Tetracarboxylate Ligands as New Chelates Supporting Copper(II) Paddlewheel-Like Structures.
Gomila, Antoine; Duval, Sylvain; Besnard, Céline; Krämer, Karl W; Liu, Shi-Xia; Decurtins, Silvio; Williams, Alan F.; Inorganic chemistry 53 (2014) 2683–2691; doi:10.1021/ic403077q

data_4337767
_publ_section_title
;
 Tetracarboxylate Ligands as New Chelates Supporting Copper(II)
 Paddlewheel-Like Structures.
;
_journal_issue                   5
_journal_name_full               'Inorganic chemistry'
_journal_page_first              2683
_journal_page_last               2691
_journal_paper_doi               10.1021/ic403077q
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety
'C80 H68 Cl Cu4 N4 O16, 3(Cl O4), 5(C3 H7 N O)'
_chemical_formula_sum            'C95 H103 Cl4 Cu4 N9 O33'
_chemical_formula_weight         2294.82
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-10-14
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                95.097(4)
_cell_angle_beta                 102.273(4)
_cell_angle_gamma                106.039(4)
_cell_formula_units_Z            2
_cell_length_a                   14.2102(6)
_cell_length_b                   17.3347(9)
_cell_length_c                   21.6372(9)
_cell_measurement_reflns_used    7424
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      72.1490
_cell_measurement_theta_min      2.7260
_cell_volume                     4943.2(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      180.15
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0639811000
_diffrn_orient_matrix_UB_12      0.0175996000
_diffrn_orient_matrix_UB_13      -0.0492276000
_diffrn_orient_matrix_UB_21      -0.0812607000
_diffrn_orient_matrix_UB_22      0.0303383000
_diffrn_orient_matrix_UB_23      -0.0407544000
_diffrn_orient_matrix_UB_31      0.0534257000
_diffrn_orient_matrix_UB_32      0.0867315000
_diffrn_orient_matrix_UB_33      0.0367436000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30386
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         66.597
_diffrn_reflns_theta_min         2.686
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.712
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45841
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'CrysAlisPro, Agilent Technologies, 
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
 (compiled Feb 1 2013,16:14:44) Empirical absorption correction
 using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description
;
;
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.4957
_exptl_crystal_size_mid          0.2377
_exptl_crystal_size_min          0.0887
_refine_diff_density_max         1.289
_refine_diff_density_min         -0.964
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1486
_refine_ls_number_reflns         30386
_refine_ls_number_restraints     400
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1505
_refine_ls_R_factor_gt           0.0981
_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^)+(0.1985P)^2^+1.2678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2609
_refine_ls_wR_factor_ref         0.3101
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18095
_reflns_number_total             30386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic403077q_si_002.cif
_cod_data_source_block           Cu4sand
_cod_original_cell_volume        4943.1(4)
_cod_database_code               4337767
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'Cu2 O4 C40 N2 H32'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1B-C3B = O1A-C3A
 1.22 with sigma of 0.02
 C3B-N1B = C3A-N1A
 1.36 with sigma of 0.02
 O1X-C3X = O1Z-C3Z
 1.22 with sigma of 0.02
 C3X-N1X = C3Z-N1Z
 1.36 with sigma of 0.02
 N1X-C2X = N1X-C1X = N1Z-C2Z = N1Z-C1Z
 1.45 with sigma of 0.02
 O1E-C3E = O1F-C3F
 1.22 with sigma of 0.02
 C3E-N1E = C3F-N1F
 1.36 with sigma of 0.02
 N1E-C2E = N1E-C1E = N1F-C2F = N1F-C1F
 1.45 with sigma of 0.02
 N1B-C2B = N1B-C1B = N1A-C2A = N1A-C1A
 1.45 with sigma of 0.02
 O1B-N1B = O1A-N1A
 2.3 with sigma of 0.04
 O1X-N1X = O1Z-N1Z
 2.3 with sigma of 0.04
 C3X-C1X = C3X-C2X = C3Z-C1Z = C3Z-C2Z
 2.45 with sigma of 0.04
 C1X-C2X = C1Z-C2Z
 2.485 with sigma of 0.04
 O1E-N1E = O1F-N1F
 2.3 with sigma of 0.04
 C3E-C1E = C3E-C2E = C3F-C1F = C3F-C2F
 2.45 with sigma of 0.04
 C1E-C2E = C1F-C2F
 2.485 with sigma of 0.04
 C3B-C1B = C3B-C2B = C3A-C1A = C3A-C2A
 2.45 with sigma of 0.04
 C1B-C2B = C1A-C2A
 2.485 with sigma of 0.04
 O29B-O30B \\sim O29B-O32B \\sim O29B-O31B \\sim O30B-O32B \\sim O30B-O31B
\\sim O32B-O31B \\sim O32A-
 O31A \\sim O32A-O30A \\sim O32A-O29A \\sim O31A-O30A \\sim O31A-O29A \\sim
O30A-O29A
 with sigma of 0.04
 Cl4-O29B \\sim Cl4-O30B \\sim Cl4-O32B \\sim Cl4-O31B \\sim Cl4-O32A \\sim
Cl4-O31A \\sim Cl4-O30A ~
 Cl4-O29A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O29B \\sim O30B \\sim Cl4 \\sim O32B \\sim O31B \\sim O32A \\sim O31A \\sim
O30A \\sim O29A: within 1A with sigma of 0.04 and sigma for terminal atoms of
0.08
C2X \\sim O1X \\sim C3X \\sim N1X \\sim C1X \\sim C2Z \\sim C1Z \\sim N1Z \\sim
C3Z \\sim O1Z: within 1A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1F \\sim C3F \\sim O1F \\sim N1F \\sim C2F \\sim C2E \\sim N1E \\sim C3E \\sim
C1E \\sim O1E: within 1A with sigma of 0.04 and sigma for terminal atoms of 0.08
C2A \\sim C3A \\sim O1A \\sim N1A \\sim C1A \\sim N1B \\sim C3B \\sim C1B \\sim
C2B \\sim O1B: within 1A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O29B, O30B, Cl4, O32B, O31B, O32A, O31A, O30A, O29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1X, O1X, C3X, C1X, C2X, N1Z, C1Z, C3Z, C2Z, O1Z
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1E, C3E, C2E, C1E, O1E, N1F, C3F, O1F, C1F, C2F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C3A, O1A, N1A, C2A, C2B, N1B, C3B, C1B, O1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O29B)=Sof(O30B)=Sof(O32B)=Sof(O31B)=1-FVAR(1)
 Sof(O32A)=Sof(O31A)=Sof(O30A)=Sof(O29A)=FVAR(1)
 Sof(C3A)=Sof(H8)=Sof(O1A)=Sof(C2A)=Sof(H9)=Sof(H10)=Sof(H11)=Sof(N1A)=
 Sof(C1A)=Sof(H12)=Sof(H13)=Sof(H14)=1-FVAR(2)
 Sof(N1B)=Sof(O1B)=Sof(C3B)=Sof(H1)=Sof(C1B)=Sof(H2)=Sof(H3)=Sof(H4)=Sof(C2B)=
 Sof(H5)=Sof(H6)=Sof(H7)=FVAR(2)
 Sof(C3F)=Sof(H19)=Sof(O1F)=Sof(N1F)=Sof(C1F)=Sof(H1A)=Sof(H1B)=Sof(H1C)=
 Sof(C2F)=Sof(H1D)=Sof(H1E)=Sof(H1F)=1-FVAR(3)
 Sof(N1E)=Sof(O1E)=Sof(C3E)=Sof(H15)=Sof(C2E)=Sof(H16)=Sof(H17)=Sof(H18)=
 Sof(C1E)=Sof(H1G)=Sof(H1H)=Sof(H1I)=FVAR(3)
 Sof(C1Z)=Sof(H1J)=Sof(H1K)=Sof(H1L)=Sof(C3Z)=Sof(H1M)=Sof(O1Z)=Sof(C2Z)=
 Sof(H1N)=Sof(H1O)=Sof(H1P)=Sof(N1Z)=1-FVAR(4)
 Sof(O1X)=Sof(C3X)=Sof(H3X)=Sof(N1X)=Sof(C1X)=Sof(H1XA)=Sof(H1XB)=Sof(H1XC)=
 Sof(C2X)=Sof(H2XA)=Sof(H2XB)=Sof(H2XC)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 N1(H), N2(HB), N4(HE), N5(HM)
6.b Secondary CH2 refined with riding coordinates:
 C17(HG,HH), C33(HN,HO), C24(HP,HQ), C65(HR,HS), C8(HT,HU), C16(HX,HY),
 C73(H1AA,H2AA), C64(H5AA,H6AA), C57(H0BA,H1BA), C25(H2CA,H3CA), C48(H7CA,H8CA),
  C56(H9CA,H0DA)
6.c Me refined with riding coordinates:
 C1B(H2,H3,H4), C2B(H5,H6,H7), C2A(H9,H10,H11), C1A(H12,H13,H14), C2E(H16,H17,
 H18), C1F(H1A,H1B,H1C), C2F(H1D,H1E,H1F), C1E(H1G,H1H,H1I), C1Z(H1J,H1K,H1L),
 C1X(H1XA,H1XB,H1XC), C2X(H2XA,H2XB,H2XC), C2Z(H1N,H1O,H1P)
6.d Aromatic/amide H refined with riding coordinates:
 C62(HA), C60(HC), C78(HD), C19(HF), C22(HI), C37(HJ), C20(HK), C38(HL),
 C63(HV), C75(HW), C11(HZ), C3(H0AA), C6(H3AA), C70(H4AA), C84(H7AA), C45(H8AA),
  C77(H9AA), C46(H2BA), C44(H3BA), C36(H4BA), C23(H5BA), C59(H6BA), C43(H7BA),
 C35(H8BA), C67(H9BA), C76(H0CA), C12(H1CA), C5(H4CA), C4(H5CA), C68(H6CA),
 C14(H1DA), C30(H2DA), C69(H3DA), C29(H4DA), C51(H5DA), C13(H6DA), C54(H7DA),
 C27(H1EA), C28(H2EA), C53(H3EA), C52(H4EA), C81(H8EA), C3B(H1), C3A(H8),
 C3E(H15), C3F(H19), C3X(H3X), C3Z(H1M)
6.e Idealised Me refined as rotating group:
 C86(H8DA,H9DA,H0EA), C85(H5EA,H6EA,H7EA), C82(H9EA,H0FA,H1FA), C83(H2FA,H3FA,
 H4FA)
;