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The organic ligands 4-methyl-1H-imidazole and 2-ethyl-4-methyl-1H-imidazole react with Cu(CF3SO3)2·6H2O to give tetrakis(5-methyl-1H-imidazole-κN3)copper(II) bis(trifluoromethanesulfonate), [Cu(C4H6N2)4](CF3SO3)2, and aquatetrakis(2-ethyl-5-methyl-1H-imidazole-κN3)copper(II) bis(tri fluoromethanesulfonate), [Cu(C6H10N2)4(H2O)](CF3SO3)2. In the former, the Cu atom has an elongated octahedral coordination environment, with four imidazole rings in equatorial positions and two trifluoromethanesulfonate ions in axial positions. This conformation is similar to those in the analogous complexes tetrakis(imidazole)copper(II) trifluoromethanesulfonate and tetrakis(2-methyl-1H-imidazole)copper(II) trifluoromethanesulfonate. In the second of the title compounds, the ethyl groups block the central Cu atom, and a square-pyramidal coordination environment is formed around the Cu atom, with the substituted imidazole rings in the basal positions and a water molecule in the axial position.
Supporting information
CCDC references: 229068; 229069
The organic ligands 4-methyl-1H-imidazole and 2-ethyl-4-methyl-1H-imidazole (Merck), 2,2'-dimethoxypropane (Aldrich), cupric oxide (Merck), trifluoromethylsulfonic acid (Aldrich), and organic solvents of reagent grade were used as received. Cu(CF3SO3)2·6H2O was prepared from CuO and CF3SO3H. The title compounds were prepared by the following procedure: Cu(CF3SO3)2·6H2O (1 mmol) and the corresponding ligand (4 mmol) were dissolved in acetonitrile containing 5% 2,2-dimethoxypropane. The mixture was stirred at room temperature for 2 h, and then diethyl ether was added dropwise until a precipitate began to appear. The solution was stored in a refrigerator for 2 d and yielded dark-blue crystal [yield 92 and 65% for (III) and (IV), respectively].
All H atoms were positioned geometrically and were treated as riding on their parent atoms in the final refinement. The ethyl group in (IV) is diorientationally disordered and was represented by atom C4/C5 and C4/C5'. The occupancies of atoms C5 and C5' were fixed at 0.55 and 0.45, respectively, in the final refinement, according to the results of occupancy refinement.
Data collection: CAD-4-PC (Enraf-Nonius, 1992) for (III); CAD-4-PC (Enraf–Nonius, 1992) for (IV). For both compounds, cell refinement: CAD-4-PC; data reduction: XCAD4/PC (Harms, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997). Program(s) used to refine structure: SHELXTL) for (III); SHELXTL for (IV). For both compounds, molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(III) tetrakis(5-methyl-1
H-imidazole-
κN3)copper(II) trifluoromethanesulfonate
top
Crystal data top
[Cu(C4H6N2)4](CF3SO3)2 | F(000) = 1404 |
Mr = 690.11 | Dx = 1.622 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 16.400 (3) Å | θ = 10.3–15.0° |
b = 10.174 (2) Å | µ = 1.01 mm−1 |
c = 17.016 (3) Å | T = 293 K |
β = 95.50 (3)° | Prism, blue |
V = 2826.1 (9) Å3 | 0.4 × 0.3 × 0.2 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2890 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ω scan | h = −19→19 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.706, Tmax = 0.817 | l = 0→20 |
5140 measured reflections | 3 standard reflections every 7200 min |
4954 independent reflections | intensity decay: none |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.001P)2 + 7P] where P = (Fo2 + 2Fc2)/3 |
4954 reflections | (Δ/σ)max = 0.006 |
370 parameters | Δρmax = 0.36 e Å−3 |
36 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
[Cu(C4H6N2)4](CF3SO3)2 | V = 2826.1 (9) Å3 |
Mr = 690.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.400 (3) Å | µ = 1.01 mm−1 |
b = 10.174 (2) Å | T = 293 K |
c = 17.016 (3) Å | 0.4 × 0.3 × 0.2 mm |
β = 95.50 (3)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2890 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.706, Tmax = 0.817 | 3 standard reflections every 7200 min |
5140 measured reflections | intensity decay: none |
4954 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 36 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
4954 reflections | Δρmin = −0.31 e Å−3 |
370 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.22066 (4) | 0.22516 (6) | 0.15852 (3) | 0.04250 (16) | |
S1 | 0.12378 (8) | −0.05689 (12) | 0.01003 (7) | 0.0441 (3) | |
S2 | 0.34659 (8) | 0.53309 (13) | 0.26798 (8) | 0.0512 (3) | |
F1 | 0.2757 (3) | −0.1386 (5) | 0.0277 (3) | 0.1318 (19) | |
F2 | 0.2496 (2) | 0.0009 (5) | −0.0651 (3) | 0.1059 (14) | |
F3 | 0.2108 (2) | −0.1983 (4) | −0.0796 (2) | 0.0950 (12) | |
F4 | 0.4582 (3) | 0.6563 (5) | 0.1991 (2) | 0.142 (2) | |
F5 | 0.3920 (3) | 0.5142 (5) | 0.1257 (2) | 0.1315 (19) | |
F6 | 0.4816 (3) | 0.4559 (7) | 0.2167 (3) | 0.159 (2) | |
O1 | 0.1471 (2) | 0.0404 (4) | 0.0688 (2) | 0.0609 (10) | |
O2 | 0.0761 (2) | −0.0098 (4) | −0.0590 (2) | 0.0673 (11) | |
O3 | 0.0968 (3) | −0.1784 (3) | 0.0409 (2) | 0.0772 (13) | |
O4 | 0.3153 (2) | 0.4033 (4) | 0.2611 (3) | 0.0755 (12) | |
O5 | 0.2870 (3) | 0.6289 (4) | 0.2411 (3) | 0.0959 (16) | |
O6 | 0.3906 (2) | 0.5710 (5) | 0.3398 (2) | 0.0961 (17) | |
N1 | 0.1252 (2) | 0.2628 (4) | 0.2190 (2) | 0.0427 (10) | |
N2 | 0.0469 (3) | 0.3349 (4) | 0.3060 (2) | 0.0573 (12) | |
H2A | 0.0305 | 0.3773 | 0.3481 | 0.069* | |
N3 | 0.2577 (2) | 0.0872 (4) | 0.2378 (2) | 0.0428 (10) | |
N4 | 0.2950 (3) | −0.1030 (4) | 0.2876 (2) | 0.0547 (12) | |
H4A | 0.3041 | −0.1901 | 0.2917 | 0.066* | |
N5 | 0.3246 (2) | 0.2032 (4) | 0.1080 (2) | 0.0419 (10) | |
N6 | 0.4529 (3) | 0.1618 (4) | 0.0973 (3) | 0.0585 (12) | |
H6A | 0.5053 | 0.1380 | 0.1104 | 0.070* | |
N7 | 0.1773 (2) | 0.3582 (4) | 0.0787 (2) | 0.0419 (10) | |
N8 | 0.1388 (3) | 0.5486 (4) | 0.0299 (2) | 0.0523 (11) | |
H8A | 0.1310 | 0.6360 | 0.0256 | 0.063* | |
C1 | 0.1229 (3) | 0.3352 (5) | 0.2824 (3) | 0.0524 (13) | |
H1A | 0.1689 | 0.3812 | 0.3083 | 0.063* | |
C2 | −0.0017 (3) | 0.2583 (5) | 0.2543 (3) | 0.0514 (13) | |
C3 | 0.0469 (3) | 0.2151 (5) | 0.2013 (3) | 0.0444 (12) | |
H3A | 0.0300 | 0.1582 | 0.1577 | 0.053* | |
C4 | −0.0900 (3) | 0.2345 (8) | 0.2636 (4) | 0.088 (2) | |
H4B | −0.1132 | 0.1789 | 0.2216 | 0.106* | |
H4C | −0.0951 | 0.1927 | 0.3134 | 0.106* | |
H4D | −0.1184 | 0.3170 | 0.2617 | 0.106* | |
C7 | 0.2908 (3) | 0.1021 (5) | 0.3148 (3) | 0.0505 (13) | |
H7A | 0.2967 | 0.1846 | 0.3421 | 0.061* | |
C6 | 0.3138 (3) | −0.0142 (5) | 0.3462 (3) | 0.0471 (12) | |
C5 | 0.2619 (3) | −0.0401 (5) | 0.2240 (3) | 0.0524 (13) | |
H5A | 0.2434 | −0.0811 | 0.1747 | 0.063* | |
C8 | 0.3533 (4) | −0.0538 (6) | 0.4250 (3) | 0.0776 (19) | |
H8B | 0.3613 | 0.0220 | 0.4585 | 0.093* | |
H8C | 0.3193 | −0.1162 | 0.4487 | 0.093* | |
H8D | 0.4054 | −0.0931 | 0.4182 | 0.093* | |
C9 | 0.3944 (3) | 0.1653 (6) | 0.1452 (3) | 0.0594 (15) | |
H9A | 0.4017 | 0.1430 | 0.2003 | 0.071* | |
C10 | 0.4210 (3) | 0.2005 (5) | 0.0239 (3) | 0.0489 (13) | |
C11 | 0.3417 (3) | 0.2255 (5) | 0.0322 (3) | 0.0464 (12) | |
H11A | 0.3026 | 0.2560 | −0.0095 | 0.056* | |
C12 | 0.4716 (4) | 0.2074 (7) | −0.0438 (3) | 0.0795 (19) | |
H12A | 0.4379 | 0.2363 | −0.0898 | 0.095* | |
H12B | 0.5154 | 0.2690 | −0.0319 | 0.095* | |
H12C | 0.4940 | 0.1224 | −0.0536 | 0.095* | |
C13 | 0.1774 (3) | 0.4850 (5) | 0.0911 (3) | 0.0490 (13) | |
H13A | 0.2025 | 0.5267 | 0.1379 | 0.059* | |
C14 | 0.1121 (3) | 0.4588 (5) | −0.0261 (3) | 0.0502 (13) | |
C15 | 0.1363 (3) | 0.3410 (5) | 0.0054 (3) | 0.0486 (13) | |
H15A | 0.1269 | 0.2582 | −0.0210 | 0.058* | |
C16 | 0.0681 (4) | 0.4970 (6) | −0.1030 (3) | 0.084 (2) | |
H16A | 0.0550 | 0.4192 | −0.1336 | 0.101* | |
H16B | 0.0185 | 0.5428 | −0.0945 | 0.101* | |
H16C | 0.1026 | 0.5531 | −0.1308 | 0.101* | |
C17 | 0.2199 (4) | −0.1017 (7) | −0.0275 (4) | 0.0677 (17) | |
C18 | 0.4214 (5) | 0.5436 (9) | 0.1974 (4) | 0.093 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0440 (3) | 0.0405 (3) | 0.0431 (3) | 0.0074 (3) | 0.0050 (2) | 0.0094 (3) |
S1 | 0.0602 (8) | 0.0303 (6) | 0.0415 (7) | 0.0044 (6) | 0.0029 (6) | 0.0007 (6) |
S2 | 0.0487 (8) | 0.0476 (8) | 0.0570 (8) | −0.0109 (7) | 0.0025 (6) | −0.0077 (7) |
F1 | 0.095 (3) | 0.193 (5) | 0.101 (3) | 0.080 (3) | −0.025 (3) | −0.050 (3) |
F2 | 0.093 (3) | 0.111 (3) | 0.121 (3) | −0.016 (3) | 0.049 (3) | −0.023 (3) |
F3 | 0.114 (3) | 0.088 (3) | 0.085 (3) | 0.016 (2) | 0.019 (2) | −0.040 (2) |
F4 | 0.178 (5) | 0.160 (5) | 0.093 (3) | −0.120 (4) | 0.045 (3) | −0.013 (3) |
F5 | 0.160 (4) | 0.179 (5) | 0.058 (2) | −0.083 (4) | 0.024 (3) | −0.029 (3) |
F6 | 0.087 (3) | 0.207 (6) | 0.191 (6) | 0.004 (4) | 0.063 (4) | −0.035 (5) |
O1 | 0.069 (3) | 0.051 (2) | 0.062 (2) | 0.0045 (19) | 0.0016 (19) | −0.0210 (19) |
O2 | 0.073 (3) | 0.077 (3) | 0.050 (2) | 0.013 (2) | −0.0019 (19) | 0.012 (2) |
O3 | 0.112 (3) | 0.036 (2) | 0.089 (3) | 0.001 (2) | 0.031 (3) | 0.013 (2) |
O4 | 0.079 (3) | 0.046 (2) | 0.105 (3) | −0.015 (2) | 0.027 (3) | −0.005 (2) |
O5 | 0.092 (3) | 0.051 (3) | 0.138 (4) | 0.011 (2) | −0.023 (3) | −0.022 (3) |
O6 | 0.062 (3) | 0.169 (5) | 0.058 (3) | −0.046 (3) | 0.005 (2) | −0.020 (3) |
N1 | 0.043 (2) | 0.042 (2) | 0.043 (2) | 0.004 (2) | 0.0046 (18) | 0.002 (2) |
N2 | 0.070 (3) | 0.055 (3) | 0.048 (3) | 0.015 (2) | 0.012 (2) | −0.005 (2) |
N3 | 0.051 (2) | 0.036 (2) | 0.042 (2) | 0.0017 (19) | 0.0060 (19) | 0.0064 (19) |
N4 | 0.075 (3) | 0.029 (2) | 0.058 (3) | 0.003 (2) | −0.001 (2) | 0.008 (2) |
N5 | 0.044 (2) | 0.039 (2) | 0.043 (2) | 0.0029 (19) | 0.0031 (19) | 0.0060 (19) |
N6 | 0.039 (2) | 0.073 (3) | 0.064 (3) | 0.014 (2) | 0.006 (2) | 0.009 (3) |
N7 | 0.050 (2) | 0.032 (2) | 0.043 (2) | 0.0050 (19) | −0.0010 (19) | 0.0019 (19) |
N8 | 0.069 (3) | 0.030 (2) | 0.057 (3) | 0.004 (2) | −0.002 (2) | 0.004 (2) |
C1 | 0.051 (3) | 0.049 (3) | 0.057 (3) | 0.000 (3) | 0.003 (3) | −0.003 (3) |
C2 | 0.048 (3) | 0.059 (3) | 0.047 (3) | 0.003 (3) | 0.001 (2) | 0.004 (3) |
C3 | 0.045 (3) | 0.046 (3) | 0.041 (3) | 0.001 (2) | −0.002 (2) | 0.000 (2) |
C4 | 0.050 (3) | 0.145 (7) | 0.071 (4) | 0.001 (4) | 0.019 (3) | 0.006 (5) |
C7 | 0.078 (4) | 0.031 (3) | 0.041 (3) | 0.002 (3) | 0.003 (3) | −0.002 (2) |
C6 | 0.059 (3) | 0.036 (3) | 0.045 (3) | 0.000 (2) | 0.002 (3) | 0.008 (2) |
C5 | 0.067 (4) | 0.042 (3) | 0.048 (3) | −0.003 (3) | −0.001 (3) | 0.000 (3) |
C8 | 0.107 (5) | 0.058 (4) | 0.063 (4) | 0.004 (4) | −0.014 (4) | 0.016 (3) |
C9 | 0.044 (3) | 0.084 (4) | 0.050 (3) | 0.011 (3) | 0.004 (3) | 0.015 (3) |
C10 | 0.053 (3) | 0.041 (3) | 0.053 (3) | 0.000 (2) | 0.009 (3) | 0.000 (2) |
C11 | 0.047 (3) | 0.047 (3) | 0.045 (3) | 0.003 (3) | 0.003 (2) | 0.008 (3) |
C12 | 0.074 (4) | 0.102 (5) | 0.066 (4) | −0.001 (4) | 0.022 (3) | −0.001 (4) |
C13 | 0.060 (3) | 0.039 (3) | 0.046 (3) | 0.004 (3) | −0.004 (3) | −0.002 (2) |
C14 | 0.064 (3) | 0.035 (3) | 0.049 (3) | 0.004 (3) | −0.004 (3) | 0.004 (2) |
C15 | 0.067 (4) | 0.031 (3) | 0.045 (3) | 0.004 (2) | −0.006 (3) | −0.003 (2) |
C16 | 0.120 (6) | 0.064 (4) | 0.062 (4) | 0.019 (4) | −0.026 (4) | 0.004 (3) |
C17 | 0.070 (4) | 0.066 (4) | 0.067 (4) | 0.006 (3) | 0.007 (3) | −0.015 (3) |
C18 | 0.091 (6) | 0.111 (6) | 0.082 (5) | −0.045 (5) | 0.029 (4) | −0.025 (5) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.992 (4) | N6—H6A | 0.9000 |
Cu1—N5 | 1.994 (4) | N7—C13 | 1.307 (6) |
Cu1—N7 | 2.000 (4) | N7—C15 | 1.369 (6) |
Cu1—N3 | 2.001 (4) | N8—C13 | 1.333 (6) |
Cu1—O1 | 2.639 (3) | N8—C14 | 1.362 (6) |
Cu1—O4 | 2.867 (4) | N8—H8A | 0.9000 |
S1—O2 | 1.429 (4) | C1—H1A | 0.9601 |
S1—O3 | 1.430 (4) | C2—C3 | 1.334 (7) |
S1—O1 | 1.433 (3) | C2—C4 | 1.491 (7) |
S1—C17 | 1.815 (6) | C3—H3A | 0.9600 |
S2—O6 | 1.412 (4) | C4—H4B | 0.9599 |
S2—O4 | 1.417 (4) | C4—H4C | 0.9600 |
S2—O5 | 1.424 (4) | C4—H4D | 0.9600 |
S2—C18 | 1.800 (7) | C7—C6 | 1.337 (6) |
F1—C17 | 1.302 (7) | C7—H7A | 0.9600 |
F2—C17 | 1.341 (7) | C6—C8 | 1.488 (7) |
F3—C17 | 1.323 (6) | C5—H5A | 0.9600 |
F4—C18 | 1.294 (8) | C8—H8B | 0.9600 |
F5—C18 | 1.303 (8) | C8—H8C | 0.9600 |
F6—C18 | 1.348 (10) | C8—H8D | 0.9601 |
N1—C1 | 1.309 (6) | C9—H9A | 0.9599 |
N1—C3 | 1.379 (6) | C10—C11 | 1.346 (6) |
N2—C1 | 1.345 (6) | C10—C12 | 1.485 (7) |
N2—C2 | 1.371 (6) | C11—H11A | 0.9601 |
N2—H2A | 0.9001 | C12—H12A | 0.9599 |
N3—C5 | 1.319 (6) | C12—H12B | 0.9599 |
N3—C7 | 1.378 (6) | C12—H12C | 0.9600 |
N4—C5 | 1.329 (6) | C13—H13A | 0.9600 |
N4—C6 | 1.359 (6) | C14—C15 | 1.357 (6) |
N4—H4A | 0.9000 | C14—C16 | 1.484 (7) |
N5—C9 | 1.312 (6) | C15—H15A | 0.9600 |
N5—C11 | 1.366 (6) | C16—H16A | 0.9600 |
N6—C9 | 1.317 (6) | C16—H16B | 0.9600 |
N6—C10 | 1.365 (6) | C16—H16C | 0.9600 |
| | | |
N1—Cu1—N5 | 172.42 (16) | C2—C4—H4C | 109.5 |
N1—Cu1—N7 | 88.55 (16) | H4B—C4—H4C | 109.5 |
N5—Cu1—N7 | 92.67 (16) | C2—C4—H4D | 109.2 |
N1—Cu1—N3 | 89.41 (16) | H4B—C4—H4D | 109.5 |
N5—Cu1—N3 | 89.70 (15) | H4C—C4—H4D | 109.5 |
N7—Cu1—N3 | 176.70 (16) | C6—C7—N3 | 110.6 (4) |
N1—Cu1—O1 | 95.62 (14) | C6—C7—H7A | 124.6 |
N5—Cu1—O1 | 91.89 (14) | N3—C7—H7A | 124.7 |
N7—Cu1—O1 | 88.63 (14) | C7—C6—N4 | 105.1 (4) |
N3—Cu1—O1 | 89.00 (14) | C7—C6—C8 | 132.9 (5) |
N1—Cu1—O4 | 88.29 (14) | N4—C6—C8 | 121.9 (5) |
N5—Cu1—O4 | 84.14 (14) | N3—C5—N4 | 110.6 (5) |
N7—Cu1—O4 | 97.01 (14) | N3—C5—H5A | 124.4 |
N3—Cu1—O4 | 85.50 (14) | N4—C5—H5A | 125.0 |
O1—Cu1—O4 | 173.23 (12) | C6—C8—H8B | 110.0 |
O2—S1—O3 | 115.3 (3) | C6—C8—H8C | 109.8 |
O2—S1—O1 | 115.5 (2) | H8B—C8—H8C | 109.5 |
O3—S1—O1 | 114.3 (2) | C6—C8—H8D | 108.7 |
O2—S1—C17 | 102.8 (3) | H8B—C8—H8D | 109.5 |
O3—S1—C17 | 102.8 (3) | H8C—C8—H8D | 109.5 |
O1—S1—C17 | 103.7 (3) | N5—C9—N6 | 111.3 (5) |
O6—S2—O4 | 118.5 (3) | N5—C9—H9A | 124.1 |
O6—S2—O5 | 111.6 (3) | N6—C9—H9A | 124.6 |
O4—S2—O5 | 112.3 (3) | C11—C10—N6 | 104.4 (4) |
O6—S2—C18 | 103.7 (3) | C11—C10—C12 | 133.6 (5) |
O4—S2—C18 | 105.3 (3) | N6—C10—C12 | 122.0 (5) |
O5—S2—C18 | 103.6 (4) | C10—C11—N5 | 110.8 (4) |
S1—O1—Cu1 | 166.5 (2) | C10—C11—H11A | 124.5 |
S2—O4—Cu1 | 144.1 (3) | N5—C11—H11A | 124.7 |
C1—N1—C3 | 106.1 (4) | C10—C12—H12A | 109.1 |
C1—N1—Cu1 | 128.4 (3) | C10—C12—H12B | 109.2 |
C3—N1—Cu1 | 125.5 (3) | H12A—C12—H12B | 109.5 |
C1—N2—C2 | 107.9 (4) | C10—C12—H12C | 110.1 |
C1—N2—H2A | 126.4 | H12A—C12—H12C | 109.5 |
C2—N2—H2A | 125.8 | H12B—C12—H12C | 109.5 |
C5—N3—C7 | 104.8 (4) | N7—C13—N8 | 111.1 (4) |
C5—N3—Cu1 | 125.9 (3) | N7—C13—H13A | 124.3 |
C7—N3—Cu1 | 129.1 (3) | N8—C13—H13A | 124.6 |
C5—N4—C6 | 108.9 (4) | C15—C14—N8 | 104.7 (4) |
C5—N4—H4A | 126.0 | C15—C14—C16 | 132.8 (5) |
C6—N4—H4A | 125.1 | N8—C14—C16 | 122.5 (5) |
C9—N5—C11 | 104.8 (4) | C14—C15—N7 | 110.3 (4) |
C9—N5—Cu1 | 124.6 (3) | C14—C15—H15A | 124.2 |
C11—N5—Cu1 | 130.5 (3) | N7—C15—H15A | 125.5 |
C9—N6—C10 | 108.7 (4) | C14—C16—H16A | 109.1 |
C9—N6—H6A | 126.0 | C14—C16—H16B | 110.0 |
C10—N6—H6A | 125.3 | H16A—C16—H16B | 109.5 |
C13—N7—C15 | 105.4 (4) | C14—C16—H16C | 109.3 |
C13—N7—Cu1 | 124.3 (3) | H16A—C16—H16C | 109.5 |
C15—N7—Cu1 | 130.0 (3) | H16B—C16—H16C | 109.5 |
C13—N8—C14 | 108.5 (4) | F1—C17—F3 | 107.2 (5) |
C13—N8—H8A | 126.6 | F1—C17—F2 | 107.9 (6) |
C14—N8—H8A | 124.9 | F3—C17—F2 | 106.4 (5) |
N1—C1—N2 | 110.2 (5) | F1—C17—S1 | 113.1 (5) |
N1—C1—H1A | 124.7 | F3—C17—S1 | 112.1 (5) |
N2—C1—H1A | 125.0 | F2—C17—S1 | 109.9 (4) |
C3—C2—N2 | 105.8 (5) | F4—C18—F5 | 110.7 (7) |
C3—C2—C4 | 131.8 (5) | F4—C18—F6 | 104.6 (7) |
N2—C2—C4 | 122.3 (5) | F5—C18—F6 | 105.8 (7) |
C2—C3—N1 | 109.9 (4) | F4—C18—S2 | 112.6 (6) |
C2—C3—H3A | 125.0 | F5—C18—S2 | 113.3 (5) |
N1—C3—H3A | 125.1 | F6—C18—S2 | 109.2 (6) |
C2—C4—H4B | 109.7 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.90 | 2.16 | 2.910 (6) | 141 |
N4—H4A···O5ii | 0.90 | 2.04 | 2.839 (6) | 147 |
N6—H6A···O6iii | 0.90 | 1.96 | 2.840 (6) | 167 |
N8—H8A···O3iv | 0.90 | 1.99 | 2.872 (5) | 165 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2; (iv) x, y+1, z. |
(IV) aquatetrakis(2-ethyl-5-methyl-1
H-imidazole-
κN3)copper(II) trifluoromethanesulfonate
top
Crystal data top
[Cu(C6H10N2)4(H2O)](CF3SO3)2 | F(000) = 1700 |
Mr = 820.34 | Dx = 1.419 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 15.408 (3) Å | θ = 8.8–12.5° |
b = 12.627 (3) Å | µ = 0.76 mm−1 |
c = 20.380 (4) Å | T = 293 K |
β = 104.37 (3)° | Prism, blue |
V = 3841.0 (14) Å3 | 0.25 × 0.15 × 0.12 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2847 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scan | h = −18→17 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→15 |
Tmin = 0.807, Tmax = 0.913 | l = 0→24 |
6948 measured reflections | 3 standard reflections every 7200 min |
6740 independent reflections | intensity decay: none |
Refinement top
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.001P)2 + 14P] where P = (Fo2 + 2Fc2)/3 |
6740 reflections | (Δ/σ)max = 0.001 |
460 parameters | Δρmax = 0.43 e Å−3 |
2 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
[Cu(C6H10N2)4(H2O)](CF3SO3)2 | V = 3841.0 (14) Å3 |
Mr = 820.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.408 (3) Å | µ = 0.76 mm−1 |
b = 12.627 (3) Å | T = 293 K |
c = 20.380 (4) Å | 0.25 × 0.15 × 0.12 mm |
β = 104.37 (3)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2847 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.807, Tmax = 0.913 | 3 standard reflections every 7200 min |
6948 measured reflections | intensity decay: none |
6740 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 2 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.001P)2 + 14P] where P = (Fo2 + 2Fc2)/3 |
6740 reflections | Δρmax = 0.43 e Å−3 |
460 parameters | Δρmin = −0.34 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.26043 (6) | 0.14810 (7) | 0.24746 (4) | 0.0621 (3) | |
S1 | 0.27679 (16) | −0.0416 (2) | −0.12107 (11) | 0.0828 (6) | |
S2 | 0.78397 (16) | 0.0321 (2) | 0.40456 (11) | 0.0846 (7) | |
O1W | 0.2678 (4) | 0.3349 (4) | 0.2382 (3) | 0.0957 (17) | |
H1A | 0.2875 | 0.3614 | 0.2775 | 0.115* | |
H1B | 0.2157 | 0.3588 | 0.2205 | 0.115* | |
O1 | 0.1911 (5) | −0.0326 (7) | −0.1595 (4) | 0.172 (4) | |
O2 | 0.2839 (7) | −0.0634 (7) | −0.0544 (3) | 0.210 (5) | |
O3 | 0.3293 (6) | 0.0387 (7) | −0.1367 (5) | 0.186 (4) | |
O4 | 0.7787 (6) | 0.0795 (7) | 0.4635 (3) | 0.171 (4) | |
O5 | 0.7124 (4) | 0.0443 (9) | 0.3492 (3) | 0.188 (4) | |
O6 | 0.8065 (7) | −0.0747 (7) | 0.4119 (6) | 0.208 (4) | |
F1 | 0.2659 (9) | −0.2300 (8) | −0.1550 (8) | 0.309 (8) | |
F2 | 0.3345 (8) | −0.1443 (8) | −0.2092 (5) | 0.262 (5) | |
F3 | 0.3914 (7) | −0.1903 (10) | −0.1187 (6) | 0.280 (7) | |
F4 | 0.8866 (5) | 0.0517 (9) | 0.3263 (4) | 0.230 (5) | |
F5 | 0.8633 (11) | 0.1902 (8) | 0.3724 (8) | 0.313 (9) | |
F6 | 0.9475 (6) | 0.0782 (11) | 0.4229 (5) | 0.273 (6) | |
N1 | 0.3922 (4) | 0.1471 (5) | 0.2960 (3) | 0.0661 (16) | |
N2 | 0.5363 (4) | 0.1265 (6) | 0.3337 (3) | 0.078 (2) | |
H2A | 0.5918 | 0.0996 | 0.3398 | 0.094* | |
N3 | 0.2288 (3) | 0.1529 (5) | 0.3368 (3) | 0.0602 (15) | |
N4 | 0.2061 (4) | 0.1216 (6) | 0.4359 (3) | 0.080 (2) | |
H4A | 0.2071 | 0.0880 | 0.4750 | 0.096* | |
N5 | 0.1292 (4) | 0.1455 (5) | 0.2007 (3) | 0.0648 (16) | |
N6 | −0.0154 (4) | 0.1234 (6) | 0.1706 (3) | 0.0761 (19) | |
H6A | −0.0697 | 0.0956 | 0.1688 | 0.091* | |
N7 | 0.2892 (4) | 0.1268 (5) | 0.1579 (3) | 0.0641 (17) | |
N8 | 0.3050 (4) | 0.0678 (6) | 0.0617 (3) | 0.079 (2) | |
H8A | 0.2991 | 0.0260 | 0.0252 | 0.095* | |
C1 | 0.4616 (5) | 0.0890 (7) | 0.2906 (4) | 0.070 (2) | |
C2 | 0.5142 (5) | 0.2124 (7) | 0.3672 (4) | 0.071 (2) | |
C3 | 0.4251 (5) | 0.2250 (6) | 0.3440 (3) | 0.066 (2) | |
H3A | 0.3903 | 0.2792 | 0.3585 | 0.079* | |
C4 | 0.4618 (7) | −0.0068 (7) | 0.2479 (4) | 0.094 (3) | |
H4B | 0.4263 | 0.0100 | 0.2028 | 0.113* | 0.55 |
H4C | 0.5229 | −0.0170 | 0.2444 | 0.113* | 0.55 |
C5 | 0.432 (2) | −0.105 (2) | 0.2657 (12) | 0.175 (15) | 0.55 |
H5A | 0.4345 | −0.1561 | 0.2317 | 0.263* | 0.55 |
H5B | 0.3709 | −0.0977 | 0.2692 | 0.263* | 0.55 |
H5C | 0.4689 | −0.1269 | 0.3085 | 0.263* | 0.55 |
H4D | 0.4006 | −0.0254 | 0.2254 | 0.113* | 0.45 |
H4E | 0.4931 | 0.0092 | 0.2133 | 0.113* | 0.45 |
C5' | 0.5036 (19) | −0.094 (3) | 0.2867 (15) | 0.149 (16) | 0.45 |
H5'1 | 0.5050 | −0.1531 | 0.2573 | 0.224* | 0.45 |
H5'2 | 0.4705 | −0.1132 | 0.3191 | 0.224* | 0.45 |
H5'3 | 0.5637 | −0.0753 | 0.3100 | 0.224* | 0.45 |
C6 | 0.5829 (5) | 0.2753 (7) | 0.4166 (4) | 0.103 (3) | |
H6B | 0.5533 | 0.3325 | 0.4332 | 0.124* | |
H6C | 0.6108 | 0.2297 | 0.4535 | 0.124* | |
H6D | 0.6277 | 0.3033 | 0.3960 | 0.124* | |
C7 | 0.2434 (5) | 0.0859 (7) | 0.3873 (3) | 0.064 (2) | |
C8 | 0.1643 (5) | 0.2145 (8) | 0.4161 (4) | 0.075 (2) | |
C9 | 0.1784 (5) | 0.2344 (7) | 0.3549 (4) | 0.073 (2) | |
H9A | 0.1575 | 0.2957 | 0.3277 | 0.088* | |
C10 | 0.2943 (5) | −0.0149 (6) | 0.3937 (4) | 0.081 (2) | |
H10A | 0.3037 | −0.0321 | 0.3501 | 0.097* | |
H10B | 0.2588 | −0.0702 | 0.4062 | 0.097* | |
C11 | 0.3848 (5) | −0.0123 (7) | 0.4449 (4) | 0.102 (3) | |
H11A | 0.4147 | −0.0793 | 0.4466 | 0.123* | |
H11B | 0.4209 | 0.0421 | 0.4321 | 0.123* | |
H11C | 0.3755 | 0.0036 | 0.4888 | 0.123* | |
C12 | 0.1174 (5) | 0.2776 (8) | 0.4588 (4) | 0.107 (3) | |
H12A | 0.0932 | 0.3409 | 0.4351 | 0.128* | |
H12B | 0.0697 | 0.2366 | 0.4687 | 0.128* | |
H12C | 0.1596 | 0.2962 | 0.5003 | 0.128* | |
C13 | 0.0636 (5) | 0.0883 (7) | 0.2113 (3) | 0.067 (2) | |
C14 | 0.0020 (6) | 0.2068 (7) | 0.1329 (4) | 0.076 (2) | |
C15 | 0.0913 (5) | 0.2207 (7) | 0.1512 (4) | 0.072 (2) | |
H15A | 0.1236 | 0.2733 | 0.1329 | 0.086* | |
C16 | 0.0692 (6) | −0.0025 (7) | 0.2570 (4) | 0.091 (3) | |
H16A | 0.0464 | 0.0191 | 0.2947 | 0.109* | |
H16B | 0.1313 | −0.0200 | 0.2743 | 0.109* | |
C17 | 0.0202 (8) | −0.0965 (9) | 0.2299 (5) | 0.169 (6) | |
H17A | 0.0279 | −0.1512 | 0.2635 | 0.203* | |
H17B | −0.0424 | −0.0806 | 0.2135 | 0.203* | |
H17C | 0.0436 | −0.1201 | 0.1929 | 0.203* | |
C18 | −0.0706 (5) | 0.2664 (8) | 0.0839 (4) | 0.111 (3) | |
H18A | −0.1285 | 0.2369 | 0.0826 | 0.133* | |
H18B | −0.0691 | 0.3392 | 0.0976 | 0.133* | |
H18C | −0.0594 | 0.2618 | 0.0397 | 0.133* | |
C19 | 0.2669 (4) | 0.0503 (7) | 0.1126 (3) | 0.066 (2) | |
C20 | 0.3527 (5) | 0.1597 (8) | 0.0732 (4) | 0.077 (2) | |
C21 | 0.3440 (5) | 0.1956 (7) | 0.1337 (4) | 0.077 (2) | |
H21A | 0.3707 | 0.2592 | 0.1555 | 0.092* | |
C22 | 0.2097 (5) | −0.0440 (7) | 0.1152 (4) | 0.086 (2) | |
H22A | 0.1987 | −0.0479 | 0.1595 | 0.103* | |
H22B | 0.2405 | −0.1073 | 0.1080 | 0.103* | |
C23 | 0.1206 (6) | −0.0405 (8) | 0.0635 (4) | 0.121 (4) | |
H23A | 0.0847 | −0.1016 | 0.0666 | 0.145* | |
H23B | 0.0894 | 0.0223 | 0.0711 | 0.145* | |
H23C | 0.1316 | −0.0376 | 0.0192 | 0.145* | |
C24 | 0.4028 (6) | 0.2048 (9) | 0.0256 (4) | 0.128 (4) | |
H24A | 0.3961 | 0.1589 | −0.0128 | 0.154* | |
H24B | 0.3795 | 0.2736 | 0.0108 | 0.154* | |
H24C | 0.4652 | 0.2107 | 0.0483 | 0.154* | |
C25 | 0.3195 (8) | −0.1534 (10) | −0.1521 (6) | 0.152 (5) | |
C26 | 0.8761 (9) | 0.0930 (15) | 0.3802 (7) | 0.143 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0600 (5) | 0.0766 (6) | 0.0480 (4) | 0.0012 (5) | 0.0105 (4) | 0.0009 (5) |
S1 | 0.0920 (16) | 0.0810 (17) | 0.0703 (13) | 0.0012 (14) | 0.0107 (12) | 0.0008 (13) |
S2 | 0.0802 (15) | 0.106 (2) | 0.0650 (13) | 0.0062 (14) | 0.0140 (11) | −0.0025 (14) |
O1W | 0.114 (4) | 0.085 (4) | 0.075 (3) | 0.005 (4) | −0.002 (3) | 0.003 (3) |
O1 | 0.086 (5) | 0.206 (9) | 0.205 (8) | 0.020 (6) | 0.000 (5) | −0.005 (7) |
O2 | 0.398 (14) | 0.172 (8) | 0.063 (4) | 0.069 (9) | 0.064 (6) | −0.001 (5) |
O3 | 0.202 (9) | 0.113 (7) | 0.250 (10) | −0.055 (6) | 0.069 (8) | 0.028 (7) |
O4 | 0.218 (8) | 0.214 (9) | 0.099 (5) | −0.046 (7) | 0.075 (6) | −0.060 (6) |
O5 | 0.076 (4) | 0.382 (14) | 0.101 (5) | 0.036 (7) | 0.011 (4) | 0.027 (7) |
O6 | 0.252 (11) | 0.110 (7) | 0.280 (12) | 0.018 (7) | 0.098 (9) | 0.018 (8) |
F1 | 0.404 (18) | 0.110 (7) | 0.49 (2) | −0.012 (10) | 0.264 (18) | −0.050 (10) |
F2 | 0.408 (15) | 0.230 (10) | 0.208 (9) | 0.122 (10) | 0.193 (10) | 0.035 (8) |
F3 | 0.243 (11) | 0.326 (15) | 0.223 (10) | 0.195 (11) | −0.035 (8) | 0.000 (9) |
F4 | 0.161 (7) | 0.397 (15) | 0.166 (7) | −0.082 (8) | 0.105 (6) | −0.086 (8) |
F5 | 0.47 (2) | 0.128 (8) | 0.396 (19) | −0.048 (11) | 0.217 (17) | 0.054 (10) |
F6 | 0.140 (7) | 0.46 (2) | 0.205 (9) | −0.118 (10) | 0.012 (6) | −0.069 (11) |
N1 | 0.063 (4) | 0.074 (4) | 0.059 (3) | 0.000 (4) | 0.011 (3) | −0.005 (4) |
N2 | 0.057 (4) | 0.103 (6) | 0.071 (4) | 0.005 (4) | 0.009 (3) | −0.001 (4) |
N3 | 0.055 (3) | 0.072 (4) | 0.052 (3) | 0.002 (3) | 0.011 (3) | 0.001 (3) |
N4 | 0.077 (4) | 0.117 (7) | 0.047 (4) | −0.005 (4) | 0.017 (3) | 0.004 (4) |
N5 | 0.061 (3) | 0.078 (5) | 0.055 (3) | −0.003 (4) | 0.015 (3) | 0.004 (4) |
N6 | 0.058 (4) | 0.098 (6) | 0.072 (4) | −0.001 (4) | 0.014 (3) | −0.001 (4) |
N7 | 0.062 (4) | 0.079 (5) | 0.052 (3) | −0.009 (3) | 0.013 (3) | −0.006 (3) |
N8 | 0.074 (4) | 0.112 (6) | 0.051 (4) | −0.004 (4) | 0.016 (3) | −0.011 (4) |
C1 | 0.076 (5) | 0.074 (6) | 0.058 (5) | 0.007 (5) | 0.012 (4) | −0.005 (4) |
C2 | 0.075 (5) | 0.081 (6) | 0.061 (5) | −0.011 (5) | 0.021 (4) | −0.001 (5) |
C3 | 0.070 (5) | 0.072 (6) | 0.051 (4) | 0.009 (4) | 0.007 (4) | −0.001 (4) |
C4 | 0.108 (7) | 0.084 (7) | 0.079 (6) | 0.024 (6) | 0.002 (5) | −0.006 (5) |
C5 | 0.36 (5) | 0.090 (18) | 0.12 (2) | −0.04 (3) | 0.14 (3) | −0.019 (17) |
C4 | 0.108 (7) | 0.084 (7) | 0.079 (6) | 0.024 (6) | 0.002 (5) | −0.006 (5) |
C5' | 0.17 (3) | 0.10 (2) | 0.13 (2) | 0.07 (2) | −0.05 (2) | −0.053 (18) |
C6 | 0.088 (6) | 0.108 (8) | 0.106 (7) | −0.026 (6) | 0.011 (5) | −0.022 (6) |
C7 | 0.061 (4) | 0.081 (6) | 0.048 (4) | −0.004 (4) | 0.008 (4) | 0.002 (4) |
C8 | 0.063 (5) | 0.102 (7) | 0.060 (5) | 0.001 (5) | 0.012 (4) | −0.013 (5) |
C9 | 0.066 (5) | 0.088 (6) | 0.062 (5) | 0.011 (5) | 0.010 (4) | −0.001 (4) |
C10 | 0.092 (6) | 0.072 (6) | 0.079 (5) | 0.009 (5) | 0.022 (5) | 0.020 (5) |
C11 | 0.090 (6) | 0.115 (8) | 0.094 (6) | 0.025 (6) | 0.005 (5) | 0.023 (6) |
C12 | 0.082 (6) | 0.152 (9) | 0.092 (6) | 0.008 (6) | 0.031 (5) | −0.038 (6) |
C13 | 0.062 (5) | 0.083 (6) | 0.054 (4) | 0.006 (5) | 0.011 (4) | −0.001 (4) |
C14 | 0.079 (6) | 0.092 (7) | 0.052 (5) | 0.011 (5) | 0.005 (4) | −0.003 (5) |
C15 | 0.075 (5) | 0.080 (6) | 0.058 (5) | 0.005 (5) | 0.013 (4) | 0.010 (4) |
C16 | 0.098 (6) | 0.106 (8) | 0.062 (5) | −0.035 (6) | 0.006 (5) | 0.009 (5) |
C17 | 0.226 (14) | 0.149 (12) | 0.116 (9) | −0.064 (11) | 0.011 (9) | 0.033 (9) |
C18 | 0.102 (7) | 0.136 (9) | 0.077 (6) | 0.032 (7) | −0.014 (5) | 0.015 (6) |
C19 | 0.055 (4) | 0.096 (7) | 0.050 (4) | 0.008 (4) | 0.015 (3) | 0.003 (4) |
C20 | 0.060 (5) | 0.116 (8) | 0.054 (4) | −0.002 (5) | 0.012 (4) | 0.012 (5) |
C21 | 0.068 (5) | 0.092 (7) | 0.072 (5) | −0.018 (5) | 0.019 (4) | −0.002 (5) |
C22 | 0.088 (6) | 0.075 (6) | 0.097 (6) | −0.005 (5) | 0.029 (5) | −0.011 (5) |
C23 | 0.115 (8) | 0.136 (9) | 0.108 (7) | −0.053 (7) | 0.020 (6) | −0.020 (7) |
C24 | 0.111 (7) | 0.197 (12) | 0.082 (6) | −0.020 (8) | 0.035 (6) | 0.031 (7) |
C25 | 0.238 (17) | 0.131 (12) | 0.093 (8) | 0.031 (13) | 0.052 (10) | 0.039 (9) |
C26 | 0.096 (8) | 0.239 (18) | 0.088 (8) | 0.009 (11) | 0.013 (7) | −0.010 (10) |
Geometric parameters (Å, º) top
Cu1—N3 | 1.999 (5) | C5—H5B | 0.9600 |
Cu1—N7 | 2.000 (5) | C5—H5C | 0.9600 |
Cu1—N5 | 2.010 (6) | C4—C5' | 1.42 (3) |
Cu1—N1 | 2.026 (5) | C4—H4D | 0.9700 |
Cu1—O1W | 2.372 (5) | C4—H4E | 0.9700 |
S1—O1 | 1.362 (7) | C5'—H5'1 | 0.9600 |
S1—O2 | 1.364 (7) | C5'—H5'2 | 0.9600 |
S1—O3 | 1.383 (7) | C5'—H5'3 | 0.9600 |
S1—C25 | 1.742 (13) | C6—H6B | 0.9600 |
S2—O4 | 1.364 (6) | C6—H6C | 0.9601 |
S2—O5 | 1.376 (6) | C6—H6D | 0.9600 |
S2—O6 | 1.391 (9) | C7—C10 | 1.483 (10) |
S2—C26 | 1.789 (14) | C8—C9 | 1.340 (9) |
O1W—H1A | 0.8499 | C8—C12 | 1.493 (10) |
O1W—H1B | 0.8500 | C9—H9A | 0.9600 |
F1—C25 | 1.264 (9) | C10—C11 | 1.521 (9) |
F2—C25 | 1.246 (12) | C10—H10A | 0.9600 |
F3—C25 | 1.239 (8) | C10—H10B | 0.9599 |
F4—C26 | 1.262 (14) | C11—H11A | 0.9600 |
F5—C26 | 1.248 (18) | C11—H11B | 0.9601 |
F6—C26 | 1.235 (13) | C11—H11C | 0.9599 |
N1—C1 | 1.323 (9) | C12—H12A | 0.9600 |
N1—C3 | 1.391 (9) | C12—H12B | 0.9600 |
N2—C1 | 1.348 (9) | C12—H12C | 0.9601 |
N2—C2 | 1.368 (9) | C13—C16 | 1.467 (10) |
N2—H2A | 0.9000 | C14—C15 | 1.345 (10) |
N3—C7 | 1.309 (8) | C14—C18 | 1.504 (10) |
N3—C9 | 1.394 (9) | C15—H15A | 0.9600 |
N4—C7 | 1.340 (8) | C16—C17 | 1.441 (11) |
N4—C8 | 1.351 (10) | C16—H16A | 0.9600 |
N4—H4A | 0.8999 | C16—H16B | 0.9599 |
N5—C13 | 1.304 (9) | C17—H17A | 0.9600 |
N5—C15 | 1.402 (9) | C17—H17B | 0.9600 |
N6—C13 | 1.365 (8) | C17—H17C | 0.9600 |
N6—C14 | 1.369 (9) | C18—H18A | 0.9600 |
N6—H6A | 0.9000 | C18—H18B | 0.9600 |
N7—C19 | 1.322 (9) | C18—H18C | 0.9601 |
N7—C21 | 1.385 (9) | C19—C22 | 1.490 (10) |
N8—C19 | 1.329 (8) | C20—C21 | 1.351 (9) |
N8—C20 | 1.363 (10) | C20—C24 | 1.494 (10) |
N8—H8A | 0.9000 | C21—H21A | 0.9600 |
C1—C4 | 1.492 (10) | C22—C23 | 1.510 (10) |
C1—C4 | 1.492 (10) | C22—H22A | 0.9600 |
C2—C3 | 1.346 (9) | C22—H22B | 0.9600 |
C2—C6 | 1.495 (10) | C23—H23A | 0.9600 |
C3—H3A | 0.9601 | C23—H23B | 0.9600 |
C4—C5 | 1.40 (2) | C23—H23C | 0.9600 |
C4—H4B | 0.9700 | C24—H24A | 0.9600 |
C4—H4C | 0.9700 | C24—H24B | 0.9600 |
C5—H5A | 0.9600 | C24—H24C | 0.9599 |
| | | |
N3—Cu1—N7 | 173.9 (3) | N3—C7—C10 | 127.4 (7) |
N3—Cu1—N5 | 89.4 (2) | N4—C7—C10 | 122.5 (7) |
N7—Cu1—N5 | 89.4 (2) | C9—C8—N4 | 105.4 (7) |
N3—Cu1—N1 | 89.8 (2) | C9—C8—C12 | 131.0 (9) |
N7—Cu1—N1 | 91.3 (2) | N4—C8—C12 | 123.6 (8) |
N5—Cu1—N1 | 178.5 (3) | C8—C9—N3 | 109.8 (7) |
N3—Cu1—O1W | 94.0 (2) | C8—C9—H9A | 125.5 |
N7—Cu1—O1W | 92.0 (2) | N3—C9—H9A | 124.8 |
N5—Cu1—O1W | 92.3 (2) | C7—C10—C11 | 114.6 (7) |
N1—Cu1—O1W | 89.0 (2) | C7—C10—H10A | 108.2 |
O1—S1—O2 | 114.6 (6) | C11—C10—H10A | 108.5 |
O1—S1—O3 | 110.3 (6) | C7—C10—H10B | 108.9 |
O2—S1—O3 | 118.1 (6) | C11—C10—H10B | 108.6 |
O1—S1—C25 | 105.0 (6) | H10A—C10—H10B | 107.9 |
O2—S1—C25 | 104.7 (5) | C10—C11—H11A | 110.9 |
O3—S1—C25 | 102.4 (6) | C10—C11—H11B | 108.8 |
O4—S2—O5 | 117.6 (5) | H11A—C11—H11B | 109.5 |
O4—S2—O6 | 113.5 (6) | C10—C11—H11C | 108.7 |
O5—S2—O6 | 108.9 (7) | H11A—C11—H11C | 109.5 |
O4—S2—C26 | 106.3 (6) | H11B—C11—H11C | 109.5 |
O5—S2—C26 | 104.7 (6) | C8—C12—H12A | 109.6 |
O6—S2—C26 | 104.6 (7) | C8—C12—H12B | 109.9 |
Cu1—O1W—H1A | 109.2 | H12A—C12—H12B | 109.5 |
Cu1—O1W—H1B | 109.1 | C8—C12—H12C | 108.9 |
H1A—O1W—H1B | 109.9 | H12A—C12—H12C | 109.5 |
C1—N1—C3 | 106.8 (6) | H12B—C12—H12C | 109.5 |
C1—N1—Cu1 | 134.1 (5) | N5—C13—N6 | 109.3 (7) |
C3—N1—Cu1 | 119.0 (5) | N5—C13—C16 | 127.8 (7) |
C1—N2—C2 | 109.0 (6) | N6—C13—C16 | 122.9 (7) |
C1—N2—H2A | 125.8 | C15—C14—N6 | 105.9 (7) |
C2—N2—H2A | 125.2 | C15—C14—C18 | 131.3 (9) |
C7—N3—C9 | 105.4 (6) | N6—C14—C18 | 122.7 (8) |
C7—N3—Cu1 | 131.6 (5) | C14—C15—N5 | 109.0 (7) |
C9—N3—Cu1 | 122.8 (5) | C14—C15—H15A | 125.1 |
C7—N4—C8 | 109.3 (7) | N5—C15—H15A | 125.8 |
C7—N4—H4A | 125.5 | C17—C16—C13 | 117.2 (7) |
C8—N4—H4A | 125.2 | C17—C16—H16A | 106.3 |
C13—N5—C15 | 107.0 (6) | C13—C16—H16A | 108.0 |
C13—N5—Cu1 | 131.3 (5) | C17—C16—H16B | 109.4 |
C15—N5—Cu1 | 121.4 (5) | C13—C16—H16B | 108.0 |
C13—N6—C14 | 108.7 (6) | H16A—C16—H16B | 107.6 |
C13—N6—H6A | 125.3 | C16—C17—H17A | 111.0 |
C14—N6—H6A | 125.9 | C16—C17—H17B | 110.3 |
C19—N7—C21 | 106.5 (6) | H17A—C17—H17B | 109.5 |
C19—N7—Cu1 | 131.1 (5) | C16—C17—H17C | 107.1 |
C21—N7—Cu1 | 122.3 (5) | H17A—C17—H17C | 109.5 |
C19—N8—C20 | 109.4 (7) | H17B—C17—H17C | 109.5 |
C19—N8—H8A | 125.0 | C14—C18—H18A | 110.9 |
C20—N8—H8A | 125.5 | C14—C18—H18B | 109.1 |
N1—C1—N2 | 109.2 (7) | H18A—C18—H18B | 109.5 |
N1—C1—C4 | 128.1 (8) | C14—C18—H18C | 108.4 |
N2—C1—C4 | 122.7 (8) | H18A—C18—H18C | 109.5 |
N1—C1—C4 | 128.1 (8) | H18B—C18—H18C | 109.5 |
N2—C1—C4 | 122.7 (8) | N7—C19—N8 | 109.5 (7) |
C4—C1—C4 | 0.0 (11) | N7—C19—C22 | 127.7 (7) |
C3—C2—N2 | 106.1 (7) | N8—C19—C22 | 122.7 (8) |
C3—C2—C6 | 131.6 (8) | C21—C20—N8 | 105.7 (7) |
N2—C2—C6 | 122.3 (7) | C21—C20—C24 | 130.5 (9) |
C2—C3—N1 | 109.0 (7) | N8—C20—C24 | 123.9 (8) |
C2—C3—H3A | 125.1 | C20—C21—N7 | 108.8 (7) |
N1—C3—H3A | 125.9 | C20—C21—H21A | 125.1 |
C5—C4—C1 | 121.0 (12) | N7—C21—H21A | 126.1 |
C5—C4—H4B | 107.1 | C19—C22—C23 | 113.3 (8) |
C1—C4—H4B | 107.1 | C19—C22—H22A | 108.6 |
C5—C4—H4C | 107.1 | C23—C22—H22A | 108.4 |
C1—C4—H4C | 107.1 | C19—C22—H22B | 109.9 |
H4B—C4—H4C | 106.8 | C23—C22—H22B | 108.4 |
C4—C5—H5A | 109.5 | H22A—C22—H22B | 108.1 |
C4—C5—H5B | 109.5 | C22—C23—H23A | 111.6 |
H5A—C5—H5B | 109.5 | C22—C23—H23B | 108.4 |
C4—C5—H5C | 109.5 | H23A—C23—H23B | 109.5 |
H5A—C5—H5C | 109.5 | C22—C23—H23C | 108.4 |
H5B—C5—H5C | 109.5 | H23A—C23—H23C | 109.5 |
C5'—C4—C1 | 111.9 (13) | H23B—C23—H23C | 109.5 |
C5'—C4—H4D | 109.2 | C20—C24—H24A | 109.3 |
C1—C4—H4D | 109.2 | C20—C24—H24B | 109.7 |
C5'—C4—H4E | 109.2 | H24A—C24—H24B | 109.5 |
C1—C4—H4E | 109.2 | C20—C24—H24C | 109.5 |
H4D—C4—H4E | 107.9 | H24A—C24—H24C | 109.5 |
C4—C5'—H5'1 | 109.5 | H24B—C24—H24C | 109.5 |
C4—C5'—H5'2 | 109.5 | F3—C25—F2 | 101.5 (12) |
H5'1—C5'—H5'2 | 109.5 | F3—C25—F1 | 102.8 (12) |
C4—C5'—H5'3 | 109.5 | F2—C25—F1 | 107.3 (14) |
H5'1—C5'—H5'3 | 109.5 | F3—C25—S1 | 118.2 (11) |
H5'2—C5'—H5'3 | 109.5 | F2—C25—S1 | 116.0 (9) |
C2—C6—H6B | 108.6 | F1—C25—S1 | 109.7 (10) |
C2—C6—H6C | 108.3 | F6—C26—F5 | 108.9 (16) |
H6B—C6—H6C | 109.5 | F6—C26—F4 | 105.5 (13) |
C2—C6—H6D | 111.6 | F5—C26—F4 | 110.2 (15) |
H6B—C6—H6D | 109.5 | F6—C26—S2 | 111.7 (11) |
H6C—C6—H6D | 109.5 | F5—C26—S2 | 110.2 (12) |
N3—C7—N4 | 110.1 (7) | F4—C26—S2 | 110.2 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5 | 0.90 | 1.95 | 2.849 (9) | 178 |
N4—H4A···O6i | 0.90 | 2.37 | 3.211 (12) | 155 |
N6—H6A···O1ii | 0.90 | 2.00 | 2.897 (10) | 177 |
N8—H8A···O2 | 0.90 | 1.94 | 2.841 (9) | 179 |
O1W—H1A···O3iii | 0.85 | 2.12 | 2.957 (10) | 167 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z; (iii) x, −y+1/2, z+1/2. |
Experimental details
| (III) | (IV) |
Crystal data |
Chemical formula | [Cu(C4H6N2)4](CF3SO3)2 | [Cu(C6H10N2)4(H2O)](CF3SO3)2 |
Mr | 690.11 | 820.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 16.400 (3), 10.174 (2), 17.016 (3) | 15.408 (3), 12.627 (3), 20.380 (4) |
β (°) | 95.50 (3) | 104.37 (3) |
V (Å3) | 2826.1 (9) | 3841.0 (14) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.01 | 0.76 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 | 0.25 × 0.15 × 0.12 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.706, 0.817 | 0.807, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5140, 4954, 2890 | 6948, 6740, 2847 |
Rint | 0.025 | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.103, 1.03 | 0.064, 0.155, 1.02 |
No. of reflections | 4954 | 6740 |
No. of parameters | 370 | 460 |
No. of restraints | 36 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
| w = 1/[σ2(Fo2) + (0.001P)2 + 7P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.001P)2 + 14P] where P = (Fo2 + 2Fc2)/3 |
Δρmax, Δρmin (e Å−3) | 0.36, −0.31 | 0.43, −0.34 |
Selected geometric parameters (Å, º) for (III) topCu1—N1 | 1.992 (4) | Cu1—N3 | 2.001 (4) |
Cu1—N5 | 1.994 (4) | Cu1—O1 | 2.639 (3) |
Cu1—N7 | 2.000 (4) | Cu1—O4 | 2.867 (4) |
| | | |
N1—Cu1—N5 | 172.42 (16) | N7—Cu1—O1 | 88.63 (14) |
N1—Cu1—N7 | 88.55 (16) | N3—Cu1—O1 | 89.00 (14) |
N5—Cu1—N7 | 92.67 (16) | N1—Cu1—O4 | 88.29 (14) |
N1—Cu1—N3 | 89.41 (16) | N5—Cu1—O4 | 84.14 (14) |
N5—Cu1—N3 | 89.70 (15) | N7—Cu1—O4 | 97.01 (14) |
N7—Cu1—N3 | 176.70 (16) | N3—Cu1—O4 | 85.50 (14) |
N1—Cu1—O1 | 95.62 (14) | O1—Cu1—O4 | 173.23 (12) |
N5—Cu1—O1 | 91.89 (14) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.90 | 2.16 | 2.910 (6) | 140.8 |
N4—H4A···O5ii | 0.90 | 2.04 | 2.839 (6) | 147.3 |
N6—H6A···O6iii | 0.90 | 1.96 | 2.840 (6) | 167.2 |
N8—H8A···O3iv | 0.90 | 1.99 | 2.872 (5) | 164.6 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2; (iv) x, y+1, z. |
Selected geometric parameters (Å, º) for (IV) topCu1—N3 | 1.999 (5) | Cu1—N1 | 2.026 (5) |
Cu1—N7 | 2.000 (5) | Cu1—O1W | 2.372 (5) |
Cu1—N5 | 2.010 (6) | | |
| | | |
N3—Cu1—N7 | 173.9 (3) | N5—Cu1—N1 | 178.5 (3) |
N3—Cu1—N5 | 89.4 (2) | N3—Cu1—O1W | 94.0 (2) |
N7—Cu1—N5 | 89.4 (2) | N7—Cu1—O1W | 92.0 (2) |
N3—Cu1—N1 | 89.8 (2) | N5—Cu1—O1W | 92.3 (2) |
N7—Cu1—N1 | 91.3 (2) | N1—Cu1—O1W | 89.0 (2) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5 | 0.90 | 1.95 | 2.849 (9) | 177.6 |
N4—H4A···O6i | 0.90 | 2.37 | 3.211 (12) | 155.3 |
N6—H6A···O1ii | 0.90 | 2.00 | 2.897 (10) | 176.9 |
N8—H8A···O2 | 0.90 | 1.94 | 2.841 (9) | 178.8 |
O1W—H1A···O3iii | 0.85 | 2.12 | 2.957 (10) | 166.7 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z; (iii) x, −y+1/2, z+1/2. |
The dihedral angles between imidazole planes and the CuN4 plane in complexes 1 to 4 topComplexes | Dihedral angles (°) | References |
1 | 59.4 (x2), 88.2 (x2) | Liu & Su, 1995 |
2 | 47.2 (2) 47.8 (3) 51.3 (2) 51.9 (3) | Liu et al., 2002 |
3 | 26.7 (2) 71.6 (2) 77.6 (2) 79.9 (1) | this work |
4 | 48.1 (3) 55.4 (2) 57.9 (3) 61.3 (3) | this work |
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It is important to synthesize simple CuII–imidazole complexes and study their structures in order to help us understand the interactions of histidyl residues with copper ions in metalloproteins (Jian et al., 1999; Wang et al., 1999; Ohtsu et al., 2001). For example, the counter-ion effects on the structures of copper complexes have been revealed by structural studies and comparisions of nitrate (McFadden et al., 1976), sulfate (Fransson & Lundgerg, 1972), perchlorate (Ivarsson, 1973) and trifluoromethanesulfonate (Liu & Su, 1995) complexes of tetrakis(imidazole)copper(II). Similarly, the substituting effects of imidazole on their complexes can be investigated by structural studies of the corresponding complexes?. The crystal structures of tetrakis(imidazole)copper(II) trifluoromethylsulfonate, (I) (Liu & Su, 1995), and tetrakis(2-methylimidazole)copper(II) trifluoromethanesulfonate, (II) (Liu et al., 2002), have been reported previously. We report here the preparation and X-ray crystal structure determination of another two analogous complexes, viz. tetrakis(5-methyl-1H-imidazole-κN3)copper(II) trifluoromethanesulfonate, (III), and tetrakis(2-ethyl-5-methyl-1H-imidazole-κN3)copper(II) trifluoromethanesulfonate, (IV).
The crystal structure of (III) (Fig. 1) consists of discrete molecules. The structure of (III) is similar to the structures of (I) and (II). The coordination environment of the central Cu ion can be described as an elongated? octahedron with four N atoms of the substituted imidazole rings at the equatorial positions and two O atoms from the trifluoromethylsulfonate groups at the axial positions. The lengths of the Cu—N bonds are in the usual range [1.992 (4)–2.001 (4) Å], while the lengths of the axial Cu—O bonds [2.639 (3) and 2.867 (4) Å] are significantly longer than those found in (I) (2.593 Å; Liu & Su, 1995) and shorter than those found in (II) (2.651 and 3.069 Å; Liu et al., 2002). However, in the (IV), the larger substituent, i.e. the ethyl group, at the 2-position of the imidazole ring blocks the central Cu atom and allows the coordination environment around the Cu atom to become square pyramidal, with four N atoms of substituted imidazole rings at basal positions and a water molecule at the axial position, as shown in Fig. 2. The Cu—N bonds have typical lengths [1.997 (5)–2.026 (6) Å] and the axial Cu—O bond is 2.373 (5) Å, which is significantly shorter than those found in the hexacoordinated copper complexes (I), (II) and (III). The closest-contact distance between the Cu atom and an O atom of a trifluoromethanesulfonate group is longer than 4 Å, which suggests that the anion groups are free counter-ions in the crystal structure of (IV). Figs. 3 and 4 show the crystal packing of (III) and (IV), respectively. The complexe cations and trifluoromethylsulfonate ions are connected by possible hydrogen-bonding interactions, which were denoted by dashed lines in Figs. 3 and 4.
It was found that the conformations of the organic ligands in (I)–(IV) are affected by the substituents on the imidazole ring and the substituted positions. The dihedral angles between the imidazole planes and the CuN4 plane of the coordination polyhedron are listed in Table 2.
In (I), which contains unsubstituted imidazole rings, two imidazole rings are almost perpendicular to the equatorial plane and the other two are tilted by 59.4°. All imidazole rings with a substituent at the 2-position in (II) and (IV) are tilted by 47.2–61.3° with respect to the CuN4 plane of the coordination polyhedron. However, one of the imidazole rings with a substituent at the 4-position is almost parallel to the equatorial plane, and the other three lie nearly perpendicular to it in (III).
We conclude that the substituents and their positions on the imidazole ring can affect the structure of copper–imidazole complexes, specifically the coordination number of the Cu ion, the bond lengths of axial Cu—O bonds and the dihedral angles between the plane of the imidazole ring and the CuN4 plane of the coordination polyhedron. However, there is almost no influence on the Cu—N bond lengths.