Synthesis of a Zr4(embonate)6–cobalt based superstructure for photocatalytic hydrogen production
Teng, Qian; He, Yan-Ping; Chen, Shu-Mei; Zhang, Jian; Dalton Transactions  (2022) –; doi:10.1039/D2DT01976K

data_7710769
_publ_section_title
;
 Synthesis of a Zr4(embonate)6--cobalt based superstructure for
 photocatalytic hydrogen production
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01976K
_journal_year                    2022
_chemical_formula_moiety
'0.5(C442 H310 Co8 N40 O106 Zr8), 2(C3 H7 N O), 2(H2 O)'
_chemical_formula_sum            'C228 H172 Co4 N22 O55 Zr4'
_chemical_formula_weight         4700.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-26 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.9570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.2228(4)
_cell_length_b                   23.4628(3)
_cell_length_c                   33.6913(4)
_cell_measurement_reflns_used    29282
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      44.0650
_cell_measurement_theta_min      2.1270
_cell_volume                     22210.3(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.956
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     17.00  44.00   0.50    2.00    --   39.69  77.00 150.00   54
  2  \w     26.00 111.00   0.50    2.00    --   39.69  57.00 150.00  170
  3  \w     29.00 105.00   0.50    2.00    --   39.69  38.00 -30.00  152
  4  \w     26.00 112.00   0.50    2.00    --   39.69  19.00 -60.00  172
  5  \w     26.00 105.00   0.50    2.00    --   39.69  57.00-180.00  158
  6  \w     11.00  36.00   0.50    2.00    --   39.69  89.00-167.41   50
  7  \w     10.00  35.00   0.50    2.00    --   39.69  92.00-123.38   50
  8  \w     10.00  35.00   0.50    2.00    --   39.69  91.00   9.26   50
  9  \w     10.00  35.00   0.50    2.00    --   39.69  91.00 -22.85   50
 10  \w     10.00  35.00   0.50    2.00    --   39.69  90.00  92.70   50
 11  \w     86.00 111.00   0.50    2.00    --   39.69 179.00 -60.00   50
 12  \w     51.00  76.00   0.50    2.00    --   39.69 179.00 -60.00   50
 13  \w     57.00 111.00   0.50    2.00    --   39.69 179.00 150.00  108
 14  \w    -32.00  50.00   0.50    2.00    --   39.69 -38.00-180.00  164
 15  \w     -7.00  29.00   0.50    2.00    --   39.69 -99.00   0.00   72
 16  \w     48.00  74.00   0.50    2.00    --   39.69 -99.00   0.00   52
 17  \w     88.00 113.00   0.50    2.00    --   39.69-179.00   0.00   50
 18  \w     55.00 110.00   0.50    2.00    --   39.69-179.00 120.00  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0127187000
_diffrn_orient_matrix_UB_12      -0.0541886000
_diffrn_orient_matrix_UB_13      0.0036738000
_diffrn_orient_matrix_UB_21      0.0391229000
_diffrn_orient_matrix_UB_22      -0.0074916000
_diffrn_orient_matrix_UB_23      0.0314060000
_diffrn_orient_matrix_UB_31      -0.0240815000
_diffrn_orient_matrix_UB_32      0.0163227000
_diffrn_orient_matrix_UB_33      0.0266118000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.956
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            63137
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        44.130
_diffrn_reflns_theta_max         44.130
_diffrn_reflns_theta_min         3.275
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    3.052
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74913
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic blackish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       block
_exptl_crystal_F_000             9608
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_platon_squeeze_details
;
TITL hy        C 1 2/c 1    R = 0.15
CELL   29.2228   23.4628   33.6913     90.00    105.96     90.00
SPGR C2/c
C101 0.837 0.351 0.149 !       3.56 eA-3
C102 0.835 0.425 0.099 !       3.15 eA-3
Q103 0.882 0.467 0.053 !       2.90 eA-3
Q104 0.226 0.387 0.156 !       2.70 eA-3
C105 1.000 0.195 0.247 !       2.42 eA-3
C106 0.866 0.307 0.173 !       2.41 eA-3
C107 0.359 0.075 0.064 !       2.29 eA-3
Q108 0.109 0.489 0.046 !       2.28 eA-3
C109 0.713 0.020 0.414 !       2.12 eA-3
C110 0.287 0.147 0.647 !       1.87 eA-3
C111 0.976 0.215 0.225 !       1.55 eA-3
Q112 0.294 0.060 0.850 !       1.54 eA-3
Q113 0.777 0.503 0.843 !       1.38 eA-3
Q114 0.853 0.062 0.174 !       1.19 eA-3
Q115 0.940 0.338 0.336 !       1.02 eA-3
Q116 0.991 0.246 0.328 !       0.95 eA-3
Q117 0.491 0.746 0.328 !       0.95 eA-3
C118 0.015 0.218 0.209 !       0.93 eA-3
Q119 0.129 0.319 0.023 !       0.90 eA-3
C120 0.669 0.036 0.946 !       0.89 eA-3
Q121 0.760 0.171 0.451 !       0.87 eA-3
C122 0.158 0.504 0.452 !       0.87 eA-3
Q123 0.688 0.136 0.454 !       0.87 eA-3
Q124 0.696 0.408 0.469 !       0.86 eA-3
Q125 0.658 0.501 0.335 !       0.85 eA-3
Q126 0.883 0.039 0.156 !       0.85 eA-3
Q127 0.305 0.423 0.005 !       0.83 eA-3
Q128 0.099 0.309 0.142 !       0.82 eA-3
Q129 0.618 0.296 0.423 !       0.81 eA-3
Q130 0.833 0.372 0.408 !       0.79 eA-3
Q131 0.401 0.480 0.360 !       0.78 eA-3
Q132 0.267 0.369 0.982 !       0.78 eA-3
Q133 0.367 0.494 0.152 !       0.76 eA-3
Q134 0.714 0.165 0.421 !       0.76 eA-3
Q135 0.204 0.322 0.062 !       0.76 eA-3
C136 0.558 0.249 0.798 !       0.75 eA-3
Q137 0.912 0.290 0.326 !       0.75 eA-3
Q138 0.873 0.452 0.125 !       0.74 eA-3
Q139 0.937 0.464 0.509 !       0.74 eA-3
Q140 0.879 0.026 0.172 !       0.73 eA-3
Q141 0.598 0.183 0.068 !       0.71 eA-3
Q142 0.838 0.108 0.172 !       0.70 eA-3
Q143 0.930 0.276 0.358 !       0.70 eA-3
Q144 0.509 0.201 0.032 !       0.70 eA-3
Q145 0.779 0.369 0.518 !       0.69 eA-3
Q146 0.868 0.059 0.134 !       0.67 eA-3
Q147 0.977 0.268 0.399 !       0.67 eA-3
Q148 0.290 0.195 0.150 !       0.67 eA-3
Q149 0.653 0.254 0.470 !       0.67 eA-3
Q150 0.063 0.290 0.123 !       0.66 eA-3
Q151 0.622 0.079 0.852 !       0.65 eA-3
Q152 0.850 0.067 0.142 !       0.65 eA-3
Q153 0.874 0.474 0.550 !       0.62 eA-3
Q154 0.638 0.069 0.929 !       0.62 eA-3
Q155 0.249 0.353 0.108 !       0.62 eA-3
Q156 0.171 0.064 0.259 !       0.61 eA-3
Q157 0.953 0.301 0.477 !       0.61 eA-3
Q158 0.022 0.344 0.179 !       0.61 eA-3
Q159 0.615 0.056 0.110 !       0.60 eA-3
Q160 0.839 0.297 0.484 !       0.60 eA-3
Q161 0.534 0.085 0.438 !       0.60 eA-3
Q162 0.165 0.428 0.102 !       0.60 eA-3
Q163 0.648 0.240 0.047 !       0.59 eA-3
Q164 0.053 0.409 0.928 !       0.59 eA-3
Q165 0.884 0.247 0.954 !       0.59 eA-3
Q166 0.755 0.010 0.314 !       0.59 eA-3
Q167 0.844 0.369 0.313 !       0.59 eA-3
Q168 0.297 0.418 0.874 !       0.59 eA-3
Q169 0.733 0.453 0.517 !       0.58 eA-3
Q170 0.929 0.248 0.584 !       0.58 eA-3
Q171 0.337 0.406 0.704 !       0.58 eA-3
Q172 0.634 0.396 0.259 !       0.58 eA-3
Q173 0.797 0.097 0.102 !       0.58 eA-3
Q174 0.835 0.041 0.126 !       0.57 eA-3
Q175 0.633 0.144 0.445 !       0.57 eA-3
Q176 0.133 0.644 0.445 !       0.57 eA-3
Q177 0.862 0.435 0.493 !       0.57 eA-3
Q178 0.148 0.004 0.368 !       0.56 eA-3
Q179 0.306 0.207 0.172 !       0.56 eA-3
Q180 0.828 0.363 0.086 !       0.56 eA-3
Q181 0.871 0.279 0.554 !       0.56 eA-3
Q182 0.961 0.170 0.093 !       0.55 eA-3
Q183 0.649 0.172 0.038 !       0.54 eA-3
Q184 0.099 0.124 0.382 !       0.54 eA-3
Q185 0.954 0.377 0.368 !       0.53 eA-3
Q186 0.368 0.231 0.463 !       0.53 eA-3
Q187 0.739 0.338 0.204 !       0.53 eA-3
Q188 0.234 0.300 0.922 !       0.52 eA-3
Q189 0.088 0.315 0.017 !       0.52 eA-3
Q190 0.336 0.386 0.773 !       0.51 eA-3
Q191 0.704 0.423 0.274 !       0.51 eA-3
Q192 0.493 0.378 0.319 !       0.50 eA-3
;
_refine_diff_density_max         1.265
_refine_diff_density_min         -0.923
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.976
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1400
_refine_ls_number_reflns         12480
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.1260
_refine_ls_R_factor_gt           0.1023
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+200.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2685
_refine_ls_wR_factor_ref         0.2940
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9717
_reflns_number_total             12480
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01976k2.cif
_cod_data_source_block           hy_sq
_cod_database_code               7710769
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Zr Co C N O'
_shelx_estimated_absorpt_t_max   0.750
_shelx_estimated_absorpt_t_min   0.461
_reflns_odcompleteness_completeness 57.02
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     56.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 H00C_$2-H03B
 2 with sigma of 0.02
3. Rigid bond restraints
 C040, C04M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N02P, N02V
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C04J) \\sim Ueq, Uanis(C04F) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C12)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C01T) \\sim Ueq, Uanis(C04D) \\sim Ueq, Uanis(C04K) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C03A) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C03O) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C01T) \\sim Ueq, Uanis(C04K) \\sim Ueq, Uanis(C04D) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C03A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C040) \\sim Ueq, Uanis(C04G) \\sim Ueq, Uanis(C04M) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C040) \\sim Ueq, Uanis(C04M) \\sim Ueq, Uanis(C04G) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C03A) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N01L) \\sim Ueq, Uanis(N25) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C040) \\sim Ueq, Uanis(C04M) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N02P) \\sim Ueq, Uanis(N02V) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C03E, C03I, C04F, C04J, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C040, N02P, C04G, C04M, N02V
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Zr2(0.75) H00E(0.5) H00F(0.5) H00G(0.5) H00H(0.5) C04D(0.5)
 H04D(0.5) C04K(0.5) H04K(0.5) C04M(0.5) H04M(0.5) C19(0.5) H19(0.5) C04F(0.5)
 H04F(0.5) C12(0.5) H12(0.5) Zr(0.25) C5(0.5) H5(0.5)
7.a Riding coordinates:
 O027(H02A,H02B), O02A(H02C,H02D), O030(H03A,H03B), O037(H03C,H03D), O4(H4A,H4B)
7.b Rotating group:
 O00E(H00A,H00B), O00J(H00C,H00D)
7.c Secondary CH2 refined with riding coordinates:
 C00Q(H00E,H00F), C00V(H00G,H00H), C00W(H00I,H00J), C01S(H01A,H01B)
7.d Aromatic/amide H refined with riding coordinates:
 C013(H013), C019(H019), C01F(H01F), C01H(H01H), C01N(H01N), C01R(H01R),
 C01U(H01U), C01Z(H01Z), C021(H021), C022(H022), C024(H024), C028(H028),
 C029(H029), C02B(H02E), C02C(H02F), C02G(H02G), C02X(H02X), C02S(H02S),
 C02N(H02N), C02H(H02H), C02J(H02J), C02K(H02K), C02L(H02L), C02Q(H02Q),
 C02T(H02T), C02U(H02U), C02W(H02W), C032(H032), C039(H039), C03B(H03E),
 C03F(H03F), C03H(H03H), C03J(H03J), C03K(H03K), C03L(H03L), C03N(H03N),
 C03P(H03P), C03R(H03R), C03S(H03S), C03T(H03T), C03X(H03X), C03Q(H03Q),
 C03V(H03V), C042(H042), C044(H044), C046(H046), C047(H047), C048(H048),
 C049(H049), C04C(H04C), C04D(H04D), C01T(H01T), C04K(H04K), C04G(H04G),
 C04M(H04M), C040(H040), C04H(H04H), C19(H19), C04F(H04F), C04J(H04J), C12(H12),
  C4(H4), C03A(H03G), C5(H5)
7.e Fitted pentagon refined as free rotating group:
 C03X(N02I,C03Q,N03D,C03V), C04D(N015,C01T,N00N,C04K), C04G(C04M,N02V,C040,
 N02P), C4(N25,C03A,N01L,C5)
7.f Fitted hexagon refined as free rotating group:
 C02G(C02X,C02S,C02N,C01P,C02F), C19(C03E,C04F,C04J,C03I,C12)
7.g Idealised Me refined as rotating group:
 C02M(H02I,H02M,H02O), C045(H04A,H04B,H04E)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.943
_oxdiff_exptl_absorpt_empirical_full_min 0.493