Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010595/wn6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010595/wn6025Isup2.hkl |
CCDC reference: 140683
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.107
- Data-to-parameter ratio = 8.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.41 From the CIF: _reflns_number_total 1538 Count of symmetry unique reflns 1605 Completeness (_total/calc) 95.83% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
4.00 g (16 mmol) of 2-(2-pyridyl)-4-carboxyquinolic acid were dissolved in 70 ml of freshly distilled benzene. 4.10 g (128 mmol) of methanol and 5 ml of H2SO4 were added successively and the reaction mixture was refluxed overnight. The reaction product was then poured into 150 ml of water and extracted with (3 x 30 ml) of ether. The ethereal layer was washed with 5% NaHCO3, then with water and was dried over MgSO4. After removal of the solvent the resultant product was recrystallized from ethanol; yield: 3.47 g (81%).
Data collection: COLLECT (Nonius BV, 1997-2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL/PC (Sheldrick 1999); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
C16H12N2O2 | F(000) = 552 |
Mr = 264.28 | Dx = 1.420 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 29.332 (3) Å | Cell parameters from 9674 reflections |
b = 3.8551 (2) Å | θ = 2.6–27.5° |
c = 11.0753 (11) Å | µ = 0.10 mm−1 |
β = 99.341 (3)° | T = 100 K |
V = 1235.76 (19) Å3 | Needle, light-gold |
Z = 4 | 0.20 × 0.10 × 0.05 mm |
Nonius KappaCCD diffractometer | 1538 independent reflections |
Radiation source: fine-focus sealed tube | 1352 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 9 pixels mm-1 | θmax = 27.4°, θmin = 2.8° |
ϕ scans, and ω scans with κ offsets | h = 0→37 |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = 0→4 |
Tmin = 0.981, Tmax = 0.995 | l = −14→14 |
9674 measured reflections |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.8852P] where P = (Fo2 + 2Fc2)/3 |
1538 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.18 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C16H12N2O2 | V = 1235.76 (19) Å3 |
Mr = 264.28 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 29.332 (3) Å | µ = 0.10 mm−1 |
b = 3.8551 (2) Å | T = 100 K |
c = 11.0753 (11) Å | 0.20 × 0.10 × 0.05 mm |
β = 99.341 (3)° |
Nonius KappaCCD diffractometer | 1538 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1352 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.995 | Rint = 0.024 |
9674 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.18 e Å−3 |
1538 reflections | Δρmin = −0.20 e Å−3 |
181 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 | ||
N1 | 0.82452 (6) | 0.7699 (6) | 0.01206 (17) | 0.0208 (5) | |
N2 | 0.92066 (7) | 0.6025 (6) | 0.25009 (16) | 0.0228 (5) | |
O1 | 0.92109 (6) | 0.3202 (6) | −0.30410 (14) | 0.0327 (5) | |
O2 | 0.95660 (5) | 0.1620 (5) | −0.11900 (14) | 0.0240 (4) | |
C1 | 0.99360 (8) | 0.0141 (7) | −0.1759 (2) | 0.0248 (6) | |
H1B | 1.0166 | −0.0859 | −0.1141 | 0.030* | |
H1C | 0.9811 | −0.1623 | −0.2330 | 0.030* | |
H1D | 1.0074 | 0.1931 | −0.2182 | 0.030* | |
C2 | 0.86551 (8) | 0.6572 (6) | 0.0646 (2) | 0.0188 (5) | |
C3 | 0.89718 (8) | 0.4967 (7) | −0.0019 (2) | 0.0197 (5) | |
H3A | 0.9260 | 0.4092 | 0.0405 | 0.024* | |
C4 | 0.88676 (8) | 0.4671 (7) | −0.1266 (2) | 0.0189 (5) | |
C5 | 0.84330 (8) | 0.5973 (7) | −0.1878 (2) | 0.0190 (5) | |
C6 | 0.82812 (8) | 0.5928 (7) | −0.3165 (2) | 0.0217 (5) | |
H6A | 0.8477 | 0.4973 | −0.3697 | 0.026* | |
C7 | 0.78599 (8) | 0.7245 (7) | −0.3652 (2) | 0.0230 (5) | |
H7A | 0.7763 | 0.7214 | −0.4522 | 0.028* | |
C8 | 0.75610 (8) | 0.8644 (7) | −0.2894 (2) | 0.0237 (5) | |
H8A | 0.7265 | 0.9557 | −0.3251 | 0.028* | |
C9 | 0.76929 (8) | 0.8713 (7) | −0.1659 (2) | 0.0224 (5) | |
H9A | 0.7488 | 0.9642 | −0.1147 | 0.027* | |
C10 | 0.81308 (8) | 0.7402 (7) | −0.1119 (2) | 0.0204 (5) | |
C11 | 0.87838 (8) | 0.7118 (6) | 0.1986 (2) | 0.0195 (5) | |
C12 | 0.84820 (8) | 0.8782 (7) | 0.2654 (2) | 0.0234 (6) | |
H12A | 0.8184 | 0.9551 | 0.2258 | 0.028* | |
C13 | 0.86200 (9) | 0.9307 (7) | 0.3892 (2) | 0.0269 (6) | |
H13A | 0.8420 | 1.0447 | 0.4371 | 0.032* | |
C14 | 0.90544 (9) | 0.8163 (8) | 0.4435 (2) | 0.0276 (6) | |
H14A | 0.9159 | 0.8479 | 0.5295 | 0.033* | |
C15 | 0.93310 (9) | 0.6549 (8) | 0.3704 (2) | 0.0263 (6) | |
H15A | 0.9631 | 0.5754 | 0.4083 | 0.032* | |
C16 | 0.92212 (8) | 0.3106 (7) | −0.1950 (2) | 0.0200 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0189 (10) | 0.0233 (12) | 0.0212 (9) | −0.0015 (9) | 0.0062 (7) | 0.0005 (9) |
N2 | 0.0216 (10) | 0.0270 (12) | 0.0202 (9) | −0.0015 (9) | 0.0049 (8) | 0.0001 (9) |
O1 | 0.0294 (10) | 0.0493 (13) | 0.0200 (8) | 0.0111 (10) | 0.0062 (7) | −0.0023 (9) |
O2 | 0.0174 (8) | 0.0318 (11) | 0.0237 (8) | 0.0066 (8) | 0.0059 (6) | 0.0003 (8) |
C1 | 0.0194 (11) | 0.0284 (15) | 0.0283 (12) | 0.0033 (11) | 0.0084 (9) | −0.0035 (11) |
C2 | 0.0167 (10) | 0.0194 (13) | 0.0212 (11) | −0.0039 (10) | 0.0057 (8) | 0.0010 (10) |
C3 | 0.0172 (11) | 0.0209 (13) | 0.0215 (11) | −0.0013 (10) | 0.0047 (9) | 0.0002 (10) |
C4 | 0.0170 (11) | 0.0186 (12) | 0.0218 (11) | −0.0018 (10) | 0.0053 (9) | −0.0019 (9) |
C5 | 0.0173 (11) | 0.0182 (12) | 0.0218 (11) | −0.0012 (10) | 0.0038 (8) | 0.0004 (10) |
C6 | 0.0216 (12) | 0.0224 (13) | 0.0218 (11) | −0.0013 (10) | 0.0056 (9) | −0.0024 (10) |
C7 | 0.0219 (11) | 0.0253 (14) | 0.0209 (11) | −0.0027 (11) | 0.0010 (9) | 0.0017 (10) |
C8 | 0.0169 (11) | 0.0250 (13) | 0.0291 (12) | −0.0004 (11) | 0.0035 (9) | 0.0049 (11) |
C9 | 0.0187 (11) | 0.0207 (13) | 0.0293 (12) | 0.0005 (10) | 0.0083 (9) | 0.0006 (11) |
C10 | 0.0179 (11) | 0.0212 (13) | 0.0227 (11) | −0.0032 (10) | 0.0052 (9) | 0.0013 (10) |
C11 | 0.0199 (11) | 0.0199 (13) | 0.0198 (11) | −0.0045 (10) | 0.0063 (8) | 0.0003 (10) |
C12 | 0.0235 (12) | 0.0244 (14) | 0.0235 (12) | −0.0007 (11) | 0.0073 (9) | −0.0014 (11) |
C13 | 0.0313 (14) | 0.0288 (15) | 0.0232 (12) | −0.0046 (12) | 0.0121 (10) | −0.0045 (11) |
C14 | 0.0352 (14) | 0.0289 (15) | 0.0186 (11) | −0.0061 (13) | 0.0043 (10) | −0.0025 (11) |
C15 | 0.0256 (12) | 0.0307 (16) | 0.0226 (11) | −0.0019 (12) | 0.0038 (9) | 0.0029 (11) |
C16 | 0.0176 (11) | 0.0214 (13) | 0.0215 (11) | −0.0008 (10) | 0.0042 (9) | −0.0001 (10) |
N1—C2 | 1.322 (3) | C5—C10 | 1.427 (3) |
N1—C10 | 1.364 (3) | C6—C7 | 1.364 (3) |
N2—C15 | 1.338 (3) | C6—H6A | 0.9600 |
N2—C11 | 1.346 (3) | C7—C8 | 1.415 (3) |
O1—C16 | 1.204 (3) | C7—H7A | 0.9600 |
O2—C16 | 1.335 (3) | C8—C9 | 1.360 (3) |
O2—C1 | 1.456 (3) | C8—H8A | 0.9601 |
C1—H1B | 0.9601 | C9—C10 | 1.419 (3) |
C1—H1C | 0.9600 | C9—H9A | 0.9600 |
C1—H1D | 0.9602 | C11—C12 | 1.398 (3) |
C2—C3 | 1.418 (3) | C12—C13 | 1.380 (3) |
C2—C11 | 1.485 (3) | C12—H12A | 0.9599 |
C3—C4 | 1.369 (3) | C13—C14 | 1.389 (4) |
C3—H3A | 0.9601 | C13—H13A | 0.9599 |
C4—C5 | 1.434 (3) | C14—C15 | 1.384 (3) |
C4—C16 | 1.507 (3) | C14—H14A | 0.9601 |
C5—C6 | 1.423 (3) | C15—H15A | 0.9601 |
C2—N1—C10 | 118.25 (19) | C9—C8—C7 | 120.1 (2) |
C15—N2—C11 | 117.3 (2) | C9—C8—H8A | 119.8 |
C16—O2—C1 | 115.88 (17) | C7—C8—H8A | 120.0 |
O2—C1—H1B | 109.6 | C8—C9—C10 | 120.5 (2) |
O2—C1—H1C | 109.3 | C8—C9—H9A | 119.8 |
H1B—C1—H1C | 109.5 | C10—C9—H9A | 119.7 |
O2—C1—H1D | 109.5 | N1—C10—C9 | 116.9 (2) |
H1B—C1—H1D | 109.5 | N1—C10—C5 | 123.4 (2) |
H1C—C1—H1D | 109.5 | C9—C10—C5 | 119.7 (2) |
N1—C2—C3 | 122.7 (2) | N2—C11—C12 | 122.6 (2) |
N1—C2—C11 | 117.32 (19) | N2—C11—C2 | 116.49 (19) |
C3—C2—C11 | 119.97 (19) | C12—C11—C2 | 120.9 (2) |
C4—C3—C2 | 120.2 (2) | C13—C12—C11 | 119.0 (2) |
C4—C3—H3A | 119.9 | C13—C12—H12A | 120.5 |
C2—C3—H3A | 119.9 | C11—C12—H12A | 120.5 |
C3—C4—C5 | 118.9 (2) | C12—C13—C14 | 118.9 (2) |
C3—C4—C16 | 118.8 (2) | C12—C13—H13A | 120.6 |
C5—C4—C16 | 122.26 (19) | C14—C13—H13A | 120.5 |
C6—C5—C10 | 118.1 (2) | C15—C14—C13 | 118.2 (2) |
C6—C5—C4 | 125.4 (2) | C15—C14—H14A | 120.9 |
C10—C5—C4 | 116.49 (19) | C13—C14—H14A | 120.9 |
C7—C6—C5 | 120.5 (2) | N2—C15—C14 | 124.0 (2) |
C7—C6—H6A | 119.7 | N2—C15—H15A | 118.0 |
C5—C6—H6A | 119.8 | C14—C15—H15A | 118.0 |
C6—C7—C8 | 121.1 (2) | O1—C16—O2 | 122.6 (2) |
C6—C7—H7A | 119.5 | O1—C16—C4 | 125.8 (2) |
C8—C7—H7A | 119.4 | O2—C16—C4 | 111.53 (18) |
Experimental details
Crystal data | |
Chemical formula | C16H12N2O2 |
Mr | 264.28 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 100 |
a, b, c (Å) | 29.332 (3), 3.8551 (2), 11.0753 (11) |
β (°) | 99.341 (3) |
V (Å3) | 1235.76 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.981, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9674, 1538, 1352 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.107, 0.89 |
No. of reflections | 1538 |
No. of parameters | 181 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 |
Computer programs: COLLECT (Nonius BV, 1997-2001), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL/PC (Sheldrick 1999), SHELXTL/PC.
N1—C2 | 1.322 (3) | O2—C16 | 1.335 (3) |
N1—C10 | 1.364 (3) | O2—C1 | 1.456 (3) |
N2—C15 | 1.338 (3) | C2—C3 | 1.418 (3) |
N2—C11 | 1.346 (3) | C3—C4 | 1.369 (3) |
O1—C16 | 1.204 (3) | ||
C2—N1—C10 | 118.25 (19) | N1—C2—C3 | 122.7 (2) |
C15—N2—C11 | 117.3 (2) | N1—C2—C11 | 117.32 (19) |
C16—O2—C1 | 115.88 (17) | C4—C3—C2 | 120.2 (2) |
The photophysical properties and the excited-state chemistry of tris(bipyridyl)ruthenium(II) complexes have been investigated to a great extent because of their unique and interesting features such as chemical stability, reversible redox property, long excited-state life time and chelation properties (Juris et al., 1988). 2,2'-Bipyridine is the prototype ligand of almost all reported Ru(II) tris-chelate complexes (Kaes et al., 2000). Synthetically, it lacks a suitable peripheral chemical functionality that allows it to be bound into a diverse array of substrates. To address this dilemma, a rigorous synthetic research effort towards the structural variation of the commonly used ligands, such as bipyridines, phenanthrolines and terpyridines, must be conducted in order to develop such analogues, where differences in electronic and steric properties may lead to modification of the resulting metal complexes. We have synthesized and characterized a novel diimine ligand, methyl 2-(2-pyridyl)quinoline-4-carboxylate, (I), and covalently bound it into a polymeric matrix (Farah et al., 2000) and on to CdS nanoparticle (Veinot et al., 2000). We report here the synthesis and crystal structure of (I).
The ORTEPII (Johnson, 1976) diagram of (I) (Fig. 1) reveals the expected conformation of the ligand in the solid state as the two N atoms are in the trans configuration to minimize electronic repulsion. The packing (Fig. 2) also precludes interaction between adjacent molecules and reveals an alternating flat/tilt array typical of molecular crystals (Gray & Goodby, 1984). All observed C—C, C—N and C—O bond lengths are in good agreement with those reported in the literature and do not merit any further discussion (International Tables for Crystallography, 1995, Vol. C).