[μ-10,21-Di-tert-butyl-4(S),5(S),15(S),16(S)-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-diolato](μ-ethyl­ene glycol)­dinickel(II) diperchlorate dihydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

S1. Comment

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 Ni^II 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).

S2. Experimental

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.

S3. Refinement

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.

Computing details

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.

Figures

	Fig. 1. A view of the molecular structure of (I), showing 50% displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of (I), viewed down the c axis. The dashed lines indicate the hydrogen bonds.

(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

Crystal data

[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) Å^3	Block, orange
Z = 4	0.35 × 0.29 × 0.27 mm
F(000) = 2456

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.105P)^2 + 1.99P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ni1—O1^i	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—Ni1^i	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—C10^i	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—C27^i	1.520 (10)
C10—N1	1.364 (5)	C27—H27A	0.9599
C10—C2^i	1.392 (5)	C27—H27B	0.9600
C10—H10A	0.9599	O1—Ni1^i	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
O1^i—Ni1—N2	172.65 (13)	H13B—C13—H13C	109.5
O1^i—Ni1—O1	78.35 (12)	C11—C14—H14A	109.5
N2—Ni1—O1	95.77 (12)	C11—C14—H14B	109.5
O1^i—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
O1^i—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)
O1^i—Ni1—Ni1^i	40.09 (8)	C15—C16—C17	118.5 (5)
N2—Ni1—Ni1^i	134.29 (10)	C15—C16—H16A	120.8
O1—Ni1—Ni1^i	38.53 (8)	C17—C16—H16A	120.8
N1—Ni1—Ni1^i	135.13 (10)	C18—C17—C16	118.2 (4)
O2—Ni1—Ni1^i	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—C10^i	128.3 (3)	C19—C18—H18A	119.0
C1—C2—C3	116.3 (3)	C20—C19—C18	117.4 (5)
C10^i—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—C27^i	100.0 (4)
C21—C9—C8	109.9 (3)	O2—C27—H27A	110.4
N1—C9—H9A	107.0	C27^i—C27—H27A	101.1
C21—C9—H9A	107.0	O2—C27—H27B	111.2
C8—C9—H9A	107.0	C27^i—C27—H27B	123.8
N1—C10—C2^i	127.1 (3)	H27A—C27—H27B	109.5
N1—C10—H10A	109.2	C10—N1—C9	127.6 (3)
C2^i—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—Ni1^i	131.4 (2)
C13—C11—C4	103.9 (3)	C1—O1—Ni1	126.5 (2)
C11—C12—H12A	109.5	Ni1^i—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)

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···O14^ii	0.85	2.17	2.898 (7)	144
O4—H4C···O12^ii	0.85	2.41	2.956 (8)	123
O4—H4C···Cl1^ii	0.85	2.86	3.608 (7)	147

Symmetry code: (ii) y+1, x, −z.