Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015474/os1090sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015474/os1090Isup2.hkl |
CCDC reference: 143226
The ligand C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane was prepared according to Hay & Piplani (1977). Equimolar quantities of copper(II) sulfate pentahydrate and C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane were dissolved in water and left to react for ca 30 min in a steam bath. The resulting solution was evaporated to dryness by rotatory evaporation. The crystals were obtained from 2 M NaCl aqueous solution on slow evaporation.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: NRCVAX; software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids. The chloride anions, the uncoordinated water molecules and the H atoms have been omitted for clarity. |
[Cu(C12H28N4)(H2O)2]Cl2·2H2O | F(000) = 924 |
Mr = 434.89 | Dx = 1.380 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.043 (1) Å | Cell parameters from 25 reflections |
b = 17.482 (4) Å | θ = 9.4–17.3° |
c = 15.237 (3) Å | µ = 1.32 mm−1 |
β = 102.30 (1)° | T = 293 K |
V = 2093.4 (7) Å3 | Pillar, blue |
Z = 4 | 0.38 × 0.31 × 0.28 mm |
Enraf-Nonius CAD-4 diffractometer | 2947 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 25°, θmin = 1.8° |
ω/2θ scans | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −20→20 |
Tmin = 0.619, Tmax = 0.691 | l = −18→17 |
7942 measured reflections | 3 standard reflections every 60 min |
3688 independent reflections | intensity decay: 1% |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: mixed |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.3263P] where P = (Fo2 + 2Fc2)/3 |
3688 reflections | (Δ/σ)max = 0.002 |
210 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Cu(C12H28N4)(H2O)2]Cl2·2H2O | V = 2093.4 (7) Å3 |
Mr = 434.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.043 (1) Å | µ = 1.32 mm−1 |
b = 17.482 (4) Å | T = 293 K |
c = 15.237 (3) Å | 0.38 × 0.31 × 0.28 mm |
β = 102.30 (1)° |
Enraf-Nonius CAD-4 diffractometer | 2947 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.028 |
Tmin = 0.619, Tmax = 0.691 | 3 standard reflections every 60 min |
7942 measured reflections | intensity decay: 1% |
3688 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.39 e Å−3 |
3688 reflections | Δρmin = −0.31 e Å−3 |
210 parameters |
Experimental. The maximum 2θ for data collection is 50.0°. The data collection would not go beyond this limit, because of the crystal quality. |
Refinement. The H atoms were fixed geometrically and water H atoms were located from the difference-Fourier map. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.44739 (3) | 0.74283 (1) | 0.83515 (1) | 0.0343 (1) | |
O1 | 0.2851 (2) | 0.75121 (10) | 0.96090 (11) | 0.0634 (5) | |
H1O1 | 0.3186 | 0.7139 | 0.9995 | 0.080* | |
H2O1 | 0.2728 | 0.7907 | 0.9936 | 0.080* | |
O2 | 0.6086 (2) | 0.74014 (10) | 0.71150 (11) | 0.0608 (4) | |
H1O2 | 0.5873 | 0.7819 | 0.6749 | 0.080* | |
H2O2 | 0.6377 | 0.7082 | 0.6823 | 0.080* | |
N1 | 0.2727 (2) | 0.66922 (11) | 0.77006 (11) | 0.0468 (4) | |
H1N1 | 0.2944 | 0.6628 | 0.7143 | 0.056* | |
N2 | 0.5721 (2) | 0.64784 (10) | 0.89347 (11) | 0.0446 (4) | |
H1N2 | 0.5454 | 0.6432 | 0.9483 | 0.054* | |
N3 | 0.6204 (2) | 0.81596 (10) | 0.90132 (11) | 0.0432 (4) | |
H1N3 | 0.5963 | 0.8228 | 0.9565 | 0.052* | |
N4 | 0.3205 (2) | 0.83762 (11) | 0.77679 (11) | 0.0456 (4) | |
H1N4 | 0.3465 | 0.8420 | 0.7217 | 0.055* | |
C1 | 0.3048 (4) | 0.59523 (14) | 0.81591 (18) | 0.0672 (8) | |
H1A | 0.2497 | 0.5547 | 0.7769 | 0.081* | |
H1B | 0.2591 | 0.5954 | 0.8699 | 0.081* | |
C2 | 0.4930 (4) | 0.58199 (13) | 0.83966 (17) | 0.0646 (7) | |
H2A | 0.5180 | 0.5351 | 0.8740 | 0.078* | |
H2B | 0.5374 | 0.5774 | 0.7855 | 0.078* | |
C3 | 0.7617 (3) | 0.64786 (16) | 0.90960 (17) | 0.0597 (7) | |
H3 | 0.7945 | 0.6511 | 0.8514 | 0.072* | |
C4 | 0.8321 (3) | 0.71707 (19) | 0.96464 (17) | 0.0674 (8) | |
H4A | 0.7828 | 0.7190 | 1.0174 | 0.081* | |
H4B | 0.9540 | 0.7104 | 0.9852 | 0.081* | |
C5 | 0.8003 (3) | 0.79279 (17) | 0.91627 (18) | 0.0619 (7) | |
H5A | 0.8705 | 0.8318 | 0.9514 | 0.074* | |
H5B | 0.8334 | 0.7889 | 0.8588 | 0.074* | |
C6 | 0.5887 (3) | 0.88993 (13) | 0.85394 (17) | 0.0574 (6) | |
H6A | 0.6350 | 0.8890 | 0.8002 | 0.069* | |
H6B | 0.6437 | 0.9308 | 0.8924 | 0.069* | |
C7 | 0.4007 (4) | 0.90353 (13) | 0.82935 (17) | 0.0598 (7) | |
H7A | 0.3558 | 0.9093 | 0.8832 | 0.072* | |
H7B | 0.3767 | 0.9500 | 0.7941 | 0.072* | |
C8 | 0.1313 (3) | 0.83803 (17) | 0.76081 (16) | 0.0629 (7) | |
H8 | 0.0991 | 0.8362 | 0.8193 | 0.075* | |
C9 | 0.0598 (3) | 0.7674 (2) | 0.70815 (19) | 0.0746 (9) | |
H9A | −0.0623 | 0.7737 | 0.6887 | 0.090* | |
H9B | 0.1067 | 0.7646 | 0.6546 | 0.090* | |
C10 | 0.0935 (3) | 0.69282 (18) | 0.75715 (18) | 0.0682 (8) | |
H1OA | 0.0635 | 0.6975 | 0.8153 | 0.082* | |
H10B | 0.0217 | 0.6536 | 0.7235 | 0.082* | |
C11 | 0.8368 (5) | 0.5742 (2) | 0.9563 (2) | 0.1062 (13) | |
H11A | 0.7999 | 0.5684 | 1.0118 | 0.127* | |
H11B | 0.9587 | 0.5769 | 0.9682 | 0.127* | |
H11C | 0.7987 | 0.5312 | 0.9181 | 0.127* | |
C12 | 0.0548 (5) | 0.9100 (2) | 0.7124 (2) | 0.1045 (13) | |
H12A | 0.0923 | 0.9539 | 0.7493 | 0.125* | |
H12B | −0.0671 | 0.9069 | 0.7009 | 0.125* | |
H12C | 0.0910 | 0.9148 | 0.6565 | 0.125* | |
Cl1 | 0.45811 (13) | 0.87780 (4) | 0.58995 (4) | 0.0885 (3) | |
Cl2 | 0.23711 (8) | 0.59497 (4) | 0.56513 (4) | 0.06240 (18) | |
O3 | 0.6291 (2) | 0.87627 (11) | 1.09328 (13) | 0.0740 (5) | |
H1O3 | 0.7050 | 0.9100 | 1.0866 | 0.080* | |
H2O3 | 0.5040 | 0.9023 | 1.0761 | 0.080* | |
O4 | 0.1110 (3) | 0.47642 (12) | 0.40706 (13) | 0.0786 (6) | |
H1O4 | 0.0277 | 0.4507 | 0.4186 | 0.080* | |
H2O4 | 0.1505 | 0.5135 | 0.4563 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0348 (1) | 0.0358 (1) | 0.0323 (1) | −0.0024 (1) | 0.0068 (1) | −0.0010 (1) |
O1 | 0.0760 (12) | 0.0708 (12) | 0.0465 (9) | 0.0042 (9) | 0.0202 (9) | −0.0031 (8) |
O2 | 0.0714 (11) | 0.0691 (11) | 0.0463 (9) | 0.0036 (9) | 0.0229 (8) | −0.0038 (8) |
N1 | 0.0460 (11) | 0.0600 (12) | 0.0365 (9) | −0.0149 (9) | 0.0132 (8) | −0.0098 (8) |
N2 | 0.0576 (11) | 0.0450 (10) | 0.0331 (9) | 0.0086 (8) | 0.0136 (8) | 0.0029 (7) |
N3 | 0.0437 (10) | 0.0494 (10) | 0.0387 (9) | −0.0092 (8) | 0.0139 (8) | −0.0108 (8) |
N4 | 0.0526 (11) | 0.0522 (11) | 0.0355 (9) | 0.0121 (9) | 0.0169 (8) | 0.0063 (8) |
C1 | 0.090 (2) | 0.0501 (14) | 0.0628 (16) | −0.0305 (14) | 0.0202 (15) | −0.0090 (12) |
C2 | 0.104 (2) | 0.0356 (12) | 0.0562 (15) | 0.0018 (13) | 0.0209 (15) | −0.0003 (11) |
C3 | 0.0541 (15) | 0.0768 (18) | 0.0478 (13) | 0.0260 (13) | 0.0101 (11) | 0.0034 (12) |
C4 | 0.0399 (13) | 0.108 (2) | 0.0507 (14) | 0.0140 (14) | 0.0003 (11) | −0.0032 (15) |
C5 | 0.0368 (13) | 0.0854 (19) | 0.0630 (15) | −0.0129 (13) | 0.0096 (11) | −0.0197 (14) |
C6 | 0.0795 (18) | 0.0422 (12) | 0.0564 (14) | −0.0207 (12) | 0.0274 (13) | −0.0089 (11) |
C7 | 0.091 (2) | 0.0371 (12) | 0.0569 (15) | 0.0105 (12) | 0.0289 (14) | 0.0039 (10) |
C8 | 0.0519 (15) | 0.092 (2) | 0.0446 (13) | 0.0292 (14) | 0.0103 (11) | 0.0060 (13) |
C9 | 0.0398 (14) | 0.130 (3) | 0.0497 (15) | 0.0120 (15) | −0.0005 (11) | −0.0073 (17) |
C10 | 0.0412 (14) | 0.106 (2) | 0.0585 (15) | −0.0223 (14) | 0.0127 (12) | −0.0212 (16) |
C11 | 0.110 (3) | 0.106 (3) | 0.094 (2) | 0.060 (2) | 0.001 (2) | 0.016 (2) |
C12 | 0.102 (3) | 0.128 (3) | 0.078 (2) | 0.065 (2) | 0.0076 (19) | 0.023 (2) |
Cl1 | 0.1804 (10) | 0.0481 (4) | 0.0508 (4) | −0.0025 (4) | 0.0553 (5) | −0.0022 (3) |
Cl2 | 0.0678 (4) | 0.0620 (4) | 0.0600 (4) | −0.0188 (3) | 0.0194 (3) | −0.0117 (3) |
O3 | 0.0685 (12) | 0.0704 (12) | 0.0865 (13) | 0.0016 (10) | 0.0243 (11) | 0.0129 (10) |
O4 | 0.0739 (12) | 0.0824 (13) | 0.0899 (14) | −0.0217 (11) | 0.0410 (11) | −0.0296 (11) |
Cu1—O1 | 2.542 (2) | C3—H3 | 0.98 |
Cu1—O2 | 2.505 (2) | C4—C5 | 1.510 (4) |
Cu1—N3 | 1.997 (2) | C4—H4A | 0.97 |
Cu1—N1 | 2.005 (2) | C4—H4B | 0.97 |
Cu1—N2 | 2.043 (2) | C5—H5A | 0.97 |
Cu1—N4 | 2.047 (2) | C5—H5B | 0.97 |
O1—H1O1 | 0.88 | C6—C7 | 1.497 (4) |
O1—H2O1 | 0.86 | C6—H6A | 0.97 |
O2—H1O2 | 0.91 | C6—H6B | 0.97 |
O2—H2O2 | 0.78 | C7—H7A | 0.97 |
N1—C1 | 1.467 (3) | C7—H7B | 0.97 |
N1—C10 | 1.472 (3) | C8—C9 | 1.518 (4) |
N1—H1N1 | 0.91 | C8—C12 | 1.521 (4) |
N2—C2 | 1.477 (3) | C8—H8 | 0.98 |
N2—C3 | 1.492 (3) | C9—C10 | 1.498 (4) |
N2—H1N2 | 0.91 | C9—H9A | 0.97 |
N3—C5 | 1.473 (3) | C9—H9B | 0.97 |
N3—C6 | 1.476 (3) | C10—H1OA | 0.97 |
N3—H1N3 | 0.91 | C10—H10B | 0.97 |
N4—C7 | 1.471 (3) | C11—H11A | 0.96 |
N4—C8 | 1.489 (3) | C11—H11B | 0.96 |
N4—H1N4 | 0.91 | C11—H11C | 0.96 |
C1—C2 | 1.497 (4) | C12—H12A | 0.96 |
C1—H1A | 0.97 | C12—H12B | 0.96 |
C1—H1B | 0.97 | C12—H12C | 0.96 |
C2—H2A | 0.97 | O3—H1O3 | 0.87 |
C2—H2B | 0.97 | O3—H2O3 | 1.08 |
C3—C4 | 1.512 (4) | O4—H1O4 | 0.85 |
C3—C11 | 1.531 (4) | O4—H2O4 | 0.99 |
O1—Cu1—O2 | 177.77 (6) | C11—C3—H3 | 108.3 |
N1—Cu1—O1 | 89.51 (7) | C5—C4—C3 | 115.2 (2) |
N2—Cu1—O1 | 90.13 (6) | C5—C4—H4A | 108.5 |
N3—Cu1—O1 | 89.83 (7) | C3—C4—H4A | 108.5 |
N4—Cu1—O1 | 89.56 (6) | C5—C4—H4B | 108.5 |
N1—Cu1—O2 | 92.09 (7) | C3—C4—H4B | 108.5 |
N2—Cu1—O2 | 91.55 (7) | H4A—C4—H4B | 107.5 |
N3—Cu1—O2 | 88.58 (7) | N3—C5—C4 | 112.0 (2) |
N4—Cu1—O2 | 88.77 (7) | N3—C5—H5A | 109.2 |
N3—Cu1—N1 | 179.31 (7) | C4—C5—H5A | 109.2 |
N3—Cu1—N2 | 94.36 (8) | N3—C5—H5B | 109.2 |
N1—Cu1—N2 | 85.45 (8) | C4—C5—H5B | 109.2 |
N3—Cu1—N4 | 86.00 (8) | H5A—C5—H5B | 107.9 |
N1—Cu1—N4 | 94.18 (8) | N3—C6—C7 | 108.75 (19) |
N2—Cu1—N4 | 179.52 (8) | N3—C6—H6A | 109.9 |
H1O1—O1—H2O1 | 105.1 | C7—C6—H6A | 109.9 |
H1O2—O2—H2O2 | 105.3 | N3—C6—H6B | 109.9 |
C1—N1—C10 | 112.3 (2) | C7—C6—H6B | 109.9 |
C1—N1—Cu1 | 107.26 (14) | H6A—C6—H6B | 108.3 |
C10—N1—Cu1 | 116.71 (16) | N4—C7—C6 | 108.29 (19) |
C1—N1—H1N1 | 106.7 | N4—C7—H7A | 110.0 |
C10—N1—H1N1 | 106.7 | C6—C7—H7A | 110.0 |
Cu1—N1—H1N1 | 106.7 | N4—C7—H7B | 110.0 |
C2—N2—C3 | 113.3 (2) | C6—C7—H7B | 110.0 |
C2—N2—Cu1 | 106.19 (14) | H7A—C7—H7B | 108.4 |
C3—N2—Cu1 | 117.47 (16) | N4—C8—C9 | 110.0 (2) |
C2—N2—H1N2 | 106.4 | N4—C8—C12 | 112.2 (3) |
C3—N2—H1N2 | 106.4 | C9—C8—C12 | 110.4 (2) |
Cu1—N2—H1N2 | 106.4 | N4—C8—H8 | 108.1 |
C5—N3—C6 | 112.2 (2) | C9—C8—H8 | 108.1 |
C5—N3—Cu1 | 117.24 (15) | C12—C8—H8 | 108.1 |
C6—N3—Cu1 | 106.53 (14) | C10—C9—C8 | 115.9 (2) |
C5—N3—H1N3 | 106.8 | C10—C9—H9A | 108.3 |
C6—N3—H1N3 | 106.8 | C8—C9—H9A | 108.3 |
Cu1—N3—H1N3 | 106.8 | C10—C9—H9B | 108.3 |
C7—N4—C8 | 113.5 (2) | C8—C9—H9B | 108.3 |
C7—N4—Cu1 | 106.11 (14) | H9A—C9—H9B | 107.4 |
C8—N4—Cu1 | 118.18 (16) | N1—C10—C9 | 112.2 (2) |
C7—N4—H1N4 | 106.1 | N1—C10—H1OA | 109.2 |
C8—N4—H1N4 | 106.1 | C9—C10—H1OA | 109.2 |
Cu1—N4—H1N4 | 106.1 | N1—C10—H10B | 109.2 |
N1—C1—C2 | 108.5 (2) | C9—C10—H10B | 109.2 |
N1—C1—H1A | 110.0 | H1OA—C10—H10B | 107.9 |
C2—C1—H1A | 110.0 | C3—C11—H11A | 109.5 |
N1—C1—H1B | 110.0 | C3—C11—H11B | 109.5 |
C2—C1—H1B | 110.0 | H11A—C11—H11B | 109.5 |
H1A—C1—H1B | 108.4 | C3—C11—H11C | 109.5 |
N2—C2—C1 | 107.9 (2) | H11A—C11—H11C | 109.5 |
N2—C2—H2A | 110.1 | H11B—C11—H11C | 109.5 |
C1—C2—H2A | 110.1 | C8—C12—H12A | 109.5 |
N2—C2—H2B | 110.1 | C8—C12—H12B | 109.5 |
C1—C2—H2B | 110.1 | H12A—C12—H12B | 109.5 |
H2A—C2—H2B | 108.4 | C8—C12—H12C | 109.5 |
N2—C3—C4 | 109.9 (2) | H12A—C12—H12C | 109.5 |
N2—C3—C11 | 111.4 (3) | H12B—C12—H12C | 109.5 |
C4—C3—C11 | 110.5 (2) | H1O3—O3—H2O3 | 109.0 |
N2—C3—H3 | 108.3 | H1O4—O4—H2O4 | 109.0 |
C4—C3—H3 | 108.3 | ||
Cu1—N1—C1—C2 | −41.3 (2) | C6—C7—N4—Cu1 | 39.1 (2) |
N1—C1—C2—N2 | 55.6 (3) | C7—N4—Cu1—N3 | −12.9 (1) |
C1—C2—N2—Cu1 | −40.6 (2) | N4—Cu1—N3—C6 | −15.9 (1) |
C2—N2—Cu1—N1 | 14.5 (2) | Cu1—N4—C8—C9 | −53.5 (2) |
N2—Cu1—N1—C1 | 14.7 (2) | N4—C8—C9—C10 | 68.9 (3) |
Cu1—N2—C3—C4 | 55.3 (2) | C8—C9—C10—N1 | −72.0 (3) |
N2—C3—C4—C5 | −70.3 (3) | C9—C10—N1—Cu1 | 57.1 (3) |
C3—C4—C5—N3 | 71.5 (3) | C10—N1—Cu1—N4 | −38.1 (2) |
C4—C5—N3—Cu1 | −56.1 (2) | N1—Cu1—N4—C8 | 37.6 (2) |
C5—N3—Cu1—N2 | 37.8 (2) | C2—N2—C3—C11 | −57.4 (3) |
N3—Cu1—N2—C3 | −38.1 (2) | C11—C3—C4—C5 | 166.3 (2) |
Cu1—N3—C6—C7 | 42.1 (2) | C7—N4—C8—C12 | 58.0 (3) |
N3—C6—C7—N4 | −55.4 (2) | C12—C8—C9—C10 | −166.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl2 | 0.91 | 2.52 | 3.337 (2) | 150 |
N2—H1N2···Cl1i | 0.91 | 2.44 | 3.343 (2) | 175 |
N3—H1N3···O3 | 0.91 | 2.25 | 3.096 (3) | 155 |
N4—H1N4···Cl1 | 0.91 | 2.49 | 3.341 (2) | 167 |
O1—H1O1···Cl1i | 0.88 | 2.25 | 3.118 (2) | 168 |
O1—H2O1···Cl2i | 0.87 | 2.32 | 3.188 (2) | 173 |
O2—H1O2···Cl1 | 0.91 | 2.23 | 3.120 (2) | 163 |
O2—H2O2···O3ii | 0.78 | 2.00 | 2.746 (3) | 161 |
O3—H1O3···O4iii | 0.87 | 1.87 | 2.728 (3) | 170 |
O3—H2O3···Cl2i | 1.08 | 2.12 | 3.131 (2) | 154 |
O4—H1O4···Cl2iv | 0.85 | 2.34 | 3.175 (2) | 167 |
O4—H2O4···Cl2 | 0.99 | 2.18 | 3.175 (2) | 180 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H28N4)(H2O)2]Cl2·2H2O |
Mr | 434.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.043 (1), 17.482 (4), 15.237 (3) |
β (°) | 102.30 (1) |
V (Å3) | 2093.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.38 × 0.31 × 0.28 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.619, 0.691 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7942, 3688, 2947 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.076, 1.02 |
No. of reflections | 3688 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.31 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), NRCVAX, SHELXL97.
Cu1—O1 | 2.542 (2) | Cu1—N1 | 2.005 (2) |
Cu1—O2 | 2.505 (2) | Cu1—N2 | 2.043 (2) |
Cu1—N3 | 1.997 (2) | Cu1—N4 | 2.047 (2) |
O1—Cu1—O2 | 177.77 (6) | N4—Cu1—O2 | 88.77 (7) |
N1—Cu1—O1 | 89.51 (7) | N3—Cu1—N1 | 179.31 (7) |
N2—Cu1—O1 | 90.13 (6) | N3—Cu1—N2 | 94.36 (8) |
N3—Cu1—O1 | 89.83 (7) | N1—Cu1—N2 | 85.45 (8) |
N4—Cu1—O1 | 89.56 (6) | N3—Cu1—N4 | 86.00 (8) |
N1—Cu1—O2 | 92.09 (7) | N1—Cu1—N4 | 94.18 (8) |
N2—Cu1—O2 | 91.55 (7) | N2—Cu1—N4 | 179.52 (8) |
N3—Cu1—O2 | 88.58 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl2 | 0.91 | 2.52 | 3.337 (2) | 150 |
N2—H1N2···Cl1i | 0.91 | 2.44 | 3.343 (2) | 175 |
N3—H1N3···O3 | 0.91 | 2.25 | 3.096 (3) | 155 |
N4—H1N4···Cl1 | 0.91 | 2.49 | 3.341 (2) | 167 |
O1—H1O1···Cl1i | 0.88 | 2.25 | 3.118 (2) | 168 |
O1—H2O1···Cl2i | 0.87 | 2.32 | 3.188 (2) | 173 |
O2—H1O2···Cl1 | 0.91 | 2.23 | 3.120 (2) | 163 |
O2—H2O2···O3ii | 0.78 | 2.00 | 2.746 (3) | 161 |
O3—H1O3···O4iii | 0.87 | 1.87 | 2.728 (3) | 170 |
O3—H2O3···Cl2i | 1.08 | 2.12 | 3.131 (2) | 154 |
O4—H1O4···Cl2iv | 0.85 | 2.34 | 3.175 (2) | 167 |
O4—H2O4···Cl2 | 0.99 | 2.18 | 3.175 (2) | 180 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x, −y+1, −z+1. |
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The macrocyclic ligand 5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane exists as two isomers, i.e. C-meso and C-rac. The coordination behaviour of transition metal complexes of C-meso- and C-rac-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane has been widely studied (Chen et al., 1994; Hay et al., 1984; Hay & Govan, 1992; Hay & Piplani, 1977). The crystal structures of complexes of the C-rac isomer with CuII and CoIII have been reported previously (Panneerselvam et al., 1999; Tahirov et al., 1994). The present paper reports the crystal structure of the copper(II) complex of the C-meso isomer, (I).
The CuII ion is six-coordinated in a distorted octahedral geometry with the four N atoms of the macrocyclic ligand in equatorial positions and two O atoms of two water molecules in axial positions. This compound is not a symmetric complex, since the two trans water molecules and the four N atoms of the tetradentate ligand are coordinated at different distances. In the majority of monomeric trans-diaquacopper(II) complexes, the Cu atom is located at a center of symmetry or on a twofold axis (Allen & Kennard, 1993). There are only a few examples where the trans-diaquacopper(II) octahedral complex is not centrosymmetric (Kozhemyak et al., 1980; Biagini Cingi et al., 1989; Petrovčič et al., 1999).
The CuII ion and the four N-donor atoms are coplanar within 0.004 (1) Å. The Cu—N distances are in the range 1.997 (2)–2.047 (2) Å and the average Cu—N distance, 2.023 (2) Å, is similar to the average Cu—N distance found for CuII tetraaza macrocyclic complexes [2.03 (3) Å; Lu et al., 1991]. The Cu—Owater distances, 2.542 (2) and 2.505 (2) Å, are shorter than those found in trans-diaquacopper(II) tetraaza macrocyclic complexes of the type trans-[Cu(C-meso-1,5,8,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane)- (OH2)2]X2, i.e. 2.624 (3) Å for X = NO2, 2.692 (2) Å for X = Cl, 2.695 (16) Å for X = Br and 2.725 (3) Å for X = I (Lu et al., 1999). The tetradentate ligand adopts a conformation with two six-membered rings in a chair form and two five-membered rings in a gauche form. The arrangement of the four chiral nitrogen centers is in the type-III configuration designated by Bosnich et al. (1965). The two C-methyl groups occupy equatorial positions. The complex has a 1SR,4RS,8RS,11SR configuration for the four chiral N-atom centers and a 5SR,12RS configuration for the two chiral C-atom centers. The crystal structure is stabilized by hydrogen bonds (Table 2).