Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018427/cv6213sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018427/cv6213Isup2.hkl |
CCDC reference: 222830
An ethanolic solution of 8-quinolinol (2 mmol in 20 ml of ethanol) was mixed with Zn(OAc)2 (1 mmol in 20 ml of H2O). The resulting solution was left to stand for 5 h and a pale-yellowish solid was obtained. The product was recrystallized from ethanol-water (Ratio?). After several days, pale-yellowish crystals of (I) were harvested. Analysis, found: C 55.41, H 4.23, N 7.42%; calculated: C 55.52, H 4.14, N 7.47%.
The H atoms of the water ligands were located in a difference Fourier map and refined with a common isotropic displacement parameter. O—H and H···H distances were restrained to ensure a reasonable geometry for the water molecules. H atoms bound to C atoms were fixed geometrically and were treated as riding on the parent C atoms, with C—H = 0.93 Å and Uiso(H) = 1.2–1.5Ueq(C).
Data collection: SMART (Bruker, 1996); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the molecule of (I) with the atom-numbering scheme and with 30% probability displacement ellipsoids. | |
Fig. 2. Packing view of (I). |
C18H16N2O4Zn | F(000) = 400 |
Mr = 389.70 | Dx = 1.643 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 2881 reflections |
a = 12.955 (2) Å | θ = 1–27.5° |
b = 5.5463 (10) Å | µ = 1.59 mm−1 |
c = 11.423 (2) Å | T = 294 K |
β = 106.288 (4)° | Plate, yellow |
V = 787.8 (2) Å3 | 0.30 × 0.24 × 0.12 mm |
Z = 2 |
Siemens SMART CCD area-detector diffractometer | 1820 independent reflections |
Radiation source: fine-focus sealed tube | 1382 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 27.6°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | h = −15→16 |
Tmin = 0.648, Tmax = 0.833 | k = −5→7 |
5060 measured reflections | l = −14→14 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0725P)2] where P = (Fo2 + 2Fc2)/3 |
1820 reflections | (Δ/σ)max < 0.001 |
115 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C18H16N2O4Zn | V = 787.8 (2) Å3 |
Mr = 389.70 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.955 (2) Å | µ = 1.59 mm−1 |
b = 5.5463 (10) Å | T = 294 K |
c = 11.423 (2) Å | 0.30 × 0.24 × 0.12 mm |
β = 106.288 (4)° |
Siemens SMART CCD area-detector diffractometer | 1820 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | 1382 reflections with I > 2σ(I) |
Tmin = 0.648, Tmax = 0.833 | Rint = 0.035 |
5060 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.60 e Å−3 |
1820 reflections | Δρmin = −0.37 e Å−3 |
115 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 | ||
Zn1 | 0.5000 | 0.5000 | 0.5000 | 0.02949 (18) | |
O2 | 0.50256 (19) | 0.2156 (4) | 0.33660 (19) | 0.0455 (6) | |
H2A | 0.5172 | 0.0717 | 0.3613 | 0.055* | |
H2B | 0.4901 | 0.2173 | 0.2595 | 0.055* | |
O1 | 0.56840 (15) | 0.7428 (3) | 0.42094 (17) | 0.0301 (4) | |
N1 | 0.65223 (18) | 0.3964 (4) | 0.57992 (19) | 0.0282 (5) | |
C1 | 0.7222 (2) | 0.5406 (5) | 0.5430 (2) | 0.0276 (6) | |
C2 | 0.6746 (2) | 0.7249 (5) | 0.4561 (2) | 0.0277 (6) | |
C3 | 0.7427 (2) | 0.8711 (6) | 0.4150 (3) | 0.0389 (7) | |
H3 | 0.7143 | 0.9907 | 0.3581 | 0.047* | |
C4 | 0.8539 (2) | 0.8422 (6) | 0.4576 (3) | 0.0446 (8) | |
H4 | 0.8980 | 0.9440 | 0.4281 | 0.053* | |
C5 | 0.9005 (2) | 0.6691 (6) | 0.5412 (3) | 0.0403 (7) | |
H5 | 0.9750 | 0.6560 | 0.5690 | 0.048* | |
C6 | 0.8349 (2) | 0.5114 (5) | 0.5847 (3) | 0.0327 (6) | |
C7 | 0.8730 (2) | 0.3211 (6) | 0.6687 (3) | 0.0406 (7) | |
H7 | 0.9465 | 0.2949 | 0.7000 | 0.049* | |
C8 | 0.8020 (3) | 0.1775 (6) | 0.7034 (3) | 0.0423 (8) | |
H8 | 0.8266 | 0.0520 | 0.7581 | 0.051* | |
C9 | 0.6913 (2) | 0.2195 (5) | 0.6561 (3) | 0.0345 (6) | |
H9 | 0.6436 | 0.1181 | 0.6797 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0244 (3) | 0.0300 (3) | 0.0321 (3) | 0.00157 (17) | 0.00474 (19) | 0.00763 (18) |
O2 | 0.0730 (17) | 0.0278 (11) | 0.0322 (11) | 0.0081 (10) | 0.0088 (11) | −0.0004 (9) |
O1 | 0.0266 (10) | 0.0295 (10) | 0.0319 (10) | 0.0020 (8) | 0.0045 (8) | 0.0088 (8) |
N1 | 0.0283 (12) | 0.0292 (12) | 0.0250 (11) | 0.0025 (10) | 0.0039 (10) | 0.0010 (10) |
C1 | 0.0249 (14) | 0.0305 (15) | 0.0255 (13) | 0.0013 (10) | 0.0038 (11) | −0.0038 (10) |
C2 | 0.0281 (14) | 0.0283 (14) | 0.0253 (13) | −0.0016 (11) | 0.0051 (11) | −0.0019 (10) |
C3 | 0.0364 (17) | 0.0416 (19) | 0.0374 (16) | −0.0044 (13) | 0.0083 (14) | 0.0068 (14) |
C4 | 0.0362 (17) | 0.051 (2) | 0.0479 (19) | −0.0133 (14) | 0.0149 (15) | −0.0024 (15) |
C5 | 0.0258 (15) | 0.0492 (19) | 0.0444 (18) | −0.0027 (13) | 0.0076 (13) | −0.0077 (14) |
C6 | 0.0260 (14) | 0.0390 (17) | 0.0299 (15) | 0.0014 (12) | 0.0023 (12) | −0.0063 (12) |
C7 | 0.0297 (16) | 0.0458 (18) | 0.0410 (17) | 0.0087 (13) | 0.0013 (13) | −0.0004 (14) |
C8 | 0.0444 (19) | 0.0396 (17) | 0.0361 (16) | 0.0145 (14) | 0.0000 (14) | 0.0035 (13) |
C9 | 0.0357 (16) | 0.0331 (16) | 0.0322 (15) | 0.0045 (12) | 0.0054 (13) | 0.0045 (12) |
Zn1—O1 | 1.9655 (18) | C2—C3 | 1.375 (4) |
Zn1—O1i | 1.9655 (18) | C3—C4 | 1.394 (4) |
Zn1—N1i | 2.011 (2) | C3—H3 | 0.9300 |
Zn1—N1 | 2.011 (2) | C4—C5 | 1.370 (5) |
Zn1—O2i | 2.451 (2) | C4—H4 | 0.9300 |
Zn1—O2 | 2.451 (2) | C5—C6 | 1.404 (4) |
O2—H2A | 0.8500 | C5—H5 | 0.9300 |
O2—H2B | 0.8501 | C6—C7 | 1.419 (4) |
O1—C2 | 1.324 (3) | C7—C8 | 1.357 (5) |
N1—C9 | 1.315 (4) | C7—H7 | 0.9300 |
N1—C1 | 1.362 (4) | C8—C9 | 1.402 (4) |
C1—C6 | 1.412 (4) | C8—H8 | 0.9300 |
C1—C2 | 1.438 (4) | C9—H9 | 0.9300 |
O1—Zn1—O1i | 180.0 | O1—C2—C3 | 124.3 (3) |
O1—Zn1—N1i | 96.12 (8) | O1—C2—C1 | 118.1 (2) |
O1i—Zn1—N1i | 83.88 (8) | C3—C2—C1 | 117.6 (3) |
O1—Zn1—N1 | 83.88 (8) | C2—C3—C4 | 120.9 (3) |
O1i—Zn1—N1 | 96.12 (8) | C2—C3—H3 | 119.6 |
N1i—Zn1—N1 | 180.0 | C4—C3—H3 | 119.6 |
O1—Zn1—O2i | 90.75 (8) | C5—C4—C3 | 122.2 (3) |
O1i—Zn1—O2i | 89.25 (7) | C5—C4—H4 | 118.9 |
N1i—Zn1—O2i | 86.60 (8) | C3—C4—H4 | 118.9 |
N1—Zn1—O2i | 93.40 (8) | C4—C5—C6 | 119.4 (3) |
O1—Zn1—O2 | 89.25 (7) | C4—C5—H5 | 120.3 |
O1i—Zn1—O2 | 90.75 (8) | C6—C5—H5 | 120.3 |
N1i—Zn1—O2 | 93.40 (8) | C5—C6—C1 | 118.7 (3) |
N1—Zn1—O2 | 86.60 (8) | C5—C6—C7 | 124.9 (3) |
O2i—Zn1—O2 | 180.0 | C1—C6—C7 | 116.4 (3) |
Zn1—O2—H2A | 113.6 | C8—C7—C6 | 119.9 (3) |
Zn1—O2—H2B | 138.0 | C8—C7—H7 | 120.0 |
H2A—O2—H2B | 108.4 | C6—C7—H7 | 120.0 |
C2—O1—Zn1 | 111.90 (16) | C7—C8—C9 | 119.6 (3) |
C9—N1—C1 | 118.5 (2) | C7—C8—H8 | 120.2 |
C9—N1—Zn1 | 131.3 (2) | C9—C8—H8 | 120.2 |
C1—N1—Zn1 | 110.18 (17) | N1—C9—C8 | 122.8 (3) |
N1—C1—C6 | 122.9 (2) | N1—C9—H9 | 118.6 |
N1—C1—C2 | 115.9 (2) | C8—C9—H9 | 118.6 |
C6—C1—C2 | 121.2 (3) | ||
N1i—Zn1—O1—C2 | 179.56 (17) | C6—C1—C2—O1 | −179.9 (2) |
N1—Zn1—O1—C2 | −0.44 (17) | N1—C1—C2—C3 | −178.8 (2) |
O2i—Zn1—O1—C2 | 92.90 (17) | C6—C1—C2—C3 | 0.2 (4) |
O2—Zn1—O1—C2 | −87.10 (17) | O1—C2—C3—C4 | 179.3 (3) |
O1—Zn1—N1—C9 | −177.9 (3) | C1—C2—C3—C4 | −0.8 (4) |
O1i—Zn1—N1—C9 | 2.1 (3) | C2—C3—C4—C5 | 0.1 (5) |
O2i—Zn1—N1—C9 | 91.7 (3) | C3—C4—C5—C6 | 1.1 (5) |
O2—Zn1—N1—C9 | −88.3 (3) | C4—C5—C6—C1 | −1.6 (4) |
O1—Zn1—N1—C1 | 1.01 (18) | C4—C5—C6—C7 | 178.3 (3) |
O1i—Zn1—N1—C1 | −178.99 (18) | N1—C1—C6—C5 | 179.9 (3) |
O2i—Zn1—N1—C1 | −89.38 (18) | C2—C1—C6—C5 | 1.0 (4) |
O2—Zn1—N1—C1 | 90.62 (18) | N1—C1—C6—C7 | 0.0 (4) |
C9—N1—C1—C6 | −1.3 (4) | C2—C1—C6—C7 | −178.9 (3) |
Zn1—N1—C1—C6 | 179.6 (2) | C5—C6—C7—C8 | −179.1 (3) |
C9—N1—C1—C2 | 177.7 (2) | C1—C6—C7—C8 | 0.8 (4) |
Zn1—N1—C1—C2 | −1.4 (3) | C6—C7—C8—C9 | −0.3 (5) |
Zn1—O1—C2—C3 | 179.7 (2) | C1—N1—C9—C8 | 1.8 (4) |
Zn1—O1—C2—C1 | −0.2 (3) | Zn1—N1—C9—C8 | −179.3 (2) |
N1—C1—C2—O1 | 1.1 (4) | C7—C8—C9—N1 | −1.0 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1ii | 0.85 | 1.99 | 2.841 (3) | 174 |
O2—H2B···O1iii | 0.85 | 1.99 | 2.829 (3) | 169 |
Symmetry codes: (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H16N2O4Zn |
Mr | 389.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 12.955 (2), 5.5463 (10), 11.423 (2) |
β (°) | 106.288 (4) |
V (Å3) | 787.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.30 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.648, 0.833 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5060, 1820, 1382 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.117, 1.02 |
No. of reflections | 1820 |
No. of parameters | 115 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.37 |
Computer programs: SMART (Bruker, 1996), SMART, SHELXTL (Bruker, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.85 | 1.99 | 2.841 (3) | 174 |
O2—H2B···O1ii | 0.85 | 1.99 | 2.829 (3) | 169 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2. |
8-Quinolinol has been widely used in the quantitative analysis of W and Mo (Marcel & Rene, 1950). The complexes of 8-quinolinol with Nb, Mo, W and Hf emit interesting fluorescence (Schneider & Roselli, 1970). The crystal structure of the title compound, (I), was orginally determined by Merrit et al. (1954) with R1 = 0.226, and was then refined by Palenik (1964) to R1 = 0.13. Here, we present the results of a redetermination of the structure of (I) with better R factors (R1 = 0.0471) and higher accuracy.
In (I), the ZnII atom is six-coordinated, by one N and one O atom from each of the two 8-quinolinolate ligands and one O atom from each of the two aqua ligands. This ZnO4N2 coordination forms an octahedral geometry (Fig. 1). The chelate ligands are connected to the central atom through a Zn—O [1.965 (18) Å] single bond and a Zn—N [2.011 (2) Å] coordinative bond, with a bite angle of 83.88 (8)°, and they occupy the equatorial plane. The two aqua ligands occupy the apical positions of the octahedron, with a Zn—O bond length very close to that of W—O [1.968 (4) Å], but shorter than that of W—N [2.336 (4) Å], in dioxobis(8-quinolinolato-N, O)tungsten (VI) (Raj et al., 1999).
The bond angles in the aromatic ring system of (I) are found to be between 118.2 (5) and 121.7 (5)°. In the 8-quinolinolate ligands, the absence of any unusually long bonds and the marginally longer carbonyl bond [1.355 (6) Å versus 1.28 Å], shorter than the normal single bond in ether and alcohols (>1.4 Å), suggest that the delocalization extends over the entire molecule and will therefore withdraw more negative charge from the cation (Barton et al., 1983).
The coordinated water molecules of (I) interact with the O atom of the 8-quinolinolato ligands via intermolecuar hydrogen bonds (Table 1). These hydrogen bonds interconnect the molecules into chains along the c direction (Fig.2).