Metal-to-Ligand Ratio As a Design Factor in the One-Pot Synthesis of Coordination Polymers with [MS4Cun] (M = W or Mo,n= 3 or 5) Cluster Nodes and a Flexible Pyrazole-Based Bridging Ligand
Beheshti, Azizolla; Clegg, William; Nobakht, Valiollah; Harrington, Ross W.; Crystal Growth & Design 13 (2013) 1023–; doi:10.1021/cg301106g

data_4507445
_publ_section_title
;
 Metal-to-Ligand Ratio As a Design Factor in the One-Pot Synthesis of
 Coordination Polymers with [MS4Cun] (M = W or Mo,n= 3 or 5) Cluster Nodes
 and a Flexible Pyrazole-Based Bridging Ligand
;
_journal_issue                   3
_journal_name_full               'Crystal Growth &amp; Design'
_journal_page_first              1023
_journal_paper_doi               10.1021/cg301106g
_journal_volume                  13
_journal_year                    2013
_chemical_formula_moiety         'C42 H66 Cu6 I2 Mo2 N12 S8,C3 H7 N O'
_chemical_formula_sum            'C45 H73 Cu6 I2 Mo2 N13 O S8'
_chemical_formula_weight         1895.56
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 97.164(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   19.937(6)
_cell_length_b                   10.001(3)
_cell_length_c                   35.707(14)
_cell_measurement_reflns_used    9959
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      25.0
_cell_measurement_theta_min      2.50
_cell_volume                     7064(4)
_computing_cell_refinement       'Bruker APEX2'
_computing_data_collection       'Rigaku CrystalClear'
_computing_data_reduction        'Bruker APEX2'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type
'Crystal Logic diffractometer and Rigaku Saturn 724+ CCD'
_diffrn_measurement_method       'thick-slice \w scans'
_diffrn_radiation_monochromator  'silicon double crystal'
_diffrn_radiation_source         'Diamond beamline I19'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_sigmaI/netI    0.0396
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            30134
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.55
_diffrn_reflns_theta_min         2.16
_exptl_absorpt_coefficient_mu    2.985
_exptl_absorpt_correction_T_max  0.985
_exptl_absorpt_correction_T_min  0.795
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.782
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3736
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_platon_squeeze_details
; The results are consistent with 0.5-1.0 molecules of DMF in each void,
corresponding to the chemical formula as given (which has 0.5)
;
_refine_diff_density_max         1.204
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         7060
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0397
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0446P)^2^+26.2090P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1077
_reflns_number_gt                5548
_reflns_number_total             7060
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            cg301106g_si_002.cif
_cod_data_source_block           ab107_3
_cod_original_sg_symbol_H-M      'I 2/a'
_cod_database_code               4507445
_computing_special_details
;
TITL ab107 in I2/a
CELL 0.6889   19.937  10.001  35.707  90.000  97.164  90.000
ZERR    4.00   0.006   0.003   0.014   0.000   0.004   0.000
LATT  2
SYMM 0.5-X, Y, -Z
SFAC C H N S CU MO I O
DISP    S    0.10019   0.11693      478.92
DISP    Cu   0.20206   1.20214     4755.30
DISP    Mo  -2.00400   0.65343     2734.60
DISP    I   -0.83032   1.72301     7013.87
UNIT 180 292 52 32 24 8 8 4

REM red plate
SIZE 0.08 0.08 0.005
TEMP -123

L.S. 8
ACTA 50
BIND CU2 I
BOND $H
FMAP 2
PLAN 10
EQIV $1 -x+3/2, -y+3/2, -z+3/2
SADI 0.01 C20 C21 C21 C21_$1 C20 C21X C21X C21X_$1

REM DMF squeezed - one molecule per 2 Mo atoms

REM EXTI    0.000438
WGHT    0.044600   26.209005
FVAR       0.43647   0.57477
CU1   5    0.686797    0.415127    0.570283    11.00000    0.08659    0.02981 =
         0.03707   -0.00114    0.00809   -0.00585
CU2   5    0.677743    0.520119    0.657122    11.00000    0.09652    0.05036 =
         0.03225    0.00013    0.00062   -0.00718
CU3   5    0.782435    0.666942    0.603152    11.00000    0.07408    0.04498 =
         0.03506   -0.00660    0.00118   -0.00867
MO    6    0.645792    0.652150    0.592715    11.00000    0.07285    0.02951 =
         0.03902   -0.00107   -0.00273   -0.00324
I     7    0.808878    0.397897    0.631125    11.00000    0.08690    0.04350 =
         0.04179    0.00205    0.00680    0.00565
S1    4    0.714625    0.619211    0.548172    11.00000    0.08178    0.03516 =
         0.03215    0.00211   -0.00148   -0.01100
S2    4    0.604831    0.451407    0.607605    11.00000    0.07788    0.03577 =
         0.03840   -0.00069    0.00359   -0.00594
S3    4    0.709490    0.732722    0.644547    11.00000    0.08009    0.03989 =
         0.04275   -0.01228    0.00036   -0.00342
S4    4    0.565522    0.784781    0.572225    11.00000    0.09128    0.04318 =
         0.08107    0.00488   -0.00837    0.00164
N1    3    0.627024    0.746602    0.397741    11.00000    0.07264    0.04282 =
         0.03497    0.00561    0.00371    0.00871
N2    3    0.590741    0.746003    0.428044    11.00000    0.06855    0.03285 =
         0.03882    0.00463    0.00812   -0.00244
N3    3    0.669008    0.240645    0.503460    11.00000    0.07357    0.02991 =
         0.03472    0.00088    0.00199   -0.00428
N4    3    0.682043    0.247967    0.541996    11.00000    0.07726    0.02970 =
         0.03095    0.00282    0.00307   -0.00422
N5    3    0.677236    0.438994    0.706541    11.00000    0.09492    0.08715 =
         0.03709    0.00537    0.00875    0.01649
N6    3    0.724080    0.467241    0.736964    11.00000    0.12236    0.08034 =
         0.03049   -0.00252    0.00716    0.03269
C1    1    0.617297    0.855159    0.335047    11.00000    0.09411    0.13620 =
         0.05688    0.04513    0.01988    0.04182
AFIX 137
H1A   2    0.631163    0.770733    0.324389    11.00000   -1.50000
H1B   2    0.656022    0.916169    0.338759    11.00000   -1.50000
H1C   2    0.581057    0.895837    0.317679    11.00000   -1.50000
AFIX   0
C2    1    0.592216    0.828677    0.372348    11.00000    0.08590    0.06140 =
         0.03895    0.01350    0.00047    0.00957
C3    1    0.535056    0.878268    0.386401    11.00000    0.07070    0.04553 =
         0.05782    0.00962    0.00427    0.00418
AFIX  43
H3A   2    0.502215    0.937399    0.373987    11.00000   -1.20000
AFIX   0
C4    1    0.535745    0.824439    0.421829    11.00000    0.06903    0.03411 =
         0.05120    0.00151    0.00646   -0.00159
C5    1    0.488099    0.844307    0.450659    11.00000    0.08286    0.04691 =
         0.07020    0.00698    0.02126    0.00176
AFIX 137
H5A   2    0.513789    0.868854    0.474886    11.00000   -1.50000
H5B   2    0.463256    0.761185    0.453602    11.00000   -1.50000
H5C   2    0.456093    0.915876    0.442345    11.00000   -1.50000
AFIX   0
C6    1    0.605867    0.649838    0.458561    11.00000    0.07809    0.03683 =
         0.03376    0.00407    0.00612   -0.00098
AFIX  23
H6A   2    0.593503    0.688298    0.482313    11.00000   -1.20000
H6B   2    0.654981    0.630830    0.462193    11.00000   -1.20000
AFIX   0
C7    1    0.566655    0.519345    0.449619    11.00000    0.06515    0.03734 =
         0.04522    0.00727   -0.00366   -0.00624
AFIX  23
H7A   2    0.576430    0.485464    0.424818    11.00000   -1.20000
H7B   2    0.517602    0.538275    0.447663    11.00000   -1.20000
AFIX   0
C8    1    0.584453    0.410464    0.479529    11.00000    0.06265    0.04065 =
         0.04469    0.01007    0.00545   -0.00687
AFIX  23
H8A   2    0.578273    0.446821    0.504658    11.00000   -1.20000
H8B   2    0.552845    0.334495    0.474268    11.00000   -1.20000
AFIX   0
C9    1    0.656276    0.359937    0.480502    11.00000    0.07551    0.03220 =
         0.03450    0.00300    0.00068   -0.00803
AFIX  23
H9A   2    0.665246    0.340048    0.454425    11.00000   -1.20000
H9B   2    0.687957    0.431170    0.490622    11.00000   -1.20000
AFIX   0
C10   1    0.644979    0.076800    0.451128    11.00000    0.09590    0.04456 =
         0.04731   -0.01144    0.00150   -0.01244
AFIX 137
H10A  2    0.671014    0.133344    0.435783    11.00000   -1.50000
H10B  2    0.596564    0.091543    0.443656    11.00000   -1.50000
H10C  2    0.655833   -0.017355    0.447231    11.00000   -1.50000
AFIX   0
C11   1    0.662544    0.111650    0.491841    11.00000    0.06980    0.02903 =
         0.04094   -0.00515    0.00309   -0.00929
C12   1    0.671846    0.033373    0.523610    11.00000    0.07367    0.02766 =
         0.05055    0.00135    0.00786   -0.00501
AFIX  43
H12A  2    0.670683   -0.061515    0.524583    11.00000   -1.20000
AFIX   0
C13   1    0.683383    0.120903    0.554285    11.00000    0.07574    0.03048 =
         0.04107    0.00384    0.00023   -0.00153
C14   1    0.694880    0.088094    0.595615    11.00000    0.09670    0.04227 =
         0.04084    0.00849    0.00141   -0.01098
AFIX 137
H14A  2    0.731610    0.143716    0.607997    11.00000   -1.50000
H14B  2    0.707102   -0.006474    0.598887    11.00000   -1.50000
H14C  2    0.653435    0.105622    0.606941    11.00000   -1.50000
AFIX   0
C15   1    0.579477    0.284180    0.691504    11.00000    0.13090    0.15548 =
         0.09214    0.05718    0.00244   -0.03285
AFIX 137
H15A  2    0.595561    0.264684    0.667246    11.00000   -1.50000
H15B  2    0.541528    0.347006    0.687588    11.00000   -1.50000
H15C  2    0.564577    0.201127    0.702468    11.00000   -1.50000
AFIX   0
C16   1    0.636768    0.346077    0.718325    11.00000    0.11005    0.11497 =
         0.05970    0.03222    0.02593    0.01749
C17   1    0.656489    0.315541    0.755680    11.00000    0.12170    0.14821 =
         0.05742    0.03684    0.03365    0.04157
AFIX  43
H17A  2    0.635464    0.252961    0.770493    11.00000   -1.20000
AFIX   0
C18   1    0.711491    0.391383    0.767390    11.00000    0.15737    0.11072 =
         0.03457    0.01473    0.01991    0.06890
C19   1    0.756520    0.403790    0.804574    11.00000    0.23099    0.11337 =
         0.03204    0.00321   -0.00250    0.06553
AFIX 137
H19A  2    0.745261    0.333148    0.821758    11.00000   -1.50000
H19B  2    0.749570    0.491362    0.815787    11.00000   -1.50000
H19C  2    0.803911    0.394899    0.800272    11.00000   -1.50000
AFIX   0
C20   1    0.773000    0.572731    0.735936    11.00000    0.17573    0.05735 =
         0.04694   -0.01662   -0.02759    0.03123
PART 1
AFIX  23
H20A  2    0.785345    0.588095    0.710273    21.00000   -1.20000
H20B  2    0.814209    0.558079    0.753994    21.00000   -1.20000
AFIX  23
PART 2
H20C  2    0.771455    0.591828    0.708637   -21.00000   -1.20000
H20D  2    0.816657    0.526583    0.743066   -21.00000   -1.20000
AFIX   0
PART 1
C21   1    0.726337    0.687441    0.749073    21.00000    0.09428    0.03684 =
         0.03443   -0.00190    0.01422   -0.00560
AFIX  23
H21A  2    0.685582    0.700635    0.730573    21.00000   -1.20000
H21B  2    0.712275    0.667251    0.774095    21.00000   -1.20000
AFIX   0
PART 2
C21X  1    0.785037    0.714481    0.754629   -21.00000    0.07549    0.05114 =
         0.02589   -0.00031    0.01211   -0.00436
AFIX  23
H21C  2    0.797897    0.706761    0.782232   -21.00000   -1.20000
H21D  2    0.820873    0.763786    0.743564   -21.00000   -1.20000

HKLF 4

REM  ab107 in I2/a
REM R1 =  0.0397 for   5548 Fo > 4sig(Fo)  and  0.0516 for all   7060 data
REM    341 parameters refined using      6 restraints

END
;