Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003857/sk1465sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003857/sk1465Isup2.hkl |
CCDC reference: 166963
For related literature, see: Adam et al. (1991); Barefield, Bianchi, Billo, Connolly, Paoletti, Summers & Van Derveer (1986); Barefield, Freeman & Van Derveer (1986); Choi et al. (1999); Curtis et al. (1973); Flack (1983); Glidewell et al. (2000); Hambley (1986); Hay et al. (1982); Ito et al. (1984); Mochizuki & Kondo (1995); Prasad & McAuley (1983); Sheldrick (1997); Whimp et al. (1970).
A sample of compound (I) was isolated as a purple microcrystalline solid from the reaction between [Ni(cyclam)]2+·2ClO4- and the disodium salt of terephthalic acid in aqueous methanol. Crystals of (I) suitable for single-crystal X-ray diffraction were grown from solution in water.
Compound (I) crystallized in the monoclinic system, space group P21 or P21/m from the systematic absences. P21 was assumed and confirmed by the analysis. H atoms were treated as riding, with C—H = 0.95 (aromatic) and 0.99 Å (aliphatic CH2), and N—H = 0.93 Å. Water H atoms were clearly visible in difference maps and were initially refined isotropically using a DFIX command (SHELXL97; Sheldrick, 1997), with a free variable for the common O—H distance and a free variable for the overall Uiso value. The final refinement had the water O—H distance set to 0.85 Å. Refinement of the Flack parameter (Flack, 1983) using 3083 Friedel-related reflections suggested that the data should be treated as a racemic twin, using the TWIN and BASF commands in SHELXL97. The structure of (I) approximates closely to a centrosymmetric one, with the terephthalate moiety lying about an inversion centre in space group P21/n. There is an almost perfect fit of atoms, except for all the C and H atoms of the cyclam residues. Inspection of the reflection data shows clearly that the h0l glide reflections (h+l = 2n+1), which would be absent in P21/n, are clearly present, although many are weak.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
[Ni2(C10H24N4)2(H2O)2(C8H4O4)](ClO4)2 | F(000) = 964 |
Mr = 917.09 | Dx = 1.557 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2842 (3) Å | Cell parameters from 7654 reflections |
b = 14.9172 (4) Å | θ = 2.8–27.5° |
c = 13.0621 (4) Å | µ = 1.17 mm−1 |
β = 102.5220 (11)° | T = 150 K |
V = 1956.21 (10) Å3 | Plate, purple |
Z = 2 | 0.18 × 0.18 × 0.07 mm |
Kappa-CCD diffractometer | 7654 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 5458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = −13→13 |
Tmin = 0.817, Tmax = 0.922 | k = −19→17 |
13566 measured reflections | l = −16→16 |
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.019P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
7654 reflections | Δρmax = 0.70 e Å−3 |
501 parameters | Δρmin = −0.44 e Å−3 |
5 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.38 (3) |
[Ni2(C10H24N4)2(H2O)2(C8H4O4)](ClO4)2 | V = 1956.21 (10) Å3 |
Mr = 917.09 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.2842 (3) Å | µ = 1.17 mm−1 |
b = 14.9172 (4) Å | T = 150 K |
c = 13.0621 (4) Å | 0.18 × 0.18 × 0.07 mm |
β = 102.5220 (11)° |
Kappa-CCD diffractometer | 7654 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 5458 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.922 | Rint = 0.052 |
13566 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | Δρmax = 0.70 e Å−3 |
S = 1.01 | Δρmin = −0.44 e Å−3 |
7654 reflections | Absolute structure: Flack (1983) |
501 parameters | Absolute structure parameter: 0.38 (3) |
5 restraints |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file. |
Geometry. Mean-plane data from the final SHELXL97 refinement run:- ########################################################################## Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.7013 (0.0061) x + 9.5657 (0.0090) y - 3.3217 (0.0164) z = 2.2537 (0.0081) * -0.0064 (0.0046) C1 * -0.0089 (0.0046) C2 * 0.0004 (0.0049) C3 * 0.0155 (0.0047) C4 * 0.0070 (0.0047) C5 * -0.0157 (0.0048) C6 * 0.0131 (0.0047) C7 * -0.0050 (0.0049) C8 Rms deviation of fitted atoms = 0.0103 - 7.1702 (0.0237) x + 10.0577 (0.0356) y + 5.0802 (0.0341) z = 4.4222 (0.0322) Angle to previous plane (with approximate e.s.d.) = 38.0 (2) * 0.0009 (0.0013) C1 * -0.0031 (0.0048) C7 * 0.0011 (0.0017) O1 * 0.0011 (0.0017) O2 Rms deviation of fitted atoms = 0.0018 ######################################################################### - 6.7013 (0.0061) x + 9.5657 (0.0090) y - 3.3217 (0.0164) z = 2.2537 (0.0081) * -0.0064 (0.0046) C1 * -0.0089 (0.0046) C2 * 0.0004 (0.0049) C3 * 0.0155 (0.0047) C4 * 0.0070 (0.0047) C5 * -0.0157 (0.0048) C6 * 0.0131 (0.0047) C7 * -0.0050 (0.0049) C8 Rms deviation of fitted atoms = 0.0103 - 7.1482 (0.0235) x + 10.3230 (0.0344) y + 4.4540 (0.0350) z = 4.4624 (0.0134) Angle to previous plane (with approximate e.s.d.) = 35.2 (2) * 0.0013 (0.0014) C4 * -0.0048 (0.0050) C8 * 0.0017 (0.0018) O3 * 0.0017 (0.0018) O4 Rms deviation of fitted atoms = 0.0028 |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.68641 (7) | 0.74680 (4) | 0.38396 (6) | 0.01733 (16) | |
O5 | 0.8430 (4) | 0.8439 (3) | 0.4538 (3) | 0.0245 (11) | |
N11 | 0.6599 (5) | 0.8093 (4) | 0.2392 (4) | 0.0250 (12) | |
N14 | 0.8279 (5) | 0.6711 (4) | 0.3318 (4) | 0.0303 (12) | |
N18 | 0.7122 (5) | 0.6837 (4) | 0.5287 (4) | 0.0350 (15) | |
N111 | 0.5483 (5) | 0.8251 (4) | 0.4356 (4) | 0.0269 (12) | |
C12 | 0.7696 (6) | 0.7819 (4) | 0.1918 (5) | 0.0360 (17) | |
C13 | 0.8000 (7) | 0.6839 (5) | 0.2156 (5) | 0.0387 (17) | |
C15 | 0.8343 (6) | 0.5766 (4) | 0.3604 (5) | 0.0384 (16) | |
C16 | 0.8602 (6) | 0.5638 (4) | 0.4780 (5) | 0.0428 (17) | |
C17 | 0.7421 (6) | 0.5838 (4) | 0.5264 (5) | 0.0405 (18) | |
C19 | 0.5928 (7) | 0.7062 (5) | 0.5678 (5) | 0.045 (2) | |
C110 | 0.5683 (6) | 0.8045 (5) | 0.5502 (4) | 0.0395 (19) | |
C112 | 0.5455 (7) | 0.9189 (4) | 0.4087 (6) | 0.0434 (18) | |
C113 | 0.5234 (6) | 0.9330 (4) | 0.2916 (5) | 0.0457 (19) | |
C114 | 0.6387 (7) | 0.9069 (4) | 0.2415 (5) | 0.0390 (18) | |
Ni2 | −0.18413 (7) | 0.25284 (4) | 0.11557 (6) | 0.01788 (16) | |
O6 | −0.3443 (4) | 0.1574 (3) | 0.0511 (3) | 0.0213 (10) | |
N21 | −0.1797 (5) | 0.2092 (3) | 0.2650 (4) | 0.0279 (12) | |
N24 | −0.3223 (5) | 0.3445 (4) | 0.1457 (4) | 0.0289 (13) | |
N28 | −0.1939 (5) | 0.2965 (4) | −0.0378 (4) | 0.0343 (14) | |
N211 | −0.0487 (5) | 0.1595 (4) | 0.0875 (4) | 0.0355 (14) | |
C22 | −0.2953 (5) | 0.2507 (4) | 0.2989 (4) | 0.0290 (14) | |
C23 | −0.3099 (7) | 0.3447 (5) | 0.2595 (5) | 0.0391 (17) | |
C25 | −0.3157 (7) | 0.4349 (4) | 0.0983 (5) | 0.0413 (18) | |
C26 | −0.3261 (7) | 0.4280 (4) | −0.0201 (5) | 0.049 (2) | |
C27 | −0.2042 (7) | 0.3913 (4) | −0.0539 (5) | 0.0459 (19) | |
C29 | −0.0725 (6) | 0.2532 (6) | −0.0663 (4) | 0.049 (2) | |
C210 | −0.0596 (6) | 0.1571 (5) | −0.0282 (5) | 0.0425 (18) | |
C213 | −0.0479 (7) | 0.0740 (4) | 0.2502 (5) | 0.0476 (19) | |
C212 | −0.0564 (6) | 0.0687 (5) | 0.1331 (5) | 0.047 (2) | |
C214 | −0.1676 (6) | 0.1124 (4) | 0.2832 (5) | 0.0382 (17) | |
O1 | 0.5332 (4) | 0.6538 (3) | 0.3288 (3) | 0.0210 (10) | |
O2 | 0.4479 (4) | 0.6792 (3) | 0.1583 (3) | 0.0239 (11) | |
O3 | −0.0244 (4) | 0.3442 (3) | 0.1653 (3) | 0.0236 (10) | |
O4 | 0.0527 (4) | 0.3232 (3) | 0.3379 (3) | 0.0269 (11) | |
C1 | 0.3491 (6) | 0.5647 (4) | 0.2454 (4) | 0.0180 (13) | |
C2 | 0.3097 (6) | 0.5075 (4) | 0.1610 (4) | 0.0208 (14) | |
C3 | 0.2136 (6) | 0.4419 (4) | 0.1630 (5) | 0.0226 (15) | |
C4 | 0.1556 (6) | 0.4327 (4) | 0.2490 (4) | 0.0191 (14) | |
C5 | 0.1970 (6) | 0.4907 (4) | 0.3350 (5) | 0.0235 (14) | |
C6 | 0.2927 (6) | 0.5546 (4) | 0.3330 (5) | 0.0221 (15) | |
C7 | 0.4518 (6) | 0.6382 (4) | 0.2440 (4) | 0.0182 (13) | |
C8 | 0.0547 (6) | 0.3610 (4) | 0.2521 (5) | 0.0212 (14) | |
Cl1 | 0.17207 (15) | 0.80653 (12) | 0.39094 (11) | 0.0262 (4) | |
O11 | 0.0568 (4) | 0.8591 (4) | 0.3416 (4) | 0.0396 (13) | |
O12 | 0.2517 (4) | 0.8581 (3) | 0.4746 (3) | 0.0361 (11) | |
O13 | 0.1263 (4) | 0.7258 (3) | 0.4336 (4) | 0.0412 (13) | |
O14 | 0.2506 (4) | 0.7836 (3) | 0.3155 (3) | 0.0372 (12) | |
Cl2 | 0.33011 (15) | 0.19328 (12) | 0.11237 (11) | 0.0280 (4) | |
O21 | 0.4401 (4) | 0.1345 (4) | 0.1595 (4) | 0.0345 (12) | |
O22 | 0.2529 (4) | 0.1515 (4) | 0.0206 (3) | 0.0411 (12) | |
O23 | 0.3851 (4) | 0.2758 (3) | 0.0830 (4) | 0.0483 (14) | |
O24 | 0.2479 (4) | 0.2099 (4) | 0.1864 (3) | 0.0481 (15) | |
H11 | 0.5828 | 0.7851 | 0.1978 | 0.030* | |
H14 | 0.9109 | 0.6962 | 0.3595 | 0.036* | |
H18 | 0.7845 | 0.7108 | 0.5732 | 0.042* | |
H111 | 0.4651 | 0.8023 | 0.4041 | 0.032* | |
H12A | 0.8494 | 0.8186 | 0.2203 | 0.043* | |
H12B | 0.7449 | 0.7911 | 0.1149 | 0.043* | |
H13A | 0.7230 | 0.6466 | 0.1817 | 0.046* | |
H13B | 0.8782 | 0.6654 | 0.1880 | 0.046* | |
H15A | 0.9063 | 0.5473 | 0.3331 | 0.046* | |
H15B | 0.7492 | 0.5472 | 0.3275 | 0.046* | |
H16A | 0.9351 | 0.6031 | 0.5112 | 0.051* | |
H16B | 0.8883 | 0.5010 | 0.4945 | 0.051* | |
H17A | 0.7604 | 0.5602 | 0.5990 | 0.049* | |
H17B | 0.6627 | 0.5524 | 0.4859 | 0.049* | |
H19A | 0.6069 | 0.6920 | 0.6435 | 0.054* | |
H19B | 0.5154 | 0.6713 | 0.5297 | 0.054* | |
H11A | 0.6452 | 0.8388 | 0.5899 | 0.047* | |
H11B | 0.4882 | 0.8224 | 0.5758 | 0.047* | |
H11C | 0.6310 | 0.9469 | 0.4435 | 0.052* | |
H11D | 0.4733 | 0.9488 | 0.4351 | 0.052* | |
H11E | 0.5029 | 0.9971 | 0.2766 | 0.055* | |
H11F | 0.4440 | 0.8981 | 0.2573 | 0.055* | |
H11G | 0.6211 | 0.9302 | 0.1689 | 0.047* | |
H11H | 0.7212 | 0.9357 | 0.2810 | 0.047* | |
H21 | −0.1040 | 0.2346 | 0.3070 | 0.033* | |
H24 | −0.4060 | 0.3212 | 0.1164 | 0.035* | |
H28 | −0.2690 | 0.2705 | −0.0800 | 0.041* | |
H211 | 0.0354 | 0.1820 | 0.1170 | 0.043* | |
H22A | −0.3775 | 0.2164 | 0.2701 | 0.035* | |
H22B | −0.2803 | 0.2502 | 0.3764 | 0.035* | |
H23A | −0.3899 | 0.3723 | 0.2768 | 0.047* | |
H23B | −0.2311 | 0.3803 | 0.2935 | 0.047* | |
H25A | −0.2306 | 0.4642 | 0.1314 | 0.050* | |
H25B | −0.3894 | 0.4726 | 0.1120 | 0.050* | |
H26A | −0.4031 | 0.3893 | −0.0501 | 0.059* | |
H26B | −0.3452 | 0.4885 | −0.0509 | 0.059* | |
H27A | −0.2105 | 0.4049 | −0.1290 | 0.055* | |
H27B | −0.1232 | 0.4209 | −0.0130 | 0.055* | |
H29A | −0.0817 | 0.2547 | −0.1433 | 0.059* | |
H29B | 0.0086 | 0.2872 | −0.0337 | 0.059* | |
H21A | −0.1386 | 0.1219 | −0.0627 | 0.051* | |
H21B | 0.0207 | 0.1290 | −0.0446 | 0.051* | |
H21C | −0.0322 | 0.0129 | 0.2797 | 0.057* | |
H21D | 0.0306 | 0.1108 | 0.2818 | 0.057* | |
H21E | 0.0175 | 0.0312 | 0.1195 | 0.057* | |
H21F | −0.1414 | 0.0398 | 0.0987 | 0.057* | |
H21G | −0.2489 | 0.0824 | 0.2436 | 0.046* | |
H21H | −0.1606 | 0.1002 | 0.3587 | 0.046* | |
H2 | 0.3482 | 0.5130 | 0.1014 | 0.025* | |
H3 | 0.1875 | 0.4029 | 0.1046 | 0.027* | |
H5 | 0.1587 | 0.4856 | 0.3947 | 0.028* | |
H6 | 0.3209 | 0.5926 | 0.3920 | 0.027* | |
H51 | 0.869 (6) | 0.832 (4) | 0.5187 (12) | 0.042 (7)* | |
H52 | 0.904 (4) | 0.863 (4) | 0.425 (4) | 0.042 (7)* | |
H61 | −0.373 (6) | 0.153 (4) | −0.0148 (12) | 0.042 (7)* | |
H62 | −0.414 (3) | 0.159 (4) | 0.076 (4) | 0.042 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0159 (3) | 0.0199 (4) | 0.0154 (3) | −0.0029 (3) | 0.0015 (3) | 0.0011 (3) |
O5 | 0.023 (2) | 0.028 (3) | 0.021 (2) | −0.003 (2) | 0.0018 (19) | −0.002 (2) |
N11 | 0.023 (2) | 0.033 (3) | 0.016 (2) | −0.016 (2) | −0.0024 (18) | 0.004 (2) |
N14 | 0.023 (2) | 0.031 (3) | 0.036 (3) | −0.007 (2) | 0.003 (2) | −0.014 (2) |
N18 | 0.026 (3) | 0.053 (4) | 0.020 (2) | −0.018 (2) | −0.007 (2) | 0.007 (2) |
N111 | 0.013 (2) | 0.036 (3) | 0.028 (3) | −0.004 (2) | −0.0019 (19) | −0.012 (2) |
C12 | 0.036 (3) | 0.053 (4) | 0.021 (3) | −0.021 (3) | 0.009 (2) | −0.004 (3) |
C13 | 0.030 (3) | 0.062 (5) | 0.028 (3) | −0.012 (3) | 0.014 (2) | −0.020 (3) |
C15 | 0.025 (3) | 0.028 (3) | 0.057 (4) | 0.000 (2) | −0.004 (3) | −0.011 (3) |
C16 | 0.035 (3) | 0.025 (3) | 0.058 (4) | 0.005 (2) | −0.013 (3) | 0.014 (3) |
C17 | 0.042 (4) | 0.030 (3) | 0.039 (4) | −0.013 (3) | −0.017 (3) | 0.023 (3) |
C19 | 0.038 (4) | 0.079 (5) | 0.016 (3) | −0.029 (3) | 0.004 (2) | 0.002 (3) |
C110 | 0.022 (3) | 0.077 (5) | 0.022 (3) | −0.007 (4) | 0.010 (2) | −0.020 (4) |
C112 | 0.026 (3) | 0.027 (3) | 0.071 (5) | 0.009 (3) | −0.002 (3) | −0.019 (3) |
C113 | 0.033 (3) | 0.028 (3) | 0.062 (4) | 0.004 (3) | −0.021 (3) | 0.001 (3) |
C114 | 0.040 (4) | 0.023 (3) | 0.044 (4) | −0.012 (3) | −0.014 (3) | 0.017 (3) |
Ni2 | 0.0163 (3) | 0.0205 (4) | 0.0158 (3) | −0.0026 (3) | 0.0011 (3) | −0.0002 (3) |
O6 | 0.013 (2) | 0.031 (3) | 0.018 (2) | −0.003 (2) | −0.0009 (17) | −0.002 (2) |
N21 | 0.029 (3) | 0.026 (2) | 0.024 (2) | −0.011 (2) | −0.008 (2) | 0.0069 (19) |
N24 | 0.019 (2) | 0.028 (3) | 0.036 (3) | 0.001 (2) | −0.0023 (19) | −0.008 (2) |
N28 | 0.027 (3) | 0.052 (3) | 0.020 (2) | −0.022 (2) | −0.004 (2) | 0.004 (2) |
N211 | 0.021 (2) | 0.049 (4) | 0.036 (3) | 0.002 (2) | 0.005 (2) | −0.016 (2) |
C22 | 0.023 (3) | 0.050 (4) | 0.017 (2) | −0.012 (3) | 0.0091 (19) | −0.008 (3) |
C23 | 0.030 (3) | 0.051 (4) | 0.037 (4) | −0.002 (3) | 0.009 (3) | −0.015 (3) |
C25 | 0.045 (4) | 0.016 (3) | 0.056 (5) | 0.007 (3) | −0.004 (3) | 0.006 (3) |
C26 | 0.051 (5) | 0.032 (4) | 0.049 (4) | −0.006 (3) | −0.021 (3) | 0.013 (3) |
C27 | 0.048 (4) | 0.044 (4) | 0.036 (4) | −0.019 (3) | −0.011 (3) | 0.021 (3) |
C29 | 0.026 (3) | 0.105 (6) | 0.018 (3) | −0.023 (5) | 0.008 (2) | −0.001 (5) |
C210 | 0.024 (3) | 0.065 (5) | 0.038 (4) | −0.005 (3) | 0.005 (2) | −0.020 (3) |
C213 | 0.054 (4) | 0.018 (3) | 0.057 (4) | 0.004 (3) | −0.018 (3) | 0.011 (3) |
C212 | 0.025 (3) | 0.025 (3) | 0.086 (6) | 0.005 (2) | 0.000 (4) | −0.014 (4) |
C214 | 0.033 (3) | 0.038 (4) | 0.036 (3) | −0.014 (3) | −0.011 (3) | 0.013 (3) |
O1 | 0.017 (2) | 0.027 (3) | 0.016 (2) | −0.0088 (19) | −0.0052 (16) | 0.0041 (19) |
O2 | 0.025 (2) | 0.028 (3) | 0.0166 (19) | −0.0109 (19) | −0.0006 (16) | 0.003 (2) |
O3 | 0.021 (2) | 0.027 (3) | 0.020 (2) | −0.007 (2) | −0.0001 (18) | −0.0007 (19) |
O4 | 0.028 (2) | 0.028 (3) | 0.021 (2) | −0.010 (2) | −0.0011 (17) | 0.004 (2) |
C1 | 0.014 (3) | 0.022 (3) | 0.015 (3) | 0.000 (3) | −0.006 (2) | 0.006 (3) |
C2 | 0.024 (3) | 0.022 (3) | 0.014 (3) | −0.006 (3) | 0.000 (2) | 0.002 (2) |
C3 | 0.029 (3) | 0.019 (3) | 0.019 (3) | −0.005 (3) | 0.002 (3) | −0.003 (3) |
C4 | 0.019 (3) | 0.012 (3) | 0.024 (3) | −0.002 (3) | 0.001 (2) | −0.002 (3) |
C5 | 0.024 (3) | 0.026 (4) | 0.020 (3) | −0.001 (3) | 0.005 (3) | 0.001 (3) |
C6 | 0.016 (3) | 0.021 (4) | 0.026 (3) | −0.004 (3) | −0.004 (3) | −0.002 (3) |
C7 | 0.016 (3) | 0.016 (3) | 0.022 (3) | 0.000 (3) | 0.003 (2) | 0.002 (3) |
C8 | 0.016 (3) | 0.024 (4) | 0.022 (3) | −0.001 (3) | 0.001 (3) | −0.002 (3) |
Cl1 | 0.0179 (8) | 0.0302 (9) | 0.0287 (8) | 0.0001 (7) | 0.0010 (7) | 0.0013 (7) |
O11 | 0.021 (2) | 0.055 (3) | 0.039 (2) | 0.012 (2) | −0.001 (2) | 0.016 (3) |
O12 | 0.034 (2) | 0.038 (2) | 0.033 (2) | −0.006 (2) | 0.000 (2) | −0.007 (2) |
O13 | 0.033 (2) | 0.040 (3) | 0.050 (3) | −0.005 (2) | 0.007 (2) | 0.008 (2) |
O14 | 0.025 (2) | 0.051 (3) | 0.038 (3) | 0.004 (2) | 0.013 (2) | −0.007 (2) |
Cl2 | 0.0200 (8) | 0.0349 (10) | 0.0271 (8) | −0.0026 (8) | 0.0005 (7) | −0.0010 (7) |
O21 | 0.026 (3) | 0.041 (3) | 0.033 (2) | 0.004 (2) | −0.001 (2) | 0.004 (2) |
O22 | 0.033 (2) | 0.059 (3) | 0.026 (2) | −0.009 (2) | −0.0068 (19) | −0.004 (2) |
O23 | 0.031 (3) | 0.029 (3) | 0.082 (3) | −0.004 (2) | 0.005 (2) | 0.013 (2) |
O24 | 0.025 (2) | 0.089 (4) | 0.030 (3) | 0.003 (3) | 0.005 (2) | −0.008 (3) |
Ni1—N11 | 2.072 (5) | N24—C25 | 1.493 (8) |
Ni1—N14 | 2.071 (5) | N24—H24 | 0.93 |
Ni1—N18 | 2.077 (5) | N28—C27 | 1.431 (9) |
Ni1—N111 | 2.062 (5) | N28—C29 | 1.521 (9) |
Ni1—O1 | 2.106 (4) | N28—H28 | 0.93 |
Ni1—O5 | 2.211 (4) | N211—C210 | 1.491 (7) |
O5—H51 | 0.85 (2) | N211—C212 | 1.490 (9) |
O5—H52 | 0.85 (5) | N211—H211 | 0.93 |
N11—C114 | 1.474 (8) | C22—C23 | 1.489 (8) |
N11—C12 | 1.459 (8) | C22—H22A | 0.99 |
N11—H11 | 0.93 | C22—H22B | 0.99 |
N14—C13 | 1.494 (8) | C23—H23A | 0.99 |
N14—C15 | 1.457 (8) | C23—H23B | 0.99 |
N14—H14 | 0.9300 | C25—C26 | 1.530 (8) |
N18—C17 | 1.524 (9) | C25—H25A | 0.99 |
N18—C19 | 1.467 (9) | C25—H25B | 0.99 |
N18—H18 | 0.93 | C26—C27 | 1.519 (9) |
N111—C110 | 1.499 (7) | C26—H26A | 0.99 |
N111—C112 | 1.441 (8) | C26—H26B | 0.99 |
N111—H111 | 0.93 | C27—H27A | 0.99 |
C12—C13 | 1.512 (9) | C27—H27B | 0.99 |
C12—H12A | 0.99 | C29—C210 | 1.514 (10) |
C12—H12B | 0.99 | C29—H29A | 0.99 |
C13—H13A | 0.99 | C29—H29B | 0.99 |
C13—H13B | 0.99 | C210—H21A | 0.99 |
C15—C16 | 1.513 (8) | C210—H21B | 0.99 |
C15—H15A | 0.99 | C213—C214 | 1.503 (9) |
C15—H15B | 0.99 | C213—C212 | 1.515 (8) |
C16—C17 | 1.515 (9) | C213—H21C | 0.99 |
C16—H16A | 0.99 | C213—H21D | 0.99 |
C16—H16B | 0.99 | C212—H21E | 0.99 |
C17—H17A | 0.99 | C212—H21F | 0.99 |
C17—H17B | 0.99 | C214—H21G | 0.99 |
C19—C110 | 1.497 (10) | C214—H21H | 0.99 |
C19—H19A | 0.99 | O1—C7 | 1.257 (6) |
C19—H19B | 0.99 | O2—C7 | 1.269 (6) |
C110—H11A | 0.99 | O3—C8 | 1.268 (6) |
C110—H11B | 0.99 | O4—C8 | 1.259 (7) |
C112—C113 | 1.511 (9) | C1—C2 | 1.384 (7) |
C112—H11C | 0.99 | C1—C6 | 1.399 (8) |
C112—H11D | 0.99 | C1—C7 | 1.524 (8) |
C113—C114 | 1.524 (9) | C2—C3 | 1.395 (8) |
C113—H11E | 0.99 | C2—H2 | 0.95 |
C113—H11F | 0.99 | C3—C4 | 1.389 (8) |
C114—H11G | 0.99 | C3—H3 | 0.95 |
C114—H11H | 0.99 | C4—C5 | 1.409 (7) |
Ni2—N21 | 2.049 (5) | C4—C8 | 1.496 (8) |
Ni2—N24 | 2.070 (5) | C5—C6 | 1.374 (8) |
Ni2—N28 | 2.089 (5) | C5—H5 | 0.95 |
Ni2—N211 | 2.057 (6) | C6—H6 | 0.95 |
Ni2—O3 | 2.125 (4) | Cl1—O12 | 1.438 (4) |
Ni2—O6 | 2.202 (4) | Cl1—O14 | 1.443 (5) |
O6—H61 | 0.85 (2) | Cl1—O13 | 1.448 (5) |
O6—H62 | 0.85 (4) | Cl1—O11 | 1.451 (5) |
N21—C214 | 1.464 (8) | Cl2—O22 | 1.429 (4) |
N21—C22 | 1.491 (7) | Cl2—O24 | 1.437 (5) |
N21—H21 | 0.93 | Cl2—O23 | 1.441 (5) |
N24—C23 | 1.463 (8) | Cl2—O21 | 1.459 (5) |
N111—Ni1—N14 | 178.5 (3) | C214—N21—Ni2 | 116.8 (4) |
N111—Ni1—N11 | 94.6 (2) | C22—N21—Ni2 | 107.2 (3) |
N14—Ni1—N11 | 84.7 (2) | C214—N21—H21 | 106.0 |
N111—Ni1—N18 | 85.4 (2) | C22—N21—H21 | 106.0 |
N14—Ni1—N18 | 95.3 (2) | Ni2—N21—H21 | 106.0 |
N11—Ni1—N18 | 179.7 (2) | C23—N24—C25 | 114.7 (5) |
N111—Ni1—O1 | 88.14 (19) | C23—N24—Ni2 | 106.4 (4) |
N14—Ni1—O1 | 93.19 (19) | C25—N24—Ni2 | 115.0 (4) |
N11—Ni1—O1 | 92.51 (17) | C23—N24—H24 | 106.7 |
N18—Ni1—O1 | 87.21 (19) | C25—N24—H24 | 106.7 |
N111—Ni1—O5 | 89.17 (18) | Ni2—N24—H24 | 106.7 |
N14—Ni1—O5 | 89.54 (19) | C27—N28—C29 | 115.0 (6) |
N11—Ni1—O5 | 91.24 (18) | C27—N28—Ni2 | 115.8 (5) |
N18—Ni1—O5 | 89.04 (19) | C29—N28—Ni2 | 103.4 (4) |
O1—Ni1—O5 | 175.55 (17) | C27—N28—H28 | 107.4 |
Ni1—O5—H51 | 109 (4) | C29—N28—H28 | 107.4 |
Ni1—O5—H52 | 126 (4) | Ni2—N28—H28 | 107.4 |
H51—O5—H52 | 114 (6) | C212—N211—C210 | 112.6 (5) |
C12—N11—C114 | 114.7 (5) | C212—N211—Ni2 | 116.6 (4) |
C12—N11—Ni1 | 107.5 (4) | C210—N211—Ni2 | 107.0 (4) |
C114—N11—Ni1 | 114.6 (4) | C212—N211—H211 | 106.7 |
C12—N11—H11 | 106.5 | C210—N211—H211 | 106.7 |
C114—N11—H11 | 106.5 | Ni2—N211—H211 | 106.7 |
Ni1—N11—H11 | 106.5 | C23—C22—N21 | 108.4 (5) |
C15—N14—C13 | 111.9 (5) | C23—C22—H22A | 110.0 |
C15—N14—Ni1 | 116.0 (4) | N21—C22—H22A | 110.0 |
C13—N14—Ni1 | 105.7 (4) | C23—C22—H22B | 110.0 |
C15—N14—H14 | 107.6 | N21—C22—H22B | 110.0 |
C13—N14—H14 | 107.6 | H22A—C22—H22B | 108.4 |
Ni1—N14—H14 | 107.6 | N24—C23—C22 | 109.2 (5) |
C19—N18—C17 | 114.7 (6) | N24—C23—H23A | 109.8 |
C19—N18—Ni1 | 105.2 (4) | C22—C23—H23A | 109.8 |
C17—N18—Ni1 | 114.3 (4) | N24—C23—H23B | 109.8 |
C19—N18—H18 | 107.4 | C22—C23—H23B | 109.8 |
C17—N18—H18 | 107.4 | H23A—C23—H23B | 108.3 |
Ni1—N18—H18 | 107.4 | N24—C25—C26 | 111.1 (5) |
C112—N111—C110 | 115.7 (5) | N24—C25—H25A | 109.4 |
C112—N111—Ni1 | 116.7 (5) | C26—C25—H25A | 109.4 |
C110—N111—Ni1 | 104.8 (4) | N24—C25—H25B | 109.4 |
C112—N111—H111 | 106.3 | C26—C25—H25B | 109.4 |
C110—N111—H111 | 106.3 | H25A—C25—H25B | 108.0 |
Ni1—N111—H111 | 106.3 | C27—C26—C25 | 115.9 (5) |
N11—C12—C13 | 109.1 (5) | C27—C26—H26A | 108.3 |
N11—C12—H12A | 109.9 | C25—C26—H26A | 108.3 |
C13—C12—H12A | 109.9 | C27—C26—H26B | 108.3 |
N11—C12—H12B | 109.9 | C25—C26—H26B | 108.3 |
C13—C12—H12B | 109.9 | H26A—C26—H26B | 107.4 |
H12A—C12—H12B | 108.3 | N28—C27—C26 | 110.7 (6) |
N14—C13—C12 | 108.5 (6) | N28—C27—H27A | 109.5 |
N14—C13—H13A | 110.0 | C26—C27—H27A | 109.5 |
C12—C13—H13A | 110.0 | N28—C27—H27B | 109.5 |
N14—C13—H13B | 110.0 | C26—C27—H27B | 109.5 |
C12—C13—H13B | 110.0 | H27A—C27—H27B | 108.1 |
H13A—C13—H13B | 108.4 | C210—C29—N28 | 109.9 (5) |
N14—C15—C16 | 111.8 (5) | C210—C29—H29A | 109.7 |
N14—C15—H15A | 109.3 | N28—C29—H29A | 109.7 |
C16—C15—H15A | 109.3 | C210—C29—H29B | 109.7 |
N14—C15—H15B | 109.3 | N28—C29—H29B | 109.7 |
C16—C15—H15B | 109.3 | H29A—C29—H29B | 108.2 |
H15A—C15—H15B | 107.9 | N211—C210—C29 | 107.0 (6) |
C15—C16—C17 | 114.7 (5) | N211—C210—H21A | 110.3 |
C15—C16—H16A | 108.6 | C29—C210—H21A | 110.3 |
C17—C16—H16A | 108.6 | N211—C210—H21B | 110.3 |
C15—C16—H16B | 108.6 | C29—C210—H21B | 110.3 |
C17—C16—H16B | 108.6 | H21A—C210—H21B | 108.6 |
H16A—C16—H16B | 107.6 | C214—C213—C212 | 116.0 (5) |
C16—C17—N18 | 112.6 (5) | C214—C213—H21C | 108.3 |
C16—C17—H17A | 109.1 | C212—C213—H21C | 108.3 |
N18—C17—H17A | 109.1 | C214—C213—H21D | 108.3 |
C16—C17—H17B | 109.1 | C212—C213—H21D | 108.3 |
N18—C17—H17B | 109.1 | H21C—C213—H21D | 107.4 |
H17A—C17—H17B | 107.8 | N211—C212—C213 | 111.1 (6) |
N18—C19—C110 | 107.2 (6) | N211—C212—H21E | 109.4 |
N18—C19—H19A | 110.3 | C213—C212—H21E | 109.4 |
C110—C19—H19A | 110.3 | N211—C212—H21F | 109.4 |
N18—C19—H19B | 110.3 | C213—C212—H21F | 109.4 |
C110—C19—H19B | 110.3 | H21E—C212—H21F | 108.0 |
H19A—C19—H19B | 108.5 | N21—C214—C213 | 112.1 (6) |
C19—C110—N111 | 109.7 (6) | N21—C214—H21G | 109.2 |
C19—C110—H11A | 109.7 | C213—C214—H21G | 109.2 |
N111—C110—H11A | 109.7 | N21—C214—H21H | 109.2 |
C19—C110—H11B | 109.7 | C213—C214—H21H | 109.2 |
N111—C110—H11B | 109.7 | H21G—C214—H21H | 107.9 |
H11A—C110—H11B | 108.2 | C7—O1—Ni1 | 136.8 (4) |
N111—C112—C113 | 111.8 (5) | C8—O3—Ni2 | 134.7 (4) |
N111—C112—H11C | 109.2 | C2—C1—C6 | 118.9 (5) |
C113—C112—H11C | 109.2 | C2—C1—C7 | 121.2 (5) |
N111—C112—H11D | 109.2 | C6—C1—C7 | 119.9 (5) |
C113—C112—H11D | 109.2 | C1—C2—C3 | 120.3 (5) |
H11C—C112—H11D | 107.9 | C1—C2—H2 | 119.9 |
C112—C113—C114 | 116.0 (5) | C3—C2—H2 | 119.9 |
C112—C113—H11E | 108.3 | C4—C3—C2 | 121.0 (6) |
C114—C113—H11E | 108.3 | C4—C3—H3 | 119.5 |
C112—C113—H11F | 108.3 | C2—C3—H3 | 119.5 |
C114—C113—H11F | 108.3 | C3—C4—C5 | 118.4 (5) |
H11E—C113—H11F | 107.4 | C3—C4—C8 | 120.9 (5) |
N11—C114—C113 | 113.2 (6) | C5—C4—C8 | 120.6 (5) |
N11—C114—H11G | 108.9 | C6—C5—C4 | 120.3 (6) |
C113—C114—H11G | 108.9 | C6—C5—H5 | 119.8 |
N11—C114—H11H | 108.9 | C4—C5—H5 | 119.8 |
C113—C114—H11H | 108.9 | C5—C6—C1 | 121.1 (6) |
H11G—C114—H11H | 107.8 | C5—C6—H6 | 119.5 |
N21—Ni2—N211 | 94.5 (2) | C1—C6—H6 | 119.5 |
N21—Ni2—N24 | 84.4 (2) | O1—C7—O2 | 125.2 (5) |
N211—Ni2—N24 | 178.7 (3) | O1—C7—C1 | 116.9 (5) |
N21—Ni2—N28 | 178.5 (2) | O2—C7—C1 | 117.9 (5) |
N211—Ni2—N28 | 86.2 (2) | O4—C8—O3 | 125.2 (5) |
N24—Ni2—N28 | 94.9 (2) | O4—C8—C4 | 119.3 (5) |
N21—Ni2—O3 | 93.23 (17) | O3—C8—C4 | 115.6 (5) |
N211—Ni2—O3 | 88.9 (2) | O12—Cl1—O14 | 109.5 (3) |
N24—Ni2—O3 | 92.03 (19) | O12—Cl1—O13 | 109.3 (3) |
N28—Ni2—O3 | 88.09 (19) | O14—Cl1—O13 | 110.0 (3) |
N21—Ni2—O6 | 91.10 (17) | O12—Cl1—O11 | 108.9 (3) |
N211—Ni2—O6 | 88.5 (2) | O14—Cl1—O11 | 110.4 (3) |
N24—Ni2—O6 | 90.69 (18) | O13—Cl1—O11 | 108.6 (3) |
N28—Ni2—O6 | 87.60 (18) | O22—Cl2—O24 | 109.8 (3) |
O3—Ni2—O6 | 175.09 (16) | O22—Cl2—O23 | 109.1 (3) |
Ni2—O6—H61 | 120 (4) | O24—Cl2—O23 | 110.7 (4) |
Ni2—O6—H62 | 117 (4) | O22—Cl2—O21 | 109.3 (3) |
H61—O6—H62 | 105 (5) | O24—Cl2—O21 | 109.6 (3) |
C214—N21—C22 | 114.0 (6) | O23—Cl2—O21 | 108.3 (3) |
N11—C12—C13—N14 | −55.8 (7) | C210—N211—C212—C213 | −178.8 (5) |
C12—C13—N14—C15 | 169.6 (5) | N211—C212—C213—C214 | 71.1 (8) |
C13—N14—C15—C16 | −179.0 (5) | C212—C213—C214—N21 | −71.7 (8) |
N14—C15—C16—C17 | 73.8 (7) | C213—C214—N21—C22 | −178.7 (4) |
C15—C16—C17—N18 | −72.2 (7) | C214—N21—C22—C23 | −170.3 (5) |
C16—C17—N18—C19 | 175.7 (5) | C6—C1—C2—C3 | 1.0 (7) |
C17—N18—C19—C110 | −172.1 (5) | C7—C1—C2—C3 | −178.7 (5) |
N18—C19—C110—N111 | 59.5 (7) | C1—C2—C3—C4 | 0.2 (8) |
C19—C110—N111—C112 | −170.1 (6) | C2—C3—C4—C5 | −0.7 (8) |
C110—N111—C112—C113 | −179.3 (5) | C2—C3—C4—C8 | −178.6 (5) |
N111—C112—C113—C114 | −70.2 (8) | C3—C4—C5—C6 | 0.0 (7) |
C112—C113—C114—N11 | 70.2 (7) | C8—C4—C5—C6 | 178.0 (5) |
C113—C114—N11—C12 | 180.0 (5) | C4—C5—C6—C1 | 1.2 (8) |
C114—N11—C12—C13 | 167.6 (5) | C2—C1—C6—C5 | −1.7 (8) |
N21—C22—C23—N24 | 55.6 (6) | C7—C1—C6—C5 | 178.0 (5) |
C22—C23—N24—C25 | −170.7 (5) | C2—C1—C7—O1 | −142.6 (6) |
C23—N24—C25—C26 | 178.6 (5) | C6—C1—C7—O1 | 37.7 (8) |
N24—C25—C26—C27 | −72.8 (7) | C2—C1—C7—O2 | 38.0 (8) |
C25—C26—C27—N28 | 74.6 (7) | C6—C1—C7—O2 | −141.7 (6) |
C26—C27—N28—C29 | −178.3 (5) | C3—C4—C8—O4 | 144.1 (6) |
C27—N28—C29—C210 | 170.0 (5) | C5—C4—C8—O4 | −33.8 (8) |
N28—C29—C210—N211 | −58.3 (6) | C3—C4—C8—O3 | −36.8 (8) |
C29—C210—N211—C212 | 171.1 (5) | C5—C4—C8—O3 | 145.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O2 | 0.93 | 2.09 | 2.939 (6) | 151 |
N21—H21···O4 | 0.93 | 2.06 | 2.920 (7) | 154 |
N111—H111···O14 | 0.93 | 2.27 | 3.183 (7) | 165 |
N211—H211···O24 | 0.93 | 2.22 | 3.135 (7) | 170 |
N14—H14···O13i | 0.93 | 2.26 | 3.175 (7) | 168 |
O5—H52···O11i | 0.85 (5) | 2.10 (5) | 2.904 (6) | 158 (6) |
N24—H24···O23ii | 0.93 | 2.20 | 3.116 (7) | 166 |
O6—H62···O21ii | 0.85 (4) | 2.07 (4) | 2.898 (6) | 165 (6) |
N18—H18···O4iii | 0.93 | 2.47 | 3.373 (7) | 163 |
O5—H51···O4iii | 0.85 (2) | 1.88 (2) | 2.717 (6) | 170 (4) |
N28—H28···O2iv | 0.93 | 2.34 | 3.253 (7) | 167 |
O6—H61···O2iv | 0.85 (2) | 1.91 (2) | 2.730 (5) | 163 (6) |
C12—H12A···O11i | 0.99 | 2.44 | 3.372 (8) | 157 |
C22—H22A···O21ii | 0.99 | 2.43 | 3.402 (7) | 166 |
C19—H19A···O24iii | 0.99 | 2.41 | 3.273 (8) | 146 |
C29—H29A···O14iv | 0.99 | 2.56 | 3.402 (7) | 142 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C10H24N4)2(H2O)2(C8H4O4)](ClO4)2 |
Mr | 917.09 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 10.2842 (3), 14.9172 (4), 13.0621 (4) |
β (°) | 102.5220 (11) |
V (Å3) | 1956.21 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.17 |
Crystal size (mm) | 0.18 × 0.18 × 0.07 |
Data collection | |
Diffractometer | Kappa-CCD diffractometer |
Absorption correction | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.817, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13566, 7654, 5458 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.097, 1.01 |
No. of reflections | 7654 |
No. of parameters | 501 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.70, −0.44 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.38 (3) |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2001), SHELXL97 and PRPKAPPA (Ferguson, 1999).
Ni1—N11 | 2.072 (5) | Ni2—N21 | 2.049 (5) |
Ni1—N14 | 2.071 (5) | Ni2—N24 | 2.070 (5) |
Ni1—N18 | 2.077 (5) | Ni2—N28 | 2.089 (5) |
Ni1—N111 | 2.062 (5) | Ni2—N211 | 2.057 (6) |
Ni1—O1 | 2.106 (4) | Ni2—O3 | 2.125 (4) |
Ni1—O5 | 2.211 (4) | Ni2—O6 | 2.202 (4) |
N11—C114 | 1.474 (8) | N21—C214 | 1.464 (8) |
N11—C12 | 1.459 (8) | N21—C22 | 1.491 (7) |
N14—C13 | 1.494 (8) | N24—C23 | 1.463 (8) |
N14—C15 | 1.457 (8) | N24—C25 | 1.493 (8) |
N18—C17 | 1.524 (9) | N28—C27 | 1.431 (9) |
N18—C19 | 1.467 (9) | N28—C29 | 1.521 (9) |
N111—C110 | 1.499 (7) | N211—C210 | 1.491 (7) |
N111—C112 | 1.441 (8) | N211—C212 | 1.490 (9) |
N11—C12—C13—N14 | −55.8 (7) | N21—C22—C23—N24 | 55.6 (6) |
C12—C13—N14—C15 | 169.6 (5) | C22—C23—N24—C25 | −170.7 (5) |
C13—N14—C15—C16 | −179.0 (5) | C23—N24—C25—C26 | 178.6 (5) |
N14—C15—C16—C17 | 73.8 (7) | N24—C25—C26—C27 | −72.8 (7) |
C15—C16—C17—N18 | −72.2 (7) | C25—C26—C27—N28 | 74.6 (7) |
C16—C17—N18—C19 | 175.7 (5) | C26—C27—N28—C29 | −178.3 (5) |
C17—N18—C19—C110 | −172.1 (5) | C27—N28—C29—C210 | 170.0 (5) |
N18—C19—C110—N111 | 59.5 (7) | N28—C29—C210—N211 | −58.3 (6) |
C19—C110—N111—C112 | −170.1 (6) | C29—C210—N211—C212 | 171.1 (5) |
C110—N111—C112—C113 | −179.3 (5) | C210—N211—C212—C213 | −178.8 (5) |
N111—C112—C113—C114 | −70.2 (8) | N211—C212—C213—C214 | 71.1 (8) |
C112—C113—C114—N11 | 70.2 (7) | C212—C213—C214—N21 | −71.7 (8) |
C113—C114—N11—C12 | 180.0 (5) | C213—C214—N21—C22 | −178.7 (4) |
C114—N11—C12—C13 | 167.6 (5) | C214—N21—C22—C23 | −170.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O2 | 0.93 | 2.09 | 2.939 (6) | 151 |
N21—H21···O4 | 0.93 | 2.06 | 2.920 (7) | 154 |
N111—H111···O14 | 0.93 | 2.27 | 3.183 (7) | 165 |
N211—H211···O24 | 0.93 | 2.22 | 3.135 (7) | 170 |
N14—H14···O13i | 0.93 | 2.26 | 3.175 (7) | 168 |
O5—H52···O11i | 0.85 (5) | 2.10 (5) | 2.904 (6) | 158 (6) |
N24—H24···O23ii | 0.93 | 2.20 | 3.116 (7) | 166 |
O6—H62···O21ii | 0.85 (4) | 2.07 (4) | 2.898 (6) | 165 (6) |
N18—H18···O4iii | 0.93 | 2.47 | 3.373 (7) | 163 |
O5—H51···O4iii | 0.85 (2) | 1.88 (2) | 2.717 (6) | 170 (4) |
N28—H28···O2iv | 0.93 | 2.34 | 3.253 (7) | 167 |
O6—H61···O2iv | 0.85 (2) | 1.91 (2) | 2.730 (5) | 163 (6) |
C12—H12A···O11i | 0.99 | 2.44 | 3.372 (8) | 157 |
C22—H22A···O21ii | 0.99 | 2.43 | 3.402 (7) | 166 |
C19—H19A···O24iii | 0.99 | 2.41 | 3.273 (8) | 146 |
C29—H29A···O14iv | 0.99 | 2.56 | 3.402 (7) | 142 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z. |
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The [Ni(cyclam)]2+ cation [(1,4,8,11-tetraazacyclotetradecane)nickel(II)], [Ni(C10H24N4)]2+, reacts readily with two equivalents of the 4-hydroxybenzoate anion to yield a neutral complex containing a trans octahedral NiN4O2 chromophore (Glidewell et al., 2000). In this complex, [(HOC6H4COO)2Ni(cyclam)], the square-planar [Ni(cyclam)] fragment has two axial sites available for coordination, in this case by the hydroxybenzoate ligands, and a well defined array of axial N—H bonds, two on each face of the nearly-planar macrocycle, available for hydrogen-bond formation. The [Ni(cyclam)]2+ cation is thus an attractive building block for the construction of pre-designed coordination polymer networks, using, for example, polycarboxylate anions as the axial ligands. It is reasonable to envisage that growth of coordination polymer networks proceeds in a stepwise fashion via low- and medium-molecularity intermediates. By use of the 1,4-benzenedicarboxylate (terephthalate) anion, [C6H4(COO)2]2-, we have now isolated the title anion-bridged dinuclear complex, (I), and its structure is presented here. \sch
In the cation of (I) (Fig. 1), the bridging dianionic ligand utilizes one O atom of each carboxylate group to coordinate to the Ni, while the other O atom in each group accepts a hydrogen bond, forming an S(6) motif, precisely as observed in the 4-hydroxybenzoate complex (Glidewell et al., 2000). This coordination mode, with direct Ni—O bonds to the carboxylate anion, differs from that observed with 1,3,5-benzenetricarboxylate, where the anions are simply hydrogen-bonded to trans [Ni(cyclam)(H2O)2]2+ cations (Choi et al., 1999). Each Ni atom is also coordinated by four N atoms from the cyclam ligand, which occupy the equatorial sites of an axially elongated octahedron. A water molecule occupies the second axial site of each Ni.
The cyclam ligands adopt the usual trans-III conformation (Barefield, Bianchi et al., 1986), with all torsion angles in the ring within 15° of either 180° (antiperiplanar) or ±60° (synclinal) (Table 1). The Ni—N distances are closely similar, ranging only from 2.049 (5) to 2.089 (5) Å; these distances are typical of those observed in octahedral NiII complexes of cyclam and its C-methyl derivatives (Whimp et al., 1970; Curtis et al., 1973; Hay et al., 1982; Ito et al., 1984; Barefield, Bianchi et al., 1986; Barefield, Freeman & Van Derveer, 1986; Hambley, 1986; Mochizuki & Kondo, 1995; Choi et al., 1999; Glidewell et al., 2000), although they are significantly shorter than those observed in the square-planar systems (Prasad & McAuley, 1983; Barefield, Bianchi et al., 1986; Adam et al., 1991). The mean value of the Ni—O distances, 2.161 (4) Å, is virtually identical with those observed in salts of trans [Ni(cyclam)(H2O)2]2+ cations (Mochizuki & Kondo, 1995; Choi et al., 1999). On the other hand, the C—N distances exhibit a much wider range, from 1.431 (9) to 1.524 (9) Å.
Although the two [Ni(cyclam)] fragments in the cation are fully eclipsed with respect to the Ni···Ni vector, the detailed differences in the C—N distances and in the magnitudes of the torsion angles involving corresponding sets of atoms in the two [Ni(cyclam)] fragments prevent the cation from attaining a centrosymmetric configuration. Nonetheless, the O—Ni(N4)-benzenedicarboxylato-Ni(N4)-O unit (i.e. the entire cation except for the C atoms of the cyclam ligands) is very close to being centrosymmetric. In the bridging ligand, the carboxylate groups based on C7 and C8 are rotated out of the plane of the aryl ring by 38.0 (2)° and 35.2 (2)°, respectively, with the sense of the rotations mimicking centrosymmetry (Fig. 1).
The two perchlorate anions are both fully ordered. Each participates in three hydrogen bonds (Table 2), and it is these which prevent the almost free rotation often observed with this anion. Within the selected asymmetric unit (Fig. 1), N111 and N211 act as hydrogen-bond donors to O14 and O24, respectively (Table 2).
Apart from the formation of the four N—H···O hydrogen bonds within the selected asymmetric unit, the cation of (I) has four N—H and four O—H bonds available for the formation of hydrogen bonds to other aggregates. Four of the resulting hydrogen bonds (entries 5–8 in Table 2) link the three-ion aggregates into chains running parallel to the [100] direction, while the other four (entries 9–12 in Table 2) link each [100] to four of its neighbours, so generating a continuous three-dimensional framework. Atom N14 in the cation at (x, y, z) acts as a donor to perchlorate atom O13 at (1 + x, y, z), while atom O5 at (x, y, z) acts as a donor, via H52, to O11 in the same perchlorate at (1 + x, y, z). In an entirely similar manner, atoms N24 and O6 at (x, y, z) act as donors to O23 and O21, respectively, at (-1 + x, y, z), so forming a molecular ladder parallel to [100] in which each upright is a C(8) C(8)[R22(8)] chain of rings, while the Ni-(benzenedicarboxylato)-Ni units form the rungs (Fig. 2). This ladder runs approximately along the line (x, 1/2, 1/4) and a second similar ladder runs approximately along the line (x, 0, 3/4). Each ladder is directly linked to four neighbouring ladders: atoms N18 and O5 at (x, y, z), which are components of the ladder along (x, 1/2, 1/4), both act as hydrogen-bond donors to O4 at (1 - x, 1/2 + y, 1 - z), which is a component of the ladder along (x, 1, 3/4). Similarly, atoms N28 and O6 at (x, y, z) both act as donors to O2 at (-x, y - 1/2, -z), which is a component of the ladder along (x, 0, -1/4). In this manner, the ladder along (x, 1/2, 1/4) is directly linked to the four ladders along (x, 0, 3/4), (x, 0, -1/4), (x, 1, 3/4) and (x, 1, -1/4) (Fig. 3), and propagation of these hydrogen bonds by the space group links all of the [100] ladders into a three-dimensional framework.
In addition to the O—H···O and N—H···O hydrogen bonds, there are also four significant C—H···O hydrogen bonds. Two of these (entries 13 and 14 in Table 2) reinforce the [100] chains, while the other two reinforce the links between these chains.
For the two intracation N—H···O hydrogen bonds, the short N···O distances are probably largely determined by the adjacent Ni—O coordination. The remainder of the N—H···O hydrogen bonds fall into two clear groups (Table 2): those having perchlorate O as acceptor have significantly shorter N···O distances than those having carboxylate O as acceptor. By contrast, the O—H···O hydrogen bonds with perchlorate O as acceptor have significantly longer O···O distances than those with carboxylate O acceptors. The D—H···A angles for the hard interion hydrogen bonds are all closely clustered around the mean value of 166°. Hence, the pattern of the H···A distances closely follows that of the D···A distances.