rdkit/Code/GraphMol/ConjugHybrid.cpp

// $Id$
//
//  Copyright (C) 2001-2008 Greg Landrum and Rational Discovery LLC
//
//   @@ All Rights Reserved @@
//  This file is part of the RDKit.
//  The contents are covered by the terms of the BSD license
//  which is included in the file license.txt, found at the root
//  of the RDKit source tree.
//
#include "ROMol.h"
#include "RWMol.h"
#include "Atom.h"
#include "Bond.h"
#include "MolOps.h"
#include "PeriodicTable.h"
#include "AtomIterators.h"
#include "BondIterators.h"

namespace RDKit {
// local utility namespace:
namespace {
bool isAtomConjugCand(const Atom *at) {
  // the second check here is for Issue211, where the c-P bonds in
  // Pc1ccccc1 were being marked as conjugated.  This caused the P atom
  // itself to be SP2 hybridized.  This is wrong.  For now we'll do a quick
  // hack and forbid this check from adding conjugation to anything out of
  // the first row of the periodic table.  (Conjugation in aromatic rings
  // has already been attended to, so this is safe.)
  int nouter = PeriodicTable::getTable()->getNouterElecs(at->getAtomicNum());
  if (((at->getAtomicNum() <= 10) || (nouter != 5 && nouter != 6) ||
       (nouter == 6 && at->getTotalDegree() < 2)) &&
      (MolOps::countAtomElec(at) > 0)) {
    return true;
  }
  return false;
}

void markConjAtomBonds(Atom *at) {
  if (!isAtomConjugCand(at)) return;
  ROMol &mol = at->getOwningMol();
  Atom *at2;

  int atx = at->getIdx();
  // make sure that have either 2 or 3 subtitutions on this atom
  int sbo = at->getDegree() + at->getTotalNumHs();
  if ((sbo < 2) || (sbo > 3)) {
    return;
  }

  ROMol::OEDGE_ITER bnd1, end1, bnd2, end2;
  boost::tie(bnd1, end1) = mol.getAtomBonds(at);
  while (bnd1 != end1) {
    if (mol[*bnd1]->getValenceContrib(at) < 1.5) {
      bnd1++;
      continue;
    }
    boost::tie(bnd2, end2) = mol.getAtomBonds(at);
    while (bnd2 != end2) {
      if (bnd1 == bnd2) {
        bnd2++;
        continue;
      }
      at2 = mol.getAtomWithIdx(mol[*bnd2]->getOtherAtomIdx(atx));
      sbo = at2->getDegree() + at2->getTotalNumHs();
      if (sbo > 3) {
        bnd2++;
        continue;
      }
      if (isAtomConjugCand(at2)) {
        mol[*bnd1]->setIsConjugated(true);
        mol[*bnd2]->setIsConjugated(true);
      }
      bnd2++;
    }
    bnd1++;
  }
}

int numBondsPlusLonePairs(Atom *at) {
  PRECONDITION(at, "bad atom");
  int deg = at->getTotalDegree();
  ROMol::OEDGE_ITER beg, end;
  boost::tie(beg, end) = at->getOwningMol().getAtomBonds(at);
  while (beg != end) {
    Bond* bond = at->getOwningMol()[*beg];
    if (bond->getBondType() == Bond::ZERO) --deg;
    ++beg;
  }

  if (at->getAtomicNum() <= 1) {
    return deg;
  }
  int nouter = PeriodicTable::getTable()->getNouterElecs(at->getAtomicNum());
  int totalValence = at->getExplicitValence() + at->getImplicitValence();
  int chg = at->getFormalCharge();

  int numFreeElectrons = nouter - (totalValence + chg);
  if (totalValence + nouter - chg < 8) {
    // we're below an octet, so we need to think
    // about radicals:
    int numRadicals = at->getNumRadicalElectrons();
    int numLonePairs = (numFreeElectrons - numRadicals) / 2;
    return deg + numLonePairs + numRadicals;
  } else {
    int numLonePairs = numFreeElectrons / 2;
    return deg + numLonePairs;
  }
}
}  // end of utility namespace

namespace MolOps {
bool atomHasConjugatedBond(const Atom *at) {
  PRECONDITION(at, "bad atom");

  ROMol::OEDGE_ITER beg, end;
  boost::tie(beg, end) = at->getOwningMol().getAtomBonds(at);
  while (beg != end) {
    if (at->getOwningMol()[*beg]->getIsConjugated()) return true;
    beg++;
  }
  return false;
}

void setConjugation(ROMol &mol) {
  // start with all bonds being marked unconjugated
  // except for aromatic bonds
  ROMol::BondIterator bi;
  for (bi = mol.beginBonds(); bi != mol.endBonds(); bi++) {
    if ((*bi)->getIsAromatic()) {
      (*bi)->setIsConjugated(true);
    } else {
      (*bi)->setIsConjugated(false);
    }
  }

  ROMol::AtomIterator ai;
  // loop over each atom and check if the bonds connecting to it can
  // be conjugated
  for (ai = mol.beginAtoms(); ai != mol.endAtoms(); ai++) {
    markConjAtomBonds(*ai);
  }
}

void setHybridization(ROMol &mol) {
  ROMol::AtomIterator ai;
  int norbs;
  for (ai = mol.beginAtoms(); ai != mol.endAtoms(); ai++) {
    if ((*ai)->getAtomicNum() == 0) {
      (*ai)->setHybridization(Atom::UNSPECIFIED);
    } else {
      norbs = numBondsPlusLonePairs(*ai);
      switch (norbs) {
        case 0:
          // This occurs for things like Na+
          (*ai)->setHybridization(Atom::S);
          break;
        case 1:
          (*ai)->setHybridization(Atom::S);
          break;
        case 2:
          (*ai)->setHybridization(Atom::SP);
          break;
        case 3:
          (*ai)->setHybridization(Atom::SP2);
          break;
        case 4:
          // potentially SP3, but we'll set it down to SP2
          // if we have a conjugated bond (like the second O
          // in O=CO)
          // we'll also avoid setting the hybridization down to
          // SP2 in the case of an atom with degree higher than 3
          // (e.g. things like CP1(C)=CC=CN=C1C, where the P
          //   has norbs = 4, and a conjugated bond, but clearly should
          //   not be SP2)
          // This is Issue276
          if ((*ai)->getDegree() > 3 || !MolOps::atomHasConjugatedBond(*ai)) {
            (*ai)->setHybridization(Atom::SP3);
          } else {
            (*ai)->setHybridization(Atom::SP2);
          }
          break;
        case 5:
          (*ai)->setHybridization(Atom::SP3D);
          break;
        case 6:
          (*ai)->setHybridization(Atom::SP3D2);
          break;
        default:
          (*ai)->setHybridization(Atom::UNSPECIFIED);
      }
    }
  }
}
}  // end of namespace MolOps
}  // end of namespace RDKit