Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104029592/ga1088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104029592/ga1088IIsup2.hkl |
CCDC reference: 264788
For the preparation of ligand (I), 2-(aminomethyl)pyridine (2.88 g, 25.85 mmol) was added to a stirred solution of 2-carboxybenzaldehyde (4.00 g, 26.64 mmol) and NaOH (1.07 g, 26.64 mmol) in methanol (50 ml). The solution was refluxed at 323 K for 2 h, whereupon the solution turned yellow and was cooled in an ice-bath. Excess NaBH4 (1.24 g, 32.72 mmol) was added to the solution, and the yellow color slowly discharged. After stirring for 30 min, excess HCl was added until the pH of the solution was 5.0. The solution was filtered and the filtrate was evaporated to dryness. The residue was purified by silica gel column chromatography using CH3OH/CH2Cl2 (5:95) to give (I) (yield 4.4 g, 76%). For the preparation of (II), ligand (I) (0.07 g, 0.33 mmol) was added to a solution of [NEt4]2[Re(CO)3Br3] (0.25 g, 0.33 mmol) in methanol (30 ml), and the solution was refluxed for 2 h. After cooling to room temperature, the reaction mixture was evaporated to dryness. The residue was dissolved in a minimum amount of chloroform. Colorless crystals suitable for X-ray crystallography were obtained from the solution after 30 min (yield 0.15 g, 80%). Analysis found: C 35.6, H 2.23, N 4.76%; calculated: C 35.5, H 2.11, N 4.88%. IR (KBr, cm−1): ν 2026, 1997, 1868 {ν[fac-Re(CO)3]}.
All H atoms were located in difference Fourier maps and refined as riding on their parent atoms? (C—H = 0.93–0.77 Å), with Uiso(H) values of 1.2Ueq(parent atom). A residual peak of electron density (1.64 e Å−3) was located in the vicinity of the Re atom. However, the absorption correction could not be adjusted to further minimize this residual. Such residuals are not uncommon in structures containing atoms with large absorption coefficients.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT-NT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2000); software used to prepare material for publication: SHELXTL-NT.
[ReBr(C14H12N2O)(CO)3]·CH3OH | F(000) = 1152 |
Mr = 606.44 | Dx = 2.165 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6164 reflections |
a = 7.3195 (7) Å | θ = 1.8–31.5° |
b = 15.5186 (14) Å | µ = 8.71 mm−1 |
c = 16.4240 (15) Å | T = 90 K |
β = 94.182 (2)° | Block, colorless |
V = 1860.6 (3) Å3 | 0.24 × 0.14 × 0.10 mm |
Z = 4 |
Bruker SMART APEX CCD detector diffractometer | 6164 independent reflections |
Radiation source: fine-focus sealed tube | 5404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 512 pixels mm-1 | θmax = 31.5°, θmin = 1.8° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | k = −22→22 |
Tmin = 0.229, Tmax = 0.421 | l = −23→23 |
21761 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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0314P)2 + 0.1451P] where P = (Fo2 + 2Fc2)/3 |
6164 reflections | (Δ/σ)max = 0.002 |
246 parameters | Δρmax = 1.64 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
[ReBr(C14H12N2O)(CO)3]·CH3OH | V = 1860.6 (3) Å3 |
Mr = 606.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.3195 (7) Å | µ = 8.71 mm−1 |
b = 15.5186 (14) Å | T = 90 K |
c = 16.4240 (15) Å | 0.24 × 0.14 × 0.10 mm |
β = 94.182 (2)° |
Bruker SMART APEX CCD detector diffractometer | 6164 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 5404 reflections with I > 2σ(I) |
Tmin = 0.229, Tmax = 0.421 | Rint = 0.035 |
21761 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.64 e Å−3 |
6164 reflections | Δρmin = −0.81 e Å−3 |
246 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 | ||
Re1 | −0.130324 (16) | 0.846209 (7) | 0.092222 (7) | 0.01236 (4) | |
Br1 | −0.43226 (4) | 0.75261 (2) | 0.08734 (2) | 0.01835 (7) | |
N1 | −0.1569 (4) | 0.82914 (16) | −0.04347 (16) | 0.0138 (5) | |
N2 | 0.1569 (3) | 0.68839 (16) | −0.01211 (15) | 0.0127 (5) | |
O1 | −0.1306 (4) | 0.84466 (16) | 0.27846 (16) | 0.0289 (6) | |
O2 | 0.2191 (4) | 0.95403 (17) | 0.10857 (17) | 0.0307 (6) | |
O3 | −0.3282 (4) | 1.01925 (16) | 0.08551 (17) | 0.0307 (6) | |
O4 | 0.0020 (3) | 0.72027 (13) | 0.10224 (13) | 0.0143 (4) | |
O5 | 0.2457 (4) | 0.87471 (19) | 0.73288 (17) | 0.0288 (6) | |
H5 | 0.2404 | 0.8407 | 0.6946 | 0.043* | |
C1 | −0.1287 (5) | 0.8469 (2) | 0.2084 (2) | 0.0182 (6) | |
C2 | 0.0900 (5) | 0.9126 (2) | 0.1005 (2) | 0.0197 (6) | |
C3 | −0.2567 (5) | 0.9531 (2) | 0.0881 (2) | 0.0214 (7) | |
C4 | −0.3217 (4) | 0.8490 (2) | −0.08119 (19) | 0.0158 (6) | |
H4 | −0.4090 | 0.8742 | −0.0504 | 0.019* | |
C5 | −0.3674 (5) | 0.8337 (2) | −0.1629 (2) | 0.0190 (7) | |
H5A | −0.4834 | 0.8475 | −0.1861 | 0.023* | |
C6 | −0.2384 (5) | 0.7976 (2) | −0.2095 (2) | 0.0200 (7) | |
H6 | −0.2662 | 0.7856 | −0.2645 | 0.024* | |
C7 | −0.0666 (5) | 0.7795 (2) | −0.17272 (19) | 0.0182 (6) | |
H7 | 0.0236 | 0.7563 | −0.2033 | 0.022* | |
C8 | −0.0289 (4) | 0.79598 (19) | −0.09030 (19) | 0.0139 (6) | |
C9 | 0.1560 (4) | 0.77363 (19) | −0.04950 (18) | 0.0129 (5) | |
H9A | 0.2468 | 0.7754 | −0.0896 | 0.015* | |
H9B | 0.1895 | 0.8163 | −0.0079 | 0.015* | |
C10 | 0.0888 (4) | 0.67047 (19) | 0.05949 (18) | 0.0116 (5) | |
C11 | 0.1367 (4) | 0.58012 (19) | 0.08062 (18) | 0.0132 (5) | |
C12 | 0.2299 (4) | 0.54660 (19) | 0.01705 (19) | 0.0132 (5) | |
C13 | 0.2489 (4) | 0.61458 (19) | −0.04629 (19) | 0.0146 (6) | |
H13A | 0.3766 | 0.6271 | −0.0532 | 0.018* | |
H13B | 0.1891 | 0.5975 | −0.0984 | 0.018* | |
C14 | 0.1008 (4) | 0.5327 (2) | 0.14925 (19) | 0.0161 (6) | |
H14 | 0.0377 | 0.5564 | 0.1910 | 0.019* | |
C15 | 0.1638 (4) | 0.4480 (2) | 0.1526 (2) | 0.0175 (6) | |
H15 | 0.1461 | 0.4144 | 0.1983 | 0.021* | |
C16 | 0.2529 (4) | 0.4129 (2) | 0.0883 (2) | 0.0180 (6) | |
H16 | 0.2914 | 0.3558 | 0.0914 | 0.022* | |
C17 | 0.2859 (4) | 0.4610 (2) | 0.0195 (2) | 0.0166 (6) | |
H17 | 0.3437 | 0.4367 | −0.0236 | 0.020* | |
C18 | 0.1110 (5) | 0.9402 (2) | 0.7179 (2) | 0.0287 (8) | |
H18A | 0.0698 | 0.9598 | 0.7689 | 0.043* | |
H18B | 0.0092 | 0.9173 | 0.6846 | 0.043* | |
H18C | 0.1634 | 0.9876 | 0.6901 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.01328 (6) | 0.01081 (6) | 0.01285 (6) | 0.00211 (4) | 0.00001 (4) | −0.00170 (4) |
Br1 | 0.01366 (13) | 0.01971 (15) | 0.02155 (15) | −0.00052 (11) | 0.00033 (11) | 0.00112 (12) |
N1 | 0.0148 (12) | 0.0106 (11) | 0.0158 (12) | 0.0008 (9) | −0.0005 (9) | 0.0007 (9) |
N2 | 0.0130 (11) | 0.0106 (11) | 0.0144 (12) | 0.0021 (9) | 0.0014 (9) | −0.0008 (9) |
O1 | 0.0413 (16) | 0.0287 (14) | 0.0171 (12) | 0.0037 (12) | 0.0040 (11) | −0.0011 (10) |
O2 | 0.0283 (13) | 0.0245 (14) | 0.0393 (16) | −0.0083 (11) | 0.0020 (12) | −0.0052 (12) |
O3 | 0.0382 (15) | 0.0211 (13) | 0.0320 (15) | 0.0138 (12) | −0.0019 (12) | −0.0024 (11) |
O4 | 0.0144 (10) | 0.0124 (10) | 0.0166 (10) | 0.0037 (8) | 0.0032 (8) | 0.0000 (8) |
O5 | 0.0233 (12) | 0.0341 (15) | 0.0285 (14) | 0.0000 (11) | −0.0024 (11) | −0.0064 (12) |
C1 | 0.0188 (15) | 0.0133 (14) | 0.0222 (16) | 0.0037 (12) | 0.0002 (12) | −0.0024 (12) |
C2 | 0.0244 (16) | 0.0159 (15) | 0.0187 (16) | 0.0030 (13) | 0.0016 (12) | −0.0024 (12) |
C3 | 0.0228 (16) | 0.0212 (17) | 0.0197 (16) | 0.0051 (13) | −0.0012 (12) | −0.0037 (13) |
C4 | 0.0152 (13) | 0.0160 (15) | 0.0161 (14) | 0.0032 (11) | 0.0001 (11) | 0.0006 (11) |
C5 | 0.0175 (14) | 0.0196 (16) | 0.0188 (15) | 0.0007 (12) | −0.0059 (12) | 0.0073 (12) |
C6 | 0.0257 (16) | 0.0211 (16) | 0.0126 (14) | 0.0004 (13) | −0.0036 (12) | 0.0026 (12) |
C7 | 0.0220 (15) | 0.0197 (16) | 0.0132 (14) | 0.0016 (12) | 0.0034 (11) | 0.0039 (12) |
C8 | 0.0162 (13) | 0.0113 (13) | 0.0144 (14) | 0.0003 (11) | 0.0032 (11) | 0.0019 (11) |
C9 | 0.0126 (12) | 0.0127 (13) | 0.0135 (13) | −0.0006 (10) | 0.0022 (10) | 0.0031 (11) |
C10 | 0.0090 (12) | 0.0114 (13) | 0.0141 (13) | −0.0013 (10) | −0.0007 (10) | 0.0000 (10) |
C11 | 0.0100 (12) | 0.0132 (13) | 0.0158 (14) | 0.0013 (10) | −0.0020 (10) | −0.0021 (11) |
C12 | 0.0102 (12) | 0.0107 (13) | 0.0184 (14) | 0.0020 (10) | −0.0009 (10) | 0.0003 (11) |
C13 | 0.0128 (13) | 0.0151 (14) | 0.0161 (14) | 0.0024 (11) | 0.0018 (11) | −0.0014 (11) |
C14 | 0.0170 (14) | 0.0152 (14) | 0.0160 (14) | −0.0001 (11) | 0.0005 (11) | 0.0014 (11) |
C15 | 0.0171 (14) | 0.0144 (14) | 0.0207 (15) | 0.0002 (12) | −0.0003 (11) | 0.0040 (12) |
C16 | 0.0136 (13) | 0.0123 (14) | 0.0276 (17) | 0.0003 (11) | −0.0009 (12) | −0.0015 (12) |
C17 | 0.0129 (13) | 0.0140 (14) | 0.0226 (15) | 0.0038 (11) | 0.0006 (11) | −0.0033 (12) |
C18 | 0.0308 (19) | 0.0226 (18) | 0.033 (2) | 0.0050 (15) | 0.0016 (15) | 0.0023 (15) |
Re1—C3 | 1.898 (3) | C7—C8 | 1.385 (4) |
Re1—C1 | 1.907 (3) | C7—H7 | 0.9300 |
Re1—C2 | 1.910 (4) | C8—C9 | 1.506 (4) |
Re1—O4 | 2.182 (2) | C9—H9A | 0.9700 |
Re1—N1 | 2.239 (3) | C9—H9B | 0.9700 |
Re1—Br1 | 2.6409 (4) | C10—C11 | 1.480 (4) |
N1—C4 | 1.351 (4) | C11—C14 | 1.387 (4) |
N1—C8 | 1.356 (4) | C11—C12 | 1.389 (4) |
N2—C10 | 1.340 (4) | C12—C17 | 1.390 (4) |
N2—C9 | 1.458 (4) | C12—C13 | 1.495 (4) |
N2—C13 | 1.461 (4) | C13—H13A | 0.9700 |
O1—C1 | 1.152 (4) | C13—H13B | 0.9700 |
O2—C2 | 1.143 (4) | C14—C15 | 1.394 (4) |
O3—C3 | 1.151 (4) | C14—H14 | 0.9300 |
O4—C10 | 1.248 (3) | C15—C16 | 1.392 (5) |
O5—C18 | 1.425 (4) | C15—H15 | 0.9300 |
O5—H5 | 0.8200 | C16—C17 | 1.389 (5) |
C4—C5 | 1.380 (4) | C16—H16 | 0.9300 |
C4—H4 | 0.9300 | C17—H17 | 0.9300 |
C5—C6 | 1.377 (5) | C18—H18A | 0.9600 |
C5—H5A | 0.9300 | C18—H18B | 0.9600 |
C6—C7 | 1.384 (4) | C18—H18C | 0.9600 |
C6—H6 | 0.9300 | ||
C3—Re1—C1 | 89.90 (14) | C7—C8—C9 | 120.0 (3) |
C3—Re1—C2 | 86.44 (14) | N2—C9—C8 | 111.9 (2) |
C1—Re1—C2 | 88.95 (14) | N2—C9—H9A | 109.2 |
C3—Re1—O4 | 176.30 (12) | C8—C9—H9A | 109.2 |
C1—Re1—O4 | 87.68 (11) | N2—C9—H9B | 109.2 |
C2—Re1—O4 | 96.31 (11) | C8—C9—H9B | 109.2 |
C3—Re1—N1 | 93.49 (12) | H9A—C9—H9B | 107.9 |
C1—Re1—N1 | 172.06 (12) | O4—C10—N2 | 127.0 (3) |
C2—Re1—N1 | 98.41 (12) | O4—C10—C11 | 125.2 (3) |
O4—Re1—N1 | 88.56 (9) | N2—C10—C11 | 107.8 (3) |
C3—Re1—Br1 | 94.30 (11) | C14—C11—C12 | 123.0 (3) |
C1—Re1—Br1 | 88.73 (10) | C14—C11—C10 | 129.6 (3) |
C2—Re1—Br1 | 177.57 (10) | C12—C11—C10 | 107.4 (3) |
O4—Re1—Br1 | 82.85 (6) | C11—C12—C17 | 119.7 (3) |
N1—Re1—Br1 | 83.86 (7) | C11—C12—C13 | 109.5 (3) |
C4—N1—C8 | 117.2 (3) | C17—C12—C13 | 130.7 (3) |
C4—N1—Re1 | 116.1 (2) | N2—C13—C12 | 102.5 (2) |
C8—N1—Re1 | 126.6 (2) | N2—C13—H13A | 111.3 |
C10—N2—C9 | 124.6 (3) | C12—C13—H13A | 111.3 |
C10—N2—C13 | 112.7 (2) | N2—C13—H13B | 111.3 |
C9—N2—C13 | 122.5 (2) | C12—C13—H13B | 111.3 |
C10—O4—Re1 | 138.9 (2) | H13A—C13—H13B | 109.2 |
C18—O5—H5 | 109.5 | C11—C14—C15 | 116.8 (3) |
O1—C1—Re1 | 177.7 (3) | C11—C14—H14 | 121.6 |
O2—C2—Re1 | 176.9 (3) | C15—C14—H14 | 121.6 |
O3—C3—Re1 | 177.8 (3) | C16—C15—C14 | 120.7 (3) |
N1—C4—C5 | 123.5 (3) | C16—C15—H15 | 119.6 |
N1—C4—H4 | 118.2 | C14—C15—H15 | 119.6 |
C5—C4—H4 | 118.2 | C17—C16—C15 | 121.7 (3) |
C6—C5—C4 | 118.9 (3) | C17—C16—H16 | 119.1 |
C6—C5—H5A | 120.6 | C15—C16—H16 | 119.1 |
C4—C5—H5A | 120.6 | C16—C17—C12 | 117.9 (3) |
C5—C6—C7 | 118.5 (3) | C16—C17—H17 | 121.0 |
C5—C6—H6 | 120.7 | C12—C17—H17 | 121.0 |
C7—C6—H6 | 120.7 | O5—C18—H18A | 109.5 |
C6—C7—C8 | 119.9 (3) | O5—C18—H18B | 109.5 |
C6—C7—H7 | 120.0 | H18A—C18—H18B | 109.5 |
C8—C7—H7 | 120.0 | O5—C18—H18C | 109.5 |
N1—C8—C7 | 121.9 (3) | H18A—C18—H18C | 109.5 |
N1—C8—C9 | 118.1 (3) | H18B—C18—H18C | 109.5 |
C3—Re1—N1—C4 | −42.7 (2) | C7—C8—C9—N2 | −93.7 (3) |
C2—Re1—N1—C4 | −129.6 (2) | Re1—O4—C10—N2 | 11.6 (5) |
O4—Re1—N1—C4 | 134.2 (2) | Re1—O4—C10—C11 | −169.3 (2) |
Br1—Re1—N1—C4 | 51.2 (2) | C9—N2—C10—O4 | 6.2 (5) |
C3—Re1—N1—C8 | 141.8 (3) | C13—N2—C10—O4 | −179.1 (3) |
C2—Re1—N1—C8 | 54.9 (3) | C9—N2—C10—C11 | −173.1 (2) |
O4—Re1—N1—C8 | −41.2 (2) | C13—N2—C10—C11 | 1.6 (3) |
Br1—Re1—N1—C8 | −124.2 (2) | O4—C10—C11—C14 | −0.9 (5) |
C1—Re1—O4—C10 | −163.6 (3) | N2—C10—C11—C14 | 178.3 (3) |
C2—Re1—O4—C10 | −74.9 (3) | O4—C10—C11—C12 | 179.0 (3) |
N1—Re1—O4—C10 | 23.4 (3) | N2—C10—C11—C12 | −1.8 (3) |
Br1—Re1—O4—C10 | 107.4 (3) | C14—C11—C12—C17 | 2.2 (4) |
C8—N1—C4—C5 | 2.9 (5) | C10—C11—C12—C17 | −177.7 (3) |
Re1—N1—C4—C5 | −173.0 (2) | C14—C11—C12—C13 | −178.9 (3) |
N1—C4—C5—C6 | −1.1 (5) | C10—C11—C12—C13 | 1.2 (3) |
C4—C5—C6—C7 | −1.2 (5) | C10—N2—C13—C12 | −0.9 (3) |
C5—C6—C7—C8 | 1.4 (5) | C9—N2—C13—C12 | 174.0 (2) |
C4—N1—C8—C7 | −2.6 (4) | C11—C12—C13—N2 | −0.3 (3) |
Re1—N1—C8—C7 | 172.8 (2) | C17—C12—C13—N2 | 178.5 (3) |
C4—N1—C8—C9 | 179.9 (3) | C12—C11—C14—C15 | 0.3 (4) |
Re1—N1—C8—C9 | −4.7 (4) | C10—C11—C14—C15 | −179.8 (3) |
C6—C7—C8—N1 | 0.5 (5) | C11—C14—C15—C16 | −2.0 (4) |
C6—C7—C8—C9 | 178.0 (3) | C14—C15—C16—C17 | 1.4 (5) |
C10—N2—C9—C8 | −78.5 (3) | C15—C16—C17—C12 | 1.1 (5) |
C13—N2—C9—C8 | 107.3 (3) | C11—C12—C17—C16 | −2.8 (4) |
N1—C8—C9—N2 | 83.9 (3) | C13—C12—C17—C16 | 178.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···Br1i | 0.82 | 2.54 | 3.296 (3) | 153 |
C4—H4···O3ii | 0.93 | 2.57 | 3.275 (4) | 133 |
C5—H5A···O5iii | 0.93 | 2.34 | 3.263 (5) | 169 |
C14—H14···O5iv | 0.93 | 2.53 | 3.351 (4) | 147 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x−1, −y+2, −z; (iii) x−1, y, z−1; (iv) x−1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [ReBr(C14H12N2O)(CO)3]·CH3OH |
Mr | 606.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 7.3195 (7), 15.5186 (14), 16.4240 (15) |
β (°) | 94.182 (2) |
V (Å3) | 1860.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.71 |
Crystal size (mm) | 0.24 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.229, 0.421 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21761, 6164, 5404 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.735 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.063, 1.04 |
No. of reflections | 6164 |
No. of parameters | 246 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.64, −0.81 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT-NT (Bruker, 2000), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Bruker, 2000), SHELXTL-NT.
Re1—C3 | 1.898 (3) | Re1—O4 | 2.182 (2) |
Re1—C1 | 1.907 (3) | Re1—N1 | 2.239 (3) |
Re1—C2 | 1.910 (4) | Re1—Br1 | 2.6409 (4) |
C3—Re1—C1 | 89.90 (14) | C2—Re1—N1 | 98.41 (12) |
C3—Re1—C2 | 86.44 (14) | O4—Re1—N1 | 88.56 (9) |
C1—Re1—C2 | 88.95 (14) | C3—Re1—Br1 | 94.30 (11) |
C3—Re1—O4 | 176.30 (12) | C1—Re1—Br1 | 88.73 (10) |
C1—Re1—O4 | 87.68 (11) | C2—Re1—Br1 | 177.57 (10) |
C2—Re1—O4 | 96.31 (11) | O4—Re1—Br1 | 82.85 (6) |
C3—Re1—N1 | 93.49 (12) | N1—Re1—Br1 | 83.86 (7) |
C1—Re1—N1 | 172.06 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···Br1i | 0.82 | 2.54 | 3.296 (3) | 153 |
C4—H4···O3ii | 0.93 | 2.57 | 3.275 (4) | 133 |
C5—H5A···O5iii | 0.93 | 2.34 | 3.263 (5) | 169 |
C14—H14···O5iv | 0.93 | 2.53 | 3.351 (4) | 147 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x−1, −y+2, −z; (iii) x−1, y, z−1; (iv) x−1/2, −y+3/2, z−1/2. |
The ligand 2-pyridin-2-yl-methyl-2,3-dihydro-isoindol-1-one [C14H12N2O, (I)] was an unexpected product from the reaction of 2-(aminomethyl) pyridine with 2-carboxybenzaldehyde, NaOH and sodium borohydride in methanol (see scheme). Following the literature procedure (Li et al., 2003; Musie et al., 2003), we attempted to prepare N-(2-methylpyridine)-2-aminomethyl benzoic acid, (III). Although one equivalent of NaOH was added to protect the carboxylic acid group, a coupling reaction between the carboxylic acid group and the primary amine group occurred, forming intermediate 1. Condensation of the carboxyaldehyde and the amine group of 1 provided Schiff base 2, which upon reduction using sodium borohydride in methanol gave the ligand (I). Complex (II) was synthesized upon refluxing a methanol solution of the common Re(I)–tricarbonyl starting material [NEt4]2[Re(CO)3Br3] (Alberto et al., 1994) with (I). The structure of complex (II) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1.
The ligand adopts a bidentate coordination mode through the pyridine N atom and the ketone O atom to form an unusual seven-membered chelate ring. The formation of the seven-membered ring illustrates the flexibility of the ligand. The ligand folds at the methylene group adjacent to the pyridine ring (C9), thus providing appropriate chelate bite distances and angles. The Re—Ccarbonyl bond distances [1.898 (3)–1.910 (4) Å] are consistent with those found in other Re–tricarbonyl complexes (Banerjee et al., 2002; Wei et al., 2004; Moya et al., 1994). The Re—Br [2.6409 (4) Å] and Re—Npyridine [2.239 (3) Å] bond lengths are comparable to those of 6-coordinated Re compounds with ligands trans to carbonyl groups (Banerjee et al., 2002; Wei et al., 2004). For example, in [Re(CO)3Br{(2-pyridylmethyl)NH2}] and [Re(CO)3Br{(2-pyridylmethyl)NH(2-thiophenemethyl)}], the average Re—Br and Re—Npyridine bond distances are 2.636 (6) Å and 2.190 (4) Å, respectively (Banerjee et al., 2002). The C10=O4 bond length in (II) [1.248 (3) Å] is as expected for a C=O double bond. The Re—O bond distance [2.182 (2) Å] lies within the range of the bond lengths between Re and ketone O atoms reported previously (Creber et al., 2000; Wang et al., 2003; Jiménez et al., 2001). The cis and trans angles fall in the ranges 82.85 (6)–98.41 (12) and 172.06 (12)–177.57 (10)°, respectively, showing minor deviations from the idealized octahedral limits. The steric requirement of the CO ligands is manifested in the mean C—Re—N and C—Re—O cis angles of 94.0 (4)° and in the mean C—Re—N and C—Re—O trans angles of 174.2 (1)°.
The crystal packing consists of antiparallel stacks of (II), with a network of hydrogen bonds between the methanol solvate and adjacent fac-[Re(CO)3Br(C14H12N2O)] molecules (Table 2). This arrangement leads to the formation of a classical intramolecular O—H···Br hydrogen bond and intermolecular non-classical C—H···O hydrogen bonds (Fig. 2). The bond distances and angles of the hydrogen bonds are of the same order as those reported in other compounds containing such bonds (Bakir, 2001; Bakir, 2002; Correia et al., 2001). For example, in fac-[ReCl(C17H13N5O2)(CO)3]·C2H6OS (Bakir, 2001), hydrogen bonds with O—H and O—C distances of 2.47—2.55 and 3.183 (7)–3.436 (7) Å, respectively, and C—H···O angles of 142–174° are observed.