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The title pendent-arm macrocyclic hexaamine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous NiII and ZnII complexes (both as perchlorate salts), namely (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-κ6N)nickel(II) diperchlorate, [Ni(C12H30N6)](ClO4)2, and (cis-6,13-dimethyl-1,4,8,11-tetraaza-cyclotetradecane-6,13-diamine-κ6N)zinc(II) diperchlorate, [Zn(C12H30N6)](ClO4)2. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal-ion size and the present results are compared with other structures of this ligand.
Supporting information
CCDC references: 147604; 147605
The title complexes were both readily synthesized by mixing equimolar amounts of the metal ion and ligand hydrochloride salt (L2·6HCl) in water adjusted to pH 7 with NaOH solution. Both compounds were precipitated by addition of excess NaClO4. Crystals of each complex suitable for X-ray work were obtained by slow evaporation of their aqueous solutions.
In both structures, rotational disorder in one of the perchlorate anions (about the Cl2—O2A bond) was modelled by refining atoms O2B/O2B', O2C/O2C' and O2D/O2D' with complementary occupancies and applying tetrahedral restraints to the O atoms of each contributor. All H atoms were visible in difference maps and were allowed for as riding atoms using the SHELXL97 (Sheldrick, 1997) default bond lengths and angles.
For both compounds, data collection: CAD-4 Manual (Enraf-Nonius, 1988); cell refinement: SET4 in CAD-4 Manual; data reduction: Xtal3.2 (Hall, 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.
(I)
cis(6,13-dimethyl-1,4,8,11-tetraazacyclotetradecan-6,13-diamine)nickel(II) perchlorate
top
Crystal data top
[Ni(C12H30N6)]·2ClO4 | F(000) = 540 |
Mr = 516.03 | Dx = 1.605 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.198 (4) Å | Cell parameters from 25 reflections |
b = 12.771 (1) Å | θ = 10–14° |
c = 9.880 (5) Å | µ = 1.21 mm−1 |
β = 113.09 (2)° | T = 295 K |
V = 1067.6 (7) Å3 | Prism, purple |
Z = 2 | 0.50 × 0.50 × 0.50 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1892 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→15 |
Tmin = 0.404, Tmax = 0.546 | l = −11→10 |
2097 measured reflections | 3 standard reflections every 120 min |
1971 independent reflections | intensity decay: less than 5% |
Refinement top
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.117 | Calculated w = 1/[σ2(Fo2) + (0.0981P)2 + 0.2008P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1971 reflections | Δρmax = 0.57 e Å−3 |
278 parameters | Δρmin = −0.83 e Å−3 |
20 restraints | Absolute structure: Flack (1983) |
Primary atom site location: Patterson | Absolute structure parameter: 0.03 (3) |
Crystal data top
[Ni(C12H30N6)]·2ClO4 | V = 1067.6 (7) Å3 |
Mr = 516.03 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.198 (4) Å | µ = 1.21 mm−1 |
b = 12.771 (1) Å | T = 295 K |
c = 9.880 (5) Å | 0.50 × 0.50 × 0.50 mm |
β = 113.09 (2)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1892 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.026 |
Tmin = 0.404, Tmax = 0.546 | 3 standard reflections every 120 min |
2097 measured reflections | intensity decay: less than 5% |
1971 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.117 | Δρmax = 0.57 e Å−3 |
S = 1.08 | Δρmin = −0.83 e Å−3 |
1971 reflections | Absolute structure: Flack (1983) |
278 parameters | Absolute structure parameter: 0.03 (3) |
20 restraints | |
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) |
Ni | 0.37769 (6) | 0.49801 (16) | 0.17169 (6) | 0.0330 (2) | |
N1 | 0.4011 (6) | 0.5834 (4) | 0.3578 (5) | 0.0429 (11) | |
H1 | 0.4408 | 0.6475 | 0.3512 | 0.051* | |
N2 | 0.3545 (6) | 0.3550 (5) | 0.2758 (6) | 0.0483 (12) | |
H2 | 0.2724 | 0.3608 | 0.3049 | 0.058* | |
N3 | 0.3244 (6) | 0.4015 (4) | −0.0107 (6) | 0.0441 (12) | |
H3 | 0.4169 | 0.3764 | −0.0110 | 0.053* | |
N4 | 0.1430 (5) | 0.5573 (4) | 0.0901 (5) | 0.0414 (10) | |
H4 | 0.0744 | 0.5039 | 0.0819 | 0.050* | |
N5 | 0.6165 (5) | 0.4739 (5) | 0.3056 (5) | 0.0453 (14) | |
H5A | 0.6594 | 0.4233 | 0.2696 | 0.054* | |
H5B | 0.6732 | 0.5331 | 0.3175 | 0.054* | |
N6 | 0.3879 (6) | 0.6076 (4) | 0.0139 (6) | 0.0419 (11) | |
H6A | 0.3882 | 0.6740 | 0.0442 | 0.050* | |
H6B | 0.4726 | 0.5969 | −0.0085 | 0.050* | |
C1 | 0.5172 (8) | 0.5284 (6) | 0.4881 (7) | 0.0554 (17) | |
H1A | 0.4625 | 0.4985 | 0.5453 | 0.067* | |
H1B | 0.5936 | 0.5786 | 0.5498 | 0.067* | |
C2 | 0.6040 (7) | 0.4413 (6) | 0.4434 (7) | 0.0526 (15) | |
C3 | 0.5055 (9) | 0.3413 (6) | 0.4084 (7) | 0.0597 (17) | |
H3A | 0.5662 | 0.2847 | 0.3908 | 0.072* | |
H3B | 0.4812 | 0.3223 | 0.4923 | 0.072* | |
C4 | 0.3207 (10) | 0.2696 (6) | 0.1647 (8) | 0.0628 (18) | |
H4A | 0.2575 | 0.2158 | 0.1850 | 0.075* | |
H4B | 0.4192 | 0.2380 | 0.1714 | 0.075* | |
C5 | 0.2341 (8) | 0.3115 (6) | 0.0130 (9) | 0.0579 (17) | |
H5C | 0.2231 | 0.2572 | −0.0589 | 0.069* | |
H5D | 0.1292 | 0.3342 | 0.0014 | 0.069* | |
C6 | 0.2482 (9) | 0.4629 (6) | −0.1436 (8) | 0.0583 (18) | |
H6C | 0.1421 | 0.4363 | −0.1969 | 0.070* | |
H6D | 0.3065 | 0.4549 | −0.2062 | 0.070* | |
C7 | 0.2389 (8) | 0.5812 (6) | −0.1102 (7) | 0.0491 (14) | |
C8 | 0.1077 (7) | 0.6035 (6) | −0.0582 (7) | 0.0539 (15) | |
H8A | 0.0944 | 0.6786 | −0.0540 | 0.065* | |
H8B | 0.0094 | 0.5746 | −0.1281 | 0.065* | |
C9 | 0.1364 (7) | 0.6345 (6) | 0.2016 (7) | 0.0532 (15) | |
H9A | 0.0284 | 0.6418 | 0.1935 | 0.064* | |
H9B | 0.1725 | 0.7025 | 0.1835 | 0.064* | |
C10 | 0.2400 (7) | 0.5974 (5) | 0.3541 (7) | 0.0499 (14) | |
H10A | 0.2409 | 0.6487 | 0.4268 | 0.060* | |
H10B | 0.2006 | 0.5317 | 0.3755 | 0.060* | |
C11 | 0.7637 (10) | 0.4185 (8) | 0.5673 (9) | 0.076 (2) | |
H11A | 0.8130 | 0.3606 | 0.5399 | 0.114* | |
H11B | 0.7483 | 0.4012 | 0.6553 | 0.114* | |
H11C | 0.8301 | 0.4792 | 0.5846 | 0.114* | |
C12 | 0.2123 (11) | 0.6445 (8) | −0.2511 (8) | 0.076 (2) | |
H12A | 0.2024 | 0.7174 | −0.2330 | 0.114* | |
H12B | 0.1175 | 0.6207 | −0.3293 | 0.114* | |
H12C | 0.3006 | 0.6346 | −0.2785 | 0.114* | |
Cl1 | 0.1946 (2) | 0.2566 (2) | 0.5614 (2) | 0.0610 (4) | |
O1A | 0.0702 (9) | 0.2374 (9) | 0.6035 (9) | 0.115 (3) | |
O1B | 0.1829 (11) | 0.2000 (9) | 0.4319 (10) | 0.138 (4) | |
O1C | 0.3418 (10) | 0.2377 (9) | 0.6753 (9) | 0.111 (3) | |
O1D | 0.1922 (12) | 0.3636 (6) | 0.5182 (9) | 0.107 (3) | |
Cl2 | −0.2585 (2) | 0.43254 (17) | −0.0120 (2) | 0.0623 (5) | |
O2A | −0.1447 (6) | 0.3968 (5) | −0.0602 (7) | 0.093 (2) | |
O2B | −0.3448 (8) | 0.3500 (4) | 0.0107 (11) | 0.104 (4) | 0.87 (2) |
O2C | −0.3614 (10) | 0.5008 (7) | −0.1165 (11) | 0.163 (6) | 0.87 (2) |
O2D | −0.1850 (10) | 0.4872 (10) | 0.1203 (9) | 0.262 (13) | 0.87 (2) |
O2B' | −0.3999 (14) | 0.379 (2) | −0.085 (3) | 0.12 (3)* | 0.13 (2) |
O2C' | −0.283 (3) | 0.5393 (6) | −0.039 (4) | 0.058 (14)* | 0.13 (2) |
O2D' | −0.210 (3) | 0.414 (3) | 0.1384 (12) | 0.12 (3)* | 0.13 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0373 (3) | 0.0246 (3) | 0.0390 (3) | −0.0013 (3) | 0.0171 (2) | −0.0033 (3) |
N1 | 0.053 (3) | 0.035 (3) | 0.045 (2) | −0.001 (2) | 0.024 (2) | −0.006 (2) |
N2 | 0.056 (3) | 0.030 (2) | 0.067 (3) | −0.001 (2) | 0.034 (2) | 0.001 (2) |
N3 | 0.044 (3) | 0.035 (3) | 0.054 (3) | 0.000 (2) | 0.020 (2) | −0.009 (2) |
N4 | 0.040 (2) | 0.034 (3) | 0.051 (2) | 0.0005 (19) | 0.0192 (19) | −0.004 (2) |
N5 | 0.041 (2) | 0.050 (4) | 0.045 (2) | 0.0019 (19) | 0.0164 (19) | −0.003 (2) |
N6 | 0.046 (3) | 0.036 (2) | 0.045 (3) | −0.005 (2) | 0.020 (2) | 0.001 (2) |
C1 | 0.069 (4) | 0.057 (4) | 0.038 (2) | 0.005 (3) | 0.019 (2) | −0.006 (3) |
C2 | 0.053 (3) | 0.059 (4) | 0.045 (3) | 0.011 (3) | 0.018 (3) | 0.010 (3) |
C3 | 0.080 (5) | 0.042 (4) | 0.056 (3) | 0.012 (3) | 0.026 (3) | 0.013 (3) |
C4 | 0.077 (4) | 0.033 (3) | 0.080 (4) | −0.009 (3) | 0.033 (4) | −0.004 (3) |
C5 | 0.057 (4) | 0.033 (3) | 0.090 (5) | −0.013 (3) | 0.035 (3) | −0.019 (3) |
C6 | 0.068 (4) | 0.057 (4) | 0.045 (3) | 0.002 (3) | 0.018 (3) | −0.014 (3) |
C7 | 0.055 (3) | 0.048 (4) | 0.039 (3) | −0.001 (3) | 0.013 (3) | 0.003 (3) |
C8 | 0.045 (3) | 0.053 (4) | 0.054 (3) | 0.011 (3) | 0.010 (2) | 0.005 (3) |
C9 | 0.058 (3) | 0.045 (4) | 0.066 (4) | 0.013 (3) | 0.034 (3) | −0.003 (3) |
C10 | 0.062 (3) | 0.040 (3) | 0.060 (3) | 0.005 (3) | 0.038 (3) | −0.008 (3) |
C11 | 0.072 (5) | 0.080 (6) | 0.061 (4) | 0.014 (4) | 0.011 (4) | 0.007 (4) |
C12 | 0.084 (5) | 0.085 (6) | 0.053 (4) | 0.002 (5) | 0.022 (3) | 0.021 (4) |
Cl1 | 0.0698 (9) | 0.0488 (9) | 0.0772 (10) | −0.0010 (8) | 0.0427 (8) | −0.0083 (8) |
O1A | 0.109 (5) | 0.130 (7) | 0.133 (6) | −0.015 (6) | 0.077 (5) | 0.006 (6) |
O1B | 0.128 (6) | 0.161 (10) | 0.147 (7) | −0.048 (7) | 0.079 (6) | −0.096 (8) |
O1C | 0.092 (4) | 0.124 (7) | 0.116 (6) | 0.035 (5) | 0.039 (4) | 0.017 (5) |
O1D | 0.164 (8) | 0.062 (4) | 0.105 (5) | 0.005 (5) | 0.063 (5) | 0.019 (4) |
Cl2 | 0.0631 (9) | 0.0561 (10) | 0.0847 (12) | −0.0070 (8) | 0.0472 (9) | −0.0050 (9) |
O2A | 0.078 (4) | 0.091 (5) | 0.133 (6) | 0.000 (4) | 0.067 (4) | −0.024 (4) |
O2B | 0.076 (5) | 0.054 (4) | 0.204 (11) | −0.006 (4) | 0.080 (6) | 0.003 (5) |
O2C | 0.145 (10) | 0.111 (9) | 0.269 (16) | 0.049 (9) | 0.121 (11) | 0.078 (13) |
O2D | 0.300 (17) | 0.38 (3) | 0.205 (12) | −0.27 (2) | 0.204 (13) | −0.206 (17) |
Geometric parameters (Å, º) top
Ni—N1 | 2.075 (5) | C4—H4B | 0.9700 |
Ni—N3 | 2.077 (5) | C5—H5C | 0.9700 |
Ni—N5 | 2.096 (5) | C5—H5D | 0.9700 |
Ni—N6 | 2.124 (5) | C6—C7 | 1.556 (11) |
Ni—N4 | 2.126 (5) | C6—H6C | 0.9700 |
Ni—N2 | 2.147 (5) | C6—H6D | 0.9700 |
N1—C10 | 1.479 (7) | C7—C8 | 1.512 (9) |
N1—C1 | 1.487 (8) | C7—C12 | 1.544 (9) |
N1—H1 | 0.9100 | C8—H8A | 0.9700 |
N2—C4 | 1.491 (9) | C8—H8B | 0.9700 |
N2—C3 | 1.499 (8) | C9—C10 | 1.509 (9) |
N2—H2 | 0.9100 | C9—H9A | 0.9700 |
N3—C6 | 1.452 (9) | C9—H9B | 0.9700 |
N3—C5 | 1.489 (8) | C10—H10A | 0.9700 |
N3—H3 | 0.9100 | C10—H10B | 0.9700 |
N4—C8 | 1.492 (8) | C11—H11A | 0.9600 |
N4—C9 | 1.498 (8) | C11—H11B | 0.9600 |
N4—H4 | 0.9100 | C11—H11C | 0.9600 |
N5—C2 | 1.470 (8) | C12—H12A | 0.9600 |
N5—H5A | 0.9000 | C12—H12B | 0.9600 |
N5—H5B | 0.9000 | C12—H12C | 0.9600 |
N6—C7 | 1.476 (7) | Cl1—O1A | 1.385 (7) |
N6—H6A | 0.9000 | Cl1—O1C | 1.401 (8) |
N6—H6B | 0.9000 | Cl1—O1D | 1.430 (8) |
C1—C2 | 1.533 (10) | Cl1—O1B | 1.436 (8) |
C1—H1A | 0.9700 | Cl2—O2A | 1.386 (4) |
C1—H1B | 0.9700 | Cl2—O2B | 1.389 (5) |
C2—C3 | 1.525 (11) | Cl2—O2C' | 1.391 (5) |
C2—C11 | 1.526 (9) | Cl2—O2D' | 1.394 (5) |
C3—H3A | 0.9700 | Cl2—O2B' | 1.394 (5) |
C3—H3B | 0.9700 | Cl2—O2C | 1.399 (5) |
C4—C5 | 1.493 (11) | Cl2—O2D | 1.400 (5) |
C4—H4A | 0.9700 | | |
| | | |
N1—Ni—N3 | 171.0 (2) | C5—C4—H4A | 109.5 |
N1—Ni—N5 | 78.39 (19) | N2—C4—H4B | 109.5 |
N3—Ni—N5 | 107.0 (2) | C5—C4—H4B | 109.5 |
N1—Ni—N6 | 106.6 (2) | H4A—C4—H4B | 108.1 |
N3—Ni—N6 | 79.5 (2) | N3—C5—C4 | 108.9 (6) |
N5—Ni—N6 | 102.9 (2) | N3—C5—H5C | 109.9 |
N1—Ni—N4 | 83.47 (19) | C4—C5—H5C | 109.9 |
N3—Ni—N4 | 91.33 (19) | N3—C5—H5D | 109.9 |
N5—Ni—N4 | 161.63 (18) | C4—C5—H5D | 109.9 |
N6—Ni—N4 | 79.5 (2) | H5C—C5—H5D | 108.3 |
N1—Ni—N2 | 91.0 (2) | N3—C6—C7 | 112.3 (6) |
N3—Ni—N2 | 82.9 (2) | N3—C6—H6C | 109.1 |
N5—Ni—N2 | 81.3 (2) | C7—C6—H6C | 109.1 |
N6—Ni—N2 | 162.4 (2) | N3—C6—H6D | 109.1 |
N4—Ni—N2 | 101.98 (19) | C7—C6—H6D | 109.1 |
C10—N1—C1 | 116.8 (5) | H6C—C6—H6D | 107.9 |
C10—N1—Ni | 106.7 (3) | N6—C7—C8 | 106.2 (5) |
C1—N1—Ni | 108.0 (4) | N6—C7—C12 | 113.4 (6) |
C10—N1—H1 | 108.4 | C8—C7—C12 | 110.0 (6) |
C1—N1—H1 | 108.4 | N6—C7—C6 | 106.7 (6) |
Ni—N1—H1 | 108.4 | C8—C7—C6 | 111.9 (6) |
C4—N2—C3 | 114.3 (6) | C12—C7—C6 | 108.6 (6) |
C4—N2—Ni | 107.5 (4) | N4—C8—C7 | 111.3 (5) |
C3—N2—Ni | 106.6 (4) | N4—C8—H8A | 109.4 |
C4—N2—H2 | 109.4 | C7—C8—H8A | 109.4 |
C3—N2—H2 | 109.4 | N4—C8—H8B | 109.4 |
Ni—N2—H2 | 109.4 | C7—C8—H8B | 109.4 |
C6—N3—C5 | 117.3 (6) | H8A—C8—H8B | 108.0 |
C6—N3—Ni | 109.3 (4) | N4—C9—C10 | 109.6 (5) |
C5—N3—Ni | 106.1 (4) | N4—C9—H9A | 109.7 |
C6—N3—H3 | 108.0 | C10—C9—H9A | 109.7 |
C5—N3—H3 | 108.0 | N4—C9—H9B | 109.7 |
Ni—N3—H3 | 108.0 | C10—C9—H9B | 109.7 |
C8—N4—C9 | 113.9 (5) | H9A—C9—H9B | 108.2 |
C8—N4—Ni | 108.1 (3) | N1—C10—C9 | 107.3 (5) |
C9—N4—Ni | 106.5 (3) | N1—C10—H10A | 110.3 |
C8—N4—H4 | 109.4 | C9—C10—H10A | 110.3 |
C9—N4—H4 | 109.4 | N1—C10—H10B | 110.3 |
Ni—N4—H4 | 109.4 | C9—C10—H10B | 110.3 |
C2—N5—Ni | 100.6 (3) | H10A—C10—H10B | 108.5 |
C2—N5—H5A | 111.7 | C2—C11—H11A | 109.5 |
Ni—N5—H5A | 111.7 | C2—C11—H11B | 109.5 |
C2—N5—H5B | 111.7 | H11A—C11—H11B | 109.5 |
Ni—N5—H5B | 111.7 | C2—C11—H11C | 109.5 |
H5A—N5—H5B | 109.4 | H11A—C11—H11C | 109.5 |
C7—N6—Ni | 99.5 (4) | H11B—C11—H11C | 109.5 |
C7—N6—H6A | 111.9 | C7—C12—H12A | 109.5 |
Ni—N6—H6A | 111.9 | C7—C12—H12B | 109.5 |
C7—N6—H6B | 111.9 | H12A—C12—H12B | 109.5 |
Ni—N6—H6B | 111.9 | C7—C12—H12C | 109.5 |
H6A—N6—H6B | 109.6 | H12A—C12—H12C | 109.5 |
N1—C1—C2 | 111.8 (5) | H12B—C12—H12C | 109.5 |
N1—C1—H1A | 109.3 | O1A—Cl1—O1C | 112.4 (5) |
C2—C1—H1A | 109.3 | O1A—Cl1—O1D | 109.9 (6) |
N1—C1—H1B | 109.3 | O1C—Cl1—O1D | 107.5 (6) |
C2—C1—H1B | 109.3 | O1A—Cl1—O1B | 113.4 (6) |
H1A—C1—H1B | 107.9 | O1C—Cl1—O1B | 109.9 (6) |
N5—C2—C3 | 106.4 (5) | O1D—Cl1—O1B | 103.2 (6) |
N5—C2—C11 | 113.4 (6) | O2A—Cl2—O2B | 111.2 (2) |
C3—C2—C11 | 108.7 (6) | O2A—Cl2—O2C' | 110.1 (3) |
N5—C2—C1 | 107.5 (5) | O2A—Cl2—O2D' | 109.8 (3) |
C3—C2—C1 | 110.0 (6) | O2C'—Cl2—O2D' | 109.5 (3) |
C11—C2—C1 | 110.7 (6) | O2A—Cl2—O2B' | 109.8 (3) |
N2—C3—C2 | 111.4 (5) | O2C'—Cl2—O2B' | 109.5 (3) |
N2—C3—H3A | 109.4 | O2D'—Cl2—O2B' | 108.0 (10) |
C2—C3—H3A | 109.4 | O2A—Cl2—O2C | 109.6 (3) |
N2—C3—H3B | 109.4 | O2B—Cl2—O2C | 109.2 (3) |
C2—C3—H3B | 109.4 | O2A—Cl2—O2D | 109.4 (3) |
H3A—C3—H3B | 108.0 | O2B—Cl2—O2D | 108.9 (3) |
N2—C4—C5 | 110.6 (6) | O2C—Cl2—O2D | 108.5 (3) |
N2—C4—H4A | 109.5 | | |
| | | |
N3—Ni—N1—C10 | −32.1 (16) | N4—Ni—N5—C2 | 59.2 (8) |
N5—Ni—N1—C10 | −160.3 (4) | N2—Ni—N5—C2 | −42.6 (4) |
N6—Ni—N1—C10 | 99.6 (4) | N1—Ni—N6—C7 | −125.5 (4) |
N4—Ni—N1—C10 | 22.6 (4) | N3—Ni—N6—C7 | 47.7 (4) |
N2—Ni—N1—C10 | −79.4 (4) | N5—Ni—N6—C7 | 153.0 (4) |
N3—Ni—N1—C1 | 94.2 (14) | N4—Ni—N6—C7 | −45.6 (4) |
N5—Ni—N1—C1 | −34.0 (4) | N2—Ni—N6—C7 | 50.9 (8) |
N6—Ni—N1—C1 | −134.1 (4) | C10—N1—C1—C2 | 131.0 (6) |
N4—Ni—N1—C1 | 148.9 (4) | Ni—N1—C1—C2 | 10.9 (7) |
N2—Ni—N1—C1 | 47.0 (4) | Ni—N5—C2—C3 | 61.2 (5) |
N1—Ni—N2—C4 | 175.5 (5) | Ni—N5—C2—C11 | −179.3 (6) |
N3—Ni—N2—C4 | 2.1 (4) | Ni—N5—C2—C1 | −56.7 (5) |
N5—Ni—N2—C4 | −106.4 (5) | N1—C1—C2—N5 | 31.4 (7) |
N6—Ni—N2—C4 | −1.1 (9) | N1—C1—C2—C3 | −84.1 (7) |
N4—Ni—N2—C4 | 91.9 (5) | N1—C1—C2—C11 | 155.7 (6) |
N1—Ni—N2—C3 | −61.5 (4) | C4—N2—C3—C2 | 131.5 (6) |
N3—Ni—N2—C3 | 125.1 (4) | Ni—N2—C3—C2 | 12.9 (7) |
N5—Ni—N2—C3 | 16.6 (4) | N5—C2—C3—N2 | −50.9 (7) |
N6—Ni—N2—C3 | 121.9 (7) | C11—C2—C3—N2 | −173.4 (6) |
N4—Ni—N2—C3 | −145.1 (4) | C1—C2—C3—N2 | 65.2 (7) |
N1—Ni—N3—C6 | 104.6 (14) | C3—N2—C4—C5 | −147.6 (6) |
N5—Ni—N3—C6 | −129.1 (4) | Ni—N2—C4—C5 | −29.5 (7) |
N6—Ni—N3—C6 | −28.6 (4) | C6—N3—C5—C4 | −171.1 (6) |
N4—Ni—N3—C6 | 50.4 (5) | Ni—N3—C5—C4 | −48.7 (6) |
N2—Ni—N3—C6 | 152.3 (5) | N2—C4—C5—N3 | 53.2 (7) |
N1—Ni—N3—C5 | −22.7 (16) | C5—N3—C6—C7 | 124.1 (7) |
N5—Ni—N3—C5 | 103.6 (4) | Ni—N3—C6—C7 | 3.4 (7) |
N6—Ni—N3—C5 | −156.0 (4) | Ni—N6—C7—C8 | 62.1 (5) |
N4—Ni—N3—C5 | −76.9 (4) | Ni—N6—C7—C12 | −176.9 (6) |
N2—Ni—N3—C5 | 25.0 (4) | Ni—N6—C7—C6 | −57.4 (5) |
N1—Ni—N4—C8 | 129.8 (4) | N3—C6—C7—N6 | 37.9 (8) |
N3—Ni—N4—C8 | −57.5 (4) | N3—C6—C7—C8 | −77.9 (8) |
N5—Ni—N4—C8 | 120.9 (7) | N3—C6—C7—C12 | 160.5 (6) |
N6—Ni—N4—C8 | 21.6 (4) | C9—N4—C8—C7 | 125.5 (6) |
N2—Ni—N4—C8 | −140.5 (4) | Ni—N4—C8—C7 | 7.4 (6) |
N1—Ni—N4—C9 | 7.0 (4) | N6—C7—C8—N4 | −47.8 (7) |
N3—Ni—N4—C9 | 179.7 (4) | C12—C7—C8—N4 | −170.9 (6) |
N5—Ni—N4—C9 | −1.9 (8) | C6—C7—C8—N4 | 68.3 (7) |
N6—Ni—N4—C9 | −101.2 (4) | C8—N4—C9—C10 | −154.5 (5) |
N2—Ni—N4—C9 | 96.7 (4) | Ni—N4—C9—C10 | −35.5 (6) |
N1—Ni—N5—C2 | 50.2 (4) | C1—N1—C10—C9 | −169.0 (5) |
N3—Ni—N5—C2 | −122.4 (4) | Ni—N1—C10—C9 | −48.1 (6) |
N6—Ni—N5—C2 | 154.8 (4) | N4—C9—C10—N1 | 57.0 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Ci | 0.91 | 2.41 | 3.192 (10) | 144 |
N2—H2···O1D | 0.91 | 2.49 | 3.283 (10) | 146 |
N3—H3···O2Bii | 0.91 | 2.14 | 3.039 (8) | 167 |
N3—H3···O2B′ii | 0.91 | 2.08 | 2.917 (11) | 152 |
N4—H4···O2A | 0.91 | 2.38 | 3.213 (7) | 151 |
N4—H4···O2D | 0.91 | 2.57 | 3.271 (9) | 135 |
N5—H5A···O2Dii | 0.90 | 2.56 | 3.056 (8) | 116 |
N5—H5A···O2D′ii | 0.90 | 2.09 | 2.819 (10) | 137 |
N5—H5B···O1Ci | 0.90 | 2.62 | 3.389 (13) | 144 |
N6—H6A···O2Biii | 0.90 | 2.31 | 3.120 (8) | 150 |
N6—H6A···O2B′iii | 0.90 | 2.64 | 3.53 (3) | 168 |
N6—H6B···O2Cii | 0.90 | 2.50 | 3.341 (10) | 156 |
N6—H6B···O2C′ii | 0.90 | 2.49 | 3.382 (13) | 170 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x, y+1/2, −z. |
(II)
cis(6,13-dimethyl-1,4,8,11-tetraazacyclotetradecan-6,13-diamine)zinc(II) perchlorate
top
Crystal data top
[Zn(C12H30N6)]·2ClO4 | F(000) = 544 |
Mr = 522.69 | Dx = 1.611 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.075 (1) Å | Cell parameters from 25 reflections |
b = 12.891 (1) Å | θ = 10–14° |
c = 9.963 (3) Å | µ = 1.44 mm−1 |
β = 112.438 (9)° | T = 295 K |
V = 1077.3 (4) Å3 | Prism, colourless |
Z = 2 | 0.30 × 0.13 × 0.10 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 916 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.073 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→15 |
Tmin = 0.779, Tmax = 0.866 | l = −11→10 |
2115 measured reflections | 3 standard reflections every 120 min |
1987 independent reflections | intensity decay: less than 5% |
Refinement top
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)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.175 | Calculated w = 1/[σ2(Fo2) + (0.0782P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
1987 reflections | Δρmax = 0.72 e Å−3 |
258 parameters | Δρmin = −0.66 e Å−3 |
20 restraints | Absolute structure: Flack (1983) |
Primary atom site location: Patterson | Absolute structure parameter: −0.04 (5) |
Crystal data top
[Zn(C12H30N6)]·2ClO4 | V = 1077.3 (4) Å3 |
Mr = 522.69 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.075 (1) Å | µ = 1.44 mm−1 |
b = 12.891 (1) Å | T = 295 K |
c = 9.963 (3) Å | 0.30 × 0.13 × 0.10 mm |
β = 112.438 (9)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 916 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.073 |
Tmin = 0.779, Tmax = 0.866 | 3 standard reflections every 120 min |
2115 measured reflections | intensity decay: less than 5% |
1987 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.175 | Δρmax = 0.72 e Å−3 |
S = 0.99 | Δρmin = −0.66 e Å−3 |
1987 reflections | Absolute structure: Flack (1983) |
258 parameters | Absolute structure parameter: −0.04 (5) |
20 restraints | |
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) |
Zn1 | 0.3904 (2) | 0.4998 (7) | 0.17406 (18) | 0.0360 (5) | |
N1 | 0.3989 (16) | 0.4215 (13) | 0.3698 (15) | 0.045 (4) | |
H1 | 0.4396 | 0.3568 | 0.3711 | 0.054* | |
N2 | 0.3704 (16) | 0.6515 (12) | 0.2785 (15) | 0.042 (3) | |
H2 | 0.2883 | 0.6481 | 0.3096 | 0.050* | |
N3 | 0.3193 (18) | 0.6016 (14) | −0.0095 (17) | 0.046 (5) | |
H3 | 0.4091 | 0.6265 | −0.0181 | 0.056* | |
N4 | 0.1437 (15) | 0.4383 (12) | 0.0991 (15) | 0.044 (4) | |
H4 | 0.0754 | 0.4919 | 0.0907 | 0.052* | |
N5 | 0.6324 (14) | 0.5196 (16) | 0.3192 (13) | 0.046 (4) | |
H5A | 0.6868 | 0.4595 | 0.3333 | 0.055* | |
H5B | 0.6821 | 0.5677 | 0.2860 | 0.055* | |
N6 | 0.3838 (18) | 0.3990 (13) | 0.0027 (15) | 0.043 (4) | |
H6A | 0.4614 | 0.4142 | −0.0295 | 0.052* | |
H6B | 0.3925 | 0.3321 | 0.0305 | 0.052* | |
C1 | 0.516 (2) | 0.483 (2) | 0.493 (2) | 0.074 (8) | |
H1A | 0.4570 | 0.5224 | 0.5395 | 0.088* | |
H1B | 0.5846 | 0.4351 | 0.5649 | 0.088* | |
C2 | 0.615 (2) | 0.5543 (16) | 0.4518 (17) | 0.046 (5) | |
C3 | 0.523 (2) | 0.6603 (17) | 0.405 (2) | 0.069 (6) | |
H3A | 0.5026 | 0.6880 | 0.4868 | 0.082* | |
H3B | 0.5915 | 0.7093 | 0.3822 | 0.082* | |
C4 | 0.340 (3) | 0.7328 (17) | 0.170 (2) | 0.074 (6) | |
H4A | 0.4395 | 0.7580 | 0.1682 | 0.088* | |
H4B | 0.2853 | 0.7904 | 0.1941 | 0.088* | |
C5 | 0.2360 (19) | 0.6884 (17) | 0.022 (2) | 0.062 (6) | |
H5C | 0.1346 | 0.6654 | 0.0229 | 0.075* | |
H5D | 0.2155 | 0.7412 | −0.0523 | 0.075* | |
C6 | 0.232 (3) | 0.5394 (15) | −0.1399 (19) | 0.056 (6) | |
H6C | 0.2829 | 0.5480 | −0.2090 | 0.067* | |
H6D | 0.1241 | 0.5658 | −0.1847 | 0.067* | |
C7 | 0.225 (2) | 0.4215 (14) | −0.1079 (19) | 0.035 (4) | |
C8 | 0.1068 (19) | 0.3919 (17) | −0.0464 (18) | 0.051 (5) | |
H8A | 0.1047 | 0.3169 | −0.0387 | 0.062* | |
H8B | 0.0018 | 0.4144 | −0.1114 | 0.062* | |
C9 | 0.141 (2) | 0.3679 (16) | 0.214 (2) | 0.059 (6) | |
H9A | 0.1827 | 0.3007 | 0.2030 | 0.070* | |
H9B | 0.0314 | 0.3583 | 0.2059 | 0.070* | |
C10 | 0.238 (2) | 0.4114 (16) | 0.3599 (18) | 0.055 (5) | |
H10A | 0.1961 | 0.4786 | 0.3720 | 0.066* | |
H10B | 0.2334 | 0.3655 | 0.4355 | 0.066* | |
C11 | 0.773 (2) | 0.579 (2) | 0.578 (2) | 0.091 (8) | |
H11A | 0.8294 | 0.5157 | 0.6150 | 0.136* | |
H11B | 0.7516 | 0.6140 | 0.6533 | 0.136* | |
H11C | 0.8369 | 0.6228 | 0.5434 | 0.136* | |
C12 | 0.192 (2) | 0.3603 (19) | −0.2535 (19) | 0.070 (6) | |
H12A | 0.1728 | 0.2886 | −0.2398 | 0.105* | |
H12B | 0.2821 | 0.3662 | −0.2805 | 0.105* | |
H12C | 0.0994 | 0.3890 | −0.3291 | 0.105* | |
Cl1 | 0.2082 (7) | 0.7406 (8) | 0.5682 (7) | 0.0712 (16) | |
O1A | 0.358 (2) | 0.747 (2) | 0.683 (2) | 0.152 (9) | |
O1B | 0.212 (2) | 0.8053 (18) | 0.456 (3) | 0.157 (11) | |
O1C | 0.186 (2) | 0.6408 (15) | 0.517 (2) | 0.136 (8) | |
O1D | 0.088 (2) | 0.771 (2) | 0.609 (2) | 0.155 (9) | |
Cl2 | −0.2609 (5) | 0.5700 (6) | −0.0080 (5) | 0.0599 (14) | |
O2A | −0.1466 (11) | 0.6051 (10) | −0.0601 (11) | 0.077 (4) | |
O2B | −0.326 (3) | 0.6541 (10) | 0.039 (3) | 0.114 (5)* | 0.66 (4) |
O2C | −0.383 (2) | 0.5182 (17) | −0.1203 (15) | 0.114 (5)* | 0.66 (4) |
O2D | −0.1899 (16) | 0.501 (2) | 0.107 (2) | 0.114 (5)* | 0.66 (4) |
O2B' | −0.326 (5) | 0.4763 (17) | −0.076 (5) | 0.114 (5)* | 0.34 (4) |
O2C' | −0.382 (4) | 0.6443 (15) | −0.038 (6) | 0.114 (5)* | 0.34 (4) |
O2D' | −0.188 (2) | 0.555 (5) | 0.1427 (14) | 0.114 (5)* | 0.34 (4) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0348 (9) | 0.0339 (10) | 0.0395 (9) | 0.0000 (14) | 0.0145 (7) | 0.0028 (14) |
N1 | 0.050 (9) | 0.037 (9) | 0.048 (9) | 0.009 (8) | 0.020 (8) | 0.011 (8) |
N2 | 0.050 (9) | 0.020 (8) | 0.062 (9) | 0.005 (7) | 0.028 (8) | −0.001 (7) |
N3 | 0.044 (10) | 0.047 (11) | 0.050 (10) | 0.014 (9) | 0.021 (9) | 0.010 (9) |
N4 | 0.031 (7) | 0.033 (8) | 0.073 (11) | 0.009 (7) | 0.026 (7) | 0.016 (8) |
N5 | 0.040 (7) | 0.057 (14) | 0.043 (7) | 0.014 (8) | 0.018 (6) | 0.020 (9) |
N6 | 0.058 (11) | 0.036 (9) | 0.036 (9) | 0.019 (8) | 0.018 (8) | 0.011 (7) |
C1 | 0.067 (12) | 0.10 (2) | 0.041 (10) | −0.023 (16) | 0.010 (9) | 0.001 (14) |
C2 | 0.042 (10) | 0.055 (12) | 0.029 (9) | −0.005 (9) | −0.001 (8) | −0.015 (9) |
C3 | 0.071 (15) | 0.058 (15) | 0.070 (14) | 0.000 (12) | 0.020 (12) | −0.017 (12) |
C4 | 0.091 (17) | 0.042 (13) | 0.091 (17) | 0.017 (12) | 0.039 (15) | 0.000 (14) |
C5 | 0.030 (10) | 0.055 (13) | 0.091 (16) | 0.024 (10) | 0.011 (10) | 0.015 (12) |
C6 | 0.077 (14) | 0.055 (16) | 0.031 (10) | 0.017 (11) | 0.014 (10) | 0.008 (10) |
C7 | 0.052 (12) | 0.012 (9) | 0.042 (11) | 0.010 (9) | 0.019 (10) | 0.013 (8) |
C8 | 0.032 (10) | 0.076 (14) | 0.040 (10) | 0.002 (10) | 0.006 (8) | −0.017 (10) |
C9 | 0.039 (11) | 0.044 (12) | 0.072 (14) | −0.015 (9) | −0.002 (10) | 0.014 (11) |
C10 | 0.063 (13) | 0.057 (13) | 0.058 (13) | −0.007 (10) | 0.039 (11) | 0.016 (11) |
C11 | 0.066 (14) | 0.15 (2) | 0.054 (13) | −0.018 (16) | 0.015 (11) | −0.001 (15) |
C12 | 0.071 (14) | 0.081 (16) | 0.047 (13) | 0.010 (13) | 0.010 (11) | 0.002 (11) |
Cl1 | 0.090 (4) | 0.048 (3) | 0.102 (5) | 0.005 (3) | 0.066 (4) | 0.013 (3) |
O1A | 0.067 (12) | 0.19 (2) | 0.162 (19) | −0.025 (13) | 0.001 (12) | 0.018 (19) |
O1B | 0.151 (19) | 0.16 (2) | 0.22 (2) | 0.057 (16) | 0.134 (19) | 0.109 (19) |
O1C | 0.20 (2) | 0.061 (12) | 0.164 (18) | −0.048 (13) | 0.082 (16) | −0.044 (12) |
O1D | 0.151 (18) | 0.20 (2) | 0.174 (18) | 0.027 (17) | 0.130 (16) | −0.011 (18) |
Cl2 | 0.050 (3) | 0.072 (3) | 0.064 (3) | 0.011 (3) | 0.029 (3) | 0.003 (3) |
O2A | 0.068 (9) | 0.087 (11) | 0.104 (10) | 0.001 (8) | 0.065 (8) | 0.009 (9) |
Geometric parameters (Å, º) top
Zn1—N6 | 2.128 (14) | C4—H4B | 0.9700 |
Zn1—N5 | 2.134 (12) | C5—H5C | 0.9700 |
Zn1—N3 | 2.141 (15) | C5—H5D | 0.9700 |
Zn1—N1 | 2.170 (13) | C6—C7 | 1.56 (2) |
Zn1—N4 | 2.219 (13) | C6—H6C | 0.9700 |
Zn1—N2 | 2.255 (12) | C6—H6D | 0.9700 |
N1—C10 | 1.44 (2) | C7—C8 | 1.48 (2) |
N1—C1 | 1.51 (2) | C7—C12 | 1.58 (2) |
N1—H1 | 0.9100 | C8—H8A | 0.9700 |
N2—C4 | 1.45 (2) | C8—H8B | 0.9700 |
N2—C3 | 1.48 (2) | C9—C10 | 1.49 (2) |
N2—H2 | 0.9100 | C9—H9A | 0.9700 |
N3—C5 | 1.45 (2) | C9—H9B | 0.9700 |
N3—C6 | 1.47 (2) | C10—H10A | 0.9700 |
N3—H3 | 0.9100 | C10—H10B | 0.9700 |
N4—C9 | 1.47 (2) | C11—H11A | 0.9600 |
N4—C8 | 1.48 (2) | C11—H11B | 0.9600 |
N4—H4 | 0.9100 | C11—H11C | 0.9600 |
N5—C2 | 1.46 (2) | C12—H12A | 0.9600 |
N5—H5A | 0.9000 | C12—H12B | 0.9600 |
N5—H5B | 0.9000 | C12—H12C | 0.9600 |
N6—C7 | 1.47 (2) | Cl1—O1D | 1.356 (16) |
N6—H6A | 0.9000 | Cl1—O1C | 1.370 (17) |
N6—H6B | 0.9000 | Cl1—O1B | 1.402 (18) |
C1—C2 | 1.45 (3) | Cl1—O1A | 1.407 (17) |
C1—H1A | 0.9700 | Cl2—O2B | 1.397 (8) |
C1—H1B | 0.9700 | Cl2—O2B' | 1.399 (8) |
C2—C11 | 1.53 (2) | Cl2—O2A | 1.400 (8) |
C2—C3 | 1.57 (2) | Cl2—O2D | 1.400 (8) |
C3—H3A | 0.9700 | Cl2—O2C' | 1.401 (8) |
C3—H3B | 0.9700 | Cl2—O2D' | 1.404 (8) |
C4—C5 | 1.53 (2) | Cl2—O2C | 1.406 (8) |
C4—H4A | 0.9700 | | |
| | | |
N6—Zn1—N5 | 108.9 (6) | C5—C4—H4A | 110.0 |
N6—Zn1—N3 | 77.4 (5) | N2—C4—H4B | 110.0 |
N5—Zn1—N3 | 113.7 (6) | C5—C4—H4B | 110.0 |
N6—Zn1—N1 | 114.7 (6) | H4A—C4—H4B | 108.3 |
N5—Zn1—N1 | 76.9 (5) | N3—C5—C4 | 108.6 (14) |
N3—Zn1—N1 | 161.5 (5) | N3—C5—H5C | 110.0 |
N6—Zn1—N4 | 78.2 (6) | C4—C5—H5C | 110.0 |
N5—Zn1—N4 | 156.4 (5) | N3—C5—H5D | 110.0 |
N3—Zn1—N4 | 89.7 (5) | C4—C5—H5D | 110.0 |
N1—Zn1—N4 | 79.7 (5) | H5C—C5—H5D | 108.3 |
N6—Zn1—N2 | 156.5 (5) | N3—C6—C7 | 113.6 (15) |
N5—Zn1—N2 | 80.0 (6) | N3—C6—H6C | 108.9 |
N3—Zn1—N2 | 79.2 (5) | C7—C6—H6C | 108.9 |
N1—Zn1—N2 | 88.3 (5) | N3—C6—H6D | 108.9 |
N4—Zn1—N2 | 102.5 (5) | C7—C6—H6D | 108.9 |
C10—N1—C1 | 119.0 (15) | H6C—C6—H6D | 107.7 |
C10—N1—Zn1 | 107.2 (10) | N6—C7—C8 | 107.3 (13) |
C1—N1—Zn1 | 105.2 (11) | N6—C7—C6 | 103.9 (16) |
C10—N1—H1 | 108.3 | C8—C7—C6 | 115.5 (16) |
C1—N1—H1 | 108.3 | N6—C7—C12 | 112.4 (14) |
Zn1—N1—H1 | 108.3 | C8—C7—C12 | 109.8 (15) |
C4—N2—C3 | 115.4 (15) | C6—C7—C12 | 107.9 (15) |
C4—N2—Zn1 | 108.0 (10) | C7—C8—N4 | 111.9 (14) |
C3—N2—Zn1 | 104.2 (10) | C7—C8—H8A | 109.2 |
C4—N2—H2 | 109.7 | N4—C8—H8A | 109.2 |
C3—N2—H2 | 109.7 | C7—C8—H8B | 109.2 |
Zn1—N2—H2 | 109.7 | N4—C8—H8B | 109.2 |
C5—N3—C6 | 117.5 (15) | H8A—C8—H8B | 107.9 |
C5—N3—Zn1 | 107.5 (12) | N4—C9—C10 | 110.3 (13) |
C6—N3—Zn1 | 107.8 (11) | N4—C9—H9A | 109.6 |
C5—N3—H3 | 107.9 | C10—C9—H9A | 109.6 |
C6—N3—H3 | 107.9 | N4—C9—H9B | 109.6 |
Zn1—N3—H3 | 107.9 | C10—C9—H9B | 109.6 |
C9—N4—C8 | 116.6 (14) | H9A—C9—H9B | 108.1 |
C9—N4—Zn1 | 106.0 (9) | N1—C10—C9 | 108.0 (14) |
C8—N4—Zn1 | 107.2 (9) | N1—C10—H10A | 110.1 |
C9—N4—H4 | 108.9 | C9—C10—H10A | 110.1 |
C8—N4—H4 | 108.9 | N1—C10—H10B | 110.1 |
Zn1—N4—H4 | 108.9 | C9—C10—H10B | 110.1 |
C2—N5—Zn1 | 102.2 (9) | H10A—C10—H10B | 108.4 |
C2—N5—H5A | 111.3 | C2—C11—H11A | 109.5 |
Zn1—N5—H5A | 111.3 | C2—C11—H11B | 109.5 |
C2—N5—H5B | 111.3 | H11A—C11—H11B | 109.5 |
Zn1—N5—H5B | 111.3 | C2—C11—H11C | 109.5 |
H5A—N5—H5B | 109.2 | H11A—C11—H11C | 109.5 |
C7—N6—Zn1 | 101.6 (10) | H11B—C11—H11C | 109.5 |
C7—N6—H6A | 111.5 | C7—C12—H12A | 109.5 |
Zn1—N6—H6A | 111.5 | C7—C12—H12B | 109.5 |
C7—N6—H6B | 111.5 | H12A—C12—H12B | 109.5 |
Zn1—N6—H6B | 111.5 | C7—C12—H12C | 109.5 |
H6A—N6—H6B | 109.3 | H12A—C12—H12C | 109.5 |
C2—C1—N1 | 114.8 (14) | H12B—C12—H12C | 109.5 |
C2—C1—H1A | 108.6 | O1D—Cl1—O1C | 111.2 (14) |
N1—C1—H1A | 108.6 | O1D—Cl1—O1B | 109.3 (13) |
C2—C1—H1B | 108.6 | O1C—Cl1—O1B | 107.8 (14) |
N1—C1—H1B | 108.6 | O1D—Cl1—O1A | 112.1 (14) |
H1A—C1—H1B | 107.5 | O1C—Cl1—O1A | 108.5 (14) |
C1—C2—N5 | 110.9 (16) | O1B—Cl1—O1A | 107.8 (13) |
C1—C2—C11 | 112.7 (16) | O2B—Cl2—O2A | 110.0 (3) |
N5—C2—C11 | 114.5 (15) | O2B'—Cl2—O2A | 109.7 (3) |
C1—C2—C3 | 108.5 (17) | O2B—Cl2—O2D | 109.8 (3) |
N5—C2—C3 | 103.1 (14) | O2A—Cl2—O2D | 109.6 (3) |
C11—C2—C3 | 106.5 (16) | O2B'—Cl2—O2C' | 109.6 (3) |
N2—C3—C2 | 113.8 (14) | O2A—Cl2—O2C' | 109.5 (3) |
N2—C3—H3A | 108.8 | O2B'—Cl2—O2D' | 109.7 (10) |
C2—C3—H3A | 108.8 | O2A—Cl2—O2D' | 109.2 (3) |
N2—C3—H3B | 108.8 | O2C'—Cl2—O2D' | 109.2 (3) |
C2—C3—H3B | 108.8 | O2B—Cl2—O2C | 109.3 (3) |
H3A—C3—H3B | 107.7 | O2A—Cl2—O2C | 109.1 (3) |
N2—C4—C5 | 108.7 (16) | O2D—Cl2—O2C | 109.1 (3) |
N2—C4—H4A | 110.0 | | |
| | | |
N6—Zn1—N1—C10 | −93.3 (12) | N4—Zn1—N5—C2 | −55 (2) |
N5—Zn1—N1—C10 | 161.7 (12) | N2—Zn1—N5—C2 | 43.1 (12) |
N3—Zn1—N1—C10 | 35 (2) | N5—Zn1—N6—C7 | −161.6 (10) |
N4—Zn1—N1—C10 | −21.5 (11) | N3—Zn1—N6—C7 | −50.6 (11) |
N2—Zn1—N1—C10 | 81.5 (12) | N1—Zn1—N6—C7 | 114.6 (10) |
N6—Zn1—N1—C1 | 139.1 (13) | N4—Zn1—N6—C7 | 41.8 (10) |
N5—Zn1—N1—C1 | 34.1 (13) | N2—Zn1—N6—C7 | −52.4 (19) |
N3—Zn1—N1—C1 | −93 (2) | C10—N1—C1—C2 | −135.1 (18) |
N4—Zn1—N1—C1 | −149.1 (13) | Zn1—N1—C1—C2 | −15 (2) |
N2—Zn1—N1—C1 | −46.0 (12) | N1—C1—C2—N5 | −26 (2) |
N6—Zn1—N2—C4 | −4 (2) | N1—C1—C2—C11 | −155.3 (19) |
N5—Zn1—N2—C4 | 110.4 (12) | N1—C1—C2—C3 | 87 (2) |
N3—Zn1—N2—C4 | −6.3 (12) | Zn1—N5—C2—C1 | 53.1 (17) |
N1—Zn1—N2—C4 | −172.7 (12) | Zn1—N5—C2—C11 | −178.0 (15) |
N4—Zn1—N2—C4 | −93.6 (12) | Zn1—N5—C2—C3 | −62.8 (14) |
N6—Zn1—N2—C3 | −127.6 (15) | C4—N2—C3—C2 | −136.7 (17) |
N5—Zn1—N2—C3 | −12.8 (12) | Zn1—N2—C3—C2 | −18.5 (18) |
N3—Zn1—N2—C3 | −129.5 (12) | C1—C2—C3—N2 | −61 (2) |
N1—Zn1—N2—C3 | 64.2 (12) | N5—C2—C3—N2 | 56 (2) |
N4—Zn1—N2—C3 | 143.3 (11) | C11—C2—C3—N2 | 177.0 (16) |
N6—Zn1—N3—C5 | 156.4 (12) | C3—N2—C4—C5 | 150.6 (15) |
N5—Zn1—N3—C5 | −98.4 (12) | Zn1—N2—C4—C5 | 34.6 (17) |
N1—Zn1—N3—C5 | 24 (3) | C6—N3—C5—C4 | 172.9 (16) |
N4—Zn1—N3—C5 | 78.4 (12) | Zn1—N3—C5—C4 | 51.3 (17) |
N2—Zn1—N3—C5 | −24.4 (11) | N2—C4—C5—N3 | −59 (2) |
N6—Zn1—N3—C6 | 28.8 (12) | C5—N3—C6—C7 | −124.3 (19) |
N5—Zn1—N3—C6 | 134.1 (12) | Zn1—N3—C6—C7 | −3 (2) |
N1—Zn1—N3—C6 | −104 (2) | Zn1—N6—C7—C8 | −62.5 (14) |
N4—Zn1—N3—C6 | −49.1 (12) | Zn1—N6—C7—C6 | 60.4 (14) |
N2—Zn1—N3—C6 | −151.9 (12) | Zn1—N6—C7—C12 | 176.8 (12) |
N6—Zn1—N4—C9 | 108.7 (11) | N3—C6—C7—N6 | −39 (2) |
N5—Zn1—N4—C9 | −2 (2) | N3—C6—C7—C8 | 78 (2) |
N3—Zn1—N4—C9 | −174.1 (11) | N3—C6—C7—C12 | −158.4 (14) |
N1—Zn1—N4—C9 | −9.4 (11) | N6—C7—C8—N4 | 51.3 (19) |
N2—Zn1—N4—C9 | −95.3 (11) | C6—C7—C8—N4 | −64 (2) |
N6—Zn1—N4—C8 | −16.5 (11) | C12—C7—C8—N4 | 173.6 (14) |
N5—Zn1—N4—C8 | −126.8 (15) | C9—N4—C8—C7 | −131.6 (15) |
N3—Zn1—N4—C8 | 60.7 (12) | Zn1—N4—C8—C7 | −13.0 (17) |
N1—Zn1—N4—C8 | −134.6 (12) | C8—N4—C9—C10 | 158.0 (15) |
N2—Zn1—N4—C8 | 139.5 (11) | Zn1—N4—C9—C10 | 38.8 (16) |
N6—Zn1—N5—C2 | −159.3 (11) | C1—N1—C10—C9 | 167.9 (16) |
N3—Zn1—N5—C2 | 116.5 (12) | Zn1—N1—C10—C9 | 49.0 (16) |
N1—Zn1—N5—C2 | −47.4 (12) | N4—C9—C10—N1 | −61.0 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Ai | 0.91 | 2.54 | 3.33 (2) | 146 |
N2—H2···O1C | 0.91 | 2.57 | 3.39 (2) | 150 |
N3—H3···O2Bii | 0.91 | 2.28 | 3.14 (2) | 158 |
N3—H3···O2C′ii | 0.91 | 1.99 | 2.88 (2) | 166 |
N4—H4···O2A | 0.91 | 2.48 | 3.300 (16) | 151 |
N4—H4···O2D | 0.91 | 2.48 | 3.165 (18) | 133 |
N5—H5B···O2Dii | 0.90 | 2.61 | 3.12 (2) | 116 |
N5—H5B···O2D′ii | 0.90 | 2.18 | 2.853 (19) | 132 |
N6—H6A···O2Cii | 0.90 | 2.37 | 3.22 (2) | 158 |
N6—H6A···O2B′ii | 0.90 | 2.29 | 3.18 (2) | 169 |
N6—H6B···O2Biii | 0.90 | 2.41 | 3.201 (19) | 147 |
N6—H6B···O2C′iii | 0.90 | 2.42 | 3.30 (3) | 165 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x+1, y, z; (iii) −x, y−1/2, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Ni(C12H30N6)]·2ClO4 | [Zn(C12H30N6)]·2ClO4 |
Mr | 516.03 | 522.69 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 9.198 (4), 12.771 (1), 9.880 (5) | 9.075 (1), 12.891 (1), 9.963 (3) |
β (°) | 113.09 (2) | 112.438 (9) |
V (Å3) | 1067.6 (7) | 1077.3 (4) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.21 | 1.44 |
Crystal size (mm) | 0.50 × 0.50 × 0.50 | 0.30 × 0.13 × 0.10 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.404, 0.546 | 0.779, 0.866 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2097, 1971, 1892 | 2115, 1987, 916 |
Rint | 0.026 | 0.073 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.117, 1.08 | 0.060, 0.175, 0.99 |
No. of reflections | 1971 | 1987 |
No. of parameters | 278 | 258 |
No. of restraints | 20 | 20 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.83 | 0.72, −0.66 |
Absolute structure | Flack (1983) | Flack (1983) |
Absolute structure parameter | 0.03 (3) | −0.04 (5) |
Selected geometric parameters (Å, º) for (I) topNi—N1 | 2.075 (5) | Ni—N6 | 2.124 (5) |
Ni—N3 | 2.077 (5) | Ni—N4 | 2.126 (5) |
Ni—N5 | 2.096 (5) | Ni—N2 | 2.147 (5) |
| | | |
N1—Ni—N3 | 171.0 (2) | N5—Ni—N4 | 161.63 (18) |
N1—Ni—N5 | 78.39 (19) | N6—Ni—N4 | 79.5 (2) |
N3—Ni—N5 | 107.0 (2) | N1—Ni—N2 | 91.0 (2) |
N1—Ni—N6 | 106.6 (2) | N3—Ni—N2 | 82.9 (2) |
N3—Ni—N6 | 79.5 (2) | N5—Ni—N2 | 81.3 (2) |
N5—Ni—N6 | 102.9 (2) | N6—Ni—N2 | 162.4 (2) |
N1—Ni—N4 | 83.47 (19) | N4—Ni—N2 | 101.98 (19) |
N3—Ni—N4 | 91.33 (19) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Ci | 0.91 | 2.41 | 3.192 (10) | 144.3 |
N2—H2···O1D | 0.91 | 2.49 | 3.283 (10) | 145.7 |
N3—H3···O2Bii | 0.91 | 2.14 | 3.039 (8) | 167.3 |
N3—H3···O2B'ii | 0.91 | 2.08 | 2.917 (11) | 151.8 |
N4—H4···O2A | 0.91 | 2.38 | 3.213 (7) | 151.4 |
N4—H4···O2D | 0.91 | 2.57 | 3.271 (9) | 134.5 |
N5—H5A···O2Dii | 0.90 | 2.56 | 3.056 (8) | 115.5 |
N5—H5A···O2D'ii | 0.90 | 2.09 | 2.819 (10) | 137.4 |
N5—H5B···O1Ci | 0.90 | 2.62 | 3.389 (13) | 143.9 |
N6—H6A···O2Biii | 0.90 | 2.31 | 3.120 (8) | 149.5 |
N6—H6A···O2B'iii | 0.90 | 2.64 | 3.53 (3) | 168.3 |
N6—H6B···O2Cii | 0.90 | 2.50 | 3.341 (10) | 155.8 |
N6—H6B···O2C'ii | 0.90 | 2.49 | 3.382 (13) | 169.5 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x, y+1/2, −z. |
Selected geometric parameters (Å, º) for (II) topZn1—N6 | 2.128 (14) | Zn1—N1 | 2.170 (13) |
Zn1—N5 | 2.134 (12) | Zn1—N4 | 2.219 (13) |
Zn1—N3 | 2.141 (15) | Zn1—N2 | 2.255 (12) |
| | | |
N6—Zn1—N5 | 108.9 (6) | N3—Zn1—N4 | 89.7 (5) |
N6—Zn1—N3 | 77.4 (5) | N1—Zn1—N4 | 79.7 (5) |
N5—Zn1—N3 | 113.7 (6) | N6—Zn1—N2 | 156.5 (5) |
N6—Zn1—N1 | 114.7 (6) | N5—Zn1—N2 | 80.0 (6) |
N5—Zn1—N1 | 76.9 (5) | N3—Zn1—N2 | 79.2 (5) |
N3—Zn1—N1 | 161.5 (5) | N1—Zn1—N2 | 88.3 (5) |
N6—Zn1—N4 | 78.2 (6) | N4—Zn1—N2 | 102.5 (5) |
N5—Zn1—N4 | 156.4 (5) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Ai | 0.91 | 2.54 | 3.33 (2) | 146.2 |
N2—H2···O1C | 0.91 | 2.57 | 3.39 (2) | 150.3 |
N3—H3···O2Bii | 0.91 | 2.28 | 3.14 (2) | 158.4 |
N3—H3···O2C'ii | 0.91 | 1.99 | 2.88 (2) | 166.0 |
N4—H4···O2A | 0.91 | 2.48 | 3.300 (16) | 150.5 |
N4—H4···O2D | 0.91 | 2.48 | 3.165 (18) | 132.5 |
N5—H5B···O2Dii | 0.90 | 2.61 | 3.12 (2) | 116.1 |
N5—H5B···O2D'ii | 0.90 | 2.18 | 2.853 (19) | 131.5 |
N6—H6A···O2Cii | 0.90 | 2.37 | 3.22 (2) | 157.5 |
N6—H6A···O2B'ii | 0.90 | 2.29 | 3.18 (2) | 168.8 |
N6—H6B···O2Biii | 0.90 | 2.41 | 3.201 (19) | 147.4 |
N6—H6B···O2C'iii | 0.90 | 2.42 | 3.30 (3) | 165.0 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x+1, y, z; (iii) −x, y−1/2, −z. |
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The coordination chemistry of the isomeric pendent arm macrocycles trans- and cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L1 and L2, respectively) has revealed a number of interesting variations in the structural and physical properties of their complexes. Complexes of the hexadentate coordinated trans isomer (Curtis et al., 1987; Bernhardt et al., 1989, 1990, 1991; Borzel et al., 1998) are more common than the corresponding cis complexes (Bernhardt et al., 1992, 1993, 1997; Lye et al., 1994). It is an interesting feature that L1 and L2 can only bind in one configuration when coordinated as hexadentates, so the structure of the organic ligand determines the isomerism of the resulting complexes.
The hexadentate trans isomers coordinate such that the metal is coplanar with the four secondary amines, and the pendent amines bind in trans coordination sites. By contrast, in the corresponding cis isomers, the macrocycle adopts a folded conformation and the pendent amines coordinate in cis sites. Molecular-mechanics calculations (Bernhardt & Comba, 1991) predicted that the cis isomer L2, bound as a hexadentate, would be able to complex both small and large metal ions, whereas the hexadentate-coordinated trans isomer could only accommodate metals up to a certain size; until one or both axial M—N bonds were broken as a consequence of strain in the complex. These computational results have been borne out by subsequent experimental data.
The two complexes [NiL2](ClO4)2, (I), and [ZnL2](ClO4)2, (II), are isomorphous, and the absolute configuration was determined in each case. The NiII and ZnII crystals studied here, both grown from racemic solutions, were found to be enantiomorphs. Views of the two complex cations are shown in Figures 1 and 2. The folded conformation of the macrocycle is evident, with the coordinated four secondary amines having the same absolute configuration i.e. RRRR (SSSS). Each complex cation has (non-crystallographic) C2 symmetry; the principal axis bisecting the N5—M—N6 angle, and the M—N bond lengths separate into three distinct pairs (Tables 1 and 3). Both macrocyclic five-membered chelate rings adopt the same conformation (δ δ or λ λ), where the C—C bond in each ring is oblique to the C2 axis. This conformation was predicted (Bernhardt & Comba, 1991) to be dominant for complexes containing both small and large metal ions, and indeed no other conformation of a hexadentate coordinated complex of L2 has been identified. Hydrogen bonding between perchlorate O atoms and most amine H atoms is found (Tables 2 and 4). These hydrogen bonds result in chains comprising cations linked by perchlorate anions extending along the b axis. \sch
The M—N bond lengths in both structures are typical of hexaamine complexes of NiII and ZnII, and significantly longer than those observed in the respective trans isomers: [NiL1](ClO4)2 2.07sec and 2.13prim Å (Curtis et al., 1987); [ZnL1](ClO4)2 2.10sec and 2.21prim Å (Bernhardt et al., 1991). This is a feature that has now been observed in the trans and cis isomers of a number of complexes in this series (CoIII, CrIII, NiII and ZnII), where the trans isomers invariably exhibit unusually short M—N bond lengths in contrast to the corresponding coordinate bond lengths in the cis isomers, which are normal. Molecular mechanics calculations predicted this disparity some time ago (Bernhardt & Comba, 1991).
The valence angles involving the metal centres (Tables 1 and 3) indicate that the larger ZnII ion exhibits a greater distortion from octahedral geometry than its NiII analogue. This again is a general trend across the series of known structures of L2 complexes ranging from the smallest (CoIII; Bernhardt et al., 1997) to the largest (PbII; Lye et al., 1994). There are a number of structural indicators of this distortion. It may be viewed as a pseudo-trigonal twist of the N1—N2—N5 and N4—N3—N6 octahedral faces, by analogy with tris-bidentate complexes. This definition is somewhat limited in this case as there is no threefold axis in complexes of L2. A more reliable indicator of the distortion present in these complexes is the N5—M—N6 valence angle, which increases with the M—N bond length, and this is illustrated in Figure 3. The CdII (Bernhardt et al., 1992) and PbII (Lye et al., 1994) structures exhibit somewhat exaggerated bite angles caused by (or resulting in) coordination of perchlorate anions, and their structures approximate distorted square antiprismatic geometries (N6O2). It is difficult to say whether the presence of these weakly bound ions (M—O > 3.0 Å) in the CdII PbII structures significantly perturb the valence angles involving the coordinated macrocycle, or, conversely, whether these distortions are driven by the macrocycles, which prize open the N5—M—N6 angles thus making room for incoming ligands.
The observed distortions from octahedral geometry with increasing M—N bond length were predicted by molecular-mechanics calculations. However, electronic contributions from transition metal ions will oppose distortions away from octahedral geometry (ligand-field stabilization energy), and neglecting this effect can lead to an overestimation of the observed distortion (Bernhardt & Comba, 1993). That is, the geometries of the d10 ZnII and CdII complexes represent true ligand-dictated distortions, whereas the CoIII, CrIII and NiII structures reflect a balance between ligand-directed steric and metal-based electronic effects.