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Dealing with metals

keitaroyam edited this page Mar 31, 2025 · 12 revisions

We are updating metal-containing entries using a newly developed mechanism:

acedrg -c input.cif -o ${out}
metalCoord update -i ${out}_final.cif -o ${out}_mc.cif
servalcat refine_geom --update_dictionary ${out}_mc.cif

However, in many cases CCD's cif files need corrections. Major correction types are:

  1. All sandwich and half sandwich had errors in bond orders, charges or hydrogen atoms
  2. C-O triple bonds were replaced with double bonds
  3. Metal-metal bonds were removed
  4. Some haem like structures have been corrected. They may need to be dealt with again.
  5. In many metal containing components there are some atoms as place holders. They are replaced with protein atoms within the molecule. We changed only some of them. Perhaps for all of them we should remove place holders.

The following is the list of corrections we made so far

ID correction
067 Sandwich, missing H atoms and charge on rings
2T8 C-O triple bond should be double
498 Sandwich, missing H atoms and charge
4IR Half sandwich, bond orders and charge are missing
4WV C-O triple bond should be double
4WW C-O triple bond should be double
4WX C-O triple bond should be double
670 Sandwich, missing H atoms and charge on rings
7G4 Sandwich, bond orders and charges
82N Metal-metal bond should be removed
84A Sandwich, missing H atoms and charge on rings
8CY Sandwich, missing H atoms and charge on rings
8TH Half sandwich, bond orders and charge
9Q8 C-O triple bond should be double
9SQ C-O triple bond should be double
9UX delete hydrogen
AG1 C-O triple bond should be double
B13 Problem in pyrroles
B1R Sandwich, missing H atoms and charge on rings
B9F Sandwich, missing H atoms and charge on rings
BE7 CL1 should be removed (it is a general problem)
C4R H atoms on C atoms bonded to the metal
CFC Sandwich, missing charge on rings, wrong bond order
CJI metal-metal bond should be removed
CUA metal-metal bond should be removed
CUZ metal-metal bond should be removed
CWO Double bond for P-O bond should be added
CZL Wrong H atoms on S and metal-metal bonds should be removed
D3I metal-metal
D5A metal-metal
DW1 C-O triple bond should be double. RU to C12/C13/C14/C16/C17 bonds are needed
DW2 C-O triple bond should be double
DWC Half sandwich, bond orders and charge
E52 Half sandwich, charge
F3I metal-metal
F5I metal-metal
F5T metal-metal
FE9 O1/S1/HS1/H2 should be removed to make it consistent with the PDB
FLL C-O triple bond should be double
FNE C-O triple bond should be double
FS2 metal-metal; bonding pattern should be checked
FSX metal-metal
FU8 C-O triple bond should be double
G9R Missing metal pyrrole bond
GXW double bond for P-O bond
GXZ double bond for P-O bond
H57 Sandwich, metal ring bonds, H atoms and charge
H58 Sandwich, metal ring bonds, H atoms and charge
H79 Sandwich, missing charge on rings, wrong bond order
HB1 Half sandwich, bond orders and charge
HBF Sandwich, missing charge on rings, wrong bond order
HC0 Metal-metal
HC1 Metal-metal
HCO Bond orders on pyrrole
HEC wrong chemistry. HEM should be used
HDD Bond orders on pyrrole
HDE Bond orders on pyrrole
HE5 Bond orders on pyrrole
HFM bond orders on pyrrole
HFW double bond for P-O bond
HRU Half sandwich, bond orders
ISW One of the pyrroles had wrong H atom
J0K Half sandwich, bond orders, charge
J0N Half sandwich, bond orders, charge
J52 C-O triple bond should be double
JCT Half sandwich, bond orders, charge
JGH double bond for P-O bond
JM1 Half sandwich, bond orders, charge
JR3 Half sandwich, bond orders, charge
JSC Sandwich, metal ring bonds, H atoms and charge
JSD Sandwich, metal ring bonds, H atoms and charge
JSE Sandwich, metal ring bonds, H atoms and charge
K3G double bond for P-O bond
KEG double bond for P-O bond
L8W Sandwich, metal ring bonds, H atoms and charge
LFH C-O triple bond should be double
LSI Sandwich, metal ring bonds, H atoms and charge
ME3 Half sandwich, bond orders, charge
MHX C-O triple bond should be double
N7H Fix nitro group
NFR Metal-metal
NFU Metal-metal
NFV C-O triple bond should be double
NOF Half sandwich, bond orders, charge
NT3 N-O triple bond should be double
O1N Half sandwich, H atoms, bond orders, charge
ORS Half sandwich, bond orders, charge
OS1 C-O triple bond should be double
OSV C-S bond changed from triple to single, N-C bond from single to triple
OT1 Half sandwich, bond orders, charge
PNQ Nitro group: N-O bonds changed to double (these are equivalent)
PW9 double bond for P-O bond
R1N Half sandwich, bond orders, charge
R2I Metal-metal
REI C-O triple bond should be double
REJ C-O triple bond should be double
REP C-O triple bond should be double
REQ C-O triple bond should be double
RMD Half sandwich, bond orders, charge
RSW Half sandwich, bond orders
RTC C-O triple bond should be double
RU0 Metal-metal
RU1 C-O triple bond should be double
RU2 C-O triple bond should be double
RUI Half sandwich, H atoms, charge
RUX C-O triple bond should be double
SRX Half sandwich, bond orders, charge
TDJ Sandwich, metal ring bonds, H atoms and charge
TPT CL1 removed to make it consistent with the PDB
TZ6 Metal-metal
UWE C-O triple bond should be double
V7F Add H atoms on N02 and N04
VER O in the larger ring of the porphyrin should have single bonds
VHR C-O triple bond should be double
VKZ Half sandwich, bond orders
VL2 Half sandwich, bond orders
WO2 double bond for P-O bond
YJT Metal-metal
YMQ Metal-metal
YWV Metal-metal
ZJK Metal-metal
ZJO Metal-metal
ZKG double bond for P-O bond
ZQ2 Metal-metal
ZWH Metal-metal
ZWO Metal-metal
ZXE Metal-metal

Fixing HEC

HEC would never exist as an isolated ligand, but should always be linked to CYS residues. We fixed HEC bonding pattern and used charge -1 trick for CAC and CAB atoms. See https://github.com/MonomerLibrary/monomers/pull/60.

Links

CYS-HEMB:

LINK: RES-NAME-1 CYS ATOM-NAME-1 SG RES-NAME-2 HEM ATOM-NAME-2 CAB CHANGE BOND CAB CBB SINGLE 2 FILE-2 ../HEM_mc_refined_updated.cif

CYS-HEMC:

LINK: RES-NAME-1 CYS ATOM-NAME-1 SG RES-NAME-2 HEM ATOM-NAME-2 CAC CHANGE BOND CAC CBC SINGLE 2 FILE-2 ../HEM_mc_refined_updated.cif

H31 should be renamed to H32.

HEC-CYS1:

LINK: RES-NAME-1 CYS ATOM-NAME-1 SG RES-NAME-2 HEC ATOM-NAME-2 CAC CHANGE CHARGE 2 CAC 0 FILE-2 ../AcedrgOut.cif

HEC-CYS2:

LINK: RES-NAME-1 CYS ATOM-NAME-1 SG RES-NAME-2 HEC ATOM-NAME-2 CAB CHANGE CHARGE 2 CAB 0 FILE-2 ../AcedrgOut.cif

Typical interatomic distances

The typical distances between metal sites and surrounding atoms are provided in the file metals.json. The data is organized by metal element, element of its interaction partner, and the metal's coordination number.

For instance, typical distance for iron-sulphur interaction, relevant for the Fe-S clusters, can be explored. We can select the section for "Fe" and its subsection "S" - open the file metals.json in a text editor or inpect it using the following Python commands:

import json
import pprint
with open('metals.json', 'r') as metals_file:
    data = json.load(metals_file)

pprint.pprint(data['metal_coordination']['Fe']['S'])

We find out 7 possible coordination numbers, denoted as "coord": 3, 4, 5, 6, 7, 8 and 11. For each coordination number, the following information is provided:

  • Median interatomic distance and its absolute deviation.
  • Mean interatomic distance and its standard deviation.
  • Number of reference structures where such coordination was observed, denoted as "count". In this example, note that the coordination numbers 7 and 11 are extremely rare, with only one reference structure for each, thus, the reported values for these coordination numbers may be misleading.

Let's focus on coordination number 6 which is the most common (752 reference structures).

coord_6 = next(c for c in data['metal_coordination']['Fe']['S'] if c['coord'] == 6)
pprint.pprint(coord_6)

Output:

{'coord': 6,
 'count': 752,
 'mad': 0.055011272422031965,
 'mean': 2.354311549366653,
 'median': 2.315759378691282,
 'modes': [{'mode': 2.2918619816782826,
            'std': 0.044788392111853155,
            'weight': 0.7156127571039738},
           {'mode': 2.5114554031426977,
            'std': 0.07950441399256195,
            'weight': 0.2843872428960263}],
 'std': 0.1142177002047632}

There are two entries under the subsection "modes", indicating that two options for a typical interatomic distance, as multiple coordination classes are possible for the same coordination number. The "weight" of each mode refers to the ratio of reference structures with a particular mode. Thus, the ideal Fe-S interatomic distances, when considering iron with a coordination number of 6, are (2.29 ± 0.05) Å and (2.51 ± 0.08) Å as identified in 71.6 % and 28.4 % of the 752 reference structures, respectively.

Note: The records in the file metals.json are updated in time and could slightly change from January 2025, when this text was written.

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