# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2014

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#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
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# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
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#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
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#  except for the purpose of generating routine backup copies
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#  data retrieval see:
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data_1a

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H11 Br Mn N3 O3'
_chemical_formula_sum            'C18 H11 Br Mn N3 O3'
_chemical_formula_weight         452.15

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c'
_symmetry_space_group_name_Hall  '-P 2ybc'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.8469(3)
_cell_length_b                   6.99830(10)
_cell_length_c                   16.9166(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 115.8320(10)
_cell_angle_gamma                90.00
_cell_volume                     1688.61(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5975
_cell_measurement_theta_min      2.68
_cell_measurement_theta_max      30.46

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.779
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             896
_exptl_absorpt_coefficient_mu    3.172
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5140
_exptl_absorpt_correction_T_max  0.7810
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  'curved graphite crystal'
_diffrn_measurement_device_type  'Bruker KAPPA APEX II DUO CCD'
_diffrn_measurement_device       '62mm x 62mm CCD camera on \k-goniostat'
_diffrn_detector_area_resol_mean 16 # 8 for binned mode
_diffrn_measurement_method       '\f scans and \w scans with \k offset'
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            19066
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_sigmaI/netI    0.0293
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         2.42
_diffrn_reflns_theta_max         30.59
_reflns_number_total             5168
_reflns_number_gt                4262
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT (Bruker AXS, 2009)'
_computing_data_reduction        'SAINT (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Diamond v.3.2e (Brandenburg, 2010)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'

_refine_special_details          
; 
 Refinement of F^2^ against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F^2^, conventional R-factors R are based 
 on F, with F set to zero for negative F^2^. The threshold expression of 
 F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F^2^ are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0295P)^2^+0.8021P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5168
_refine_ls_number_parameters     235
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0258
_refine_ls_wR_factor_ref         0.0616
_refine_ls_wR_factor_gt          0.0574
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_restrained_S_all      1.021
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.194643(11) 0.42627(3) 0.897453(11) 0.01522(5) Uani 1 1 d . . .
Mn1 Mn 0.300262(16) 0.13913(4) 0.914761(16) 0.01074(6) Uani 1 1 d . . .
O1 O 0.39321(9) 0.2313(2) 1.10491(8) 0.0194(3) Uani 1 1 d . . .
O2 O 0.43910(9) 0.4026(2) 0.90138(9) 0.0198(3) Uani 1 1 d . . .
O3 O 0.43373(9) -0.1715(2) 0.93798(8) 0.0189(3) Uani 1 1 d . . .
N1 N 0.22994(9) 0.0907(2) 0.78261(9) 0.0122(3) Uani 1 1 d . . .
N2 N 0.18600(9) -0.0246(2) 0.90832(9) 0.0121(3) Uani 1 1 d . . .
N3 N 0.22382(10) -0.0626(2) 1.13072(10) 0.0153(3) Uani 1 1 d . . .
C1 C 0.35540(11) 0.1897(3) 1.03207(11) 0.0140(3) Uani 1 1 d . . .
C2 C 0.38465(11) 0.3018(3) 0.90638(11) 0.0143(3) Uani 1 1 d . . .
C3 C 0.37964(11) -0.0540(3) 0.92861(10) 0.0135(3) Uani 1 1 d . . .
C4 C 0.26224(12) 0.1240(3) 0.72242(11) 0.0146(3) Uani 1 1 d . . .
H4 H 0.3236 0.1749 0.7414 0.017 Uiso 1 1 calc R . .
C5 C 0.20961(13) 0.0870(3) 0.63368(11) 0.0162(3) Uani 1 1 d . . .
H5 H 0.2340 0.1140 0.5926 0.019 Uiso 1 1 calc R . .
C6 C 0.12109(12) 0.0104(3) 0.60633(11) 0.0171(3) Uani 1 1 d . . .
H6 H 0.0839 -0.0173 0.5460 0.020 Uiso 1 1 calc R . .
C7 C 0.08673(12) -0.0260(3) 0.66743(11) 0.0161(3) Uani 1 1 d . . .
H7 H 0.0259 -0.0787 0.6497 0.019 Uiso 1 1 calc R . .
C8 C 0.14312(11) 0.0163(3) 0.75529(11) 0.0131(3) Uani 1 1 d . . .
C9 C 0.11475(11) -0.0213(3) 0.82579(11) 0.0134(3) Uani 1 1 d . . .
C10 C 0.02148(12) -0.0480(3) 0.80837(11) 0.0165(3) Uani 1 1 d . . .
H10 H -0.0264 -0.0429 0.7498 0.020 Uiso 1 1 calc R . .
C11 C -0.00056(12) -0.0821(3) 0.87787(12) 0.0167(3) Uani 1 1 d . . .
H11 H -0.0640 -0.0912 0.8687 0.020 Uiso 1 1 calc R . .
C12 C 0.07247(12) -0.1025(3) 0.96118(11) 0.0152(3) Uani 1 1 d . . .
H12 H 0.0594 -0.1335 1.0094 0.018 Uiso 1 1 calc R . .
C13 C 0.16500(11) -0.0778(3) 0.97442(11) 0.0129(3) Uani 1 1 d . . .
C14 C 0.24122(11) -0.1182(3) 1.06299(11) 0.0137(3) Uani 1 1 d . . .
C15 C 0.32070(12) -0.2209(3) 1.07362(11) 0.0144(3) Uani 1 1 d . . .
H15 H 0.3285 -0.2650 1.0241 0.017 Uiso 1 1 calc R . .
C16 C 0.38835(12) -0.2573(3) 1.15830(11) 0.0179(4) Uani 1 1 d . . .
H16 H 0.4439 -0.3251 1.1678 0.021 Uiso 1 1 calc R . .
C17 C 0.37351(13) -0.1931(3) 1.22902(12) 0.0192(4) Uani 1 1 d . . .
H17 H 0.4196 -0.2116 1.2876 0.023 Uiso 1 1 calc R . .
C18 C 0.28965(13) -0.1013(3) 1.21178(11) 0.0178(4) Uani 1 1 d . . .
H18 H 0.2783 -0.0638 1.2602 0.021 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Br1 0.01369(8) 0.01462(9) 0.01368(8) -0.00163(6) 0.00254(6) 0.00276(6)
Mn1 0.00920(10) 0.01256(13) 0.00921(11) -0.00040(9) 0.00285(8) 0.00029(9)
O1 0.0182(6) 0.0253(7) 0.0131(6) -0.0046(5) 0.0054(5) -0.0025(5)
O2 0.0175(6) 0.0210(7) 0.0187(6) 0.0029(5) 0.0059(5) -0.0032(5)
O3 0.0172(6) 0.0207(7) 0.0173(6) -0.0005(5) 0.0062(5) 0.0050(5)
N1 0.0123(6) 0.0124(7) 0.0106(6) -0.0003(5) 0.0039(5) 0.0006(5)
N2 0.0119(6) 0.0124(7) 0.0112(6) -0.0005(5) 0.0041(5) 0.0000(5)
N3 0.0179(7) 0.0161(8) 0.0124(6) -0.0014(6) 0.0069(5) -0.0022(6)
C1 0.0120(7) 0.0142(8) 0.0169(8) 0.0006(6) 0.0074(6) 0.0010(6)
C2 0.0135(7) 0.0162(8) 0.0108(7) 0.0005(6) 0.0031(6) 0.0034(6)
C3 0.0126(7) 0.0174(9) 0.0091(7) -0.0006(6) 0.0035(6) -0.0030(6)
C4 0.0157(7) 0.0144(8) 0.0136(7) 0.0007(6) 0.0064(6) 0.0001(6)
C5 0.0217(8) 0.0156(9) 0.0129(7) 0.0000(6) 0.0093(6) 0.0014(7)
C6 0.0204(8) 0.0173(9) 0.0103(7) -0.0017(6) 0.0037(6) 0.0023(7)
C7 0.0148(7) 0.0176(9) 0.0120(7) -0.0015(6) 0.0022(6) -0.0003(6)
C8 0.0127(7) 0.0131(8) 0.0116(7) -0.0007(6) 0.0036(6) 0.0014(6)
C9 0.0127(7) 0.0141(8) 0.0115(7) -0.0006(6) 0.0036(6) -0.0002(6)
C10 0.0137(7) 0.0192(9) 0.0140(7) -0.0012(6) 0.0038(6) -0.0014(6)
C11 0.0124(7) 0.0175(9) 0.0195(8) -0.0016(7) 0.0064(6) -0.0013(7)
C12 0.0146(7) 0.0167(9) 0.0153(8) -0.0004(6) 0.0074(6) -0.0012(6)
C13 0.0129(7) 0.0126(8) 0.0123(7) -0.0012(6) 0.0047(6) -0.0008(6)
C14 0.0146(7) 0.0135(9) 0.0124(7) 0.0003(6) 0.0054(6) -0.0020(6)
C15 0.0164(7) 0.0147(8) 0.0130(7) 0.0008(6) 0.0073(6) -0.0012(6)
C16 0.0163(8) 0.0193(9) 0.0169(8) 0.0038(7) 0.0063(7) 0.0009(7)
C17 0.0200(8) 0.0214(10) 0.0129(8) 0.0014(7) 0.0040(6) -0.0029(7)
C18 0.0221(8) 0.0195(10) 0.0128(7) -0.0017(7) 0.0086(7) -0.0033(7)

_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 Mn1 2.5492(3) . yes
Mn1 C3 1.7908(18) . yes
Mn1 C2 1.8082(18) . yes
Mn1 C1 1.8209(17) . yes
Mn1 N1 2.0454(14) . yes
Mn1 N2 2.1050(14) . yes
O1 C1 1.148(2) . ?
O2 C2 1.146(2) . ?
O3 C3 1.148(2) . ?
N1 C4 1.344(2) . ?
N1 C8 1.350(2) . ?
N2 C13 1.351(2) . ?
N2 C9 1.360(2) . ?
N3 C18 1.340(2) . ?
N3 C14 1.347(2) . ?
C4 C5 1.387(2) . ?
C4 H4 0.9500 . ?
C5 C6 1.380(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.386(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.392(2) . ?
C7 H7 0.9500 . ?
C8 C9 1.470(2) . ?
C9 C10 1.388(2) . ?
C10 C11 1.385(2) . ?
C10 H10 0.9500 . ?
C11 C12 1.387(2) . ?
C11 H11 0.9500 . ?
C12 C13 1.394(2) . ?
C12 H12 0.9500 . ?
C13 C14 1.485(2) . ?
C14 C15 1.392(2) . ?
C15 C16 1.389(2) . ?
C15 H15 0.9500 . ?
C16 C17 1.391(3) . ?
C16 H16 0.9500 . ?
C17 C18 1.388(3) . ?
C17 H17 0.9500 . ?
C18 H18 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 Mn1 C2 89.09(8) . . ?
C3 Mn1 C1 91.60(8) . . ?
C2 Mn1 C1 86.74(8) . . yes
C3 Mn1 N1 92.00(7) . . ?
C2 Mn1 N1 95.05(7) . . ?
C1 Mn1 N1 176.00(7) . . ?
C3 Mn1 N2 97.78(7) . . ?
C2 Mn1 N2 170.91(7) . . ?
C1 Mn1 N2 98.95(7) . . ?
N1 Mn1 N2 78.84(6) . . yes
C3 Mn1 Br1 176.94(6) . . yes
C2 Mn1 Br1 88.03(6) . . ?
C1 Mn1 Br1 87.21(5) . . ?
N1 Mn1 Br1 89.28(4) . . ?
N2 Mn1 Br1 85.19(4) . . ?
C4 N1 C8 118.36(14) . . ?
C4 N1 Mn1 126.38(11) . . ?
C8 N1 Mn1 115.26(11) . . ?
C13 N2 C9 117.42(14) . . ?
C13 N2 Mn1 128.60(11) . . ?
C9 N2 Mn1 110.76(11) . . ?
C18 N3 C14 117.08(15) . . ?
O1 C1 Mn1 175.51(16) . . ?
O2 C2 Mn1 178.95(15) . . ?
O3 C3 Mn1 176.74(15) . . ?
N1 C4 C5 122.64(16) . . ?
N1 C4 H4 118.7 . . ?
C5 C4 H4 118.7 . . ?
C6 C5 C4 118.64(16) . . ?
C6 C5 H5 120.7 . . ?
C4 C5 H5 120.7 . . ?
C5 C6 C7 119.59(16) . . ?
C5 C6 H6 120.2 . . ?
C7 C6 H6 120.2 . . ?
C6 C7 C8 118.64(16) . . ?
C6 C7 H7 120.7 . . ?
C8 C7 H7 120.7 . . ?
N1 C8 C7 122.12(15) . . ?
N1 C8 C9 114.68(14) . . ?
C7 C8 C9 123.18(15) . . ?
N2 C9 C10 123.12(15) . . ?
N2 C9 C8 115.16(14) . . ?
C10 C9 C8 121.71(15) . . ?
C11 C10 C9 118.81(16) . . ?
C11 C10 H10 120.6 . . ?
C9 C10 H10 120.6 . . ?
C10 C11 C12 118.21(15) . . ?
C10 C11 H11 120.9 . . ?
C12 C11 H11 120.9 . . ?
C11 C12 C13 120.25(16) . . ?
C11 C12 H12 119.9 . . ?
C13 C12 H12 119.9 . . ?
N2 C13 C12 121.51(15) . . ?
N2 C13 C14 120.14(14) . . ?
C12 C13 C14 118.32(15) . . ?
N3 C14 C15 123.23(15) . . ?
N3 C14 C13 115.15(15) . . ?
C15 C14 C13 121.39(15) . . ?
C16 C15 C14 118.46(16) . . ?
C16 C15 H15 120.8 . . ?
C14 C15 H15 120.8 . . ?
C15 C16 C17 118.96(17) . . ?
C15 C16 H16 120.5 . . ?
C17 C16 H16 120.5 . . ?
C18 C17 C16 118.31(16) . . ?
C18 C17 H17 120.8 . . ?
C16 C17 H17 120.8 . . ?
N3 C18 C17 123.78(16) . . ?
N3 C18 H18 118.1 . . ?
C17 C18 H18 118.1 . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        30.59
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.714
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.082
_database_code_depnum_ccdc_archive 'CCDC 961705'