{[μ-Bis­(salicyl­idene)-1,3-propane­diaminato]­bis(N,N-di­methyl­form­amide)­nickel(II)}di­iodo­zinc(II)

In the crystal structure of the title mol­ecule, [NiZnI₂(C₁₇H₁₆N₂O₂)(C₃H₇NO)₂], Ni²⁺ and Zn²⁺ ions are bridged by the two phenolic O atoms of the N,N′-bis­(salicyl­idene)-2,2-di­methyl-1,3-propane­diaminate (salpd²⁻, C₁₇H₁₆N₂O₂²⁻) ligand. The Ni²⁺ ion has an irregular octahedral geometry involving two phenolic O and two iminic N atoms of the salpd²⁻ in the equatorial plane. The compound includes two DMF (di­methyl­form­amide) solvent mol­ecules coordinated to the Ni²⁺ ion at the apical position. The coordination around the Zn²⁺ ion is distorted tetrahedral, involving two bridging O atoms and two I atoms.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 10.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_213  Alert C Atom C19B    has ADP max/min Ratio ...........       3.60 prolate

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.66
         From the CIF: _reflns_number_total               3420
         Count of symmetry unique reflns         3416
         Completeness (_total/calc)            100.12%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         4
         Fraction of Friedel pairs measured     0.001
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Schiff base complexes are one of the most important stereochemical models in main group and transition metal coordination chemistry. Oxygen-bridged polynuclear complexes of the transition series are of interest because of their magnetic properties. These complexes may be homo- or heteronuclear. The ligand stereochemistry around the metal ions and the structure of the O-atom bridges influence the magnetic exchange interactions.

Mononuclear and polynuclear metal complexes based on Schiff base ligands have been the subject of considerable interest in our laboratory, e.g. [Zn(C₁₃H₉N₂O₃)₂] (Tatar, Ülkü & Atakol, 1999), [NiZnBr₂(C₁₇H₁₆N₂O₂)(C₃H₇NO)(CH₄O)] (Tatar, Atakol & Arıcı, 2002), [Co{Ni(C₁₇H₁₆N₂O₂)(NO₂)(C₃H₇NO)}₂] (Atakol et al., 1999), [{Zn₂ClN₃(C₁₇H₁₆N₂O₂)}₂] (Tatar, Ülkü et al., 2002).

In the present study, the synthesis and structure of a heterodinuclear nickel(II)–zinc(II) complex of a Schiff base ligand, [NiZnI₂(C₁₇H₁₆N₂O₂)(C₃H₇NO)₂], (I), is reported. ZnI₂ was added to the square-planar complex of N,N'-bis(salicylidene)-1,3-propanediamine and nickel(II) (Drew et al., 1985) to form a heterodinuclear complex. The structure includes one octahedron and one tetrahedron which share one edge. The coordination polyhedron around the Ni²⁺ ion is a distorted octahedron (Fig. 1). Two iminic N and two phenolic O atoms of the salpd^2- ligand constitute the basal plane of the octahedron, while the O atoms of the two DMF groups occupy apical positions and complete the sixfold coordination. The average Ni—O and Ni—N distances in the basal plane are 2.017 (5) and 2.020 (6) Å, while the Ni—O3 and Ni—O4 distances in the apical position are 2.124 (5) and 2.137 (5) Å, respectively. The Ni²⁺ ion is located 0.0177 (8) Å from the best coordination plane consisting of atoms O1, O2, N1 and N2. The dihedral angle between the Ni/O1/C1/C6/C7/N2 and Ni/O2/C17/C12/C11/N1 chelate rings is 2.58 (14)°. All the chelate rings around Ni except for one, are planar. The Ni/N2/C8/C9/C10/N1 ring is in a half-chair conformation, the C9 atom is located 0.70 (1) Å from the best plane defined by other five atoms.

The Zn²⁺ ion has a distorted tetrahedral coordination, which is common for terminal a zinc(II) ion in dimeric complexes. The I1—Zn—I2 and O1—Zn—O2 angles are 117.51 (3) and 80.19 (18)°, respectively. I1/Zn/I2 plane and the least-squares plane defined by the salpd^-2 ligand are almost perpendicular to one another; the dihedral angle is 85.42 (5)°. The bridging plane is not completely planar, the dihedral angle between the planes through atoms O1/Zn/O2 and O1/Ni/O2 is 8.95 (16)°. The Ni···Zn distance [3.0695 (11) Å] is long for a direct interaction. A comparison of the dihedral angle (ϕ) between the O—M1—O and O—M2—O bridging planes, where M indicatesa metal ion (Zn²⁺, Ni²⁺ or Cu²⁺), along with the related M—O distance ranges, O—M—O angle ranges and M—M distances, are given in Table 3 for the four oxygen-bridged dimeric complexes reported previously. From this table, the remarkable similarity of the five structures is obvious.

The title molecule as a whole is fairly planar except for the DMF groups, the I atoms and atom C9, with a dihedral angle of 3.57 (11)° between the planes through O1/C1—C8/N2 and O2/C10—C17/N1. The bond lengths and angles within the ligands show no unusual values. There is an intramolecular hydrogen bond given in Table 2. Fig. 2 gives a perspective view of the crystal packing.

S2. Experimental

N,N'-Bis(salicylidene)-1,3-propanediamine (0.565 g, 2 mmol) was dissolved in 50 ml hot EtOH. To this solution was added 10 ml 20% ammonia and a solution of NiCl₂·6H₂O (0.475 g, 2 mmol) in hot water (30 ml). The mixture was set aside for 2 h. The light-green complex which resulted was filtered off and dried in an oven at 423 K. This complex (0.338 g, 1 mmol) was dissolved in hot DMF (50 ml) with stirring. To this solution was added a solution of ZnI₂ (0.320 g, 1 mmol) in hot MeOH (10 ml). This resulting mixture was set aside for 5 d and light-blue crystals were filtered off and dried in air.

S3. Refinement

All non-H atoms were refined with anisotropic displacement parameters. The H atoms were positioned geometrically from the corresponding C atoms, with U_eq(H) = 1.2U_eq(C), and a riding model was used during the refinement process. One of the DMF groups has a disordered atom (C19), the atom with suffix A has occupancy 0.45. Two components of C19 were refined with anisotropic displacement parameters and their H atoms were positioned geometrically.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure and atomic numbering scheme of (I) (40% probability displacement ellipsoids) (Farrugia, 1997).
	Fig. 2. Packing diagram of complex (I) (Spek, 2000).

(I)

Crystal data

[ZnI2Ni(C17H16N2O2)(C3H7NO)2]	F(000) = 1568
Mr = 804.39	Dx = 1.822 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 15 reflections
a = 10.6018 (11) Å	θ = 10.4–12.1°
b = 15.3204 (15) Å	µ = 3.60 mm^−1
c = 18.2690 (17) Å	T = 295 K
β = 98.727 (12)°	Prism, light blue
V = 2933.0 (5) Å^3	0.4 × 0.4 × 0.3 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	3064 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 27.7°, θmin = 2.4°
ω/2θ scans	h = −13→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.270, Tmax = 0.340	l = −23→23
3420 measured reflections	3 standard reflections every 120 min
3420 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0505P)^2 + 4.1535P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max = 0.001
wR(F^2) = 0.086	Δρmax = 1.03 e Å^−3
S = 1.06	Δρmin = −0.51 e Å^−3
3420 reflections	Absolute structure: (Flack, 1983), 175 Friedel pairs
327 parameters	Absolute structure parameter: 0.00 (2)
2 restraints

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)
Ni	0.97854 (7)	0.59200 (5)	0.59778 (4)	0.04186 (18)
Zn	0.82479 (7)	0.68329 (5)	0.70505 (4)	0.04389 (17)
O1	1.0023 (4)	0.6440 (3)	0.7005 (3)	0.0453 (10)
O2	0.8061 (4)	0.6463 (3)	0.5997 (2)	0.0432 (9)
I2	0.69518 (6)	0.58517 (5)	0.77662 (3)	0.0850 (2)
I1	0.81354 (7)	0.84679 (3)	0.72695 (4)	0.0792 (2)
O3	0.9198 (5)	0.4711 (3)	0.6384 (3)	0.0577 (12)
C2	1.0960 (8)	0.6782 (5)	0.8224 (4)	0.0594 (19)
H2	1.0195	0.7022	0.8317	0.071*
O4	1.0432 (5)	0.7071 (3)	0.5487 (3)	0.0593 (12)
C1	1.1023 (6)	0.6432 (4)	0.7527 (4)	0.0475 (15)
C6	1.2201 (7)	0.6068 (4)	0.7397 (5)	0.0531 (17)
C11	0.8118 (9)	0.5599 (5)	0.4579 (4)	0.0601 (19)
H11	0.7992	0.5367	0.4103	0.072*
C16	0.5916 (8)	0.6869 (6)	0.5620 (5)	0.068 (2)
H16	0.5894	0.7146	0.6072	0.081*
C17	0.7052 (7)	0.6469 (4)	0.5483 (4)	0.0474 (15)
C12	0.7033 (8)	0.6071 (5)	0.4792 (4)	0.0536 (17)
N2	1.1634 (6)	0.5535 (4)	0.6118 (4)	0.0586 (15)
N1	0.9195 (7)	0.5463 (4)	0.4949 (3)	0.0545 (14)
C5	1.3229 (8)	0.6064 (6)	0.7985 (6)	0.074 (3)
H5	1.3995	0.5811	0.7908	0.088*
C10	1.0099 (11)	0.4931 (6)	0.4612 (6)	0.079 (3)
H10A	0.9817	0.4896	0.4083	0.095*
H10B	1.0106	0.4343	0.4811	0.095*
C3	1.2000 (10)	0.6782 (6)	0.8782 (5)	0.074 (3)
H3	1.1932	0.703	0.9239	0.089*
C9	1.1415 (11)	0.5292 (7)	0.4750 (6)	0.088 (3)
H9A	1.1367	0.592	0.4679	0.105*
H9B	1.1893	0.5055	0.4383	0.105*
C15	0.4849 (11)	0.6857 (9)	0.5101 (7)	0.091 (3)
H15	0.4109	0.7116	0.5215	0.11*
C13	0.5899 (11)	0.6097 (7)	0.4268 (5)	0.080 (3)
H13	0.5893	0.5843	0.3805	0.096*
C14	0.4817 (10)	0.6488 (9)	0.4431 (6)	0.091 (3)
H14	0.4076	0.6498	0.4086	0.109*
N4	1.0847 (6)	0.8506 (4)	0.5459 (4)	0.0600 (17)
N3	0.9285 (7)	0.3697 (4)	0.7290 (4)	0.0610 (15)
C18	0.9597 (8)	0.4425 (4)	0.6998 (4)	0.0562 (17)
H18	1.0196	0.4768	0.7292	0.067*
C23	1.1577 (11)	0.8470 (6)	0.4863 (7)	0.083 (3)
H23A	1.188	0.9044	0.477	0.124*
H23B	1.105	0.8256	0.4426	0.124*
H23C	1.2291	0.8086	0.4993	0.124*
C7	1.2414 (8)	0.5683 (5)	0.6709 (6)	0.066 (2)
H7	1.3252	0.5516	0.6691	0.079*
C21	1.0328 (7)	0.7812 (5)	0.5710 (4)	0.0548 (16)
H21	0.9842	0.7893	0.6089	0.066*
C8	1.2147 (11)	0.5107 (7)	0.5514 (6)	0.089 (3)
H8A	1.2153	0.4482	0.5597	0.107*
H8B	1.3024	0.5293	0.5525	0.107*
C20	0.9846 (15)	0.3400 (8)	0.8028 (6)	0.101 (4)
H20A	0.9472	0.2851	0.8132	0.151*
H20B	0.9684	0.3824	0.8389	0.151*
H20C	1.075	0.3328	0.8047	0.151*
C22	1.0725 (14)	0.9369 (6)	0.5780 (10)	0.117 (5)
H22A	1.1173	0.9789	0.5525	0.176*
H22B	1.1084	0.9359	0.6295	0.176*
H22C	0.984	0.9526	0.5729	0.176*
C4	1.3148 (10)	0.6413 (6)	0.8658 (7)	0.088 (3)
H4	1.3849	0.6406	0.9031	0.106*
C19A	0.873 (3)	0.3007 (18)	0.6812 (19)	0.077 (8)	0.45
H191	0.8581	0.2508	0.7105	0.115*	0.45
H192	0.9305	0.285	0.6475	0.115*	0.45
H193	0.7937	0.3202	0.6537	0.115*	0.45
C19B	0.808 (4)	0.3273 (19)	0.695 (2)	0.138 (17)	0.55
H194	0.7961	0.274	0.7212	0.207*	0.55
H195	0.8111	0.3147	0.6442	0.207*	0.55
H196	0.7374	0.3659	0.6988	0.207*	0.55

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0479 (4)	0.0340 (4)	0.0466 (4)	0.0031 (3)	0.0166 (3)	0.0040 (3)
Zn	0.0494 (4)	0.0449 (4)	0.0384 (3)	0.0125 (3)	0.0102 (3)	0.0042 (3)
O1	0.043 (2)	0.043 (2)	0.049 (2)	0.0068 (18)	0.0043 (19)	−0.0024 (18)
O2	0.045 (2)	0.047 (2)	0.039 (2)	0.0083 (19)	0.0094 (18)	0.0042 (17)
I2	0.0849 (4)	0.0977 (5)	0.0825 (4)	0.0155 (3)	0.0450 (3)	0.0393 (3)
I1	0.1140 (5)	0.0503 (3)	0.0738 (4)	0.0287 (3)	0.0157 (3)	−0.0023 (2)
O3	0.069 (3)	0.040 (2)	0.065 (3)	−0.002 (2)	0.016 (2)	0.012 (2)
C2	0.064 (5)	0.052 (4)	0.057 (4)	0.000 (3)	−0.010 (4)	0.003 (3)
O4	0.072 (3)	0.044 (3)	0.066 (3)	−0.006 (2)	0.023 (3)	0.005 (2)
C1	0.044 (3)	0.031 (3)	0.065 (4)	−0.005 (2)	0.001 (3)	0.011 (3)
C6	0.046 (4)	0.034 (3)	0.081 (5)	−0.002 (3)	0.012 (3)	0.011 (3)
C11	0.086 (6)	0.048 (4)	0.048 (4)	−0.017 (4)	0.015 (4)	−0.004 (3)
C16	0.049 (4)	0.083 (6)	0.070 (5)	0.017 (4)	0.005 (4)	0.004 (4)
C17	0.048 (3)	0.047 (3)	0.047 (3)	−0.005 (3)	0.004 (3)	0.016 (3)
C12	0.067 (5)	0.049 (3)	0.046 (3)	−0.021 (3)	0.009 (3)	0.003 (3)
N2	0.055 (4)	0.051 (3)	0.075 (4)	0.011 (3)	0.027 (3)	0.011 (3)
N1	0.077 (4)	0.041 (3)	0.050 (3)	−0.006 (3)	0.023 (3)	−0.002 (2)
C5	0.046 (4)	0.057 (5)	0.110 (8)	−0.004 (4)	−0.010 (5)	0.018 (5)
C10	0.107 (7)	0.061 (5)	0.079 (6)	−0.007 (5)	0.045 (5)	−0.022 (4)
C3	0.086 (7)	0.060 (5)	0.066 (5)	−0.005 (4)	−0.021 (5)	0.003 (4)
C9	0.105 (8)	0.076 (6)	0.095 (7)	0.016 (6)	0.058 (6)	−0.006 (5)
C15	0.061 (6)	0.116 (9)	0.092 (7)	0.009 (6)	−0.003 (5)	0.006 (6)
C13	0.097 (8)	0.090 (6)	0.048 (4)	−0.030 (6)	−0.008 (5)	0.004 (4)
C14	0.061 (6)	0.137 (10)	0.067 (6)	−0.007 (6)	−0.017 (5)	0.015 (6)
N4	0.046 (3)	0.041 (3)	0.096 (5)	−0.002 (2)	0.019 (3)	0.016 (3)
N3	0.069 (4)	0.053 (3)	0.063 (4)	−0.003 (3)	0.016 (3)	0.017 (3)
C18	0.068 (4)	0.038 (3)	0.064 (4)	−0.002 (3)	0.012 (4)	0.002 (3)
C23	0.083 (6)	0.076 (6)	0.096 (7)	−0.011 (5)	0.032 (5)	0.022 (5)
C7	0.045 (4)	0.044 (4)	0.112 (7)	0.008 (3)	0.023 (4)	0.023 (4)
C21	0.051 (4)	0.049 (4)	0.067 (4)	−0.001 (3)	0.014 (3)	0.015 (3)
C8	0.092 (7)	0.087 (7)	0.101 (7)	0.042 (6)	0.053 (6)	0.013 (5)
C20	0.138 (11)	0.091 (7)	0.075 (6)	−0.003 (7)	0.019 (7)	0.024 (5)
C22	0.120 (10)	0.042 (5)	0.205 (15)	−0.002 (5)	0.073 (10)	0.008 (7)
C4	0.068 (6)	0.073 (6)	0.110 (8)	−0.017 (5)	−0.031 (6)	0.010 (6)
C19A	0.10 (2)	0.048 (12)	0.081 (14)	−0.009 (13)	0.000 (15)	0.019 (10)
C19B	0.15 (3)	0.08 (2)	0.15 (3)	−0.08 (2)	−0.05 (3)	0.06 (2)

Geometric parameters (Å, º)

Ni—N1	2.014 (6)	C3—H3	0.93
Ni—O2	2.014 (4)	C9—C8	1.517 (16)
Ni—O1	2.019 (5)	C9—H9A	0.97
Ni—N2	2.025 (6)	C9—H9B	0.97
Ni—O3	2.124 (5)	C15—C14	1.345 (18)
Ni—O4	2.137 (5)	C15—H15	0.93
Ni—Zn	3.0695 (11)	C13—C14	1.366 (17)
Zn—O2	1.986 (4)	C13—H13	0.93
Zn—O1	1.989 (4)	C14—H14	0.93
Zn—I2	2.5303 (9)	N4—C21	1.312 (9)
Zn—I1	2.5424 (9)	N4—C23	1.429 (13)
O1—C1	1.315 (8)	N4—C22	1.459 (13)
O2—C17	1.312 (8)	N3—C18	1.302 (10)
O3—C18	1.218 (9)	N3—C19A	1.44 (3)
C2—C3	1.383 (12)	N3—C20	1.460 (13)
C2—C1	1.391 (12)	N3—C19B	1.48 (3)
C2—H2	0.93	C18—H18	0.93
O4—C21	1.218 (9)	C23—H23A	0.96
C1—C6	1.421 (11)	C23—H23B	0.96
C6—C5	1.409 (12)	C23—H23C	0.96
C6—C7	1.436 (13)	C7—H7	0.93
C11—N1	1.253 (11)	C21—H21	0.93
C11—C12	1.461 (12)	C8—H8A	0.97
C11—H11	0.93	C8—H8B	0.97
C16—C15	1.362 (14)	C20—H20A	0.96
C16—C17	1.407 (11)	C20—H20B	0.96
C16—H16	0.93	C20—H20C	0.96
C17—C12	1.399 (10)	C22—H22A	0.96
C12—C13	1.419 (12)	C22—H22B	0.96
N2—C7	1.278 (12)	C22—H22C	0.96
N2—C8	1.458 (11)	C4—H4	0.93
N1—C10	1.463 (11)	C19A—H191	0.96
C5—C4	1.356 (17)	C19A—H192	0.96
C5—H5	0.93	C19A—H193	0.96
C10—C9	1.487 (15)	C19B—H194	0.96
C10—H10A	0.97	C19B—H195	0.96
C10—H10B	0.97	C19B—H196	0.96
C3—C4	1.391 (17)
N1—Ni—O2	90.3 (2)	C8—C9—H9A	108.5
N1—Ni—O1	169.0 (2)	C10—C9—H9B	108.5
O2—Ni—O1	78.80 (18)	C8—C9—H9B	108.5
N1—Ni—N2	100.0 (3)	H9A—C9—H9B	107.5
O2—Ni—N2	169.0 (2)	C14—C15—C16	122.9 (11)
O1—Ni—N2	90.9 (2)	C14—C15—H15	118.5
N1—Ni—O3	87.5 (2)	C16—C15—H15	118.5
O2—Ni—O3	92.2 (2)	C14—C13—C12	121.2 (9)
O1—Ni—O3	91.2 (2)	C14—C13—H13	119.4
N2—Ni—O3	91.8 (2)	C12—C13—H13	119.4
N1—Ni—O4	88.2 (2)	C15—C14—C13	118.5 (9)
O2—Ni—O4	90.9 (2)	C15—C14—H14	120.8
O1—Ni—O4	93.5 (2)	C13—C14—H14	120.8
N2—Ni—O4	85.9 (2)	C21—N4—C23	122.6 (7)
O3—Ni—O4	174.7 (2)	C21—N4—C22	121.8 (9)
O2—Zn—O1	80.19 (18)	C23—N4—C22	115.6 (8)
O2—Zn—I2	110.41 (14)	C18—N3—C19A	119.1 (14)
O1—Zn—I2	115.68 (13)	C18—N3—C20	123.6 (9)
O2—Zn—I1	115.67 (12)	C19A—N3—C20	113.8 (14)
O1—Zn—I1	111.82 (13)	C18—N3—C19B	117.5 (12)
I2—Zn—I1	117.51 (3)	C20—N3—C19B	116.8 (15)
C1—O1—Zn	129.5 (5)	O3—C18—N3	127.7 (8)
C1—O1—Ni	130.1 (4)	O3—C18—H18	116.2
Zn—O1—Ni	99.96 (19)	N3—C18—H18	116.2
C17—O2—Zn	130.0 (4)	N4—C23—H23A	109.5
C17—O2—Ni	129.3 (4)	N4—C23—H23B	109.5
Zn—O2—Ni	100.22 (19)	H23A—C23—H23B	109.5
C18—O3—Ni	123.7 (5)	N4—C23—H23C	109.5
C3—C2—C1	122.1 (9)	H23A—C23—H23C	109.5
C3—C2—H2	119	H23B—C23—H23C	109.5
C1—C2—H2	119	N2—C7—C6	130.2 (7)
C21—O4—Ni	125.2 (5)	N2—C7—H7	114.9
O1—C1—C2	121.0 (7)	C6—C7—H7	114.9
O1—C1—C6	121.0 (7)	O4—C21—N4	125.1 (8)
C2—C1—C6	118.0 (7)	O4—C21—H21	117.5
C5—C6—C1	118.1 (8)	N4—C21—H21	117.5
C5—C6—C7	117.3 (8)	N2—C8—C9	114.5 (7)
C1—C6—C7	124.6 (7)	N2—C8—H8A	108.6
N1—C11—C12	128.9 (7)	C9—C8—H8A	108.6
N1—C11—H11	115.5	N2—C8—H8B	108.6
C12—C11—H11	115.5	C9—C8—H8B	108.6
C15—C16—C17	120.9 (9)	H8A—C8—H8B	107.6
C15—C16—H16	119.6	N3—C20—H20A	109.5
C17—C16—H16	119.6	N3—C20—H20B	109.5
O2—C17—C12	122.8 (7)	H20A—C20—H20B	109.5
O2—C17—C16	120.1 (7)	N3—C20—H20C	109.5
C12—C17—C16	117.1 (7)	H20A—C20—H20C	109.5
C17—C12—C13	119.4 (8)	H20B—C20—H20C	109.5
C17—C12—C11	123.5 (7)	N4—C22—H22A	109.5
C13—C12—C11	117.0 (7)	N4—C22—H22B	109.5
C7—N2—C8	116.9 (8)	H22A—C22—H22B	109.5
C7—N2—Ni	123.0 (6)	N4—C22—H22C	109.5
C8—N2—Ni	120.0 (6)	H22A—C22—H22C	109.5
C11—N1—C10	117.8 (7)	H22B—C22—H22C	109.5
C11—N1—Ni	125.1 (5)	C5—C4—C3	119.1 (8)
C10—N1—Ni	117.1 (6)	C5—C4—H4	120.5
C4—C5—C6	122.8 (9)	C3—C4—H4	120.5
C4—C5—H5	118.6	N3—C19A—H191	109.5
C6—C5—H5	118.6	N3—C19A—H192	109.5
N1—C10—C9	112.2 (7)	H191—C19A—H192	109.5
N1—C10—H10A	109.2	N3—C19A—H193	109.5
C9—C10—H10A	109.2	H191—C19A—H193	109.5
N1—C10—H10B	109.2	H192—C19A—H193	109.5
C9—C10—H10B	109.2	N3—C19B—H194	109.5
H10A—C10—H10B	107.9	N3—C19B—H195	109.5
C2—C3—C4	119.9 (10)	H194—C19B—H195	109.5
C2—C3—H3	120	N3—C19B—H196	109.5
C4—C3—H3	120	H194—C19B—H196	109.5
C10—C9—C8	114.9 (9)	H195—C19B—H196	109.5
C10—C9—H9A	108.5
O2—Zn—O1—C1	180.0 (5)	O2—C17—C12—C13	179.3 (7)
I2—Zn—O1—C1	−72.0 (5)	C16—C17—C12—C13	0.7 (10)
I1—Zn—O1—C1	66.1 (5)	O2—C17—C12—C11	1.1 (10)
O2—Zn—O1—Ni	−7.00 (18)	C16—C17—C12—C11	−177.4 (7)
I2—Zn—O1—Ni	101.03 (16)	N1—C11—C12—C17	0.5 (12)
I1—Zn—O1—Ni	−120.85 (13)	N1—C11—C12—C13	−177.7 (8)
N1—Ni—O1—C1	171.2 (10)	N1—Ni—N2—C7	−179.8 (6)
O2—Ni—O1—C1	179.9 (5)	O2—Ni—N2—C7	19.4 (15)
N2—Ni—O1—C1	−3.9 (5)	O1—Ni—N2—C7	−0.8 (6)
O3—Ni—O1—C1	87.9 (5)	O3—Ni—N2—C7	−92.0 (6)
O4—Ni—O1—C1	−89.8 (5)	O4—Ni—N2—C7	92.7 (6)
N1—Ni—O1—Zn	−1.8 (12)	N1—Ni—N2—C8	3.5 (7)
O2—Ni—O1—Zn	6.93 (18)	O2—Ni—N2—C8	−157.2 (10)
N2—Ni—O1—Zn	−176.9 (2)	O1—Ni—N2—C8	−177.4 (7)
O3—Ni—O1—Zn	−85.1 (2)	O3—Ni—N2—C8	91.3 (7)
O4—Ni—O1—Zn	97.2 (2)	O4—Ni—N2—C8	−83.9 (7)
O1—Zn—O2—C17	179.4 (5)	C12—C11—N1—C10	177.2 (7)
I2—Zn—O2—C17	65.5 (5)	C12—C11—N1—Ni	−2.7 (11)
I1—Zn—O2—C17	−71.0 (5)	O2—Ni—N1—C11	2.4 (6)
O1—Zn—O2—Ni	7.02 (19)	O1—Ni—N1—C11	11.0 (15)
I2—Zn—O2—Ni	−106.86 (15)	N2—Ni—N1—C11	−174.0 (6)
I1—Zn—O2—Ni	116.61 (13)	O3—Ni—N1—C11	94.7 (6)
N1—Ni—O2—C17	−1.0 (5)	O4—Ni—N1—C11	−88.5 (6)
O1—Ni—O2—C17	−179.4 (5)	O2—Ni—N1—C10	−177.4 (6)
N2—Ni—O2—C17	160.0 (11)	O1—Ni—N1—C10	−168.9 (10)
O3—Ni—O2—C17	−88.6 (5)	N2—Ni—N1—C10	6.2 (6)
O4—Ni—O2—C17	87.2 (5)	O3—Ni—N1—C10	−85.2 (6)
N1—Ni—O2—Zn	171.4 (2)	O4—Ni—N1—C10	91.6 (6)
O1—Ni—O2—Zn	−6.95 (19)	C1—C6—C5—C4	−1.8 (12)
N2—Ni—O2—Zn	−27.5 (12)	C7—C6—C5—C4	179.4 (8)
O3—Ni—O2—Zn	83.9 (2)	C11—N1—C10—C9	137.9 (9)
O4—Ni—O2—Zn	−100.4 (2)	Ni—N1—C10—C9	−42.2 (10)
N1—Ni—O3—C18	158.6 (7)	C1—C2—C3—C4	−1.1 (13)
O2—Ni—O3—C18	−111.2 (6)	N1—C10—C9—C8	78.6 (11)
O1—Ni—O3—C18	−32.3 (6)	C17—C16—C15—C14	−1.5 (18)
N2—Ni—O3—C18	58.6 (7)	C17—C12—C13—C14	−1.4 (14)
N1—Ni—O4—C21	139.9 (7)	C11—C12—C13—C14	176.9 (9)
O2—Ni—O4—C21	49.6 (6)	C16—C15—C14—C13	1 (2)
O1—Ni—O4—C21	−29.3 (6)	C12—C13—C14—C15	0.6 (17)
N2—Ni—O4—C21	−119.9 (7)	Ni—O3—C18—N3	179.6 (7)
Zn—O1—C1—C2	−4.4 (9)	C19A—N3—C18—O3	21.1 (19)
Ni—O1—C1—C2	−175.4 (5)	C20—N3—C18—O3	178.3 (10)
Zn—O1—C1—C6	175.7 (4)	C19B—N3—C18—O3	−19 (2)
Ni—O1—C1—C6	4.7 (8)	C8—N2—C7—C6	−178.3 (8)
C3—C2—C1—O1	−179.9 (7)	Ni—N2—C7—C6	5.0 (11)
C3—C2—C1—C6	0.1 (11)	C5—C6—C7—N2	173.4 (8)
O1—C1—C6—C5	−178.7 (6)	C1—C6—C7—N2	−5.2 (12)
C2—C1—C6—C5	1.3 (10)	Ni—O4—C21—N4	172.1 (6)
O1—C1—C6—C7	−0.1 (10)	C23—N4—C21—O4	2.1 (14)
C2—C1—C6—C7	179.9 (7)	C22—N4—C21—O4	−177.2 (10)
Zn—O2—C17—C12	−170.7 (5)	C7—N2—C8—C9	−154.5 (9)
Ni—O2—C17—C12	−0.4 (9)	Ni—N2—C8—C9	22.4 (12)
Zn—O2—C17—C16	7.8 (9)	C10—C9—C8—N2	−66.6 (12)
Ni—O2—C17—C16	178.1 (6)	C6—C5—C4—C3	0.9 (14)
C15—C16—C17—O2	−178.0 (9)	C2—C3—C4—C5	0.6 (14)
C15—C16—C17—C12	0.6 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O4	0.97	2.59	3.279 (12)	128