An [FeIII30] molecular metal oxide
Dearle, Alice E.; Cutler, Daniel J.; Coletta, Marco; Lee, Edward; Dey, Sourav; Sanz, Sergio; Fraser, Hector W. L.; Nichol, Gary S.; Rajaraman, Gopalan; Schnack, Jürgen; Cronin, Leroy; Brechin, Euan K.; Chemical Communications  (2021) –; doi:10.1039/D1CC06224G

data_7129278
_publ_section_title
;
 An [FeIII30] molecular metal oxide
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06224G
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C105 H135 Br9 Fe30 N15 O47, 3(Br), 1[C7H9N], [solvent]'
_chemical_formula_sum            'C112 H159 Br12 Fe30 N16 O47'
_chemical_formula_weight         5115.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-04-09
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-26 deposited with the CCDC.	2021-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.882(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.929(3)
_cell_length_b                   21.777(2)
_cell_length_c                   32.273(4)
_cell_measurement_reflns_used    9629
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      18.27
_cell_measurement_theta_min      2.15
_cell_volume                     21581(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'GDA - generic data acquisition software'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Photon counting pixel array'
_diffrn_detector_type            'Dectris PILATUS 2M'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Fixed \c 3-circle diffractometer'
_diffrn_measurement_device_type  'Diamond Light Source I-19 EH1'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMount'
_diffrn_radiation_monochromator  'Silicon 111'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0752
_diffrn_reflns_av_unetI/netI     0.0812
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            168652
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        20.136
_diffrn_reflns_theta_max         20.136
_diffrn_reflns_theta_min         0.835
_diffrn_source                   Synchrotron
_diffrn_source_current           0.0
_diffrn_source_details           'Allan et al. (2017)'
_diffrn_source_power             0.0
_diffrn_source_type              'Diamond Light Source Beamline I19-1'
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_entry.id                        xia2
_exptl_absorpt_coefficient_mu    3.885
_exptl_absorpt_correction_T_max  0.4251
_exptl_absorpt_correction_T_min  0.2287
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1294 before and 0.0795 after correction.
The Ratio of minimum to maximum transmission is 0.5380.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       plate
_exptl_crystal_F_000             10076
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetonitrile and isopropanol  by vapour diffusion'
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.468
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.159(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3442
_refine_ls_number_reflns         44728
_refine_ls_number_restraints     9631
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.0794
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0830P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1405
_refine_ls_wR_factor_ref         0.1530
_reflns_Friedel_coverage         0.989
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                32432
_reflns_number_total             44728
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06224g2.cif
_cod_data_source_block           eb20195
_cod_original_cell_volume        21580(4)
_cod_database_code               7129278
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.854
_shelx_estimated_absorpt_t_min   0.599
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.841(10)
 0.159(10)
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
 C93-C89 = C86-C82 = C58-C54 = C44-C40 = C30-C26 = C23-C19 = C37-C33 = C51-C47
 = C96-C100 = C7-C3 = C14-C10 = C79-C75 = C72-C68 = C65-C61
 1.51 with sigma of 0.02
 C207-C203 = C214-C210 = C221-C217 = C228-C224 = C235-C231 = C242-C238 = C249-
 C245 = C256-C252 = C263-C259 = C270-C266 = C277-C273 = C284-C280 = C291-C287 =
 C298-C294 = C305-C301
 1.5 with sigma of 0.02
 C7-C6 = C14-C13 = C23-C22 = C30-C29 = C36-C37 = C43-C44 = C51-C50 = C57-C58 =
 C64-C65 = C72-C71 = C79-C78 = C86-C85 = C92-C93 = C99-C100 = C106-C107
 2.97 with sigma of 0.02
 C207-C206 = C213-C214 = C220-C221 = C228-C227 = C234-C235 = C241-C242 = C248-
 C249 = C256-C255 = C263-C262 = C270-C269 = C276-C277 = C283-C284 = C290-C291 =
 C297-C298 = C304-C305
 2.97 with sigma of 0.02
 C57-C53 = C43-C39 = C22-C18 = C36-C32 = C99-C95 = C92-C88 = C85-C81 = C78-C74
 = C71-C67 = C64-C60 = C9-C13 = C6-C2
 1.5 with sigma of 0.02
 C206-C202 = C213-C209 = C220-C216 = C227-C223 = C234-C230 = C241-C237 = C248-
 C244 = C255-C251 = C262-C258 = C269-C265 = C276-C272 = C283-C279 = C290-C286 =
 C297-C293 = C304-C300
 1.51 with sigma of 0.02
 C107-C103
 1.51 with sigma of 0.02
 C50-C46
 1.5 with sigma of 0.02
 C106-C104
 1.5 with sigma of 0.02
 C29-C25
 1.5 with sigma of 0.02
4. Restrained planarity
 N10, C66, C67, C68, C69, C70, C71, C72
 with sigma of 0.1
 N205, C229, C230, C231, C232, C233, C234, C235
 with sigma of 0.1
 N2, C8, C9, C10, C11, C12, C13, C14
 with sigma of 0.1
 N6, C38, C39, C40, C41, C42, C43, C44
 with sigma of 0.1
 N13, C87, C88, C89, C90, C91, C92, C93
 with sigma of 0.1
 N203, C215, C216, C217, C218, C219, C220, C221
 with sigma of 0.1
 N211, C271, C272, C273, C274, C275, C276, C277
 with sigma of 0.1
 N214, C292, C293, C294, C295, C296, C297, C298
 with sigma of 0.1
 N7, C45, C46, C47, C48, C49, C50, C51
 with sigma of 0.1
 N8, C52, C53, C54, C55, C56, C57, C58
 with sigma of 0.1
 N209, C257, C258, C259, C260, C261, C262, C263
 with sigma of 0.1
 N4, C24, C25, C26, C27, C28, C29, C30
 with sigma of 0.1
 N215, C299, C300, C301, C302, C303, C305
 with sigma of 0.1
 N15, C101, C102, C103, C104, C105, C106, C107
 with sigma of 0.1
 N208, C250, C251, C252, C253, C254, C255, C256
 with sigma of 0.1
 N206, C236, C237, C238, C239, C240, C241, C242
 with sigma of 0.1
 N11, C73, C74, C75, C76, C77, C78, C79
 with sigma of 0.1
 N9, C59, C60, C61, C62, C63, C64, C65
 with sigma of 0.1
 N5, C31, C32, C33, C34, C35, C36, C37
 with sigma of 0.1
 N12, C80, C81, C82, C83, C84, C85, C86
 with sigma of 0.1
 N1, C1, C2, C3, C4, C5, C6, C7
 with sigma of 0.1
 N14, C94, C95, C96, C97, C98, C99, C100
 with sigma of 0.1
 N3, C17, C18, C19, C20, C21, C22, C23
 with sigma of 0.1
 N207, C243, C244, C245, C246, C247, C248, C249
 with sigma of 0.1
 N213, C285, C286, C287, C288, C289, C290, C291
 with sigma of 0.1
 N210, C264, C265, C266, C267, C268, C269, C270
 with sigma of 0.1
 N201, C201, C202, C203, C204, C205, C206, C207
 with sigma of 0.1
 N212, C278, C279, C280, C281, C282, C283, C284
 with sigma of 0.1
 N202, C208, C209, C210, C211, C212, C213, C214
 with sigma of 0.1
 N204, C222, C223, C224, C225, C226, C227, C228
 with sigma of 0.1
5. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. 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
7. 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
8.a Me refined with riding coordinates:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C29(H29A,H29B,H29C), C44(H44A,H44B,
 H44C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C57(H57A,H57B,H57C), C71(H71A,
 H71B,H71C), C93(H93A,H93B,H93C), C106(H10D,H10E,H10F), C107(H10G,H10H,H10I),
 C220(H22D,H22E,H22F), C221(H22G,H22H,H22I), C234(H23D,H23E,H23F), C235(H23G,
 H23H,H23I), C242(H24D,H24E,H24F), C256(H25D,H25E,H25F), C263(H26D,H26E,H26F),
 C276(H27D,H27E,H27F), C297(H29J,H29K,H29L), C298(H29M,H29N,H29O), C305(H30G,
 H30H,H30I)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C8(H8), C11(H11), C12(H12), C17(H17), C20(H20),
 C21(H21), C28(H28), C27(H27), C24(H24), C35(H35), C34(H34), C31(H31), C42(H42),
  C41(H41), C38(H38), C45(H45), C48(H48), C49(H49), C56(H56), C55(H55),
 C52(H52), C63(H63), C62(H62), C59(H59), C66(H66), C69(H69), C70(H70), C73(H73),
  C76(H76), C77(H77), C84(H84), C83(H83), C80(H80), C91(H91), C90(H90),
 C87(H87), C98(H98), C97(H97), C94(H94), C105(H105), C102(H102), C101(H101),
 C205(H205), C204(H204), C201(H201), C208(H208), C211(H211), C212(H212),
 C215(H215), C218(H218), C219(H219), C226(H226), C225(H225), C222(H222),
 C229(H229), C232(H232), C233(H233), C240(H240), C239(H239), C236(H236),
 C243(H243), C246(H246), C247(H247), C250(H250), C253(H253), C254(H254),
 C257(H257), C260(H260), C261(H261), C264(H264), C267(H267), C268(H268),
 C275(H275), C274(H274), C271(H271), C278(H278), C281(H281), C282(H282),
 C285(H285), C288(H288), C289(H289), C296(H296), C295(H295), C292(H292),
 C299(H299), C302(H302), C303(H303)
8.c Fitted hexagon refined as free rotating group:
 N1(C1,C2,C3,C4,C5), N2(C8,C9,C10,C11,C12), N3(C17,C18,C19,C20,C21), N4(C28,
 C27,C26,C25,C24), N5(C35,C34,C33,C32,C31), N6(C42,C41,C40,C39,C38), N7(C45,C46,
 C47,C48,C49), N8(C56,C55,C54,C53,C52), N9(C63,C62,C61,C60,C59), N10(C66,C67,
 C68,C69,C70), N11(C73,C74,C75,C76,C77), N12(C84,C83,C82,C81,C80), N13(C91,C90,
 C89,C88,C87), N14(C98,C97,C96,C95,C94), N15(C105,C104,C103,C102,C101),
 N201(C205,C204,C203,C202,C201), N202(C208,C209,C210,C211,C212), N203(C215,C216,
 C217,C218,C219), N204(C226,C225,C224,C223,C222), N205(C229,C230,C231,C232,
 C233), N206(C240,C239,C238,C237,C236), N207(C243,C244,C245,C246,C247),
 N208(C250,C251,C252,C253,C254), N209(C257,C258,C259,C260,C261), N210(C264,C265,
 C266,C267,C268), N211(C275,C274,C273,C272,C271), N212(C278,C279,C280,C281,
 C282), N213(C285,C286,C287,C288,C289), N214(C296,C295,C294,C293,C292),
 N215(C299,C300,C301,C302,C303)
8.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C),
 C30(H30A,H30B,H30C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C43(H43A,H43B,
 H43C), C58(H58A,H58B,H58C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C72(H72A,
 H72B,H72C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C85(H85A,H85B,H85C),
 C86(H86A,H86B,H86C), C92(H92A,H92B,H92C), C99(H99A,H99B,H99C), C100(H10A,H10B,
 H10C), C206(H20A,H20B,H20C), C207(H20D,H20E,H20F), C213(H21A,H21B,H21C),
 C214(H21D,H21E,H21F), C227(H22J,H22K,H22L), C228(H22M,H22N,H22O), C241(H24A,
 H24B,H24C), C248(H24G,H24H,H24I), C249(H24J,H24K,H24L), C255(H25A,H25B,H25C),
 C262(H26A,H26B,H26C), C269(H26G,H26H,H26I), C270(H27A,H27B,H27C), C277(H27G,
 H27H,H27I), C283(H28A,H28B,H28C), C284(H28D,H28E,H28F), C290(H29D,H29E,H29F),
 C291(H29G,H29H,H29I), C304(H30D,H30E,H30F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1520 electrons were 
found in a volume of 7494\%A^3^ in 1 void per unit cell. 
 
Charge balance requires the presence of two bromide per Fe30 cluster. 
The asymmetric unit contains six bromide, four of which balance the Fe30 charge. 
The remaining two bromide are assumed to be balanced by the presence of two additional 
lutidinium cations in the asymmetric unit which are highly disordered in the residual 
electron density and cannot be modelled. This accounts for 232 electrons in the asymmetric unit. 
 
Solvent masking indicates a further 528 electrons in the asymmetric unit. This is assumed 
to be solvent but no attempt has been made to model this. It is worth noting that, before 
solvent masking, the largest residual peak was less than 3 electrons high. This indicates that 
the residual density remaining when the two Fe30 clusters and six bromide anions were located 
is very diffuse and almost impossible to model using discrete atoms.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              70559
_shelx_fab_checksum              82574
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id 'MC_Exp 1321_iPrOH'
_olex2_submission_special_instructions 'No special instructions were received'