å (5) V Å (4) Z 8 ρ calc, g/cm temperature 293(2) K λ, Å µ, mm GOF F(000) 5664 no. of data collcd 4234 no. of unique data 2201 no. of obsd data [I>2σ(I)] 1185 no. of variables 134 Crystal size 0.3 x 0.15 x 0.15 mm θ range for data collection 3.13 to º Limiting indices -29 h 29, -20 k 20, -20 l 20 Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Final R indices [I>2σ(I)] [a] R 1 = , [b] wr2 = R indices (all data) R [a] 1 = , wr [b] 2 = Largest diff. peak and hole and e Å -3 [a] R = Σ Fo - F c /Σ F o [b] wr(f 2 ) = [Σw(F o 2 - Fc 2 ) 2 /Σw(F o 2 ) 2 ] ½ where w = 1/[σ 2 (F o 2 ) + (0.1890P) 2 + (0.0000)P], P = (Fo 2 + 2F c 2 )/3 S14

15 Table S11. Fractional atomic coordinates and equivalent displacement parameters (Å 2 ) for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [raw data] atom x y z U eq * O (16) Zn (5) (5) (5) (5) Zn (5) (5) (5) (7) N (3) (3) (3) 0.075(3) O (4) (5) (4) 0.066(3) O (4) (5) (4) 0.067(3) O (4) (5) (5) 0.065(3) O (6) (5) (7) 0.107(4) C (4) (3) (3) 0.067(2) C (3) (3) (3) (17) C (4) (4) (5) 0.128(4) C (4) (4) (5) 0.122(4) C (3) (3) (3) (18) C (3) (3) (4) 0.101(3) C (3) (3) (4) 0.094(3) C1S (3) (3) (4) 0.186(13) N1S (3) (3) (4) 0.74(7) C2S (3) (3) (4) 0.28(2) t * U eq =(1/3)Σ i Σ j U ij a * i a* j a i a j S15

16 Table S12. Selected bond distances (Å) and angles ( ) for [Zn 4 O(NTB) 2 ] 3DEF EtOH (1) [raw data] Zn1---Zn (2) Zn1---Zn1A 3.185(2) N1-C (5) Zn2-O (2) Zn2-O (8) Zn1-O (11) Zn1-O (8) Zn1-O (8) Zn1-O (12) O4-C (10) O5-C (14) C1-O2B 1.249(12) C1-O3C 1.289(12) C1-C (8) C2-C (10) C2-C (9) C3-C (11) C4-C (10) C5-C (10) C6-C (9) Zn2-Zn1-Zn1A 59.87(3) Zn1-Zn2-Zn1A 60.26(5) C5-N1-C5D (5) O1-Zn2-O (3) O4D-Zn2-O (3) O5-Zn1-O (5) O5-Zn1-O (6) O2-Zn1-O (4) O5-Zn1-O (4) O2-Zn1-O (3) O3-Zn1-O (3) Zn2-O1-Zn (3) Zn1-O1-Zn1E (3) C1C-O2-Zn (7) C1B-O3-Zn (7) C1-O4-Zn (7) C1-O5-Zn (8) O2B-C1-O3C 130.8(8) O4-C1-O (8) O4-C1-C (7) O2B-C1-C (8) O3C-C1-C (8) O5-C1-C (7) C3-C2-C (6) C3-C2-C (6) C7-C2-C (6) C2-C3-C (7) C3-C4-C (7) C6-C5-C (6) C6-C5-N (6) C4-C5-N (6) C5-C6-C (7) C2-C7-C (6) Symmetry code: A: 0.5-z, 1-x, y-0.5, B: z, 0.5+x, 1-y, C: y-0.5, 1-z, x, D: y, z, x, E: z, x, y. S16