In the title compound, [Ni2(C52H50N4O2)(C2H6O2)](ClO4)2·2H2O, the two Ni atoms are bridged by two O atoms from the Robson macrocyclic ligand, forming a parallelogram, which has a twofold axis. The macrocyclic plane is formed from an Ni2O2 center and four N atoms from the ligand. Above the macrocyclic plane an ethylene glycol molecule bridges the two Ni atoms, and the coordination geometry around each Ni atom is square pyramidal.
Supporting information
CCDC reference: 217382
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.047
- wR factor = 0.159
- Data-to-parameter ratio = 15.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ......................... 7.00 Perc.
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.00
From the CIF: _reflns_number_total 5296
Count of symmetry unique reflns 3338
Completeness (_total/calc) 158.66%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1958
Fraction of Friedel pairs measured 0.587
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
To a solution of 2,6-diformyl-4-tert-butylphenol (1 mmol) in 5 ml e thanol at room temperature, NaOH ethanol solution (5 ml, 0.2M) was added. This mixture was stirred for 1 h and a yellow precipitate appeared. 1(S),2(S)-Diphenyl-1,2-diaminoethane (1 mmol) dissolved in ethanol was then added and the resulting mixture stirred at room temperature for 0.5 h. After that, a solution of Ni2(ClO4)2 in ethanol (5 ml, 0.2 M) was added and stirring continued for another 2 h. The reaction mixture was filtered and the precipitates obtained were washed with ethanol and dried in a vacuum. Crystals of (I) were grown from an ethanol–ethylene glycol solution.
There are two independent water molecules of crystallization. One, O3, lies on a twofold axis, while the other, O4, shows a positional disorder over two sites with 50% probability each. The positions of all H atoms were fixed geometrically and distances to H atoms were set by the program.
Data collection: CAD-4 SDP/VAX (Enraf-Nonius, 1989); cell refinement: CAD-4 SDP/VAX; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(
R,
R,
R,
R)10,21-Di-
tert-butyl-4,5,15,16-tetraphenyl-3,6,14,17-tetraaza -tricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12 (24),13,17, 19,21-decaene-23,24-diol ethane-1,2-diol dinuclear Nickel(II) diperchlorate bishydrate complex
top
Crystal data top
[Ni2(C52H50N4O2)(C2H6O2)](ClO4)2·2H2O | Dx = 1.366 Mg m−3 |
Mr = 1177.38 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P41212 | Cell parameters from 25 reflections |
Hall symbol: P 4abw 2nw | θ = 2.2–16.7° |
a = 11.536 (3) Å | µ = 0.82 mm−1 |
c = 43.015 (3) Å | T = 293 K |
V = 5724 (2) Å3 | Block, orange |
Z = 4 | 0.35 × 0.29 × 0.27 mm |
F(000) = 2456 | |
Data collection top
Siemens P4 diffractometer | 4763 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 26.0°, θmin = 1.8° |
ω scans | h = −9→13 |
Absorption correction: ψ scan (XPREP; Bruker, 2000) | k = −14→13 |
Tmin = 0.750, Tmax = 0.799 | l = −52→51 |
8048 measured reflections | 3 standard reflections every 97 reflections |
5296 independent reflections | intensity decay: 4.0% |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.105P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
5296 reflections | Δρmax = 0.49 e Å−3 |
348 parameters | Δρmin = −0.58 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2037 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (2) |
Crystal data top
[Ni2(C52H50N4O2)(C2H6O2)](ClO4)2·2H2O | Z = 4 |
Mr = 1177.38 | Mo Kα radiation |
Tetragonal, P41212 | µ = 0.82 mm−1 |
a = 11.536 (3) Å | T = 293 K |
c = 43.015 (3) Å | 0.35 × 0.29 × 0.27 mm |
V = 5724 (2) Å3 | |
Data collection top
Siemens P4 diffractometer | 4763 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XPREP; Bruker, 2000) | Rint = 0.011 |
Tmin = 0.750, Tmax = 0.799 | 3 standard reflections every 97 reflections |
8048 measured reflections | intensity decay: 4.0% |
5296 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.159 | Δρmax = 0.49 e Å−3 |
S = 1.09 | Δρmin = −0.58 e Å−3 |
5296 reflections | Absolute structure: Flack (1983), 2037 Friedel pairs |
348 parameters | Absolute structure parameter: 0.02 (2) |
0 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) |
Ni1 | 0.61132 (6) | 0.47418 (6) | 0.021273 (14) | 0.0605 (2) | |
C1 | 0.4452 (4) | 0.6438 (3) | 0.04607 (8) | 0.0429 (8) | |
C2 | 0.3486 (3) | 0.7116 (3) | 0.03981 (8) | 0.0399 (8) | |
C3 | 0.2930 (3) | 0.7643 (3) | 0.06624 (8) | 0.0420 (8) | |
H3A | 0.2312 | 0.8145 | 0.0627 | 0.050* | |
C4 | 0.3248 (4) | 0.7453 (3) | 0.09515 (8) | 0.0433 (8) | |
C5 | 0.4194 (3) | 0.6655 (3) | 0.10038 (8) | 0.0410 (8) | |
H5A | 0.4404 | 0.6475 | 0.1207 | 0.049* | |
C6 | 0.4813 (3) | 0.6138 (3) | 0.07542 (8) | 0.0406 (8) | |
C7 | 0.5714 (3) | 0.5253 (3) | 0.08392 (7) | 0.0393 (7) | |
H7A | 0.5874 | 0.5134 | 0.1049 | 0.047* | |
C8 | 0.7258 (4) | 0.3862 (4) | 0.07330 (8) | 0.0455 (9) | |
H8A | 0.7980 | 0.4309 | 0.0722 | 0.055* | |
C9 | 0.7313 (4) | 0.2885 (4) | 0.04769 (8) | 0.0446 (9) | |
H9A | 0.6671 | 0.2351 | 0.0518 | 0.053* | |
C10 | 0.7431 (4) | 0.3035 (4) | −0.01101 (8) | 0.0455 (9) | |
H10A | 0.7910 | 0.2360 | −0.0085 | 0.055* | |
C11 | 0.2621 (4) | 0.8043 (4) | 0.12367 (9) | 0.0500 (10) | |
C12 | 0.1701 (4) | 0.8873 (4) | 0.11299 (9) | 0.0518 (10) | |
H12A | 0.1338 | 0.9223 | 0.1307 | 0.078* | |
H12B | 0.1131 | 0.8463 | 0.1011 | 0.078* | |
H12C | 0.2047 | 0.9465 | 0.1003 | 0.078* | |
C13 | 0.3603 (4) | 0.8734 (4) | 0.14004 (10) | 0.0557 (11) | |
H13A | 0.3293 | 0.9127 | 0.1579 | 0.084* | |
H13B | 0.3920 | 0.9292 | 0.1258 | 0.084* | |
H13C | 0.4202 | 0.8210 | 0.1465 | 0.084* | |
C14 | 0.2186 (4) | 0.7150 (4) | 0.14649 (10) | 0.0564 (10) | |
H14A | 0.1812 | 0.7534 | 0.1636 | 0.085* | |
H14B | 0.2827 | 0.6702 | 0.1541 | 0.085* | |
H14C | 0.1642 | 0.6648 | 0.1363 | 0.085* | |
C15 | 0.7160 (4) | 0.3381 (4) | 0.10516 (9) | 0.0483 (9) | |
C16 | 0.8023 (4) | 0.3690 (4) | 0.12664 (10) | 0.0557 (11) | |
H16A | 0.8606 | 0.4210 | 0.1212 | 0.067* | |
C17 | 0.7985 (4) | 0.3175 (4) | 0.15773 (10) | 0.0566 (11) | |
H17A | 0.8537 | 0.3366 | 0.1726 | 0.068* | |
C18 | 0.7126 (4) | 0.2416 (4) | 0.16418 (10) | 0.0595 (12) | |
H18A | 0.7094 | 0.2081 | 0.1838 | 0.071* | |
C19 | 0.6289 (4) | 0.2122 (4) | 0.14241 (9) | 0.0560 (11) | |
H19A | 0.5712 | 0.1585 | 0.1469 | 0.067* | |
C20 | 0.6344 (4) | 0.2635 (4) | 0.11495 (9) | 0.0537 (10) | |
H20A | 0.5756 | 0.2461 | 0.1009 | 0.064* | |
C21 | 0.8404 (4) | 0.2209 (4) | 0.05109 (8) | 0.0455 (9) | |
C22 | 0.9477 (4) | 0.2652 (4) | 0.03869 (9) | 0.0489 (9) | |
H22A | 0.9520 | 0.3402 | 0.0309 | 0.059* | |
C23 | 1.0483 (4) | 0.1908 (4) | 0.03869 (10) | 0.0549 (10) | |
H23A | 1.1180 | 0.2150 | 0.0300 | 0.066* | |
C24 | 1.0378 (4) | 0.0852 (4) | 0.05163 (10) | 0.0531 (10) | |
H24A | 1.1026 | 0.0373 | 0.0525 | 0.064* | |
C25 | 0.9300 (4) | 0.0440 (4) | 0.06418 (10) | 0.0552 (10) | |
H25A | 0.9259 | −0.0295 | 0.0730 | 0.066* | |
C26 | 0.8364 (4) | 0.1103 (4) | 0.06325 (9) | 0.0489 (9) | |
H26A | 0.7667 | 0.0818 | 0.0709 | 0.059* | |
C27 | 0.3476 (5) | 0.3592 (5) | 0.01754 (12) | 0.0668 (13) | |
H27A | 0.3014 | 0.2923 | 0.0223 | 0.080* | |
H27B | 0.3156 | 0.4260 | 0.0277 | 0.080* | |
N1 | 0.7087 (3) | 0.3420 (3) | 0.01752 (7) | 0.0436 (7) | |
N2 | 0.6252 (3) | 0.4679 (3) | 0.06464 (7) | 0.0428 (7) | |
O1 | 0.5006 (2) | 0.5959 (2) | 0.02063 (6) | 0.0464 (6) | |
O2 | 0.4579 (3) | 0.3417 (3) | 0.02603 (8) | 0.0645 (9) | |
H2A | 0.4837 | 0.2715 | 0.0157 | 0.077* | |
Cl1 | 0.47318 (11) | 0.03186 (12) | 0.03666 (3) | 0.0616 (3) | |
O11 | 0.5058 (3) | 0.0492 (3) | 0.06532 (8) | 0.0640 (9) | |
O12 | 0.5367 (3) | −0.0787 (3) | 0.02955 (7) | 0.0638 (9) | |
O13 | 0.3482 (3) | 0.0249 (3) | 0.03502 (7) | 0.0640 (9) | |
O14 | 0.5133 (3) | 0.1183 (3) | 0.00996 (8) | 0.0646 (9) | |
O4 | 0.9711 (7) | 0.6489 (6) | 0.03078 (15) | 0.0647 (17) | 0.50 |
H4A | 1.0256 | 0.6983 | 0.0294 | 0.097* | 0.50 |
H4C | 0.9907 | 0.5871 | 0.0214 | 0.097* | 0.50 |
O3 | 0.7495 (4) | 0.7495 (4) | 0.0000 | 0.0728 (14) | |
H3B | 0.8145 | 0.7554 | 0.0092 | 0.087* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0673 (4) | 0.0686 (4) | 0.0455 (3) | 0.0253 (3) | −0.0011 (3) | −0.0033 (3) |
C1 | 0.057 (2) | 0.046 (2) | 0.0264 (17) | 0.0168 (16) | 0.0019 (15) | −0.0046 (14) |
C2 | 0.0479 (19) | 0.048 (2) | 0.0241 (16) | 0.0133 (16) | 0.0015 (14) | −0.0025 (14) |
C3 | 0.049 (2) | 0.048 (2) | 0.0292 (17) | 0.0133 (16) | 0.0015 (15) | −0.0049 (14) |
C4 | 0.052 (2) | 0.046 (2) | 0.0317 (17) | 0.0126 (16) | 0.0024 (15) | −0.0030 (15) |
C5 | 0.051 (2) | 0.0462 (19) | 0.0262 (16) | 0.0136 (15) | 0.0031 (14) | 0.0000 (14) |
C6 | 0.0502 (19) | 0.0437 (18) | 0.0280 (16) | 0.0117 (15) | 0.0015 (14) | −0.0040 (14) |
C7 | 0.0477 (19) | 0.0479 (18) | 0.0221 (15) | 0.0106 (16) | 0.0009 (13) | −0.0027 (14) |
C8 | 0.056 (2) | 0.056 (2) | 0.0241 (16) | 0.0206 (19) | −0.0027 (15) | −0.0018 (15) |
C9 | 0.054 (2) | 0.051 (2) | 0.0279 (17) | 0.0147 (17) | 0.0014 (15) | 0.0005 (15) |
C10 | 0.058 (2) | 0.055 (2) | 0.0228 (16) | 0.0185 (18) | −0.0027 (15) | 0.0004 (14) |
C11 | 0.058 (2) | 0.053 (2) | 0.039 (2) | 0.0174 (19) | 0.0012 (17) | −0.0045 (17) |
C12 | 0.062 (2) | 0.063 (2) | 0.0303 (18) | 0.017 (2) | 0.0026 (17) | −0.0099 (18) |
C13 | 0.065 (3) | 0.062 (3) | 0.040 (2) | 0.013 (2) | 0.0047 (19) | −0.0132 (19) |
C14 | 0.057 (2) | 0.065 (3) | 0.047 (2) | 0.010 (2) | −0.0034 (19) | −0.003 (2) |
C15 | 0.060 (2) | 0.052 (2) | 0.0329 (19) | 0.0184 (19) | −0.0004 (17) | −0.0009 (16) |
C16 | 0.065 (3) | 0.064 (3) | 0.038 (2) | 0.028 (2) | −0.0014 (18) | −0.0004 (18) |
C17 | 0.069 (3) | 0.063 (3) | 0.038 (2) | 0.022 (2) | −0.0052 (19) | −0.0034 (18) |
C18 | 0.078 (3) | 0.065 (3) | 0.036 (2) | 0.027 (2) | 0.000 (2) | 0.0041 (19) |
C19 | 0.071 (3) | 0.064 (3) | 0.033 (2) | 0.020 (2) | 0.0017 (19) | 0.0033 (17) |
C20 | 0.072 (3) | 0.056 (2) | 0.0337 (19) | 0.022 (2) | 0.0004 (18) | 0.0027 (17) |
C21 | 0.051 (2) | 0.054 (2) | 0.0315 (18) | 0.0133 (17) | −0.0024 (15) | −0.0022 (16) |
C22 | 0.054 (2) | 0.058 (2) | 0.0342 (19) | 0.0127 (18) | −0.0007 (16) | −0.0026 (16) |
C23 | 0.064 (3) | 0.061 (3) | 0.039 (2) | 0.017 (2) | −0.0062 (19) | −0.0027 (18) |
C24 | 0.056 (2) | 0.063 (3) | 0.040 (2) | 0.012 (2) | −0.0044 (17) | −0.0030 (17) |
C25 | 0.061 (2) | 0.062 (3) | 0.042 (2) | 0.016 (2) | −0.0078 (18) | −0.0042 (19) |
C26 | 0.054 (2) | 0.057 (2) | 0.0364 (19) | 0.0140 (19) | −0.0042 (16) | −0.0010 (18) |
C27 | 0.072 (3) | 0.071 (3) | 0.057 (3) | 0.027 (3) | −0.004 (2) | −0.005 (2) |
N1 | 0.0531 (18) | 0.0517 (17) | 0.0260 (14) | 0.0157 (14) | 0.0035 (13) | −0.0010 (13) |
N2 | 0.0551 (18) | 0.0498 (17) | 0.0235 (13) | 0.0156 (15) | −0.0031 (12) | −0.0018 (12) |
O1 | 0.0528 (15) | 0.0567 (15) | 0.0297 (12) | 0.0238 (12) | 0.0019 (11) | 0.0013 (11) |
O2 | 0.067 (2) | 0.075 (2) | 0.0520 (18) | 0.0257 (17) | −0.0014 (15) | −0.0071 (15) |
Cl1 | 0.0683 (7) | 0.0699 (7) | 0.0466 (6) | 0.0244 (6) | −0.0021 (5) | −0.0032 (5) |
O11 | 0.071 (2) | 0.072 (2) | 0.0489 (17) | 0.0274 (17) | 0.0021 (15) | 0.0000 (15) |
O12 | 0.070 (2) | 0.073 (2) | 0.0476 (17) | 0.0220 (17) | −0.0018 (15) | −0.0047 (14) |
O13 | 0.071 (2) | 0.072 (2) | 0.0489 (17) | 0.0274 (17) | 0.0021 (14) | −0.0001 (16) |
O14 | 0.072 (2) | 0.071 (2) | 0.0502 (17) | 0.0241 (17) | −0.0019 (15) | −0.0015 (15) |
O4 | 0.084 (5) | 0.061 (4) | 0.049 (4) | 0.010 (3) | 0.002 (3) | −0.001 (3) |
O3 | 0.085 (2) | 0.085 (2) | 0.049 (2) | 0.010 (3) | 0.0013 (16) | −0.0013 (16) |
Geometric parameters (Å, º) top
Ni1—O1i | 1.837 (3) | C14—H14A | 0.9600 |
Ni1—N2 | 1.874 (3) | C14—H14B | 0.9600 |
Ni1—O1 | 1.899 (3) | C14—H14C | 0.9600 |
Ni1—N1 | 1.901 (3) | C15—C20 | 1.343 (7) |
Ni1—O2 | 2.347 (4) | C15—C16 | 1.404 (6) |
Ni1—Ni1i | 2.8905 (12) | C16—C17 | 1.464 (6) |
C1—C6 | 1.374 (5) | C16—H16A | 0.9300 |
C1—O1 | 1.382 (4) | C17—C18 | 1.352 (7) |
C1—C2 | 1.388 (5) | C17—H17A | 0.9300 |
C2—C10i | 1.392 (5) | C18—C19 | 1.386 (7) |
C2—C3 | 1.440 (5) | C18—H18A | 0.9300 |
C3—C4 | 1.315 (5) | C19—C20 | 1.323 (6) |
C3—H3A | 0.9300 | C19—H19A | 0.9300 |
C4—C5 | 1.445 (5) | C20—H20A | 0.9300 |
C4—C11 | 1.578 (5) | C21—C26 | 1.379 (6) |
C5—C6 | 1.421 (5) | C21—C22 | 1.441 (6) |
C5—H5A | 0.9300 | C22—C23 | 1.444 (6) |
C6—C7 | 1.502 (5) | C22—H22A | 0.9300 |
C7—N2 | 1.230 (5) | C23—C24 | 1.344 (7) |
C7—H7A | 0.9300 | C23—H23A | 0.9300 |
C8—C15 | 1.483 (5) | C24—C25 | 1.437 (7) |
C8—N2 | 1.541 (5) | C24—H24A | 0.9300 |
C8—C9 | 1.578 (5) | C25—C26 | 1.323 (6) |
C8—H8A | 0.9800 | C25—H25A | 0.9300 |
C9—N1 | 1.460 (5) | C26—H26A | 0.9300 |
C9—C21 | 1.488 (5) | C27—O2 | 1.339 (6) |
C9—H9A | 0.9800 | C27—C27i | 1.520 (10) |
C10—N1 | 1.364 (5) | C27—H27A | 0.9599 |
C10—C2i | 1.392 (5) | C27—H27B | 0.9600 |
C10—H10A | 0.9599 | O1—Ni1i | 1.837 (3) |
C11—C12 | 1.502 (6) | O2—H2A | 0.9700 |
C11—C14 | 1.509 (7) | Cl1—O11 | 1.304 (4) |
C11—C13 | 1.554 (7) | Cl1—O13 | 1.445 (4) |
C12—H12A | 0.9600 | Cl1—O12 | 1.503 (3) |
C12—H12B | 0.9600 | Cl1—O14 | 1.589 (4) |
C12—H12C | 0.9600 | O4—H4A | 0.8500 |
C13—H13A | 0.9600 | O4—H4C | 0.8501 |
C13—H13B | 0.9600 | O3—H3B | 0.8501 |
C13—H13C | 0.9600 | | |
| | | |
O1i—Ni1—N2 | 172.65 (13) | H13B—C13—H13C | 109.5 |
O1i—Ni1—O1 | 78.35 (12) | C11—C14—H14A | 109.5 |
N2—Ni1—O1 | 95.77 (12) | C11—C14—H14B | 109.5 |
O1i—Ni1—N1 | 96.12 (12) | H14A—C14—H14B | 109.5 |
N2—Ni1—N1 | 90.18 (13) | C11—C14—H14C | 109.5 |
O1—Ni1—N1 | 171.78 (14) | H14A—C14—H14C | 109.5 |
O1i—Ni1—O2 | 96.92 (13) | H14B—C14—H14C | 109.5 |
N2—Ni1—O2 | 87.26 (14) | C20—C15—C16 | 117.0 (4) |
O1—Ni1—O2 | 88.59 (12) | C20—C15—C8 | 125.7 (4) |
N1—Ni1—O2 | 86.02 (14) | C16—C15—C8 | 117.3 (4) |
O1i—Ni1—Ni1i | 40.09 (8) | C15—C16—C17 | 118.5 (5) |
N2—Ni1—Ni1i | 134.29 (10) | C15—C16—H16A | 120.8 |
O1—Ni1—Ni1i | 38.53 (8) | C17—C16—H16A | 120.8 |
N1—Ni1—Ni1i | 135.13 (10) | C18—C17—C16 | 118.2 (4) |
O2—Ni1—Ni1i | 89.93 (8) | C18—C17—H17A | 120.9 |
C6—C1—O1 | 119.1 (3) | C16—C17—H17A | 120.9 |
C6—C1—C2 | 124.3 (3) | C17—C18—C19 | 122.0 (4) |
O1—C1—C2 | 116.3 (3) | C17—C18—H18A | 119.0 |
C1—C2—C10i | 128.3 (3) | C19—C18—H18A | 119.0 |
C1—C2—C3 | 116.3 (3) | C20—C19—C18 | 117.4 (5) |
C10i—C2—C3 | 115.2 (3) | C20—C19—H19A | 121.3 |
C4—C3—C2 | 123.5 (3) | C18—C19—H19A | 121.3 |
C4—C3—H3A | 118.3 | C19—C20—C15 | 126.9 (5) |
C2—C3—H3A | 118.3 | C19—C20—H20A | 116.6 |
C3—C4—C5 | 117.7 (3) | C15—C20—H20A | 116.6 |
C3—C4—C11 | 122.3 (3) | C26—C21—C22 | 119.8 (4) |
C5—C4—C11 | 120.0 (3) | C26—C21—C9 | 119.6 (4) |
C6—C5—C4 | 121.9 (3) | C22—C21—C9 | 120.2 (4) |
C6—C5—H5A | 119.0 | C21—C22—C23 | 118.6 (4) |
C4—C5—H5A | 119.0 | C21—C22—H22A | 120.7 |
C1—C6—C5 | 115.9 (3) | C23—C22—H22A | 120.7 |
C1—C6—C7 | 127.2 (3) | C24—C23—C22 | 117.8 (5) |
C5—C6—C7 | 116.7 (3) | C24—C23—H23A | 121.1 |
N2—C7—C6 | 123.5 (3) | C22—C23—H23A | 121.1 |
N2—C7—H7A | 118.3 | C23—C24—C25 | 122.2 (4) |
C6—C7—H7A | 118.3 | C23—C24—H24A | 118.9 |
C15—C8—N2 | 113.2 (3) | C25—C24—H24A | 118.9 |
C15—C8—C9 | 112.4 (3) | C26—C25—C24 | 120.2 (4) |
N2—C8—C9 | 107.4 (3) | C26—C25—H25A | 119.9 |
C15—C8—H8A | 107.9 | C24—C25—H25A | 119.9 |
N2—C8—H8A | 107.9 | C25—C26—C21 | 121.2 (5) |
C9—C8—H8A | 107.9 | C25—C26—H26A | 119.4 |
N1—C9—C21 | 117.4 (3) | C21—C26—H26A | 119.4 |
N1—C9—C8 | 108.1 (3) | O2—C27—C27i | 100.0 (4) |
C21—C9—C8 | 109.9 (3) | O2—C27—H27A | 110.4 |
N1—C9—H9A | 107.0 | C27i—C27—H27A | 101.1 |
C21—C9—H9A | 107.0 | O2—C27—H27B | 111.2 |
C8—C9—H9A | 107.0 | C27i—C27—H27B | 123.8 |
N1—C10—C2i | 127.1 (3) | H27A—C27—H27B | 109.5 |
N1—C10—H10A | 109.2 | C10—N1—C9 | 127.6 (3) |
C2i—C10—H10A | 123.7 | C10—N1—Ni1 | 120.6 (2) |
C12—C11—C14 | 113.5 (4) | C9—N1—Ni1 | 111.6 (2) |
C12—C11—C13 | 109.0 (4) | C7—N2—C8 | 123.1 (3) |
C14—C11—C13 | 107.3 (4) | C7—N2—Ni1 | 127.4 (3) |
C12—C11—C4 | 111.2 (3) | C8—N2—Ni1 | 109.2 (2) |
C14—C11—C4 | 111.3 (3) | C1—O1—Ni1i | 131.4 (2) |
C13—C11—C4 | 103.9 (3) | C1—O1—Ni1 | 126.5 (2) |
C11—C12—H12A | 109.5 | Ni1i—O1—Ni1 | 101.38 (12) |
C11—C12—H12B | 109.5 | C27—O2—Ni1 | 126.5 (3) |
H12A—C12—H12B | 109.5 | C27—O2—H2A | 107.0 |
C11—C12—H12C | 109.5 | Ni1—O2—H2A | 105.8 |
H12A—C12—H12C | 109.5 | O11—Cl1—O13 | 110.0 (2) |
H12B—C12—H12C | 109.5 | O11—Cl1—O12 | 100.5 (2) |
C11—C13—H13A | 109.5 | O13—Cl1—O12 | 115.4 (2) |
C11—C13—H13B | 109.5 | O11—Cl1—O14 | 120.2 (2) |
H13A—C13—H13B | 109.5 | O13—Cl1—O14 | 106.9 (2) |
C11—C13—H13C | 109.5 | O12—Cl1—O14 | 104.07 (19) |
H13A—C13—H13C | 109.5 | H4A—O4—H4C | 109.5 |
Symmetry code: (i) y, x, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O14 | 0.97 | 1.82 | 2.744 (5) | 159 |
O2—H2A···Cl1 | 0.97 | 2.91 | 3.608 (4) | 130 |
O3—H3B···O4 | 0.85 | 2.37 | 3.104 (8) | 144 |
O4—H4C···O14ii | 0.85 | 2.17 | 2.898 (7) | 144 |
O4—H4C···O12ii | 0.85 | 2.41 | 2.956 (8) | 123 |
O4—H4C···Cl1ii | 0.85 | 2.86 | 3.608 (7) | 147 |
Symmetry code: (ii) y+1, x, −z. |
Experimental details
Crystal data |
Chemical formula | [Ni2(C52H50N4O2)(C2H6O2)](ClO4)2·2H2O |
Mr | 1177.38 |
Crystal system, space group | Tetragonal, P41212 |
Temperature (K) | 293 |
a, c (Å) | 11.536 (3), 43.015 (3) |
V (Å3) | 5724 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.35 × 0.29 × 0.27 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (XPREP; Bruker, 2000) |
Tmin, Tmax | 0.750, 0.799 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8048, 5296, 4763 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.159, 1.09 |
No. of reflections | 5296 |
No. of parameters | 348 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.58 |
Absolute structure | Flack (1983), 2037 Friedel pairs |
Absolute structure parameter | 0.02 (2) |
Selected geometric parameters (Å, º) topNi1—O1i | 1.837 (3) | Ni1—N1 | 1.901 (3) |
Ni1—N2 | 1.874 (3) | Ni1—O2 | 2.347 (4) |
Ni1—O1 | 1.899 (3) | Ni1—Ni1i | 2.8905 (12) |
| | | |
O1i—Ni1—N2 | 172.65 (13) | O1—Ni1—O2 | 88.59 (12) |
O1i—Ni1—O1 | 78.35 (12) | N1—Ni1—O2 | 86.02 (14) |
N2—Ni1—O1 | 95.77 (12) | O1i—Ni1—Ni1i | 40.09 (8) |
O1i—Ni1—N1 | 96.12 (12) | N2—Ni1—Ni1i | 134.29 (10) |
N2—Ni1—N1 | 90.18 (13) | O1—Ni1—Ni1i | 38.53 (8) |
O1—Ni1—N1 | 171.78 (14) | N1—Ni1—Ni1i | 135.13 (10) |
O1i—Ni1—O2 | 96.92 (13) | O2—Ni1—Ni1i | 89.93 (8) |
N2—Ni1—O2 | 87.26 (14) | | |
Symmetry code: (i) y, x, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O14 | 0.97 | 1.82 | 2.744 (5) | 159 |
O3—H3B···O4 | 0.85 | 2.37 | 3.104 (8) | 144 |
O4—H4C···O14ii | 0.85 | 2.17 | 2.898 (7) | 144 |
O4—H4C···O12ii | 0.85 | 2.41 | 2.956 (8) | 123 |
Symmetry code: (ii) y+1, x, −z. |
It is well known that dinuclear cores exist at the active sites of many metalloenzymes and play an essential role in biological systems (Furuta et al., 1999; Arimura et al., 2001). The two caves of the Robson macrocyclic Schiff base ligand, RobsonH2, can accomodate two metal ions, forming a planar complex [Tandon, 1992; RobsonH2 = 10,21-di-tert-butyl-4,5,15,16-tetraphenyl-3,6,14,17- tetraazatricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12 (24),13,17,19,21- decaene-23,24-diol]. In the present study, the chiral RobsonH2 ligand was derived from the condensation of 2,6-diformyl-o-methylphenol and 1(S),2(S)-diphenyl-1,2-diaminoethane in the presence of NaOH, and the title dinuclear NiII compound, (I), was synthesized in order to investigate its biochemical effect. In this paper, the crystal structure of (I) is reported.
The two Ni atoms are bridged by O1 and O1i atoms, forminga parallelogram (Fig. 1 and Table 1). There are also four N atoms from the ligand coordinated to the two Ni atoms in a macrocyclic plane. In the plane above, two O atoms from a glycol molecule coordinate to two Ni atoms in the axial directions. The coordination geometry around each Ni atom is square pyramidal. In the basal planes of the square pyramids, two Ni atoms are exposed. This may be the catalyze active site of the complex. There are O—H···O intermolecular hydrogen bonds (Fig. 2 and Table 2).