Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101006849/de1170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006849/de1170Isup2.hkl |
CCDC reference: 169929
The oxamato-nickel(II) complex Na2[Ni(opba)]·3H2O was synthesized by a modified procedure analogous to that for Na2[Cu(opba)] 3H2O (Stumpf et al., 1993) and the tetraazamacrocyclic NiII complex [Ni(meso-cth)](ClO4)2 was prepared by the literature method (Tait et al., 1978).
[Ni(meso-cth)][M(opba)] 2H2O, (I), was obtained as red orange crystals by slow diffusion between an aqueous solution (20 ml) of Na2[Ni(opba)]·3H2O (0.123 g, 0.3 mmol) and an acetonitrile solution (20 ml) of [Ni(meso-cth)](ClO4)2 (0.163 g, 0.3 mmol) in an H-shaped tube.
The structure was solved by direct methods. All non-H atoms were refined anisotropically. One of the water molecules is disordered, and two fractional oxygen sites (Ow2 and Ow2') with occupancy factors of 0.5 were refined. The hydrogen atoms of all amino groups and one hydrogen atom of one water molecule (Ow1) were located in the difference Fourier map. The other hydrogen atoms of water molecules were not added, and hydrogen atoms bound to carbon were located geometrically. Hydrogen atoms were isotropically refined. The C1—C2 and C3—C4 distances are consistent with the Csp2—Csp2 bond distance in other oxamato complexes in the literature (see, for example, Cervera et al., 1998).
Data collection: SMART1000 software (Bruker, 1998); cell refinement: SMART1000 software; data reduction: SAINT (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
[Ni(C16H36N4)][Ni(C10H4N2O6)]·2H2O | F(000) = 724 |
Mr = 686.09 | Dx = 1.542 Mg m−3 |
Triclinic, P1 | Melting point: not measured K |
a = 10.0460 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4964 (10) Å | Cell parameters from 4890 reflections |
c = 12.7901 (10) Å | θ = 2.3–25.0° |
α = 92.488 (2)° | µ = 1.33 mm−1 |
β = 110.247 (2)° | T = 298 K |
γ = 99.408 (2)° | Prism, orange |
V = 1477.5 (2) Å3 | 0.3 × 0.15 × 0.1 mm |
Z = 2 |
CCD area detector diffractometer | 5173 independent reflections |
Radiation source: fine-focus sealed tube | 4408 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −11→8 |
Tmin = 0.691, Tmax = 0.878 | k = −14→14 |
6157 measured reflections | l = −10→15 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.3612P] where P = (Fo2 + 2Fc2)/3 |
5173 reflections | (Δ/σ)max = 0.001 |
411 parameters | Δρmax = 0.43 e Å−3 |
5 restraints | Δρmin = −0.25 e Å−3 |
[Ni(C16H36N4)][Ni(C10H4N2O6)]·2H2O | γ = 99.408 (2)° |
Mr = 686.09 | V = 1477.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0460 (8) Å | Mo Kα radiation |
b = 12.4964 (10) Å | µ = 1.33 mm−1 |
c = 12.7901 (10) Å | T = 298 K |
α = 92.488 (2)° | 0.3 × 0.15 × 0.1 mm |
β = 110.247 (2)° |
CCD area detector diffractometer | 5173 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4408 reflections with I > 2σ(I) |
Tmin = 0.691, Tmax = 0.878 | Rint = 0.015 |
6157 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 5 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.43 e Å−3 |
5173 reflections | Δρmin = −0.25 e Å−3 |
411 parameters |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.9227 (0.0062) x + 10.1059 (0.0063) y + 4.1080 (0.0096) z = 3.5866 (0.0096) * 0.0010 (0.0011) N1 * -0.0010 (0.0011) N2 * -0.0009 (0.0009) O1 * 0.0009 (0.0009) O2 0.0099 (0.0011) Ni3 Rms deviation of fitted atoms = 0.0010 - 7.3741 (0.0055) x + 9.7247 (0.0064) y + 3.8961 (0.0118) z = 2.7438 (0.0109) Angle to previous plane (with approximate e.s.d.) = 4.04 (0.11) * 0.0089 (0.0022) C1 * 0.0020 (0.0023) C2 * -0.0761 (0.0014) N1 * 0.0738 (0.0014) O1 * -0.0701 (0.0014) O5 * 0.0615 (0.0014) O6 Rms deviation of fitted atoms = 0.0578 - 7.1160 (0.0058) x + 9.8668 (0.0062) y + 4.3773 (0.0115) z = 3.3492 (0.0090) Angle to previous plane (with approximate e.s.d.) = 3.42 (0.11) * 0.0073 (0.0024) C3 * 0.0074 (0.0021) C4 * -0.0375 (0.0014) N2 * 0.0318 (0.0014) O2 * 0.0264 (0.0013) O3 * -0.0355 (0.0015) O4 Rms deviation of fitted atoms = 0.0274 |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.5 | 0.5 | 0.5 | 0.02707 (12) | |
Ni2 | 0 | 0 | 0 | 0.03056 (13) | |
Ni3 | 0.88728 (3) | 0.75816 (2) | 0.50559 (3) | 0.03268 (11) | |
O1 | 0.8391 (2) | 0.67964 (16) | 0.61494 (17) | 0.0489 (5) | |
O2 | 0.7268 (2) | 0.69986 (16) | 0.37633 (16) | 0.0472 (5) | |
O3 | 0.8906 (2) | 0.88163 (18) | 0.23166 (16) | 0.0528 (5) | |
O5 | 0.9337 (3) | 0.66372 (19) | 0.79683 (19) | 0.0634 (6) | |
O4 | 0.6458 (2) | 0.7157 (2) | 0.19357 (19) | 0.0690 (7) | |
O6 | 1.1557 (2) | 0.83919 (18) | 0.81282 (15) | 0.0541 (5) | |
N1 | 1.0517 (2) | 0.82356 (16) | 0.61960 (16) | 0.0312 (5) | |
N2 | 0.9551 (2) | 0.84050 (16) | 0.41470 (16) | 0.0306 (4) | |
C1 | 1.0631 (3) | 0.8000 (2) | 0.7220 (2) | 0.0361 (6) | |
C2 | 0.9373 (3) | 0.7072 (2) | 0.7135 (2) | 0.0421 (6) | |
C3 | 0.7348 (3) | 0.7424 (2) | 0.2879 (2) | 0.0450 (7) | |
C4 | 0.8705 (3) | 0.8314 (2) | 0.3078 (2) | 0.0357 (6) | |
C5 | 1.0914 (3) | 0.90860 (19) | 0.4701 (2) | 0.0296 (5) | |
C6 | 1.1713 (3) | 0.9776 (2) | 0.4230 (2) | 0.0392 (6) | |
H6A | 1.1356 | 0.985 | 0.3467 | 0.047* | |
C7 | 1.3055 (3) | 1.0359 (2) | 0.4913 (3) | 0.0485 (7) | |
H7A | 1.3605 | 1.082 | 0.4602 | 0.058* | |
C8 | 1.3585 (3) | 1.0267 (2) | 0.6041 (3) | 0.0481 (7) | |
H8A | 1.4489 | 1.0667 | 0.6482 | 0.058* | |
C9 | 1.2796 (3) | 0.9587 (2) | 0.6533 (2) | 0.0387 (6) | |
H9A | 1.3157 | 0.9531 | 0.73 | 0.046* | |
C10 | 1.1458 (3) | 0.89929 (19) | 0.5861 (2) | 0.0292 (5) | |
N3 | 0.3316 (2) | 0.53726 (17) | 0.38712 (18) | 0.0326 (5) | |
N4 | 0.4273 (2) | 0.51884 (17) | 0.62182 (18) | 0.0330 (5) | |
C11 | 0.3567 (3) | 0.5460 (3) | 0.2797 (2) | 0.0455 (7) | |
H11A | 0.4073 | 0.6187 | 0.2784 | 0.055* | |
H11B | 0.2654 | 0.5314 | 0.217 | 0.055* | |
C12 | 0.5542 (3) | 0.5366 (2) | 0.7277 (2) | 0.0456 (7) | |
H12A | 0.5231 | 0.5276 | 0.7912 | 0.055* | |
H12B | 0.6099 | 0.6097 | 0.7371 | 0.055* | |
C13 | 0.2654 (3) | 0.6285 (2) | 0.4171 (2) | 0.0412 (6) | |
C14 | 0.2148 (3) | 0.5965 (2) | 0.5123 (2) | 0.0444 (7) | |
H14A | 0.1527 | 0.6457 | 0.5203 | 0.053* | |
H14B | 0.1559 | 0.5238 | 0.4906 | 0.053* | |
C15 | 0.3304 (3) | 0.5969 (2) | 0.6259 (2) | 0.0427 (6) | |
H15A | 0.3897 | 0.6704 | 0.6477 | 0.051* | |
C16 | 0.1319 (4) | 0.6403 (3) | 0.3172 (3) | 0.0695 (10) | |
H16A | 0.0627 | 0.5731 | 0.2978 | 0.104* | |
H16B | 0.1598 | 0.6572 | 0.2543 | 0.104* | |
H16C | 0.0896 | 0.6979 | 0.3368 | 0.104* | |
C17 | 0.3782 (4) | 0.7341 (2) | 0.4507 (3) | 0.0598 (9) | |
H17A | 0.4604 | 0.7247 | 0.5135 | 0.09* | |
H17B | 0.3371 | 0.7922 | 0.4711 | 0.09* | |
H17C | 0.4079 | 0.7516 | 0.3888 | 0.09* | |
C18 | 0.2612 (4) | 0.5718 (3) | 0.7131 (3) | 0.0729 (11) | |
H18A | 0.3354 | 0.5732 | 0.7851 | 0.109* | |
H18B | 0.2003 | 0.5008 | 0.6924 | 0.109* | |
H18C | 0.2043 | 0.6255 | 0.7169 | 0.109* | |
N5 | 0.1022 (2) | −0.12291 (18) | 0.02236 (17) | 0.0341 (5) | |
N6 | 0.1694 (2) | 0.10498 (19) | 0.00537 (17) | 0.0353 (5) | |
C22 | 0.3470 (3) | −0.0135 (2) | 0.0670 (2) | 0.0418 (6) | |
H22A | 0.3329 | −0.0249 | −0.0119 | 0.05* | |
H22B | 0.4481 | −0.013 | 0.1091 | 0.05* | |
C23 | 0.3162 (3) | 0.0989 (2) | 0.0900 (2) | 0.0387 (6) | |
C24 | 0.3174 (3) | −0.2121 (3) | 0.0835 (3) | 0.0574 (8) | |
H24A | 0.2607 | −0.2728 | 0.1019 | 0.086* | |
H24B | 0.416 | −0.2022 | 0.1337 | 0.086* | |
H24C | 0.3128 | −0.2263 | 0.0078 | 0.086* | |
C25 | 0.4322 (3) | 0.1853 (3) | 0.0740 (3) | 0.0552 (8) | |
H25A | 0.4331 | 0.1726 | −0.0003 | 0.083* | |
H25B | 0.525 | 0.1812 | 0.1279 | 0.083* | |
H25C | 0.4112 | 0.2564 | 0.0843 | 0.083* | |
C26 | 0.3130 (3) | 0.1174 (3) | 0.2077 (2) | 0.0526 (8) | |
H26A | 0.2401 | 0.0625 | 0.2166 | 0.079* | |
H26B | 0.2913 | 0.1882 | 0.2184 | 0.079* | |
H26C | 0.4055 | 0.1133 | 0.262 | 0.079* | |
OW1 | 1.1023 (4) | 0.5286 (3) | 0.9507 (3) | 0.1003 (10) | |
OW2 | 0.6433 (5) | 0.5527 (4) | 0.0291 (4) | 0.0638 (12) | 0.5 |
OW2' | 0.5845 (7) | 0.4370 (6) | −0.0278 (6) | 0.106 (2) | 0.5 |
C20 | 0.1395 (3) | 0.2168 (2) | 0.0078 (3) | 0.0487 (7) | |
H20A | 0.1992 | 0.2637 | −0.0239 | 0.058* | |
H20B | 0.1612 | 0.2466 | 0.0844 | 0.058* | |
C21 | 0.2583 (3) | −0.1095 (2) | 0.0946 (2) | 0.0400 (6) | |
H21A | 0.2667 | −0.0955 | 0.1729 | 0.048* | |
C19 | 0.0168 (3) | −0.2112 (2) | 0.0594 (3) | 0.0455 (7) | |
H19A | 0.0344 | −0.196 | 0.1386 | 0.055* | |
H19B | 0.0445 | −0.2803 | 0.0479 | 0.055* | |
H6N | 0.173 (3) | 0.086 (2) | −0.0625 (12) | 0.034 (7)* | |
H3N | 0.260 (2) | 0.4784 (16) | 0.376 (2) | 0.047 (8)* | |
H5N | 0.090 (3) | −0.150 (2) | −0.0477 (12) | 0.040 (8)* | |
H4N | 0.374 (3) | 0.4526 (13) | 0.621 (3) | 0.053 (9)* | |
H1W | 1.087 (4) | 0.579 (3) | 0.903 (3) | 0.091 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0255 (2) | 0.0235 (2) | 0.0350 (3) | 0.00552 (17) | 0.01364 (18) | 0.00566 (18) |
Ni2 | 0.0270 (2) | 0.0433 (3) | 0.0245 (2) | 0.01211 (19) | 0.01013 (18) | 0.00836 (19) |
Ni3 | 0.03288 (19) | 0.03058 (18) | 0.03100 (19) | −0.00165 (13) | 0.01059 (14) | 0.00232 (13) |
O1 | 0.0555 (12) | 0.0410 (11) | 0.0502 (13) | −0.0063 (9) | 0.0254 (10) | 0.0099 (9) |
O2 | 0.0421 (11) | 0.0438 (11) | 0.0430 (12) | −0.0069 (9) | 0.0071 (9) | −0.0041 (9) |
O3 | 0.0584 (13) | 0.0715 (14) | 0.0277 (10) | 0.0150 (11) | 0.0127 (9) | 0.0107 (10) |
O5 | 0.0791 (16) | 0.0697 (15) | 0.0570 (14) | 0.0148 (12) | 0.0403 (12) | 0.0337 (12) |
O4 | 0.0533 (13) | 0.0831 (17) | 0.0451 (13) | 0.0054 (12) | −0.0085 (11) | −0.0110 (12) |
O6 | 0.0590 (13) | 0.0720 (14) | 0.0255 (10) | 0.0058 (11) | 0.0103 (9) | 0.0091 (10) |
N1 | 0.0331 (11) | 0.0332 (11) | 0.0268 (11) | 0.0043 (9) | 0.0108 (9) | 0.0062 (9) |
N2 | 0.0312 (11) | 0.0343 (11) | 0.0253 (11) | 0.0059 (9) | 0.0090 (9) | 0.0044 (9) |
C1 | 0.0431 (15) | 0.0375 (14) | 0.0323 (14) | 0.0118 (12) | 0.0167 (12) | 0.0084 (11) |
C2 | 0.0554 (17) | 0.0381 (15) | 0.0453 (17) | 0.0140 (13) | 0.0305 (14) | 0.0125 (13) |
C3 | 0.0392 (15) | 0.0463 (16) | 0.0412 (17) | 0.0110 (13) | 0.0043 (13) | −0.0069 (13) |
C4 | 0.0395 (14) | 0.0423 (15) | 0.0264 (13) | 0.0159 (12) | 0.0098 (11) | 0.0005 (11) |
C5 | 0.0306 (12) | 0.0287 (12) | 0.0311 (13) | 0.0079 (10) | 0.0120 (10) | 0.0043 (10) |
C6 | 0.0454 (15) | 0.0392 (15) | 0.0389 (15) | 0.0081 (12) | 0.0215 (12) | 0.0120 (12) |
C7 | 0.0440 (16) | 0.0443 (16) | 0.061 (2) | −0.0014 (13) | 0.0276 (15) | 0.0123 (14) |
C8 | 0.0319 (14) | 0.0468 (17) | 0.0584 (19) | −0.0021 (12) | 0.0119 (13) | 0.0029 (14) |
C9 | 0.0318 (13) | 0.0411 (15) | 0.0363 (14) | 0.0036 (11) | 0.0052 (11) | 0.0034 (12) |
C10 | 0.0294 (12) | 0.0281 (12) | 0.0314 (13) | 0.0070 (10) | 0.0115 (10) | 0.0050 (10) |
N3 | 0.0302 (11) | 0.0294 (11) | 0.0406 (12) | 0.0075 (9) | 0.0148 (9) | 0.0067 (9) |
N4 | 0.0353 (11) | 0.0301 (11) | 0.0389 (12) | 0.0080 (9) | 0.0189 (10) | 0.0059 (9) |
C11 | 0.0437 (16) | 0.0568 (18) | 0.0383 (16) | 0.0166 (14) | 0.0132 (13) | 0.0139 (13) |
C12 | 0.0472 (16) | 0.0544 (18) | 0.0363 (15) | 0.0122 (14) | 0.0157 (13) | 0.0009 (13) |
C13 | 0.0394 (15) | 0.0357 (14) | 0.0522 (17) | 0.0173 (12) | 0.0159 (13) | 0.0107 (13) |
C14 | 0.0373 (15) | 0.0426 (15) | 0.0618 (19) | 0.0154 (12) | 0.0246 (14) | 0.0083 (14) |
C15 | 0.0489 (16) | 0.0381 (15) | 0.0518 (17) | 0.0169 (12) | 0.0273 (14) | 0.0060 (13) |
C16 | 0.067 (2) | 0.090 (3) | 0.063 (2) | 0.054 (2) | 0.0191 (18) | 0.022 (2) |
C17 | 0.082 (2) | 0.0295 (15) | 0.076 (2) | 0.0095 (15) | 0.0382 (19) | 0.0119 (15) |
C18 | 0.083 (3) | 0.099 (3) | 0.073 (2) | 0.052 (2) | 0.055 (2) | 0.026 (2) |
N5 | 0.0326 (11) | 0.0467 (13) | 0.0260 (11) | 0.0131 (9) | 0.0112 (9) | 0.0080 (10) |
N6 | 0.0310 (11) | 0.0498 (13) | 0.0271 (12) | 0.0108 (10) | 0.0110 (9) | 0.0083 (10) |
C22 | 0.0274 (13) | 0.0628 (18) | 0.0361 (15) | 0.0151 (12) | 0.0087 (11) | 0.0111 (13) |
C23 | 0.0270 (13) | 0.0576 (17) | 0.0282 (13) | 0.0058 (12) | 0.0064 (10) | 0.0070 (12) |
C24 | 0.0415 (17) | 0.068 (2) | 0.069 (2) | 0.0261 (15) | 0.0183 (15) | 0.0282 (17) |
C25 | 0.0361 (15) | 0.068 (2) | 0.060 (2) | 0.0057 (14) | 0.0164 (14) | 0.0130 (16) |
C26 | 0.0564 (18) | 0.066 (2) | 0.0314 (15) | 0.0112 (15) | 0.0106 (13) | 0.0048 (14) |
OW1 | 0.108 (2) | 0.098 (2) | 0.097 (2) | 0.0292 (19) | 0.0331 (19) | 0.034 (2) |
OW2 | 0.078 (3) | 0.053 (3) | 0.052 (3) | −0.005 (2) | 0.022 (2) | 0.000 (2) |
OW2' | 0.107 (5) | 0.110 (5) | 0.101 (5) | 0.029 (4) | 0.032 (4) | 0.011 (4) |
C20 | 0.0401 (15) | 0.0459 (17) | 0.063 (2) | 0.0108 (13) | 0.0196 (14) | 0.0095 (14) |
C21 | 0.0341 (14) | 0.0586 (17) | 0.0290 (14) | 0.0182 (12) | 0.0082 (11) | 0.0122 (12) |
C19 | 0.0430 (16) | 0.0479 (17) | 0.0543 (18) | 0.0176 (13) | 0.0223 (14) | 0.0199 (14) |
Ni1—N3 | 1.947 (2) | C7—C8 | 1.371 (4) |
Ni1—N3i | 1.947 (2) | C8—C9 | 1.386 (4) |
Ni1—N4 | 1.957 (2) | C9—C10 | 1.384 (3) |
Ni1—N4i | 1.957 (2) | N3—C11 | 1.486 (3) |
Ni2—N6 | 1.951 (2) | N3—C13 | 1.508 (3) |
Ni2—N6ii | 1.951 (2) | N4—C12 | 1.481 (3) |
Ni2—N5ii | 1.961 (2) | N4—C15 | 1.497 (3) |
Ni2—N5 | 1.961 (2) | C11—C12i | 1.492 (4) |
Ni3—N2 | 1.8159 (19) | C12—C11i | 1.492 (4) |
Ni3—N1 | 1.819 (2) | C13—C14 | 1.519 (4) |
Ni3—O2 | 1.8790 (18) | C13—C17 | 1.528 (4) |
Ni3—O1 | 1.8935 (18) | C13—C16 | 1.532 (4) |
O1—C2 | 1.293 (4) | C14—C15 | 1.514 (4) |
O2—C3 | 1.293 (4) | C15—C18 | 1.524 (4) |
O3—C4 | 1.237 (3) | N5—C19 | 1.482 (3) |
O5—C2 | 1.226 (3) | N5—C21 | 1.497 (3) |
O4—C3 | 1.219 (3) | N6—C20 | 1.478 (4) |
O6—C1 | 1.228 (3) | N6—C23 | 1.514 (3) |
N1—C1 | 1.325 (3) | C22—C21 | 1.505 (4) |
N1—C10 | 1.413 (3) | C22—C23 | 1.524 (4) |
N2—C4 | 1.325 (3) | C23—C26 | 1.525 (4) |
N2—C5 | 1.413 (3) | C23—C25 | 1.529 (4) |
C1—C2 | 1.539 (4) | C24—C21 | 1.519 (4) |
C3—C4 | 1.549 (4) | OW2—OW2' | 1.517 (8) |
C5—C6 | 1.380 (3) | C20—C19ii | 1.494 (4) |
C5—C10 | 1.410 (3) | C19—C20ii | 1.494 (4) |
C6—C7 | 1.385 (4) | ||
N3—Ni1—N3i | 180.0000 (10) | C8—C7—C6 | 121.1 (3) |
N3—Ni1—N4 | 93.79 (9) | C7—C8—C9 | 121.0 (3) |
N3i—Ni1—N4 | 86.21 (9) | C10—C9—C8 | 118.6 (3) |
N3—Ni1—N4i | 86.21 (9) | C9—C10—C5 | 120.4 (2) |
N3i—Ni1—N4i | 93.79 (9) | C9—C10—N1 | 127.0 (2) |
N4—Ni1—N4i | 180.0000 (10) | C5—C10—N1 | 112.5 (2) |
N6—Ni2—N6ii | 180.00 (16) | C11—N3—C13 | 113.4 (2) |
N6—Ni2—N5ii | 86.32 (9) | C11—N3—Ni1 | 109.68 (15) |
N6ii—Ni2—N5ii | 93.68 (9) | C13—N3—Ni1 | 119.02 (17) |
N6—Ni2—N5 | 93.68 (9) | C12—N4—C15 | 109.7 (2) |
N6ii—Ni2—N5 | 86.32 (9) | C12—N4—Ni1 | 106.72 (16) |
N5ii—Ni2—N5 | 180.00 (11) | C15—N4—Ni1 | 124.20 (16) |
N2—Ni3—N1 | 86.54 (9) | N3—C11—C12i | 106.9 (2) |
N2—Ni3—O2 | 86.58 (9) | N4—C12—C11i | 107.1 (2) |
N1—Ni3—O2 | 173.10 (9) | N3—C13—C14 | 107.6 (2) |
N2—Ni3—O1 | 172.77 (9) | N3—C13—C17 | 109.1 (2) |
N1—Ni3—O1 | 86.25 (9) | C14—C13—C17 | 111.8 (3) |
O2—Ni3—O1 | 100.62 (9) | N3—C13—C16 | 109.7 (2) |
C2—O1—Ni3 | 111.56 (16) | C14—C13—C16 | 107.4 (2) |
C3—O2—Ni3 | 112.25 (17) | C17—C13—C16 | 111.1 (3) |
C1—N1—C10 | 128.9 (2) | C15—C14—C13 | 117.0 (2) |
C1—N1—Ni3 | 116.85 (18) | N4—C15—C14 | 111.4 (2) |
C10—N1—Ni3 | 114.14 (15) | N4—C15—C18 | 111.4 (2) |
C4—N2—C5 | 128.9 (2) | C14—C15—C18 | 110.1 (3) |
C4—N2—Ni3 | 116.79 (17) | C19—N5—C21 | 109.2 (2) |
C5—N2—Ni3 | 114.28 (15) | C19—N5—Ni2 | 107.64 (15) |
O6—C1—N1 | 129.7 (3) | C21—N5—Ni2 | 122.10 (18) |
O6—C1—C2 | 121.5 (2) | C20—N6—C23 | 111.7 (2) |
N1—C1—C2 | 108.8 (2) | C20—N6—Ni2 | 109.92 (16) |
O5—C2—O1 | 123.5 (3) | C23—N6—Ni2 | 119.54 (16) |
O5—C2—C1 | 120.5 (3) | C21—C22—C23 | 117.0 (2) |
O1—C2—C1 | 116.0 (2) | N6—C23—C22 | 107.3 (2) |
O4—C3—O2 | 124.4 (3) | N6—C23—C26 | 108.8 (2) |
O4—C3—C4 | 120.3 (3) | C22—C23—C26 | 111.9 (2) |
O2—C3—C4 | 115.3 (2) | N6—C23—C25 | 109.8 (2) |
O3—C4—N2 | 128.5 (3) | C22—C23—C25 | 108.6 (2) |
O3—C4—C3 | 122.5 (2) | C26—C23—C25 | 110.4 (2) |
N2—C4—C3 | 109.0 (2) | N6—C20—C19ii | 108.0 (2) |
C6—C5—C10 | 120.0 (2) | N5—C21—C22 | 110.8 (2) |
C6—C5—N2 | 127.4 (2) | N5—C21—C24 | 111.6 (2) |
C10—C5—N2 | 112.5 (2) | C22—C21—C24 | 110.1 (2) |
C5—C6—C7 | 118.8 (3) | N5—C19—C20ii | 108.1 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W···O5 | 0.89 (4) | 2.13 (4) | 2.917 (5) | 147 (4) |
N3—H3N···O1i | 0.91 (2) | 2.09 (2) | 2.955 (3) | 159 (2) |
N4—H4N···O2i | 0.91 (2) | 2.01 (2) | 2.918 (3) | 175 (3) |
N5—H5N···O6iii | 0.90 (2) | 2.11 (2) | 2.944 (3) | 153 (2) |
N6—H6N···O3iv | 0.90 (2) | 2.11 (2) | 2.897 (3) | 145 (2) |
OW2···O4 | ? | ? | 2.855 (5) | ? |
OW2′···O4iv | ? | ? | 2.881 (8) | ? |
OW1···OW1v | ? | ? | 2.778 (6) | ? |
OW1···OW2vi | ? | ? | 2.836 (7) | ? |
OW1···OW2′vi | ? | ? | 2.904 (9) | ? |
OW2···OW2iv | ? | ? | 2.788 | ? |
OW2′···OW2′iv | ? | ? | 2.735 | ? |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x−1, y−1, z−1; (iv) −x+1, −y+1, −z; (v) −x+2, −y+1, −z+2; (vi) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C16H36N4)][Ni(C10H4N2O6)]·2H2O |
Mr | 686.09 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.0460 (8), 12.4964 (10), 12.7901 (10) |
α, β, γ (°) | 92.488 (2), 110.247 (2), 99.408 (2) |
V (Å3) | 1477.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.33 |
Crystal size (mm) | 0.3 × 0.15 × 0.1 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.691, 0.878 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6157, 5173, 4408 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.091, 1.04 |
No. of reflections | 5173 |
No. of parameters | 411 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.25 |
Computer programs: SMART1000 software (Bruker, 1998), SMART1000 software, SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1997), SHELXL97.
Ni1—N3 | 1.947 (2) | O2—C3 | 1.293 (4) |
Ni1—N4 | 1.957 (2) | O3—C4 | 1.237 (3) |
Ni2—N6 | 1.951 (2) | O5—C2 | 1.226 (3) |
Ni2—N5 | 1.961 (2) | O4—C3 | 1.219 (3) |
Ni3—N2 | 1.8159 (19) | O6—C1 | 1.228 (3) |
Ni3—N1 | 1.819 (2) | N1—C1 | 1.325 (3) |
Ni3—O2 | 1.8790 (18) | N2—C4 | 1.325 (3) |
Ni3—O1 | 1.8935 (18) | C1—C2 | 1.539 (4) |
O1—C2 | 1.293 (4) | C3—C4 | 1.549 (4) |
N3—Ni1—N3i | 180.0000 (10) | O2—Ni3—O1 | 100.62 (9) |
N3—Ni1—N4 | 93.79 (9) | C2—O1—Ni3 | 111.56 (16) |
N3—Ni1—N4i | 86.21 (9) | C3—O2—Ni3 | 112.25 (17) |
N6—Ni2—N6ii | 180.00 (16) | C1—N1—Ni3 | 116.85 (18) |
N6—Ni2—N5ii | 86.32 (9) | C10—N1—Ni3 | 114.14 (15) |
N6—Ni2—N5 | 93.68 (9) | C4—N2—Ni3 | 116.79 (17) |
N5ii—Ni2—N5 | 180.00 (11) | C5—N2—Ni3 | 114.28 (15) |
N2—Ni3—N1 | 86.54 (9) | N1—C1—C2 | 108.8 (2) |
N2—Ni3—O2 | 86.58 (9) | O1—C2—C1 | 116.0 (2) |
N1—Ni3—O2 | 173.10 (9) | O2—C3—C4 | 115.3 (2) |
N2—Ni3—O1 | 172.77 (9) | N2—C4—C3 | 109.0 (2) |
N1—Ni3—O1 | 86.25 (9) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W···O5 | 0.89 (4) | 2.13 (4) | 2.917 (5) | 147 (4) |
N3—H3N···O1i | 0.91 (2) | 2.09 (2) | 2.955 (3) | 159.0 (19) |
N4—H4N···O2i | 0.91 (2) | 2.01 (2) | 2.918 (3) | 175 (3) |
N5—H5N···O6iii | 0.904 (17) | 2.11 (2) | 2.944 (3) | 153 (2) |
N6—H6N···O3iv | 0.904 (19) | 2.111 (16) | 2.897 (3) | 145 (2) |
OW2···O4 | ? | ? | 2.855 (5) | ? |
OW2'···O4iv | ? | ? | 2.881 (8) | ? |
OW1···OW1v | ? | ? | 2.778 (6) | ? |
OW1···OW2vi | ? | ? | 2.836 (7) | ? |
OW1···OW2'vi | ? | ? | 2.904 (9) | ? |
OW2···OW2iv | ? | ? | 2.788 | ? |
OW2'···OW2'iv | ? | ? | 2.735 | ? |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x−1, y−1, z−1; (iv) −x+1, −y+1, −z; (v) −x+2, −y+1, −z+2; (vi) −x+2, −y+1, −z+1. |
One-, two- or three-dimensional supramolecular architectures assembled via intermolecular noncovalent interactions are of considerable interest for crystal engineering of new functional solid-state materials as well as for their fascinating structures (see for example, MacDonald et al., 1994; Brunet et al., 1997; Munakata et al., 1997; Tadokoro et al., 1999). Hydrogen bonding, which combines directionality, selectivity and strength, has been noted as the most versatile organizing force for supramolecular assembly. Ionic interactions also play important roles in construction of hydrogen-bonded crystals from charged subunits (Braga et al., 1998; Burrows et al., 1996).
Among various supramolecular architectures, those containing internal channels or chambers of various sizes have received great attention. A number of such materials have been recognized as zeolite analogues, with interesting properties such as selective guest inclusion and exchange, and catalytic activity (Brunet et al., 1997; Endo et al., 1997; Kepert et al., 1998).
Here, we describe a novel microporous hydrogen-bonded framework built from [Ni(meso-cth)]2+ (meso-cth = meso-5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane) and [Ni(opba)]2- (opba = ortho-phenylenebis(oxamato)). The compound, (I), is of formula [Ni(meso-cth)][M(opba)]2H2O. \sch
A perspective view of the above building blocks with the atom-labelling scheme is depicted in Figure 1. Selected bond distances and angles are listed in Table 1.
In the anionic bis(oxamato)-nickel(II) complex moiety, the metal atom is ligated by two deprotonated amido N atoms and two carboxylate O atoms. The NiO2N2 coordination chromophore exhibits nearly strict planarity: the largest deviation of the donor atoms from the O2N2 mean plan is only 0.0010 (11) Å, and the nickel atom is displaced out of the plan by 0.0099 (11) Å. The Ni3—N distances (average 1.817 Å) are significantly shorter than the Ni3—O ones (average 1.886 Å), consistent with the greater basicity of the deprotonated amido nitrogen donors. The constrained N1—Ni3—N2 chelating angle [86.54 (9)°] is also significantly smaller than the O1—Ni3—O2 non-chelating angle [100.62 (9)°]. The above features lead to a planar trapezoidal coordination environment around Ni3, with the O···O distance being remarkably larger than the N···N one.
In the cationic complex moiety, the metal atom, which resides on an inversion center, is coordinated by the four amino N atoms of the macrocyclic ligand. The NiN4 chromophore exhibits strict planarity. There are two sets of crystallographically independent cationic moieties, with no significant differences in molecular structure, as shown in Table 1.
What interests us is the way in which the two ionic complex building blocks are linked to each other via hydrogen bonds to produce a supramolecular architecture. Relevant hydrogen bond parameters are listed in Table 2. A l l amino groups in the complex cations and all oxygen atoms in the complex anions are involved in extended hydrogen bonding. The two sets of crystallographically independent cations adopt different hydrogen-bonding modes. The Ni1 cation is linked to two Ni3 anions through two hydrogen bonds between amino groups and the coordinated O atoms of carboxylate groups (O1···N3A and O2···N4A, symmetry code: A = 1 - x, 1 - y, 1 - z), with the Ni3···Ni1 separation being query 4.6080 (4) Å. The Ni2 cation is linked to four anions by single hydrogen bonds to amido O atoms (O3···N6B and O6···N5C, symmetry code: B = 1 - x, 1 - y, -z; C = x + 1, y + 1, z + 1), with the Ni3···Ni2B and Ni3···Ni2C separations being 7.6078 (6) and 6.5321 (6) Å, respectively. Therefore, each Ni3 anion is linked to three cations via four hydrogen bonds. These hydrogen bonds arrange the two complexes in space to result in a neutral and extended two-dimensional heterobimetallic sheet along the <-110> plane, as shown in Figure 2. This unique sheet contains open cavities, each of which is defined by four anionic complexes and four cationic complexes connected through twelve N—H···O hydrogen bonds. Stacking the sheets in a slipped fashion results in one-dimensional channels that run along the a axis (Figure 3). Lined with the carbonyl oxygen atoms (O4 and O5) that arise from the oxamato ligand, the channels are expected to be quite hydrophilic. Water molecules are enclosed in the channels and linked to the walls of the channels through hydrogen bonds to the carbonyl O atoms (O4···Ow2 and O5···Ow1). In addition, these water molecules are hydrogen-bonded to one another to form helix-like chains along the channels (Figure 4), the average O···O distance being about 2.81 Å. Taking into consideration these hydrogen bonds involving water molecules, the structure may be described as a three-dimensional hydrogen-bonded network.
In conclusion, we described an unusual supramolecular microporous three-dimensional architecture assembled via the concurrent action of hydrogen bonds and ionic interactions. The material contains two different transition metal complexes as building blocks. Recently, increasing efforts have been directed towards incorporating transition metal ions into hydrogen-bonded networks, in hopes of introducing new magnetic, electronic and optical properties into supramolecules (Burrows et al., 1995; Tadokoro et al., 1999; Braga et al., 1998). Obviously, the introduction of two (or more) different transition metal chromophores into hydrogen-bonded networks may also lead to interesting properties. However, the diamagnetic nature of the nickel(II) ions in the present material precludes magnetic investigation in relation to magnetic interaction through hydrogen bonds.