A One-Hole Cu<sub>4</sub>S Cluster with N<sub>2</sub>O Reductase Activity: A Structural and Functional Model for Cu<sub>Z</sub>.
Johnson, Brittany J.; Antholine, William E.; Lindeman, Sergey V.; Graham, Michael J.; Mankad, Neal P.; Journal of the American Chemical Society 138 (2016) 13107–13110; doi:10.1021/jacs.6b05480

data_4130640
_publ_section_title
;
 A One-Hole Cu<sub>4</sub>S Cluster with N<sub>2</sub>O Reductase
 Activity: A Structural and Functional Model for Cu<sub>Z</sub>.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13107
_journal_page_last               13110
_journal_paper_doi               10.1021/jacs.6b05480
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety
'0.5(C76 H92 Cu4 N8 S), 0.25(C176 H232 Cu8 K2 N16 O12 S2), 0.5(C12 H24 K O6), C H2 Cl2, C4 H10 O'
_chemical_formula_sum            'C93 H128 Cl2 Cu4 K N8 O7 S'
_chemical_formula_weight         1866.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 102.9912(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   15.17028(12)
_cell_length_b                   22.32611(16)
_cell_length_c                   29.9089(3)
_cell_measurement_reflns_used    42932
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.8030
_cell_measurement_theta_min      3.5590
_cell_volume                     9870.67(15)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_details
;
  1 omega -124.00  -79.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -99.0000  150.0000 45

  2 omega -124.00  -79.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -99.0000  -30.0000 45

  3 omega -124.00  -79.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -99.0000 -120.0000 45

  4 omega -124.00  -79.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -99.0000   60.0000 45

  5 omega   23.00   99.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5237 -125.0000   30.0000 76

  6 omega   30.00   90.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000   90.0000 60

  7 omega   30.00   90.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000 -180.0000 60

  8 omega   94.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  125.0000 -180.0000 84

  9 omega   94.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  125.0000  120.0000 84

 10 omega   25.00  170.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -15.0000  -30.0000 145

 11 omega -115.00  -12.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -57.0000  -90.0000 103

 12 omega -115.00  -12.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -57.0000  150.0000 103

 13 omega -115.00  -12.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5237  -57.0000   30.0000 103

 14 omega   78.00  158.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   30.0000 -180.0000 80

 15 omega   81.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   45.0000   90.0000 97

 16 omega   94.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  125.0000  -30.0000 84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0395889000
_diffrn_orient_matrix_UB_12      -0.0632941000
_diffrn_orient_matrix_UB_13      0.0106727000
_diffrn_orient_matrix_UB_21      0.0731221000
_diffrn_orient_matrix_UB_22      0.0139314000
_diffrn_orient_matrix_UB_23      -0.0268494000
_diffrn_orient_matrix_UB_31      0.0628456000
_diffrn_orient_matrix_UB_32      0.0237336000
_diffrn_orient_matrix_UB_33      0.0442525000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            52258
_diffrn_reflns_theta_full        72.00
_diffrn_reflns_theta_max         74.71
_diffrn_reflns_theta_min         2.99
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.459
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73720
_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            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3932
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.842
_refine_diff_density_min         -1.158
_refine_diff_density_rms         0.130
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.026(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2113
_refine_ls_number_reflns         52258
_refine_ls_number_restraints     594
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0860
_refine_ls_R_factor_gt           0.0761
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1514P)^2^+12.3463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2148
_refine_ls_wR_factor_ref         0.2270
_reflns_number_gt                45459
_reflns_number_total             52258
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja6b05480_si_002.cif
_cod_data_source_block           neal1r5
_cod_original_cell_volume        9870.65(14)
_cod_database_code               4130640
_chemical_oxdiff_formula         'Cu4 S N8 K O6 C88 H116'
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6184(6) 0.3816(6)
2. 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
3. Restrained distances
 O7-C89 = O7-C100 = O8-C90 = O8-C91 = O9-C92 = O9-C93
 1.426 with sigma of 0.02
 O10-C94 = O10-C95 = O11-C96 = O11-C97 = O12-C98 = O12-C99
 1.426 with sigma of 0.02
 O7A-C89A = O7A-C00A = O8A-C90A = O8A-C91A = O9A-C92A = O9A-C93A
 1.426 with sigma of 0.02
 O10A-C94A = O10A-C95A = O11A-C96A = O11A-C97A = O12A-C98A = O12A-C99A
 1.426 with sigma of 0.02
 C89-C90 = C91-C92 = C93-C94 = C95-C96 = C97-C98 = C99-C100
 1.515 with sigma of 0.02
 C89A-C90A = C91A-C92A = C93A-C94A = C95A-C96A = C97A-C98A = C99A-C00A
 1.515 with sigma of 0.02
4. Rigid bond restraints
 Cu1, Cu2, Cu3, Cu4, S1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu1A, Cu2A, Cu3A, Cu4A, S1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16,
  C17, C18, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A,
  C14A, C15A, C16A, C17A, C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3, N4, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
 C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3A, N4A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A,
 C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N5, N6, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52,
 C53, C54, C55, C56, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N5A, N6A, C39A, C40A, C41A, C42A, C43A, C44A, C45A, C46A, C47A, C48A, C49A,
 C50A, C51A, C52A, C53A, C54A, C55A, C56A, C57A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N7, N8, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70, C71,
 C72, C73, C74, C75, C76
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N7A, N8A, C58A, C59A, C60A, C61A, C62A, C63A, C64A, C65A, C66A, C67A, C68A,
 C69A, C70A, C71A, C72A, C73A, C74A, C75A, C76A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6S, C5S, O1S, C3S, C4S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8S, C7S, O2S, C9S, C10S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(O1S) \\sim Ueq, Uanis(C3S) \\sim Ueq, Uanis(C4S) \\sim Ueq, Uanis(C5S)
\\sim Ueq, Uanis(C6S) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(O2S) \\sim Ueq, Uanis(C7S) \\sim Ueq, Uanis(C8S) \\sim Ueq, Uanis(C9S)
\\sim Ueq, Uanis(C10S) \\sim Ueq: with sigma of 0.1 and sigma for terminal
atoms of 0.2
Uanis(K1) = Uanis(K1A)
Uanis(K2) = Uanis(K2A)
Uiso(C93) = Uiso(C95A)
Uiso(C95) = Uiso(C93A)
Uiso(C98A) = Uiso(C90)
Uiso(C89) = Uiso(C99A)
Uiso(C00A) = Uiso(C100)
Uiso(C99) = Uiso(C89A)
Uiso(C90A) = Uiso(C98)
Uiso(C97) = Uiso(O8A)
Uiso(C96) = Uiso(O9A)
Uiso(C96A) = Uiso(O9)
Uiso(C97A) = Uiso(O8)
6. Same fragment restrains
{O1S, C3S, C4S, C5S, C6S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O2S, C7S, C8S, C9S, C10S}
7. Others
 Sof(K1A)=1-FVAR(1)
 Sof(K1)=FVAR(1)
 Sof(K2A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=Sof(C89A)=
 Sof(H89C)=Sof(H89D)=Sof(C90A)=Sof(H90C)=Sof(H90D)=Sof(C91A)=Sof(H91C)=
 Sof(H91D)=Sof(C92A)=Sof(H92C)=Sof(H92D)=Sof(C93A)=Sof(H93C)=Sof(H93D)=
 Sof(C94A)=Sof(H94C)=Sof(H94D)=Sof(C95A)=Sof(H95C)=Sof(H95D)=Sof(C96A)=
 Sof(H96C)=Sof(H96D)=Sof(C97A)=Sof(H97C)=Sof(H97D)=Sof(C98A)=Sof(H98C)=
 Sof(H98D)=Sof(C99A)=Sof(H99C)=Sof(H99D)=Sof(C00A)=Sof(H00A)=Sof(H00B)=1-FVAR(2)
 Sof(K2)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(O10)=Sof(O11)=Sof(O12)=Sof(C89)=Sof(H89A)=
 Sof(H89B)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C92)=
 Sof(H92A)=Sof(H92B)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(C97)=Sof(H97A)=
 Sof(H97B)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(C100)=
 Sof(H10G)=Sof(H10H)=FVAR(2)
 Fixed Sof: H81A(0.5) H81B(0.5) H81C(0.5) H81D(0.5) C82(0.5) H82A(0.5)
 H82B(0.5) O4(0.5) C83(0.5) H83A(0.5) H83B(0.5) C84(0.5) H84A(0.5) H84B(0.5)
 C82A(0.5) H82C(0.5) H82D(0.5) O4A(0.5) C83A(0.5) H83C(0.5) H83D(0.5) C84A(0.5)
 H84C(0.5) H84D(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,
 H81B), C81(H81C,H81D), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B),
 C82A(H82C,H82D), C83A(H83C,H83D), C84A(H84C,H84D), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B),
 C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B),
  C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B), C99(H99A,H99B), C100(H10G,
 H10H), C89A(H89C,H89D), C90A(H90C,H90D), C91A(H91C,H91D), C92A(H92C,H92D),
 C93A(H93C,H93D), C94A(H94C,H94D), C95A(H95C,H95D), C96A(H96C,H96D), C97A(H97C,
 H97D), C98A(H98C,H98D), C99A(H99C,H99D), C00A(H00A,H00B), C1S(H1SA,H1SB),
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C5S(H5SA,H5SB), C7S(H7SB,H7SA), C9S(H9SA,H9SB)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C6(H6), C13(H13), C15(H15), C20(H20), C23(H23), C25(H25),
 C32(H32), C34(H34), C39(H39), C42(H42), C44(H44), C51(H51), C53(H53), C58(H58),
  C61(H61), C63(H63), C70(H70), C72(H72), C1A(H1A), C4A(H4A), C6A(H6A),
 C13A(H13A), C15A(H15A), C20A(H20A), C23A(H23A), C25A(H25A), C32A(H32A),
 C34A(H34A), C39A(H39A), C42A(H42A), C44A(H44A), C51A(H51A), C53A(H53A),
 C58A(H58A), C61A(H61A), C63A(H63A), C70A(H70A), C72A(H72A)
8.c Idealised Me refined with riding coordinates:
 C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC), C8S(H8SA,H8SB,H8SC), C10S(H10I,H10J,
 H10K)
8.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C),
 C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C76(H76A,H76B,H76C), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC),
 C10A(H10D,H10E,H10F), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C19A(H19D,
 H19E,H19F), C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F),
 C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F), C38A(H38D,H38E,H38F), C46A(H46D,
 H46E,H46F), C47A(H47D,H47E,H47F), C48A(H48D,H48E,H48F), C55A(H55D,H55E,H55F),
 C56A(H56D,H56E,H56F), C57A(H57D,H57E,H57F), C65A(H65D,H65E,H65F), C66A(H66D,
 H66E,H66F), C67A(H67D,H67E,H67F), C74A(H74D,H74E,H74F), C75A(H75D,H75E,H75F),
 C76A(H76D,H76E,H76F)
;
_olex2_date_sample_data_collection 2015-08-19
_olex2_date_sample_submission    2015-08-12
_olex2_submission_special_instructions 'No special instructions were received'