Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107039686/gd3124sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124IIIsup4.hkl |
CCDC references: 665482; 665483; 665484
Compound (I) was prepared by a modified procedure based on the synthesis of bab (Wu et al., 2001). 2,6-Dibromopyridine (8.6 mmol, 2.0407 g), 7-azaindole (18 mmol, 2.1415 g), potassium carbonate (14.8 mmol, 2.0526 g) and cupric sulfate (1.75 mmol, 0.2792 g) were added to a flask under an argon atmosphere. The mixture was heated with stirring for 4 h at 483 K. After cooling to room temperature, the resulting mixture was extracted with methylene chloride and water. The organic layer was separated, dried with MgSO4 and filtered, and the solvent volume was reduced. Hexanes were added to precipitate (I) as a white crystalline solid (2.1 mmol, 0.6700 g, 25% yield). Colorless crystals suitable for X-ray analysis were grown by slow evaporation of a methanol–methylene chloride solution.
FeCl3·6H2O in methanol was layered over a solution of (I) in methylene chloride (1:1 molar ratio of reactants, 5 ml of each solvent) in a test tube. The test tube was covered with Parafilm. Crystallite formation occurred within a few hours at room temperature. Yellow, X-ray quality crystals of (II) were harvested after 1–2 weeks.
In an analogous fashion, equimolar amounts of Cu(NO3)2·3H2O and (I) in methanol and methylene chloride, respectively, were allowed to react. Light-green, X-ray quality crystals of (III) were obtained after 1–2 weeks.
Initial refinement of (I) in P1 yielded a structure solution with R1 ≈ 19%. Subsequent refinements included the twin law (1 0 0, 0 1 0, 0 1 1) obtained from ROTAX (Parsons & Gould, 2001) as implemented in CRYSTALS (Betteridge et al., 2003). The twin fraction ratio is 42:58. The N-bound H atom in (II) was located directly; the position and isotropic displacement parameters were refined. All remaining H atoms were either located or calculated and treated as riding (C—H = 0.95 Å); the isotropic displacement parameters were defined as 1.2Ueq(C).
Data collection: SMART (Bruker, 2003) for (I), (II); APEX2 (Bruker, 2005) for (III). Cell refinement: SAINT (Bruker, 2003) for (I), (II); SAINT (Bruker, 2005) for (III). Data reduction: SAINT (Bruker, 2003) for (I), (II); SAINT (Bruker, 2005) for (III). For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2003); program(s) used to refine structure: SHELXTL. Molecular graphics: SHELXTL for (I); SHELXTL and DIAMOND (Brandenburg, 2007) for (II), (III). For all compounds, software used to prepare material for publication: SHELXTL.
C19H13N5 | Z = 4 |
Mr = 311.34 | F(000) = 648 |
Triclinic, P1 | Dx = 1.444 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 6.6377 (2) Å | Cell parameters from 6337 reflections |
b = 10.1397 (3) Å | θ = 4.2–67.4° |
c = 21.9214 (6) Å | µ = 0.72 mm−1 |
α = 76.609 (1)° | T = 150 K |
β = 86.563 (10)° | Blade, colorless |
γ = 90.004 (1)° | 0.35 × 0.10 × 0.05 mm |
V = 1432.56 (7) Å3 |
Bruker SMART 6000 CCD diffractometer | 4847 independent reflections |
Radiation source: fine-focus sealed tube | 4215 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 0.8 pixels mm-1 | θmax = 67.4°, θmin = 2.1° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.787, Tmax = 0.965 | l = −26→24 |
11609 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0853P)2 + 0.017P] where P = (Fo2 + 2Fc2)/3 |
4847 reflections | (Δ/σ)max < 0.001 |
434 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C19H13N5 | γ = 90.004 (1)° |
Mr = 311.34 | V = 1432.56 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 6.6377 (2) Å | Cu Kα radiation |
b = 10.1397 (3) Å | µ = 0.72 mm−1 |
c = 21.9214 (6) Å | T = 150 K |
α = 76.609 (1)° | 0.35 × 0.10 × 0.05 mm |
β = 86.563 (10)° |
Bruker SMART 6000 CCD diffractometer | 4847 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4215 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.965 | Rint = 0.026 |
11609 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.32 e Å−3 |
4847 reflections | Δρmin = −0.24 e Å−3 |
434 parameters |
Experimental. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size. 1H NMR (CHCl3): 8.870(d), 8.492(d), 8.472(dd), 8.099(t), 7.230(dd), 6.710(d). Elemental Analysis for C19H13N5: calc. C, 73.30; H, 4.21; N, 22.49. found. C, 70.99; H, 4.12, N, 21.82. MS: 312.149(M+) m/z |
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. The twin law (obtained from ROTAX (Parsons & Gould, 2001) as implemented in CRYSTALS (Watkin, et al., 2001) was applied in the refinement: −1 0 0 0 1 0 0 1 − 1 The twin fraction ratio is 42:58. |
x | y | z | Uiso*/Ueq | ||
N1A | 1.2093 (3) | 0.0078 (2) | 0.38200 (11) | 0.0331 (6) | |
N2A | 0.9641 (3) | 0.1468 (2) | 0.42534 (10) | 0.0276 (5) | |
N3A | 0.9622 (3) | 0.2678 (2) | 0.50197 (10) | 0.0280 (5) | |
N4A | 0.9163 (3) | 0.3937 (2) | 0.57642 (10) | 0.0263 (5) | |
N5A | 1.1214 (3) | 0.4534 (3) | 0.65468 (11) | 0.0315 (5) | |
C1A | 1.2334 (4) | −0.0635 (3) | 0.33766 (14) | 0.0360 (7) | |
H1A | 1.3569 | −0.1097 | 0.3349 | 0.043* | |
C2A | 1.0901 (5) | −0.0744 (3) | 0.29556 (14) | 0.0409 (8) | |
H2A | 1.1188 | −0.1252 | 0.2648 | 0.049* | |
C3A | 0.9052 (4) | −0.0118 (3) | 0.29807 (13) | 0.0347 (7) | |
H3A | 0.8055 | −0.0186 | 0.2696 | 0.042* | |
C4A | 0.8716 (4) | 0.0615 (3) | 0.34393 (13) | 0.0285 (6) | |
C5A | 1.0295 (4) | 0.0671 (3) | 0.38304 (13) | 0.0269 (6) | |
C6A | 0.7058 (4) | 0.1356 (3) | 0.36362 (13) | 0.0334 (6) | |
H6A | 0.5776 | 0.1477 | 0.3462 | 0.040* | |
C7A | 0.7672 (4) | 0.1850 (3) | 0.41186 (12) | 0.0302 (6) | |
H7A | 0.6864 | 0.2388 | 0.4337 | 0.036* | |
C8A | 1.0671 (4) | 0.1855 (3) | 0.47358 (12) | 0.0266 (6) | |
C9A | 1.2584 (4) | 0.1395 (3) | 0.48988 (12) | 0.0282 (6) | |
H9A | 1.3301 | 0.0806 | 0.4686 | 0.034* | |
C10A | 1.3389 (4) | 0.1836 (3) | 0.53843 (12) | 0.0304 (6) | |
H10A | 1.4695 | 0.1548 | 0.5509 | 0.036* | |
C11A | 1.2331 (4) | 0.2688 (3) | 0.56931 (13) | 0.0306 (6) | |
H11A | 1.2874 | 0.2986 | 0.6030 | 0.037* | |
C12A | 1.0438 (4) | 0.3087 (3) | 0.54876 (12) | 0.0254 (6) | |
C13A | 0.7206 (4) | 0.4250 (3) | 0.55896 (13) | 0.0314 (6) | |
H13A | 0.6584 | 0.3948 | 0.5266 | 0.038* | |
C14A | 0.6310 (4) | 0.5040 (3) | 0.59412 (13) | 0.0325 (6) | |
H14A | 0.4977 | 0.5380 | 0.5912 | 0.039* | |
C15A | 0.9525 (4) | 0.4568 (3) | 0.62463 (12) | 0.0263 (6) | |
C16A | 0.7742 (4) | 0.5268 (3) | 0.63644 (13) | 0.0300 (6) | |
C17A | 0.7763 (4) | 0.6000 (3) | 0.68338 (13) | 0.0330 (7) | |
H17A | 0.6622 | 0.6496 | 0.6932 | 0.040* | |
C18A | 0.9506 (4) | 0.5973 (3) | 0.71476 (13) | 0.0331 (6) | |
H18A | 0.9578 | 0.6453 | 0.7470 | 0.040* | |
C19A | 1.1155 (4) | 0.5247 (3) | 0.69956 (13) | 0.0334 (7) | |
H19A | 1.2326 | 0.5253 | 0.7224 | 0.040* | |
N1B | 0.3449 (3) | 1.0995 (3) | −0.15837 (11) | 0.0324 (6) | |
N2B | 0.5512 (3) | 0.9733 (2) | −0.07774 (10) | 0.0275 (5) | |
N3B | 0.5174 (3) | 0.7710 (2) | −0.00275 (10) | 0.0260 (5) | |
N4B | 0.5224 (3) | 0.5744 (2) | 0.07439 (10) | 0.0275 (5) | |
N5B | 0.2898 (3) | 0.3844 (2) | 0.11605 (11) | 0.0323 (6) | |
C1B | 0.3484 (4) | 1.2103 (3) | −0.20667 (13) | 0.0363 (7) | |
H1B | 0.2310 | 1.2289 | −0.2297 | 0.044* | |
C2B | 0.5125 (4) | 1.2986 (3) | −0.22478 (14) | 0.0399 (7) | |
H2B | 0.5054 | 1.3743 | −0.2594 | 0.048* | |
C3B | 0.6847 (4) | 1.2765 (3) | −0.19261 (14) | 0.0367 (7) | |
H3B | 0.7976 | 1.3366 | −0.2042 | 0.044* | |
C4B | 0.6898 (4) | 1.1636 (3) | −0.14249 (13) | 0.0303 (6) | |
C5B | 0.5137 (4) | 1.0800 (3) | −0.12846 (12) | 0.0270 (6) | |
C6B | 0.8350 (4) | 1.1042 (3) | −0.09937 (13) | 0.0346 (7) | |
H6B | 0.9675 | 1.1379 | −0.0975 | 0.041* | |
C7B | 0.7488 (4) | 0.9907 (3) | −0.06147 (13) | 0.0317 (6) | |
H7B | 0.8134 | 0.9315 | −0.0285 | 0.038* | |
C8B | 0.4288 (4) | 0.8593 (3) | −0.04827 (12) | 0.0271 (6) | |
C9B | 0.2371 (4) | 0.8393 (3) | −0.06649 (12) | 0.0285 (6) | |
H9B | 0.1783 | 0.9031 | −0.0992 | 0.034* | |
C10B | 0.1350 (4) | 0.7217 (3) | −0.03476 (12) | 0.0305 (6) | |
H10B | 0.0033 | 0.7041 | −0.0460 | 0.037* | |
C11B | 0.2217 (4) | 0.6292 (3) | 0.01308 (12) | 0.0290 (6) | |
H11B | 0.1524 | 0.5488 | 0.0352 | 0.035* | |
C12B | 0.4156 (4) | 0.6605 (3) | 0.02702 (12) | 0.0263 (6) | |
C13B | 0.7177 (4) | 0.6047 (3) | 0.08766 (12) | 0.0299 (6) | |
H13B | 0.7924 | 0.6841 | 0.0672 | 0.036* | |
C14B | 0.7863 (4) | 0.5044 (3) | 0.13412 (13) | 0.0328 (6) | |
H14B | 0.9148 | 0.5014 | 0.1512 | 0.039* | |
C15B | 0.4644 (4) | 0.4492 (3) | 0.11488 (12) | 0.0271 (6) | |
C16B | 0.6286 (4) | 0.4047 (3) | 0.15235 (12) | 0.0275 (6) | |
C17B | 0.6045 (4) | 0.2802 (3) | 0.19563 (13) | 0.0349 (7) | |
H17B | 0.7082 | 0.2449 | 0.2226 | 0.042* | |
C18B | 0.4243 (4) | 0.2099 (3) | 0.19793 (13) | 0.0361 (7) | |
H18B | 0.4033 | 0.1243 | 0.2265 | 0.043* | |
C19B | 0.2738 (4) | 0.2648 (3) | 0.15838 (13) | 0.0349 (7) | |
H19B | 0.1515 | 0.2143 | 0.1615 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0353 (12) | 0.0293 (13) | 0.0341 (14) | −0.0027 (10) | 0.0065 (10) | −0.0084 (11) |
N2A | 0.0305 (11) | 0.0257 (13) | 0.0265 (12) | −0.0015 (9) | 0.0025 (9) | −0.0070 (10) |
N3A | 0.0336 (12) | 0.0246 (12) | 0.0250 (12) | −0.0028 (10) | 0.0024 (9) | −0.0052 (10) |
N4A | 0.0301 (11) | 0.0257 (12) | 0.0240 (12) | −0.0013 (9) | 0.0018 (9) | −0.0088 (9) |
N5A | 0.0304 (11) | 0.0337 (14) | 0.0329 (13) | 0.0024 (10) | −0.0017 (10) | −0.0125 (11) |
C1A | 0.0390 (15) | 0.0312 (16) | 0.0383 (18) | −0.0027 (13) | 0.0118 (13) | −0.0126 (13) |
C2A | 0.0548 (19) | 0.0341 (16) | 0.0362 (17) | −0.0039 (14) | 0.0122 (14) | −0.0166 (14) |
C3A | 0.0452 (16) | 0.0303 (16) | 0.0302 (15) | −0.0029 (13) | −0.0002 (12) | −0.0110 (13) |
C4A | 0.0354 (14) | 0.0250 (15) | 0.0246 (14) | −0.0044 (12) | 0.0027 (11) | −0.0061 (12) |
C5A | 0.0343 (14) | 0.0201 (14) | 0.0248 (14) | −0.0038 (11) | 0.0077 (11) | −0.0043 (11) |
C6A | 0.0362 (14) | 0.0291 (15) | 0.0336 (15) | −0.0025 (12) | −0.0014 (12) | −0.0048 (12) |
C7A | 0.0282 (13) | 0.0274 (15) | 0.0338 (16) | 0.0042 (11) | 0.0025 (11) | −0.0060 (12) |
C8A | 0.0306 (13) | 0.0212 (13) | 0.0268 (14) | −0.0022 (11) | 0.0054 (11) | −0.0052 (11) |
C9A | 0.0305 (13) | 0.0257 (14) | 0.0278 (14) | 0.0004 (11) | 0.0040 (11) | −0.0064 (11) |
C10A | 0.0287 (13) | 0.0282 (15) | 0.0325 (15) | 0.0026 (11) | 0.0021 (11) | −0.0044 (12) |
C11A | 0.0321 (14) | 0.0303 (15) | 0.0281 (14) | −0.0009 (12) | 0.0000 (11) | −0.0044 (12) |
C12A | 0.0284 (13) | 0.0208 (13) | 0.0247 (14) | −0.0021 (10) | 0.0060 (10) | −0.0022 (11) |
C13A | 0.0299 (13) | 0.0310 (15) | 0.0345 (16) | 0.0010 (11) | −0.0006 (11) | −0.0105 (12) |
C14A | 0.0284 (13) | 0.0323 (15) | 0.0363 (16) | 0.0035 (12) | 0.0021 (11) | −0.0077 (12) |
C15A | 0.0302 (13) | 0.0226 (14) | 0.0239 (14) | −0.0055 (11) | 0.0057 (10) | −0.0026 (11) |
C16A | 0.0320 (14) | 0.0220 (15) | 0.0319 (16) | 0.0004 (11) | 0.0067 (12) | 0.0000 (12) |
C17A | 0.0396 (15) | 0.0253 (14) | 0.0304 (15) | 0.0001 (12) | 0.0094 (12) | −0.0017 (12) |
C18A | 0.0430 (16) | 0.0298 (15) | 0.0269 (14) | −0.0044 (12) | 0.0073 (12) | −0.0099 (12) |
C19A | 0.0399 (15) | 0.0329 (16) | 0.0289 (15) | −0.0024 (13) | −0.0006 (12) | −0.0108 (13) |
N1B | 0.0387 (13) | 0.0241 (13) | 0.0336 (13) | 0.0013 (10) | 0.0003 (10) | −0.0058 (11) |
N2B | 0.0288 (11) | 0.0254 (12) | 0.0287 (12) | 0.0011 (9) | 0.0039 (9) | −0.0085 (10) |
N3B | 0.0300 (11) | 0.0245 (12) | 0.0250 (12) | 0.0022 (9) | 0.0029 (9) | −0.0098 (10) |
N4B | 0.0296 (11) | 0.0264 (13) | 0.0257 (12) | 0.0023 (10) | 0.0018 (9) | −0.0052 (10) |
N5B | 0.0352 (12) | 0.0283 (13) | 0.0323 (13) | −0.0020 (10) | 0.0071 (10) | −0.0075 (11) |
C1B | 0.0446 (16) | 0.0304 (16) | 0.0322 (16) | 0.0041 (13) | 0.0012 (13) | −0.0046 (12) |
C2B | 0.0509 (17) | 0.0270 (15) | 0.0382 (17) | 0.0061 (14) | 0.0110 (14) | −0.0038 (13) |
C3B | 0.0438 (16) | 0.0209 (14) | 0.0415 (17) | −0.0038 (13) | 0.0171 (13) | −0.0044 (13) |
C4B | 0.0325 (14) | 0.0260 (16) | 0.0346 (16) | 0.0030 (11) | 0.0083 (12) | −0.0140 (12) |
C5B | 0.0305 (13) | 0.0227 (14) | 0.0278 (15) | 0.0012 (11) | 0.0055 (11) | −0.0080 (11) |
C6B | 0.0325 (14) | 0.0293 (15) | 0.0404 (17) | −0.0037 (12) | 0.0074 (12) | −0.0074 (12) |
C7B | 0.0321 (14) | 0.0300 (15) | 0.0344 (15) | −0.0014 (12) | 0.0001 (12) | −0.0109 (12) |
C8B | 0.0312 (13) | 0.0248 (14) | 0.0270 (15) | 0.0008 (11) | 0.0045 (11) | −0.0109 (11) |
C9B | 0.0310 (13) | 0.0274 (15) | 0.0277 (14) | 0.0029 (11) | −0.0040 (11) | −0.0072 (12) |
C10B | 0.0273 (13) | 0.0311 (15) | 0.0336 (15) | −0.0030 (12) | 0.0001 (11) | −0.0092 (12) |
C11B | 0.0327 (13) | 0.0251 (14) | 0.0287 (14) | −0.0037 (11) | 0.0034 (11) | −0.0066 (11) |
C12B | 0.0319 (13) | 0.0250 (14) | 0.0245 (14) | 0.0037 (11) | 0.0027 (10) | −0.0117 (11) |
C13B | 0.0288 (13) | 0.0340 (16) | 0.0291 (15) | −0.0025 (12) | 0.0015 (11) | −0.0124 (12) |
C14B | 0.0350 (14) | 0.0322 (15) | 0.0309 (15) | 0.0010 (12) | −0.0034 (12) | −0.0065 (12) |
C15B | 0.0314 (13) | 0.0260 (15) | 0.0260 (15) | 0.0011 (12) | 0.0060 (11) | −0.0120 (12) |
C16B | 0.0339 (13) | 0.0268 (15) | 0.0225 (14) | 0.0049 (12) | 0.0024 (11) | −0.0084 (12) |
C17B | 0.0423 (16) | 0.0325 (17) | 0.0288 (15) | 0.0046 (14) | 0.0014 (12) | −0.0059 (13) |
C18B | 0.0504 (17) | 0.0268 (15) | 0.0283 (15) | 0.0005 (13) | 0.0092 (13) | −0.0035 (12) |
C19B | 0.0385 (15) | 0.0347 (18) | 0.0336 (17) | −0.0051 (13) | 0.0073 (12) | −0.0145 (14) |
N1A—C5A | 1.337 (3) | N1B—C5B | 1.324 (3) |
N1A—C1A | 1.342 (4) | N1B—C1B | 1.353 (4) |
N2A—C7A | 1.392 (3) | N2B—C5B | 1.395 (3) |
N2A—C5A | 1.415 (3) | N2B—C7B | 1.402 (3) |
N2A—C8A | 1.421 (3) | N2B—C8B | 1.416 (3) |
N3A—C8A | 1.326 (3) | N3B—C12B | 1.322 (3) |
N3A—C12A | 1.334 (3) | N3B—C8B | 1.341 (4) |
N4A—C15A | 1.388 (4) | N4B—C13B | 1.395 (3) |
N4A—C13A | 1.392 (3) | N4B—C15B | 1.408 (4) |
N4A—C12A | 1.417 (3) | N4B—C12B | 1.418 (3) |
N5A—C15A | 1.331 (3) | N5B—C15B | 1.328 (4) |
N5A—C19A | 1.348 (4) | N5B—C19B | 1.345 (4) |
C1A—C2A | 1.386 (4) | C1B—C2B | 1.389 (4) |
C1A—H1A | 0.9500 | C1B—H1B | 0.9500 |
C2A—C3A | 1.386 (4) | C2B—C3B | 1.370 (4) |
C2A—H2A | 0.9500 | C2B—H2B | 0.9500 |
C3A—C4A | 1.390 (4) | C3B—C4B | 1.393 (4) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.403 (4) | C4B—C5B | 1.420 (4) |
C4A—C6A | 1.434 (4) | C4B—C6B | 1.425 (4) |
C6A—C7A | 1.354 (4) | C6B—C7B | 1.357 (4) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—H7A | 0.9500 | C7B—H7B | 0.9500 |
C8A—C9A | 1.390 (4) | C8B—C9B | 1.385 (4) |
C9A—C10A | 1.381 (4) | C9B—C10B | 1.387 (4) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.382 (4) | C10B—C11B | 1.388 (4) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—C12A | 1.389 (4) | C11B—C12B | 1.393 (4) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C13A—C14A | 1.349 (4) | C13B—C14B | 1.361 (4) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C16A | 1.422 (4) | C14B—C16B | 1.428 (4) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.421 (4) | C15B—C16B | 1.415 (4) |
C16A—C17A | 1.402 (4) | C16B—C17B | 1.395 (4) |
C17A—C18A | 1.378 (4) | C17B—C18B | 1.385 (4) |
C17A—H17A | 0.9500 | C17B—H17B | 0.9500 |
C18A—C19A | 1.385 (4) | C18B—C19B | 1.393 (4) |
C18A—H18A | 0.9500 | C18B—H18B | 0.9500 |
C19A—H19A | 0.9500 | C19B—H19B | 0.9500 |
C5A—N1A—C1A | 113.5 (3) | C5B—N1B—C1B | 114.5 (3) |
C7A—N2A—C5A | 106.8 (2) | C5B—N2B—C7B | 107.3 (2) |
C7A—N2A—C8A | 123.1 (2) | C5B—N2B—C8B | 129.7 (2) |
C5A—N2A—C8A | 130.0 (2) | C7B—N2B—C8B | 122.8 (2) |
C8A—N3A—C12A | 118.5 (2) | C12B—N3B—C8B | 118.5 (2) |
C15A—N4A—C13A | 107.5 (2) | C13B—N4B—C15B | 107.5 (2) |
C15A—N4A—C12A | 129.3 (2) | C13B—N4B—C12B | 122.4 (2) |
C13A—N4A—C12A | 123.2 (2) | C15B—N4B—C12B | 130.0 (2) |
C15A—N5A—C19A | 114.6 (2) | C15B—N5B—C19B | 114.1 (3) |
N1A—C1A—C2A | 124.4 (3) | N1B—C1B—C2B | 124.3 (3) |
N1A—C1A—H1A | 117.8 | N1B—C1B—H1B | 117.8 |
C2A—C1A—H1A | 117.8 | C2B—C1B—H1B | 117.8 |
C3A—C2A—C1A | 120.4 (3) | C3B—C2B—C1B | 119.9 (3) |
C3A—C2A—H2A | 119.8 | C3B—C2B—H2B | 120.0 |
C1A—C2A—H2A | 119.8 | C1B—C2B—H2B | 120.0 |
C2A—C3A—C4A | 117.3 (3) | C2B—C3B—C4B | 118.2 (3) |
C2A—C3A—H3A | 121.3 | C2B—C3B—H3B | 120.9 |
C4A—C3A—H3A | 121.3 | C4B—C3B—H3B | 120.9 |
C3A—C4A—C5A | 116.9 (3) | C3B—C4B—C5B | 116.9 (3) |
C3A—C4A—C6A | 135.3 (3) | C3B—C4B—C6B | 135.8 (3) |
C5A—C4A—C6A | 107.8 (2) | C5B—C4B—C6B | 107.3 (3) |
N1A—C5A—C4A | 127.3 (3) | N1B—C5B—N2B | 126.2 (2) |
N1A—C5A—N2A | 125.3 (3) | N1B—C5B—C4B | 126.2 (3) |
C4A—C5A—N2A | 107.4 (2) | N2B—C5B—C4B | 107.6 (2) |
C7A—C6A—C4A | 106.8 (2) | C7B—C6B—C4B | 107.3 (3) |
C7A—C6A—H6A | 126.6 | C7B—C6B—H6B | 126.4 |
C4A—C6A—H6A | 126.6 | C4B—C6B—H6B | 126.4 |
C6A—C7A—N2A | 111.1 (2) | C6B—C7B—N2B | 110.5 (3) |
C6A—C7A—H7A | 124.4 | C6B—C7B—H7B | 124.8 |
N2A—C7A—H7A | 124.4 | N2B—C7B—H7B | 124.8 |
N3A—C8A—C9A | 123.5 (3) | N3B—C8B—C9B | 123.3 (3) |
N3A—C8A—N2A | 113.5 (2) | N3B—C8B—N2B | 114.1 (2) |
C9A—C8A—N2A | 123.0 (2) | C9B—C8B—N2B | 122.6 (2) |
C10A—C9A—C8A | 116.8 (2) | C8B—C9B—C10B | 116.8 (3) |
C10A—C9A—H9A | 121.6 | C8B—C9B—H9B | 121.6 |
C8A—C9A—H9A | 121.6 | C10B—C9B—H9B | 121.6 |
C9A—C10A—C11A | 121.3 (2) | C9B—C10B—C11B | 121.2 (2) |
C9A—C10A—H10A | 119.4 | C9B—C10B—H10B | 119.4 |
C11A—C10A—H10A | 119.4 | C11B—C10B—H10B | 119.4 |
C10A—C11A—C12A | 116.9 (3) | C10B—C11B—C12B | 116.6 (3) |
C10A—C11A—H11A | 121.6 | C10B—C11B—H11B | 121.7 |
C12A—C11A—H11A | 121.6 | C12B—C11B—H11B | 121.7 |
N3A—C12A—C11A | 123.1 (3) | N3B—C12B—C11B | 123.6 (2) |
N3A—C12A—N4A | 113.4 (2) | N3B—C12B—N4B | 114.0 (2) |
C11A—C12A—N4A | 123.4 (2) | C11B—C12B—N4B | 122.5 (3) |
C14A—C13A—N4A | 110.9 (2) | C14B—C13B—N4B | 110.5 (3) |
C14A—C13A—H13A | 124.5 | C14B—C13B—H13B | 124.7 |
N4A—C13A—H13A | 124.5 | N4B—C13B—H13B | 124.7 |
C13A—C14A—C16A | 107.0 (2) | C13B—C14B—C16B | 107.1 (2) |
C13A—C14A—H14A | 126.5 | C13B—C14B—H14B | 126.4 |
C16A—C14A—H14A | 126.5 | C16B—C14B—H14B | 126.4 |
N5A—C15A—N4A | 127.1 (2) | N5B—C15B—N4B | 126.0 (3) |
N5A—C15A—C16A | 125.7 (3) | N5B—C15B—C16B | 126.9 (3) |
N4A—C15A—C16A | 107.2 (2) | N4B—C15B—C16B | 107.1 (2) |
C17A—C16A—C15A | 117.4 (3) | C17B—C16B—C15B | 116.8 (3) |
C17A—C16A—C14A | 135.1 (3) | C17B—C16B—C14B | 135.5 (3) |
C15A—C16A—C14A | 107.4 (2) | C15B—C16B—C14B | 107.7 (2) |
C18A—C17A—C16A | 117.3 (3) | C18B—C17B—C16B | 117.7 (3) |
C18A—C17A—H17A | 121.3 | C18B—C17B—H17B | 121.1 |
C16A—C17A—H17A | 121.3 | C16B—C17B—H17B | 121.1 |
C17A—C18A—C19A | 120.3 (3) | C17B—C18B—C19B | 120.0 (3) |
C17A—C18A—H18A | 119.8 | C17B—C18B—H18B | 120.0 |
C19A—C18A—H18A | 119.8 | C19B—C18B—H18B | 120.0 |
N5A—C19A—C18A | 124.6 (3) | N5B—C19B—C18B | 124.5 (3) |
N5A—C19A—H19A | 117.7 | N5B—C19B—H19B | 117.8 |
C18A—C19A—H19A | 117.7 | C18B—C19B—H19B | 117.8 |
C5A—N1A—C1A—C2A | 1.2 (4) | C5B—N1B—C1B—C2B | 0.0 (4) |
N1A—C1A—C2A—C3A | −1.4 (5) | N1B—C1B—C2B—C3B | −0.5 (5) |
C1A—C2A—C3A—C4A | 0.2 (4) | C1B—C2B—C3B—C4B | 0.7 (4) |
C2A—C3A—C4A—C5A | 1.0 (4) | C2B—C3B—C4B—C5B | −0.3 (4) |
C2A—C3A—C4A—C6A | −177.7 (3) | C2B—C3B—C4B—C6B | 178.3 (3) |
C1A—N1A—C5A—C4A | 0.1 (4) | C1B—N1B—C5B—N2B | −179.2 (2) |
C1A—N1A—C5A—N2A | 179.3 (2) | C1B—N1B—C5B—C4B | 0.4 (4) |
C3A—C4A—C5A—N1A | −1.2 (4) | C7B—N2B—C5B—N1B | 179.0 (3) |
C6A—C4A—C5A—N1A | 177.8 (3) | C8B—N2B—C5B—N1B | 3.5 (4) |
C3A—C4A—C5A—N2A | 179.5 (2) | C7B—N2B—C5B—C4B | −0.6 (3) |
C6A—C4A—C5A—N2A | −1.5 (3) | C8B—N2B—C5B—C4B | −176.2 (2) |
C7A—N2A—C5A—N1A | −178.1 (3) | C3B—C4B—C5B—N1B | −0.2 (4) |
C8A—N2A—C5A—N1A | 1.8 (4) | C6B—C4B—C5B—N1B | −179.2 (3) |
C7A—N2A—C5A—C4A | 1.3 (3) | C3B—C4B—C5B—N2B | 179.4 (2) |
C8A—N2A—C5A—C4A | −178.9 (3) | C6B—C4B—C5B—N2B | 0.4 (3) |
C3A—C4A—C6A—C7A | 179.9 (3) | C3B—C4B—C6B—C7B | −178.7 (3) |
C5A—C4A—C6A—C7A | 1.2 (3) | C5B—C4B—C6B—C7B | 0.0 (3) |
C4A—C6A—C7A—N2A | −0.4 (3) | C4B—C6B—C7B—N2B | −0.4 (3) |
C5A—N2A—C7A—C6A | −0.6 (3) | C5B—N2B—C7B—C6B | 0.6 (3) |
C8A—N2A—C7A—C6A | 179.6 (2) | C8B—N2B—C7B—C6B | 176.5 (2) |
C12A—N3A—C8A—C9A | −0.2 (4) | C12B—N3B—C8B—C9B | −1.2 (4) |
C12A—N3A—C8A—N2A | 179.0 (2) | C12B—N3B—C8B—N2B | −179.2 (2) |
C7A—N2A—C8A—N3A | −3.8 (4) | C5B—N2B—C8B—N3B | 176.1 (2) |
C5A—N2A—C8A—N3A | 176.4 (2) | C7B—N2B—C8B—N3B | 1.1 (3) |
C7A—N2A—C8A—C9A | 175.4 (2) | C5B—N2B—C8B—C9B | −2.0 (4) |
C5A—N2A—C8A—C9A | −4.5 (4) | C7B—N2B—C8B—C9B | −176.9 (2) |
N3A—C8A—C9A—C10A | 0.1 (4) | N3B—C8B—C9B—C10B | 0.6 (4) |
N2A—C8A—C9A—C10A | −178.9 (2) | N2B—C8B—C9B—C10B | 178.4 (2) |
C8A—C9A—C10A—C11A | 0.3 (4) | C8B—C9B—C10B—C11B | 0.2 (4) |
C9A—C10A—C11A—C12A | −0.6 (4) | C9B—C10B—C11B—C12B | −0.4 (4) |
C8A—N3A—C12A—C11A | −0.2 (4) | C8B—N3B—C12B—C11B | 1.0 (4) |
C8A—N3A—C12A—N4A | −178.6 (2) | C8B—N3B—C12B—N4B | −179.7 (2) |
C10A—C11A—C12A—N3A | 0.6 (4) | C10B—C11B—C12B—N3B | −0.2 (4) |
C10A—C11A—C12A—N4A | 178.9 (2) | C10B—C11B—C12B—N4B | −179.4 (2) |
C15A—N4A—C12A—N3A | −178.4 (2) | C13B—N4B—C12B—N3B | −0.3 (3) |
C13A—N4A—C12A—N3A | 3.6 (4) | C15B—N4B—C12B—N3B | −179.4 (2) |
C15A—N4A—C12A—C11A | 3.2 (4) | C13B—N4B—C12B—C11B | 179.0 (2) |
C13A—N4A—C12A—C11A | −174.9 (2) | C15B—N4B—C12B—C11B | −0.2 (4) |
C15A—N4A—C13A—C14A | −0.4 (3) | C15B—N4B—C13B—C14B | 0.5 (3) |
C12A—N4A—C13A—C14A | 178.0 (2) | C12B—N4B—C13B—C14B | −178.8 (2) |
N4A—C13A—C14A—C16A | 0.4 (3) | N4B—C13B—C14B—C16B | −0.4 (3) |
C19A—N5A—C15A—N4A | 179.7 (2) | C19B—N5B—C15B—N4B | 178.6 (2) |
C19A—N5A—C15A—C16A | −0.3 (4) | C19B—N5B—C15B—C16B | 0.5 (4) |
C13A—N4A—C15A—N5A | −179.7 (3) | C13B—N4B—C15B—N5B | −178.7 (2) |
C12A—N4A—C15A—N5A | 2.0 (5) | C12B—N4B—C15B—N5B | 0.6 (4) |
C13A—N4A—C15A—C16A | 0.3 (3) | C13B—N4B—C15B—C16B | −0.3 (3) |
C12A—N4A—C15A—C16A | −178.0 (2) | C12B—N4B—C15B—C16B | 178.9 (2) |
N5A—C15A—C16A—C17A | 0.7 (4) | N5B—C15B—C16B—C17B | −0.7 (4) |
N4A—C15A—C16A—C17A | −179.3 (2) | N4B—C15B—C16B—C17B | −179.0 (2) |
N5A—C15A—C16A—C14A | 179.9 (3) | N5B—C15B—C16B—C14B | 178.4 (3) |
N4A—C15A—C16A—C14A | 0.0 (3) | N4B—C15B—C16B—C14B | 0.1 (3) |
C13A—C14A—C16A—C17A | 178.9 (3) | C13B—C14B—C16B—C17B | 179.1 (3) |
C13A—C14A—C16A—C15A | −0.2 (3) | C13B—C14B—C16B—C15B | 0.2 (3) |
C15A—C16A—C17A—C18A | −0.6 (4) | C15B—C16B—C17B—C18B | 0.8 (4) |
C14A—C16A—C17A—C18A | −179.6 (3) | C14B—C16B—C17B—C18B | −178.1 (3) |
C16A—C17A—C18A—C19A | 0.2 (4) | C16B—C17B—C18B—C19B | −0.8 (4) |
C15A—N5A—C19A—C18A | −0.1 (4) | C15B—N5B—C19B—C18B | −0.5 (4) |
C17A—C18A—C19A—N5A | 0.1 (5) | C17B—C18B—C19B—N5B | 0.7 (4) |
(C19H14N5)[FeCl4] | F(000) = 1028 |
Mr = 510.00 | Dx = 1.656 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 7864 reflections |
a = 6.6695 (1) Å | θ = 3.8–67.9° |
b = 23.2657 (4) Å | µ = 10.86 mm−1 |
c = 13.3959 (2) Å | T = 150 K |
β = 100.312 (1)° | Rod, yellow |
V = 2045.07 (6) Å3 | 0.19 × 0.04 × 0.02 mm |
Z = 4 |
Bruker SMART 6000 CCD diffractometer | 3653 independent reflections |
Radiation source: fine-focus sealed tube | 3210 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 0.8 pixels mm-1 | θmax = 68.0°, θmin = 3.8° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −27→27 |
Tmin = 0.232, Tmax = 0.812 | l = −15→15 |
17199 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0412P)2 + 0.4538P] where P = (Fo2 + 2Fc2)/3 |
3653 reflections | (Δ/σ)max = 0.001 |
266 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
(C19H14N5)[FeCl4] | V = 2045.07 (6) Å3 |
Mr = 510.00 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 6.6695 (1) Å | µ = 10.86 mm−1 |
b = 23.2657 (4) Å | T = 150 K |
c = 13.3959 (2) Å | 0.19 × 0.04 × 0.02 mm |
β = 100.312 (1)° |
Bruker SMART 6000 CCD diffractometer | 3653 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3210 reflections with I > 2σ(I) |
Tmin = 0.232, Tmax = 0.812 | Rint = 0.041 |
17199 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.34 e Å−3 |
3653 reflections | Δρmin = −0.25 e Å−3 |
266 parameters |
Experimental. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size. Spectroscopic characterization: UV-vis (λmax, methanol, room temp): 317 nm |
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 | ||
Fe | 0.24826 (5) | 0.656709 (14) | 1.04461 (2) | 0.02627 (11) | |
Cl1 | −0.04490 (9) | 0.63538 (3) | 1.08877 (5) | 0.04501 (17) | |
Cl2 | 0.19512 (9) | 0.72098 (2) | 0.92257 (4) | 0.03491 (14) | |
Cl3 | 0.45343 (9) | 0.69060 (2) | 1.17814 (4) | 0.03408 (14) | |
Cl4 | 0.38472 (11) | 0.57906 (3) | 0.99304 (4) | 0.04551 (17) | |
N1 | 0.2212 (3) | 0.61000 (8) | 0.44891 (13) | 0.0231 (4) | |
H20 | 0.223 (4) | 0.5728 (12) | 0.4349 (19) | 0.035 (7)* | |
N2 | 0.2900 (3) | 0.60012 (8) | 0.63369 (12) | 0.0243 (4) | |
N3 | 0.2688 (2) | 0.51067 (8) | 0.55802 (12) | 0.0231 (4) | |
N4 | 0.2442 (3) | 0.42441 (7) | 0.46941 (13) | 0.0251 (4) | |
N5 | 0.2089 (3) | 0.50207 (8) | 0.34382 (13) | 0.0251 (4) | |
C1 | 0.1861 (4) | 0.64788 (10) | 0.37103 (17) | 0.0313 (5) | |
H1 | 0.1615 | 0.6338 | 0.3033 | 0.038* | |
C2 | 0.1853 (4) | 0.70629 (10) | 0.38758 (18) | 0.0351 (5) | |
H2 | 0.1593 | 0.7319 | 0.3315 | 0.042* | |
C3 | 0.2222 (3) | 0.72811 (10) | 0.48580 (18) | 0.0322 (5) | |
H3 | 0.2223 | 0.7684 | 0.4976 | 0.039* | |
C4 | 0.2588 (3) | 0.68972 (10) | 0.56600 (17) | 0.0275 (5) | |
C5 | 0.2551 (3) | 0.63021 (9) | 0.54446 (15) | 0.0234 (4) | |
C6 | 0.2985 (3) | 0.69449 (10) | 0.67409 (17) | 0.0321 (5) | |
H6 | 0.3106 | 0.7292 | 0.7120 | 0.039* | |
C7 | 0.3155 (3) | 0.64099 (10) | 0.71230 (17) | 0.0310 (5) | |
H7 | 0.3411 | 0.6320 | 0.7826 | 0.037* | |
C8 | 0.2927 (3) | 0.53972 (9) | 0.64524 (15) | 0.0239 (4) | |
C9 | 0.3176 (3) | 0.51435 (10) | 0.74024 (16) | 0.0305 (5) | |
H9 | 0.3314 | 0.5367 | 0.8004 | 0.037* | |
C10 | 0.3214 (3) | 0.45496 (11) | 0.74326 (17) | 0.0342 (5) | |
H10 | 0.3394 | 0.4357 | 0.8067 | 0.041* | |
C11 | 0.2991 (3) | 0.42353 (10) | 0.65449 (17) | 0.0315 (5) | |
H11 | 0.3021 | 0.3827 | 0.6556 | 0.038* | |
C12 | 0.2718 (3) | 0.45380 (9) | 0.56286 (16) | 0.0234 (4) | |
C13 | 0.2399 (3) | 0.36419 (10) | 0.46016 (18) | 0.0312 (5) | |
H13 | 0.2567 | 0.3382 | 0.5157 | 0.037* | |
C14 | 0.2089 (3) | 0.34837 (9) | 0.36190 (19) | 0.0334 (5) | |
H14 | 0.1994 | 0.3101 | 0.3367 | 0.040* | |
C15 | 0.2143 (3) | 0.44682 (9) | 0.37025 (16) | 0.0231 (4) | |
C16 | 0.1931 (3) | 0.39961 (10) | 0.30255 (18) | 0.0293 (5) | |
C17 | 0.1642 (3) | 0.41114 (11) | 0.19900 (18) | 0.0352 (5) | |
H17 | 0.1489 | 0.3810 | 0.1504 | 0.042* | |
C18 | 0.1588 (4) | 0.46809 (11) | 0.16961 (18) | 0.0359 (5) | |
H18 | 0.1401 | 0.4779 | 0.0997 | 0.043* | |
C19 | 0.1807 (3) | 0.51077 (10) | 0.24289 (16) | 0.0305 (5) | |
H19 | 0.1754 | 0.5495 | 0.2200 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0317 (2) | 0.02549 (19) | 0.02148 (18) | −0.00005 (14) | 0.00449 (14) | 0.00114 (13) |
Cl1 | 0.0327 (3) | 0.0534 (4) | 0.0491 (4) | −0.0008 (3) | 0.0075 (3) | 0.0239 (3) |
Cl2 | 0.0489 (3) | 0.0316 (3) | 0.0250 (3) | 0.0015 (2) | 0.0087 (2) | 0.0052 (2) |
Cl3 | 0.0432 (3) | 0.0321 (3) | 0.0252 (3) | −0.0036 (2) | 0.0014 (2) | −0.0025 (2) |
Cl4 | 0.0652 (4) | 0.0380 (3) | 0.0296 (3) | 0.0163 (3) | −0.0014 (3) | −0.0083 (2) |
N1 | 0.0253 (9) | 0.0226 (9) | 0.0223 (9) | −0.0014 (7) | 0.0064 (7) | −0.0019 (7) |
N2 | 0.0231 (9) | 0.0301 (9) | 0.0201 (8) | 0.0013 (7) | 0.0045 (7) | −0.0040 (7) |
N3 | 0.0209 (9) | 0.0261 (9) | 0.0228 (8) | −0.0003 (7) | 0.0048 (7) | −0.0009 (7) |
N4 | 0.0247 (9) | 0.0221 (9) | 0.0288 (9) | −0.0011 (7) | 0.0056 (7) | 0.0010 (7) |
N5 | 0.0248 (9) | 0.0262 (9) | 0.0237 (9) | 0.0005 (7) | 0.0029 (7) | −0.0021 (7) |
C1 | 0.0394 (13) | 0.0307 (12) | 0.0251 (11) | −0.0007 (10) | 0.0092 (10) | 0.0010 (9) |
C2 | 0.0448 (14) | 0.0275 (12) | 0.0353 (12) | 0.0001 (10) | 0.0129 (11) | 0.0050 (10) |
C3 | 0.0316 (12) | 0.0242 (11) | 0.0431 (13) | −0.0024 (9) | 0.0129 (10) | −0.0027 (10) |
C4 | 0.0214 (11) | 0.0279 (11) | 0.0346 (12) | −0.0011 (8) | 0.0088 (9) | −0.0073 (9) |
C5 | 0.0163 (10) | 0.0271 (11) | 0.0268 (10) | 0.0003 (8) | 0.0041 (8) | −0.0035 (9) |
C6 | 0.0277 (12) | 0.0336 (12) | 0.0350 (12) | 0.0003 (9) | 0.0053 (10) | −0.0131 (10) |
C7 | 0.0284 (12) | 0.0399 (13) | 0.0243 (11) | 0.0021 (10) | 0.0036 (9) | −0.0113 (10) |
C8 | 0.0175 (10) | 0.0306 (11) | 0.0238 (10) | 0.0001 (8) | 0.0042 (8) | 0.0001 (9) |
C9 | 0.0276 (11) | 0.0419 (13) | 0.0216 (10) | −0.0018 (10) | 0.0032 (9) | 0.0000 (10) |
C10 | 0.0304 (12) | 0.0442 (14) | 0.0271 (11) | −0.0017 (10) | 0.0025 (9) | 0.0120 (10) |
C11 | 0.0280 (12) | 0.0316 (12) | 0.0336 (12) | −0.0015 (9) | 0.0021 (9) | 0.0069 (10) |
C12 | 0.0167 (10) | 0.0255 (11) | 0.0283 (11) | 0.0001 (8) | 0.0047 (8) | 0.0027 (9) |
C13 | 0.0288 (12) | 0.0215 (11) | 0.0442 (13) | 0.0003 (9) | 0.0091 (10) | 0.0056 (10) |
C14 | 0.0299 (12) | 0.0231 (11) | 0.0489 (14) | −0.0014 (9) | 0.0112 (11) | −0.0093 (10) |
C15 | 0.0162 (10) | 0.0266 (10) | 0.0266 (10) | −0.0013 (8) | 0.0039 (8) | −0.0024 (9) |
C16 | 0.0191 (11) | 0.0311 (12) | 0.0380 (12) | −0.0033 (9) | 0.0061 (9) | −0.0094 (10) |
C17 | 0.0300 (12) | 0.0397 (14) | 0.0356 (12) | −0.0043 (10) | 0.0050 (10) | −0.0156 (11) |
C18 | 0.0344 (13) | 0.0461 (14) | 0.0262 (11) | −0.0004 (10) | 0.0024 (9) | −0.0063 (11) |
C19 | 0.0308 (12) | 0.0343 (12) | 0.0256 (11) | 0.0023 (10) | 0.0033 (9) | 0.0006 (10) |
Fe—Cl4 | 2.1895 (7) | C4—C5 | 1.414 (3) |
Fe—Cl3 | 2.1949 (6) | C4—C6 | 1.429 (3) |
Fe—Cl2 | 2.1970 (6) | C6—C7 | 1.343 (3) |
Fe—Cl1 | 2.1985 (7) | C6—H6 | 0.9500 |
N1—C5 | 1.344 (3) | C7—H7 | 0.9500 |
N1—C1 | 1.354 (3) | C8—C9 | 1.386 (3) |
N1—H20 | 0.89 (3) | C9—C10 | 1.382 (3) |
N2—C5 | 1.369 (3) | C9—H9 | 0.9500 |
N2—C7 | 1.406 (3) | C10—C11 | 1.381 (3) |
N2—C8 | 1.414 (3) | C10—H10 | 0.9500 |
N3—C12 | 1.325 (3) | C11—C12 | 1.398 (3) |
N3—C8 | 1.335 (3) | C11—H11 | 0.9500 |
N4—C13 | 1.406 (3) | C13—C14 | 1.347 (3) |
N4—C15 | 1.408 (3) | C13—H13 | 0.9500 |
N4—C12 | 1.409 (3) | C14—C16 | 1.426 (3) |
N5—C15 | 1.332 (3) | C14—H14 | 0.9500 |
N5—C19 | 1.347 (3) | C15—C16 | 1.415 (3) |
C1—C2 | 1.377 (3) | C16—C17 | 1.392 (3) |
C1—H1 | 0.9500 | C17—C18 | 1.381 (4) |
C2—C3 | 1.391 (3) | C17—H17 | 0.9500 |
C2—H2 | 0.9500 | C18—C19 | 1.385 (3) |
C3—C4 | 1.385 (3) | C18—H18 | 0.9500 |
C3—H3 | 0.9500 | C19—H19 | 0.9500 |
Cl4—Fe—Cl3 | 108.65 (3) | N2—C7—H7 | 124.7 |
Cl4—Fe—Cl2 | 110.34 (3) | N3—C8—C9 | 124.3 (2) |
Cl3—Fe—Cl2 | 110.85 (3) | N3—C8—N2 | 114.24 (17) |
Cl4—Fe—Cl1 | 109.79 (3) | C9—C8—N2 | 121.41 (19) |
Cl3—Fe—Cl1 | 108.45 (3) | C10—C9—C8 | 116.8 (2) |
Cl2—Fe—Cl1 | 108.73 (3) | C10—C9—H9 | 121.6 |
C5—N1—C1 | 118.84 (19) | C8—C9—H9 | 121.6 |
C5—N1—H20 | 122.5 (16) | C11—C10—C9 | 120.4 (2) |
C1—N1—H20 | 118.7 (16) | C11—C10—H10 | 119.8 |
C5—N2—C7 | 106.68 (18) | C9—C10—H10 | 119.8 |
C5—N2—C8 | 126.93 (17) | C10—C11—C12 | 117.8 (2) |
C7—N2—C8 | 126.35 (18) | C10—C11—H11 | 121.1 |
C12—N3—C8 | 117.69 (18) | C12—C11—H11 | 121.1 |
C13—N4—C15 | 106.78 (18) | N3—C12—C11 | 123.0 (2) |
C13—N4—C12 | 123.99 (18) | N3—C12—N4 | 116.28 (18) |
C15—N4—C12 | 129.23 (18) | C11—C12—N4 | 120.7 (2) |
C15—N5—C19 | 113.84 (19) | C14—C13—N4 | 110.8 (2) |
N1—C1—C2 | 121.6 (2) | C14—C13—H13 | 124.6 |
N1—C1—H1 | 119.2 | N4—C13—H13 | 124.6 |
C2—C1—H1 | 119.2 | C13—C14—C16 | 107.4 (2) |
C1—C2—C3 | 120.5 (2) | C13—C14—H14 | 126.3 |
C1—C2—H2 | 119.8 | C16—C14—H14 | 126.3 |
C3—C2—H2 | 119.8 | N5—C15—N4 | 126.92 (19) |
C4—C3—C2 | 118.4 (2) | N5—C15—C16 | 125.7 (2) |
C4—C3—H3 | 120.8 | N4—C15—C16 | 107.36 (19) |
C2—C3—H3 | 120.8 | C17—C16—C15 | 118.0 (2) |
C3—C4—C5 | 118.6 (2) | C17—C16—C14 | 134.4 (2) |
C3—C4—C6 | 135.3 (2) | C15—C16—C14 | 107.6 (2) |
C5—C4—C6 | 106.0 (2) | C18—C17—C16 | 117.4 (2) |
N1—C5—N2 | 128.8 (2) | C18—C17—H17 | 121.3 |
N1—C5—C4 | 122.1 (2) | C16—C17—H17 | 121.3 |
N2—C5—C4 | 109.18 (18) | C17—C18—C19 | 119.4 (2) |
C7—C6—C4 | 107.6 (2) | C17—C18—H18 | 120.3 |
C7—C6—H6 | 126.2 | C19—C18—H18 | 120.3 |
C4—C6—H6 | 126.2 | N5—C19—C18 | 125.6 (2) |
C6—C7—N2 | 110.5 (2) | N5—C19—H19 | 117.2 |
C6—C7—H7 | 124.7 | C18—C19—H19 | 117.2 |
C5—N1—C1—C2 | 0.3 (3) | C9—C10—C11—C12 | −0.3 (3) |
N1—C1—C2—C3 | 0.4 (4) | C8—N3—C12—C11 | −0.1 (3) |
C1—C2—C3—C4 | −0.3 (3) | C8—N3—C12—N4 | 179.43 (16) |
C2—C3—C4—C5 | −0.6 (3) | C10—C11—C12—N3 | 0.7 (3) |
C2—C3—C4—C6 | −178.8 (2) | C10—C11—C12—N4 | −178.78 (19) |
C1—N1—C5—N2 | 178.7 (2) | C13—N4—C12—N3 | −178.96 (18) |
C1—N1—C5—C4 | −1.2 (3) | C15—N4—C12—N3 | 0.3 (3) |
C7—N2—C5—N1 | −179.8 (2) | C13—N4—C12—C11 | 0.6 (3) |
C8—N2—C5—N1 | −1.9 (3) | C15—N4—C12—C11 | 179.8 (2) |
C7—N2—C5—C4 | 0.1 (2) | C15—N4—C13—C14 | −0.1 (2) |
C8—N2—C5—C4 | 178.05 (18) | C12—N4—C13—C14 | 179.27 (19) |
C3—C4—C5—N1 | 1.3 (3) | N4—C13—C14—C16 | 0.4 (3) |
C6—C4—C5—N1 | −179.98 (18) | C19—N5—C15—N4 | 179.06 (19) |
C3—C4—C5—N2 | −178.61 (18) | C19—N5—C15—C16 | −0.1 (3) |
C6—C4—C5—N2 | 0.1 (2) | C13—N4—C15—N5 | −179.5 (2) |
C3—C4—C6—C7 | 178.1 (2) | C12—N4—C15—N5 | 1.2 (3) |
C5—C4—C6—C7 | −0.3 (2) | C13—N4—C15—C16 | −0.2 (2) |
C4—C6—C7—N2 | 0.4 (3) | C12—N4—C15—C16 | −179.56 (18) |
C5—N2—C7—C6 | −0.3 (2) | N5—C15—C16—C17 | 0.1 (3) |
C8—N2—C7—C6 | −178.27 (19) | N4—C15—C16—C17 | −179.19 (18) |
C12—N3—C8—C9 | −1.0 (3) | N5—C15—C16—C14 | 179.7 (2) |
C12—N3—C8—N2 | 179.31 (17) | N4—C15—C16—C14 | 0.4 (2) |
C5—N2—C8—N3 | 3.8 (3) | C13—C14—C16—C17 | 179.0 (2) |
C7—N2—C8—N3 | −178.71 (18) | C13—C14—C16—C15 | −0.5 (2) |
C5—N2—C8—C9 | −176.0 (2) | C15—C16—C17—C18 | 0.1 (3) |
C7—N2—C8—C9 | 1.6 (3) | C14—C16—C17—C18 | −179.4 (2) |
N3—C8—C9—C10 | 1.3 (3) | C16—C17—C18—C19 | −0.3 (3) |
N2—C8—C9—C10 | −178.99 (19) | C15—N5—C19—C18 | −0.2 (3) |
C8—C9—C10—C11 | −0.6 (3) | C17—C18—C19—N5 | 0.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H20···N5 | 0.89 (3) | 2.04 (3) | 2.873 (3) | 156 (2) |
C3—H3···Cl1i | 0.95 | 2.87 | 3.692 (2) | 146 |
C19—H19···Cl1ii | 0.95 | 2.88 | 3.718 (2) | 147 |
C13—H13···Cl2iii | 0.95 | 2.85 | 3.676 (2) | 146 |
C9—H9···Cl4 | 0.95 | 2.73 | 3.660 (2) | 168 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x, y, z−1; (iii) −x+1/2, y−1/2, −z+3/2. |
[Cu(NO3)2(C19H13N5)] | F(000) = 1012 |
Mr = 498.90 | Dx = 1.774 Mg m−3 |
Monoclinic, C2/c | Synchrotron radiation, λ = 0.77490 Å |
Hall symbol: -C 2yc | Cell parameters from 6914 reflections |
a = 17.3858 (12) Å | θ = 3.5–31.1° |
b = 12.8324 (8) Å | µ = 1.55 mm−1 |
c = 8.4011 (6) Å | T = 193 K |
β = 94.726 (2)° | Block, light green |
V = 1867.9 (2) Å3 | 0.06 × 0.04 × 0.04 mm |
Z = 4 |
Bruker Platinum 200 diffractometer | 2319 independent reflections |
Radiation source: synchrotron | 2155 reflections with I > 2σ(I) |
Si-<111> channel cut crystal monochromator | Rint = 0.105 |
ω scans | θmax = 31.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −23→23 |
Tmin = 0.913, Tmax = 0.941 | k = −17→17 |
10400 measured reflections | l = −11→11 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0999P)2] where P = (Fo2 + 2Fc2)/3 |
2319 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[Cu(NO3)2(C19H13N5)] | V = 1867.9 (2) Å3 |
Mr = 498.90 | Z = 4 |
Monoclinic, C2/c | Synchrotron radiation, λ = 0.77490 Å |
a = 17.3858 (12) Å | µ = 1.55 mm−1 |
b = 12.8324 (8) Å | T = 193 K |
c = 8.4011 (6) Å | 0.06 × 0.04 × 0.04 mm |
β = 94.726 (2)° |
Bruker Platinum 200 diffractometer | 2319 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2155 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.941 | Rint = 0.105 |
10400 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.65 e Å−3 |
2319 reflections | Δρmin = −0.59 e Å−3 |
151 parameters |
Experimental. A suitable crystal was mounted on a loop using paratone-N and immediately transferred to the goniostat bathed in a cold stream. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size. |
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 | ||
Cu | 0.5000 | 0.24229 (2) | 0.2500 | 0.01959 (16) | |
O1 | 0.62850 (14) | 0.26401 (13) | 0.1072 (3) | 0.0408 (5) | |
O2 | 0.57340 (8) | 0.11953 (12) | 0.16803 (18) | 0.0331 (4) | |
O3 | 0.67996 (10) | 0.11592 (16) | 0.0500 (2) | 0.0450 (5) | |
N1 | 0.43589 (11) | 0.23703 (11) | 0.0466 (2) | 0.0230 (4) | |
N2 | 0.38335 (9) | 0.40958 (12) | 0.08054 (19) | 0.0230 (3) | |
N3 | 0.5000 | 0.40723 (16) | 0.2500 | 0.0191 (4) | |
N4 | 0.62831 (9) | 0.16708 (14) | 0.1063 (2) | 0.0267 (4) | |
C1 | 0.42788 (12) | 0.14922 (15) | −0.0438 (3) | 0.0279 (4) | |
H1 | 0.4630 | 0.0934 | −0.0209 | 0.033* | |
C2 | 0.37129 (13) | 0.13744 (16) | −0.1671 (3) | 0.0323 (4) | |
H2 | 0.3698 | 0.0756 | −0.2295 | 0.039* | |
C3 | 0.31621 (12) | 0.21463 (19) | −0.2019 (3) | 0.0305 (4) | |
H3 | 0.2762 | 0.2063 | −0.2850 | 0.037* | |
C4 | 0.32248 (11) | 0.30497 (16) | −0.1089 (2) | 0.0258 (4) | |
C5 | 0.38480 (10) | 0.31237 (14) | 0.0091 (2) | 0.0214 (4) | |
C6 | 0.28003 (12) | 0.40102 (18) | −0.1029 (3) | 0.0320 (5) | |
H6 | 0.2342 | 0.4185 | −0.1667 | 0.038* | |
C7 | 0.31711 (11) | 0.46146 (17) | 0.0095 (2) | 0.0299 (4) | |
H7 | 0.3012 | 0.5294 | 0.0374 | 0.036* | |
C8 | 0.44387 (10) | 0.46267 (14) | 0.1666 (2) | 0.0207 (4) | |
C9 | 0.44355 (12) | 0.57160 (14) | 0.1590 (2) | 0.0265 (4) | |
H9 | 0.4054 | 0.6077 | 0.0929 | 0.032* | |
C10 | 0.5000 | 0.6251 (2) | 0.2500 | 0.0288 (6) | |
H10 | 0.5000 | 0.6992 | 0.2500 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0197 (2) | 0.0155 (2) | 0.0231 (2) | 0.000 | −0.00104 (15) | 0.000 |
O1 | 0.0446 (11) | 0.0331 (9) | 0.0441 (12) | 0.0063 (7) | 0.0005 (9) | 0.0064 (7) |
O2 | 0.0312 (7) | 0.0336 (8) | 0.0350 (9) | 0.0039 (6) | 0.0052 (7) | −0.0004 (6) |
O3 | 0.0387 (9) | 0.0606 (12) | 0.0367 (9) | 0.0283 (8) | 0.0095 (7) | 0.0039 (8) |
N1 | 0.0237 (9) | 0.0192 (7) | 0.0259 (9) | −0.0014 (6) | 0.0008 (7) | −0.0017 (6) |
N2 | 0.0221 (7) | 0.0225 (7) | 0.0239 (8) | 0.0056 (6) | −0.0012 (6) | −0.0009 (6) |
N3 | 0.0197 (9) | 0.0164 (9) | 0.0213 (10) | 0.000 | 0.0033 (8) | 0.000 |
N4 | 0.0242 (8) | 0.0342 (9) | 0.0212 (8) | 0.0105 (6) | −0.0015 (6) | 0.0019 (6) |
C1 | 0.0305 (9) | 0.0203 (8) | 0.0322 (10) | −0.0008 (7) | −0.0023 (8) | −0.0031 (8) |
C2 | 0.0388 (11) | 0.0268 (10) | 0.0306 (10) | −0.0040 (8) | −0.0017 (9) | −0.0075 (8) |
C3 | 0.0285 (9) | 0.0355 (11) | 0.0264 (10) | −0.0041 (9) | −0.0047 (8) | −0.0010 (9) |
C4 | 0.0219 (8) | 0.0298 (9) | 0.0252 (9) | −0.0008 (7) | −0.0002 (7) | 0.0015 (8) |
C5 | 0.0204 (8) | 0.0218 (8) | 0.0221 (9) | 0.0009 (6) | 0.0024 (7) | −0.0002 (6) |
C6 | 0.0248 (9) | 0.0393 (11) | 0.0310 (11) | 0.0077 (8) | −0.0023 (8) | 0.0011 (9) |
C7 | 0.0263 (9) | 0.0330 (10) | 0.0300 (10) | 0.0110 (8) | −0.0001 (7) | −0.0009 (8) |
C8 | 0.0231 (8) | 0.0205 (8) | 0.0188 (8) | 0.0026 (6) | 0.0039 (6) | −0.0004 (6) |
C9 | 0.0340 (10) | 0.0200 (9) | 0.0260 (10) | 0.0065 (7) | 0.0056 (8) | 0.0023 (7) |
C10 | 0.0418 (15) | 0.0149 (11) | 0.0313 (14) | 0.000 | 0.0130 (12) | 0.000 |
Cu—N1 | 1.963 (2) | C1—H1 | 0.9500 |
Cu—N1i | 1.963 (2) | C2—C3 | 1.392 (3) |
Cu—N3 | 2.117 (2) | C2—H2 | 0.9500 |
Cu—O2i | 2.1746 (14) | C3—C4 | 1.397 (3) |
Cu—O2 | 2.1746 (14) | C3—H3 | 0.9500 |
O1—N4 | 1.244 (2) | C4—C5 | 1.410 (3) |
O2—N4 | 1.278 (2) | C4—C6 | 1.439 (3) |
O3—N4 | 1.237 (2) | C6—C7 | 1.345 (3) |
N1—C5 | 1.333 (2) | C6—H6 | 0.9500 |
N1—C1 | 1.360 (2) | C7—H7 | 0.9500 |
N2—C5 | 1.386 (2) | C8—C9 | 1.399 (3) |
N2—C8 | 1.403 (2) | C9—C10 | 1.377 (2) |
N2—C7 | 1.419 (2) | C9—H9 | 0.9500 |
N3—C8 | 1.355 (2) | C10—C9i | 1.377 (2) |
N3—C8i | 1.355 (2) | C10—H10 | 0.9500 |
C1—C2 | 1.377 (3) | ||
N1—Cu—N1i | 176.05 (8) | C1—C2—H2 | 119.5 |
N1—Cu—N3 | 91.97 (4) | C3—C2—H2 | 119.5 |
N1i—Cu—N3 | 91.97 (4) | C2—C3—C4 | 116.91 (19) |
N1—Cu—O2i | 86.84 (6) | C2—C3—H3 | 121.5 |
N1i—Cu—O2i | 90.30 (6) | C4—C3—H3 | 121.5 |
N3—Cu—O2i | 136.42 (4) | C3—C4—C5 | 117.96 (17) |
N1—Cu—O2 | 90.30 (6) | C3—C4—C6 | 135.5 (2) |
N1i—Cu—O2 | 86.84 (6) | C5—C4—C6 | 106.52 (18) |
N3—Cu—O2 | 136.42 (4) | N1—C5—N2 | 125.88 (18) |
O2i—Cu—O2 | 87.16 (8) | N1—C5—C4 | 125.16 (18) |
N4—O2—Cu | 105.07 (12) | N2—C5—C4 | 108.95 (15) |
C5—N1—C1 | 115.69 (19) | C7—C6—C4 | 107.50 (18) |
C5—N1—Cu | 120.02 (14) | C7—C6—H6 | 126.2 |
C1—N1—Cu | 122.65 (14) | C4—C6—H6 | 126.2 |
C5—N2—C8 | 128.38 (15) | C6—C7—N2 | 110.51 (18) |
C5—N2—C7 | 106.46 (16) | C6—C7—H7 | 124.7 |
C8—N2—C7 | 122.50 (16) | N2—C7—H7 | 124.7 |
C8—N3—C8i | 116.7 (2) | N3—C8—C9 | 123.23 (18) |
C8—N3—Cu | 121.67 (11) | N3—C8—N2 | 119.28 (16) |
C8i—N3—Cu | 121.67 (11) | C9—C8—N2 | 117.48 (17) |
O3—N4—O1 | 122.1 (2) | C10—C9—C8 | 118.24 (19) |
O3—N4—O2 | 119.44 (19) | C10—C9—H9 | 120.9 |
O1—N4—O2 | 118.47 (18) | C8—C9—H9 | 120.9 |
N1—C1—C2 | 123.04 (19) | C9—C10—C9i | 120.1 (2) |
N1—C1—H1 | 118.5 | C9—C10—H10 | 119.9 |
C2—C1—H1 | 118.5 | C9i—C10—H10 | 119.9 |
C1—C2—C3 | 121.08 (19) | ||
N1—Cu—O2—N4 | 93.05 (13) | Cu—N1—C5—N2 | 16.6 (2) |
N1i—Cu—O2—N4 | −89.67 (13) | C1—N1—C5—C4 | 3.5 (3) |
N3—Cu—O2—N4 | −0.13 (15) | Cu—N1—C5—C4 | −162.30 (15) |
O2i—Cu—O2—N4 | 179.87 (15) | C8—N2—C5—N1 | 21.6 (3) |
N3—Cu—N1—C5 | −30.90 (15) | C7—N2—C5—N1 | −176.81 (19) |
O2i—Cu—N1—C5 | 105.49 (15) | C8—N2—C5—C4 | −159.28 (17) |
O2—Cu—N1—C5 | −167.37 (15) | C7—N2—C5—C4 | 2.26 (19) |
N3—Cu—N1—C1 | 164.33 (16) | C3—C4—C5—N1 | −4.6 (3) |
O2i—Cu—N1—C1 | −59.28 (17) | C6—C4—C5—N1 | 176.72 (18) |
O2—Cu—N1—C1 | 27.86 (17) | C3—C4—C5—N2 | 176.34 (16) |
N1—Cu—N3—C8 | 23.00 (10) | C6—C4—C5—N2 | −2.4 (2) |
N1i—Cu—N3—C8 | −157.00 (10) | C3—C4—C6—C7 | −176.8 (2) |
O2i—Cu—N3—C8 | −64.49 (10) | C5—C4—C6—C7 | 1.5 (2) |
O2—Cu—N3—C8 | 115.51 (10) | C4—C6—C7—N2 | −0.1 (2) |
N1—Cu—N3—C8i | −157.00 (10) | C5—N2—C7—C6 | −1.3 (2) |
N1i—Cu—N3—C8i | 23.00 (10) | C8—N2—C7—C6 | 161.57 (17) |
O2i—Cu—N3—C8i | 115.51 (10) | C8i—N3—C8—C9 | 2.47 (12) |
O2—Cu—N3—C8i | −64.49 (10) | Cu—N3—C8—C9 | −177.53 (12) |
Cu—O2—N4—O3 | 179.42 (15) | C8i—N3—C8—N2 | −178.74 (16) |
Cu—O2—N4—O1 | 0.5 (2) | Cu—N3—C8—N2 | 1.25 (16) |
C5—N1—C1—C2 | 0.3 (3) | C5—N2—C8—N3 | −30.3 (2) |
Cu—N1—C1—C2 | 165.64 (16) | C7—N2—C8—N3 | 170.78 (14) |
N1—C1—C2—C3 | −2.8 (3) | C5—N2—C8—C9 | 148.54 (17) |
C1—C2—C3—C4 | 1.6 (3) | C7—N2—C8—C9 | −10.4 (2) |
C2—C3—C4—C5 | 1.8 (3) | N3—C8—C9—C10 | −4.9 (2) |
C2—C3—C4—C6 | 180.0 (2) | N2—C8—C9—C10 | 176.34 (13) |
C1—N1—C5—N2 | −177.58 (17) | C8—C9—C10—C9i | 2.27 (11) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O1ii | 0.95 | 2.39 | 3.249 (3) | 150 |
C6—H6···O3iii | 0.95 | 2.53 | 3.277 (3) | 136 |
C7—H7···O3iv | 0.95 | 2.39 | 3.141 (2) | 135 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, y+1/2, z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C19H13N5 | (C19H14N5)[FeCl4] | [Cu(NO3)2(C19H13N5)] |
Mr | 311.34 | 510.00 | 498.90 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n | Monoclinic, C2/c |
Temperature (K) | 150 | 150 | 193 |
a, b, c (Å) | 6.6377 (2), 10.1397 (3), 21.9214 (6) | 6.6695 (1), 23.2657 (4), 13.3959 (2) | 17.3858 (12), 12.8324 (8), 8.4011 (6) |
α, β, γ (°) | 76.609 (1), 86.563 (10), 90.004 (1) | 90, 100.312 (1), 90 | 90, 94.726 (2), 90 |
V (Å3) | 1432.56 (7) | 2045.07 (6) | 1867.9 (2) |
Z | 4 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Synchrotron, λ = 0.77490 Å |
µ (mm−1) | 0.72 | 10.86 | 1.55 |
Crystal size (mm) | 0.35 × 0.10 × 0.05 | 0.19 × 0.04 × 0.02 | 0.06 × 0.04 × 0.04 |
Data collection | |||
Diffractometer | Bruker SMART 6000 CCD diffractometer | Bruker SMART 6000 CCD diffractometer | Bruker Platinum 200 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.787, 0.965 | 0.232, 0.812 | 0.913, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11609, 4847, 4215 | 17199, 3653, 3210 | 10400, 2319, 2155 |
Rint | 0.026 | 0.041 | 0.105 |
(sin θ/λ)max (Å−1) | 0.599 | 0.601 | 0.668 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.122, 1.06 | 0.029, 0.075, 1.04 | 0.052, 0.134, 1.01 |
No. of reflections | 4847 | 3653 | 2319 |
No. of parameters | 434 | 266 | 151 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.24 | 0.34, −0.25 | 0.65, −0.59 |
Computer programs: SMART (Bruker, 2003), APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2003), SHELXTL and DIAMOND (Brandenburg, 2007).
C5A—N2A—C8A—N3A | 176.4 (2) | C5B—N2B—C8B—N3B | 176.1 (2) |
C15A—N4A—C12A—N3A | −178.4 (2) | C15B—N4B—C12B—N3B | −179.4 (2) |
Fe—Cl4 | 2.1895 (7) | Fe—Cl2 | 2.1970 (6) |
Fe—Cl3 | 2.1949 (6) | Fe—Cl1 | 2.1985 (7) |
Cl4—Fe—Cl3 | 108.65 (3) | Cl4—Fe—Cl1 | 109.79 (3) |
Cl4—Fe—Cl2 | 110.34 (3) | Cl3—Fe—Cl1 | 108.45 (3) |
Cl3—Fe—Cl2 | 110.85 (3) | Cl2—Fe—Cl1 | 108.73 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H20···N5 | 0.89 (3) | 2.04 (3) | 2.873 (3) | 156 (2) |
C3—H3···Cl1i | 0.95 | 2.87 | 3.692 (2) | 146 |
C19—H19···Cl1ii | 0.95 | 2.88 | 3.718 (2) | 147 |
C13—H13···Cl2iii | 0.95 | 2.85 | 3.676 (2) | 146 |
C9—H9···Cl4 | 0.95 | 2.73 | 3.660 (2) | 168 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x, y, z−1; (iii) −x+1/2, y−1/2, −z+3/2. |
Cu—N1 | 1.963 (2) | Cu—O2 | 2.1746 (14) |
Cu—N3 | 2.117 (2) | ||
N1—Cu—N1i | 176.05 (8) | N1i—Cu—O2 | 86.84 (6) |
N1—Cu—N3 | 91.97 (4) | N3—Cu—O2 | 136.42 (4) |
N1—Cu—O2 | 90.30 (6) | O2i—Cu—O2 | 87.16 (8) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O1ii | 0.95 | 2.39 | 3.249 (3) | 150 |
C6—H6···O3iii | 0.95 | 2.53 | 3.277 (3) | 136 |
C7—H7···O3iv | 0.95 | 2.39 | 3.141 (2) | 135 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, y+1/2, z. |
Organometallic supramolecular structures and materials remain a popular area of interest because of their spectral and electrochemical properties, and are thus potentially useful as molecular devices, sensors and catalysts (James, 2003; Braga, 2003; Blake et al., 1999; Balzani & Juris, 2001). A plethora of geometric frameworks, dependent on the coordination preferences of the metal ion and the nature of the bridging ligand, have been reported (Moulton & Zaworotko, 2001). We were further inspired by the inorganic crystal engineering work reported by Mukherjee and coworkers (Mukherjee et al., 2003; Balamurugan et al., 2004), where C—H···Cl hydrogen bonding interactions proved a useful tool in forming supramolecular networks composed of [(L3)MnCl2(EtOH)] and [(L6)FeCl3] [L3 is 2-[3-(2'-pyridyl)pyrazol-1-ylmethyl]pyridine; L6 is methyl[2-(2-pyridyl)ethyl](2-pyridylmethyl)amine].
Our continuing research effort focuses on cyclometallating aryldiamine and polypyridyl ligands (i) as a mechanism to tune the electronic structure of square-planar platinum(II) and palladium(II) (Jude et al., 2005; Tastan et al., 2006), and (ii) as potential bridges to form more elaborate molecular architectures, such as triangles or larger polygons (Schweiger et al., 2001, 2002). Thus, an ongoing effort is to synthesize a library of appropriate ligands. The synthesis and structural characterization of 2,6-bis(azaindole)pyridine, (I) (bap), is described here. Furthermore, in addition to complexes with PtII and PdII, we would like to expand our studies to include other transition metals. In this report, we present our findings when FeIII and CuII salts are reacted with (I).
Compound (I) (Fig. 1) crystallizes with two independent molecules in the asymmetric unit. Both molecules adopt a trans,trans conformation (see Table 1). Similar torsion angles are observed for the monoclinic (Bowes et al., 2005) and orthorhombic forms (Bessel et al., 1992) of 2,2':6',2"-terpyridine (tpy) and 2,6-bis(5,6,7,8-tetrahydroquinol-2-yl)pyridine (the torsion angles about the Cquinolyl—Cpyridine bond are −168.5 and 165.7°; Sasaki et al., 1998). On the other hand, 1,3-bis(7-azaindolyl)benzene (bab; Wu et al., 2001) and 1-bromo-3,5-bis(7-azaindolyl)benzene (babBr; Song et al., 2001) crystallize with noncoplanar azaindolyl rings, giving rise to a curved conformation (the torsion angles about the Nazaindolyl—Cbenzene bonds are in the 20–45° range).
Self-assembly of FeCl3·6H2O with (I) forms the salt (bapH)FeCl4, (II) (Fig. 2). The bapH+ cation is protonated at atom N1. A typical intramolecular N—H···N hydrogen bond occurs between atoms N1 and N5 [N1···N5 = 2.873 (3) Å]. The through-space separations N1···N3 and N5···N3 are 2.722 (3) and 2.832 (2) Å, respectively. The presence of the intramolecular hydrogen bond causes a conformational change in the molecule, giving rise to a cis,cis conformation [the torsion angles about the Nazaindolyl—Cpyridine bonds are 3.8 (3) and 0.03 (3)°] with the azaindolyl rings essentially coplanar [the dihedral angles between the azaindolyl and pyridine rings are 3.32 (1) and 1.29 (1)°]. The Cl—Fe—Cl angles (Table 2) are consistent with tetrahedral geometry about the FeIII center. The Fe—Cl distances are comparable to those in related complexes containing the FeCl4− anion (for example, Zora et al., 1990; Chan & Baird, 2004; Lewis et al., 2002).
Weak C—H···Cl interactions (Aullón et al., 1998, Brammer et al., 2001), forming a zigzag network, are observed between the bapH+ cation and the FeCl4− anion (see Table 3). π-Stacked interactions between neighboring cations run down the a axis; the interleaved layers are separated by ~3.4 Å [every second layer is in register [please clarify what is meant by this] with a separation of 6.6695 (1) Å (the a axis cell length)]. Typical π–π interactions in organic compounds are less than 3.8 Å (Janiak, 2000).
Focused on forming square-planar complexes where (I) adopts a tridentate binding motif, we turned our attention to RuIII and CuII salts. Attempts to react (I) with RuCl3.nH2O failed to yield a product. However, reaction of Cu(NO3)2·3H2O with (I) resulted in the formation of (bap)Cu(NO3)2, (III) (Fig. 3a). The molecule crystallizes such that molecular and crystallographic twofold rotation symmetry coincide. The geometry about the CuII center is trigonal–bipyramidal, with an N3O2 environment. Both NO3− ions coordinate in a monodentate fashion through an O atom [Cu—O2 = 2.1746 (14) Å and Cu···O1 = 2.636 (2) Å]. Bond lengths and angles (see Table 4) are typical and comparable to those in [(phtpy)Cu(OH)(NO3)][(phtpy)Cu(NO3)2] (Kumar or Padhi & Manivannan, 2006) and (tpyBr2)Cu(NO3)2 (Lam et al., 2006). C—H···O interactions (see Table 5) give rise to a ribbon motif.
The bap ligand in (III) adopts a twisted, tridentate binding mode [C8—N3—Cu—N1 = 23.0 (1)°; Fig. 3b]. Perusal of the literature shows that the related structures [(tpyOH)Cu(OH2](ClO4)2 (Jeitler & Turnbull, 2005), [(phtpy)Cu(OH)(NO3)][(phtpy)Cu(NO3)2] (Kumar or Padhi & Manivannan, 2006) and (tpyBr2)Cu(NO3)2 (Lam et al., 2006) sport a tridentate-bound tpy ligand; however, the tpy rings are nearly planar (the C—N—M—N torsion angles are less than 6°). The chelate distortion from planarity in bap is echoed by the closely related bab and babR ligands in (bab)MCl and (babBr)MCl (M = Pd and Pt) (with twisted geometry, having C—N—M—N torsion angles in the range 20–34°; Song et al., 2001). For (babR)Re(CO)3 (R = H, F, CF3 and MeO) complexes, the chelate takes on a folded, butterfly geometry (Tani et al., 2004). Characteristic of these structures is the increased nonplanarity of the tridentate ligand (twist or butterfly conformations) as the progression tpy, tpyOH, tpyO, phtpy ~ tpyBr2 < bap, bab, bapR is made, consistent with a direct relationship between increased steric effects near the metal coordination plane and the degree of nonplanarity.