Crystal engineering of a rectangular sql coordination network to enable xylenes selectivity over ethylbenzene
Zaworotko, Michael; Kumar, Naveen; Chang, Ze; Yu, Mei-Hui; Kumar, Amrit; O’Nolan, Daniel; Bu, Xian-He; Patyk-Kaźmierczak, Ewa; Bezrukov, Andrey A.; Mukherjee, Soumya; Wang, Shi-Qiang; Chemical Science  (2020) –; doi:10.1039/D0SC02123G

data_1558321
_publ_section_title
;
 Crystal engineering of a rectangular sql coordination network to enable
 xylenes selectivity over ethylbenzene
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02123G
_journal_year                    2020
_chemical_formula_moiety         'C52 H32 Co2 N28 S4, 4(C8 H10)'
_chemical_formula_sum            'C84 H72 Co2 N28 S4'
_chemical_formula_weight         1719.79
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-14 deposited with the CCDC.	2020-06-16 downloaded from the CCDC.
;
_cell_angle_alpha                78.892(2)
_cell_angle_beta                 73.265(2)
_cell_angle_gamma                79.327(2)
_cell_formula_units_Z            2
_cell_length_a                   13.6994(5)
_cell_length_b                   20.4799(7)
_cell_length_c                   21.1055(7)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      50.39
_cell_measurement_theta_min      2.89
_cell_volume                     5511.1(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.01
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_unetI/netI     0.1287
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            13415
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        54.366
_diffrn_reflns_theta_max         54.366
_diffrn_reflns_theta_min         2.220
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.452
_exptl_absorpt_correction_T_max  0.928528
_exptl_absorpt_correction_T_min  0.779076
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 239541 reflections, Rint = 0.1743
 (56228 with I > 3sig(I), Rint = 0.0766)
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.036
_exptl_crystal_description       rod
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.609
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1440
_refine_ls_number_reflns         13415
_refine_ls_number_restraints     1101
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.2223
_refine_ls_R_factor_gt           0.1356
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1371P)^2^+46.0089P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3066
_refine_ls_wR_factor_ref         0.3684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7695
_reflns_number_total             13415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02123g2.cif
_cod_data_source_block           tri2
_cod_database_code               1558321
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.770
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.631(3)
 0.369(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C2T-C9T
 1.5 with sigma of 0.02
 C1T-C8T
 1.5 with sigma of 0.02
 C7M-C2M
 1.5 with sigma of 0.02
 C7V-C1V
 1.5 with sigma of 0.02
 C8U-C1T
 1.5 with sigma of 0.02
 C8U-C2U
 1.5 with sigma of 0.02
 C8O-C6N
 1.5 with sigma of 0.02
 C8V-C7V
 -2.75 with sigma of 0.02
 C8V-C2V
 1.5 with sigma of 0.02
 C9T-C1T
 2.45 with sigma of 0.04
 C9T-C3T
 2.45 with sigma of 0.04
 C8T-C2T
 2.45 with sigma of 0.04
 C8T-C7T
 2.45 with sigma of 0.04
 C7M-C3M
 2.45 with sigma of 0.04
 C7M-C1M
 2.45 with sigma of 0.04
 C7V-C6V
 2.45 with sigma of 0.04
 C8U-C1U
 2.45 with sigma of 0.04
 C8U-C3U
 2.45 with sigma of 0.04
 C7U-C6U
 2.45 with sigma of 0.04
 C7U-C2U
 2.45 with sigma of 0.04
 C6M-C2M
 2.45 with sigma of 0.04
 C6M-C0CA
 2.45 with sigma of 0.04
 C8V-C3V
 2.45 with sigma of 0.04
 C8V-C1V
 2.45 with sigma of 0.04
 C8S-C3S
 2.45 with sigma of 0.04
 C8S-C1S
 2.45 with sigma of 0.04
 C7S-C6S
 2.45 with sigma of 0.04
 C7S-C2S
 2.45 with sigma of 0.04
4. Restrained planarity
 C8T, C1T, C9T, C3T, C5T
 with sigma of 0.01
 C7V, C8V, C2V, C1V, C6V, C5V, C4V, C3V
 with sigma of 0.01
 C8S, C2S, C6S, C7S, C5S, C3S, C4S, C1S
 with sigma of 0.01
 C8O, C6N, C1N, C7N, C2N, C8N, C3N, C5N, C4N
 with sigma of 0.01
5. Rigid bond restraints
 C7E, N8E, N9E, C10E, N11E, N12E
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
6. Uiso/Uaniso restraints and constraints
C7T \\sim C5T \\sim C1T \\sim C4T \\sim C2T \\sim C3T: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C8T \\sim C1T \\sim C7T \\sim C5T \\sim C4T \\sim C3T \\sim C2T \\sim C9T:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C8U \\sim C2U \\sim C1U \\sim C7U \\sim C6U \\sim C5U \\sim C4U \\sim C3U:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C3M \\sim C2M \\sim C7M \\sim C1M \\sim C0CA \\sim C5M \\sim C4M \\sim C6M:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C7V \\sim C1V \\sim C8V \\sim C2V \\sim C3V \\sim C4V \\sim C5V \\sim C6V:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C7Q \\sim C8Q \\sim C2Q \\sim C1Q \\sim C6Q \\sim C5Q \\sim C4Q \\sim C3Q:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C2L \\sim C1L \\sim C6L \\sim C5L \\sim C4L \\sim C3L: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
N16D \\sim C17D \\sim C18D \\sim C13D \\sim C14D \\sim C15D: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C2G \\sim S3G: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1S \\sim C6S \\sim C2S \\sim C7S \\sim C5S \\sim C3S \\sim C8S \\sim C4S:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C7R \\sim C1R \\sim C2R \\sim C8R \\sim C3R \\sim C4R \\sim C5R \\sim C6R:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N8E \\sim N9E \\sim N12E \\sim N11E: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C2T) \\sim Ueq, Uanis(C7T) \\sim Ueq, Uanis(C5T) \\sim Ueq, Uanis(C1T)
\\sim Ueq, Uanis(C4T) \\sim Ueq, Uanis(C3T) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C2U) \\sim Ueq, Uanis(C5U) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9T) \\sim Ueq, Uanis(C8T) \\sim Ueq, Uanis(C8U) \\sim Ueq, Uanis(C2U)
\\sim Ueq, Uanis(C3U) \\sim Ueq, Uanis(C4U) \\sim Ueq, Uanis(C6U) \\sim Ueq,
Uanis(C1U) \\sim Ueq, Uanis(C7U) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1M) \\sim Ueq, Uanis(C2M) \\sim Ueq, Uanis(C7M) \\sim Ueq, Uanis(C3M)
\\sim Ueq, Uanis(C4M) \\sim Ueq, Uanis(C0CA) \\sim Ueq, Uanis(C5M) \\sim Ueq,
Uanis(C6M) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C7V) \\sim Ueq, Uanis(C2V) \\sim Ueq, Uanis(C1V) \\sim Ueq, Uanis(C3V)
\\sim Ueq, Uanis(C8V) \\sim Ueq, Uanis(C6V) \\sim Ueq, Uanis(C4V) \\sim Ueq,
Uanis(C5V) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C5Q) \\sim Ueq, Uanis(C6Q) \\sim Ueq, Uanis(C1Q) \\sim Ueq, Uanis(C2Q)
\\sim Ueq, Uanis(C3Q) \\sim Ueq, Uanis(C4Q) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C8L) \\sim Ueq, Uanis(C7L) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C3L) \\sim Ueq, Uanis(C1L) \\sim Ueq, Uanis(C6L) \\sim Ueq, Uanis(C2L)
\\sim Ueq, Uanis(C5L) \\sim Ueq, Uanis(C4L) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(N16D) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C2G) \\sim Ueq, Uanis(S3G) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N16B) \\sim Ueq, Uanis(C17B) \\sim Ueq, Uanis(C18B) \\sim Ueq,
Uanis(C13B) \\sim Ueq, Uanis(C14B) \\sim Ueq, Uanis(C15B) \\sim Ueq,
Uanis(C10B) \\sim Ueq, Uanis(N11B) \\sim Ueq, Uanis(N12B) \\sim Ueq, Uanis(C7B)
\\sim Ueq, Uanis(N8B) \\sim Ueq, Uanis(N9B) \\sim Ueq, Uanis(C4B) \\sim Ueq,
Uanis(C5B) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(N1B) \\sim Ueq, Uanis(C2B)
\\sim Ueq, Uanis(C3B) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(N1C) \\sim Ueq, Uanis(C6C) \\sim Ueq, Uanis(C5C) \\sim Ueq, Uanis(C4C)
\\sim Ueq, Uanis(C3C) \\sim Ueq, Uanis(C2C) \\sim Ueq, Uanis(C7C) \\sim Ueq,
Uanis(N12C) \\sim Ueq, Uanis(N11C) \\sim Ueq, Uanis(N9C) \\sim Ueq, Uanis(N8C)
\\sim Ueq, Uanis(C10C) \\sim Ueq, Uanis(C13C) \\sim Ueq, Uanis(C18C) \\sim Ueq,
Uanis(C14C) \\sim Ueq, Uanis(C15C) \\sim Ueq, Uanis(N16C) \\sim Ueq,
Uanis(C17C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2S) \\sim Ueq, Uanis(C1S) \\sim Ueq, Uanis(C6S) \\sim Ueq, Uanis(C7S)
\\sim Ueq, Uanis(C5S) \\sim Ueq, Uanis(C3S) \\sim Ueq, Uanis(C8S) \\sim Ueq,
Uanis(C4S) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C2H) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4N) \\sim Ueq, Uanis(C5N) \\sim Ueq, Uanis(C6N) \\sim Ueq, Uanis(C1N)
\\sim Ueq, Uanis(C2N) \\sim Ueq, Uanis(C3N) \\sim Ueq, Uanis(C8N) \\sim Ueq,
Uanis(C7N) \\sim Ueq, Uanis(C8O) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
7. Others
 Sof(N16C)=Sof(C17C)=Sof(H17C)=Sof(C18C)=Sof(H18C)=Sof(C13C)=Sof(C14C)=
 Sof(H14C)=Sof(C15C)=Sof(H15C)=Sof(N1C)=Sof(C2C)=Sof(H2C)=Sof(C3C)=Sof(H3C)=
 Sof(C4C)=Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(H6C)=Sof(C10C)=Sof(N11C)=Sof(N12C)=
 Sof(C7C)=Sof(N8C)=Sof(N9C)=1-FVAR(1)
 Sof(N16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C13B)=Sof(C14B)=
 Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C7B)=Sof(N8B)=Sof(N9B)=Sof(C10B)=Sof(N11B)=
 Sof(N12B)=Sof(N1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(C5B)=
 Sof(H5B)=Sof(C6B)=Sof(H6B)=FVAR(1)
 Sof(H2N)=Sof(C8O)=Sof(H8OA)=Sof(H8OB)=Sof(H8OC)=1-FVAR(2)
 Sof(H6N)=Sof(C8N)=Sof(H8NA)=Sof(H8NB)=Sof(H8NC)=FVAR(2)
 Sof(S3H)=Sof(C2H)=1-FVAR(3)
 Sof(S3G)=Sof(C2G)=FVAR(3)
 Fixed Sof: C1R(0.8) C2R(0.8) C3R(0.8) H3R(0.8) C4R(0.8) H4R(0.8) C5R(0.8)
 H5R(0.8) C6R(0.8) H6R(0.8) C8R(0.8) H8RA(0.8) H8RB(0.8) H8RC(0.8) C1L(0.5)
 C6L(0.5) H6L(0.5) C5L(0.5) H5L(0.5) C4L(0.5) H4L(0.5) C3L(0.5) H3L(0.5)
 C2L(0.5) C7R(0.8) H7RA(0.8) H7RB(0.8) H7RC(0.8) C3Q(0.5) H3Q(0.5) C4Q(0.5)
 H4Q(0.5) C5Q(0.5) H5Q(0.5) C6Q(0.5) H6Q(0.5) C1Q(0.5) C2Q(0.5) C7T(0.25)
 H7T(0.25) C5T(0.25) H5T(0.25) C4T(0.25) H4T(0.25) C3T(0.25) H3T(0.25)
 C2T(0.25) C1T(0.25) C8Q(0.5) H8QA(0.5) H8QB(0.5) H8QC(0.5) C7Q(0.5) H7QA(0.5)
 H7QB(0.5) H7QC(0.5) C8L(0.5) H8LA(0.5) H8LB(0.5) H8LC(0.5) C7L(0.5) H7LA(0.5)
 H7LB(0.5) H7LC(0.5) C6U(0.25) H6U(0.25) C5U(0.25) H5U(0.25) C4U(0.25)
 H4U(0.25) C3U(0.25) H3U(0.25) C2U(0.25) C1U(0.25) C8U(0.25) H8UA(0.25)
 H8UB(0.25) H8UC(0.25) C7U(0.25) H7UA(0.25) H7UB(0.25) H7UC(0.25) C9T(0.25)
 H9TA(0.25) H9TB(0.25) H9TC(0.25) C8T(0.25) H8TA(0.25) H8TB(0.25) H8TC(0.25)
 C0CA(0.25) H0CA(0.25) C1M(0.25) C2M(0.25) C3M(0.25) H3M(0.25) C4M(0.25)
 H4M(0.25) C5M(0.25) H5M(0.25) C1S(0.2) C6S(0.2) H6S(0.2) C5S(0.2) H5S(0.2)
 C4S(0.2) H4S(0.2) C3S(0.2) H3S(0.2) C2S(0.2) C2V(0.25) C1V(0.25) C6V(0.25)
 H6V(0.25) C5V(0.25) H5V(0.25) C4V(0.25) H4V(0.25) C3V(0.25) H3V(0.25)
 C7V(0.25) H7VA(0.25) H7VB(0.25) H7VC(0.25) C8V(0.25) H8VA(0.25) H8VB(0.25)
 H8VC(0.25) C7M(0.25) H7MA(0.25) H7MB(0.25) H7MC(0.25) C7S(0.2) H7SA(0.2)
 H7SB(0.2) H7SC(0.2) C6M(0.25) H6MA(0.25) H6MB(0.25) H6MC(0.25) C8S(0.2)
 H8SA(0.2) H8SB(0.2) H8SC(0.2)
8.a Aromatic/amide H refined with riding coordinates:
 C17C(H17C), C18C(H18C), C14C(H14C), C15C(H15C), C2C(H2C), C3C(H3C), C5C(H5C),
 C6C(H6C), C2A(H2A), C15D(H15D), C14D(H14D), C3A(H3A), C5D(H5D), C15A(H15A),
 C17D(H17D), C2E(H2E), C6D(H6D), C3E(H3E), C17E(H17E), C18E(H18E), C14A(H14A),
 C2D(H2D), C6A(H6A), C17A(H17A), C5A(H5A), C18D(H18D), C18A(H18A), C6E(H6E),
 C15E(H15E), C3D(H3D), C5E(H5E), C14E(H14E), C2N(H2N), C3N(H3N), C4N(H4N),
 C5N(H5N), C6N(H6N), C3R(H3R), C4R(H4R), C5R(H5R), C6R(H6R), C6L(H6L), C5L(H5L),
  C4L(H4L), C3L(H3L), C3Q(H3Q), C4Q(H4Q), C5Q(H5Q), C6Q(H6Q), C17B(H17B),
 C18B(H18B), C14B(H14B), C15B(H15B), C2B(H2B), C3B(H3B), C5B(H5B), C6B(H6B),
 C7T(H7T), C5T(H5T), C4T(H4T), C3T(H3T), C6U(H6U), C5U(H5U), C4U(H4U), C3U(H3U),
  C0CA(H0CA), C3M(H3M), C4M(H4M), C5M(H5M), C6S(H6S), C5S(H5S), C4S(H4S),
 C3S(H3S), C6V(H6V), C5V(H5V), C4V(H4V), C3V(H3V)
8.b Fitted hexagon refined as free rotating group:
 N16C(C17C,C18C,C13C,C14C,C15C), N1C(C2C,C3C,C4C,C5C,C6C), C1N(C2N,C3N,C4N,C5N,
 C6N), C10C(N11C,N12C,C7C,N8C,N9C), C1R(C2R,C3R,C4R,C5R,C6R), C1L(C6L,C5L,C4L,
 C3L,C2L), C3Q(C4Q,C5Q,C6Q,C1Q,C2Q), N16B(C17B,C18B,C13B,C14B,C15B), C7B(N8B,
 N9B,C10B,N11B,N12B), N1B(C2B,C3B,C4B,C5B,C6B), C7T(C5T,C4T,C3T,C2T,C1T),
 C6U(C5U,C4U,C3U,C2U,C1U), C0CA(C1M,C2M,C3M,C4M,C5M), C1S(C6S,C5S,C4S,C3S,C2S),
 C2V(C1V,C6V,C5V,C4V,C3V)
8.c Idealised Me refined with riding coordinates:
 C7N(H7NA,H7NB,H7NC), C8R(H8RA,H8RB,H8RC), C7R(H7RA,H7RB,H7RC), C8L(H8LA,H8LB,
 H8LC), C7L(H7LA,H7LB,H7LC), C8U(H8UA,H8UB,H8UC), C7U(H7UA,H7UB,H7UC), C9T(H9TA,
 H9TB,H9TC), C8T(H8TA,H8TB,H8TC), C7V(H7VA,H7VB,H7VC), C8V(H8VA,H8VB,H8VC),
 C7M(H7MA,H7MB,H7MC), C7S(H7SA,H7SB,H7SC), C6M(H6MA,H6MB,H6MC), C8S(H8SA,H8SB,
 H8SC)
8.d Idealised Me refined as rotating group:
 C8N(H8NA,H8NB,H8NC), C8Q(H8QA,H8QB,H8QC), C7Q(H7QA,H7QB,H7QC), C8O(H8OA,H8OB,
 H8OC)
;
_shelx_res_checksum              93790
_olex2_submission_special_instructions 'No special instructions were received'