A binuclear unsymmetrical compartmental Ni^II complex: [μ-11,24-dimethyl-16,19-dioxa-3,7,15,20-tetra­aza­tricyclo[20.3.1.1^9,13]hepta­cosa-1(25),2,7,9,11,13(27),14,20,22(26),23-deca­ene-26,27-diolato]bis­[diaqua­nickel(II)] bis(per­chlorate) tetra­hydrate

In the title compound, [Ni₂(C₂₃H₂₄N₄O₄)(H₂O)₄](ClO₄)₂·4H₂O, each Ni^II atom is coordinated by two bridging phenoxide O atoms, two azomethine N atoms and two water mol­ecules in a slightly distorted octa­hedral geometry. The crystal packing is stabilized by inter­molecular O—H...O hydrogen bonds mediated through the water mol­ecules and perchlorate anions. The bis­(amino­oxy)ethane and diamino­propane groups are disordered across the centre of the mol­ecule, and as a result the complex mol­ecule and the crystal structure is centrosymmetric.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.034
• wR factor = 0.113
• Data-to-parameter ratio = 24.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.93
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT301_ALERT_3_C Main Residue  Disorder .........................      16.00 Perc.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C9
PLAT731_ALERT_1_C Bond    Calc   0.837(17), Rep    0.838(8) ......       2.12 su-Ra
              O1   -H1B     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.839(10) ......       3.00 su-Ra
              O4   -H4A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.83(3), Rep   0.831(10) ......       3.00 su-Ra
              O4   -H4B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc   0.837(17), Rep    0.838(8) ......       2.12 su-Ra
              O1   -H1B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.839(10) ......       3.00 su-Ra
              O4   -H4A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(3), Rep   0.831(10) ......       3.00 su-Ra
              O4   -H4B     1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      16.40 Deg.
              O5   -N1   -C12     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      14.20 Deg.
              O6   -N2   -C10     1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl O4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.931
            Tmax scaled      0.768 Tmin scaled      0.681
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           37.33
           From the CIF: _reflns_number_total               7176
           From the CIF: _diffrn_reflns_limit_ max hkl   12.   15.   17.
           From the CIF: _diffrn_reflns_limit_ min hkl   -9.  -15.  -18.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   12.   17.   20.
           Calculated minimum hkl  -12.  -17.  -20.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         25

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  15 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

  10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Dinuclear metal complexes of diphenolic Schiff base macrocyclic ligands have attracted much attention as they have contributed significantly to the understanding of the relationship between chemical behaviour and structural properties (Hong et al., 2005). Complexes of ligands which contain two or more metal ions in close proximity are important as potential catalysts (Mckenzie & Robson, 1988), models of reaction centers for metalloenzymes (Tsou et al., 1982) and non-linear optical materials (Lacroix et al., 2001). Stability of the complexes depend upon the cavity size of the ligand and the radius of the metal ion. In continuation of our earlier studies (Krishnapriya & Kandaswamy, 2005) we report here the crystal structure of a dinuclear Ni^II complex with a ligand containing two compartments with different compartmental sizes, in which one of the compartments has 1,3-diamino propane and the another compartment has 1,2-bis(aminooxy)ethane.

The coordination geometry at each Ni^II ion is distorted octahedral (Fig. 1), in which the equatorial plane is formed by two bridging phenoxide O atoms and two azomethine N atoms while the axial coordination sites are occupied by two water molecules. The trans angles at the Ni^II centres are close to 180°, ranging from 170.78 (5) to 173.88 (4)°. All other angles subtended at the Ni^II centres are close to 90°, ranging from 81.64 (4) to 99.47 (5), which indicates a slightly distorted octahedral geometry of Ni^II atoms. The Ni—N and Ni—O bond lengths lie in the range 1.9984 (13)–2.0263 (13) Å and 2.0122 (10)–2.1604 (11) Å, respectively, and the bond lengths are comparable to those observed in a related structure (Black et al., 1998). The two benzene rings in the molecule are parallel to each other, within the limits of standard deviations.

The crystal packing is stabilized by intermolecular O—H···O hydrogen bonding involving the water molecules and perchlorate anions. The inversion disorder of bis-aminooxy ethane and diamino propane groups shows an apparent centrosymmetry in the crystal structure.

Related literature

For synthesis, see: Dixon & Weiss (1984); Verani et al. (2000). For general background on dinuclear metal complexes, see: Hong et al. (2005); Krishnapriya & Kandaswamy (2005); Lacroix (2001); Mckenzie & Robson (1988); Tsou et al. (1982). For a related structure, see: Black et al. (1998).

S2. Experimental

To a vigorously stirred suspension of N,N'-propylene-bis(3-formyl-5-methyl-salicylaldimino)nickel(II) (Verani et al., 2000) (1.0 g, 2.36 mmol) in methanol (25 ml), a methanolic solution (10 ml) of Ni(ClO₄)₂.6H₂O (0.86 g, 2.36 mmol) was added slowly and the mixture was stirred for 15 min to obtain a clear solution. Then a methanolic solution (5 ml) of 1,2-bis(aminooxy)ethane (Dixon & Weiss, 1984) (0.10 g, 2.36 mmol) was added dropwise to the above solution. The resulting solution was refluxed for 3 h. A pale green coloured solid was separated on evaporating the solution at 398 K and the compound was washed with ether and dried. Green crystals suitable for X-ray analysis were obtained after several days by slow evaporation of a acetonitrile solution (yield 69%).

S3. Refinement

Eventhough there is only one molecule in the unit cell and molecule does not possess center of symmetry, a near perfect inversion disorder makes it possible for structure to be solved in the centrosymmetric space group P1. Physically, it may be interpreted as, 50% of the unit cells are inversion of the other 50%. Hence, strictly speaking, the space group of the unit cell is P1. The structure could be solved and refined to the same R-factor in P1 space group with appropriate disorder on either side of the molecule. However, The shift/e.s.d. parameters were oscillating rather than converging. Therefore, it was decided to adopt the P1 space group for solving and refining the structure, with the bis-aminooxy ethane and diamino propane groups disordered across the inversion center. As electron densities of these groups may overlap at many places, the unrestrained refinement will lead to abnormal geometries. Therefore the following restraints on distances were applied to atoms of the disordered groups: N—O = 1.450 (1) Å, N—C = 1.470 (1) Å, C—C = 1.530 (1) Å and O—C = 1.470 (1) Å. Water H atoms were located in a difference map and refined isotropically, with O—H and H···H distance restraints of 0.85 (1) and 1.38 (1) Å, respectively. Further Ni···H distances were fixed at 2.6Å for H atoms of coordinated water molecules. All the hydrogen atoms except the ones at disordered sites were located in difference maps. They were relocated in idealized positions (C—H = 0.93–0.97 Å) and refined as riding with U_iso(H) = 1.2–1.5 U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The unit-cell contents of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Only one disorder component is shown. Symmetry code (i): -x, -y, -z
	Fig. 2. The crystal packing of the title compound, viewed down the a axis. C-bound H atoms have been omitted for clarity. Both disorder components are shown.

[µ-11,24-dimethyl-16,19-dioxa-3,7,15,20- tetraazatricyclo[20.3.1.1^9,13]heptacosa- 1(25),2,7,9,11,13 (27),14,20,22 (26),23-decaene-26,27- diolato]bis[diaquanickel(II)] bis(perchlorate) tetrahydrate

Crystal data

[Ni2(C23H24N4O4)(H2O)4](ClO4)2·4H2O	Z = 1
Mr = 880.91	F(000) = 456
Triclinic, P1	Dx = 1.674 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5227 (3) Å	Cell parameters from 7997 reflections
b = 10.3081 (3) Å	θ = 2.2–33.5°
c = 12.2764 (5) Å	µ = 1.32 mm^−1
α = 107.167 (2)°	T = 293 K
β = 94.932 (2)°	Block, green
γ = 103.092 (2)°	0.30 × 0.20 × 0.20 mm
V = 873.89 (6) Å^3

Data collection

Bruker Kappa-APEXII area-detector diffractometer	7176 independent reflections
Radiation source: fine-focus sealed tube	5831 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω and φ scans	θmax = 37.3°, θmin = 1.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −9→12
Tmin = 0.732, Tmax = 0.825	k = −15→15
24651 measured reflections	l = −18→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 0.1283P] where P = (Fo^2 + 2Fc^2)/3
7176 reflections	(Δ/σ)max = 0.001
295 parameters	Δρmax = 0.59 e Å^−3
25 restraints	Δρmin = −0.36 e Å^−3

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)
C1	0.0971 (2)	0.15878 (19)	−0.23328 (13)	0.0444 (3)
H1	0.1215	0.1875	−0.2968	0.053*
C2	0.13711 (19)	0.27002 (16)	−0.12198 (13)	0.0371 (3)
C3	0.2263 (2)	0.40586 (18)	−0.12170 (15)	0.0428 (3)
H3	0.2584	0.4173	−0.1904	0.051*
C4	0.26796 (19)	0.52242 (17)	−0.02416 (16)	0.0433 (3)
C5	0.2108 (2)	0.50310 (16)	0.07479 (15)	0.0414 (3)
H5	0.2314	0.5814	0.1406	0.050*
C6	0.12309 (18)	0.37082 (15)	0.08068 (12)	0.0353 (3)
C7	0.08787 (16)	0.24933 (14)	−0.01828 (12)	0.0322 (2)
C8	0.0622 (2)	0.37031 (16)	0.18958 (13)	0.0412 (3)
H8	0.0627	0.4570	0.2414	0.049*
C9	0.3681 (3)	0.66680 (19)	−0.0250 (2)	0.0554 (4)
H9C	0.3963	0.6606	−0.1009	0.083*
H9B	0.4809	0.7017	0.0297	0.083*
H9A	0.2908	0.7297	−0.0044	0.083*
N1	−0.00792 (18)	−0.26233 (14)	−0.22116 (10)	0.0388 (2)
N2	0.03246 (19)	0.02623 (15)	−0.25431 (10)	0.0415 (3)
O5	0.0838 (8)	−0.2869 (9)	−0.3212 (5)	0.0556 (13)	0.50
O6	0.0362 (10)	−0.0402 (6)	−0.3736 (5)	0.0577 (14)	0.50
C13	−0.0346 (6)	−0.2933 (5)	−0.4219 (3)	0.0556 (9)	0.50
H13A	−0.1384	−0.3761	−0.4412	0.067*	0.50
H13B	0.0337	−0.3050	−0.4861	0.067*	0.50
C14	−0.1078 (7)	−0.1681 (5)	−0.4099 (4)	0.0531 (10)	0.50
H14B	−0.1774	−0.1781	−0.4835	0.064*	0.50
H14A	−0.1918	−0.1638	−0.3540	0.064*	0.50
C10	−0.0080 (15)	−0.0655 (8)	−0.3768 (6)	0.0563 (18)	0.50
H10B	0.1043	−0.0476	−0.4095	0.068*	0.50
H10A	−0.0988	−0.0351	−0.4173	0.068*	0.50
C11	−0.0782 (7)	−0.2234 (5)	−0.4048 (4)	0.0521 (10)	0.50
H11C	−0.0815	−0.2676	−0.4868	0.063*	0.50
H11D	−0.2044	−0.2444	−0.3901	0.063*	0.50
C12	0.0324 (12)	−0.2907 (11)	−0.3390 (6)	0.0520 (16)	0.50
H12B	0.0008	−0.3916	−0.3779	0.062*	0.50
H12A	0.1635	−0.2531	−0.3369	0.062*	0.50
O1	0.29581 (15)	−0.01748 (13)	−0.08643 (10)	0.0431 (2)
O2	0.00840 (13)	0.12288 (10)	−0.01495 (8)	0.03364 (18)
O3	−0.29405 (15)	−0.11087 (13)	−0.15299 (10)	0.0420 (2)
O4	−0.5126 (3)	−0.3673 (2)	−0.30007 (17)	0.0826 (5)
O7	0.6566 (5)	0.3989 (3)	−0.4449 (3)	0.1479 (12)
O8	0.5456 (5)	0.1699 (4)	−0.5264 (3)	0.1534 (14)
O9	0.4749 (5)	0.2772 (5)	−0.3522 (3)	0.1690 (15)
O10	0.7589 (4)	0.2542 (3)	−0.3600 (2)	0.1299 (10)
O11	−0.4866 (3)	0.03465 (19)	−0.25509 (14)	0.0650 (4)
Cl1	0.60736 (8)	0.27329 (6)	−0.42118 (4)	0.06240 (13)
Ni1	0.00424 (2)	−0.064272 (18)	−0.128772 (13)	0.03218 (6)
H1A	0.3359 (15)	0.028 (2)	−0.0145 (8)	0.073 (8)*
H1B	0.3590 (14)	0.023 (2)	−0.1257 (13)	0.054 (6)*
H3B	−0.3473 (15)	−0.1940 (11)	−0.191 (2)	0.077 (8)*
H3A	−0.3323 (15)	−0.0541 (17)	−0.180 (2)	0.076 (8)*
H11A	−0.518 (5)	−0.030 (2)	−0.3197 (15)	0.110 (13)*
H11B	−0.443 (4)	0.1130 (16)	−0.266 (2)	0.099 (11)*
H4A	−0.498 (6)	−0.449 (2)	−0.318 (3)	0.150 (18)*
H4B	−0.589 (4)	−0.357 (3)	−0.348 (2)	0.101 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0518 (8)	0.0572 (9)	0.0346 (7)	0.0199 (7)	0.0128 (6)	0.0246 (7)
C2	0.0355 (6)	0.0454 (7)	0.0374 (7)	0.0126 (5)	0.0087 (5)	0.0214 (6)
C3	0.0399 (6)	0.0514 (8)	0.0477 (8)	0.0141 (6)	0.0125 (6)	0.0289 (7)
C4	0.0343 (6)	0.0448 (7)	0.0575 (9)	0.0094 (5)	0.0066 (6)	0.0273 (7)
C5	0.0395 (6)	0.0382 (7)	0.0465 (8)	0.0091 (5)	0.0033 (6)	0.0156 (6)
C6	0.0337 (5)	0.0369 (6)	0.0374 (7)	0.0100 (5)	0.0048 (5)	0.0148 (5)
C7	0.0280 (5)	0.0388 (6)	0.0345 (6)	0.0112 (4)	0.0062 (4)	0.0166 (5)
C8	0.0490 (7)	0.0376 (7)	0.0364 (7)	0.0133 (6)	0.0086 (6)	0.0092 (5)
C9	0.0479 (8)	0.0468 (9)	0.0750 (13)	0.0043 (7)	0.0080 (8)	0.0318 (9)
N1	0.0432 (6)	0.0421 (6)	0.0316 (5)	0.0131 (5)	0.0116 (4)	0.0099 (5)
N2	0.0469 (6)	0.0548 (7)	0.0274 (5)	0.0161 (5)	0.0096 (4)	0.0175 (5)
O5	0.066 (3)	0.066 (2)	0.040 (2)	0.022 (2)	0.0271 (19)	0.0164 (18)
O6	0.081 (4)	0.055 (2)	0.0329 (16)	0.005 (2)	0.0250 (17)	0.0149 (14)
C13	0.069 (2)	0.054 (2)	0.0342 (18)	0.0033 (18)	0.0128 (15)	0.0085 (16)
C14	0.054 (2)	0.069 (3)	0.0304 (16)	0.009 (2)	0.0015 (13)	0.014 (2)
C10	0.074 (5)	0.067 (4)	0.030 (2)	0.009 (3)	0.013 (2)	0.027 (2)
C11	0.070 (3)	0.054 (3)	0.0280 (16)	0.014 (2)	0.0050 (15)	0.0098 (19)
C12	0.073 (5)	0.047 (2)	0.037 (3)	0.017 (3)	0.027 (3)	0.0095 (19)
O1	0.0356 (4)	0.0546 (6)	0.0416 (6)	0.0117 (4)	0.0110 (4)	0.0180 (5)
O2	0.0370 (4)	0.0354 (4)	0.0302 (4)	0.0085 (3)	0.0089 (3)	0.0130 (4)
O3	0.0366 (5)	0.0490 (6)	0.0403 (6)	0.0107 (4)	0.0044 (4)	0.0152 (5)
O4	0.0912 (13)	0.0749 (12)	0.0683 (11)	0.0135 (10)	−0.0104 (9)	0.0165 (9)
O7	0.179 (3)	0.0998 (18)	0.171 (3)	0.0049 (18)	−0.002 (2)	0.084 (2)
O8	0.171 (3)	0.138 (2)	0.0934 (18)	0.050 (2)	−0.0225 (18)	−0.0410 (17)
O9	0.139 (3)	0.268 (5)	0.126 (2)	0.066 (3)	0.080 (2)	0.076 (3)
O10	0.138 (2)	0.145 (2)	0.1073 (18)	0.0674 (19)	−0.0220 (16)	0.0308 (17)
O11	0.0833 (10)	0.0713 (10)	0.0509 (8)	0.0242 (8)	0.0179 (7)	0.0304 (8)
Cl1	0.0776 (3)	0.0597 (3)	0.0468 (2)	0.0139 (2)	0.0083 (2)	0.0164 (2)
Ni1	0.03454 (9)	0.03765 (10)	0.02645 (9)	0.00998 (6)	0.00817 (6)	0.01227 (7)

Geometric parameters (Å, º)

C1—N2	1.280 (2)	C13—H13A	0.97
C1—C2	1.456 (2)	C13—H13B	0.97
C1—H1	0.93	C14—H14B	0.97
C2—C3	1.408 (2)	C14—H14A	0.97
C2—C7	1.4174 (18)	C10—C11	1.515 (7)
C3—C4	1.375 (3)	C10—H10B	0.97
C3—H3	0.93	C10—H10A	0.97
C4—C5	1.376 (2)	C11—C12	1.518 (8)
C4—C9	1.512 (2)	C11—H11C	0.97
C5—C6	1.400 (2)	C11—H11D	0.97
C5—H5	0.93	C12—H12B	0.97
C6—C7	1.418 (2)	C12—H12A	0.97
C6—C8	1.451 (2)	O1—Ni1	2.1191 (11)
C7—O2	1.3193 (16)	O1—H1A	0.858 (9)
C8—N1^i	1.277 (2)	O1—H1B	0.838 (8)
C8—H8	0.93	O2—Ni1	2.0122 (10)
C9—H9C	0.96	O2—Ni1^i	2.0297 (10)
C9—H9B	0.96	O3—Ni1	2.1604 (11)
C9—H9A	0.96	O3—H3B	0.831 (9)
N1—C8^i	1.277 (2)	O3—H3A	0.846 (9)
N1—O5	1.445 (5)	O4—H4A	0.839 (10)
N1—C12	1.461 (7)	O4—H4B	0.831 (10)
N1—Ni1	1.9984 (13)	O7—Cl1	1.386 (2)
N2—O6	1.427 (5)	O8—Cl1	1.371 (2)
N2—C10	1.483 (7)	O9—Cl1	1.362 (3)
N2—Ni1	2.0263 (13)	O10—Cl1	1.394 (3)
O5—C13	1.437 (6)	O11—H11A	0.846 (10)
O6—C14	1.426 (6)	O11—H11B	0.856 (10)
C13—C14	1.488 (6)	Ni1—O2^i	2.0297 (10)
N2—C1—C2	127.86 (13)	O6—C14—H14A	109.2
N2—C1—H1	116.1	C13—C14—H14A	109.2
C2—C1—H1	116.1	H14B—C14—H14A	107.9
C3—C2—C7	119.81 (14)	N2—C10—C11	119.2 (5)
C3—C2—C1	115.97 (13)	N2—C10—H10B	107.5
C7—C2—C1	124.19 (13)	C11—C10—H10B	107.5
C4—C3—C2	122.83 (14)	N2—C10—H10A	107.5
C4—C3—H3	118.6	C11—C10—H10A	107.5
C2—C3—H3	118.6	H10B—C10—H10A	107.0
C3—C4—C5	117.12 (14)	C10—C11—C12	116.2 (7)
C3—C4—C9	121.99 (16)	C10—C11—H11C	108.2
C5—C4—C9	120.87 (16)	C12—C11—H11C	108.2
C4—C5—C6	122.87 (15)	C10—C11—H11D	108.2
C4—C5—H5	118.6	C12—C11—H11D	108.2
C6—C5—H5	118.6	H11C—C11—H11D	107.4
C5—C6—C7	120.13 (13)	N1—C12—C11	109.9 (5)
C5—C6—C8	115.70 (14)	N1—C12—H12B	109.7
C7—C6—C8	124.03 (13)	C11—C12—H12B	109.7
O2—C7—C2	121.32 (12)	N1—C12—H12A	109.7
O2—C7—C6	121.57 (12)	C11—C12—H12A	109.7
C2—C7—C6	117.08 (12)	H12B—C12—H12A	108.2
N1^i—C8—C6	126.29 (14)	Ni1—O1—H1A	112.7 (9)
N1^i—C8—H8	116.9	Ni1—O1—H1B	117.1 (9)
C6—C8—H8	116.9	H1A—O1—H1B	108.8 (12)
C4—C9—H9C	109.5	C7—O2—Ni1	127.60 (8)
C4—C9—H9B	109.5	C7—O2—Ni1^i	126.25 (9)
H9C—C9—H9B	109.5	Ni1—O2—Ni1^i	98.36 (4)
C4—C9—H9A	109.5	Ni1—O3—H3B	113.9 (9)
H9C—C9—H9A	109.5	Ni1—O3—H3A	111.3 (9)
H9B—C9—H9A	109.5	H3B—O3—H3A	111.6 (13)
C8^i—N1—O5	114.5 (3)	H4A—O4—H4B	113.0 (17)
C8^i—N1—C12	115.8 (4)	H11A—O11—H11B	108.9 (16)
O5—N1—C12	16.4 (5)	O9—Cl1—O8	112.2 (3)
C8^i—N1—Ni1	125.50 (10)	O9—Cl1—O7	110.1 (3)
O5—N1—Ni1	118.8 (3)	O8—Cl1—O7	105.8 (2)
C12—N1—Ni1	118.5 (4)	O9—Cl1—O10	106.5 (2)
C1—N2—O6	106.9 (3)	O8—Cl1—O10	112.06 (19)
C1—N2—C10	117.7 (3)	O7—Cl1—O10	110.2 (2)
O6—N2—C10	14.2 (5)	N1—Ni1—O2	170.85 (4)
C1—N2—Ni1	123.23 (11)	N1—Ni1—N2	99.47 (5)
O6—N2—Ni1	127.8 (3)	O2—Ni1—N2	89.65 (5)
C10—N2—Ni1	118.9 (3)	N1—Ni1—O2^i	89.29 (5)
C13—O5—N1	111.0 (4)	O2—Ni1—O2^i	81.64 (4)
C14—O6—N2	106.3 (4)	N2—Ni1—O2^i	170.78 (5)
O5—C13—C14	114.9 (4)	N1—Ni1—O1	90.78 (5)
O5—C13—H13A	108.5	O2—Ni1—O1	89.95 (4)
C14—C13—H13A	108.5	N2—Ni1—O1	90.20 (5)
O5—C13—H13B	108.5	O2^i—Ni1—O1	86.79 (4)
C14—C13—H13B	108.5	N1—Ni1—O3	91.14 (5)
H13A—C13—H13B	107.5	O2—Ni1—O3	87.24 (4)
O6—C14—C13	112.1 (5)	N2—Ni1—O3	95.21 (5)
O6—C14—H14B	109.2	O2^i—Ni1—O3	87.43 (4)
C13—C14—H14B	109.2	O1—Ni1—O3	173.88 (4)
N2—C1—C2—C3	173.41 (16)	Ni1—N1—C12—C11	−49.5 (8)
N2—C1—C2—C7	−8.3 (3)	C10—C11—C12—N1	76.3 (8)
C7—C2—C3—C4	−0.5 (2)	C2—C7—O2—Ni1	18.74 (17)
C1—C2—C3—C4	177.90 (14)	C6—C7—O2—Ni1	−163.04 (9)
C2—C3—C4—C5	−3.0 (2)	C2—C7—O2—Ni1^i	161.14 (9)
C2—C3—C4—C9	178.42 (15)	C6—C7—O2—Ni1^i	−20.64 (17)
C3—C4—C5—C6	3.5 (2)	C8^i—N1—Ni1—N2	−165.19 (14)
C9—C4—C5—C6	−177.85 (15)	O5—N1—Ni1—N2	27.8 (3)
C4—C5—C6—C7	−0.6 (2)	C12—N1—Ni1—N2	9.1 (4)
C4—C5—C6—C8	−176.51 (14)	C8^i—N1—Ni1—O2^i	17.70 (14)
C3—C2—C7—O2	−178.27 (13)	O5—N1—Ni1—O2^i	−149.3 (3)
C1—C2—C7—O2	3.5 (2)	C12—N1—Ni1—O2^i	−168.0 (4)
C3—C2—C7—C6	3.43 (19)	C8^i—N1—Ni1—O1	104.47 (14)
C1—C2—C7—C6	−174.83 (13)	O5—N1—Ni1—O1	−62.5 (3)
C5—C6—C7—O2	178.79 (12)	C12—N1—Ni1—O1	−81.2 (4)
C8—C6—C7—O2	−5.7 (2)	C8^i—N1—Ni1—O3	−69.72 (14)
C5—C6—C7—C2	−2.92 (19)	O5—N1—Ni1—O3	123.3 (3)
C8—C6—C7—C2	172.64 (13)	C12—N1—Ni1—O3	104.6 (4)
C5—C6—C8—N1^i	−167.56 (16)	C7—O2—Ni1—N2	−26.78 (11)
C7—C6—C8—N1^i	16.7 (2)	Ni1^i—O2—Ni1—N2	−176.96 (5)
C2—C1—N2—O6	−173.9 (4)	C7—O2—Ni1—O2^i	150.18 (13)
C2—C1—N2—C10	176.1 (5)	Ni1^i—O2—Ni1—O2^i	0.0
C2—C1—N2—Ni1	−9.3 (2)	C7—O2—Ni1—O1	63.42 (11)
C8^i—N1—O5—C13	105.4 (5)	Ni1^i—O2—Ni1—O1	−86.76 (4)
C12—N1—O5—C13	7 (2)	C7—O2—Ni1—O3	−122.01 (11)
Ni1—N1—O5—C13	−86.3 (6)	Ni1^i—O2—Ni1—O3	87.81 (4)
C1—N2—O6—C14	−152.8 (5)	C1—N2—Ni1—N1	−159.75 (13)
C10—N2—O6—C14	−12 (3)	O6—N2—Ni1—N1	1.5 (4)
Ni1—N2—O6—C14	43.5 (7)	C10—N2—Ni1—N1	14.8 (5)
N1—O5—C13—C14	55.4 (7)	C1—N2—Ni1—O2	21.03 (14)
N2—O6—C14—C13	−104.3 (5)	O6—N2—Ni1—O2	−177.7 (4)
O5—C13—C14—O6	54.2 (6)	C10—N2—Ni1—O2	−164.4 (5)
C1—N2—C10—C11	177.8 (6)	C1—N2—Ni1—O1	−68.92 (13)
O6—N2—C10—C11	135 (4)	O6—N2—Ni1—O1	92.3 (4)
Ni1—N2—C10—C11	3.0 (11)	C10—N2—Ni1—O1	105.6 (5)
N2—C10—C11—C12	−50.5 (11)	C1—N2—Ni1—O3	108.22 (13)
C8^i—N1—C12—C11	125.4 (5)	O6—N2—Ni1—O3	−90.5 (4)
O5—N1—C12—C11	−145 (3)	C10—N2—Ni1—O3	−77.2 (5)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3^i	0.86 (1)	2.06 (1)	2.8475 (15)	152 (1)
O1—H1B···O11^ii	0.84 (1)	2.06 (1)	2.8455 (19)	155 (2)
O3—H3B···O4	0.83 (1)	1.96 (1)	2.766 (2)	165 (2)
O3—H3A···O11	0.85 (1)	1.95 (1)	2.775 (2)	164 (1)
O11—H11A···O8^iii	0.85 (1)	1.97 (1)	2.806 (3)	170 (3)
O11—H11B···O9^iv	0.86 (1)	2.40 (2)	3.127 (5)	143 (3)
O11—H11B···O10^iv	0.86 (1)	2.46 (2)	3.229 (4)	150 (3)
O4—H4A···O7^v	0.84 (1)	2.43 (3)	3.137 (5)	142 (4)
O4—H4B···O7^iii	0.83 (1)	2.43 (2)	3.120 (4)	140 (3)

Symmetry codes: (i) −x, −y, −z; (ii) x+1, y, z; (iii) −x, −y, −z−1; (iv) x−1, y, z; (v) x−1, y−1, z.