Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004789/da1118sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004789/da1118Isup2.hkl |
CCDC reference: 147613
The ligand 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane dihydrochloride was prepared by the reaction of 1,5-diazacyclooctane hydrobromide and 1-methyl-2-chloromethylimidazole hydrochloride in ethanol solution in the presence of KOH (Buhle et al., 1943; Billman et al., 1962) and the details will be published elsewhere.
A mixture of Co(ClO4)2·6H2O(370 mg, 1 mmol) and 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane hydrochloride (340 mg, 1 mmol) was dissolved in methanol (30 ml, room temperature). The ligand was neutralized by slow addition of a KOH-methanol solution to the above mixture, and the resulting solution was allowed to stand for ca 7 days. Purple block-shaped crystals were deposited slowly upon evaporation of the solvent. FT—IR data (KBr pellet, cm-1): 3127(w), 2908(w), 1628(m), 1551(w), 1501(m), 1453(m), 1082(s), 762 (m), 624(m).
The structure was solved by direct and difference Fourier methods and refined by full-matrix least-squares methods.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998).
[CoCl(C16H26N6)]ClO4 | Z = 2 |
Mr = 496.26 | F(000) = 514 |
Triclinic, P1 | Dx = 1.576 Mg m−3 |
a = 7.5865 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.8102 (14) Å | Cell parameters from 2632 reflections |
c = 12.2307 (15) Å | θ = 1.7–25.0° |
α = 78.612 (3)° | µ = 1.11 mm−1 |
β = 84.519 (2)° | T = 293 K |
γ = 77.170 (2)° | Rectangular, purple |
V = 1045.9 (2) Å3 | 0.25 × 0.20 × 0.15 mm |
Bruker SMART 1000 diffractometer | 2856 reflections with I > 2σ(I) |
ω scans | Rint = 0.048 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | θmax = 25.0° |
Tmin = 0.732, Tmax = 0.808 | h = −8→9 |
4361 measured reflections | k = −14→11 |
3638 independent reflections | l = −11→14 |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.064 | Calc. w = 1/[σ2(Fo2) + (0.1P)2] P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.163 | (Δ/σ)max = 0.012 |
S = 1.18 | Δρmax = 0.87 e Å−3 |
3638 reflections | Δρmin = −0.73 e Å−3 |
263 parameters |
[CoCl(C16H26N6)]ClO4 | γ = 77.170 (2)° |
Mr = 496.26 | V = 1045.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5865 (9) Å | Mo Kα radiation |
b = 11.8102 (14) Å | µ = 1.11 mm−1 |
c = 12.2307 (15) Å | T = 293 K |
α = 78.612 (3)° | 0.25 × 0.20 × 0.15 mm |
β = 84.519 (2)° |
Bruker SMART 1000 diffractometer | 3638 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 2856 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 0.808 | Rint = 0.048 |
4361 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 263 parameters |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.87 e Å−3 |
3638 reflections | Δρmin = −0.73 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.25349 (7) | 0.30123 (5) | 0.75968 (5) | 0.0393 (3) | |
Cl1 | 0.50300 (16) | 0.30680 (12) | 0.85261 (11) | 0.0596 (4) | |
Cl2 | −0.07121 (17) | −0.15971 (10) | 0.68235 (10) | 0.0529 (3) | |
O1 | −0.2087 (8) | −0.1934 (5) | 0.7619 (6) | 0.134 (2) | |
O2 | −0.1347 (6) | −0.0486 (3) | 0.6155 (3) | 0.0740 (11) | |
O3 | 0.0724 (9) | −0.1545 (5) | 0.7456 (5) | 0.131 (2) | |
O4 | −0.0093 (11) | −0.2487 (4) | 0.6187 (4) | 0.133 (3) | |
N1 | 0.1356 (5) | 0.1650 (3) | 0.8758 (3) | 0.0428 (9) | |
N2 | 0.3591 (5) | 0.1558 (3) | 0.6716 (3) | 0.0443 (9) | |
N3 | 0.0334 (5) | 0.4032 (3) | 0.8285 (3) | 0.0424 (9) | |
N4 | −0.1669 (5) | 0.4201 (3) | 0.9686 (3) | 0.0434 (9) | |
N5 | 0.2783 (5) | 0.3932 (3) | 0.5981 (3) | 0.0457 (9) | |
N6 | 0.4029 (5) | 0.3888 (4) | 0.4305 (3) | 0.0537 (10) | |
C1 | 0.2750 (7) | 0.0596 (4) | 0.9201 (4) | 0.0559 (12) | |
C2 | 0.3653 (7) | −0.0126 (4) | 0.8352 (4) | 0.0577 (13) | |
C3 | 0.4724 (7) | 0.0502 (4) | 0.7399 (4) | 0.0586 (13) | |
C4 | 0.2019 (7) | 0.1249 (4) | 0.6286 (4) | 0.0519 (12) | |
C5 | 0.0223 (6) | 0.1712 (4) | 0.6860 (4) | 0.0519 (12) | |
C6 | −0.0009 (6) | 0.1341 (4) | 0.8119 (4) | 0.0490 (11) | |
C7 | 0.0466 (7) | 0.2226 (4) | 0.9681 (4) | 0.0529 (12) | |
C8 | −0.0327 (6) | 0.3476 (4) | 0.9235 (3) | 0.0419 (10) | |
C9 | −0.0657 (6) | 0.5176 (4) | 0.8143 (4) | 0.0462 (11) | |
C10 | −0.1880 (6) | 0.5286 (4) | 0.9010 (4) | 0.0480 (11) | |
C11 | −0.2754 (7) | 0.3891 (5) | 1.0718 (4) | 0.0603 (13) | |
C12 | 0.4744 (7) | 0.2029 (5) | 0.5775 (4) | 0.0597 (13) | |
C13 | 0.3861 (6) | 0.3263 (4) | 0.5338 (4) | 0.0457 (11) | |
C14 | 0.2248 (6) | 0.5012 (4) | 0.5333 (4) | 0.0509 (11) | |
C15 | 0.3009 (7) | 0.5002 (5) | 0.4297 (4) | 0.0535 (12) | |
C16 | 0.5132 (8) | 0.3461 (6) | 0.3360 (4) | 0.0721 (16) | |
H1A | 0.2183 | 0.0096 | 0.9792 | 0.067* | |
H1B | 0.3669 | 0.0857 | 0.9529 | 0.067* | |
H2A | 0.2733 | −0.0401 | 0.8038 | 0.069* | |
H2B | 0.4465 | −0.0817 | 0.8730 | 0.069* | |
H3A | 0.5680 | 0.0750 | 0.7705 | 0.070* | |
H3B | 0.5291 | −0.0051 | 0.6915 | 0.070* | |
H4A | 0.2207 | 0.0397 | 0.6381 | 0.062* | |
H4B | 0.1970 | 0.1566 | 0.5492 | 0.062* | |
H5A | −0.0713 | 0.1473 | 0.6525 | 0.062* | |
H5B | −0.0003 | 0.2568 | 0.6691 | 0.062* | |
H6A | −0.1212 | 0.1716 | 0.8367 | 0.059* | |
H6B | 0.0076 | 0.0494 | 0.8295 | 0.059* | |
H7A | 0.1339 | 0.2181 | 1.0226 | 0.064* | |
H7B | −0.0479 | 0.1827 | 1.0048 | 0.064* | |
H9A | −0.0506 | 0.5775 | 0.7544 | 0.055* | |
H10A | −0.2706 | 0.5968 | 0.9126 | 0.058* | |
H11A | −0.2326 | 0.3076 | 1.1039 | 0.090* | |
H11B | −0.4001 | 0.4015 | 1.0551 | 0.090* | |
H11C | −0.2644 | 0.4379 | 1.1239 | 0.090* | |
H12A | 0.4890 | 0.1558 | 0.5193 | 0.072* | |
H12B | 0.5932 | 0.2000 | 0.6024 | 0.072* | |
H14A | 0.1474 | 0.5656 | 0.5571 | 0.061* | |
H15A | 0.2870 | 0.5627 | 0.3695 | 0.064* | |
H16A | 0.5718 | 0.2650 | 0.3588 | 0.108* | |
H16B | 0.6030 | 0.3929 | 0.3115 | 0.108* | |
H16C | 0.4370 | 0.3525 | 0.2758 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0370 (4) | 0.0447 (4) | 0.0382 (4) | −0.0081 (3) | −0.0010 (2) | −0.0135 (3) |
Cl1 | 0.0443 (7) | 0.0732 (8) | 0.0723 (8) | −0.0126 (6) | −0.0171 (6) | −0.0321 (7) |
Cl2 | 0.0602 (7) | 0.0440 (6) | 0.0569 (7) | −0.0065 (5) | −0.0120 (6) | −0.0155 (5) |
O1 | 0.103 (4) | 0.088 (4) | 0.176 (6) | −0.008 (3) | 0.038 (4) | 0.023 (4) |
O2 | 0.089 (3) | 0.050 (2) | 0.076 (3) | −0.005 (2) | −0.004 (2) | −0.0053 (19) |
O3 | 0.153 (5) | 0.114 (4) | 0.140 (5) | −0.038 (4) | −0.080 (4) | −0.012 (4) |
O4 | 0.244 (7) | 0.066 (3) | 0.070 (3) | 0.028 (4) | −0.020 (4) | −0.027 (2) |
N1 | 0.048 (2) | 0.039 (2) | 0.0403 (19) | −0.0057 (16) | −0.0040 (16) | −0.0067 (16) |
N2 | 0.043 (2) | 0.048 (2) | 0.0403 (19) | 0.0007 (16) | −0.0036 (16) | −0.0128 (17) |
N3 | 0.046 (2) | 0.043 (2) | 0.0367 (19) | −0.0038 (16) | 0.0038 (16) | −0.0122 (16) |
N4 | 0.0374 (19) | 0.057 (2) | 0.040 (2) | −0.0107 (17) | 0.0036 (16) | −0.0185 (18) |
N5 | 0.041 (2) | 0.053 (2) | 0.042 (2) | −0.0084 (17) | 0.0049 (16) | −0.0126 (18) |
N6 | 0.043 (2) | 0.080 (3) | 0.042 (2) | −0.019 (2) | 0.0048 (17) | −0.017 (2) |
C1 | 0.068 (3) | 0.048 (3) | 0.050 (3) | −0.010 (2) | −0.014 (2) | 0.000 (2) |
C2 | 0.060 (3) | 0.041 (3) | 0.066 (3) | 0.005 (2) | −0.017 (3) | −0.005 (2) |
C3 | 0.047 (3) | 0.054 (3) | 0.068 (3) | 0.011 (2) | −0.008 (2) | −0.019 (3) |
C4 | 0.059 (3) | 0.055 (3) | 0.045 (3) | −0.007 (2) | −0.009 (2) | −0.019 (2) |
C5 | 0.049 (3) | 0.049 (3) | 0.061 (3) | −0.010 (2) | −0.022 (2) | −0.012 (2) |
C6 | 0.044 (2) | 0.041 (2) | 0.064 (3) | −0.0085 (19) | −0.002 (2) | −0.013 (2) |
C7 | 0.065 (3) | 0.054 (3) | 0.039 (2) | −0.014 (2) | 0.006 (2) | −0.009 (2) |
C8 | 0.043 (2) | 0.050 (3) | 0.036 (2) | −0.014 (2) | 0.0003 (19) | −0.0133 (19) |
C9 | 0.046 (2) | 0.042 (2) | 0.051 (3) | −0.008 (2) | −0.006 (2) | −0.009 (2) |
C10 | 0.041 (2) | 0.046 (3) | 0.059 (3) | −0.003 (2) | −0.001 (2) | −0.021 (2) |
C11 | 0.052 (3) | 0.083 (4) | 0.048 (3) | −0.019 (3) | 0.016 (2) | −0.021 (3) |
C12 | 0.052 (3) | 0.066 (3) | 0.057 (3) | −0.002 (2) | 0.014 (2) | −0.019 (3) |
C13 | 0.039 (2) | 0.059 (3) | 0.041 (2) | −0.012 (2) | 0.0017 (19) | −0.012 (2) |
C14 | 0.047 (3) | 0.054 (3) | 0.051 (3) | −0.009 (2) | 0.001 (2) | −0.011 (2) |
C15 | 0.049 (3) | 0.063 (3) | 0.047 (3) | −0.013 (2) | −0.006 (2) | −0.005 (2) |
C16 | 0.066 (4) | 0.108 (5) | 0.045 (3) | −0.019 (3) | 0.016 (3) | −0.028 (3) |
Co1—N3 | 2.046 (3) | C8—N4 | 1.329 (5) |
Co1—N5 | 2.071 (4) | N3—C9 | 1.379 (5) |
Co1—N2 | 2.169 (4) | C9—C10 | 1.347 (7) |
Co1—N1 | 2.214 (4) | C10—N4 | 1.367 (6) |
Co1—Cl1 | 2.3184 (13) | N4—C11 | 1.469 (5) |
N1—C7 | 1.465 (6) | C12—C13 | 1.479 (7) |
N1—C1 | 1.490 (6) | C13—N5 | 1.322 (6) |
N1—C6 | 1.500 (6) | C13—N6 | 1.341 (6) |
C1—C2 | 1.492 (7) | N5—C14 | 1.361 (6) |
C2—C3 | 1.522 (7) | C14—C15 | 1.342 (7) |
C3—N2 | 1.497 (6) | C15—N6 | 1.369 (7) |
N2—C12 | 1.473 (6) | N6—C16 | 1.466 (6) |
N2—C4 | 1.490 (6) | Cl2—O4 | 1.402 (5) |
C4—C5 | 1.512 (7) | Cl2—O2 | 1.411 (4) |
C5—C6 | 1.521 (7) | Cl2—O3 | 1.414 (6) |
C7—C8 | 1.480 (6) | Cl2—O1 | 1.425 (5) |
C8—N3 | 1.329 (5) | ||
N3—Co1—N5 | 103.38 (14) | N3—C8—N4 | 110.8 (4) |
N3—Co1—N2 | 148.09 (15) | N3—C8—C7 | 120.9 (4) |
N5—Co1—N2 | 79.71 (15) | N4—C8—C7 | 128.3 (4) |
N3—Co1—N1 | 78.80 (14) | C8—N3—C9 | 105.7 (4) |
N5—Co1—N1 | 147.75 (15) | C8—N3—Co1 | 113.3 (3) |
N2—Co1—N1 | 82.41 (14) | C9—N3—Co1 | 140.8 (3) |
N3—Co1—Cl1 | 107.04 (11) | C10—C9—N3 | 109.1 (4) |
N5—Co1—Cl1 | 107.92 (11) | C9—C10—N4 | 106.6 (4) |
N2—Co1—Cl1 | 101.91 (10) | C8—N4—C10 | 107.8 (4) |
N1—Co1—Cl1 | 101.89 (10) | C8—N4—C11 | 126.3 (4) |
C7—N1—C1 | 109.5 (4) | C10—N4—C11 | 125.9 (4) |
C7—N1—C6 | 110.8 (4) | N2—C12—C13 | 108.1 (4) |
C1—N1—C6 | 112.2 (4) | N5—C13—N6 | 109.8 (4) |
C7—N1—Co1 | 105.4 (3) | N5—C13—C12 | 121.9 (4) |
C1—N1—Co1 | 112.7 (3) | N6—C13—C12 | 128.3 (4) |
C6—N1—Co1 | 106.1 (3) | C13—N5—C14 | 106.8 (4) |
N1—C1—C2 | 114.7 (4) | C13—N5—Co1 | 111.1 (3) |
C1—C2—C3 | 115.6 (4) | C14—N5—Co1 | 142.1 (3) |
N2—C3—C2 | 113.4 (4) | C15—C14—N5 | 109.4 (4) |
C12—N2—C4 | 109.8 (4) | C14—C15—N6 | 106.3 (4) |
C12—N2—C3 | 108.2 (4) | C13—N6—C15 | 107.7 (4) |
C4—N2—C3 | 111.5 (4) | C13—N6—C16 | 126.2 (5) |
C12—N2—Co1 | 105.4 (3) | C15—N6—C16 | 126.1 (5) |
C4—N2—Co1 | 107.4 (3) | O4—Cl2—O2 | 112.3 (3) |
C3—N2—Co1 | 114.4 (3) | O4—Cl2—O3 | 108.2 (4) |
N2—C4—C5 | 113.6 (4) | O2—Cl2—O3 | 110.4 (3) |
C4—C5—C6 | 118.2 (4) | O4—Cl2—O1 | 108.9 (4) |
N1—C6—C5 | 114.0 (4) | O2—Cl2—O1 | 111.1 (3) |
N1—C7—C8 | 109.1 (4) | O3—Cl2—O1 | 105.7 (4) |
Experimental details
Crystal data | |
Chemical formula | [CoCl(C16H26N6)]ClO4 |
Mr | 496.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.5865 (9), 11.8102 (14), 12.2307 (15) |
α, β, γ (°) | 78.612 (3), 84.519 (2), 77.170 (2) |
V (Å3) | 1045.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.732, 0.808 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4361, 3638, 2856 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.163, 1.18 |
No. of reflections | 3638 |
No. of parameters | 263 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −0.73 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
Co1—N3 | 2.046 (3) | Co1—N1 | 2.214 (4) |
Co1—N5 | 2.071 (4) | Co1—Cl1 | 2.3184 (13) |
Co1—N2 | 2.169 (4) | ||
N3—Co1—N5 | 103.38 (14) | N2—Co1—N1 | 82.41 (14) |
N3—Co1—N2 | 148.09 (15) | N3—Co1—Cl1 | 107.04 (11) |
N5—Co1—N2 | 79.71 (15) | N5—Co1—Cl1 | 107.92 (11) |
N3—Co1—N1 | 78.80 (14) | N2—Co1—Cl1 | 101.91 (10) |
N5—Co1—N1 | 147.75 (15) | N1—Co1—Cl1 | 101.89 (10) |
1,5-Diazacyclooctane (DACO) derivatives bearing two additional functional donor pendants can strongly coordinate to transitional metal centers, forming square-pyramidal five-coordinate or square-planar four-coordinate complexes (Grapperhous & Darensbourg, 1998; Nielson et al., 1971; Bu et al., 1999).
The four donor atoms of such tetradentate ligands coordinate to the central metal ions nearly in a plane and the DACO backbone usually takes a boat-chair configuration. This configuration will force a portion of the chelate framework across to the axial coordination position, and will sterically restrict further axial coordination to the metal center. Therefore, such DACO derivatives can be used as very good ligands for the construction of metal complexes with square-planar or square-pyramidal configuration. The interesting chemistry of such DACO derivatives prompted us to create more of such ligands by modifying DACO with heterocyclic donor pendants to obtain new complexes with functional properties. We synthesized a new mesocyclic ligand functionalized by two imidazole donor pendants, 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane and its cobalt(II) complex, [Co(C16H26N6)Cl]ClO4, (I). We report herein the crystal structure of this new complex. \sch
The structure of (I) comprises discrete [CoCl(C16H26N6)]+ cations and perchlorate anions (Fig.1). In the complex cation, the CoII atom is five-coordinate. 1,5-bis(N-1-methylimidazol-2-ylmethyl)-1,5-diazacyclooctane acts as a tetradentate ligand, through one pair of nitrogen donors of the mesoocyclic ring and the two N atoms of the imidazole pendants. The coordination geometry about the CoII atom can be described as square pyramidal. The four nitrogen donors of the ligand coordinate to the central CoII in one plane, with a chloride anion occupying an apical position. The τ value used to describe the degree of trigonal distortion is 0.006 (Addison et al., 1984), i.e. nearly zero, indicating that the distortion is very small. The cobalt atom is above the mean plane formed by atoms N1, N2, N3, and N5 by 0.549 Å towards the apical Cl ligand. The two imidazole pendants are not coplanar, their planes forming an angle of 15.97°.
The six-membered CoNCH2CH2CH2N rings in [Co(C16H26N6)Cl]ClO4 adopt chair/boat configurations. The boat-form ring causes one H atom (H5B on C5) to lie about 2.509 Å from the metal, at the axial position. Thus the cobalt atom is well shielded from axial interactions opposite the Cl ligand. All of the Co—N and the Co—Cl distances are normal. The conformation of the ligand restricts the placement of the N atoms in the coordination sphere, so the N1—Co1—N2 angle is reduced to 82.41 (14)°, whereas the N3—Co1—N5 angle is 103.38 (14)°.