#------------------------------------------------------------------------------
#$Date: 2019-12-25 21:58:08 +0200 (Wed, 25 Dec 2019) $
#$Revision: 245816 $
#$URL: file:///home/coder/svn-repositories/cod/cif/2/31/13/2311350.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/. The original data for this entry
# were provided by IUCr Journals, http://journals.iucr.org/.
#
# The file may be used within the scientific community so long as
# proper attribution is given to the journal article from which the
# data were obtained.
#
data_2311350
loop_
_publ_author_name
'Corfield, Peter W. R.'
'Sabatino, Alexander'
_publ_section_title
;
 Crystal structures of two mixed-valence copper cyanide complexes with
 N-methyl-ethylenedi-amine.
;
_journal_coeditor_code           PK2594
_journal_issue                   'Pt 2'
_journal_name_full
'Acta crystallographica. Section E, Crystallographic communications'
_journal_page_first              141
_journal_page_last               146
_journal_paper_doi               10.1107/S2056989017000111
_journal_volume                  73
_journal_year                    2017
_chemical_formula_iupac          '[Cu4 (C N)5 (C3 H10 N2)2]'
_chemical_formula_moiety         'C11 H20 Cu4 N9'
_chemical_formula_sum            'C11 H20 Cu4 N9'
_chemical_formula_weight         532.52
_chemical_name_systematic
;Poly[bis(μ₃-cyanido-κ³C:C:N)tris(μ₂-cyanido-κ²C:N)bis(N-methylethane-1,2-diamine\-
κ²N,N')tricopper(I)copper(II)]
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.509(2)
_cell_length_b                   8.2306(13)
_cell_length_c                   11.100(2)
_cell_measurement_reflns_used    474
_cell_measurement_temperature    303(2)
_cell_measurement_theta_max      20.18
_cell_measurement_theta_min      1.83
_cell_volume                     1782.3(5)
_computing_cell_refinement
;
SCALEPACK (Otwinowski & Minor, 1997)
;
_computing_data_collection
;
KappaCCD Server Software (Nonius, 1997)
;
_computing_data_reduction
;
DENZO and SCALEPACK (Otwinowski & Minor, 1997)
;
_computing_molecular_graphics
;
ORTEPIII (Burnett & Johnson, 1996)
;
_computing_publication_material
;
publCIF (Westrip, 2010)
;
_computing_structure_refinement
;
SHELXL2014 (Sheldrick, 2015)
;
_computing_structure_solution
;
SHELXS-97 (Sheldrick, 2008)
;
_diffrn_ambient_temperature      303.0(10)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_measurement_device_type  'Enraf--Nonius KappaCCD'
_diffrn_measurement_method       'combination of ω and φ scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71070
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_sigmaI/netI    0.0275
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            15054
_diffrn_reflns_theta_full        25.241
_diffrn_reflns_theta_max         27.461
_diffrn_reflns_theta_min         2.088
_exptl_absorpt_coefficient_mu    4.721
_exptl_absorpt_correction_T_max  0.146
_exptl_absorpt_correction_T_min  0.103
_exptl_absorpt_correction_type   refdelf
_exptl_absorpt_process_details
;
(SCALEPACK; Otwinowski & Minor, 1997)
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.985
_exptl_crystal_density_meas      2.01(7)
_exptl_crystal_density_method
; flotation in 1,2-dibromopropane/1,2,3-trichloropropane mixtures.
Three independent determinations were made.
;
_exptl_crystal_description
;
block cut from large polyhedral crystal
;
_exptl_crystal_F_000             1060
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.383
_refine_ls_abs_structure_details
;
Flack x determined using 1806 quotients
[(I⁺)-(I⁻)]/[(I⁺)+(I⁻)]
(Parsons et al., 2013)
;
_refine_ls_abs_structure_Flack   0.010(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         4062
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0189
_refine_ls_R_factor_gt           0.0180
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0220P)²+0.0400P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0445
_refine_ls_wR_factor_ref         0.0447
_reflns_number_gt                3964
_reflns_number_total             4062
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            pk2594sup1.cif
_cod_data_source_block           I
_cod_database_code               2311350
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, z+1/2'
'-x, -y, z+1/2'
'x+1/2, -y+1/2, z'
loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_calc_flag
_atom_site_occupancy
Cu Cu1 0.07836(2) 0.38153(5) 0.00021(3) 0.02552(9) Uani d 1
Cu Cu2 0.06847(2) 0.28058(5) 0.21765(4) 0.03143(10) Uani d 1
Cu Cu3 0.20761(2) 0.76738(5) 0.26057(4) 0.03009(10) Uani d 1
Cu Cu4 -0.11518(2) -0.01338(4) 0.15874(4) 0.02352(9) Uani d 1
C C1 0.00592(15) 0.2214(4) 0.0390(3) 0.0252(6) Uani d 1
N N1 -0.03914(15) 0.1363(3) 0.0471(3) 0.0358(7) Uani d 1
C C2 0.12936(15) 0.4885(4) 0.1399(3) 0.0279(7) Uani d 1
N N2 0.16340(14) 0.5829(3) 0.1840(2) 0.0318(6) Uani d 1
C C3 0.12207(16) 0.0852(4) 0.2405(3) 0.0326(9) Uani d 0.79(3)
N N3 0.15237(15) -0.0341(4) 0.2510(3) 0.0402(9) Uani d 0.79(3)
N N3A 0.12207(16) 0.0852(4) 0.2405(3) 0.0326(9) Uani d 0.21(3)
C C3A 0.15237(15) -0.0341(4) 0.2510(3) 0.0402(9) Uani d 0.21(3)
C C4 -0.00363(15) 0.6193(4) -0.1714(3) 0.0270(8) Uani d 0.78(3)
N N4 0.03183(14) 0.5501(4) -0.1084(3) 0.0298(7) Uani d 0.78(3)
N N4A -0.00363(15) 0.6193(4) -0.1714(3) 0.0270(8) Uani d 0.22(3)
C C4A 0.03183(14) 0.5501(4) -0.1084(3) 0.0298(7) Uani d 0.22(3)
C C5 0.20639(16) 0.2799(4) -0.1578(3) 0.0274(7) Uani d 1
N N5 0.15765(14) 0.3019(4) -0.1041(3) 0.0311(6) Uani d 1
N N11 -0.03685(14) -0.1076(3) 0.2519(3) 0.0332(6) Uani d 1
H H11A -0.0058 -0.0310 0.2667 0.040 Uiso calc 1
H H11B -0.0518 -0.1462 0.3221 0.040 Uiso calc 1
C C12 -0.00592(18) -0.2392(4) 0.1810(4) 0.0410(9) Uani d 1
H H12A 0.0220 -0.3080 0.2323 0.049 Uiso calc 1
H H12B 0.0230 -0.1946 0.1181 0.049 Uiso calc 1
C C13 -0.06375(19) -0.3366(5) 0.1261(3) 0.0385(8) Uani d 1
H H13A -0.0455 -0.4207 0.0740 0.046 Uiso calc 1
H H13B -0.0906 -0.3880 0.1890 0.046 Uiso calc 1
N N14 -0.10737(15) -0.2222(3) 0.0553(3) 0.0310(6) Uani d 1
H H14 -0.0807 -0.1925 -0.0161 0.037 Uiso calc 1
C C15 -0.1702(2) -0.3019(5) 0.0107(4) 0.0465(9) Uani d 1
H H15A -0.1581 -0.3981 -0.0333 0.056 Uiso calc 1
H H15B -0.1945 -0.2286 -0.0413 0.056 Uiso calc 1
H H15C -0.1988 -0.3307 0.0777 0.056 Uiso calc 1
N N16 -0.19542(14) 0.0806(4) 0.0694(3) 0.0329(6) Uani d 1
H H16A -0.1875 0.0790 -0.0096 0.040 Uiso calc 1
H H16B -0.2331 0.0230 0.0843 0.040 Uiso calc 1
C C17 -0.2044(2) 0.2508(5) 0.1118(4) 0.0470(10) Uani d 1
H H17A -0.2484 0.2933 0.0863 0.056 Uiso calc 1
H H17B -0.1685 0.3199 0.0797 0.056 Uiso calc 1
C C18 -0.2003(2) 0.2437(5) 0.2477(4) 0.0479(10) Uani d 1
H H18A -0.2019 0.3528 0.2805 0.058 Uiso calc 1
H H18B -0.2392 0.1835 0.2790 0.058 Uiso calc 1
N N19 -0.13606(15) 0.1637(3) 0.2845(3) 0.0326(6) Uani d 1
H H19 -0.1000 0.2456 0.2755 0.039 Uiso calc 1
C C20 -0.1379(2) 0.1228(5) 0.4134(4) 0.0493(10) Uani d 1
H H20A -0.1495 0.2180 0.4591 0.059 Uiso calc 1
H H20B -0.0938 0.0837 0.4381 0.059 Uiso calc 1
H H20C -0.1717 0.0401 0.4270 0.059 Uiso calc 1
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
C1 Cu1 C2 . . 118.01(13)
C1 Cu1 N4 . . 105.22(12)
C1 Cu1 N5 . . 116.79(13)
C2 Cu1 N4 . . 111.75(12)
C2 Cu1 N5 . . 101.54(12)
N4 Cu1 N5 . . 102.67(12)
C1 Cu1 Cu2 . . 61.64(10)
C2 Cu1 Cu2 . . 57.36(9)
N4 Cu1 Cu2 . . 137.79(8)
N5 Cu1 Cu2 . . 119.22(8)
C1 Cu2 C2 . . 96.13(11)
C1 Cu2 C3 . . 102.49(12)
C1 Cu2 C4 . 3_565 106.29(12)
C2 Cu2 C3 . . 113.35(12)
C2 Cu2 C4 . 3_565 105.25(12)
C3 Cu2 C4 . 3_565 128.27(13)
C1 Cu2 Cu1 . . 47.10(7)
C2 Cu2 Cu1 . . 49.69(8)
C3 Cu2 Cu1 . . 110.66(10)
C4 Cu2 Cu1 3_565 . 120.51(9)
N2 Cu3 C5 . 2 129.79(13)
N2 Cu3 N3 . 1_565 112.56(12)
N3 Cu3 C5 1_565 2 117.64(13)
N11 Cu4 N14 . . 84.76(12)
N16 Cu4 N19 . . 84.72(12)
N11 Cu4 N16 . . 178.39(13)
N14 Cu4 N19 . . 167.74(11)
N11 Cu4 N19 . . 94.30(12)
N14 Cu4 N16 . . 95.92(12)
N1 Cu4 N11 . . 89.64(11)
N1 Cu4 N14 . . 95.67(11)
N1 Cu4 N16 . . 91.74(12)
N1 Cu4 N19 . . 96.55(11)
N1 C1 Cu1 . . 170.9(3)
N1 C1 Cu2 . . 117.4(3)
Cu1 C1 Cu2 . . 71.26(10)
C1 N1 Cu4 . . 151.8(3)
N2 C2 Cu1 . . 155.4(3)
N2 C2 Cu2 . . 131.6(3)
Cu1 C2 Cu2 . . 72.94(9)
C2 N2 Cu3 . . 170.2(3)
N3 C3 Cu2 . . 177.3(3)
C3 N3 Cu3 . 1_545 176.5(3)
N4 C4 Cu2 . 3_564 174.9(3)
C4 N4 Cu1 . . 166.0(3)
N5 C5 Cu3 . 2_544 172.9(3)
C5 N5 Cu1 . . 169.4(3)
C12 N11 Cu4 . . 108.8(2)
Cu4 N11 H11A . . 109.9
Cu4 N11 H11B . . 109.9
C12 N11 H11A . . 109.9
C12 N11 H11B . . 109.9
H11A N11 H11B . . 108.3
N11 C12 C13 . . 107.5(3)
N11 C12 H12A . . 110.2
C13 C12 H12A . . 110.2
N11 C12 H12B . . 110.2
C13 C12 H12B . . 110.2
H12A C12 H12B . . 108.5
C12 C13 N14 . . 107.6(3)
C12 C13 H13A . . 110.2
C12 C13 H13B . . 110.2
N14 C13 H13A . . 110.2
N14 C13 H13B . . 110.2
H13A C13 H13B . . 108.5
C13 N14 C15 . . 111.7(3)
C13 N14 Cu4 . . 105.9(2)
C15 N14 Cu4 . . 119.6(2)
C13 N14 H14 . . 106.3
C15 N14 H14 . . 106.3
Cu4 N14 H14 . . 106.3
N14 C15 H15A . . 109.5
N14 C15 H15B . . 109.5
N14 C15 H15C . . 109.5
H15A C15 H15B . . 109.5
H15A C15 H15C . . 109.5
H15B C15 H15C . . 109.5
C17 N16 Cu4 . . 107.3(2)
C17 N16 H16A . . 110.2
C17 N16 H16B . . 110.2
Cu4 N16 H16A . . 110.2
Cu4 N16 H16B . . 110.2
H16A N16 H16B . . 108.5
N16 C17 C18 . . 105.8(3)
N16 C17 H17A . . 110.6
N16 C17 H17B . . 110.6
C18 C17 H17A . . 110.6
C18 C17 H17B . . 110.6
H17A C17 H17B . . 108.7
C17 C18 N19 . . 109.8(3)
C17 C18 H18A . . 109.7
C17 C18 H18B . . 109.7
N19 C18 H18A . . 109.7
N19 C18 H18B . . 109.7
H18A C18 H18B . . 108.2
C18 N19 C20 . . 110.6(3)
C18 N19 Cu4 . . 107.2(2)
C20 N19 Cu4 . . 120.2(2)
Cu4 N19 H19 . . 106.0
C18 N19 H19 . . 106.0
C20 N19 H19 . . 106.0
N19 C20 H20A . . 109.5
N19 C20 H20B . . 109.5
N19 C20 H20C . . 109.5
H20A C20 H20B . . 109.5
H20A C20 H20C . . 109.5
H20B C20 H20C . . 109.5
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Cu1 C1 . 1.980(3) y
Cu1 C2 . 2.042(3) y
Cu1 N4 . 2.050(3) y
Cu1 N5 . 2.041(3) y
Cu1 Cu2 . 2.5599(7) y
Cu2 C1 . 2.379(3) y
Cu2 C2 . 2.255(3) y
Cu2 C3 . 1.935(3) y
Cu2 C4 3_565 1.948(3) y
Cu3 N2 . 1.942(3) y
Cu3 N3 1_565 1.961(3) y
Cu3 C5 2 1.910(3) y
Cu4 N11 . 2.002(3) y
Cu4 N14 . 2.072(3) y
Cu4 N16 . 2.009(3) y
Cu4 N19 . 2.059(3) y
Cu4 N1 . 2.292(3) y
C1 N1 . 1.127(4) ?
C2 N2 . 1.133(4) ?
C3 N3 . 1.152(4) ?
C4 N4 . 1.137(4) ?
C5 N5 . 1.136(4) ?
N11 C12 . 1.469(5) ?
N11 H11A . 0.8900 ?
N11 H11B . 0.8900 ?
C12 C13 . 1.512(6) ?
C12 H12A . 0.9700 ?
C12 H12B . 0.9700 ?
C13 N14 . 1.493(5) ?
C13 H13A . 0.9700 ?
C13 H13B . 0.9700 ?
N14 C15 . 1.475(5) ?
N14 H14 . 0.9800 ?
C15 H15A . 0.9600 ?
C15 H15B . 0.9600 ?
C15 H15C . 0.9600 ?
N16 C17 . 1.488(5) ?
N16 H16A . 0.8900 ?
N16 H16B . 0.8900 ?
C17 C18 . 1.512(7) ?
C17 H17A . 0.9700 ?
C17 H17B . 0.9700 ?
C18 N19 . 1.474(5) ?
C18 H18A . 0.9700 ?
C18 H18B . 0.9700 ?
N19 C20 . 1.470(5) ?
N19 H19 . 0.9800 ?
C20 H20A . 0.9600 ?
C20 H20B . 0.9600 ?
C20 H20C . 0.9600 ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
N14 C13 C12 N11 56.0(4)
N19 C18 C17 N16 54.6(4)
C15 N14 C13 C12 -172.8(3)
C20 N19 C18 C17 -167.4(3)
C15 N14 Cu4 N11 141.85(19)
C20 N19 Cu4 N16 133.9(2)
