Bridge improvement work: maximising non-linear optical performance in polyoxometalate derivatives.
Jones, Claire F.; Hood, Bethany R.; de Coene, Yovan; Lopez-Poves, Ivan; Champagne, Benoît; Clays, Koen; Fielden, John; Chemical communications (Cambridge, England) 60 (2024) 1731–1734; doi:10.1039/d3cc05433k

data_7132613
_publ_section_title
;
 Bridge improvement work: maximising non-linear optical performance in
 polyoxometalate derivatives.
;
_journal_issue                   13
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1731
_journal_page_last               1734
_journal_paper_doi               10.1039/d3cc05433k
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C18 H14 Mo6 N2 O18, 3(C2 H3 N), 2(C16 H36 N)'
_chemical_formula_sum            'C56 H95 Mo6 N7 O18'
_chemical_formula_weight         1730.02
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-12-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-12-19 deposited with the CCDC.	2024-01-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.5480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.44060(10)
_cell_length_b                   29.2646(3)
_cell_length_c                   18.9032(2)
_cell_measurement_reflns_used    22066
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2500
_cell_measurement_theta_min      3.0510
_cell_volume                     6875.27(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.932
_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    -69.00  21.00   0.50    2.42    --  -47.47  94.00  18.00  180
  2  \w      7.00  36.00   0.50    2.42    --   47.47 -94.00 -92.00   58
  3  \w    -77.00 -52.00   0.50    9.68    --  -91.75  94.00  18.00   50
  4  \w    -46.00 -20.00   0.50    9.68    --  -91.75  94.00  18.00   52
  5  \w     34.00 105.00   0.50    9.68    --  106.59 -94.00 -92.00  142
  6  \w    106.00 146.00   0.50    9.68    --  106.59  94.00  18.00   80
  7  \w   -120.00 -94.00   0.50    2.42    --  -47.47 -57.00   0.00   52
  8  \w   -119.00 -92.00   0.50    2.42    --  -47.47-125.00   0.00   54
  9  \w   -120.00 -95.00   0.50    2.42    --  -47.47 -57.00 -60.00   50
 10  \w   -118.00 -92.00   0.50    2.42    --  -47.47-125.00-180.00   52
 11  \w   -120.00 -94.00   0.50    2.42    --  -47.47 -57.00 -30.00   52
 12  \w     94.00 120.00   0.50    2.42    --   47.47  57.00  30.00   52
 13  \w     94.00 120.00   0.50    2.42    --   47.47  57.00   0.00   52
 14  \w     94.00 119.00   0.50    2.42    --   47.47  57.00  60.00   50
 15  \w    -51.00 -26.00   0.50    9.68    --  -91.75  45.00-180.00   50
 16  \w    -48.00 -22.00   0.50    9.68    --  -91.75  45.00-120.00   52
 17  \w    -50.00 -20.00   0.50    9.68    --  -91.75  45.00 -30.00   60
 18  \w   -137.00-111.00   0.50    9.68    --  -91.75 -77.00 150.00   52
 19  \w    -46.00 -20.00   0.50    9.68    --  -91.75  45.00 -60.00   52
 20  \w    -51.00 -20.00   0.50    9.68    --  -91.75  61.00   0.00   62
 21  \w    -46.00 -20.00   0.50    9.68    --  -91.75  45.00  30.00   52
 22  \w    -46.00 -20.00   0.50    9.68    --  -91.75  45.00   0.00   52
 23  \w   -123.00 -98.00   0.50    9.68    --  -91.75 -94.00 -92.00   50
 24  \w    -51.00 -25.00   0.50    9.68    --  -91.75  45.00 120.00   52
 25  \w    -50.00 -20.00   0.50    9.68    --  -91.75  45.00  90.00   60
 26  \w    -66.00 -27.00   0.50    9.68    --  -91.75  61.00 -30.00   78
 27  \w     41.00  70.00   0.50    9.68    --  106.59 -61.00 150.00   58
 28  \w     44.00  69.00   0.50    9.68    --  106.59 -61.00 120.00   50
 29  \w     42.00  67.00   0.50    9.68    --  106.59 -77.00 -60.00   50
 30  \w    145.00 176.00   0.50    9.68    --  106.59 125.00  90.00   62
 31  \w     39.00  66.00   0.50    9.68    --  106.59 -61.00-180.00   54
 32  \w     81.00 106.00   0.50    9.68    --  106.59 -77.00 -60.00   50
 33  \w     95.00 120.00   0.50    9.68    --  106.59 125.00  90.00   50
 34  \w     34.00  59.00   0.50    9.68    --  106.59 -61.00  90.00   50
 35  \w     34.00  71.00   0.50    9.68    --  106.59 -61.00  30.00   74
 36  \w     40.00  71.00   0.50    9.68    --  106.59 -61.00  60.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0779655000
_diffrn_orient_matrix_UB_12      -0.0391039000
_diffrn_orient_matrix_UB_13      0.0164214000
_diffrn_orient_matrix_UB_21      -0.0482333000
_diffrn_orient_matrix_UB_22      0.0292886000
_diffrn_orient_matrix_UB_23      0.0584134000
_diffrn_orient_matrix_UB_31      -0.0834127000
_diffrn_orient_matrix_UB_32      0.0196125000
_diffrn_orient_matrix_UB_33      -0.0545309000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            50359
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.123
_diffrn_reflns_theta_min         2.785
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.273
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61311
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.671
_exptl_crystal_description       block
_exptl_crystal_F_000             3504
_exptl_crystal_preparation       'Crystallised from hot acetonitrile'
_exptl_crystal_recrystallization_method 'Crystallised from hot acetonitrile'
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.160
_refine_diff_density_min         -1.040
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     846
_refine_ls_number_reflns         13558
_refine_ls_number_restraints     780
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0576P)^2^+20.9510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1270
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11462
_reflns_number_total             13558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05433k2.cif
_cod_data_source_block           ilp1x_auto
_cod_depositor_comments          'Adding full bibliography for 7132613.cif.'
_cod_database_code               7132613
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Mo6 O18 N4 C50 H86'
_shelx_estimated_absorpt_t_max   0.697
_shelx_estimated_absorpt_t_min   0.320
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Mo5-Mo4
 3.301 with sigma of 0.001
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C49-C54 \\sim C49A-C54A
 with sigma of 0.02
 N48-C49 \\sim N48-C49A
 with sigma of 0.02
 C50-C54 \\sim C50A-C54A
 with sigma of 0.04
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C53-C52 \\sim C53A-C52A
 with sigma of 0.02
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C52-C51 \\sim C52A-C51A
 with sigma of 0.02
 C53-C51 \\sim C53A-C51A
 with sigma of 0.04
 N48-C50 \\sim N48-C50A
 with sigma of 0.04
 N48-C54 \\sim N48-C54A
 with sigma of 0.04
 C49-C53 \\sim C49A-C53A
 with sigma of 0.04
 C49-C51 \\sim C49A-C51A
 with sigma of 0.04
 C54-C52 \\sim C54A-C52A
 with sigma of 0.04
 C69-C71 \\sim C69-C71A
 with sigma of 0.02
 C2_$1-N3 \\sim C2_$1-N3A
 with sigma of 0.02
 N3A-C2 \\sim C2-N3
 with sigma of 0.02
 C81-N80 \\sim C2-N3A
 with sigma of 0.02
 C81-N80 \\sim N2-C3
 with sigma of 0.02
 N80-C81 \\sim N2-C3 \\sim N3A-C2
 with sigma of 0.02
 C4-C3 \\sim C82-C81 \\sim C1-C2
 with sigma of 0.02
3. Restrained planarity
 C55, C56, C57, C58, C59, C60
 with sigma of 0.1
 C42, C43, C44, C45, C46, C47
 with sigma of 0.1
 C49, C50, C51, C52, C53, C54
 with sigma of 0.1
4. Rigid bond restraints
 C63, C64, C65, C66, C66A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3, N3A, C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, N3, N3A, N80
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(N3A) = Uanis(N3)
Uanis(N3A) = Uanis(N3) = Uanis(C2) = Uanis(C1)
Uanis(N2) = Uanis(C3) = Uanis(C4)
Uanis(C66) = Uanis(C66A)
6. Others
 Sof(H65C)=Sof(H65D)=Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=1-FVAR(1)
 Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(1)
 Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=1-FVAR(2)
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(H54)=FVAR(2)
 Sof(H69C)=Sof(H69D)=Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=1-FVAR(3)
 Sof(H69A)=Sof(H69B)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=FVAR(3)
 Sof(N3A)=1-FVAR(4)
 Sof(N3)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C63(H63A,H63B), C64(H64A,H64B),
  C65(H65A,H65B), C65(H65C,H65D), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,
 H69B), C69(H69C,H69D), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
 C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B)
7.b Aromatic/amide H refined with riding coordinates:
 C43(H43), C44(H44), C46(H46), C47(H47), C50(H50), C50A(H50A), C51(H51),
 C51A(H51A), C52(H52), C52A(H52A), C53(H53), C53A(H53A), C54(H54), C54A(H54A),
 C56(H56), C57(H57), C58(H58), C59(H59), C60(H60)
7.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C1(H1A,H1B,H1C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C),
 C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C66(H66A,H66B,H66C), C66A(H66D,H66E,
 H66F), C71(H71A,H71B,H71C), C71A(H71D,H71E,H71F), C75(H75A,H75B,H75C),
 C79(H79A,H79B,H79C), C82(H82A,H82B,H82C)
;
_shelx_res_checksum              82687
_shelx_hkl_checksum              67551
_olex2_exptl_crystal_mounting_method 'Loop with paratone oil'
_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 1.719
_oxdiff_exptl_absorpt_empirical_full_min 0.592