Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105012497/sk1836sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105012497/sk1836Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105012497/sk1836IIsup3.hkl |
CCDC references: 275503; 275504
For the preparation of complex (I), salicylaldehyde (0.1 mmol, 12.2 mg) and 1,3-diaminopropane (0.1 mmol, 7.4 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution, to which was added an aqueous solution (2 ml) of NaN3 (0.1 mmol, 6.5 mg) and an MeOH solution (Volume?) of Co(ClO4)3·7H2O (0.1 mmol, 48.3 mg), with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 10 d, brown block-shaped crystals of (I) were formed. Complex (II) was prepared by a similar procedure to that described for (I), with NaN3 replaced by NH4NCS (0.1 mmol, 7.6 mg). Brown block-shaped crystals of (II) were obtained after evaporating the solvents from the filtrate in air for 8 d.
All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C). There were 1495 Friedel pairs measured for (I) and 1470 for (II).
For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Co(C17H16N2)(N3)] | F(000) = 784 |
Mr = 381.28 | Dx = 1.585 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 3722 reflections |
a = 11.930 (2) Å | θ = 2.5–27.5° |
b = 11.931 (3) Å | µ = 1.10 mm−1 |
c = 11.225 (2) Å | T = 298 K |
V = 1597.7 (6) Å3 | Block, brown |
Z = 4 | 0.32 × 0.28 × 0.19 mm |
Bruker SMART CCD area-detector diffractometer | 3234 independent reflections |
Radiation source: fine-focus sealed tube | 2932 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 26.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.721, Tmax = 0.819 | k = −13→14 |
8835 measured reflections | l = −13→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0889P)2 + 0.1907P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3234 reflections | Δρmax = 0.80 e Å−3 |
227 parameters | Δρmin = −0.42 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.13 (2) |
[Co(C17H16N2)(N3)] | V = 1597.7 (6) Å3 |
Mr = 381.28 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 11.930 (2) Å | µ = 1.10 mm−1 |
b = 11.931 (3) Å | T = 298 K |
c = 11.225 (2) Å | 0.32 × 0.28 × 0.19 mm |
Bruker SMART CCD area-detector diffractometer | 3234 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2932 reflections with I > 2σ(I) |
Tmin = 0.721, Tmax = 0.819 | Rint = 0.030 |
8835 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.130 | Δρmax = 0.80 e Å−3 |
S = 1.07 | Δρmin = −0.42 e Å−3 |
3234 reflections | Absolute structure: Flack (1983) |
227 parameters | Absolute structure parameter: 0.13 (2) |
1 restraint |
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 | ||
Co1 | 0.52548 (4) | 0.09636 (4) | 0.76504 (7) | 0.03257 (17) | |
O1 | 0.6456 (2) | −0.0035 (2) | 0.7474 (3) | 0.0381 (7) | |
O2 | 0.6198 (2) | 0.2029 (2) | 0.6893 (3) | 0.0356 (6) | |
N1 | 0.4254 (2) | −0.0269 (3) | 0.8354 (3) | 0.0278 (7) | |
N2 | 0.4087 (2) | 0.2180 (3) | 0.7820 (3) | 0.0282 (7) | |
N3 | 0.4395 (3) | 0.0439 (3) | 0.5849 (3) | 0.0385 (8) | |
N4 | 0.4335 (2) | −0.0369 (3) | 0.5261 (3) | 0.0320 (7) | |
N5 | 0.4268 (3) | −0.1167 (3) | 0.4637 (4) | 0.0441 (9) | |
C1 | 0.5503 (3) | −0.1773 (3) | 0.7702 (5) | 0.0374 (8) | |
C2 | 0.6414 (3) | −0.1144 (3) | 0.7354 (3) | 0.0361 (9) | |
C3 | 0.7350 (4) | −0.1693 (4) | 0.6863 (4) | 0.0484 (11) | |
H3 | 0.7980 | −0.1284 | 0.6641 | 0.058* | |
C4 | 0.7329 (5) | −0.2834 (4) | 0.6712 (5) | 0.0567 (14) | |
H4 | 0.7946 | −0.3190 | 0.6375 | 0.068* | |
C5 | 0.6429 (6) | −0.3458 (4) | 0.7043 (5) | 0.0678 (17) | |
H5 | 0.6429 | −0.4230 | 0.6927 | 0.081* | |
C6 | 0.5538 (4) | −0.2952 (3) | 0.7541 (7) | 0.0554 (13) | |
H6 | 0.4931 | −0.3384 | 0.7785 | 0.066* | |
C7 | 0.4519 (3) | −0.1301 (4) | 0.8273 (4) | 0.0367 (9) | |
H7 | 0.4025 | −0.1809 | 0.8619 | 0.044* | |
C8 | 0.3263 (3) | −0.0020 (4) | 0.9090 (4) | 0.0359 (9) | |
H8A | 0.3504 | 0.0113 | 0.9903 | 0.043* | |
H8B | 0.2775 | −0.0671 | 0.9094 | 0.043* | |
C9 | 0.2604 (3) | 0.0982 (3) | 0.8663 (4) | 0.0382 (9) | |
H9A | 0.2396 | 0.0863 | 0.7837 | 0.046* | |
H9B | 0.1919 | 0.1036 | 0.9123 | 0.046* | |
C10 | 0.3228 (3) | 0.2075 (4) | 0.8759 (4) | 0.0379 (9) | |
H10A | 0.2701 | 0.2692 | 0.8692 | 0.046* | |
H10B | 0.3584 | 0.2123 | 0.9534 | 0.046* | |
C11 | 0.4034 (3) | 0.3036 (3) | 0.7148 (4) | 0.0313 (8) | |
H11 | 0.3400 | 0.3484 | 0.7224 | 0.038* | |
C12 | 0.4856 (3) | 0.3386 (3) | 0.6282 (4) | 0.0330 (8) | |
C13 | 0.5919 (3) | 0.2884 (3) | 0.6227 (3) | 0.0301 (7) | |
C14 | 0.6726 (3) | 0.3365 (4) | 0.5465 (4) | 0.0375 (9) | |
H14 | 0.7443 | 0.3060 | 0.5429 | 0.045* | |
C15 | 0.6466 (4) | 0.4281 (4) | 0.4773 (4) | 0.0456 (10) | |
H15 | 0.7009 | 0.4585 | 0.4274 | 0.055* | |
C16 | 0.5400 (4) | 0.4761 (5) | 0.4809 (5) | 0.0540 (13) | |
H16 | 0.5224 | 0.5370 | 0.4327 | 0.065* | |
C17 | 0.4611 (4) | 0.4316 (4) | 0.5574 (5) | 0.0425 (10) | |
H17 | 0.3903 | 0.4642 | 0.5618 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0263 (3) | 0.0406 (3) | 0.0308 (3) | −0.00003 (17) | 0.0030 (2) | 0.0014 (3) |
O1 | 0.0259 (11) | 0.0388 (13) | 0.0496 (19) | 0.0064 (10) | 0.0070 (13) | 0.0042 (14) |
O2 | 0.0236 (11) | 0.0413 (14) | 0.0418 (16) | −0.0016 (10) | 0.0054 (11) | 0.0118 (13) |
N1 | 0.0234 (14) | 0.0431 (17) | 0.0169 (16) | −0.0040 (13) | −0.0032 (11) | 0.0050 (12) |
N2 | 0.0207 (12) | 0.0390 (14) | 0.0248 (18) | 0.0016 (11) | 0.0028 (13) | −0.0070 (13) |
N3 | 0.0369 (18) | 0.053 (2) | 0.0252 (18) | 0.0019 (16) | 0.0016 (14) | −0.0034 (16) |
N4 | 0.0258 (15) | 0.050 (2) | 0.0204 (16) | −0.0008 (14) | 0.0063 (13) | 0.0032 (15) |
N5 | 0.043 (2) | 0.056 (2) | 0.033 (2) | −0.0118 (18) | 0.0104 (17) | −0.0005 (17) |
C1 | 0.0413 (19) | 0.0426 (18) | 0.0283 (19) | 0.0075 (15) | −0.012 (2) | 0.001 (2) |
C2 | 0.037 (2) | 0.048 (2) | 0.023 (2) | 0.0134 (17) | −0.0043 (14) | 0.0037 (15) |
C3 | 0.043 (2) | 0.076 (3) | 0.026 (2) | 0.024 (2) | 0.0010 (18) | 0.005 (2) |
C4 | 0.074 (3) | 0.062 (3) | 0.033 (2) | 0.039 (3) | −0.013 (2) | −0.007 (2) |
C5 | 0.095 (4) | 0.048 (3) | 0.061 (3) | 0.027 (3) | −0.033 (3) | −0.011 (2) |
C6 | 0.064 (3) | 0.0362 (19) | 0.066 (4) | 0.0056 (19) | −0.020 (3) | −0.002 (3) |
C7 | 0.0351 (19) | 0.043 (2) | 0.032 (2) | −0.0107 (18) | −0.0048 (18) | 0.0080 (18) |
C8 | 0.0267 (17) | 0.053 (2) | 0.0283 (19) | −0.0056 (17) | 0.0043 (16) | 0.0037 (17) |
C9 | 0.0226 (18) | 0.064 (3) | 0.0276 (19) | −0.0042 (16) | 0.0023 (16) | 0.0086 (17) |
C10 | 0.0316 (19) | 0.054 (2) | 0.028 (2) | 0.0075 (18) | 0.0129 (16) | 0.0001 (18) |
C11 | 0.0260 (17) | 0.0355 (19) | 0.032 (2) | 0.0008 (14) | −0.0016 (14) | −0.0035 (15) |
C12 | 0.0317 (18) | 0.041 (2) | 0.026 (2) | −0.0001 (16) | −0.0024 (15) | −0.0031 (17) |
C13 | 0.0297 (17) | 0.0364 (18) | 0.0240 (18) | −0.0082 (15) | −0.0025 (15) | −0.0022 (15) |
C14 | 0.0307 (19) | 0.052 (2) | 0.029 (2) | −0.0048 (17) | 0.0032 (16) | 0.0029 (17) |
C15 | 0.050 (3) | 0.053 (2) | 0.033 (2) | −0.017 (2) | 0.005 (2) | 0.006 (2) |
C16 | 0.061 (3) | 0.059 (3) | 0.041 (3) | −0.009 (2) | −0.002 (2) | 0.016 (2) |
C17 | 0.042 (2) | 0.042 (2) | 0.044 (3) | 0.0032 (17) | −0.0065 (19) | 0.005 (2) |
Co1—O1 | 1.874 (2) | C5—H5 | 0.9300 |
Co1—O2 | 1.899 (3) | C6—H6 | 0.9300 |
Co1—N2 | 2.021 (3) | C7—H7 | 0.9300 |
Co1—N1 | 2.052 (3) | C8—C9 | 1.509 (6) |
Co1—N5i | 2.314 (4) | C8—H8A | 0.9700 |
Co1—N3 | 2.352 (4) | C8—H8B | 0.9700 |
O1—C2 | 1.331 (5) | C9—C10 | 1.505 (6) |
O2—C13 | 1.307 (5) | C9—H9A | 0.9700 |
N1—C7 | 1.274 (6) | C9—H9B | 0.9700 |
N1—C8 | 1.473 (5) | C10—H10A | 0.9700 |
N2—C11 | 1.271 (5) | C10—H10B | 0.9700 |
N2—C10 | 1.475 (5) | C11—C12 | 1.443 (6) |
N3—N4 | 1.171 (5) | C11—H11 | 0.9300 |
N4—N5 | 1.184 (5) | C12—C17 | 1.397 (6) |
N5—Co1ii | 2.314 (4) | C12—C13 | 1.404 (5) |
C1—C2 | 1.378 (6) | C13—C14 | 1.411 (5) |
C1—C6 | 1.419 (6) | C14—C15 | 1.376 (6) |
C1—C7 | 1.452 (6) | C14—H14 | 0.9300 |
C2—C3 | 1.407 (6) | C15—C16 | 1.396 (7) |
C3—C4 | 1.373 (7) | C15—H15 | 0.9300 |
C3—H3 | 0.9300 | C16—C17 | 1.380 (7) |
C4—C5 | 1.359 (8) | C16—H16 | 0.9300 |
C4—H4 | 0.9300 | C17—H17 | 0.9300 |
C5—C6 | 1.344 (8) | ||
O1—Co1—O2 | 85.72 (12) | C1—C6—H6 | 119.3 |
O1—Co1—N2 | 173.58 (11) | N1—C7—C1 | 127.3 (4) |
O2—Co1—N2 | 88.28 (12) | N1—C7—H7 | 116.3 |
O1—Co1—N1 | 91.68 (12) | C1—C7—H7 | 116.3 |
O2—Co1—N1 | 175.44 (14) | N1—C8—C9 | 113.5 (3) |
N2—Co1—N1 | 94.46 (12) | N1—C8—H8A | 108.9 |
O1—Co1—N5i | 88.86 (15) | C9—C8—H8A | 108.9 |
O2—Co1—N5i | 102.44 (14) | N1—C8—H8B | 108.9 |
N2—Co1—N5i | 90.22 (15) | C9—C8—H8B | 108.9 |
N1—Co1—N5i | 81.23 (13) | H8A—C8—H8B | 107.7 |
O1—Co1—N3 | 94.23 (14) | C10—C9—C8 | 114.0 (3) |
O2—Co1—N3 | 92.97 (14) | C10—C9—H9A | 108.8 |
N2—Co1—N3 | 88.35 (13) | C8—C9—H9A | 108.8 |
N1—Co1—N3 | 83.47 (12) | C10—C9—H9B | 108.8 |
N5i—Co1—N3 | 164.47 (13) | C8—C9—H9B | 108.8 |
C2—O1—Co1 | 127.9 (2) | H9A—C9—H9B | 107.6 |
C13—O2—Co1 | 128.8 (2) | N2—C10—C9 | 111.4 (3) |
C7—N1—C8 | 115.7 (3) | N2—C10—H10A | 109.3 |
C7—N1—Co1 | 121.4 (3) | C9—C10—H10A | 109.3 |
C8—N1—Co1 | 122.6 (3) | N2—C10—H10B | 109.3 |
C11—N2—C10 | 117.2 (3) | C9—C10—H10B | 109.3 |
C11—N2—Co1 | 123.7 (2) | H10A—C10—H10B | 108.0 |
C10—N2—Co1 | 119.0 (2) | N2—C11—C12 | 126.8 (3) |
N4—N3—Co1 | 136.9 (3) | N2—C11—H11 | 116.6 |
N3—N4—N5 | 177.9 (4) | C12—C11—H11 | 116.6 |
N4—N5—Co1ii | 118.0 (3) | C17—C12—C13 | 120.3 (4) |
C2—C1—C6 | 118.7 (4) | C17—C12—C11 | 118.1 (4) |
C2—C1—C7 | 123.5 (4) | C13—C12—C11 | 121.3 (4) |
C6—C1—C7 | 117.7 (4) | O2—C13—C12 | 122.6 (3) |
O1—C2—C1 | 122.8 (4) | O2—C13—C14 | 119.4 (3) |
O1—C2—C3 | 118.2 (4) | C12—C13—C14 | 118.0 (4) |
C1—C2—C3 | 119.0 (4) | C15—C14—C13 | 120.8 (4) |
C4—C3—C2 | 119.7 (5) | C15—C14—H14 | 119.6 |
C4—C3—H3 | 120.1 | C13—C14—H14 | 119.6 |
C2—C3—H3 | 120.1 | C14—C15—C16 | 121.0 (4) |
C5—C4—C3 | 121.6 (5) | C14—C15—H15 | 119.5 |
C5—C4—H4 | 119.2 | C16—C15—H15 | 119.5 |
C3—C4—H4 | 119.2 | C17—C16—C15 | 118.8 (5) |
C6—C5—C4 | 119.5 (5) | C17—C16—H16 | 120.6 |
C6—C5—H5 | 120.2 | C15—C16—H16 | 120.6 |
C4—C5—H5 | 120.2 | C16—C17—C12 | 121.1 (4) |
C5—C6—C1 | 121.4 (5) | C16—C17—H17 | 119.5 |
C5—C6—H6 | 119.3 | C12—C17—H17 | 119.5 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) −x+1, −y, z−1/2. |
[Co(C17H16N2)(NCS)] | F(000) = 816 |
Mr = 397.33 | Dx = 1.562 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 2121 reflections |
a = 12.566 (7) Å | θ = 2.4–21.8° |
b = 11.679 (7) Å | µ = 1.16 mm−1 |
c = 11.515 (7) Å | T = 298 K |
V = 1689.9 (17) Å3 | Block, brown |
Z = 4 | 0.33 × 0.27 × 0.21 mm |
Bruker SMART CCD area-detector diffractometer | 3316 independent reflections |
Radiation source: fine-focus sealed tube | 2686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω scans | θmax = 26.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→15 |
Tmin = 0.702, Tmax = 0.793 | k = −14→11 |
9030 measured reflections | l = −14→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0684P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3316 reflections | Δρmax = 0.52 e Å−3 |
227 parameters | Δρmin = −0.68 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.10 (3) |
[Co(C17H16N2)(NCS)] | V = 1689.9 (17) Å3 |
Mr = 397.33 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.566 (7) Å | µ = 1.16 mm−1 |
b = 11.679 (7) Å | T = 298 K |
c = 11.515 (7) Å | 0.33 × 0.27 × 0.21 mm |
Bruker SMART CCD area-detector diffractometer | 3316 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2686 reflections with I > 2σ(I) |
Tmin = 0.702, Tmax = 0.793 | Rint = 0.060 |
9030 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.129 | Δρmax = 0.52 e Å−3 |
S = 1.03 | Δρmin = −0.68 e Å−3 |
3316 reflections | Absolute structure: Flack (1983) |
227 parameters | Absolute structure parameter: 0.10 (3) |
1 restraint |
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 | ||
Co1 | 0.51572 (4) | 0.10776 (6) | 0.76500 (10) | 0.0348 (2) | |
S1 | 0.42537 (11) | −0.17706 (12) | 0.48694 (13) | 0.0414 (4) | |
O1 | 0.6314 (2) | 0.0049 (3) | 0.7616 (4) | 0.0396 (8) | |
O2 | 0.6081 (2) | 0.2101 (3) | 0.6869 (4) | 0.0346 (9) | |
N1 | 0.4235 (3) | −0.0102 (3) | 0.8517 (4) | 0.0263 (9) | |
N2 | 0.4034 (3) | 0.2344 (3) | 0.7722 (5) | 0.0279 (8) | |
N3 | 0.4404 (3) | 0.0342 (4) | 0.6029 (4) | 0.0367 (11) | |
C1 | 0.5410 (4) | −0.1702 (4) | 0.7988 (4) | 0.0322 (12) | |
C2 | 0.6265 (3) | −0.1087 (4) | 0.7589 (6) | 0.0331 (10) | |
C3 | 0.7153 (4) | −0.1692 (5) | 0.7138 (5) | 0.0456 (15) | |
H3 | 0.7751 | −0.1301 | 0.6877 | 0.055* | |
C4 | 0.7113 (5) | −0.2880 (5) | 0.7093 (6) | 0.0540 (17) | |
H4 | 0.7692 | −0.3279 | 0.6794 | 0.065* | |
C5 | 0.6245 (5) | −0.3479 (5) | 0.7475 (6) | 0.0530 (16) | |
H5 | 0.6226 | −0.4273 | 0.7419 | 0.064* | |
C6 | 0.5427 (5) | −0.2905 (5) | 0.7931 (6) | 0.0472 (16) | |
H6 | 0.4849 | −0.3314 | 0.8219 | 0.057* | |
C7 | 0.4472 (4) | −0.1181 (4) | 0.8511 (5) | 0.0347 (12) | |
H7 | 0.3996 | −0.1673 | 0.8876 | 0.042* | |
C8 | 0.3307 (4) | 0.0226 (4) | 0.9197 (5) | 0.0343 (13) | |
H8A | 0.3542 | 0.0521 | 0.9941 | 0.041* | |
H8B | 0.2877 | −0.0448 | 0.9342 | 0.041* | |
C9 | 0.2622 (4) | 0.1129 (4) | 0.8599 (5) | 0.0371 (12) | |
H9A | 0.2475 | 0.0885 | 0.7810 | 0.045* | |
H9B | 0.1949 | 0.1191 | 0.9005 | 0.045* | |
C10 | 0.3154 (4) | 0.2290 (4) | 0.8572 (5) | 0.0359 (12) | |
H10A | 0.2628 | 0.2867 | 0.8378 | 0.043* | |
H10B | 0.3429 | 0.2464 | 0.9339 | 0.043* | |
C11 | 0.4026 (4) | 0.3206 (4) | 0.7042 (5) | 0.0379 (13) | |
H11 | 0.3413 | 0.3652 | 0.7047 | 0.045* | |
C12 | 0.4860 (4) | 0.3567 (5) | 0.6266 (5) | 0.0347 (12) | |
C13 | 0.5863 (4) | 0.3021 (4) | 0.6239 (5) | 0.0310 (11) | |
C14 | 0.6673 (4) | 0.3492 (5) | 0.5553 (5) | 0.0430 (14) | |
H14 | 0.7338 | 0.3144 | 0.5531 | 0.052* | |
C15 | 0.6486 (5) | 0.4479 (5) | 0.4905 (6) | 0.0486 (15) | |
H15 | 0.7033 | 0.4779 | 0.4454 | 0.058* | |
C16 | 0.5507 (5) | 0.5025 (5) | 0.4916 (6) | 0.0528 (17) | |
H16 | 0.5395 | 0.5683 | 0.4477 | 0.063* | |
C17 | 0.4702 (5) | 0.4571 (5) | 0.5592 (6) | 0.0485 (16) | |
H17 | 0.4041 | 0.4931 | 0.5605 | 0.058* | |
C18 | 0.4343 (4) | −0.0520 (5) | 0.5548 (5) | 0.0358 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0282 (3) | 0.0370 (4) | 0.0393 (4) | 0.0004 (3) | 0.0046 (5) | 0.0009 (4) |
S1 | 0.0455 (8) | 0.0424 (8) | 0.0363 (8) | −0.0133 (6) | 0.0051 (7) | −0.0037 (7) |
O1 | 0.0261 (15) | 0.0349 (18) | 0.058 (2) | 0.0046 (13) | 0.008 (2) | 0.003 (2) |
O2 | 0.0255 (17) | 0.0349 (19) | 0.044 (2) | −0.0033 (14) | 0.0034 (17) | 0.0128 (17) |
N1 | 0.0206 (19) | 0.029 (2) | 0.029 (2) | −0.0004 (16) | −0.0010 (18) | 0.0006 (18) |
N2 | 0.0242 (16) | 0.0277 (19) | 0.032 (2) | 0.0003 (14) | 0.002 (2) | 0.001 (2) |
N3 | 0.042 (2) | 0.038 (3) | 0.031 (3) | −0.004 (2) | 0.002 (2) | −0.004 (2) |
C1 | 0.039 (3) | 0.034 (3) | 0.024 (3) | 0.009 (2) | −0.005 (2) | 0.002 (2) |
C2 | 0.033 (2) | 0.040 (3) | 0.026 (3) | 0.012 (2) | 0.003 (3) | 0.003 (3) |
C3 | 0.037 (3) | 0.055 (4) | 0.046 (4) | 0.017 (3) | 0.011 (3) | 0.008 (3) |
C4 | 0.054 (4) | 0.048 (3) | 0.059 (4) | 0.032 (3) | 0.006 (3) | 0.001 (3) |
C5 | 0.065 (4) | 0.043 (3) | 0.051 (4) | 0.017 (3) | −0.001 (4) | −0.003 (3) |
C6 | 0.052 (3) | 0.038 (3) | 0.052 (5) | 0.007 (3) | −0.003 (3) | 0.009 (3) |
C7 | 0.034 (3) | 0.043 (3) | 0.028 (3) | −0.002 (2) | 0.000 (2) | 0.007 (2) |
C8 | 0.027 (2) | 0.036 (3) | 0.039 (3) | 0.001 (2) | 0.010 (2) | −0.001 (2) |
C9 | 0.027 (2) | 0.040 (3) | 0.044 (4) | 0.001 (2) | 0.005 (2) | −0.003 (3) |
C10 | 0.033 (3) | 0.033 (3) | 0.042 (3) | 0.007 (2) | 0.011 (3) | −0.001 (2) |
C11 | 0.037 (3) | 0.037 (3) | 0.039 (3) | 0.009 (2) | −0.005 (3) | −0.011 (3) |
C12 | 0.042 (3) | 0.036 (3) | 0.026 (3) | −0.003 (2) | −0.005 (2) | −0.001 (2) |
C13 | 0.034 (3) | 0.032 (3) | 0.026 (3) | −0.009 (2) | −0.002 (2) | −0.005 (2) |
C14 | 0.041 (3) | 0.050 (3) | 0.038 (4) | −0.016 (3) | 0.001 (3) | −0.005 (3) |
C15 | 0.068 (4) | 0.042 (3) | 0.036 (3) | −0.016 (3) | 0.006 (3) | 0.002 (3) |
C16 | 0.072 (4) | 0.044 (3) | 0.043 (4) | −0.006 (3) | 0.001 (4) | 0.010 (3) |
C17 | 0.060 (4) | 0.036 (3) | 0.049 (4) | 0.009 (3) | −0.002 (3) | 0.001 (3) |
C18 | 0.023 (2) | 0.063 (4) | 0.022 (3) | −0.004 (2) | −0.003 (2) | 0.008 (3) |
Co1—O1 | 1.886 (3) | C5—H5 | 0.9300 |
Co1—O2 | 1.893 (3) | C6—H6 | 0.9300 |
Co1—N2 | 2.047 (4) | C7—H7 | 0.9300 |
Co1—N1 | 2.058 (4) | C8—C9 | 1.525 (7) |
Co1—N3 | 2.262 (5) | C8—H8A | 0.9700 |
Co1—S1i | 2.781 (2) | C8—H8B | 0.9700 |
S1—C18 | 1.660 (6) | C9—C10 | 1.512 (7) |
O1—C2 | 1.328 (5) | C9—H9A | 0.9700 |
O2—C13 | 1.324 (6) | C9—H9B | 0.9700 |
N1—C7 | 1.295 (6) | C10—H10A | 0.9700 |
N1—C8 | 1.455 (6) | C10—H10B | 0.9700 |
N2—C11 | 1.275 (7) | C11—C12 | 1.441 (8) |
N2—C10 | 1.478 (6) | C11—H11 | 0.9300 |
N3—C18 | 1.152 (7) | C12—C13 | 1.412 (7) |
C1—C2 | 1.371 (7) | C12—C17 | 1.420 (8) |
C1—C6 | 1.407 (7) | C13—C14 | 1.401 (7) |
C1—C7 | 1.456 (7) | C14—C15 | 1.393 (8) |
C2—C3 | 1.420 (7) | C14—H14 | 0.9300 |
C3—C4 | 1.389 (8) | C15—C16 | 1.385 (8) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—C5 | 1.368 (8) | C16—C17 | 1.383 (8) |
C4—H4 | 0.9300 | C16—H16 | 0.9300 |
C5—C6 | 1.335 (8) | C17—H17 | 0.9300 |
O1—Co1—O2 | 85.41 (15) | N1—C7—H7 | 116.7 |
O1—Co1—N2 | 173.16 (14) | C1—C7—H7 | 116.7 |
O2—Co1—N2 | 89.18 (16) | N1—C8—C9 | 113.1 (5) |
O1—Co1—N1 | 91.00 (15) | N1—C8—H8A | 109.0 |
O2—Co1—N1 | 176.36 (14) | C9—C8—H8A | 109.0 |
N2—Co1—N1 | 94.35 (15) | N1—C8—H8B | 109.0 |
O1—Co1—N3 | 93.64 (19) | C9—C8—H8B | 109.0 |
O2—Co1—N3 | 95.99 (18) | H8A—C8—H8B | 107.8 |
N2—Co1—N3 | 91.09 (18) | C10—C9—C8 | 112.3 (4) |
N1—Co1—N3 | 84.86 (18) | C10—C9—H9A | 109.1 |
O1—Co1—S1i | 89.96 (15) | C8—C9—H9A | 109.1 |
O2—Co1—S1i | 95.17 (15) | C10—C9—H9B | 109.1 |
N1—Co1—S1i | 84.20 (16) | C8—C9—H9B | 109.1 |
N2—Co1—S1i | 86.33 (16) | H9A—C9—H9B | 107.9 |
S1i—Co1—N3 | 168.54 (16) | N2—C10—C9 | 112.5 (4) |
C2—O1—Co1 | 127.0 (3) | N2—C10—H10A | 109.1 |
C13—O2—Co1 | 130.2 (3) | C9—C10—H10A | 109.1 |
C7—N1—C8 | 116.3 (4) | N2—C10—H10B | 109.1 |
C7—N1—Co1 | 121.3 (3) | C9—C10—H10B | 109.1 |
C8—N1—Co1 | 122.4 (3) | H10A—C10—H10B | 107.8 |
C11—N2—C10 | 115.8 (4) | N2—C11—C12 | 127.3 (5) |
C11—N2—Co1 | 123.4 (4) | N2—C11—H11 | 116.3 |
C10—N2—Co1 | 120.8 (3) | C12—C11—H11 | 116.3 |
C18—N3—Co1 | 139.2 (4) | C13—C12—C17 | 119.1 (5) |
C2—C1—C6 | 119.7 (5) | C13—C12—C11 | 122.0 (5) |
C2—C1—C7 | 123.6 (5) | C17—C12—C11 | 118.6 (5) |
C6—C1—C7 | 116.6 (5) | O2—C13—C14 | 118.5 (5) |
O1—C2—C1 | 123.4 (4) | O2—C13—C12 | 122.6 (5) |
O1—C2—C3 | 118.0 (5) | C14—C13—C12 | 118.9 (5) |
C1—C2—C3 | 118.5 (5) | C15—C14—C13 | 120.3 (5) |
C4—C3—C2 | 118.9 (5) | C15—C14—H14 | 119.9 |
C4—C3—H3 | 120.6 | C13—C14—H14 | 119.9 |
C2—C3—H3 | 120.6 | C16—C15—C14 | 121.7 (6) |
C5—C4—C3 | 121.8 (5) | C16—C15—H15 | 119.1 |
C5—C4—H4 | 119.1 | C14—C15—H15 | 119.1 |
C3—C4—H4 | 119.1 | C17—C16—C15 | 118.6 (6) |
C6—C5—C4 | 119.0 (6) | C17—C16—H16 | 120.7 |
C6—C5—H5 | 120.5 | C15—C16—H16 | 120.7 |
C4—C5—H5 | 120.5 | C16—C17—C12 | 121.4 (6) |
C5—C6—C1 | 122.1 (6) | C16—C17—H17 | 119.3 |
C5—C6—H6 | 119.0 | C12—C17—H17 | 119.3 |
C1—C6—H6 | 119.0 | N3—C18—S1 | 179.3 (5) |
N1—C7—C1 | 126.5 (5) |
Symmetry code: (i) −x+1, −y, z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Co(C17H16N2)(N3)] | [Co(C17H16N2)(NCS)] |
Mr | 381.28 | 397.33 |
Crystal system, space group | Orthorhombic, Pna21 | Orthorhombic, Pna21 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 11.930 (2), 11.931 (3), 11.225 (2) | 12.566 (7), 11.679 (7), 11.515 (7) |
V (Å3) | 1597.7 (6) | 1689.9 (17) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.10 | 1.16 |
Crystal size (mm) | 0.32 × 0.28 × 0.19 | 0.33 × 0.27 × 0.21 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.721, 0.819 | 0.702, 0.793 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8835, 3234, 2932 | 9030, 3316, 2686 |
Rint | 0.030 | 0.060 |
(sin θ/λ)max (Å−1) | 0.628 | 0.628 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.130, 1.07 | 0.054, 0.129, 1.03 |
No. of reflections | 3234 | 3316 |
No. of parameters | 227 | 227 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.42 | 0.52, −0.68 |
Absolute structure | Flack (1983) | Flack (1983) |
Absolute structure parameter | 0.13 (2) | 0.10 (3) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Co1—O1 | 1.874 (2) | Co1—N1 | 2.052 (3) |
Co1—O2 | 1.899 (3) | Co1—N5i | 2.314 (4) |
Co1—N2 | 2.021 (3) | Co1—N3 | 2.352 (4) |
O1—Co1—O2 | 85.72 (12) | N2—Co1—N5i | 90.22 (15) |
O1—Co1—N2 | 173.58 (11) | N1—Co1—N5i | 81.23 (13) |
O2—Co1—N2 | 88.28 (12) | O1—Co1—N3 | 94.23 (14) |
O1—Co1—N1 | 91.68 (12) | O2—Co1—N3 | 92.97 (14) |
O2—Co1—N1 | 175.44 (14) | N2—Co1—N3 | 88.35 (13) |
N2—Co1—N1 | 94.46 (12) | N1—Co1—N3 | 83.47 (12) |
O1—Co1—N5i | 88.86 (15) | N5i—Co1—N3 | 164.47 (13) |
O2—Co1—N5i | 102.44 (14) |
Symmetry code: (i) −x+1, −y, z+1/2. |
Co1—O1 | 1.886 (3) | Co1—N1 | 2.058 (4) |
Co1—O2 | 1.893 (3) | Co1—N3 | 2.262 (5) |
Co1—N2 | 2.047 (4) | Co1—S1i | 2.781 (2) |
O1—Co1—O2 | 85.41 (15) | N2—Co1—N3 | 91.09 (18) |
O1—Co1—N2 | 173.16 (14) | N1—Co1—N3 | 84.86 (18) |
O2—Co1—N2 | 89.18 (16) | O1—Co1—S1i | 89.96 (15) |
O1—Co1—N1 | 91.00 (15) | O2—Co1—S1i | 95.17 (15) |
O2—Co1—N1 | 176.36 (14) | N1—Co1—S1i | 84.20 (16) |
N2—Co1—N1 | 94.35 (15) | N2—Co1—S1i | 86.33 (16) |
O1—Co1—N3 | 93.64 (19) | S1i—Co1—N3 | 168.54 (16) |
O2—Co1—N3 | 95.99 (18) |
Symmetry code: (i) −x+1, −y, z+1/2. |
Investigation into the magnetic properties of molecule-based materials containing a polymetallic assembly have become a fascinating subject in the field of condensed matter physics and materials chemistry (Dalai et al., 2002; Bhaduri et al., 2003). Much attention has been focused on coordination complexes with novel magnetic properties, which may have potentially useful applications in materials science (Ray et al., 2003). The prime strategy for designing these molecular materials is to use a suitable bridging ligand that determines the nature of the magnetic interactions (Koner et al., 2003).
Our work is aimed at obtaining multidimensional polymetallic complexes. Based on the above considerations, we designed and synthesized a flexible tetradentate ligand, N,N'-bis(salicylidene)-1,3-propanediamine (BSPD). The reason we do not use a rigid ligand is that the flexible BSPD ligand can adopt different coordination modes according to the geometric need of transition metal ions and the coordination environment. The second ligand, azide or thiocyanate, is a well known? bridging group. They readily bridge different metal ions through their terminal donor atoms, forming polynuclear complexes. Cobalt(III) is a good candidate of octahedral coordination geometry. Here, we report a pair of interesting one-dimensional infinite chains formed by the reaction of the BSPD ligand and the azide or thiocyanate ligand with cobalt(III) acetate.
The two title complexes, (I) and (II), are isomorphous polynuclear cobalt(III) compounds (Figs. 1 and 2). In both structures, the smallest repeat unit contains two BSPD–CoIII cations and two bridging ligands, viz. azide for (I) and thiocyanate for (II). The CoIII atom is in an octahedral coordination environment and is six-coordinated by two N atoms and two O atoms of one Schiff base ligand defining the basal plane, and by two different but symmetry-related terminal N atoms [for (I)], or two terminal N and S atoms [for (II)], occupying the axial positions.
The angles subtended at atom Co1 in (I) are comparable with the corresponding values observed in (II) (Table 1). The bond angles formed by the two apical donor atoms and the CoIII atom deviate from 180° by 15.53 (13) and 11.50 (18)°, respectively, for (I) and (II), which is due to the strain created by the two cis-bridging ligands related to the apical axis of the octahedron in the two complexes. The mean Co—N (imine N atoms) and mean Co—O (phenolate O atoms) bond lengths in (I) are also comparable with the corresponding values in (II). However, the bond lengths between atom Co1 and the apical donor atoms are different from each other. The fact that the Co1—N3 bond length [2.352 (4) Å] in (I) is longer than that in (II) [2.263 (5) Å], while the Co1—N5i bond length in (I) [2.314 (4) Å] is much shorter than the Co1—S1ii bond length [2.780 (5) Å] in (II) [symmetry codes: (i) 1 − x, −y, 1/2 + z; (ii) 2 − x, 2 − y, 1/2 + z] indicates that the Co—S bond is not very strong.
The conformations of the six-membered chelate rings containing the CoIII atom, the azomethine N atoms and three C atoms (C8, C9 and C10) in both (I) and (II) are chair-shaped. The distances of the two para-positioned atoms, Co1 and C9, from the mean plane of the other four atoms are 0.473 (3) and −0.722 (6) Å, respectively, for (I), and 0.374 (3) and −0.753 (6) Å, respectively, for (II). In (I), the CoN2O2 basal plane forms dihedral angles of 20.5 (2) and 23.5 (2)°, respectively, with the two phenolate ring systems, which are inclined at 43.8 (2)° to each other, while in (II), the CoN2O2 basal plane forms dihedral angles of 22.1 (2) and 14.8 (2)°, respectively, with the two phenolate ring systems, which are inclined at 36.8 (2)° to each other.
In both complexes, the average C7═N1 and C11═N2 bond lengths [1.273 (6) Å in (I) and 1.286 (6) Å in (II)] conform to the normal value for double bonds, while the average C8—N1 and C10—N2 bond lengths [1.474 (5) Å in (I) and 1.466 (6) Å in (II)] conform to the normal value for single bonds (Reference for standard values?).
In the crystal structures, the N,N'-bis(salicylidene)-1,3-propanediaminatocobalt(III) moieties are linked by the bridging ligands, viz. azide for (I) and thiocyanate for (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]n in (I) or [–Co—N—C—S—Co]n (II) running along the c axis. There are no short intermolecular contacts (Figs. 3 and 4).