Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107020914/hj3036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107020914/hj3036Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107020914/hj3036IIsup3.hkl |
CCDC references: 652502; 652503
2,2'-Bipyridine-6,6'-dicarboxylic acid (122 mg, 0.5 mmol) and concentrated sulfuric acid (0.5 ml) in methanol (20 ml) were heated at reflux for 3 d. The solvent was reduced to half the original volume and cooled, causing dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (100 mg, 75%) to precipitate as a white crystalline solid. Single crystals suitable for X-ray diffraction were grown by slow cooling of a methanolic solution of the ester. Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 8.75 (d, 2H), 8.16 (d, 2H), 8.00 (t, 2H), 4.04 (s, 6H); 13 C NMR (CDCl3, δ, p.p.m.): 166.1, 155.9, 146.0, 138.5, 125.9, 125.3, 53.3; ES–MS: m/z 273 (M+ + H); IR (KBr disc, ν, cm-1): 3476 (s), 1740 (m), 1636 (m), 1580 (m), 1295 (w), 1252 (m), 1146 (m), 831 (w), 765 (m), 703 (m), 629 (m).
Dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (13.5 mg, 0.05 mmol) in dichloromethane (5 ml) and [Cu(MeCN)4](BF4) (8 mg, 0.025 mmol) in acetonitrile (5 ml) were stirred together at room temperature for ca 30 min. The solvents were removed to give the product as a dark-red solid (15 mg). Single crystals of (II) were obtained by slow diffusion of [Diethyl?] ether into a chloroform solution of the complex. Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 8.71 (d, 4H), 8.18 (m, 6H), 1.94 (s, 12H); FAB-MS: m/z 607 (M+), 335 (M+ - L); IR (KBr disc, ν, cm-1): 3503 (s), 1730 (s), 1635 (m), 1592 (m), 1447 (w), 1372 (w), 1336 (m), 1310 (w), 1296 (w), 1264 (w), 1137 (w), 1116 (m), 1076 (s), 769 (m), 721 (w), 701 (w), 668 (w), 630 (w).
H atoms were included in geometrically calculated positions, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for the pyridyl CH, and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for the methyl H atoms, and constrained as part of a riding model.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL. Software used to prepare material for publication: enCIFer (Allen et al., 2004) and PLATON (Spek, 2003) for (I); SHELXL97 and PLATON (Spek, 2003) for (II).
C14H12N2O4 | F(000) = 284 |
Mr = 272.26 | Dx = 1.509 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4182 (15) Å | Cell parameters from 1954 reflections |
b = 6.8889 (11) Å | θ = 2.6–27.5° |
c = 9.7931 (15) Å | µ = 0.11 mm−1 |
β = 109.448 (2)° | T = 150 K |
V = 599.1 (3) Å3 | Hexagonal prism, colourless |
Z = 2 | 0.67 × 0.61 × 0.21 mm |
Bruker SMART1000 CCD area-detector diffractometer | 1167 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 27.5°, θmin = 2.6° |
ω scans | h = −12→10 |
3716 measured reflections | k = −8→5 |
1360 independent reflections | l = −12→12 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0629P)2 + 0.0616P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.113 | (Δ/σ)max = 0.001 |
S = 1.13 | Δρmax = 0.41 e Å−3 |
1360 reflections | Δρmin = −0.22 e Å−3 |
92 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.015 (5) |
Primary atom site location: structure-invariant direct methods |
C14H12N2O4 | V = 599.1 (3) Å3 |
Mr = 272.26 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4182 (15) Å | µ = 0.11 mm−1 |
b = 6.8889 (11) Å | T = 150 K |
c = 9.7931 (15) Å | 0.67 × 0.61 × 0.21 mm |
β = 109.448 (2)° |
Bruker SMART1000 CCD area-detector diffractometer | 1167 reflections with I > 2σ(I) |
3716 measured reflections | Rint = 0.057 |
1360 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.41 e Å−3 |
1360 reflections | Δρmin = −0.22 e Å−3 |
92 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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.19692 (9) | 0.43661 (14) | 0.56343 (10) | 0.0176 (3) | |
C2 | 0.07443 (11) | 0.55029 (15) | 0.52528 (11) | 0.0166 (3) | |
C3 | 0.08300 (13) | 0.75356 (16) | 0.53162 (13) | 0.0200 (3) | |
H3 | −0.0061 | 0.8299 | 0.5020 | 0.024* | |
C4 | 0.22295 (13) | 0.84109 (16) | 0.58167 (13) | 0.0209 (3) | |
H4 | 0.2316 | 0.9785 | 0.5868 | 0.025* | |
C5 | 0.35080 (12) | 0.72472 (16) | 0.62438 (12) | 0.0196 (3) | |
H5 | 0.4485 | 0.7804 | 0.6606 | 0.023* | |
C6 | 0.33170 (11) | 0.52426 (16) | 0.61262 (11) | 0.0173 (3) | |
C7 | 0.46470 (12) | 0.38823 (17) | 0.65597 (12) | 0.0183 (3) | |
O8 | 0.45856 (9) | 0.21621 (12) | 0.63260 (10) | 0.0273 (3) | |
O9 | 0.59166 (8) | 0.48458 (12) | 0.72497 (9) | 0.0234 (3) | |
C10 | 0.72757 (13) | 0.36866 (17) | 0.77504 (14) | 0.0233 (3) | |
H8A | 0.8136 | 0.4527 | 0.8235 | 0.035* | |
H8B | 0.7440 | 0.3046 | 0.6922 | 0.035* | |
H8D | 0.7170 | 0.2703 | 0.8433 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0141 (5) | 0.0153 (5) | 0.0236 (5) | 0.0001 (3) | 0.0065 (4) | 0.0001 (4) |
C2 | 0.0144 (6) | 0.0143 (5) | 0.0216 (5) | −0.0003 (4) | 0.0068 (4) | 0.0003 (4) |
C3 | 0.0158 (5) | 0.0148 (5) | 0.0295 (6) | 0.0023 (4) | 0.0076 (4) | 0.0009 (5) |
C4 | 0.0212 (6) | 0.0130 (5) | 0.0294 (6) | −0.0006 (4) | 0.0095 (4) | −0.0006 (4) |
C5 | 0.0148 (5) | 0.0175 (6) | 0.0261 (6) | −0.0029 (4) | 0.0063 (4) | −0.0015 (4) |
C6 | 0.0140 (5) | 0.0164 (5) | 0.0219 (6) | 0.0007 (4) | 0.0066 (4) | −0.0001 (4) |
C7 | 0.0154 (5) | 0.0161 (6) | 0.0236 (6) | −0.0005 (4) | 0.0069 (4) | 0.0001 (4) |
O8 | 0.0183 (4) | 0.0150 (5) | 0.0452 (6) | 0.0006 (3) | 0.0063 (4) | −0.0041 (4) |
O9 | 0.0126 (4) | 0.0149 (4) | 0.0389 (5) | 0.0011 (3) | 0.0034 (3) | −0.0012 (3) |
C10 | 0.0141 (5) | 0.0178 (6) | 0.0349 (6) | 0.0034 (4) | 0.0040 (4) | 0.0013 (5) |
N1—C2 | 1.3405 (14) | C5—H5 | 0.9500 |
N1—C6 | 1.3419 (13) | C6—C7 | 1.5077 (15) |
C2—C3 | 1.4028 (15) | C7—O8 | 1.2046 (15) |
C2—C2i | 1.493 (2) | C7—O9 | 1.3375 (13) |
C3—C4 | 1.3824 (16) | O9—C10 | 1.4486 (13) |
C3—H3 | 0.9500 | C10—H8A | 0.9800 |
C4—C5 | 1.3900 (16) | C10—H8B | 0.9800 |
C4—H4 | 0.9500 | C10—H8D | 0.9800 |
C5—C6 | 1.3924 (15) | ||
C2—N1—C6 | 117.43 (9) | N1—C6—C5 | 123.82 (10) |
N1—C2—C3 | 122.64 (9) | N1—C6—C7 | 114.79 (9) |
N1—C2—C2i | 116.57 (12) | C5—C6—C7 | 121.39 (9) |
C3—C2—C2i | 120.79 (11) | O8—C7—O9 | 124.22 (10) |
C4—C3—C2 | 119.02 (10) | O8—C7—C6 | 125.11 (9) |
C4—C3—H3 | 120.5 | O9—C7—C6 | 110.67 (9) |
C2—C3—H3 | 120.5 | C7—O9—C10 | 115.98 (9) |
C3—C4—C5 | 118.90 (10) | O9—C10—H8A | 109.5 |
C3—C4—H4 | 120.5 | O9—C10—H8B | 109.5 |
C5—C4—H4 | 120.5 | H8A—C10—H8B | 109.5 |
C4—C5—C6 | 118.16 (10) | O9—C10—H8D | 109.5 |
C4—C5—H5 | 120.9 | H8A—C10—H8D | 109.5 |
C6—C5—H5 | 120.9 | H8B—C10—H8D | 109.5 |
C6—N1—C2—C3 | 1.65 (16) | C4—C5—C6—N1 | −0.53 (17) |
C6—N1—C2—C2i | −178.37 (11) | C4—C5—C6—C7 | 179.69 (10) |
N1—C2—C3—C4 | −1.24 (17) | N1—C6—C7—O8 | 9.84 (16) |
C2i—C2—C3—C4 | 178.77 (12) | C5—C6—C7—O8 | −170.36 (11) |
C2—C3—C4—C5 | −0.11 (17) | N1—C6—C7—O9 | −169.94 (9) |
C3—C4—C5—C6 | 0.94 (17) | C5—C6—C7—O9 | 9.86 (14) |
C2—N1—C6—C5 | −0.76 (16) | O8—C7—O9—C10 | −1.02 (16) |
C2—N1—C6—C7 | 179.04 (9) | C6—C7—O9—C10 | 178.76 (9) |
Symmetry code: (i) −x, −y+1, −z+1. |
[Cu(C14H12N2O4)2]BF4 | F(000) = 1416 |
Mr = 694.86 | Dx = 1.591 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.777 (2) Å | Cell parameters from 2605 reflections |
b = 27.434 (6) Å | θ = 3.1–23.2° |
c = 13.965 (3) Å | µ = 0.84 mm−1 |
β = 103.254 (3)° | T = 150 K |
V = 2900.1 (12) Å3 | Triangular prism, purple |
Z = 4 | 0.26 × 0.22 × 0.07 mm |
Bruker SMART1000 CCD area-detector diffractometer | 5406 independent reflections |
Radiation source: sealed tube | 3654 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 26.1°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker 2001) | h = −9→9 |
Tmin = 0.812, Tmax = 0.944 | k = −30→33 |
14165 measured reflections | l = −17→16 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0527P)2 + 5.7924P] where P = (Fo2 + 2Fc2)/3 |
5406 reflections | (Δ/σ)max = 0.001 |
415 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Cu(C14H12N2O4)2]BF4 | V = 2900.1 (12) Å3 |
Mr = 694.86 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.777 (2) Å | µ = 0.84 mm−1 |
b = 27.434 (6) Å | T = 150 K |
c = 13.965 (3) Å | 0.26 × 0.22 × 0.07 mm |
β = 103.254 (3)° |
Bruker SMART1000 CCD area-detector diffractometer | 5406 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 2001) | 3654 reflections with I > 2σ(I) |
Tmin = 0.812, Tmax = 0.944 | Rint = 0.048 |
14165 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.85 e Å−3 |
5406 reflections | Δρmin = −0.57 e Å−3 |
415 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 | ||
Cu1 | 0.61325 (7) | 0.146688 (18) | 0.61022 (4) | 0.02274 (16) | |
N1 | 0.6341 (4) | 0.08238 (12) | 0.5420 (2) | 0.0212 (8) | |
C2 | 0.7036 (5) | 0.04740 (15) | 0.6083 (3) | 0.0230 (9) | |
C3 | 0.7691 (6) | 0.00345 (15) | 0.5809 (3) | 0.0284 (10) | |
H3A | 0.8204 | −0.0199 | 0.6293 | 0.034* | |
C4 | 0.7580 (6) | −0.00556 (16) | 0.4827 (3) | 0.0310 (11) | |
H4A | 0.8035 | −0.0350 | 0.4626 | 0.037* | |
C5 | 0.6805 (6) | 0.02849 (16) | 0.4137 (3) | 0.0276 (10) | |
H5A | 0.6686 | 0.0225 | 0.3454 | 0.033* | |
C6 | 0.6204 (6) | 0.07167 (15) | 0.4461 (3) | 0.0229 (9) | |
N7 | 0.7186 (4) | 0.10672 (12) | 0.7361 (2) | 0.0198 (8) | |
C8 | 0.7126 (6) | 0.05902 (15) | 0.7133 (3) | 0.0232 (9) | |
C9 | 0.7114 (6) | 0.02268 (17) | 0.7825 (3) | 0.0320 (11) | |
H9A | 0.7098 | −0.0107 | 0.7643 | 0.038* | |
C10 | 0.7123 (7) | 0.03579 (18) | 0.8776 (3) | 0.0384 (12) | |
H10A | 0.7091 | 0.0116 | 0.9258 | 0.046* | |
C11 | 0.7179 (6) | 0.08461 (17) | 0.9024 (3) | 0.0345 (11) | |
H11A | 0.7178 | 0.0946 | 0.9675 | 0.041* | |
C12 | 0.7238 (6) | 0.11857 (16) | 0.8303 (3) | 0.0238 (10) | |
C13 | 0.5394 (6) | 0.10976 (17) | 0.3722 (3) | 0.0236 (10) | |
O14 | 0.5523 (4) | 0.15309 (11) | 0.3849 (2) | 0.0306 (7) | |
O15 | 0.4485 (4) | 0.08837 (11) | 0.2905 (2) | 0.0326 (8) | |
C16 | 0.3791 (7) | 0.12001 (18) | 0.2074 (3) | 0.0379 (12) | |
H16A | 0.3155 | 0.1004 | 0.1518 | 0.057* | |
H16B | 0.4768 | 0.1372 | 0.1886 | 0.057* | |
H16C | 0.2981 | 0.1438 | 0.2257 | 0.057* | |
C17 | 0.7368 (6) | 0.17135 (16) | 0.8596 (3) | 0.0262 (10) | |
O18 | 0.6949 (4) | 0.18574 (12) | 0.9327 (2) | 0.0378 (8) | |
O19 | 0.8037 (4) | 0.19936 (11) | 0.7991 (2) | 0.0289 (7) | |
C20 | 0.8168 (6) | 0.25045 (16) | 0.8245 (3) | 0.0324 (11) | |
H20A | 0.8673 | 0.2683 | 0.7766 | 0.049* | |
H20B | 0.8931 | 0.2545 | 0.8904 | 0.049* | |
H20C | 0.6989 | 0.2633 | 0.8238 | 0.049* | |
N1' | 0.4228 (4) | 0.19077 (12) | 0.6488 (2) | 0.0208 (8) | |
C2' | 0.4482 (5) | 0.23856 (15) | 0.6346 (3) | 0.0217 (9) | |
C3' | 0.3551 (6) | 0.27486 (16) | 0.6706 (3) | 0.0270 (10) | |
H3'A | 0.3741 | 0.3082 | 0.6581 | 0.032* | |
C4' | 0.2347 (6) | 0.26162 (17) | 0.7246 (3) | 0.0324 (11) | |
H4'A | 0.1712 | 0.2858 | 0.7511 | 0.039* | |
C5' | 0.2076 (6) | 0.21257 (16) | 0.7398 (3) | 0.0284 (10) | |
H5'A | 0.1242 | 0.2026 | 0.7760 | 0.034* | |
C6' | 0.3037 (6) | 0.17838 (15) | 0.7014 (3) | 0.0236 (10) | |
N7' | 0.6923 (5) | 0.21254 (12) | 0.5688 (2) | 0.0222 (8) | |
C8' | 0.5888 (5) | 0.25011 (16) | 0.5818 (3) | 0.0225 (9) | |
C9' | 0.6166 (6) | 0.29705 (15) | 0.5497 (3) | 0.0256 (10) | |
H9'A | 0.5428 | 0.3232 | 0.5598 | 0.031* | |
C10' | 0.7519 (6) | 0.30489 (17) | 0.5033 (3) | 0.0320 (11) | |
H10B | 0.7731 | 0.3367 | 0.4815 | 0.038* | |
C11' | 0.8577 (6) | 0.26616 (16) | 0.4886 (3) | 0.0286 (10) | |
H11B | 0.9515 | 0.2708 | 0.4563 | 0.034* | |
C12' | 0.8225 (6) | 0.22063 (15) | 0.5221 (3) | 0.0228 (9) | |
C13' | 0.2813 (5) | 0.12446 (16) | 0.7154 (3) | 0.0249 (10) | |
O14' | 0.3282 (4) | 0.09342 (11) | 0.6673 (2) | 0.0286 (7) | |
O15' | 0.2051 (4) | 0.11643 (11) | 0.7912 (2) | 0.0325 (8) | |
C16' | 0.1783 (7) | 0.06533 (18) | 0.8105 (4) | 0.0452 (14) | |
H16D | 0.1222 | 0.0625 | 0.8664 | 0.068* | |
H16E | 0.2926 | 0.0485 | 0.8260 | 0.068* | |
H16F | 0.1020 | 0.0504 | 0.7522 | 0.068* | |
C17' | 0.9326 (6) | 0.17690 (16) | 0.5110 (3) | 0.0262 (10) | |
O18' | 0.9474 (4) | 0.14162 (11) | 0.5630 (2) | 0.0287 (7) | |
O19' | 1.0148 (4) | 0.18273 (11) | 0.4373 (2) | 0.0343 (8) | |
C20' | 1.1190 (7) | 0.14104 (18) | 0.4209 (4) | 0.0383 (12) | |
H20D | 1.1756 | 0.1481 | 0.3665 | 0.057* | |
H20E | 1.0420 | 0.1125 | 0.4044 | 0.057* | |
H20F | 1.2099 | 0.1343 | 0.4807 | 0.057* | |
B1 | 1.1467 (8) | −0.0783 (2) | 0.8171 (5) | 0.0447 (16) | |
F1 | 1.0588 (5) | −0.10343 (14) | 0.8740 (3) | 0.0748 (11) | |
F2 | 1.2880 (5) | −0.05292 (13) | 0.8718 (2) | 0.0702 (11) | |
F3 | 1.0419 (5) | −0.04841 (13) | 0.7514 (2) | 0.0753 (11) | |
F4 | 1.2087 (5) | −0.11437 (14) | 0.7590 (3) | 0.0775 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0302 (3) | 0.0158 (3) | 0.0232 (3) | 0.0024 (2) | 0.0082 (2) | 0.0003 (2) |
N1 | 0.0206 (18) | 0.0198 (19) | 0.0228 (19) | −0.0018 (15) | 0.0046 (15) | −0.0026 (15) |
C2 | 0.025 (2) | 0.020 (2) | 0.023 (2) | −0.0026 (19) | 0.0024 (18) | −0.0015 (18) |
C3 | 0.036 (3) | 0.016 (2) | 0.029 (2) | 0.0033 (19) | 0.001 (2) | 0.0021 (18) |
C4 | 0.036 (3) | 0.022 (2) | 0.033 (3) | 0.006 (2) | 0.002 (2) | −0.006 (2) |
C5 | 0.034 (3) | 0.026 (3) | 0.023 (2) | 0.003 (2) | 0.007 (2) | −0.0065 (19) |
C6 | 0.026 (2) | 0.022 (2) | 0.022 (2) | −0.0023 (18) | 0.0069 (18) | 0.0004 (17) |
N7 | 0.0220 (19) | 0.0176 (19) | 0.0189 (18) | −0.0011 (15) | 0.0026 (15) | −0.0025 (14) |
C8 | 0.028 (2) | 0.020 (2) | 0.020 (2) | 0.0005 (19) | 0.0030 (18) | −0.0020 (17) |
C9 | 0.046 (3) | 0.021 (2) | 0.027 (3) | −0.001 (2) | 0.004 (2) | 0.0029 (19) |
C10 | 0.057 (3) | 0.030 (3) | 0.029 (3) | −0.002 (2) | 0.012 (2) | 0.012 (2) |
C11 | 0.048 (3) | 0.034 (3) | 0.021 (2) | −0.004 (2) | 0.006 (2) | −0.002 (2) |
C12 | 0.024 (2) | 0.022 (2) | 0.024 (2) | 0.0005 (19) | 0.0026 (18) | 0.0000 (18) |
C13 | 0.024 (2) | 0.027 (3) | 0.021 (2) | −0.0014 (19) | 0.0085 (18) | −0.0031 (18) |
O14 | 0.0443 (19) | 0.0214 (19) | 0.0226 (16) | 0.0034 (14) | 0.0006 (14) | −0.0022 (13) |
O15 | 0.045 (2) | 0.0237 (17) | 0.0234 (17) | −0.0043 (15) | −0.0039 (14) | 0.0002 (13) |
C16 | 0.054 (3) | 0.031 (3) | 0.022 (2) | 0.000 (2) | −0.005 (2) | 0.005 (2) |
C17 | 0.027 (2) | 0.029 (3) | 0.020 (2) | 0.002 (2) | −0.0015 (19) | −0.0018 (19) |
O18 | 0.051 (2) | 0.034 (2) | 0.0327 (19) | 0.0078 (16) | 0.0184 (16) | −0.0067 (15) |
O19 | 0.0361 (18) | 0.0211 (17) | 0.0298 (17) | −0.0034 (14) | 0.0082 (14) | −0.0071 (13) |
C20 | 0.039 (3) | 0.021 (2) | 0.033 (3) | −0.002 (2) | 0.000 (2) | −0.006 (2) |
N1' | 0.0231 (19) | 0.0182 (19) | 0.0209 (18) | −0.0003 (15) | 0.0044 (15) | −0.0015 (14) |
C2' | 0.023 (2) | 0.021 (2) | 0.019 (2) | 0.0016 (18) | 0.0005 (18) | 0.0007 (17) |
C3' | 0.034 (3) | 0.016 (2) | 0.030 (2) | 0.0044 (19) | 0.008 (2) | −0.0016 (18) |
C4' | 0.037 (3) | 0.025 (3) | 0.035 (3) | 0.012 (2) | 0.009 (2) | −0.004 (2) |
C5' | 0.031 (3) | 0.028 (3) | 0.027 (2) | 0.004 (2) | 0.010 (2) | −0.0042 (19) |
C6' | 0.025 (2) | 0.022 (2) | 0.023 (2) | 0.0008 (18) | 0.0031 (19) | −0.0033 (18) |
N7' | 0.027 (2) | 0.022 (2) | 0.0154 (18) | −0.0043 (16) | 0.0004 (15) | −0.0019 (14) |
C8' | 0.024 (2) | 0.024 (2) | 0.016 (2) | 0.0012 (19) | −0.0011 (17) | −0.0045 (17) |
C9' | 0.034 (3) | 0.019 (2) | 0.022 (2) | 0.0014 (19) | 0.001 (2) | −0.0024 (18) |
C10' | 0.046 (3) | 0.022 (3) | 0.026 (3) | −0.005 (2) | 0.005 (2) | 0.0034 (19) |
C11' | 0.035 (3) | 0.026 (3) | 0.026 (2) | −0.004 (2) | 0.010 (2) | −0.0029 (19) |
C12' | 0.029 (2) | 0.022 (2) | 0.017 (2) | −0.0041 (19) | 0.0053 (18) | −0.0020 (17) |
C13' | 0.019 (2) | 0.025 (2) | 0.029 (2) | 0.0003 (19) | 0.0033 (19) | 0.000 (2) |
O14' | 0.0294 (17) | 0.0231 (17) | 0.0342 (18) | −0.0029 (13) | 0.0089 (14) | −0.0059 (14) |
O15' | 0.042 (2) | 0.0219 (17) | 0.0385 (19) | −0.0018 (15) | 0.0189 (16) | 0.0025 (14) |
C16' | 0.052 (3) | 0.027 (3) | 0.063 (4) | −0.003 (2) | 0.027 (3) | 0.008 (2) |
C17' | 0.022 (2) | 0.028 (3) | 0.026 (2) | −0.0012 (19) | 0.0021 (19) | −0.001 (2) |
O18' | 0.0273 (16) | 0.0293 (19) | 0.0304 (17) | 0.0025 (14) | 0.0086 (14) | 0.0053 (14) |
O19' | 0.0415 (19) | 0.0322 (19) | 0.0372 (19) | 0.0027 (15) | 0.0257 (16) | 0.0031 (14) |
C20' | 0.044 (3) | 0.034 (3) | 0.043 (3) | 0.008 (2) | 0.023 (2) | 0.001 (2) |
B1 | 0.041 (4) | 0.050 (4) | 0.040 (4) | −0.010 (3) | 0.003 (3) | 0.009 (3) |
F1 | 0.084 (3) | 0.078 (3) | 0.060 (2) | −0.036 (2) | 0.012 (2) | 0.0071 (19) |
F2 | 0.076 (2) | 0.075 (3) | 0.052 (2) | −0.037 (2) | −0.0005 (18) | 0.0027 (18) |
F3 | 0.100 (3) | 0.055 (2) | 0.056 (2) | 0.023 (2) | −0.012 (2) | 0.0161 (18) |
F4 | 0.072 (3) | 0.060 (2) | 0.103 (3) | 0.002 (2) | 0.026 (2) | −0.008 (2) |
Cu1—N1 | 2.029 (3) | N1'—C2' | 1.347 (5) |
Cu1—N7' | 2.035 (3) | N1'—C6' | 1.351 (5) |
Cu1—N7 | 2.074 (3) | C2'—C3' | 1.392 (6) |
Cu1—N1' | 2.077 (3) | C2'—C8' | 1.486 (6) |
N1—C6 | 1.351 (5) | C3'—C4' | 1.379 (6) |
N1—C2 | 1.356 (5) | C3'—H3'A | 0.9500 |
C2—C3 | 1.396 (6) | C4'—C5' | 1.386 (6) |
C2—C8 | 1.487 (6) | C4'—H4'A | 0.9500 |
C3—C4 | 1.377 (6) | C5'—C6' | 1.382 (6) |
C3—H3A | 0.9500 | C5'—H5'A | 0.9500 |
C4—C5 | 1.378 (6) | C6'—C13' | 1.507 (6) |
C4—H4A | 0.9500 | N7'—C12' | 1.342 (5) |
C5—C6 | 1.387 (6) | N7'—C8' | 1.345 (5) |
C5—H5A | 0.9500 | C8'—C9' | 1.397 (6) |
C6—C13 | 1.502 (6) | C9'—C10' | 1.373 (6) |
N7—C8 | 1.345 (5) | C9'—H9'A | 0.9500 |
N7—C12 | 1.347 (5) | C10'—C11' | 1.388 (6) |
C8—C9 | 1.390 (6) | C10'—H10B | 0.9500 |
C9—C10 | 1.375 (6) | C11'—C12' | 1.383 (6) |
C9—H9A | 0.9500 | C11'—H11B | 0.9500 |
C10—C11 | 1.382 (7) | C12'—C17' | 1.502 (6) |
C10—H10A | 0.9500 | C13'—O14' | 1.193 (5) |
C11—C12 | 1.380 (6) | C13'—O15' | 1.345 (5) |
C11—H11A | 0.9500 | O15'—C16' | 1.452 (5) |
C12—C17 | 1.502 (6) | C16'—H16D | 0.9800 |
C13—O14 | 1.203 (5) | C16'—H16E | 0.9800 |
C13—O15 | 1.333 (5) | C16'—H16F | 0.9800 |
O15—C16 | 1.450 (5) | C17'—O18' | 1.199 (5) |
C16—H16A | 0.9800 | C17'—O19' | 1.340 (5) |
C16—H16B | 0.9800 | O19'—C20' | 1.450 (5) |
C16—H16C | 0.9800 | C20'—H20D | 0.9800 |
C17—O18 | 1.207 (5) | C20'—H20E | 0.9800 |
C17—O19 | 1.333 (5) | C20'—H20F | 0.9800 |
O19—C20 | 1.444 (5) | B1—F1 | 1.350 (7) |
C20—H20A | 0.9800 | B1—F3 | 1.355 (7) |
C20—H20B | 0.9800 | B1—F2 | 1.375 (7) |
C20—H20C | 0.9800 | B1—F4 | 1.432 (8) |
N1—Cu1—N7' | 125.21 (13) | C2'—N1'—C6' | 117.9 (3) |
N1—Cu1—N7 | 83.09 (13) | C2'—N1'—Cu1 | 113.0 (3) |
N7'—Cu1—N7 | 128.60 (13) | C6'—N1'—Cu1 | 127.8 (3) |
N1—Cu1—N1' | 140.05 (13) | N1'—C2'—C3' | 122.4 (4) |
N7'—Cu1—N1' | 80.61 (13) | N1'—C2'—C8' | 115.5 (4) |
N7—Cu1—N1' | 104.76 (13) | C3'—C2'—C8' | 122.0 (4) |
C6—N1—C2 | 116.8 (3) | C4'—C3'—C2' | 119.0 (4) |
C6—N1—Cu1 | 131.1 (3) | C4'—C3'—H3'A | 120.5 |
C2—N1—Cu1 | 110.9 (3) | C2'—C3'—H3'A | 120.5 |
N1—C2—C3 | 122.5 (4) | C3'—C4'—C5' | 119.0 (4) |
N1—C2—C8 | 116.3 (4) | C3'—C4'—H4'A | 120.5 |
C3—C2—C8 | 121.2 (4) | C5'—C4'—H4'A | 120.5 |
C4—C3—C2 | 119.0 (4) | C6'—C5'—C4' | 119.0 (4) |
C4—C3—H3A | 120.5 | C6'—C5'—H5'A | 120.5 |
C2—C3—H3A | 120.5 | C4'—C5'—H5'A | 120.5 |
C3—C4—C5 | 119.5 (4) | N1'—C6'—C5' | 122.6 (4) |
C3—C4—H4A | 120.2 | N1'—C6'—C13' | 115.5 (4) |
C5—C4—H4A | 120.2 | C5'—C6'—C13' | 121.8 (4) |
C4—C5—C6 | 118.5 (4) | C12'—N7'—C8' | 118.7 (4) |
C4—C5—H5A | 120.8 | C12'—N7'—Cu1 | 126.6 (3) |
C6—C5—H5A | 120.8 | C8'—N7'—Cu1 | 114.4 (3) |
N1—C6—C5 | 123.6 (4) | N7'—C8'—C9' | 121.4 (4) |
N1—C6—C13 | 117.1 (4) | N7'—C8'—C2' | 115.8 (4) |
C5—C6—C13 | 119.3 (4) | C9'—C8'—C2' | 122.8 (4) |
C8—N7—C12 | 117.2 (4) | C10'—C9'—C8' | 119.2 (4) |
C8—N7—Cu1 | 109.2 (3) | C10'—C9'—H9'A | 120.4 |
C12—N7—Cu1 | 128.2 (3) | C8'—C9'—H9'A | 120.4 |
N7—C8—C9 | 122.6 (4) | C9'—C10'—C11' | 119.6 (4) |
N7—C8—C2 | 115.7 (4) | C9'—C10'—H10B | 120.2 |
C9—C8—C2 | 121.7 (4) | C11'—C10'—H10B | 120.2 |
C10—C9—C8 | 119.0 (4) | C12'—C11'—C10' | 118.1 (4) |
C10—C9—H9A | 120.5 | C12'—C11'—H11B | 120.9 |
C8—C9—H9A | 120.5 | C10'—C11'—H11B | 120.9 |
C9—C10—C11 | 119.2 (4) | N7'—C12'—C11' | 122.9 (4) |
C9—C10—H10A | 120.4 | N7'—C12'—C17' | 115.4 (4) |
C11—C10—H10A | 120.4 | C11'—C12'—C17' | 121.6 (4) |
C12—C11—C10 | 118.4 (4) | O14'—C13'—O15' | 125.0 (4) |
C12—C11—H11A | 120.8 | O14'—C13'—C6' | 124.6 (4) |
C10—C11—H11A | 120.8 | O15'—C13'—C6' | 110.3 (4) |
N7—C12—C11 | 123.5 (4) | C13'—O15'—C16' | 114.4 (4) |
N7—C12—C17 | 118.9 (4) | O15'—C16'—H16D | 109.5 |
C11—C12—C17 | 117.6 (4) | O15'—C16'—H16E | 109.5 |
O14—C13—O15 | 124.8 (4) | H16D—C16'—H16E | 109.5 |
O14—C13—C6 | 125.4 (4) | O15'—C16'—H16F | 109.5 |
O15—C13—C6 | 109.8 (4) | H16D—C16'—H16F | 109.5 |
C13—O15—C16 | 116.6 (3) | H16E—C16'—H16F | 109.5 |
O15—C16—H16A | 109.5 | O18'—C17'—O19' | 124.3 (4) |
O15—C16—H16B | 109.5 | O18'—C17'—C12' | 124.1 (4) |
H16A—C16—H16B | 109.5 | O19'—C17'—C12' | 111.6 (4) |
O15—C16—H16C | 109.5 | C17'—O19'—C20' | 114.2 (3) |
H16A—C16—H16C | 109.5 | O19'—C20'—H20D | 109.5 |
H16B—C16—H16C | 109.5 | O19'—C20'—H20E | 109.5 |
O18—C17—O19 | 124.6 (4) | H20D—C20'—H20E | 109.5 |
O18—C17—C12 | 122.1 (4) | O19'—C20'—H20F | 109.5 |
O19—C17—C12 | 113.2 (4) | H20D—C20'—H20F | 109.5 |
C17—O19—C20 | 114.8 (3) | H20E—C20'—H20F | 109.5 |
O19—C20—H20A | 109.5 | F1—B1—F3 | 113.6 (5) |
O19—C20—H20B | 109.5 | F1—B1—F2 | 112.3 (5) |
H20A—C20—H20B | 109.5 | F3—B1—F2 | 110.5 (5) |
O19—C20—H20C | 109.5 | F1—B1—F4 | 105.2 (5) |
H20A—C20—H20C | 109.5 | F3—B1—F4 | 105.2 (5) |
H20B—C20—H20C | 109.5 | F2—B1—F4 | 109.6 (5) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C14H12N2O4 | [Cu(C14H12N2O4)2]BF4 |
Mr | 272.26 | 694.86 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 9.4182 (15), 6.8889 (11), 9.7931 (15) | 7.777 (2), 27.434 (6), 13.965 (3) |
β (°) | 109.448 (2) | 103.254 (3) |
V (Å3) | 599.1 (3) | 2900.1 (12) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.84 |
Crystal size (mm) | 0.67 × 0.61 × 0.21 | 0.26 × 0.22 × 0.07 |
Data collection | ||
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | – | Multi-scan (SADABS; Bruker 2001) |
Tmin, Tmax | – | 0.812, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3716, 1360, 1167 | 14165, 5406, 3654 |
Rint | 0.057 | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 | 0.618 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.113, 1.13 | 0.054, 0.137, 1.03 |
No. of reflections | 1360 | 5406 |
No. of parameters | 92 | 415 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.22 | 0.85, −0.57 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT and SHELXTL (Bruker, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL, enCIFer (Allen et al., 2004) and PLATON (Spek, 2003), SHELXL97 and PLATON (Spek, 2003).
As a part of our ongoing studies of multi-modal ligands for the construction of coordination polymers (Oxtoby et al., 2002, 2003, 2005; Thébault et al., 2006), we have prepared a diester-substituted 2,2'-bipyridyl ligand and a copper(I) complex that serve as potentially useful building blocks for subsequent synthetic procedures.
The diester-substituted 2,2'-bipyridyl molecule, dimethyl 2,2'-bipyridine-6,6'-dicarboxylate, (I), was synthesized by an HCl-catalysed esterification method in MeOH. Single-crystal X-ray diffraction confirmed the identity of the product and demonstrated the lower energy conformation commonly adopted by uncoordinated 2,2'-bipyridyl systems, which has the pyridyl N atoms adopting an anti arrangement to avoid repulsive interactions between the nitrogen lone pairs. The entire molecule is almost planar in the solid state. An inversion centre between atoms C2 and C2i [symmetry code: (i) -x, 1 - y, 1 - z] ensures coplanarity of the two pyridyl rings, with the two ester groups exhibiting a slight deviation from the plane formed by the bipyridyl moiety with an N1—C6—C7—O8 torsion angle of 9.84 (16)° (Fig. 1).
Compound (I) was complexed to copper(I) in a 2:1 ligand:metal ratio via reaction of [Cu(MeCN)4]BF4 with the ligand in MeCN–CH2Cl2, to give bis(dimethyl 2,2'-bipyridine-6,6'-dicarboxylate)copper(I) tetrafluoroborate, (II). The crystal structure of (II) (Fig. 2) confirms the anticipated coordination environment in which the metal centre is coordinated solely by the bipyridyl moieties, with the ester groups not participating in metal coordination.
In the structure of (II), there are two short Cu—N bonds of 2.029 (3) and 2.035 (3) Å for Cu—N1 and Cu—N7', respectively, and two slightly longer bonds of 2.074 (3) and 2.077 (3) Å for Cu—N7 and Cu—N1', respectively. Three of the ester carbonyl O atoms point towards the CuI centre but no significant interactions are present; the Cu···O distances are longer than 2.8 Å, the combined sum of the van der Waals radii (Standard reference?).
This copper(I) complex adopts a distorted tetrahedral geometry, with an angle of 70° between the planes defined by the two bipyridyl units. This distortion is only slightly greater than the comparable angles observed in bis(2,2'-bipyridine)copper(I) perchlorate (76°; Munakata et al., 1987) and bis(2,2'-bipyridine)copper(I) trifluoromethanesulfonate (85°; Tomislav, 2006). Steric interactions between the bulkier dimethyl 2,2'-biypyridine-6,6'-dicarboxlyate ligands may account for the slight increase in the distortion of the relatively malleable tetrahedral CuI coordination environment.
By comparison with the crystal structure of the free ligand, (I), it can be seen that the ligand in (II) adopts a different conformation on complexation, as anticipated, allowing chelation of the metal centre by the bipyridyl species. The coplanarity of the pyridyl rings of the free ligand is also lost on complexation, with an increase in the distortion of the ester groups with respect to the pyridyl rings, resulting from the increased steric constraints of the complex. The C═O and C—O bond lengths of the ester groups in both the free and complexed ligand show no significant deviation, further supporting the absence of ester complexation.
It is interesting to compare the twisted arrangement of the dimethyl 2,2'-bipyridine-6,6'-dicarboxylate ligand in (II) with previously reported examples. Two N—C—C—N torsion angles of 10.4 (5) and 25.1 (6)° are observed for these ligands in complex (II), revealing a significantly greater twist than observed in the three structures of metal complexes of dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (Anderberg et al., 2002; Kinnunen et al., 2000, 2002) reported prior to this study (average C—N—N—C torsion angles ca 5°). The twist in (II) is also greater than that observed in bis(2,2'-bipyridine)copper(I) trifluoromethanesulfonate (Tomislav, 2006) and the analogous perchlorate salt (Munakata et al., 1987), in which the 2,2'-bipyridine ligands remain essentially planar with average C—N—N—C torsion angles of 2.9 and 1.8°, respectively.
In summary, two single-crystal X-ray structures of dimethyl 2,2'-bipyridine-6,6'-dicarboxylate and its copper(I) complex, bis(dimethyl 2,2'-bipyridine-6,6'-dicarboxylate)copper(I) tetrafluoroborate, are reported and the relative twisting of the bipyridyl moiety compared.