Synthesis and characterization of cyclodiphosphazanes embedded macrocycle tetrabromo-resorcin[4]arene-tetrakis(cyclodiphospha-zane) and its tetra-rhodium(I) complex
Pandey, Madhusudan Kumar; Sheokand, Sonu; Balakrishna, Maravanji Shivaramaiah; Dalton Transactions  (2023) –; doi:10.1039/D3DT00880K

data_7712752
_publ_section_title
;
 Synthesis and characterization of cyclodiphosphazanes embedded macrocycle
 tetrabromo-resorcin[4]arene-tetrakis(cyclodiphospha-zane) and its
 tetra-rhodium(I) complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00880K
_journal_year                    2023
_chemical_formula_moiety         'C76 H116 Br4 N8 O8 P8, C6 H14'
_chemical_formula_sum            'C82 H130 Br4 N8 O8 P8'
_chemical_formula_weight         1923.33
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-03-23 deposited with the CCDC.	2023-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                89.631(2)
_cell_angle_beta                 72.434(2)
_cell_angle_gamma                83.770(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7606(3)
_cell_length_b                   19.6694(5)
_cell_length_c                   19.8216(5)
_cell_measurement_reflns_used    16640
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      30.1660
_cell_measurement_theta_min      2.0730
_cell_volume                     4713.3(2)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -110.00  25.00   0.50    8.00    --  -20.00   0.00  36.00  270
  2  \w   -110.00  10.00   0.50    8.00    --  -20.00 -72.00  36.00  240
  3  \w    -72.00   9.00   0.50    8.00    --  -20.00 -72.00-180.00  162
  4  \w    -53.50   2.00   0.50    8.00    --  -20.00  72.00 -36.00  111
  5  \w    -59.00 -28.50   0.50    8.00    --  -20.00  72.00-180.00   61
  6  \w    -39.00  -9.00   0.50    8.00    --  -20.00 -72.00 -36.00   60
  7  \w   -110.00  -5.00   0.50    8.00    --  -20.00   0.00 108.00  210
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0036679000
_diffrn_orient_matrix_UB_12      -0.0255101000
_diffrn_orient_matrix_UB_13      0.0248941000
_diffrn_orient_matrix_UB_21      0.0583969000
_diffrn_orient_matrix_UB_22      -0.0005626000
_diffrn_orient_matrix_UB_23      -0.0110776000
_diffrn_orient_matrix_UB_31      -0.0043245000
_diffrn_orient_matrix_UB_32      0.0258036000
_diffrn_orient_matrix_UB_33      0.0258359000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0819
_diffrn_reflns_av_unetI/netI     0.0985
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            49983
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.084
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.898
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       plate
_exptl_crystal_F_000             2004
_exptl_crystal_size_max          0.271
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.651
_refine_diff_density_min         -0.575
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1275
_refine_ls_number_reflns         16572
_refine_ls_number_restraints     595
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0579
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0512P)^2^+3.8317P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1193
_refine_ls_wR_factor_ref         0.1441
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10933
_reflns_number_total             16572
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00880k2.cif
_cod_data_source_block           compound-1
_cod_database_code               7712752
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C76H117O8P8N8Br4
_reflns_odcompleteness_completeness 89.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.11
_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
 C28-C29 = C29-C30 = C30-C31 = C31-C32
 1.54 with sigma of 0.02
 C28-C30 = C29-C31 = C30-C32
 2.51 with sigma of 0.02
 C28-C29A = C29A-C30A = C30A-C31A = C31A-C32A
 1.54 with sigma of 0.02
 C28-C30A = C29A-C31A = C30A-C32A
 2.51 with sigma of 0.02
 C49-C50 = C49-C51 = C49-C52
 1.5227 with sigma of 0.005
 C50-C51 = C50-C52 = C51-C52
 2.486569 with sigma of 0.005
 C49-C50A = C49-C51A = C49-C52A
 1.5227 with sigma of 0.005
 C50A-C51A = C50A-C52A = C51A-C52A
 2.486569 with sigma of 0.005
 C53-C54 = C53-C55 = C53-C56
 1.5227 with sigma of 0.005
 C54-C55 = C54-C56 = C55-C56
 2.486569 with sigma of 0.02
 C53-C54A = C53-C55A = C53-C56A
 1.5227 with sigma of 0.005
 C54A-C55A = C54A-C56A = C55A-C56A
 2.486569 with sigma of 0.02
 C57-C58 = C57-C59 = C57-C60
 1.5227 with sigma of 0.005
 C58-C59 = C58-C60 = C59-C60
 2.486569 with sigma of 0.02
 C57-C58A = C57-C59A = C57-C60A
 1.5227 with sigma of 0.005
 C58A-C59A = C58A-C60A = C59A-C60A
 2.486569 with sigma of 0.02
 C65-C66 = C65-C67 = C65-C68
 1.5227 with sigma of 0.005
 C66-C67 = C66-C68 = C67-C68
 2.486569 with sigma of 0.005
 C65-C66A = C65-C67A = C65-C68A
 1.5227 with sigma of 0.005
 C66A-C67A = C66A-C68A = C67A-C68A
 2.486569 with sigma of 0.005
 C77-C78 = C78-C79 = C79-C80 = C80-C81 = C81-C82
 1.5227 with sigma of 0.005
 C77-C79 = C78-C80 = C79-C81 = C80-C82
 2.486569 with sigma of 0.005
 C73-C74 = C73-C75 = C73-C76
 1.5227 with sigma of 0.005
 C74-C75 = C74-C76 = C75-C76
 2.486569 with sigma of 0.02
 C73-C74A = C73-C75A = C73-C76A
 1.5227 with sigma of 0.005
 C74A-C75A = C74A-C76A = C75A-C76A
 2.486569 with sigma of 0.02
 C77A-C78A = C78A-C79A = C79A-C80A = C80A-C81A = C81A-C82A
 1.5227 with sigma of 0.005
 C77A-C79A = C78A-C80A = C79A-C81A = C80A-C82A
 2.486569 with sigma of 0.005
3. Rigid bond restraints
 C29, C29A, C30, C30A, C31, C31A, C32, C32A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C50, C50A, C51, C51A, C52, C52A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C54, C54A, C55, C55A, C56, C56A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C58, C58A, C59, C59A, C60, C60A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C66, C66A, C67, C67A, C68, C68A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C74, C74A, C75, C75A, C76, C76A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C77, C77A, C78, C78A, C79, C79A, C80, C80A, C81, C81A, C82, C82A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
4. Uiso/Uaniso restraints and constraints
C29 \\sim C29A \\sim C30 \\sim C30A \\sim C31 \\sim C31A \\sim C32 \\sim C32A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C50 \\sim C50A \\sim C51 \\sim C51A \\sim C52 \\sim C52A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006 within 2A
C54 \\sim C54A \\sim C55 \\sim C55A \\sim C56 \\sim C56A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006 within 2A
C58 \\sim C58A \\sim C59 \\sim C59A \\sim C60 \\sim C60A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006 within 2A
C66 \\sim C66A \\sim C67 \\sim C67A \\sim C68 \\sim C68A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006 within 2A
C74 \\sim C74A \\sim C75 \\sim C75A \\sim C76 \\sim C76A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006 within 2A
C77 \\sim C77A \\sim C78 \\sim C78A \\sim C79 \\sim C79A \\sim C80 \\sim C80A
\\sim C81 \\sim C81A \\sim C82 \\sim C82A: within 2A with sigma of 0.003 and
sigma for terminal atoms of 0.006 within 2A
Uanis(C54) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C55A)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C56A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C66) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C67A)
\\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C68A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C82A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C79A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C29A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Same fragment restrains
{C29, C30, C31, C32} sigma for 1-2: 0.003, 1-3: 0.04
as in
{C29A, C30A, C31A, C32A}
6. Others
 Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=
 Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=FVAR(2)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1.633*FVAR(3)
 Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=
 Sof(H51F)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(3)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(3)
 Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=Sof(H55E)=
 Sof(H55F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(4)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(4)
 Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=
 Sof(H59F)=Sof(C60A)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(5)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(5)
 Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C67A)=Sof(H67D)=Sof(H67E)=
 Sof(H67F)=Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=1-FVAR(6)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(6)
 Sof(C77A)=Sof(H77D)=Sof(H77E)=Sof(H77F)=Sof(C78A)=Sof(H78C)=Sof(H78D)=
 Sof(C79A)=Sof(H79C)=Sof(H79D)=Sof(C80A)=Sof(H80C)=Sof(H80D)=Sof(C81A)=
 Sof(H81C)=Sof(H81D)=Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(7)
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(C79)=
 Sof(H79A)=Sof(H79B)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C81)=Sof(H81A)=Sof(H81B)=
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(7)
 Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(C75A)=Sof(H75D)=Sof(H75E)=
 Sof(H75F)=Sof(C76A)=Sof(H76D)=Sof(H76E)=Sof(H76F)=1-FVAR(8)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(8)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C14(H14), C21(H21)
7.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C29A(H29C,H29D), C30A(H30C,
 H30D), C31A(H31C,H31D), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,H41B), C42(H42A,H42B),
  C43(H43A,H43B), C78(H78A,H78B), C78A(H78C,H78D), C79(H79A,H79B), C79A(H79C,
 H79D), C80(H80A,H80B), C80A(H80C,H80D), C81(H81A,H81B), C81A(H81C,H81D)
7.c Me refined with riding coordinates:
 C82A(H82D,H82E,H82F)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C13(H13), C20(H20), C27(H27)
7.e Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F), C36(H36A,H36B,H36C), C40(H40A,H40B,
 H40C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C50(H50A,H50B,H50C), C50A(H50D,H50E,H50F), C51(H51A,H51B,H51C),
 C51A(H51D,H51E,H51F), C52(H52A,H52B,H52C), C52A(H52D,H52E,H52F), C54(H54A,H54B,
 H54C), C54A(H54D,H54E,H54F), C55(H55A,H55B,H55C), C55A(H55D,H55E,H55F),
 C56(H56A,H56B,H56C), C56A(H56D,H56E,H56F), C58(H58A,H58B,H58C), C58A(H58D,H58E,
 H58F), C59(H59A,H59B,H59C), C59A(H59D,H59E,H59F), C60(H60A,H60B,H60C),
 C60A(H60D,H60E,H60F), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C66(H66A,H66B,H66C), C66A(H66D,H66E,H66F), C67(H67A,H67B,H67C),
 C67A(H67D,H67E,H67F), C68(H68A,H68B,H68C), C68A(H68D,H68E,H68F), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C),
 C74A(H74D,H74E,H74F), C75(H75A,H75B,H75C), C75A(H75D,H75E,H75F), C76(H76A,H76B,
 H76C), C76A(H76D,H76E,H76F), C77(H77A,H77B,H77C), C77A(H77D,H77E,H77F),
 C82(H82A,H82B,H82C)
;
_shelx_res_checksum              74996
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.086
_oxdiff_exptl_absorpt_empirical_full_min 0.677