Fine-tuning polyoxometalate non-linear optical chromophores: a molecular electronic "Goldilocks" effect.
Al-Yasari, Ahmed; Spence, Philip; El Moll, Hani; Van Steerteghem, Nick; Horton, Peter N.; Brunschwig, Bruce S.; Clays, Koen; Fielden, John; Dalton transactions (Cambridge, England : 2003) 47 (2018) 10415–10419; doi:10.1039/c8dt01491d

data_7046864
_publ_section_title
;
 Fine-tuning polyoxometalate non-linear optical chromophores: a molecular
 electronic &quot;Goldilocks&quot; effect.
;
_journal_issue                   31
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10415
_journal_page_last               10419
_journal_paper_doi               10.1039/c8dt01491d
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety         'C26 H16 Mo6 N2 O18, 2(C16 H36 N)'
_chemical_formula_sum            'C58 H88 Mo6 N4 O18'
_chemical_formula_weight         1704.96
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-04-16 deposited with the CCDC.
2018-05-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.088(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8775(4)
_cell_length_b                   19.8944(9)
_cell_length_c                   28.8994(16)
_cell_measurement_reflns_used    14473
_cell_measurement_temperature    140(1)
_cell_measurement_theta_max      27.3470
_cell_measurement_theta_min      3.2330
_cell_volume                     6701.3(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1127
_diffrn_reflns_av_unetI/netI     0.0704
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            140513
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.872
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.157
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.690
_exptl_crystal_description       plate
_exptl_crystal_F_000             3440
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile, diethyl ether'
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.785
_refine_diff_density_min         -0.925
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1231
_refine_ls_number_reflns         15346
_refine_ls_number_restraints     4494
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.1866
_refine_ls_R_factor_gt           0.1103
_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^)+(0.1291P)^2^+54.2677P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2707
_refine_ls_wR_factor_ref         0.3278
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7508
_reflns_number_total             15346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt01491d2.cif
_cod_data_source_block           platon_pl
_cod_depositor_comments
'Adding full bibliography for 7046864--7046865.cif.'
_cod_database_code               7046864
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.624
_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
2. Restrained distances
 C224-C234 = C240-C246 = C240-C245 = C241-C246 = C234-C258_$2 = C246-C208
 -2.8 with sigma of 0.02
 C242-C265_$1 = C260-C264 = C265-C242_$4 = C258-C234_$3 = C246-C209
 -2.8 with sigma of 0.02
 C246-C207 = C224-C266_$5
 -2.8 with sigma of 0.02
 N2-C15 \\sim N2-C26
 with sigma of 0.02
 C43-C44 \\sim C44-C45 \\sim C45-C46 \\sim C31-C32 \\sim C32-C33 \\sim C33-C34
\\sim C35-C36 \\sim C36-C37
 \\sim C37-C38 \\sim C39-C40 \\sim C40-C41 \\sim C41-C42
 with sigma of 0.02
 C43-C45 \\sim C44-C46 \\sim C31-C33 \\sim C32-C34 \\sim C35-C37 \\sim C36-C38
\\sim C39-C41 \\sim C40-C42
 with sigma of 0.04
 C43-C31 \\sim C31-C35 \\sim C35-C39
 with sigma of 0.04
 C55-C56 \\sim C56-C57 \\sim C57-C58 \\sim C51-C52 \\sim C52-C53 \\sim C53-C54
\\sim C63-C64 \\sim C64-C65
 \\sim C65-C66 \\sim C59-C60 \\sim C60-C61 \\sim C61-C62
 with sigma of 0.02
 C55-C57 \\sim C56-C58 \\sim C51-C53 \\sim C52-C54 \\sim C63-C65 \\sim C64-C66
\\sim C59-C61 \\sim C60-C62
 with sigma of 0.04
 C55-C51 \\sim C51-C63 \\sim C63-C59
 with sigma of 0.04
 C203-C207 \\sim C207-C205
 with sigma of 0.02
 C210-C208 \\sim C208-C214
 with sigma of 0.02
 C213-N202 \\sim N202-C211
 with sigma of 0.02
 C215-N202 \\sim N202-C226
 with sigma of 0.02
 N2-C12 \\sim N202-C212
 with sigma of 0.02
 C21-C20 \\sim C220-C221
 with sigma of 0.02
 C1-N1 \\sim N1-C201
 with sigma of 0.02
 C243-C244 \\sim C244-C245 \\sim C245-C246 \\sim C231-C232 \\sim C232-C233
\\sim C233-C234 \\sim C235-
 C236 \\sim C236-C237 \\sim C237-C238 \\sim C239-C240 \\sim C240-C241 \\sim
C241-C242
 with sigma of 0.02
 C243-C245 \\sim C244-C246 \\sim C231-C233 \\sim C232-C234 \\sim C235-C237
\\sim C236-C238 \\sim C239-
 C241 \\sim C240-C242
 with sigma of 0.04
 C243-C231 \\sim C231-C235 \\sim C235-C239
 with sigma of 0.04
 C255-C256 \\sim C256-C257 \\sim C257-C258 \\sim C251-C252 \\sim C252-C253
\\sim C253-C254 \\sim C263-
 C264 \\sim C264-C265 \\sim C265-C266 \\sim C259-C260 \\sim C260-C261 \\sim
C261-C262
 with sigma of 0.02
 C255-C257 \\sim C256-C258 \\sim C251-C253 \\sim C252-C254 \\sim C263-C265
\\sim C264-C266 \\sim C259-
 C261 \\sim C260-C262
 with sigma of 0.04
 C255-C251 \\sim C251-C263 \\sim C263-C259
 with sigma of 0.04
 C35-C31 \\sim C31-C43
 with sigma of 0.02
 C31-C43 \\sim C43-C39
 with sigma of 0.02
 C43-C39 \\sim C39-C35
 with sigma of 0.02
 C39-C35 \\sim C35-C31
 with sigma of 0.02
 C63-C51 \\sim C51-C55
 with sigma of 0.02
 C51-C55 \\sim C55-C59
 with sigma of 0.02
 C55-C59 \\sim C59-C63
 with sigma of 0.02
 C59-C63 \\sim C63-C51
 with sigma of 0.02
 C239-C235 \\sim C235-C231
 with sigma of 0.02
 C235-C231 \\sim C231-C243
 with sigma of 0.02
 C231-C243 \\sim C243-C239
 with sigma of 0.02
 C243-C239 \\sim C239-C235
 with sigma of 0.02
 C259-C255 \\sim C255-C251
 with sigma of 0.02
 C255-C251 \\sim C251-C263
 with sigma of 0.02
 C251-C263 \\sim C263-C259
 with sigma of 0.02
 C263-C259 \\sim C259-C255
 with sigma of 0.02
 C40-C39 \\sim C240-C239 \\sim C256-C255 \\sim C52-C51
 with sigma of 0.02
 C241-C240 \\sim C41-C40 \\sim C257-C256 \\sim C57-C56
 with sigma of 0.02
 C258-C257 \\sim C58-C57 \\sim C42-C41 \\sim C242-C241
 with sigma of 0.02
 N31-C43 \\sim N31-C39 \\sim N31-C35 \\sim N31-C31 \\sim N231-C243 \\sim
N231-C239 \\sim N231-C235 ~
 N231-C231
 with sigma of 0.02
 N51-C55 \\sim N51-C59 \\sim N51-C63 \\sim N51-C51 \\sim N251-C255 \\sim
N251-C259 \\sim N251-C263 ~
 N251-C251
 with sigma of 0.02
 N31-C35 \\sim N231-C235 \\sim N251-C251 \\sim N51-C59
 with sigma of 0.02
 N51-C60 \\sim N251-C264 \\sim N31-C36 \\sim N231-C236
 with sigma of 0.02
3. Restrained planarity
 N2, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26
 with sigma of 0.01
4. 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
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(N202)=Sof(C201)=Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=Sof(C204)=
 Sof(C205)=Sof(H205)=Sof(C206)=Sof(H206)=Sof(C207)=Sof(C208)=Sof(C209)=
 Sof(C210)=Sof(H210)=Sof(C211)=Sof(H211)=Sof(C212)=Sof(C213)=Sof(H213)=
 Sof(C214)=Sof(H214)=Sof(C215)=Sof(C216)=Sof(H216)=Sof(C217)=Sof(H217)=
 Sof(C218)=Sof(H218)=Sof(C219)=Sof(H219)=Sof(C220)=Sof(C226)=Sof(C221)=
 Sof(C222)=Sof(H222)=Sof(C223)=Sof(H223)=Sof(C224)=Sof(H224)=Sof(C225)=
 Sof(H225)=1-FVAR(1)
 Sof(N2)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(C8)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(C20)=Sof(C19)=
 Sof(H19)=Sof(C18)=Sof(H18)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=Sof(C26)=
 Sof(C25)=Sof(H25)=Sof(C24)=Sof(H24)=Sof(C23)=Sof(H23)=Sof(C22)=Sof(H22)=
 Sof(C21)=FVAR(1)
 Sof(N251)=Sof(C251)=Sof(H25A)=Sof(H25B)=Sof(C255)=Sof(H25C)=Sof(H25D)=
 Sof(C259)=Sof(H25E)=Sof(H25F)=Sof(C263)=Sof(H26A)=Sof(H26B)=Sof(C252)=
 Sof(H25G)=Sof(H25H)=Sof(C256)=Sof(H25I)=Sof(H25J)=Sof(C260)=Sof(H26C)=
 Sof(H26D)=Sof(C264)=Sof(H26E)=Sof(H26F)=Sof(C253)=Sof(H25K)=Sof(H25L)=
 Sof(C257)=Sof(H25M)=Sof(H25N)=Sof(C261)=Sof(H26G)=Sof(H26H)=Sof(C265)=
 Sof(H26I)=Sof(H26J)=Sof(C254)=Sof(H25O)=Sof(H25P)=Sof(H25Q)=Sof(C258)=
 Sof(H25R)=Sof(H25S)=Sof(H25T)=Sof(C262)=Sof(H26K)=Sof(H26L)=Sof(H26M)=
 Sof(C266)=Sof(H26N)=Sof(H26O)=Sof(H26P)=1-FVAR(2)
 Sof(N51)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=
 Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=
 Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C65)=Sof(H65A)=
 Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(2)
 Sof(N231)=Sof(C231)=Sof(H23A)=Sof(H23B)=Sof(C235)=Sof(H23C)=Sof(H23D)=
 Sof(C239)=Sof(H23E)=Sof(H23F)=Sof(C243)=Sof(H24A)=Sof(H24B)=Sof(C232)=
 Sof(H23G)=Sof(H23H)=Sof(C236)=Sof(H23I)=Sof(H23J)=Sof(C240)=Sof(H24C)=
 Sof(H24D)=Sof(C244)=Sof(H24E)=Sof(H24F)=Sof(C233)=Sof(H23K)=Sof(H23L)=
 Sof(C237)=Sof(H23M)=Sof(H23N)=Sof(C241)=Sof(H24G)=Sof(H24H)=Sof(C245)=
 Sof(H24I)=Sof(H24J)=Sof(C234)=Sof(H23O)=Sof(H23P)=Sof(H23Q)=Sof(C238)=
 Sof(H23R)=Sof(H23S)=Sof(H23T)=Sof(C242)=Sof(H24K)=Sof(H24L)=Sof(H24M)=
 Sof(C246)=Sof(H24N)=Sof(H24O)=Sof(H24P)=1-FVAR(3)
 Sof(N31)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C55(H55A,H55B), C56(H56A,
 H56B), C57(H57A,H57B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B),
 C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C31(H31A,H31B), C32(H32A,H32B),
  C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C39(H39A,
 H39B), C40(H40A,H40B), C41(H41A,H41B), C43(H43A,H43B), C44(H44A,H44B),
 C45(H45A,H45B), C251(H25A,H25B), C255(H25C,H25D), C259(H25E,H25F), C263(H26A,
 H26B), C252(H25G,H25H), C256(H25I,H25J), C260(H26C,H26D), C264(H26E,H26F),
 C253(H25K,H25L), C257(H25M,H25N), C261(H26G,H26H), C265(H26I,H26J), C231(H23A,
 H23B), C235(H23C,H23D), C239(H23E,H23F), C243(H24A,H24B), C232(H23G,H23H),
 C236(H23I,H23J), C240(H24C,H24D), C244(H24E,H24F), C233(H23K,H23L), C237(H23M,
 H23N), C241(H24G,H24H), C245(H24I,H24J)
7.b Me refined with riding coordinates:
 C54(H54A,H54B,H54C), C58(H58A,H58B,H58C), C62(H62A,H62B,H62C), C66(H66A,H66B,
 H66C), C34(H34A,H34B,H34C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C), C46(H46A,
 H46B,H46C), C254(H25O,H25P,H25Q), C258(H25R,H25S,H25T), C262(H26K,H26L,H26M),
 C266(H26N,H26O,H26P), C234(H23O,H23P,H23Q), C238(H23R,H23S,H23T), C242(H24K,
 H24L,H24M), C246(H24N,H24O,H24P)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C11(H11), C13(H13), C14(H14),
 C19(H19), C18(H18), C17(H17), C16(H16), C25(H25), C24(H24), C23(H23), C22(H22),
  C202(H202), C203(H203), C205(H205), C206(H206), C210(H210), C211(H211),
 C213(H213), C214(H214), C216(H216), C217(H217), C218(H218), C219(H219),
 C222(H222), C223(H223), C224(H224), C225(H225)
7.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C9(C10,C11,C12,C13,C14), C15(C20,C19,C18,C17,C16),
 C26(C25,C24,C23,C22,C21), C201(C202,C203,C204,C205,C206), C209(C210,C211,C212,
 C213,C214), C215(C216,C217,C218,C219,C220), C226(C221,C222,C223,C224,C225)
;
_shelx_res_checksum              13504
_olex2_submission_special_instructions 'No special instructions were received'