Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702082X/ng2259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702082X/ng2259Isup2.hkl |
CCDC reference: 650515
A mixture of quinclorac (0.5 mmol, 0.121 g), NiCl2.6H2O (1 mmol, 0.238 g) and H2O (10 ml) was treated with aqueous HCl to a pH of 5. The mixture was placed in a Teflon-lined autoclave; this was heated at 403 K for three days. Green crystals were collected and washed with water. CH&N elemental analysis. Calculated for C20H8Cl4N2O4Ni: C 44.36, H 1.48, N 5.18%; found: C 44.58, H 1.59, N 5.30%. Selected FT—IR (KBr, cm-1): 3433(w), 1581(s), 1563(s), 1482(m), 1402(s), 1347(s), 1316(m), 1139 (m), 1101(s), 927(s), 908(s), 898(s), 814(m), 761(m), 671(m).
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C) for all H atoms.
Quinolinecarboxylates generally chelate to metal atoms, and some metal quinolinecarboxylates have been reported such as, for example, bis(6-methyl-4-hydroxy-3-quinolinecarboxylate) mono(oxo)monohydroxyvanadium(V) and Cd(H2O)(4-quinolinecarboxylato)2 (Chen et al., 2001; Yang et al., 2005). Quinclorac (3,7-dichloro-8-quinolinecarboxylic acid) is one of the most effective herbicides (Nuria et al., 1997; Pornprom et al., 2006; Sunohara & Matsumoto, 2004; Tresch & Grossmann, 2002). The title compound is a nickel derivative (I) (Fig. 1). The NiII center exhibits a distorted octahedral geometry defined by four carboxylato oxygen atoms from four quinclorac and two nitrogen atoms from two quinclorac units. The units chelate to the metal atom, and adjacent molecules are linked by carboxylate bridges into a linear chain. The chains are assembled into a three-dimensional supramolecular architecture by interchain π–π stacking interactions (perpendicular distance: 3.44 Å, centroid-centroid distance: 3.912 Å).
See Chen et al. (2001) and Yang et al. (2005) for related vanadium and cadmium complexes.
For related literature, see: Nuria et al. (1997); Pornprom et al. (2006); Sunohara & Matsumoto (2004); Tresch & Grossmann (2002).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Ni(C10H4Cl2NO2)2] | F(000) = 1080 |
Mr = 540.79 | Dx = 1.825 Mg m−3 |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 9136 reflections |
a = 13.4603 (14) Å | θ = 2.0–25.0° |
b = 15.8837 (19) Å | µ = 1.56 mm−1 |
c = 9.2040 (13) Å | T = 298 K |
V = 1967.8 (4) Å3 | Block, green |
Z = 4 | 0.62 × 0.21 × 0.18 mm |
Siemens SMART CCD area-detector diffractometer | 1736 independent reflections |
Radiation source: fine-focus sealed tube | 1407 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→12 |
Tmin = 0.68, Tmax = 0.76 | k = −18→17 |
9136 measured reflections | l = −10→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0301P)2 + 3.058P] where P = (Fo2 + 2Fc2)/3 |
1736 reflections | (Δ/σ)max = 0.001 |
141 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
[Ni(C10H4Cl2NO2)2] | V = 1967.8 (4) Å3 |
Mr = 540.79 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 13.4603 (14) Å | µ = 1.56 mm−1 |
b = 15.8837 (19) Å | T = 298 K |
c = 9.2040 (13) Å | 0.62 × 0.21 × 0.18 mm |
Siemens SMART CCD area-detector diffractometer | 1736 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1407 reflections with I > 2σ(I) |
Tmin = 0.68, Tmax = 0.76 | Rint = 0.044 |
9136 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.71 e Å−3 |
1736 reflections | Δρmin = −0.70 e Å−3 |
141 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.7500 | 0.2500 | 0.23917 (6) | 0.02149 (17) | |
Cl1 | 1.11039 (8) | 0.21431 (6) | −0.04748 (13) | 0.0600 (3) | |
Cl2 | 0.77760 (7) | −0.04046 (5) | 0.58593 (10) | 0.0409 (2) | |
N1 | 0.89128 (18) | 0.18780 (15) | 0.2319 (3) | 0.0249 (6) | |
O1 | 0.70164 (15) | 0.17179 (12) | 0.4057 (2) | 0.0272 (5) | |
O2 | 0.79907 (15) | 0.15853 (12) | 0.6024 (2) | 0.0261 (5) | |
C1 | 0.9549 (2) | 0.2156 (2) | 0.1354 (4) | 0.0302 (7) | |
H1 | 0.9477 | 0.2705 | 0.1020 | 0.036* | |
C2 | 1.0329 (2) | 0.1673 (2) | 0.0798 (4) | 0.0346 (8) | |
C3 | 1.0437 (3) | 0.0855 (2) | 0.1215 (4) | 0.0374 (8) | |
H3 | 1.0937 | 0.0521 | 0.0821 | 0.045* | |
C4 | 0.9774 (2) | 0.05242 (19) | 0.2259 (3) | 0.0302 (7) | |
C5 | 0.9032 (2) | 0.10672 (18) | 0.2842 (3) | 0.0248 (7) | |
C6 | 0.8412 (2) | 0.07861 (18) | 0.3988 (3) | 0.0242 (7) | |
C7 | 0.8512 (2) | −0.00314 (19) | 0.4443 (3) | 0.0292 (7) | |
C8 | 0.9196 (3) | −0.05881 (19) | 0.3816 (4) | 0.0382 (8) | |
H8 | 0.9215 | −0.1147 | 0.4116 | 0.046* | |
C9 | 0.9832 (3) | −0.0313 (2) | 0.2771 (4) | 0.0375 (8) | |
H9 | 1.0307 | −0.0677 | 0.2392 | 0.045* | |
C10 | 0.7738 (2) | 0.14138 (17) | 0.4749 (3) | 0.0233 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0241 (3) | 0.0229 (3) | 0.0175 (3) | 0.0024 (2) | 0.000 | 0.000 |
Cl1 | 0.0521 (6) | 0.0519 (6) | 0.0761 (8) | 0.0056 (5) | 0.0362 (6) | 0.0096 (5) |
Cl2 | 0.0442 (5) | 0.0345 (4) | 0.0441 (5) | −0.0039 (4) | 0.0032 (4) | 0.0102 (4) |
N1 | 0.0245 (13) | 0.0264 (13) | 0.0238 (14) | 0.0024 (10) | 0.0015 (11) | −0.0010 (10) |
O1 | 0.0294 (12) | 0.0308 (11) | 0.0215 (11) | 0.0044 (9) | 0.0012 (9) | 0.0039 (9) |
O2 | 0.0299 (11) | 0.0279 (11) | 0.0205 (12) | 0.0016 (9) | −0.0001 (9) | −0.0026 (9) |
C1 | 0.0282 (17) | 0.0291 (16) | 0.0334 (19) | 0.0003 (14) | 0.0015 (15) | −0.0011 (14) |
C2 | 0.0289 (17) | 0.0380 (18) | 0.037 (2) | 0.0013 (14) | 0.0080 (15) | 0.0012 (15) |
C3 | 0.0310 (18) | 0.043 (2) | 0.038 (2) | 0.0080 (15) | 0.0058 (16) | −0.0067 (16) |
C4 | 0.0309 (17) | 0.0318 (16) | 0.0280 (18) | 0.0044 (14) | −0.0009 (14) | −0.0043 (13) |
C5 | 0.0245 (15) | 0.0272 (16) | 0.0227 (16) | 0.0037 (12) | −0.0049 (13) | −0.0048 (12) |
C6 | 0.0240 (16) | 0.0259 (15) | 0.0227 (16) | 0.0027 (12) | −0.0047 (13) | −0.0040 (12) |
C7 | 0.0314 (17) | 0.0302 (17) | 0.0262 (17) | −0.0029 (14) | −0.0032 (14) | −0.0004 (13) |
C8 | 0.048 (2) | 0.0227 (16) | 0.044 (2) | 0.0058 (15) | −0.0031 (18) | −0.0004 (15) |
C9 | 0.040 (2) | 0.0315 (17) | 0.042 (2) | 0.0109 (15) | 0.0027 (17) | −0.0067 (15) |
C10 | 0.0297 (17) | 0.0195 (14) | 0.0207 (16) | −0.0029 (12) | 0.0040 (13) | 0.0010 (12) |
Ni1—O2i | 2.033 (2) | C1—H1 | 0.9300 |
Ni1—O2ii | 2.033 (2) | C2—C3 | 1.362 (5) |
Ni1—O1iii | 2.078 (2) | C3—C4 | 1.412 (5) |
Ni1—O1 | 2.078 (2) | C3—H3 | 0.9300 |
Ni1—N1iii | 2.144 (2) | C4—C9 | 1.413 (5) |
Ni1—N1 | 2.144 (2) | C4—C5 | 1.425 (4) |
Cl1—C2 | 1.738 (3) | C5—C6 | 1.417 (4) |
Cl2—C7 | 1.741 (3) | C6—C7 | 1.371 (4) |
N1—C1 | 1.310 (4) | C6—C10 | 1.519 (4) |
N1—C5 | 1.384 (4) | C7—C8 | 1.402 (4) |
O1—C10 | 1.258 (3) | C8—C9 | 1.360 (5) |
O2—C10 | 1.251 (3) | C8—H8 | 0.9300 |
O2—Ni1iv | 2.033 (2) | C9—H9 | 0.9300 |
C1—C2 | 1.398 (4) | ||
O2i—Ni1—O2ii | 103.47 (11) | C1—C2—Cl1 | 117.5 (2) |
O2i—Ni1—O1iii | 85.86 (8) | C2—C3—C4 | 118.6 (3) |
O2ii—Ni1—O1iii | 170.43 (8) | C2—C3—H3 | 120.7 |
O2i—Ni1—O1 | 170.43 (8) | C4—C3—H3 | 120.7 |
O2ii—Ni1—O1 | 85.86 (8) | C3—C4—C9 | 122.8 (3) |
O1iii—Ni1—O1 | 84.91 (11) | C3—C4—C5 | 118.3 (3) |
O2i—Ni1—N1iii | 86.54 (9) | C9—C4—C5 | 118.9 (3) |
O2ii—Ni1—N1iii | 91.26 (9) | N1—C5—C6 | 118.9 (3) |
O1iii—Ni1—N1iii | 91.45 (9) | N1—C5—C4 | 120.9 (3) |
O1—Ni1—N1iii | 91.18 (9) | C6—C5—C4 | 120.2 (3) |
O2i—Ni1—N1 | 91.26 (9) | C7—C6—C5 | 117.9 (3) |
O2ii—Ni1—N1 | 86.54 (9) | C7—C6—C10 | 122.6 (3) |
O1iii—Ni1—N1 | 91.18 (9) | C5—C6—C10 | 119.2 (2) |
O1—Ni1—N1 | 91.45 (9) | C6—C7—C8 | 122.4 (3) |
N1iii—Ni1—N1 | 176.44 (13) | C6—C7—Cl2 | 119.7 (2) |
C1—N1—C5 | 118.3 (3) | C8—C7—Cl2 | 117.9 (2) |
C1—N1—Ni1 | 116.4 (2) | C9—C8—C7 | 120.2 (3) |
C5—N1—Ni1 | 121.36 (19) | C9—C8—H8 | 119.9 |
C10—O1—Ni1 | 111.16 (18) | C7—C8—H8 | 119.9 |
C10—O2—Ni1iv | 130.39 (19) | C8—C9—C4 | 120.2 (3) |
N1—C1—C2 | 123.6 (3) | C8—C9—H9 | 119.9 |
N1—C1—H1 | 118.2 | C4—C9—H9 | 119.9 |
C2—C1—H1 | 118.2 | O2—C10—O1 | 126.9 (3) |
C3—C2—C1 | 120.1 (3) | O2—C10—C6 | 114.4 (3) |
C3—C2—Cl1 | 122.4 (3) | O1—C10—C6 | 118.6 (3) |
O2i—Ni1—N1—C1 | −9.6 (2) | C9—C4—C5—N1 | −176.6 (3) |
O2ii—Ni1—N1—C1 | 93.8 (2) | C3—C4—C5—C6 | −174.1 (3) |
O1iii—Ni1—N1—C1 | −95.5 (2) | C9—C4—C5—C6 | 4.5 (4) |
O1—Ni1—N1—C1 | 179.6 (2) | N1—C5—C6—C7 | 177.1 (3) |
O2i—Ni1—N1—C5 | −166.9 (2) | C4—C5—C6—C7 | −3.9 (4) |
O2ii—Ni1—N1—C5 | −63.5 (2) | N1—C5—C6—C10 | −8.4 (4) |
O1iii—Ni1—N1—C5 | 107.2 (2) | C4—C5—C6—C10 | 170.5 (3) |
O1—Ni1—N1—C5 | 22.3 (2) | C5—C6—C7—C8 | −0.1 (5) |
O2ii—Ni1—O1—C10 | 109.87 (19) | C10—C6—C7—C8 | −174.4 (3) |
O1iii—Ni1—O1—C10 | −67.61 (18) | C5—C6—C7—Cl2 | 179.4 (2) |
N1iii—Ni1—O1—C10 | −158.96 (19) | C10—C6—C7—Cl2 | 5.1 (4) |
N1—Ni1—O1—C10 | 23.44 (19) | C6—C7—C8—C9 | 3.8 (5) |
C5—N1—C1—C2 | 1.4 (5) | Cl2—C7—C8—C9 | −175.8 (3) |
Ni1—N1—C1—C2 | −156.6 (3) | C7—C8—C9—C4 | −3.2 (5) |
N1—C1—C2—C3 | 2.6 (5) | C3—C4—C9—C8 | 177.6 (3) |
N1—C1—C2—Cl1 | −179.9 (3) | C5—C4—C9—C8 | −0.9 (5) |
C1—C2—C3—C4 | −2.7 (5) | Ni1iv—O2—C10—O1 | −9.3 (4) |
Cl1—C2—C3—C4 | 179.9 (3) | Ni1iv—O2—C10—C6 | 169.08 (18) |
C2—C3—C4—C9 | −179.4 (3) | Ni1—O1—C10—O2 | 110.4 (3) |
C2—C3—C4—C5 | −0.9 (5) | Ni1—O1—C10—C6 | −67.9 (3) |
C1—N1—C5—C6 | 173.8 (3) | C7—C6—C10—O2 | 64.5 (4) |
Ni1—N1—C5—C6 | −29.3 (4) | C5—C6—C10—O2 | −109.7 (3) |
C1—N1—C5—C4 | −5.1 (4) | C7—C6—C10—O1 | −117.0 (3) |
Ni1—N1—C5—C4 | 151.8 (2) | C5—C6—C10—O1 | 68.8 (4) |
C3—C4—C5—N1 | 4.9 (4) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+3/2, −y+1/2, z; (iv) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C10H4Cl2NO2)2] |
Mr | 540.79 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 298 |
a, b, c (Å) | 13.4603 (14), 15.8837 (19), 9.2040 (13) |
V (Å3) | 1967.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.56 |
Crystal size (mm) | 0.62 × 0.21 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.68, 0.76 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9136, 1736, 1407 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.085, 1.10 |
No. of reflections | 1736 |
No. of parameters | 141 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.71, −0.70 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Ni1—O2i | 2.033 (2) | Ni1—N1 | 2.144 (2) |
Ni1—O1 | 2.078 (2) | O2—Ni1ii | 2.033 (2) |
O2i—Ni1—O2iii | 103.47 (11) | O1iv—Ni1—O1 | 84.91 (11) |
O2i—Ni1—O1iv | 85.86 (8) | O1—Ni1—N1 | 91.45 (9) |
O2iii—Ni1—O1iv | 170.43 (8) | N1iv—Ni1—N1 | 176.44 (13) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+3/2, y, z−1/2; (iv) −x+3/2, −y+1/2, z. |
Quinolinecarboxylates generally chelate to metal atoms, and some metal quinolinecarboxylates have been reported such as, for example, bis(6-methyl-4-hydroxy-3-quinolinecarboxylate) mono(oxo)monohydroxyvanadium(V) and Cd(H2O)(4-quinolinecarboxylato)2 (Chen et al., 2001; Yang et al., 2005). Quinclorac (3,7-dichloro-8-quinolinecarboxylic acid) is one of the most effective herbicides (Nuria et al., 1997; Pornprom et al., 2006; Sunohara & Matsumoto, 2004; Tresch & Grossmann, 2002). The title compound is a nickel derivative (I) (Fig. 1). The NiII center exhibits a distorted octahedral geometry defined by four carboxylato oxygen atoms from four quinclorac and two nitrogen atoms from two quinclorac units. The units chelate to the metal atom, and adjacent molecules are linked by carboxylate bridges into a linear chain. The chains are assembled into a three-dimensional supramolecular architecture by interchain π–π stacking interactions (perpendicular distance: 3.44 Å, centroid-centroid distance: 3.912 Å).