# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2020

data_CoBr2(4-cypy)1

_publ_contact_author_name            
'Dr Lothar Fink'   
_publ_contact_author_address             
;
Institute of Inorganic and Analytical Chemistry
Max-von-Laue-Str. 7
60438 Frankfurt am Main
Germany
;


_publ_contact_author_email           fink@chemie.uni-frankfurt.de
_publ_contact_author_fax             '+49 69 798 29235'
_publ_contact_author_phone           '+49 69 798 29123'

_publ_requested_journal              'CrystEngComm'

_publ_contact_letter
;
Please consider this CIF submission as supplementary material for a
manuscript intended for publication in CrystEngComm.
;


#==============================================================================


# 2. PROCESSING SUMMARY (IUCr Office Use Only)

_journal_date_recd_electronic     ?

_journal_date_to_coeditor         ?
_journal_date_from_coeditor       ?
_journal_date_accepted            ?

_journal_date_printers_first      ?
_journal_date_printers_final      ?
_journal_date_proofs_out          ?
_journal_date_proofs_in           ?
    
_journal_coeditor_name            ?
_journal_coeditor_code            ?
_journal_coeditor_notes
; ?
;

_journal_techeditor_code          ?
_journal_techeditor_notes
; ?
;

_journal_coden_ASTM               ?
_journal_name_full                ?
_journal_year                     ?
_journal_volume                   ?
_journal_issue                    ?
_journal_page_first               ?
_journal_page_last                ?

_journal_suppl_publ_number        ?
_journal_suppl_publ_pages         ?

#==============================================================================


loop_
_publ_author_name
_publ_author_address

'Heine, Miriam'
;
Goethe Universit�t Frankfurt am Main
Institute of Inorganic and Analytical Chemistry
Max-von-Laue-Str. 7
60438 Frankfurt am Main
Germany
;

'Fink, Lothar'
;
Goethe Universit�t Frankfurt am Main
Institute of Inorganic and Analytical Chemistry
Max-von-Laue-Str. 7
60438 Frankfurt am Main
Germany
;

'Schmidt, Martin U.'
;
Goethe Universit�t Frankfurt am Main
Institute of Inorganic and Analytical Chemistry
Max-von-Laue-Str. 7
60438 Frankfurt am Main
Germany
;

_publ_section_title
;
'4-Cyanopyridine complexes [MX2(4-CNpy)x]n (with X = Cl, Br and x = 1, 2): 
Crystal structures, thermal properties and a comparison with [MX2(3-CNpy)x]n complexes'
;

_publ_section_reCorences
;
Boultif, A. & Louër, D. (1991). J. Appl. Cryst., 24, 987-993.

Coelho, A. (2018). J. Appl. Cryst., 51, 210-218.

David, W. I. F., Shankland, K., Van de Streek, J., Pidcock, E. & Motherwell, S.
(2004). DASH. Version 3.0. Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge, England.

Esmaeili, A., Kamiyama, T., Oishi-Tomiyasu, R. (2017). J. Appl. Cryst.
50 , 651-659.

Macrea, C. F., Edingington, P. R., McCabe, P., Pidcock, E., Shields, G.,
Taylor, R., Towler, M. & Van de Streek, J. (2006). J. Appl. Cryst.
39 , 453-457.

Oishi-Tomiyasu, R. (2014).J. Appl. Cryst., 47, 593-598. 

Oishi-Tomiyasu, R. (2014).J. Appl. Cryst., 47, 2055�2059. 

STOE & Cie (2004). WinXPOW. STOE and Cie, Darmstadt, Germany.
;

_publ_section_exptl_prep
;
The compound was prepared by thermal decomposition of [CoBr2(4-cypy)2]n at around 250�C.
;
_publ_section_exptl_refinement
;

The structure is isotypic to [NiBr2(4-cypy)1]n, [MnBr2(4-cypy)1]n and [FeBr2(4-cypy)1]n.
A Pawley fit was performed in TOPAS (Coelho, 2018) using the lattice paramters of [NiBr2(4-cypy)1]n as starting values. 
Structure solution was then carried out using simulated annealing with DASH. 
First, background and instrumental parameters (zero point, axial divergence) were refined. Next, size and strain parameters were refined.  
Structure solution was then carried out with the simulated annealing algorithm of DASH (David et al. , 2004) using a
one Co atoms, two Br atoms and one 4-cypy as fragments. Co and 4-cypy were fixed on (x,0,z) during the structure solution process.
The Rietveld refinement was carried out with TOPAS (Coelho, 2018). 
The Co atom was placed on the origin, the bromine atom was fixed on (x,-1/2,z), the 4-cyanopyridine was fixed on (x,0,z).
All C-C and C-H angles of the pyridine ring were restrained to be 120°. 
Bonds within the pyridine ring were restrained as follows:

C1      C2      ,   1.38
C1      C3      ,   1.38
C1      C4      ,   1.44
C2      C5      ,   1.38
C2      H6      ,   0.99
C3      C7      ,   1.38
C3      H8      ,   0.99
C4      N9      ,   1.15
C5      N10     ,   1.34
C5      H11     ,   0.99
C7      N10     ,   1.34
C7      H12     ,   0.99


Thermal parameters of hydrogen atoms were constrained to be 1.2 time those of the non-hydrogen atoms. 


A disordered model with variable occupancy for the (4-cypy) orientation (head-to-tail-disorder) was 
applied using a mirror plane, parallel to (100) between two Co positions.
;


_chemical_name_mineral ??
_cell_length_a  12.4692(10)
_cell_length_b  3.76053(17)
_cell_length_c  9.62324(71)
_cell_angle_alpha 90
_cell_angle_beta  89.870(15)
_cell_angle_gamma 90
_cell_volume 451.241(53)
_cell_formula_units_Z   2
_space_group 		P12/m1
loop_
_symmetry_equiv_pos_as_xyz
	'-x, -y, -z'
	'-x, y, -z'
	'x, -y, z'
	'x, y, z'  	
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
_atom_site_U_iso_or_equiv

Co13 Co   0 0.2543(13) 0 0.7856(13) 1 2.20242     0.02789
Br14 Br   0 0.09338(76) 0.5 0.79656(91) 1 2.20242     0.02789
Br15 Br   0 0.39114(61) 0.5 0.74815(96) 1 2.20242     0.02789
C1 C     0  0.2582(20) 0 0.3378(14) 0.486(18) 2.20242     0.02789
C2 C     0 0.3485(11) 0 0.2553(14) 0.486(18) 2.20242     0.02789
C3 C     0 0.1671(10) 0 0.2584(14) 0.486(18) 2.20242     0.02789
C4 C     0 0.2527(22) 0 0.4889(14) 0.486(18) 2.20242     0.02789
C5 C     0 0.3456(11) 0 0.1060(14) 0.486(18) 2.20242     0.02789
H6 H     0 0.4141(30) 0 0.3171(94) 0.486(18) 2.642904     0.03347
C7 C     0 0.1678(11) 0 0.1105(14) 0.486(18) 2.20242     0.02789
H8 H     0 0.1024(31) 0 0.324(11) 0.486(18) 2.642904     0.03347
N9 N     0 0.2404(53) 0 0.6044(19) 0.486(18) 2.20242     0.02789
N10 N    0 0.2561(17) 0 0.0349(18) 0.486(18) 2.20242     0.02789
H11 H    0 0.4122(38) 0 0.0532(63) 0.486(18) 2.642904     0.03347
H12 H    0 0.0997(37) 0 0.0621(51) 0.486(18) 2.642904     0.03347


C101 C    0 0.2532(63) 0 0.2516(38) 0.514(18) 2.20242     0.02789
C102 C    0 0.3435(60) 0 0.3341(38) 0.514(18) 2.20242     0.02789
C103 C    0 0.1621(60) 0 0.331(38) 0.514(18) 2.20242     0.02789
C104 C    0 0.2477(64) 0 0.1005(38) 0.514(18) 2.20242     0.02789
C105 C    0 0.3406(61) 0 0.4834(38) 0.514(18) 2.20242     0.02789
H106 H    0 0.4091(67) 0  0.272(10) 0.514(18) 2.642904     0.03347
C107 C    0 0.1628(61) 0 0.4789(38) 0.514(18) 2.20242     0.02789
H108 H    0 0.0974(67) 0  0.265(12) 0.514(18) 2.642904     0.03347
N109 N    0 0.2354(80) 0 -0.015(40) 0.514(18) 2.20242     0.02789
N1010 N   0 0.2511(62) 0 0.5545(40) 0.514(18) 2.20242     0.02789
H1011 H   0 0.4072(71) 0 0.5362(73) 0.514(18) 2.642904     0.03347
H1012 H   0 0.0947(70) 0 0.5273(62) 0.514(18) 2.642904     0.03347

  
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



Co13	Br14	     2.752(14)    . ?
C1      C3   1.372(24)   . ?
C1      C2   1.375(24)   . ?
C1      C4   1.456(19)   . ?
C2      C5   1.437(19)    . ?
C2      H6   1.014(62)   . ?
C3      C7   1.423(19)     . ?
C3      H8   1.022(74)    . ?
C4      N9   1.120(24)  . ?
C5      N10  1.311(24)       . ?
C5      H11  0.972(53) . ?
C7      N10  1.318(24)   . ?
C7      H12  0.968(49)   . ?


C101      C103   1.372(24)    . ? 
C101      C102   1.375(24)    . ?
C101      C104   1.456(19)    . ?
C102      C105   1.437(19)    . ?
C102      H106   1.014(62)    . ?
C103      C107   1.423(19)    . ?
C103      H108   1.022(74)    . ?
C104      N109   1.120(24)    . ?
C105      N1010  1.311(24)    . ?
C105      H1011  0.972(53)    . ?
C107      N1010  1.318(24)    . ?
C107      H1012  0.968(49)    . ?
 	 
				
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   

C2      C1      C3       110.9(12)    . . ?
C2      C1      C4       127.7(20)  . . ?
C3      C1      C4       121.4(19)    . . ?
C1      C2      C5       123.6(13)   . . ?
C1      C2      H6       108.7(44)    . . ?
C5      C2      H6       127.7(44) . . ?
C1      C3      C7       123.7(13)   . . ?
C1      C3      H8       108.1(51)   . . ?
C7      C3      H8       128.1(51) . . ?
C1      C4      N9       175.4(38)   . . ?
C2      C5      N10      123.1(14)  . . ?
C2      C5      H11      119.9(36) . . ?
N10     C5      H11      117.0(37)    . . ?
C3      C7      N10      123.6814)    . . ?
C3      C7      H12      118.5(31)    . . ?
N10     C7      H12      117.9(32)      . . ?
C5      N10     C7       115.0(15)  . . ?



_chemical_name_systematic                  
; 
catena-dibromo-(4-cyanopyridine)cobalt
;				  
_chemical_name_common             'catena-dibromo-(4-cyanopyridine)cobalt'		 
_chemical_formula_iupac           'C6 H4 Br2 Co N2'				 
_chemical_formula_moiety          'C6 H4 Br2 Co N2'				 
_chemical_formula_structural      'C6 H4 Br2 Co N2'				 
_chemical_formula_analytical      ?          
_chemical_formula_sum             'C6 H4 Br2 Co N2'
_chemical_formula_weight          322.84
_chemical_melting_point           ? 
 
_exptl_crystal_colour   'red ' 
_exptl_crystal_description 'powder'
 
loop_                                       
     _atom_type_symbol                      
     _atom_type_description      
     _atom_type_scat_source                       
   C C 'International Tables Vol C Table 6.1.1.4'
   H H 'International Tables Vol C Table 6.1.1.4'
   Co Co 'International Tables Vol C Table 6.1.1.4'
   Br Br 'International Tables Vol C Table 6.1.1.4'
   N N 'International Tables Vol C Table 6.1.1.4'


_symmetry_cell_setting            monoclinic        
_symmetry_space_group_name_H-M    'P 1 2/m 1'        
_symmetry_space_group_name_Hall   '-P 2y'


_pd_spec_size_axial   12

_pd_spec_size_equat   0.7

_pd_spec_size_thick   0.7


# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                         
;
Specimen was placed in a 0.7 mm diameter borosilicate glass capillary of Hilgenberg. 
;

_pd_spec_mount_mode               'transmission'

_pd_spec_shape                    'cylinder'

_pd_char_particle_morphology      ?
_pd_char_colour                   ?       




# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu     ?
_pd_char_atten_coef_mu_obs ?								
_exptl_crystal_density_diffrn 2.376

#==============================================================================

# 7. EXPERIMENTAL DATA

_exptl_special_details
; ?
;

# The following item is used to identify the equipment used to record 
# the powder pattern when the diffractogram was measured at a laboratory 
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location
; ?
;
_pd_calibration_special_details           # description of the method used
                                          # to calibrate the instrument
; ?
;

_diffrn_ambient_temperature       523            
_diffrn_source_target             ?
_diffrn_source_type               ?
_diffrn_radiation_type            'Mo K\a~1~'       
_diffrn_measurement_device_type   'STOE Stadi-P'       
_diffrn_detector                  'Mythen 1K, Dectris'      
_diffrn_detector_type             'silicon strip detector'
_diffrn_radiation_source          'X-ray tube'
_exptl_crystal_F_000           ?	    			    

_pd_meas_scan_method              step       


_diffrn_radiation_wavelength      0.70930                    
_diffrn_radiation_monochromator   'primary focussing, Ge 111'   

#  The following four items give details of the measured (not processed)
#  powder pattern.  Angles are in degrees.

_pd_meas_number_of_points         3285
_pd_meas_2theta_range_min         1        
_pd_meas_2theta_range_max         50.26       
_pd_meas_2theta_range_inc         0.135

_cell_measurement_temperature     523


#==============================================================================
# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.


_pd_proc_ls_profile_function      
;
modified spherical harmonics(Coelho, 2018)
;        
_pd_proc_ls_background_function   'Chebychev polynomial'
_pd_proc_ls_pref_orient_corr      'none'        


_pd_proc_ls_prof_R_factor         0.01480     
_pd_proc_ls_prof_wR_factor        0.01984        
_pd_proc_ls_prof_wR_expected      0.01404       
_refine_ls_R_I_factor             1.2488073	  



_refine_ls_matrix_type            fullcycle        	
_refine_ls_weighting_scheme       sigma        		
_refine_ls_weighting_details      w=1/σ(Yobs)²	
_refine_ls_hydrogen_treatment     'mixed'        	
_refine_ls_extinction_method      'none'        	
_refine_ls_extinction_coef        ?         		
_refine_ls_number_parameters      83      		
_refine_ls_number_restraints      29        		
_refine_ls_number_constraints     1 			
_refine_ls_number_reflns	?			
     

_refine_ls_goodness_of_fit_all     1.413     
      
_refine_ls_restrained_S_all       ?        
_refine_ls_restrained_S_obs       ?
_refine_ls_shift/su_max           ?        
_refine_ls_shift/su_mean          ?

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the 
# intensities used in the refinement.

_pd_proc_2theta_range_min         1         
_pd_proc_2theta_range_max         50.26      
_pd_proc_2theta_range_inc         0.135              
_pd_proc_info_excluded_regions    'none'        


# The following items are used to identify the programs used.

_computing_molecular_graphics   'MERCURY (Macrea et al.)'
_computing_structure_refinement   'TOPAS (Coelho, 2018)'
_computing_structure_solution   'DASH (David et al., 2004)'
_computing_data_reduction   'DASH (David et al., 2004)'
_computing_cell_refinement   'DASH (David  et al. , 2004)'
_computing_data_collection   'STOE WINXPOW (STOE & Cie GmbH, 2004)'


# start Validation Reply Form
_vrf_PUBL012_GLOBAL
;
PROBLEM: _publ_section_abstract is missing.
RESPONSE: Abstract will be given later.
;
_vrf_PLAT920_CoBr24-cypy1
;
PROBLEM: Theta(Max)  in CIF and FCF DifCor by ...........       4.89 Degree
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT157_CoBr24-cypy1
;
PROBLEM: Non-standard Monoclinic Beta Angle less 90 Deg        89.87 Degree
RESPONSE: The space group setting was chosen for an easier comparison with the isotypic structures.
;
_vrf_PLAT962_CoBr24-cypy1
;
PROBLEM: Number of Input Relections with Sigma(Fo^2) =  0         76       
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT971_CoBr24-cypy1
;
PROBLEM: Check Calcd Resid. Dens.  1.03A   From Br15            4.15 eA-3 and others.
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT972_CoBr24-cypy1
;
PROBLEM: Check Calcd Resid. Dens.  0.02A   From Br15          -57.84 eA-3      and others
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT974_CoBr24-cypy1
;
PROBLEM: Check Calcd Negative Resid. Density on      Co13     -43.39 eA-3  
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT977_CoBr24-cypy1
;
PROBLEM: Check Negative Difference Density on H11              -0.84 eA-3     and others 
RESPONSE: The structure was solved from powder data.
;
_vrf_PLAT004_CoBr24-cypy1
;
PROBLEM: Polymeric Structure Found with Maximum Dimension
RESPONSE: The structure is polymeric.
;
_vrf_PLAT802_CoBr24-cypy1
;
PROBLEM: CIF Input Record(s) with more than 80 Characters         
RESPONSE: X-ray powder data.
;
_vrf_PLAT860_CoBr24-cypy1
;
PROBLEM: Number of Least-Squares Restraints .............         29 Note 
RESPONSE: X-ray powder data.
;
_vrf_PLAT301_CoBr24-cypy1
;
PROBLEM: Main Residue  Disorder ..............(Resd  1  )        79% Note 
RESPONSE: The structure is disorderd (head-to-tail-disorder of the 4cypy ring within the nets).
;
_vrf_PLAT431_CoBr24-cypy1
;
PROBLEM:  Short Inter HL..A Contact  Br14     ..N9       .       3.21 Ang.  and furthers.
RESPONSE: The structure is disorderd. 
;
_vrf_PLAT720_CoBr24-cypy1
;
PROBLEM: Number of Unusual/Non-Standard Labels .......... 
RESPONSE: Label were chosen explicitely describe the disorder with clarity.
;
_vrf_PLAT804_CoBr24-cypy1
;
PROBLEM: Number of ARU-Code Packing Problem(s) in PLATON           8 Info    
RESPONSE:The structure is disorderd.
;
# end Validation Reply Form
