Retroracemization using new forms of Belokon's original ligand: ­intermediate Ni^II complexes of N-({2-[N-(S)-alkylprolylamino]phenyl}phenylmethylene)-(S)-phenylalanine (alkyl is 2-picolyl, 3-picolyl or ethyl)

In the title compounds, [N-(phenyl{2-[N-(S)-(2-picolyl)­prolyl­amino]­phenyl}methyl­ene)-(S)-phenyl­alaninato]­nickel(II), [Ni(C₃₃H₃₀N₄O₃)], (I), [N-(phenyl{2-[N-(S)-(3-picolyl)­prolyl­amino]­phenyl}methyl­ene)-(S)-phenyl­alaninato]­nickel(II) hemihydrate, [Ni(C₃₃H₃₀N₄O₃)]·0.5H₂O, (II), and [N-({2-[N-(S)-ethyl­prolyl­amino]­phenyl}phenyl­methyl­ene)-(S)-phenyl­ala­nin­ato]­nickel(II), [Ni(C₂₉H₂₉N₃O₃)], (III), the Ni^II centres have approximate square-planar coordination geometries from N₃O donor sets. The picolyl N atoms in (I) and (II) are too remote from the metal centres to interact significantly, but the metal coordination geometries experience tetrahedral distortion and/or displacement of the metal centre from the N₃O plane. These are linked to conformational differences between the ligands of the symmetry-independent complexes (Z' = 2), which in turn are related to molecular packing. In (III), where a less sterically demanding ethyl group replaces the picolyl substituents, there are none of the distortions or displacements seen in (I) and (II).

S1. Comment

The asymmetric synthesis of α-amino acids has been an area of intense interest over the past few decades. A number of elegant approaches have established themselves for use in research or industrial scale syntheses. However, many industrial processes still involve classical resolutions in which large amounts of chemical waste in the form of amino acids of the wrong stereochemistry are produced. Belokon et al. (1983) reported the first example of a process they termed retroracemization, in which a racemic α-amino acid mixture could be enriched in one of its enantiomeric forms by selective protonation of a prochiral amino acid enolate generated in an asymmetric environment formed from the amino acid, Cu^II or Ni^II, and either (S)-2-[N-benzylprolyl)amino]benzaldehyde, acetophenone or benzophenone. The combination of Ni^II and (S)-2-[N-benzylprolyl)amino]benzophenone [(S)-BPB] proved the most successful in the retroracemizations, and in the stereoselective alkylation of complexes containing the glycine enolate. More recently, a number of modified forms of the original Belokon ligands have been investigated. These include a variety of ligands in which the N-benzyl group has been replaced by the bulkier naphthalen-1-ylmethyl group, the smaller ethyl derivative, and 2-picolyl or 3-picolyl groups, which may offer a further coordination site for binding to the metal in the complex (De & Thomas, 1997). N-(2-benzoylphenyl)pyridine-2-carbamide (PBP) was studied by Belokon et al. (2001), who have investigated glycine enolate alkylation reactions under phase-transfer catalysis (PTC) conditions, and Popkov et al. (2000), who have reported the use of (S)-2-[N-(2,4,6-trimethylbenzylprolyl)amino]benzophenone [(S)-TMBPB] to give improved diastereoselectivity and enantioselectivity in the synthesis of (S)-alanine when compared with (S)-BPB.

In our investigation, two approaches to improving the diastereoselectivity of the retroracemization process were investigated. Initially, we examined the possibility of increasing the steric bulk of the prolyl substituent by replacing the N-benzyl group of (S)-BPB with diphenylmethyl, trityl or naphthalen-1-ylmethyl groups. It proved to be impossible to form the Schiff base complexes with either (S)-2-[(N-1-diphenylmethylprolyl)amino]- or (S)-[(N-1-tritylprolyl)amino]benzophenone and either racemic phenylalanine or glycine. In the case of (S)-[(N-1-(naphthalen-1'-ylmethyl)prolyl)amino]benzophenone, a small increase in the enantiomeric excess of the product α-amino acid was observed after conducting the retroracemization procedure and decomposing the complex, when compared with the use of (S)-BPB. However, the yield of the amino acid product was generally 10–15% lower. As an alternative strategy, we investigated the introduction of prolyl substituents, which should be capable of providing a further coordination site for the metal in the Schiff base complex, such that one face of the prochiral α-amino acid enolate generated during the retroracemization process would be rendered totally inaccessible to protonation or alkylation. This was inspired by the fact that the square-planar Cu^II complex of pyruvyl Gly-D-Phe reacts with imidazole-4-carboxaldehyde to give a square-pyramidyl intermediate (Owa et al., 1988). It was anticipated that inclusion of a 2-picolyl or 3-picolyl substituent in the (S)-2-[N-alkylprolyl)amino]benzophenone would cause the Schiff base formed with Ni^II or Cu^II and an α-amino acid to adopt a square-pyramidal or octahedral geometry, the latter involving a solvent ligand. Thus the three title compounds, (I), (II) and (III), were prepared and their crystal structures are presented here. \sch

Both picolyl complexes, (I) and (II), crystallize with two independent molecules in the asymmetric unit. Each Ni^II atom adopts an approximately square-planar geometry (Figs. 1 and 2, Tables 1 and 2), with the distance from the Ni atom to the sp³-hybridized N2 atom being longer than the other three distances. However, there are significant differences in the detailed geometry of the independent molecules. In the first molecule of (I), the tetrahedral distortion is much less than in the second (r.m.s. deviation of the constituent atoms from the N₃O donor-atom plane 0.064 Å in the second molecule versus 0.148 Å in the first), as is the displacement of the Ni^II centre from this plane [0.008 (3) versus 0.038 (3) Å, the latter in the direction of atom N1A].

In (II), the two molecules also have different degrees of tetrahedral distortion, indicated by r.m.s. deviations of 0.139 and 0.074 Å, as well as different displacements of 0.001 (5) and 0.044 (4) Å (away from N1A), of the metal centre from the N₃O plane. Interestingly, there is no correlation between the degree of tetrahedral distortion and the displacement of the metal centre. In (I), the greater distortion is associated with the greater displacement, but this is not the case in (II). We believe that the origin of these differences in the coordination geometries lies in the different conformations of the ligands (see below).

The N atoms of both the 2-picolyl and 3-picolyl substituents are too remote from the metal centres to form Ni—N bonds. In both of these complexes with picolyl substituents, (I) and (II), there are two independent molecules with similar, but slightly different, conformations (Figs. 3 and 4). In the 2-picolyl complex, (I), the pyridyl N—Ni distances are 2.861 (7) and 2.954 (8) Å, while in the 3-picolyl complex, (II), these are even longer, at 5.339 (15) and 5.024 (12) Å. Despite these differences, and the presence in (II) of a poorly defined water molecule which is hydrogen bonded to the complex via atom N1 [N1···O1W 2.88 (2) Å], the space groups are the same, the unit-cell dimensions are similar and the unit-cell volumes differ by only 0.7%. We believe that the differences in the coordination geometry at the Ni atom in (I) and (II) can be traced to the different ligand conformations (Figs. 3 and 4), which induce differing types and degrees of distortion. In turn, the adoption of these ligand conformations allows efficient packing between adjacent symmetry-independent molecules. This packing involves a number of interactions between aromatic rings, including some face-to-edge interactions.

These two crystal structures show a significant similarity with those of (S)-BPB/Ni^II and a wide variety of α-amino acids that have been reported previously [(S)-BPB with Ni^II and (2S,3S)-2-(trifluoromethyl)threonine (Soloshonok et al., 1993); (S)-BPB with Ni^II and ω-ethyl-(2S,3S)-3-trifluoromethylglutamate (Soloshonok et al., 1997); (S)-BPB with Ni^II and (2S,3S,4R)-3-trifluoromethyl-4-methylpyroglutamic acid (Soloshonok et al., 1999); (S)-BPB with Ni^II and dehydroaminobutanoic acid (Belokon et al., 1990); (S)-2-N-(N'-benzylprolyl)aminoacetophenone with Cu^II and glycine (Belokon et al., 1983); (S)-2-N-(N'-benzylprolyl)aminoacetophenone with Ni^II and (R)-valine (Lindeman et al., 1985)].

Square-planar geometry around Ni^II is also observed in the third complex, (III), where the picolyl substituents have been replaced by a less sterically demanding ethyl group. Here, there is only one molecule per asymmetric unit, and the distance from the Ni atom to the sp³-hybridized N2 atom is again longer than the other three Ni—N/O distances, in this case by approximately 0.1 Å. There is no significant tetrahedral distortion (the r.m.s. deviation of the constituent atoms from the N₃O donor-atom plane is only 0.016 Å) and the metal centre lies in this plane [calculated deviation 0.003 (4) Å].

NB Belokon is spelled Belokon' in our database. With which spelling were this author's other papers published?

S2. Experimental

Complexes (I)-(III) were prepared using the standard literature methods of Belokon (1992a,b). The ligand (S)-2-[(N-1-(2-picolyl)prolyl)amino]-, (S)-2-[(N-1-(3-picolyl)prolyl)amino]- or (S)-2-[(N-1-(ethyl)prolyl)amino]benzophenone, racemic phenylalanine (5 equivalents) and nickel(II) nitrate hexahydrate (2 equivalents) were dissolved in anhydrous methanol, and a 1.3M solution of sodium methoxide (22 equivalents) in methanol was added. The resulting orange-coloured solution was heated for 2 h at 323 K, cooled in ice and then quenched with water. The resulting suspension was extracted with dichloromethane and the combined organic phases were dried over sodium sulfate, before being concentrated in vacuo to give a red-brown residue. The required complex was obtained after purification of this residue on silica gel (8:1 chloroform-acetone). All three complexes were dark red-brown and the crystals were grown in acetone with the addition of pentane and under cooling. Further optimization of the method of producing the complexes has appeared since we conducted our research (Nadvornik & Popkov, 2002; Belokon et al., 1998).

S3. Refinement

The C—H atoms in (I) and (II) were placed geometrically and refined riding on their parent atoms, at distances of 0.95–1.00 Å and with U_iso(H) = 1.2U_eq(C). The corresponding C—H range in (III) was 0.94–0.99 Å and methyl H atoms had U_iso(H) = 1.5U_eq(C). The water H atoms in (II) were not located.

Computing details

For all compounds, data collection: STADI4 (Stoe & Cie, 1995); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures

	Fig. 1. A view of one of the two independent molecules of (I), showing the atom-numbering scheme. H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of one of the two independent molecules of (II), showing the atom-numbering scheme. H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The results of a least-squares fit to the labelled donor atoms of the two molecules in (I). The molecules are distinguished by solid and dotted bonds.
	Fig. 4. The results of a least-squares fit to the labelled donor atoms of the two molecules in (II). The molecules are distinguished by solid and dotted bonds.
	Fig. 5. A view of the molecule of (III), showing the atom-numbering scheme. H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 30% probability level.

(I) [N-({2-[N-(S)-(2-picolyl)prolylamino]phenyl}phenylmethylene)-(S)- phenylalaninato]nickel(II)

Crystal data

[Ni(C33H30N4O3)]	F(000) = 2464
Mr = 589.32	Dx = 1.423 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 35 reflections
a = 11.722 (2) Å	θ = 13–15°
b = 18.391 (14) Å	µ = 0.75 mm^−1
c = 25.528 (6) Å	T = 150 K
V = 5503 (4) Å^3	Block, red
Z = 8	0.42 × 0.33 × 0.29 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	4490 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.136
Graphite monochromator	θmax = 25.1°, θmin = 2.6°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995)	k = 0→21
Tmin = 0.730, Tmax = 0.825	l = 0→30
6352 measured reflections	3 standard reflections every 60 min
5359 independent reflections	intensity decay: variation +−15.5%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.054	w = 1/[σ^2(Fo^2) + (0.0088P)^2 + 15.94P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.115	(Δ/σ)max = 0.002
S = 1.18	Δρmax = 0.48 e Å^−3
5355 reflections	Δρmin = −0.46 e Å^−3
740 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
109 restraints	Extinction coefficient: 0.00049 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983) with x Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.03 (2)

Special details

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
Ni	0.16886 (9)	0.58688 (5)	0.05129 (3)	0.0212 (2)
N1	−0.0099 (6)	0.5467 (4)	−0.0188 (3)	0.0307 (17)
C1	−0.0164 (7)	0.5536 (4)	−0.0717 (3)	0.032 (2)
H1	0.0307	0.5231	−0.0925	0.038*
C2	−0.0870 (7)	0.6018 (4)	−0.0969 (3)	0.033 (2)
H2	−0.0874	0.6052	−0.1341	0.039*
C3	−0.1570 (8)	0.6449 (5)	−0.0671 (3)	0.036 (2)
H3	−0.2066	0.6789	−0.0834	0.044*
C4	−0.1550 (7)	0.6388 (4)	−0.0136 (3)	0.0322 (19)
H4	−0.2048	0.6671	0.0076	0.039*
C5	−0.0788 (6)	0.5903 (4)	0.0091 (3)	0.0261 (17)
C6	−0.0653 (6)	0.5837 (5)	0.0678 (3)	0.0284 (18)
H6A	−0.1344	0.6034	0.0850	0.034*
H6B	−0.0596	0.5315	0.0771	0.034*
N2	0.0365 (5)	0.6224 (3)	0.0885 (2)	0.0238 (14)
C7	0.0446 (8)	0.6120 (4)	0.1471 (3)	0.033 (2)
H7A	0.1180	0.5888	0.1565	0.040*
H7B	−0.0184	0.5808	0.1597	0.040*
C8	0.0364 (7)	0.6875 (5)	0.1713 (3)	0.036 (2)
H8A	0.0836	0.6911	0.2034	0.043*
H8B	−0.0435	0.7000	0.1800	0.043*
C9	0.0827 (7)	0.7363 (4)	0.1279 (3)	0.0302 (19)
H9A	0.0569	0.7871	0.1324	0.036*
H9B	0.1671	0.7351	0.1268	0.036*
C10	0.0315 (6)	0.7024 (4)	0.0787 (3)	0.0241 (16)
H10	−0.0500	0.7177	0.0755	0.029*
C11	0.0952 (6)	0.7245 (4)	0.0299 (3)	0.0248 (17)
O1	0.0838 (5)	0.7867 (3)	0.0140 (2)	0.0348 (14)
N3	0.1639 (5)	0.6708 (3)	0.0105 (2)	0.0196 (13)
C12	0.2143 (6)	0.6765 (4)	−0.0392 (3)	0.0218 (16)
C13	0.1789 (7)	0.7300 (4)	−0.0754 (3)	0.0268 (17)
H13	0.1222	0.7640	−0.0652	0.032*
C14	0.2243 (6)	0.7343 (4)	−0.1253 (3)	0.0260 (18)
H14	0.1975	0.7706	−0.1488	0.031*
C15	0.3078 (7)	0.6868 (4)	−0.1412 (3)	0.0266 (18)
H15	0.3400	0.6906	−0.1753	0.032*
C16	0.3438 (6)	0.6341 (4)	−0.1074 (3)	0.0203 (16)
H16	0.4013	0.6012	−0.1187	0.024*
C17	0.2986 (6)	0.6265 (4)	−0.0559 (3)	0.0222 (16)
C18	0.3438 (6)	0.5671 (4)	−0.0234 (3)	0.0205 (16)
C19	0.4374 (6)	0.5220 (4)	−0.0472 (3)	0.0203 (16)
C20	0.4081 (7)	0.4645 (4)	−0.0800 (3)	0.0260 (18)
H20	0.3301	0.4525	−0.0853	0.031*
C21	0.4925 (7)	0.4246 (4)	−0.1050 (3)	0.032 (2)
H21	0.4722	0.3851	−0.1270	0.038*
C22	0.6063 (7)	0.4423 (5)	−0.0979 (3)	0.035 (2)
H22	0.6640	0.4154	−0.1155	0.042*
C23	0.6356 (6)	0.4992 (4)	−0.0652 (3)	0.0295 (19)
H23	0.7138	0.5105	−0.0599	0.035*
C24	0.5532 (6)	0.5397 (4)	−0.0400 (3)	0.0227 (17)
H24	0.5743	0.5792	−0.0181	0.027*
N4	0.2993 (5)	0.5507 (3)	0.0215 (2)	0.0228 (14)
C25	0.3482 (6)	0.4917 (4)	0.0537 (3)	0.0241 (16)
H25	0.3794	0.4530	0.0302	0.029*
C26	0.4440 (7)	0.5186 (4)	0.0911 (3)	0.031 (2)
H26A	0.4738	0.4763	0.1108	0.037*
H26B	0.5074	0.5380	0.0696	0.037*
C27	0.4084 (6)	0.5760 (4)	0.1296 (3)	0.0280 (18)
C28	0.4269 (7)	0.6486 (4)	0.1201 (4)	0.038 (2)
H28	0.4617	0.6631	0.0881	0.046*
C29	0.3957 (8)	0.7012 (5)	0.1563 (4)	0.052 (3)
H29	0.4091	0.7512	0.1489	0.063*
C30	0.3449 (9)	0.6811 (5)	0.2033 (4)	0.051 (3)
H30	0.3237	0.7170	0.2282	0.061*
C31	0.3255 (8)	0.6089 (5)	0.2132 (3)	0.044 (2)
H31	0.2903	0.5948	0.2452	0.053*
C32	0.3567 (7)	0.5565 (4)	0.1774 (3)	0.032 (2)
H32	0.3431	0.5067	0.1850	0.038*
C33	0.2511 (7)	0.4601 (4)	0.0864 (3)	0.0269 (18)
O2	0.1615 (5)	0.5004 (3)	0.08979 (19)	0.0278 (12)
O3	0.2630 (5)	0.4013 (3)	0.1088 (2)	0.0340 (14)
NiA	0.67933 (8)	0.29707 (5)	0.15465 (4)	0.0199 (2)
N1A	0.8541 (6)	0.3377 (4)	0.2327 (3)	0.041 (2)
C1A	0.8582 (8)	0.3726 (6)	0.2788 (3)	0.057 (3)
H1A	0.8037	0.3597	0.3048	0.068*
C2A	0.9366 (10)	0.4260 (6)	0.2910 (4)	0.064 (4)
H2A	0.9352	0.4494	0.3241	0.077*
C3A	1.0167 (11)	0.4444 (6)	0.2540 (4)	0.067 (4)
H3A	1.0731	0.4801	0.2616	0.080*
C4A	1.0144 (8)	0.4106 (5)	0.2058 (3)	0.043 (2)
H4A	1.0684	0.4226	0.1794	0.052*
C5A	0.9310 (7)	0.3587 (5)	0.1968 (3)	0.032 (2)
C6A	0.9184 (6)	0.3238 (5)	0.1437 (3)	0.031 (2)
H6A1	0.9807	0.3412	0.1207	0.038*
H6A2	0.9272	0.2705	0.1476	0.038*
N2A	0.8075 (5)	0.3391 (3)	0.1180 (2)	0.0210 (14)
C7A	0.8096 (7)	0.3103 (4)	0.0620 (2)	0.0253 (17)
H7A1	0.7384	0.2837	0.0538	0.030*
H7A2	0.8753	0.2773	0.0566	0.030*
C8A	0.8207 (7)	0.3781 (4)	0.0279 (3)	0.0291 (17)
H8A1	0.9008	0.3948	0.0256	0.035*
H8A2	0.7907	0.3697	−0.0078	0.035*
C9A	0.7470 (6)	0.4319 (4)	0.0581 (3)	0.0261 (18)
H9A1	0.6649	0.4208	0.0540	0.031*
H9A2	0.7615	0.4825	0.0467	0.031*
C10A	0.7868 (6)	0.4194 (4)	0.1142 (3)	0.0210 (16)
H10A	0.8604	0.4457	0.1199	0.025*
C11A	0.7001 (6)	0.4455 (4)	0.1540 (3)	0.0203 (16)
O1A	0.6901 (5)	0.5109 (3)	0.1607 (2)	0.0294 (13)
N3A	0.6370 (5)	0.3895 (3)	0.1752 (2)	0.0207 (14)
C12A	0.5581 (6)	0.4034 (4)	0.2152 (3)	0.0194 (16)
C13A	0.5664 (7)	0.4656 (4)	0.2472 (3)	0.0267 (18)
H13A	0.6286	0.4981	0.2425	0.032*
C14A	0.4854 (7)	0.4804 (4)	0.2855 (3)	0.0273 (18)
H14A	0.4930	0.5227	0.3065	0.033*
C15A	0.3936 (7)	0.4341 (4)	0.2934 (3)	0.030 (2)
H15A	0.3357	0.4457	0.3180	0.036*
C16A	0.3886 (6)	0.3712 (4)	0.2646 (3)	0.0262 (18)
H16A	0.3274	0.3384	0.2707	0.031*
C17A	0.4710 (6)	0.3532 (4)	0.2263 (3)	0.0202 (16)
C18A	0.4618 (6)	0.2809 (3)	0.2025 (3)	0.0191 (16)
C19A	0.3548 (6)	0.2378 (4)	0.2123 (3)	0.0203 (17)
C20A	0.3522 (6)	0.1808 (4)	0.2477 (3)	0.0207 (16)
H20A	0.4182	0.1696	0.2677	0.025*
C21A	0.2537 (6)	0.1397 (4)	0.2542 (3)	0.0246 (17)
H21A	0.2525	0.1004	0.2784	0.030*
C22A	0.1573 (6)	0.1565 (4)	0.2252 (3)	0.0233 (17)
H22A	0.0901	0.1282	0.2292	0.028*
C23A	0.1578 (6)	0.2138 (4)	0.1905 (3)	0.0301 (18)
H23A	0.0911	0.2251	0.1710	0.036*
C24A	0.2554 (6)	0.2548 (4)	0.1842 (3)	0.0250 (17)
H24A	0.2553	0.2949	0.1607	0.030*
N4A	0.5452 (5)	0.2527 (3)	0.1762 (2)	0.0192 (14)
C25A	0.5381 (6)	0.1777 (4)	0.1564 (3)	0.0245 (17)
H25A	0.5061	0.1459	0.1846	0.029*
C26A	0.4649 (7)	0.1685 (4)	0.1063 (3)	0.0291 (19)
H26C	0.4577	0.1160	0.0985	0.035*
H26D	0.3873	0.1875	0.1133	0.035*
C27A	0.5116 (6)	0.2062 (4)	0.0588 (3)	0.0231 (16)
C28A	0.4828 (6)	0.2779 (4)	0.0471 (3)	0.0297 (19)
H28A	0.4332	0.3039	0.0698	0.036*
C29A	0.5254 (7)	0.3119 (4)	0.0027 (3)	0.0290 (19)
H29A	0.5063	0.3611	−0.0045	0.035*
C30A	0.5965 (7)	0.2735 (4)	−0.0311 (3)	0.0291 (19)
H30A	0.6244	0.2963	−0.0620	0.035*
C31A	0.6265 (7)	0.2029 (5)	−0.0204 (3)	0.0318 (19)
H31A	0.6760	0.1773	−0.0434	0.038*
C32A	0.5841 (7)	0.1688 (4)	0.0243 (3)	0.0295 (19)
H32A	0.6045	0.1199	0.0315	0.035*
C33A	0.6604 (7)	0.1527 (4)	0.1442 (3)	0.0253 (17)
O2A	0.7348 (4)	0.2041 (3)	0.1407 (2)	0.0260 (12)
O3A	0.6789 (5)	0.0876 (3)	0.1379 (2)	0.0350 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0210 (5)	0.0231 (5)	0.0194 (4)	0.0006 (5)	0.0020 (4)	0.0045 (4)
N1	0.032 (4)	0.027 (4)	0.033 (4)	−0.004 (3)	0.000 (3)	−0.003 (3)
C1	0.025 (4)	0.034 (5)	0.037 (5)	−0.001 (4)	0.006 (4)	−0.003 (4)
C2	0.031 (5)	0.039 (5)	0.028 (4)	0.002 (4)	−0.003 (4)	0.004 (4)
C3	0.033 (5)	0.041 (5)	0.036 (5)	0.012 (4)	−0.007 (4)	0.001 (4)
C4	0.026 (5)	0.037 (5)	0.033 (4)	0.001 (4)	0.007 (4)	−0.006 (4)
C5	0.018 (4)	0.026 (4)	0.035 (4)	−0.013 (4)	−0.001 (3)	0.001 (4)
C6	0.018 (4)	0.035 (5)	0.033 (4)	−0.004 (4)	0.006 (3)	−0.001 (4)
N2	0.020 (3)	0.033 (4)	0.019 (3)	−0.011 (3)	0.003 (3)	−0.003 (3)
C7	0.046 (5)	0.032 (5)	0.021 (4)	0.001 (4)	0.009 (4)	0.004 (3)
C8	0.031 (5)	0.058 (6)	0.019 (4)	0.009 (5)	−0.002 (4)	0.004 (4)
C9	0.029 (5)	0.038 (5)	0.023 (4)	−0.003 (4)	−0.004 (4)	−0.009 (4)
C10	0.019 (4)	0.029 (4)	0.024 (4)	0.003 (4)	0.000 (3)	0.002 (4)
C11	0.020 (4)	0.024 (4)	0.030 (4)	−0.004 (3)	0.000 (3)	−0.003 (3)
O1	0.040 (3)	0.023 (3)	0.041 (3)	0.007 (3)	0.015 (3)	0.004 (3)
N3	0.019 (3)	0.024 (3)	0.016 (3)	0.001 (3)	0.002 (3)	0.004 (2)
C12	0.020 (4)	0.022 (4)	0.023 (4)	−0.008 (3)	−0.007 (3)	0.008 (3)
C13	0.025 (4)	0.032 (4)	0.024 (4)	0.005 (4)	−0.001 (4)	0.004 (3)
C14	0.024 (4)	0.036 (5)	0.018 (4)	−0.004 (4)	−0.005 (3)	0.010 (3)
C15	0.028 (4)	0.038 (4)	0.014 (3)	−0.012 (4)	−0.008 (3)	0.006 (3)
C16	0.015 (4)	0.025 (4)	0.021 (3)	0.004 (3)	0.004 (3)	−0.001 (3)
C17	0.018 (4)	0.027 (4)	0.022 (4)	−0.008 (3)	−0.007 (3)	0.000 (3)
C18	0.022 (4)	0.018 (4)	0.021 (4)	−0.005 (3)	−0.002 (3)	−0.003 (3)
C19	0.016 (4)	0.024 (4)	0.020 (4)	0.002 (3)	−0.004 (3)	0.000 (3)
C20	0.026 (4)	0.028 (4)	0.025 (4)	−0.004 (4)	−0.002 (4)	0.000 (3)
C21	0.046 (5)	0.021 (4)	0.028 (4)	−0.008 (4)	0.005 (4)	0.000 (3)
C22	0.044 (6)	0.040 (5)	0.022 (4)	0.001 (4)	0.010 (4)	−0.006 (4)
C23	0.021 (4)	0.035 (5)	0.033 (4)	−0.001 (4)	0.006 (3)	0.007 (4)
C24	0.021 (4)	0.023 (4)	0.024 (4)	0.000 (3)	0.001 (3)	−0.005 (3)
N4	0.023 (4)	0.023 (3)	0.022 (3)	−0.002 (3)	−0.002 (3)	0.003 (3)
C25	0.027 (4)	0.026 (4)	0.019 (3)	0.008 (3)	0.005 (3)	0.006 (3)
C26	0.022 (4)	0.042 (5)	0.029 (4)	0.006 (4)	−0.005 (4)	0.007 (4)
C27	0.020 (4)	0.034 (5)	0.030 (4)	0.005 (4)	−0.013 (3)	0.003 (4)
C28	0.028 (5)	0.038 (5)	0.049 (6)	−0.009 (4)	−0.014 (5)	0.015 (4)
C29	0.055 (6)	0.040 (5)	0.062 (7)	0.005 (5)	−0.035 (6)	−0.002 (6)
C30	0.051 (7)	0.047 (6)	0.054 (6)	0.017 (5)	−0.032 (6)	−0.023 (5)
C31	0.033 (5)	0.067 (7)	0.032 (4)	0.006 (5)	−0.012 (5)	−0.013 (4)
C32	0.030 (5)	0.031 (4)	0.034 (4)	0.000 (4)	−0.010 (4)	0.003 (4)
C33	0.043 (5)	0.020 (4)	0.018 (4)	−0.007 (4)	0.000 (4)	0.003 (3)
O2	0.034 (3)	0.022 (3)	0.028 (3)	0.002 (3)	0.003 (3)	0.007 (2)
O3	0.053 (4)	0.023 (3)	0.026 (3)	0.002 (3)	−0.005 (3)	0.005 (2)
NiA	0.0179 (5)	0.0192 (4)	0.0227 (5)	0.0006 (4)	0.0040 (5)	0.0000 (4)
N1A	0.033 (5)	0.064 (5)	0.027 (4)	0.011 (4)	−0.007 (3)	0.012 (4)
C1A	0.045 (6)	0.097 (9)	0.028 (5)	0.034 (6)	−0.011 (5)	0.004 (5)
C2A	0.096 (10)	0.065 (8)	0.032 (6)	0.028 (7)	−0.032 (7)	−0.018 (6)
C3A	0.088 (10)	0.057 (7)	0.055 (7)	−0.009 (7)	−0.041 (7)	−0.002 (6)
C4A	0.040 (5)	0.048 (6)	0.042 (5)	−0.007 (5)	−0.020 (4)	0.003 (5)
C5A	0.025 (4)	0.043 (5)	0.029 (4)	0.007 (4)	−0.012 (4)	0.007 (4)
C6A	0.013 (4)	0.042 (5)	0.038 (5)	0.005 (4)	0.000 (4)	0.006 (4)
N2A	0.018 (3)	0.027 (3)	0.018 (3)	0.003 (3)	−0.003 (3)	−0.001 (3)
C7A	0.024 (4)	0.035 (4)	0.018 (4)	−0.002 (4)	0.001 (3)	−0.006 (3)
C8A	0.026 (4)	0.042 (4)	0.020 (3)	−0.004 (4)	0.008 (4)	−0.006 (3)
C9A	0.022 (4)	0.034 (4)	0.023 (4)	0.002 (3)	0.001 (3)	0.000 (3)
C10A	0.019 (4)	0.022 (4)	0.022 (4)	−0.011 (3)	0.004 (3)	−0.002 (3)
C11A	0.026 (4)	0.027 (4)	0.009 (3)	−0.004 (3)	0.001 (3)	0.000 (3)
O1A	0.040 (3)	0.020 (3)	0.029 (3)	−0.006 (3)	0.007 (3)	−0.001 (2)
N3A	0.021 (3)	0.026 (3)	0.015 (3)	−0.001 (3)	0.000 (3)	0.001 (2)
C12A	0.022 (4)	0.020 (4)	0.017 (3)	0.003 (3)	0.000 (3)	0.000 (3)
C13A	0.026 (4)	0.035 (5)	0.020 (4)	−0.004 (4)	0.008 (3)	−0.008 (3)
C14A	0.042 (5)	0.019 (4)	0.021 (4)	−0.001 (4)	0.004 (4)	−0.002 (3)
C15A	0.033 (5)	0.032 (5)	0.026 (4)	0.006 (4)	0.005 (4)	−0.002 (4)
C16A	0.021 (4)	0.027 (4)	0.031 (4)	0.004 (4)	0.009 (4)	−0.005 (4)
C17A	0.020 (4)	0.024 (4)	0.017 (4)	0.004 (3)	0.004 (3)	−0.004 (3)
C18A	0.028 (4)	0.016 (4)	0.013 (3)	0.001 (3)	0.000 (3)	0.001 (3)
C19A	0.021 (4)	0.023 (4)	0.017 (3)	0.000 (3)	0.010 (3)	−0.008 (3)
C20A	0.014 (4)	0.030 (4)	0.018 (3)	0.003 (3)	−0.001 (3)	0.002 (3)
C21A	0.028 (4)	0.023 (4)	0.023 (4)	−0.005 (4)	0.004 (3)	−0.001 (3)
C22A	0.015 (4)	0.026 (4)	0.029 (4)	−0.003 (3)	0.005 (3)	−0.004 (3)
C23A	0.019 (4)	0.037 (5)	0.033 (4)	0.008 (4)	0.003 (4)	0.002 (4)
C24A	0.030 (4)	0.023 (4)	0.022 (4)	0.005 (4)	0.002 (4)	0.003 (3)
N4A	0.020 (3)	0.019 (3)	0.018 (3)	0.001 (3)	0.004 (3)	−0.001 (3)
C25A	0.024 (4)	0.019 (4)	0.030 (4)	−0.004 (3)	0.009 (4)	−0.001 (3)
C26A	0.026 (4)	0.028 (4)	0.034 (4)	−0.001 (4)	0.006 (4)	−0.012 (4)
C27A	0.015 (3)	0.028 (4)	0.027 (4)	−0.008 (3)	−0.006 (3)	−0.007 (3)
C28A	0.017 (4)	0.040 (5)	0.033 (4)	−0.001 (4)	0.001 (4)	−0.014 (4)
C29A	0.027 (4)	0.032 (5)	0.028 (4)	−0.001 (4)	−0.001 (4)	−0.003 (4)
C30A	0.030 (4)	0.035 (5)	0.023 (4)	−0.005 (4)	−0.006 (4)	0.001 (3)
C31A	0.030 (4)	0.038 (5)	0.027 (4)	−0.003 (4)	0.003 (4)	−0.012 (4)
C32A	0.024 (4)	0.033 (4)	0.032 (4)	−0.001 (4)	0.001 (4)	−0.009 (4)
C33A	0.032 (5)	0.024 (4)	0.019 (4)	0.007 (4)	0.006 (4)	−0.002 (3)
O2A	0.020 (3)	0.021 (3)	0.038 (3)	−0.001 (2)	0.010 (2)	0.000 (2)
O3A	0.044 (3)	0.021 (3)	0.040 (3)	0.008 (3)	0.022 (3)	0.004 (2)

Geometric parameters (Å, º)

Ni—N2	1.932 (6)	NiA—N2A	1.932 (6)
Ni—N3	1.862 (5)	NiA—N3A	1.846 (6)
Ni—N4	1.833 (6)	NiA—N4A	1.855 (6)
Ni—O2	1.872 (5)	NiA—O2A	1.863 (5)
Ni—N1	2.861 (7)	NiA—N1A	2.954 (8)
N1—C5	1.343 (9)	N1A—C1A	1.341 (10)
N1—C1	1.358 (9)	N1A—C5A	1.343 (10)
C1—C2	1.373 (10)	C1A—C2A	1.381 (13)
C1—H1	0.9500	C1A—H1A	0.9500
C2—C3	1.372 (10)	C2A—C3A	1.374 (14)
C2—H2	0.9500	C2A—H2A	0.9500
C3—C4	1.371 (10)	C3A—C4A	1.379 (12)
C3—H3	0.9500	C3A—H3A	0.9500
C4—C5	1.388 (10)	C4A—C5A	1.385 (10)
C4—H4	0.9500	C4A—H4A	0.9500
C5—C6	1.511 (9)	C5A—C6A	1.507 (10)
C6—N2	1.486 (8)	C6A—N2A	1.484 (8)
C6—H6A	0.9900	C6A—H6A1	0.9900
C6—H6B	0.9900	C6A—H6A2	0.9900
N2—C10	1.494 (9)	N2A—C10A	1.500 (8)
N2—C7	1.511 (8)	N2A—C7A	1.524 (8)
C7—C8	1.523 (10)	C7A—C8A	1.525 (9)
C7—H7A	0.9900	C7A—H7A1	0.9900
C7—H7B	0.9900	C7A—H7A2	0.9900
C8—C9	1.527 (10)	C8A—C9A	1.522 (9)
C8—H8A	0.9900	C8A—H8A1	0.9900
C8—H8B	0.9900	C8A—H8A2	0.9900
C9—C10	1.523 (9)	C9A—C10A	1.525 (9)
C9—H9A	0.9900	C9A—H9A1	0.9900
C9—H9B	0.9900	C9A—H9A2	0.9900
C10—C11	1.509 (9)	C10A—C11A	1.515 (9)
C10—H10	1.0000	C10A—H10A	1.0000
C11—O1	1.222 (8)	C11A—O1A	1.220 (8)
C11—N3	1.366 (8)	C11A—N3A	1.380 (8)
N3—C12	1.404 (8)	N3A—C12A	1.402 (8)
C12—C13	1.413 (9)	C12A—C17A	1.405 (9)
C12—C17	1.417 (9)	C12A—C13A	1.409 (9)
C13—C14	1.382 (9)	C13A—C14A	1.389 (9)
C13—H13	0.9500	C13A—H13A	0.9500
C14—C15	1.374 (10)	C14A—C15A	1.386 (10)
C14—H14	0.9500	C14A—H14A	0.9500
C15—C16	1.365 (9)	C15A—C16A	1.372 (10)
C15—H15	0.9500	C15A—H15A	0.9500
C16—C17	1.423 (9)	C16A—C17A	1.414 (9)
C16—H16	0.9500	C16A—H16A	0.9500
C17—C18	1.470 (9)	C17A—C18A	1.465 (9)
C18—N4	1.294 (8)	C18A—N4A	1.296 (8)
C18—C19	1.505 (9)	C18A—C19A	1.505 (9)
C19—C20	1.391 (9)	C19A—C20A	1.384 (9)
C19—C24	1.407 (9)	C19A—C24A	1.403 (9)
C20—C21	1.386 (10)	C20A—C21A	1.389 (9)
C20—H20	0.9500	C20A—H20A	0.9500
C21—C22	1.385 (11)	C21A—C22A	1.387 (10)
C21—H21	0.9500	C21A—H21A	0.9500
C22—C23	1.382 (10)	C22A—C23A	1.375 (9)
C22—H22	0.9500	C22A—H22A	0.9500
C23—C24	1.379 (9)	C23A—C24A	1.380 (10)
C23—H23	0.9500	C23A—H23A	0.9500
C24—H24	0.9500	C24A—H24A	0.9500
N4—C25	1.477 (8)	N4A—C25A	1.470 (8)
C25—C33	1.526 (9)	C25A—C33A	1.538 (9)
C25—C26	1.555 (10)	C25A—C26A	1.551 (10)
C25—H25	1.0000	C25A—H25A	1.0000
C26—C27	1.502 (10)	C26A—C27A	1.501 (10)
C26—H26A	0.9900	C26A—H26C	0.9900
C26—H26B	0.9900	C26A—H26D	0.9900
C27—C28	1.375 (10)	C27A—C28A	1.393 (10)
C27—C32	1.409 (10)	C27A—C32A	1.404 (9)
C28—C29	1.387 (11)	C28A—C29A	1.387 (10)
C28—H28	0.9500	C28A—H28A	0.9500
C29—C30	1.390 (12)	C29A—C30A	1.393 (10)
C29—H29	0.9500	C29A—H29A	0.9500
C30—C31	1.372 (11)	C30A—C31A	1.373 (10)
C30—H30	0.9500	C30A—H30A	0.9500
C31—C32	1.378 (10)	C31A—C32A	1.392 (10)
C31—H31	0.9500	C31A—H31A	0.9500
C32—H32	0.9500	C32A—H32A	0.9500
C33—O3	1.232 (8)	C33A—O3A	1.225 (8)
C33—O2	1.288 (9)	C33A—O2A	1.290 (8)
N2—Ni—N3	88.2 (3)	N2A—NiA—N3A	88.8 (2)
N2—Ni—N4	175.1 (3)	N2A—NiA—N4A	168.2 (2)
N2—Ni—O2	89.5 (2)	N2A—NiA—O2A	90.2 (2)
N3—Ni—N4	95.4 (2)	N3A—NiA—N4A	95.3 (3)
N3—Ni—O2	175.0 (3)	N3A—NiA—O2A	173.0 (3)
N4—Ni—O2	87.0 (2)	N4A—NiA—O2A	87.1 (2)
C5—N1—C1	116.0 (7)	C1A—N1A—C5A	116.0 (8)
N1—C1—C2	124.0 (8)	N1A—C1A—C2A	124.1 (10)
N1—C1—H1	118.0	N1A—C1A—H1A	118.0
C2—C1—H1	118.0	C2A—C1A—H1A	118.0
C3—C2—C1	118.2 (7)	C3A—C2A—C1A	118.5 (9)
C3—C2—H2	120.9	C3A—C2A—H2A	120.8
C1—C2—H2	120.9	C1A—C2A—H2A	120.8
C4—C3—C2	119.7 (8)	C2A—C3A—C4A	119.2 (10)
C4—C3—H3	120.1	C2A—C3A—H3A	120.4
C2—C3—H3	120.1	C4A—C3A—H3A	120.4
C3—C4—C5	118.6 (7)	C3A—C4A—C5A	118.2 (9)
C3—C4—H4	120.7	C3A—C4A—H4A	120.9
C5—C4—H4	120.7	C5A—C4A—H4A	120.9
N1—C5—C4	123.3 (7)	N1A—C5A—C4A	124.0 (8)
N1—C5—C6	114.5 (7)	N1A—C5A—C6A	115.2 (7)
C4—C5—C6	122.2 (7)	C4A—C5A—C6A	120.8 (7)
N2—C6—C5	113.4 (6)	N2A—C6A—C5A	113.8 (6)
N2—C6—H6A	108.9	N2A—C6A—H6A1	108.8
C5—C6—H6A	108.9	C5A—C6A—H6A1	108.8
N2—C6—H6B	108.9	N2A—C6A—H6A2	108.8
C5—C6—H6B	108.9	C5A—C6A—H6A2	108.8
H6A—C6—H6B	107.7	H6A1—C6A—H6A2	107.7
C6—N2—C10	112.4 (6)	C6A—N2A—C10A	110.9 (6)
C6—N2—C7	110.0 (6)	C6A—N2A—C7A	109.6 (6)
C10—N2—C7	106.9 (5)	C10A—N2A—C7A	106.5 (5)
C6—N2—Ni	108.0 (4)	C6A—N2A—NiA	113.0 (4)
C10—N2—Ni	106.4 (4)	C10A—N2A—NiA	107.4 (4)
C7—N2—Ni	113.1 (5)	C7A—N2A—NiA	109.2 (4)
N2—C7—C8	106.5 (6)	N2A—C7A—C8A	104.6 (5)
N2—C7—H7A	110.4	N2A—C7A—H7A1	110.8
C8—C7—H7A	110.4	C8A—C7A—H7A1	110.8
N2—C7—H7B	110.4	N2A—C7A—H7A2	110.8
C8—C7—H7B	110.4	C8A—C7A—H7A2	110.8
H7A—C7—H7B	108.6	H7A1—C7A—H7A2	108.9
C7—C8—C9	102.6 (6)	C9A—C8A—C7A	101.2 (6)
C7—C8—H8A	111.3	C9A—C8A—H8A1	111.5
C9—C8—H8A	111.2	C7A—C8A—H8A1	111.5
C7—C8—H8B	111.2	C9A—C8A—H8A2	111.5
C9—C8—H8B	111.2	C7A—C8A—H8A2	111.5
H8A—C8—H8B	109.2	H8A1—C8A—H8A2	109.3
C10—C9—C8	102.6 (6)	C8A—C9A—C10A	101.8 (6)
C10—C9—H9A	111.2	C8A—C9A—H9A1	111.4
C8—C9—H9A	111.2	C10A—C9A—H9A1	111.4
C10—C9—H9B	111.2	C8A—C9A—H9A2	111.4
C8—C9—H9B	111.2	C10A—C9A—H9A2	111.4
H9A—C9—H9B	109.2	H9A1—C9A—H9A2	109.3
N2—C10—C11	112.5 (6)	N2A—C10A—C11A	112.2 (5)
N2—C10—C9	104.5 (6)	N2A—C10A—C9A	104.9 (5)
C11—C10—C9	112.1 (6)	C11A—C10A—C9A	112.1 (6)
N2—C10—H10	109.2	N2A—C10A—H10A	109.2
C11—C10—H10	109.2	C11A—C10A—H10A	109.2
C9—C10—H10	109.2	C9A—C10A—H10A	109.2
O1—C11—N3	128.4 (7)	O1A—C11A—N3A	129.1 (6)
O1—C11—C10	118.2 (7)	O1A—C11A—C10A	118.0 (6)
N3—C11—C10	113.3 (6)	N3A—C11A—C10A	112.7 (6)
C11—N3—C12	121.4 (6)	C11A—N3A—C12A	120.2 (6)
C11—N3—Ni	114.5 (4)	C11A—N3A—NiA	115.6 (4)
C12—N3—Ni	123.6 (5)	C12A—N3A—NiA	123.5 (5)
N3—C12—C13	121.4 (6)	N3A—C12A—C17A	120.4 (6)
N3—C12—C17	121.2 (6)	N3A—C12A—C13A	121.7 (6)
C13—C12—C17	117.3 (6)	C17A—C12A—C13A	117.8 (6)
C14—C13—C12	122.0 (7)	C14A—C13A—C12A	121.3 (7)
C14—C13—H13	119.0	C14A—C13A—H13A	119.4
C12—C13—H13	119.0	C12A—C13A—H13A	119.4
C15—C14—C13	120.6 (7)	C15A—C14A—C13A	120.9 (7)
C15—C14—H14	119.7	C15A—C14A—H14A	119.6
C13—C14—H14	119.7	C13A—C14A—H14A	119.6
C16—C15—C14	119.0 (7)	C16A—C15A—C14A	118.2 (7)
C16—C15—H15	120.5	C16A—C15A—H15A	120.9
C14—C15—H15	120.5	C14A—C15A—H15A	120.9
C15—C16—C17	122.6 (7)	C15A—C16A—C17A	122.6 (7)
C15—C16—H16	118.7	C15A—C16A—H16A	118.7
C17—C16—H16	118.7	C17A—C16A—H16A	118.7
C12—C17—C16	118.3 (6)	C12A—C17A—C16A	118.8 (6)
C12—C17—C18	124.2 (6)	C12A—C17A—C18A	124.5 (6)
C16—C17—C18	117.4 (6)	C16A—C17A—C18A	116.6 (6)
N4—C18—C17	121.9 (6)	N4A—C18A—C17A	121.6 (6)
N4—C18—C19	121.6 (6)	N4A—C18A—C19A	120.2 (6)
C17—C18—C19	116.3 (6)	C17A—C18A—C19A	118.1 (6)
C20—C19—C24	119.5 (6)	C20A—C19A—C24A	119.0 (6)
C20—C19—C18	118.8 (6)	C20A—C19A—C18A	121.7 (6)
C24—C19—C18	121.5 (6)	C24A—C19A—C18A	119.3 (6)
C21—C20—C19	120.1 (7)	C19A—C20A—C21A	120.5 (7)
C21—C20—H20	120.0	C19A—C20A—H20A	119.7
C19—C20—H20	120.0	C21A—C20A—H20A	119.7
C22—C21—C20	120.3 (7)	C22A—C21A—C20A	119.4 (6)
C22—C21—H21	119.9	C22A—C21A—H21A	120.3
C20—C21—H21	119.9	C20A—C21A—H21A	120.3
C23—C22—C21	119.7 (8)	C23A—C22A—C21A	120.8 (7)
C23—C22—H22	120.2	C23A—C22A—H22A	119.6
C21—C22—H22	120.2	C21A—C22A—H22A	119.6
C24—C23—C22	121.1 (7)	C22A—C23A—C24A	119.8 (7)
C24—C23—H23	119.4	C22A—C23A—H23A	120.1
C22—C23—H23	119.4	C24A—C23A—H23A	120.1
C23—C24—C19	119.3 (7)	C23A—C24A—C19A	120.4 (7)
C23—C24—H24	120.4	C23A—C24A—H24A	119.8
C19—C24—H24	120.4	C19A—C24A—H24A	119.8
C18—N4—C25	120.5 (6)	C18A—N4A—C25A	120.8 (6)
C18—N4—Ni	128.3 (5)	C18A—N4A—NiA	128.1 (5)
C25—N4—Ni	111.1 (4)	C25A—N4A—NiA	111.0 (4)
N4—C25—C33	107.1 (6)	N4A—C25A—C33A	107.3 (6)
N4—C25—C26	112.8 (6)	N4A—C25A—C26A	114.6 (6)
C33—C25—C26	108.9 (6)	C33A—C25A—C26A	108.4 (6)
N4—C25—H25	109.3	N4A—C25A—H25A	108.8
C33—C25—H25	109.3	C33A—C25A—H25A	108.8
C26—C25—H25	109.3	C26A—C25A—H25A	108.8
C27—C26—C25	115.2 (6)	C27A—C26A—C25A	114.5 (6)
C27—C26—H26A	108.5	C27A—C26A—H26C	108.6
C25—C26—H26A	108.5	C25A—C26A—H26C	108.6
C27—C26—H26B	108.5	C27A—C26A—H26D	108.6
C25—C26—H26B	108.5	C25A—C26A—H26D	108.6
H26A—C26—H26B	107.5	H26C—C26A—H26D	107.6
C28—C27—C32	117.9 (7)	C28A—C27A—C32A	118.5 (7)
C28—C27—C26	121.5 (7)	C28A—C27A—C26A	121.4 (7)
C32—C27—C26	120.5 (7)	C32A—C27A—C26A	120.1 (7)
C27—C28—C29	121.2 (8)	C29A—C28A—C27A	120.9 (7)
C27—C28—H28	119.4	C29A—C28A—H28A	119.6
C29—C28—H28	119.4	C27A—C28A—H28A	119.6
C28—C29—C30	120.2 (9)	C28A—C29A—C30A	119.6 (7)
C28—C29—H29	119.9	C28A—C29A—H29A	120.2
C30—C29—H29	119.9	C30A—C29A—H29A	120.2
C31—C30—C29	119.3 (9)	C31A—C30A—C29A	120.6 (7)
C31—C30—H30	120.4	C31A—C30A—H30A	119.7
C29—C30—H30	120.4	C29A—C30A—H30A	119.7
C30—C31—C32	120.7 (9)	C30A—C31A—C32A	119.8 (8)
C30—C31—H31	119.7	C30A—C31A—H31A	120.1
C32—C31—H31	119.7	C32A—C31A—H31A	120.1
C31—C32—C27	120.7 (8)	C31A—C32A—C27A	120.6 (8)
C31—C32—H32	119.6	C31A—C32A—H32A	119.7
C27—C32—H32	119.6	C27A—C32A—H32A	119.7
O3—C33—O2	124.4 (7)	O3A—C33A—O2A	126.0 (7)
O3—C33—C25	120.2 (7)	O3A—C33A—C25A	118.9 (7)
O2—C33—C25	115.3 (6)	O2A—C33A—C25A	115.1 (6)
C33—O2—Ni	114.5 (5)	C33A—O2A—NiA	115.1 (4)

(II) [N-({2-[N-(S)-(3-picolyl)prolylamino]phenyl}phenylmethylene)-(S)- phenylalaninato]nickel(II) hemihydrate

Crystal data

[Ni(C33H30N4O3)]·0.5H2O	F(000) = 2504
Mr = 598.33	Dx = 1.434 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 32 reflections
a = 11.522 (4) Å	θ = 12.4–13.7°
b = 18.623 (6) Å	µ = 0.75 mm^−1
c = 25.828 (7) Å	T = 150 K
V = 5542 (3) Å^3	Tablet, dark red
Z = 8	0.35 × 0.27 × 0.16 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	3785 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 23.5°, θmin = 2.6°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995)	k = −20→20
Tmin = 0.789, Tmax = 0.864	l = 0→29
5291 measured reflections	3 standard reflections every 60 min
4765 independent reflections	intensity decay: variation +−5.2%

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)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + 16.36P] where P = (Fo^2 + 2Fc^2)/3
S = 1.29	(Δ/σ)max = 0.004
4765 reflections	Δρmax = 0.48 e Å^−3
748 parameters	Δρmin = −0.42 e Å^−3
369 restraints	Absolute structure: Flack (1983) with 194 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (3)

Special details

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
Ni	0.81375 (12)	0.30046 (7)	0.34360 (5)	0.0280 (4)
O1	0.8069 (7)	0.5119 (3)	0.3414 (3)	0.036 (2)
O2	0.7548 (6)	0.2086 (3)	0.3552 (3)	0.039 (3)
O3	0.8069 (7)	0.0934 (3)	0.3547 (3)	0.051 (3)
N1	0.5019 (14)	0.4648 (7)	0.2469 (6)	0.096 (6)
N2	0.6812 (8)	0.3410 (4)	0.3774 (3)	0.030 (3)
N3	0.8538 (7)	0.3929 (3)	0.3239 (3)	0.025 (3)
N4	0.9469 (7)	0.2569 (4)	0.3214 (3)	0.028 (3)
C1	0.6316 (13)	0.3460 (8)	0.2546 (5)	0.070 (6)
C2	0.6307 (14)	0.3839 (10)	0.2106 (5)	0.093 (8)
C3	0.5629 (18)	0.4429 (11)	0.2069 (6)	0.110 (9)
C4	0.4953 (12)	0.4266 (7)	0.2909 (5)	0.061 (5)
C5	0.5649 (11)	0.3668 (6)	0.2973 (4)	0.052 (5)
C6	0.5708 (9)	0.3286 (6)	0.3485 (4)	0.043 (4)
C7	0.6687 (10)	0.3097 (5)	0.4316 (3)	0.039 (4)
C8	0.6638 (11)	0.3747 (5)	0.4678 (3)	0.043 (4)
C9	0.7443 (9)	0.4271 (5)	0.4406 (3)	0.035 (4)
C10	0.7040 (8)	0.4202 (4)	0.3840 (3)	0.027 (3)
C11	0.7940 (9)	0.4471 (5)	0.3468 (4)	0.027 (3)
C12	0.9389 (9)	0.4064 (5)	0.2858 (3)	0.029 (3)
C13	0.9346 (10)	0.4701 (5)	0.2564 (4)	0.039 (4)
C14	1.0208 (12)	0.4854 (5)	0.2198 (4)	0.051 (5)
C15	1.1107 (11)	0.4391 (5)	0.2108 (4)	0.046 (4)
C16	1.1137 (10)	0.3760 (5)	0.2382 (4)	0.039 (4)
C17	1.0280 (9)	0.3566 (5)	0.2749 (4)	0.025 (3)
C18	1.0339 (8)	0.2842 (4)	0.2962 (3)	0.023 (3)
C19	1.1431 (8)	0.2406 (5)	0.2865 (3)	0.022 (3)
C20	1.2418 (9)	0.2536 (5)	0.3158 (4)	0.034 (4)
C21	1.3396 (9)	0.2115 (5)	0.3090 (4)	0.042 (4)
C22	1.3403 (10)	0.1568 (5)	0.2731 (4)	0.038 (4)
C23	1.2431 (9)	0.1448 (5)	0.2431 (4)	0.031 (3)
C24	1.1441 (9)	0.1854 (5)	0.2503 (3)	0.027 (3)
C25	0.9547 (9)	0.1807 (5)	0.3393 (4)	0.036 (4)
C26	1.0266 (10)	0.1686 (6)	0.3882 (4)	0.048 (4)
C27	0.9804 (9)	0.2049 (5)	0.4366 (4)	0.037 (3)
C28	1.0112 (9)	0.2748 (6)	0.4487 (4)	0.042 (4)
C29	0.9695 (10)	0.3076 (6)	0.4931 (4)	0.043 (4)
C30	0.8928 (10)	0.2713 (6)	0.5244 (4)	0.046 (4)
C31	0.8589 (10)	0.2029 (6)	0.5125 (4)	0.045 (4)
C32	0.9032 (10)	0.1703 (6)	0.4686 (4)	0.045 (4)
C33	0.8283 (11)	0.1580 (5)	0.3494 (4)	0.043 (4)
NIA	0.66302 (13)	0.08870 (6)	0.04732 (5)	0.0268 (4)
O1A	0.5869 (7)	0.2866 (3)	0.0069 (3)	0.043 (3)
O2A	0.6452 (6)	0.0025 (3)	0.0839 (3)	0.032 (3)
O3A	0.7405 (7)	−0.0974 (3)	0.1059 (3)	0.038 (3)
N1A	0.3458 (10)	0.1478 (5)	−0.0792 (4)	0.064 (4)
N2A	0.5272 (8)	0.1270 (4)	0.0816 (3)	0.032 (3)
N3A	0.6657 (8)	0.1705 (4)	0.0066 (3)	0.029 (3)
N4A	0.7956 (7)	0.0480 (4)	0.0190 (3)	0.028 (3)
C1A	0.4757 (10)	0.0434 (5)	−0.0284 (4)	0.033 (3)
C2A	0.4727 (11)	0.0459 (6)	−0.0806 (4)	0.043 (4)
C3A	0.4110 (12)	0.0988 (7)	−0.1037 (5)	0.059 (5)
C4A	0.3533 (11)	0.1453 (6)	−0.0260 (5)	0.051 (4)
C5A	0.4156 (9)	0.0939 (6)	0.0012 (4)	0.032 (3)
C6A	0.4213 (9)	0.0921 (6)	0.0596 (4)	0.040 (3)
C7A	0.5290 (12)	0.1166 (5)	0.1401 (4)	0.047 (4)
C8A	0.5371 (10)	0.1904 (6)	0.1644 (4)	0.044 (4)
C9A	0.5876 (10)	0.2364 (5)	0.1209 (4)	0.036 (3)
C10A	0.5297 (9)	0.2064 (5)	0.0722 (3)	0.033 (3)
C11A	0.5968 (9)	0.2246 (5)	0.0239 (4)	0.033 (4)
C12A	0.7182 (8)	0.1738 (4)	−0.0425 (4)	0.026 (3)
C13A	0.6863 (9)	0.2262 (5)	−0.0790 (4)	0.034 (3)
C14A	0.7345 (9)	0.2283 (6)	−0.1282 (4)	0.036 (4)
C15A	0.8167 (10)	0.1786 (5)	−0.1428 (4)	0.035 (3)
C16A	0.8490 (9)	0.1265 (5)	−0.1082 (3)	0.033 (3)
C17A	0.8018 (8)	0.1226 (5)	−0.0578 (3)	0.025 (3)
C18A	0.8433 (8)	0.0637 (4)	−0.0248 (3)	0.025 (3)
C19A	0.9418 (8)	0.0185 (5)	−0.0461 (4)	0.023 (3)
C20A	0.9161 (10)	−0.0410 (5)	−0.0758 (4)	0.034 (4)
C21A	1.0051 (9)	−0.0797 (6)	−0.0988 (4)	0.038 (4)
C22A	1.1191 (10)	−0.0608 (6)	−0.0924 (4)	0.043 (4)
C23A	1.1431 (9)	−0.0016 (6)	−0.0621 (4)	0.037 (4)
C24A	1.0564 (9)	0.0389 (5)	−0.0397 (4)	0.034 (3)
C25A	0.8377 (9)	−0.0129 (5)	0.0512 (4)	0.031 (3)
C26A	0.9363 (9)	0.0100 (5)	0.0875 (4)	0.037 (4)
C27A	0.9078 (9)	0.0710 (5)	0.1233 (4)	0.033 (3)
C28A	0.9335 (11)	0.1403 (5)	0.1106 (5)	0.049 (5)
C29A	0.9075 (13)	0.1955 (7)	0.1442 (5)	0.071 (5)
C30A	0.8548 (12)	0.1801 (8)	0.1903 (6)	0.074 (6)
C31A	0.8270 (13)	0.1116 (8)	0.2037 (5)	0.076 (6)
C32A	0.8550 (11)	0.0563 (7)	0.1702 (4)	0.052 (4)
C33A	0.7334 (9)	−0.0396 (5)	0.0834 (4)	0.030 (3)
O1W	0.6084 (12)	0.0965 (10)	0.2842 (5)	0.158 (8)
H1	0.67840	0.30420	0.25690	0.0840*
H2	0.67740	0.36940	0.18210	0.1120*
H3	0.55920	0.46870	0.17520	0.1340*
H4	0.44310	0.44070	0.31750	0.0730*
H6A	0.50500	0.34470	0.37030	0.0510*
H6B	0.56150	0.27640	0.34250	0.0510*
H7A	0.73580	0.27870	0.44010	0.0460*
H7B	0.59670	0.28090	0.43440	0.0460*
H8A	0.58400	0.39410	0.47050	0.0520*
H8B	0.69260	0.36250	0.50280	0.0520*
H9A	0.82660	0.41290	0.44460	0.0420*
H9B	0.73380	0.47660	0.45380	0.0420*
H10	0.63010	0.44760	0.37900	0.0320*
H13	0.87260	0.50300	0.26150	0.0470*
H14	1.01680	0.52900	0.20080	0.0610*
H15	1.16940	0.45030	0.18620	0.0560*
H16	1.17620	0.34380	0.23220	0.0460*
H20	1.24240	0.29150	0.34040	0.0410*
H21	1.40680	0.22040	0.32920	0.0500*
H22	1.40720	0.12750	0.26910	0.0450*
H23	1.24430	0.10840	0.21730	0.0370*
H24	1.07650	0.17550	0.23050	0.0320*
H25	0.98710	0.15070	0.31070	0.0440*
H26A	1.03130	0.11630	0.39480	0.0580*
H26B	1.10650	0.18610	0.38180	0.0580*
H28	1.06160	0.30060	0.42630	0.0510*
H29	0.99370	0.35490	0.50190	0.0510*
H30	0.86310	0.29400	0.55450	0.0550*
H31	0.80570	0.17800	0.53420	0.0540*
H32	0.87950	0.12270	0.46030	0.0540*
H6A1	0.35180	0.11650	0.07360	0.0490*
H1A	0.51920	0.00690	−0.01160	0.0400*
H6A2	0.41890	0.04150	0.07110	0.0490*
H2A	0.51300	0.01120	−0.10070	0.0520*
H7A1	0.45730	0.09200	0.15160	0.0560*
H3A	0.41420	0.10150	−0.14040	0.0710*
H7A2	0.59650	0.08690	0.15030	0.0560*
H4A	0.31330	0.18100	−0.00680	0.0620*
H8A1	0.58890	0.19000	0.19490	0.0530*
H8A2	0.45960	0.20810	0.17490	0.0530*
H9A1	0.67310	0.23130	0.11910	0.0430*
H9A2	0.56810	0.28770	0.12590	0.0430*
H10A	0.44860	0.22520	0.06940	0.0390*
H13A	0.63020	0.26130	−0.06970	0.0400*
H14A	0.71060	0.26430	−0.15200	0.0430*
H15A	0.85050	0.18040	−0.17630	0.0420*
H16A	0.90510	0.09190	−0.11840	0.0390*
H20A	0.83770	−0.05530	−0.08050	0.0410*
H21A	0.98660	−0.12020	−0.11950	0.0460*
H22A	1.17960	−0.08760	−0.10820	0.0510*
H23A	1.22180	0.01170	−0.05660	0.0440*
H24A	1.07520	0.08040	−0.02000	0.0400*
H25A	0.86550	−0.05240	0.02810	0.0380*
H26C	0.95960	−0.03200	0.10860	0.0440*
H26D	1.00400	0.02400	0.06610	0.0440*
H28A	0.96970	0.15060	0.07840	0.0580*
H29A	0.92590	0.24370	0.13550	0.0850*
H30A	0.83720	0.21810	0.21360	0.0890*
H31A	0.78890	0.10190	0.23560	0.0910*
H32A	0.83800	0.00810	0.17940	0.0620*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0322 (8)	0.0184 (6)	0.0334 (8)	−0.0008 (7)	0.0093 (7)	0.0009 (6)
O1	0.059 (5)	0.022 (3)	0.027 (4)	0.005 (4)	0.010 (4)	0.005 (3)
O2	0.038 (4)	0.024 (4)	0.055 (5)	−0.001 (4)	0.026 (4)	−0.001 (4)
O3	0.066 (6)	0.017 (3)	0.070 (5)	−0.013 (4)	0.046 (5)	−0.004 (4)
N1	0.124 (12)	0.091 (10)	0.074 (8)	−0.014 (8)	−0.058 (9)	0.031 (8)
N2	0.032 (5)	0.030 (4)	0.027 (4)	−0.003 (4)	0.005 (4)	−0.001 (4)
N3	0.034 (5)	0.015 (4)	0.025 (4)	−0.001 (4)	0.010 (4)	0.003 (3)
N4	0.035 (5)	0.016 (4)	0.034 (5)	−0.004 (4)	0.010 (4)	−0.007 (4)
C1	0.082 (12)	0.082 (10)	0.047 (8)	−0.019 (9)	−0.010 (8)	−0.030 (7)
C2	0.084 (13)	0.171 (18)	0.025 (7)	−0.043 (11)	−0.012 (8)	−0.018 (9)
C3	0.131 (19)	0.154 (17)	0.038 (7)	0.040 (11)	−0.051 (8)	−0.037 (10)
C4	0.063 (10)	0.062 (9)	0.058 (8)	−0.004 (7)	−0.028 (7)	0.005 (7)
C5	0.051 (9)	0.051 (8)	0.055 (7)	−0.017 (7)	−0.016 (7)	−0.004 (6)
C6	0.031 (6)	0.041 (7)	0.056 (7)	−0.004 (5)	0.005 (6)	−0.004 (6)
C7	0.035 (7)	0.042 (6)	0.039 (6)	0.010 (6)	0.018 (6)	0.010 (5)
C8	0.054 (8)	0.050 (6)	0.025 (6)	0.016 (7)	0.011 (6)	0.006 (5)
C9	0.039 (7)	0.043 (6)	0.022 (6)	0.015 (5)	0.009 (5)	0.002 (5)
C10	0.025 (6)	0.023 (5)	0.033 (5)	0.004 (5)	−0.004 (5)	0.000 (4)
C11	0.029 (6)	0.032 (5)	0.021 (5)	−0.001 (5)	−0.001 (5)	0.011 (5)
C12	0.040 (6)	0.028 (5)	0.018 (5)	−0.009 (5)	0.003 (5)	−0.007 (5)
C13	0.052 (8)	0.025 (6)	0.040 (7)	0.013 (6)	0.016 (6)	−0.001 (5)
C14	0.094 (11)	0.017 (5)	0.042 (7)	0.006 (7)	0.028 (8)	0.004 (5)
C15	0.075 (9)	0.023 (6)	0.041 (7)	0.001 (6)	0.028 (7)	0.003 (5)
C16	0.052 (8)	0.030 (6)	0.034 (7)	0.004 (6)	0.016 (6)	0.000 (5)
C17	0.035 (6)	0.019 (5)	0.021 (6)	−0.002 (5)	0.007 (5)	−0.004 (4)
C18	0.032 (6)	0.021 (5)	0.015 (5)	−0.005 (5)	0.005 (5)	−0.005 (4)
C19	0.022 (6)	0.021 (5)	0.022 (5)	−0.003 (4)	0.002 (5)	0.000 (4)
C20	0.039 (7)	0.026 (6)	0.038 (7)	−0.006 (5)	0.000 (6)	0.001 (5)
C21	0.028 (6)	0.037 (6)	0.062 (7)	−0.016 (6)	−0.007 (6)	0.004 (6)
C22	0.032 (7)	0.032 (6)	0.050 (7)	0.002 (6)	0.004 (6)	0.008 (5)
C23	0.037 (7)	0.022 (5)	0.035 (6)	0.000 (5)	0.015 (5)	−0.002 (5)
C24	0.031 (6)	0.033 (6)	0.016 (5)	−0.003 (5)	0.006 (5)	−0.002 (4)
C25	0.044 (7)	0.016 (5)	0.049 (7)	0.002 (5)	0.023 (6)	0.006 (5)
C26	0.042 (7)	0.038 (6)	0.064 (8)	0.021 (6)	0.016 (6)	0.029 (6)
C27	0.033 (6)	0.034 (6)	0.044 (6)	0.009 (6)	0.005 (5)	0.025 (5)
C28	0.026 (6)	0.054 (7)	0.046 (7)	−0.003 (6)	0.002 (6)	0.025 (6)
C29	0.046 (8)	0.045 (7)	0.037 (7)	0.003 (7)	−0.010 (6)	0.015 (6)
C30	0.042 (8)	0.054 (7)	0.043 (7)	0.015 (6)	0.008 (6)	0.012 (6)
C31	0.047 (8)	0.051 (7)	0.037 (7)	0.005 (7)	0.005 (6)	0.017 (6)
C32	0.048 (8)	0.032 (6)	0.055 (8)	0.002 (6)	0.005 (6)	0.017 (5)
C33	0.061 (8)	0.031 (6)	0.038 (7)	−0.015 (6)	0.023 (7)	−0.002 (5)
NiA	0.0317 (8)	0.0216 (6)	0.0272 (7)	−0.0012 (7)	0.0017 (7)	0.0045 (6)
O1A	0.051 (5)	0.024 (4)	0.054 (5)	0.004 (4)	0.002 (4)	0.004 (4)
O2A	0.042 (5)	0.028 (4)	0.026 (4)	0.000 (4)	0.005 (4)	0.000 (3)
O3A	0.062 (5)	0.020 (4)	0.032 (4)	−0.001 (4)	−0.002 (4)	0.003 (3)
N1A	0.065 (8)	0.048 (6)	0.079 (7)	0.006 (6)	−0.028 (7)	0.012 (6)
N2A	0.041 (6)	0.019 (4)	0.036 (5)	−0.004 (4)	0.006 (4)	0.001 (4)
N3A	0.030 (5)	0.021 (4)	0.036 (5)	−0.001 (4)	0.001 (4)	0.004 (4)
N4A	0.034 (5)	0.024 (4)	0.026 (5)	0.007 (4)	−0.007 (4)	0.005 (4)
C1A	0.038 (7)	0.019 (5)	0.043 (6)	−0.012 (5)	−0.007 (6)	0.001 (5)
C2A	0.045 (8)	0.030 (6)	0.055 (8)	0.003 (6)	−0.007 (7)	−0.008 (6)
C3A	0.066 (10)	0.050 (8)	0.062 (8)	0.009 (8)	−0.022 (8)	−0.003 (7)
C4A	0.043 (8)	0.031 (6)	0.080 (8)	0.003 (6)	−0.017 (7)	0.007 (6)
C5A	0.023 (6)	0.029 (6)	0.045 (6)	−0.009 (5)	0.006 (5)	−0.008 (5)
C6A	0.034 (6)	0.029 (5)	0.058 (7)	−0.006 (6)	0.015 (6)	−0.002 (6)
C7A	0.075 (10)	0.036 (6)	0.030 (6)	0.009 (7)	0.017 (6)	−0.004 (5)
C8A	0.041 (7)	0.049 (7)	0.043 (7)	−0.005 (7)	−0.014 (6)	0.005 (6)
C9A	0.038 (7)	0.028 (5)	0.043 (6)	0.001 (6)	0.002 (6)	−0.011 (5)
C10A	0.037 (6)	0.021 (5)	0.040 (6)	−0.004 (5)	−0.002 (5)	−0.003 (5)
C11A	0.033 (7)	0.028 (6)	0.038 (6)	−0.006 (5)	−0.007 (5)	0.006 (5)
C12A	0.029 (6)	0.017 (5)	0.032 (5)	−0.009 (4)	−0.008 (5)	0.005 (4)
C13A	0.023 (6)	0.034 (6)	0.044 (6)	−0.002 (5)	−0.004 (5)	0.017 (5)
C14A	0.037 (7)	0.042 (6)	0.028 (6)	−0.010 (6)	−0.017 (5)	0.010 (5)
C15A	0.039 (7)	0.043 (6)	0.024 (5)	−0.011 (6)	−0.005 (6)	0.014 (5)
C16A	0.035 (7)	0.036 (6)	0.027 (5)	−0.005 (6)	−0.004 (5)	0.005 (5)
C17A	0.022 (6)	0.026 (5)	0.026 (5)	−0.005 (4)	−0.004 (5)	0.004 (4)
C18A	0.022 (5)	0.024 (5)	0.028 (5)	−0.003 (5)	−0.009 (5)	−0.001 (4)
C19A	0.026 (5)	0.022 (5)	0.021 (5)	0.000 (4)	−0.002 (5)	0.003 (5)
C20A	0.036 (7)	0.038 (6)	0.028 (6)	−0.006 (6)	−0.002 (6)	−0.001 (5)
C21A	0.052 (7)	0.041 (7)	0.022 (6)	0.000 (6)	0.005 (6)	−0.003 (5)
C22A	0.039 (7)	0.046 (7)	0.043 (7)	0.012 (6)	0.007 (6)	−0.011 (6)
C23A	0.029 (6)	0.050 (7)	0.031 (6)	0.005 (6)	0.002 (5)	0.003 (5)
C24A	0.037 (6)	0.038 (6)	0.027 (6)	−0.001 (5)	−0.010 (5)	−0.002 (5)
C25A	0.038 (6)	0.027 (5)	0.029 (5)	0.006 (5)	0.009 (5)	0.006 (4)
C26A	0.034 (7)	0.039 (6)	0.037 (7)	0.008 (6)	−0.002 (6)	0.012 (5)
C27A	0.028 (6)	0.047 (6)	0.025 (6)	0.008 (6)	−0.011 (5)	0.013 (5)
C28A	0.053 (9)	0.042 (7)	0.051 (8)	−0.005 (7)	−0.021 (7)	0.010 (6)
C29A	0.081 (11)	0.049 (7)	0.083 (10)	0.024 (8)	−0.058 (9)	−0.004 (8)
C30A	0.049 (10)	0.087 (10)	0.087 (10)	0.045 (9)	−0.045 (8)	−0.056 (9)
C31A	0.043 (9)	0.139 (13)	0.046 (8)	−0.017 (11)	0.006 (8)	−0.033 (9)
C32A	0.062 (9)	0.067 (8)	0.026 (6)	−0.005 (8)	−0.007 (6)	−0.001 (6)
C33A	0.043 (7)	0.025 (5)	0.021 (6)	0.001 (5)	0.001 (5)	−0.001 (5)
O1W	0.105 (11)	0.239 (17)	0.131 (11)	−0.012 (13)	0.029 (10)	0.038 (13)

Geometric parameters (Å, º)

Ni—N2	1.914 (9)	C13—H13	0.95
Ni—N3	1.853 (6)	C14—H14	0.95
Ni—N4	1.828 (8)	C15—H15	0.95
Ni—O2	1.865 (6)	C16—H16	0.95
Ni—N1	5.339 (15)	C20—H20	0.95
NiA—N2A	1.934 (9)	C21—H21	0.95
NiA—N3A	1.851 (8)	C22—H22	0.95
NiA—N4A	1.856 (8)	C23—H23	0.95
NiA—O2A	1.874 (6)	C24—H24	0.95
NiA—N1A	5.024 (12)	C25—H25	1.00
O1—C11	1.224 (11)	C26—H26B	0.99
O2—C33	1.276 (13)	C26—H26A	0.99
O3—C33	1.236 (11)	C28—H28	0.95
O1A—C11A	1.241 (11)	C29—H29	0.95
O2A—C33A	1.284 (12)	C30—H30	0.95
O3A—C33A	1.226 (11)	C31—H31	0.95
N1—C3	1.323 (18)	C32—H32	0.95
N1—C4	1.343 (14)	C1A—C2A	1.349 (15)
N2—C6	1.493 (14)	C1A—C5A	1.396 (15)
N2—C7	1.523 (11)	C2A—C3A	1.353 (18)
N2—C10	1.508 (11)	C4A—C5A	1.387 (16)
N3—C11	1.358 (12)	C5A—C6A	1.510 (15)
N3—C12	1.412 (12)	C7A—C8A	1.514 (15)
N4—C18	1.299 (12)	C8A—C9A	1.528 (15)
N4—C25	1.495 (12)	C9A—C10A	1.529 (13)
N1A—C4A	1.378 (17)	C10A—C11A	1.506 (13)
N1A—C3A	1.341 (17)	C12A—C13A	1.406 (13)
N2A—C6A	1.495 (14)	C12A—C17A	1.412 (13)
N2A—C10A	1.499 (12)	C13A—C14A	1.387 (15)
N2A—C7A	1.523 (13)	C14A—C15A	1.377 (15)
N3A—C11A	1.358 (13)	C15A—C16A	1.371 (13)
N3A—C12A	1.406 (13)	C16A—C17A	1.413 (11)
N4A—C25A	1.488 (12)	C17A—C18A	1.469 (12)
N4A—C18A	1.291 (11)	C18A—C19A	1.516 (13)
C1—C5	1.399 (18)	C19A—C20A	1.380 (14)
C1—C2	1.336 (15)	C19A—C24A	1.384 (14)
C2—C3	1.347 (17)	C20A—C21A	1.387 (15)
C4—C5	1.382 (18)	C21A—C22A	1.370 (16)
C5—C6	1.503 (15)	C22A—C23A	1.380 (15)
C7—C8	1.531 (12)	C23A—C24A	1.379 (15)
C8—C9	1.519 (14)	C25A—C26A	1.533 (15)
C9—C10	1.539 (11)	C25A—C33A	1.544 (15)
C10—C11	1.500 (13)	C26A—C27A	1.501 (14)
C12—C13	1.409 (13)	C27A—C28A	1.364 (14)
C12—C17	1.412 (14)	C27A—C32A	1.383 (15)
C13—C14	1.400 (16)	C28A—C29A	1.378 (17)
C14—C15	1.368 (17)	C29A—C30A	1.37 (2)
C15—C16	1.372 (14)	C30A—C31A	1.36 (2)
C16—C17	1.416 (15)	C31A—C32A	1.383 (19)
C17—C18	1.458 (12)	C1A—H1A	0.95
C18—C19	1.518 (13)	C2A—H2A	0.95
C19—C24	1.390 (12)	C3A—H3A	0.95
C19—C20	1.387 (14)	C4A—H4A	0.95
C20—C21	1.384 (14)	C6A—H6A1	0.99
C21—C22	1.378 (14)	C6A—H6A2	0.99
C22—C23	1.380 (15)	C7A—H7A1	0.99
C23—C24	1.381 (14)	C7A—H7A2	0.99
C25—C26	1.527 (15)	C8A—H8A1	0.99
C25—C33	1.539 (16)	C8A—H8A2	0.99
C26—C27	1.518 (15)	C9A—H9A1	0.99
C27—C28	1.385 (15)	C9A—H9A2	0.99
C27—C32	1.375 (15)	C10A—H10A	1.00
C28—C29	1.385 (15)	C13A—H13A	0.95
C29—C30	1.375 (16)	C14A—H14A	0.95
C30—C31	1.367 (16)	C15A—H15A	0.95
C31—C32	1.384 (15)	C16A—H16A	0.95
C1—H1	0.95	C20A—H20A	0.95
C2—H2	0.95	C21A—H21A	0.95
C3—H3	0.95	C22A—H22A	0.95
C4—H4	0.95	C23A—H23A	0.95
C6—H6A	0.99	C24A—H24A	0.95
C6—H6B	0.99	C25A—H25A	1.00
C7—H7A	0.99	C26A—H26C	0.99
C7—H7B	0.99	C26A—H26D	0.99
C8—H8A	0.99	C28A—H28A	0.95
C8—H8B	0.99	C29A—H29A	0.95
C9—H9A	0.99	C30A—H30A	0.95
C9—H9B	0.99	C31A—H31A	0.95
C10—H10	1.00	C32A—H32A	0.95
N2—Ni—N3	87.6 (3)	C23—C24—H24	119.90
N2—Ni—N4	171.0 (3)	C19—C24—H24	119.94
N2—Ni—O2	89.9 (3)	N4—C25—H25	108.95
N3—Ni—N4	96.7 (3)	C26—C25—H25	109.05
N3—Ni—O2	170.7 (3)	C33—C25—H25	109.00
N4—Ni—O2	87.1 (3)	H26A—C26—H26B	107.55
N2A—NiA—N3A	88.3 (4)	C25—C26—H26A	108.49
N2A—NiA—N4A	175.6 (3)	C25—C26—H26B	108.52
N2A—NiA—O2A	89.8 (3)	C27—C26—H26B	108.48
N3A—NiA—N4A	95.6 (4)	C27—C26—H26A	108.39
N3A—NiA—O2A	173.3 (4)	C29—C28—H28	119.54
N4A—NiA—O2A	86.5 (3)	C27—C28—H28	119.64
Ni—O2—C33	114.6 (7)	C28—C29—H29	120.29
NiA—O2A—C33A	115.6 (6)	C30—C29—H29	120.19
C3—N1—C4	122.1 (15)	C29—C30—H30	119.63
Ni—N2—C6	113.0 (6)	C31—C30—H30	119.75
Ni—N2—C7	110.1 (6)	C32—C31—H31	120.44
Ni—N2—C10	107.4 (6)	C30—C31—H31	120.38
C6—N2—C7	108.6 (8)	C31—C32—H32	119.16
C6—N2—C10	110.9 (7)	C27—C32—H32	119.12
C7—N2—C10	106.7 (7)	C2A—C1A—C5A	120.7 (10)
C11—N3—C12	121.6 (7)	C1A—C2A—C3A	118.6 (11)
Ni—N3—C11	116.4 (6)	N1A—C3A—C2A	125.6 (12)
Ni—N3—C12	122.0 (6)	N1A—C4A—C5A	124.1 (11)
Ni—N4—C25	112.0 (6)	C1A—C5A—C4A	116.4 (10)
Ni—N4—C18	129.1 (6)	C1A—C5A—C6A	120.7 (9)
C18—N4—C25	118.7 (8)	C4A—C5A—C6A	122.9 (10)
C3A—N1A—C4A	114.4 (10)	N2A—C6A—C5A	113.9 (8)
NiA—N2A—C10A	105.9 (6)	N2A—C7A—C8A	107.3 (8)
NiA—N2A—C7A	113.3 (7)	C7A—C8A—C9A	103.2 (8)
NiA—N2A—C6A	109.0 (6)	C8A—C9A—C10A	103.5 (8)
C6A—N2A—C7A	109.4 (8)	N2A—C10A—C9A	103.6 (7)
C6A—N2A—C10A	112.5 (8)	N2A—C10A—C11A	111.5 (7)
C7A—N2A—C10A	106.6 (7)	C9A—C10A—C11A	112.0 (8)
NiA—N3A—C11A	114.4 (7)	O1A—C11A—N3A	128.9 (10)
NiA—N3A—C12A	123.7 (6)	O1A—C11A—C10A	117.1 (9)
C11A—N3A—C12A	121.0 (8)	N3A—C11A—C10A	113.9 (8)
NiA—N4A—C18A	127.1 (6)	N3A—C12A—C13A	121.5 (8)
NiA—N4A—C25A	111.1 (6)	N3A—C12A—C17A	121.1 (8)
C18A—N4A—C25A	121.6 (8)	C13A—C12A—C17A	117.4 (9)
C2—C1—C5	121.3 (14)	C12A—C13A—C14A	121.9 (9)
C1—C2—C3	119.6 (14)	C13A—C14A—C15A	120.5 (10)
N1—C3—C2	120.4 (15)	C14A—C15A—C16A	119.0 (10)
N1—C4—C5	119.7 (12)	C15A—C16A—C17A	122.2 (9)
C1—C5—C4	116.6 (11)	C12A—C17A—C16A	119.1 (8)
C1—C5—C6	122.5 (11)	C12A—C17A—C18A	124.3 (8)
C4—C5—C6	120.8 (10)	C16A—C17A—C18A	116.6 (8)
N2—C6—C5	113.9 (9)	N4A—C18A—C17A	122.6 (8)
N2—C7—C8	105.2 (7)	N4A—C18A—C19A	120.7 (8)
C7—C8—C9	101.7 (7)	C17A—C18A—C19A	116.6 (7)
C8—C9—C10	101.6 (7)	C18A—C19A—C20A	119.1 (9)
N2—C10—C9	104.0 (6)	C18A—C19A—C24A	121.2 (8)
N2—C10—C11	112.0 (7)	C20A—C19A—C24A	119.4 (9)
C9—C10—C11	111.8 (8)	C19A—C20A—C21A	119.8 (10)
N3—C11—C10	112.4 (8)	C20A—C21A—C22A	121.6 (10)
O1—C11—N3	128.4 (10)	C21A—C22A—C23A	117.8 (10)
O1—C11—C10	119.1 (9)	C22A—C23A—C24A	122.0 (10)
N3—C12—C17	121.8 (8)	C19A—C24A—C23A	119.4 (9)
N3—C12—C13	120.1 (9)	N4A—C25A—C26A	111.8 (8)
C13—C12—C17	118.1 (9)	N4A—C25A—C33A	107.0 (8)
C12—C13—C14	120.7 (10)	C26A—C25A—C33A	109.7 (8)
C13—C14—C15	121.6 (9)	C25A—C26A—C27A	115.2 (8)
C14—C15—C16	118.1 (10)	C26A—C27A—C28A	121.4 (10)
C15—C16—C17	123.1 (10)	C26A—C27A—C32A	119.1 (9)
C12—C17—C18	124.5 (9)	C28A—C27A—C32A	119.6 (10)
C12—C17—C16	118.2 (9)	C27A—C28A—C29A	120.5 (12)
C16—C17—C18	117.1 (9)	C28A—C29A—C30A	119.2 (12)
C17—C18—C19	118.1 (8)	C29A—C30A—C31A	121.5 (14)
N4—C18—C17	121.0 (8)	C30A—C31A—C32A	119.0 (13)
N4—C18—C19	120.9 (7)	C27A—C32A—C31A	120.2 (12)
C18—C19—C24	120.9 (8)	O2A—C33A—O3A	125.8 (10)
C20—C19—C24	119.3 (9)	O2A—C33A—C25A	115.2 (8)
C18—C19—C20	119.7 (8)	O3A—C33A—C25A	119.1 (9)
C19—C20—C21	120.0 (9)	C2A—C1A—H1A	119.66
C20—C21—C22	120.6 (10)	C5A—C1A—H1A	119.60
C21—C22—C23	119.5 (10)	C1A—C2A—H2A	120.66
C22—C23—C24	120.4 (9)	C3A—C2A—H2A	120.72
C19—C24—C23	120.2 (9)	N1A—C3A—H3A	117.17
N4—C25—C33	104.8 (8)	C2A—C3A—H3A	117.26
C26—C25—C33	109.4 (8)	N1A—C4A—H4A	117.85
N4—C25—C26	115.4 (8)	C5A—C4A—H4A	118.04
C25—C26—C27	115.2 (9)	N2A—C6A—H6A1	108.79
C28—C27—C32	118.1 (10)	N2A—C6A—H6A2	108.85
C26—C27—C28	121.0 (9)	C5A—C6A—H6A1	108.65
C26—C27—C32	120.9 (9)	C5A—C6A—H6A2	108.67
C27—C28—C29	120.8 (10)	H6A1—C6A—H6A2	107.79
C28—C29—C30	119.5 (10)	N2A—C7A—H7A1	110.18
C29—C30—C31	120.6 (10)	N2A—C7A—H7A2	110.22
C30—C31—C32	119.2 (10)	C8A—C7A—H7A1	110.31
C27—C32—C31	121.7 (10)	C8A—C7A—H7A2	110.39
O2—C33—C25	116.4 (8)	H7A1—C7A—H7A2	108.49
O3—C33—C25	118.4 (10)	C7A—C8A—H8A1	111.15
O2—C33—O3	125.0 (11)	C7A—C8A—H8A2	111.12
C5—C1—H1	119.34	C9A—C8A—H8A1	111.12
C2—C1—H1	119.37	C9A—C8A—H8A2	111.00
C3—C2—H2	120.21	H8A1—C8A—H8A2	109.20
C1—C2—H2	120.22	C8A—C9A—H9A1	111.06
C2—C3—H3	119.86	C8A—C9A—H9A2	111.02
N1—C3—H3	119.76	C10A—C9A—H9A1	111.11
N1—C4—H4	120.09	C10A—C9A—H9A2	111.15
C5—C4—H4	120.23	H9A1—C9A—H9A2	108.92
N2—C6—H6A	108.73	N2A—C10A—H10A	109.82
N2—C6—H6B	108.80	C9A—C10A—H10A	109.82
C5—C6—H6A	108.79	C11A—C10A—H10A	109.92
C5—C6—H6B	108.79	C12A—C13A—H13A	119.07
H6A—C6—H6B	107.65	C14A—C13A—H13A	118.98
C8—C7—H7A	110.78	C13A—C14A—H14A	119.76
H7A—C7—H7B	108.80	C15A—C14A—H14A	119.76
N2—C7—H7B	110.70	C14A—C15A—H15A	120.53
C8—C7—H7B	110.66	C16A—C15A—H15A	120.52
N2—C7—H7A	110.69	C15A—C16A—H16A	118.95
C7—C8—H8A	111.46	C17A—C16A—H16A	118.86
H8A—C8—H8B	109.32	C19A—C20A—H20A	120.03
C9—C8—H8B	111.43	C21A—C20A—H20A	120.19
C7—C8—H8B	111.35	C20A—C21A—H21A	119.23
C9—C8—H8A	111.42	C22A—C21A—H21A	119.19
C10—C9—H9A	111.46	C21A—C22A—H22A	121.13
C10—C9—H9B	111.58	C23A—C22A—H22A	121.10
H9A—C9—H9B	109.26	C22A—C23A—H23A	118.95
C8—C9—H9B	111.36	C24A—C23A—H23A	119.06
C8—C9—H9A	111.42	C19A—C24A—H24A	120.31
N2—C10—H10	109.62	C23A—C24A—H24A	120.29
C11—C10—H10	109.58	N4A—C25A—H25A	109.38
C9—C10—H10	109.67	C26A—C25A—H25A	109.40
C12—C13—H13	119.63	C33A—C25A—H25A	109.51
C14—C13—H13	119.70	C25A—C26A—H26C	108.52
C15—C14—H14	119.20	C25A—C26A—H26D	108.38
C13—C14—H14	119.23	C27A—C26A—H26C	108.54
C14—C15—H15	120.92	C27A—C26A—H26D	108.46
C16—C15—H15	120.96	H26C—C26A—H26D	107.54
C17—C16—H16	118.49	C27A—C28A—H28A	119.79
C15—C16—H16	118.40	C29A—C28A—H28A	119.74
C21—C20—H20	120.00	C28A—C29A—H29A	120.51
C19—C20—H20	120.04	C30A—C29A—H29A	120.25
C22—C21—H21	119.66	C29A—C30A—H30A	119.33
C20—C21—H21	119.74	C31A—C30A—H30A	119.13
C21—C22—H22	120.18	C30A—C31A—H31A	120.49
C23—C22—H22	120.29	C32A—C31A—H31A	120.55
C22—C23—H23	119.82	C27A—C32A—H32A	119.83
C24—C23—H23	119.79	C31A—C32A—H32A	119.97

(III) [N-({2-[N-(S)-ethylprolylamino]phenyl}phenylmethylene)-(S)- phenylalaninato]nickel(II)

Crystal data

[Ni(C29H29N3O3)]	F(000) = 1104
Mr = 526.26	Dx = 1.377 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 35 reflections
a = 9.692 (3) Å	θ = 12.5–14.5°
b = 10.047 (2) Å	µ = 0.80 mm^−1
c = 26.060 (6) Å	T = 220 K
V = 2537.6 (11) Å^3	Block, dark red
Z = 4	0.78 × 0.47 × 0.39 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	2358 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.011
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω/θ learnt profile scans	h = 0→11
Absorption correction: numerical (X-RED; Stoe & Cie, 1995)	k = 0→11
Tmin = 0.568, Tmax = 0.765	l = 0→31
2570 measured reflections	3 standard reflections every 60 min
2560 independent reflections	intensity decay: variation +−3.6%

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.074P)^2 + 2.47P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.050	(Δ/σ)max = 0.002
wR(F^2) = 0.135	Δρmax = 0.93 e Å^−3
S = 1.08	Δρmin = −0.56 e Å^−3
2560 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
326 parameters	Extinction coefficient: 0.012 (2)
109 restraints	Absolute structure: (Flack, 1983) with x Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (3)
Hydrogen site location: inferred from neighbouring sites

Special details

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
Ni	0.44496 (7)	0.17379 (7)	0.88010 (2)	0.0465 (3)
O1	0.7891 (5)	−0.0177 (6)	0.8913 (2)	0.0803 (15)
O2	0.2827 (5)	0.2460 (5)	0.90524 (15)	0.0624 (12)
N2	0.5474 (7)	0.2202 (5)	0.94171 (19)	0.0682 (14)
O3	0.0574 (5)	0.2615 (6)	0.88950 (17)	0.0869 (17)
N3	0.6087 (5)	0.1066 (5)	0.85640 (18)	0.0497 (11)
N4	0.3456 (5)	0.1311 (5)	0.82188 (17)	0.0477 (11)
C1	0.6231 (12)	0.3483 (8)	0.9328 (4)	0.122 (4)
H1A	0.6746	0.3704	0.9640	0.146*
H1B	0.6905	0.3342	0.9053	0.146*
C2	0.5372 (12)	0.4626 (9)	0.9191 (4)	0.115 (3)
H2A	0.5955	0.5394	0.9129	0.173*
H2B	0.4742	0.4820	0.9471	0.173*
H2C	0.4849	0.4422	0.8884	0.173*
C7	0.4801 (10)	0.2292 (11)	0.9879 (3)	0.095 (2)
H7A	0.3924	0.2772	0.9850	0.114*
H7B	0.5376	0.2707	1.0144	0.114*
C8	0.4599 (10)	0.0876 (10)	0.9971 (3)	0.094 (2)
H8A	0.3918	0.0508	0.9732	0.113*
H8B	0.4282	0.0718	1.0323	0.113*
C9	0.6071 (14)	0.0222 (10)	0.9880 (3)	0.123 (4)
H9A	0.6003	−0.0686	0.9745	0.148*
H9B	0.6638	0.0226	1.0192	0.148*
C10	0.6624 (7)	0.1251 (7)	0.9459 (2)	0.0604 (15)
H10	0.7451	0.1715	0.9593	0.072*
C11	0.6953 (6)	0.0629 (7)	0.8943 (2)	0.0570 (14)
C12	0.6417 (6)	0.0877 (6)	0.8046 (2)	0.0517 (13)
C13	0.7807 (8)	0.0781 (9)	0.7900 (3)	0.076 (2)
H13	0.8504	0.0844	0.8150	0.091*
C14	0.8164 (8)	0.0594 (10)	0.7386 (3)	0.086 (2)
H14	0.9098	0.0517	0.7294	0.103*
C15	0.7169 (9)	0.0523 (10)	0.7014 (3)	0.085 (2)
H15	0.7412	0.0377	0.6669	0.102*
C16	0.5816 (8)	0.0668 (8)	0.7151 (3)	0.0692 (19)
H16	0.5133	0.0631	0.6896	0.083*
C17	0.5415 (6)	0.0870 (6)	0.7664 (2)	0.0508 (13)
C18	0.3919 (6)	0.1005 (6)	0.7763 (2)	0.0479 (13)
C19	0.2948 (6)	0.0864 (7)	0.7319 (2)	0.0489 (13)
C20	0.2497 (7)	−0.0409 (7)	0.7172 (2)	0.0607 (16)
H20	0.2812	−0.1168	0.7347	0.073*
C21	0.1588 (8)	−0.0536 (9)	0.6766 (3)	0.0756 (19)
H21	0.1281	−0.1382	0.6663	0.091*
C22	0.1131 (7)	0.0590 (10)	0.6513 (2)	0.079 (2)
H22	0.0487	0.0505	0.6245	0.095*
C23	0.1599 (8)	0.1819 (10)	0.6646 (2)	0.0779 (19)
H23	0.1307	0.2571	0.6461	0.093*
C24	0.2518 (7)	0.1967 (7)	0.7059 (2)	0.0621 (16)
H24	0.2833	0.2816	0.7155	0.074*
C25	0.1949 (6)	0.1368 (7)	0.8314 (2)	0.0564 (15)
H25	0.1483	0.1784	0.8017	0.068*
C26	0.1343 (6)	−0.0042 (8)	0.8406 (3)	0.0682 (17)
H26A	0.0353	0.0050	0.8474	0.082*
H26B	0.1442	−0.0554	0.8088	0.082*
C27	0.1972 (7)	−0.0832 (7)	0.8835 (3)	0.0613 (14)
C28	0.3234 (8)	−0.1473 (7)	0.8772 (3)	0.0789 (19)
H28	0.3716	−0.1391	0.8460	0.095*
C29	0.3779 (11)	−0.2226 (9)	0.9163 (4)	0.100 (3)
H29	0.4635	−0.2650	0.9119	0.120*
C30	0.3094 (10)	−0.2361 (8)	0.9612 (4)	0.094 (2)
H30	0.3468	−0.2894	0.9874	0.113*
C31	0.1866 (10)	−0.1731 (9)	0.9689 (3)	0.087 (2)
H31	0.1409	−0.1814	1.0005	0.105*
C32	0.1293 (8)	−0.0971 (8)	0.9303 (3)	0.0712 (18)
H32	0.0441	−0.0545	0.9356	0.085*
C33	0.1734 (7)	0.2229 (7)	0.8788 (2)	0.0620 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0469 (4)	0.0511 (4)	0.0415 (4)	0.0131 (3)	−0.0033 (3)	−0.0021 (3)
O1	0.059 (3)	0.099 (4)	0.083 (3)	0.032 (3)	−0.006 (2)	0.003 (3)
O2	0.063 (2)	0.080 (3)	0.044 (2)	0.033 (2)	−0.0041 (19)	−0.009 (2)
N2	0.081 (4)	0.073 (3)	0.051 (3)	0.027 (3)	−0.024 (3)	−0.013 (2)
O3	0.065 (3)	0.137 (5)	0.059 (3)	0.054 (3)	0.001 (2)	−0.004 (3)
N3	0.039 (2)	0.058 (3)	0.052 (2)	0.003 (2)	−0.0038 (19)	−0.004 (2)
N4	0.047 (2)	0.055 (3)	0.042 (2)	0.013 (2)	0.0015 (19)	−0.004 (2)
C1	0.155 (10)	0.085 (5)	0.125 (7)	−0.015 (5)	−0.049 (6)	−0.023 (5)
C2	0.155 (10)	0.098 (5)	0.094 (6)	−0.024 (7)	−0.005 (7)	0.009 (5)
C7	0.100 (6)	0.114 (5)	0.071 (4)	0.033 (5)	−0.014 (4)	−0.024 (4)
C8	0.091 (5)	0.115 (6)	0.076 (5)	−0.039 (6)	0.013 (5)	−0.016 (5)
C9	0.214 (11)	0.099 (6)	0.056 (4)	0.072 (7)	−0.003 (5)	0.017 (4)
C10	0.047 (3)	0.074 (4)	0.060 (3)	0.006 (3)	−0.012 (3)	−0.001 (3)
C11	0.042 (3)	0.065 (4)	0.064 (3)	0.006 (3)	−0.003 (3)	0.003 (3)
C12	0.044 (3)	0.052 (3)	0.059 (3)	0.001 (3)	0.008 (2)	−0.001 (3)
C13	0.052 (4)	0.101 (6)	0.075 (4)	0.010 (4)	0.007 (3)	0.005 (4)
C14	0.058 (4)	0.114 (7)	0.085 (5)	0.014 (5)	0.024 (3)	0.014 (5)
C15	0.078 (5)	0.105 (6)	0.071 (4)	0.005 (5)	0.029 (4)	−0.002 (4)
C16	0.068 (4)	0.085 (5)	0.054 (3)	0.009 (4)	0.011 (3)	−0.008 (4)
C17	0.054 (3)	0.048 (3)	0.050 (3)	−0.007 (3)	0.005 (2)	−0.005 (2)
C18	0.053 (3)	0.048 (3)	0.043 (3)	0.003 (3)	0.000 (2)	−0.001 (2)
C19	0.050 (3)	0.058 (3)	0.039 (3)	0.002 (3)	0.004 (2)	−0.005 (2)
C20	0.059 (4)	0.068 (4)	0.055 (3)	0.003 (3)	0.002 (3)	−0.014 (3)
C21	0.055 (4)	0.109 (5)	0.063 (4)	−0.011 (4)	0.005 (3)	−0.034 (4)
C22	0.054 (4)	0.140 (6)	0.045 (3)	0.001 (4)	−0.002 (3)	−0.022 (4)
C23	0.071 (4)	0.114 (5)	0.049 (3)	0.020 (5)	−0.004 (3)	0.003 (4)
C24	0.064 (4)	0.076 (4)	0.046 (3)	0.004 (3)	0.000 (3)	0.004 (3)
C25	0.044 (3)	0.082 (4)	0.043 (3)	0.018 (3)	−0.004 (2)	0.005 (3)
C26	0.044 (3)	0.102 (5)	0.059 (3)	0.002 (3)	0.005 (3)	−0.007 (3)
C27	0.055 (3)	0.062 (3)	0.066 (3)	−0.007 (3)	0.007 (3)	−0.004 (3)
C28	0.077 (4)	0.070 (4)	0.090 (5)	0.015 (4)	0.016 (4)	0.005 (4)
C29	0.101 (6)	0.074 (5)	0.125 (7)	0.026 (5)	0.012 (5)	0.024 (5)
C30	0.099 (6)	0.069 (5)	0.114 (6)	−0.009 (4)	−0.015 (5)	0.033 (5)
C31	0.095 (5)	0.078 (5)	0.089 (5)	−0.019 (5)	0.011 (4)	0.021 (4)
C32	0.065 (4)	0.071 (4)	0.077 (4)	−0.008 (4)	0.009 (3)	0.006 (3)
C33	0.061 (3)	0.080 (4)	0.045 (3)	0.030 (3)	0.000 (3)	0.010 (3)

Geometric parameters (Å, º)

Ni—N2	1.944 (5)	C14—H14	0.9400
Ni—N3	1.832 (5)	C15—C16	1.368 (10)
Ni—N4	1.847 (5)	C15—H15	0.9400
Ni—O2	1.851 (4)	C16—C17	1.405 (9)
O1—C11	1.220 (7)	C16—H16	0.9400
O2—C33	1.284 (8)	C17—C18	1.479 (9)
N2—C7	1.373 (10)	C18—C19	1.500 (8)
N2—C10	1.472 (8)	C19—C24	1.364 (9)
N2—C1	1.499 (8)	C19—C20	1.404 (9)
O3—C33	1.221 (7)	C20—C21	1.382 (10)
N3—C11	1.368 (7)	C20—H20	0.9400
N3—C12	1.400 (8)	C21—C22	1.382 (12)
N4—C18	1.305 (7)	C21—H21	0.9400
N4—C25	1.483 (7)	C22—C23	1.360 (12)
C1—C2	1.463 (8)	C22—H22	0.9400
C1—H1A	0.9800	C23—C24	1.406 (9)
C1—H1B	0.9800	C23—H23	0.9400
C2—H2A	0.9700	C24—H24	0.9400
C2—H2B	0.9700	C25—C33	1.522 (9)
C2—H2C	0.9700	C25—C26	1.551 (10)
C7—C8	1.456 (14)	C25—H25	0.9900
C7—H7A	0.9800	C26—C27	1.502 (10)
C7—H7B	0.9800	C26—H26A	0.9800
C8—C9	1.589 (14)	C26—H26B	0.9800
C8—H8A	0.9800	C27—C28	1.392 (10)
C8—H8B	0.9800	C27—C32	1.393 (9)
C9—C10	1.600 (11)	C28—C29	1.376 (11)
C9—H9A	0.9800	C28—H28	0.9400
C9—H9B	0.9800	C29—C30	1.352 (13)
C10—C11	1.518 (9)	C29—H29	0.9400
C10—H10	0.9900	C30—C31	1.363 (12)
C12—C17	1.392 (8)	C30—H30	0.9400
C12—C13	1.404 (9)	C31—C32	1.380 (11)
C13—C14	1.396 (11)	C31—H31	0.9400
C13—H13	0.9400	C32—H32	0.9400
C14—C15	1.369 (11)
N2—Ni—N3	85.7 (2)	C15—C14—H14	119.6
N2—Ni—N4	179.2 (2)	C13—C14—H14	119.6
N2—Ni—O2	92.7 (2)	C16—C15—C14	118.9 (7)
N3—Ni—N4	95.1 (2)	C16—C15—H15	120.5
N3—Ni—O2	178.1 (2)	C14—C15—H15	120.5
N4—Ni—O2	86.5 (2)	C15—C16—C17	122.0 (7)
C33—O2—Ni	116.1 (4)	C15—C16—H16	119.0
C7—N2—C10	109.7 (6)	C17—C16—H16	119.0
C7—N2—C1	108.1 (7)	C12—C17—C16	119.2 (6)
C10—N2—C1	101.4 (6)	C12—C17—C18	123.9 (5)
C7—N2—Ni	119.9 (6)	C16—C17—C18	116.8 (6)
C10—N2—Ni	107.0 (4)	N4—C18—C17	121.2 (5)
C1—N2—Ni	109.2 (5)	N4—C18—C19	120.6 (5)
C11—N3—C12	120.8 (5)	C17—C18—C19	118.1 (5)
C11—N3—Ni	114.0 (4)	C24—C19—C20	120.6 (6)
C12—N3—Ni	125.0 (4)	C24—C19—C18	119.9 (6)
C18—N4—C25	120.0 (5)	C20—C19—C18	119.5 (6)
C18—N4—Ni	128.5 (4)	C21—C20—C19	119.4 (7)
C25—N4—Ni	111.5 (3)	C21—C20—H20	120.3
C2—C1—N2	115.7 (8)	C19—C20—H20	120.3
C2—C1—H1A	108.4	C20—C21—C22	119.6 (7)
N2—C1—H1A	108.4	C20—C21—H21	120.2
C2—C1—H1B	108.4	C22—C21—H21	120.2
N2—C1—H1B	108.4	C23—C22—C21	121.0 (6)
H1A—C1—H1B	107.4	C23—C22—H22	119.5
C1—C2—H2A	109.5	C21—C22—H22	119.5
C1—C2—H2B	109.5	C22—C23—C24	120.2 (8)
H2A—C2—H2B	109.5	C22—C23—H23	119.9
C1—C2—H2C	109.5	C24—C23—H23	119.9
H2A—C2—H2C	109.5	C19—C24—C23	119.2 (7)
H2B—C2—H2C	109.5	C19—C24—H24	120.4
N2—C7—C8	98.3 (7)	C23—C24—H24	120.4
N2—C7—H7A	112.1	N4—C25—C33	107.0 (5)
C8—C7—H7A	112.1	N4—C25—C26	111.3 (5)
N2—C7—H7B	112.1	C33—C25—C26	110.0 (5)
C8—C7—H7B	112.1	N4—C25—H25	109.5
H7A—C7—H7B	109.7	C33—C25—H25	109.5
C7—C8—C9	105.0 (8)	C26—C25—H25	109.5
C7—C8—H8A	110.8	C27—C26—C25	116.3 (5)
C9—C8—H8A	110.8	C27—C26—H26A	108.2
C7—C8—H8B	110.7	C25—C26—H26A	108.2
C9—C8—H8B	110.7	C27—C26—H26B	108.2
H8A—C8—H8B	108.8	C25—C26—H26B	108.2
C8—C9—C10	97.8 (6)	H26A—C26—H26B	107.4
C8—C9—H9A	112.2	C28—C27—C32	118.2 (7)
C10—C9—H9A	112.2	C28—C27—C26	120.9 (6)
C8—C9—H9B	112.2	C32—C27—C26	120.9 (6)
C10—C9—H9B	112.2	C29—C28—C27	120.2 (8)
H9A—C9—H9B	109.8	C29—C28—H28	119.9
N2—C10—C11	111.1 (5)	C27—C28—H28	119.9
N2—C10—C9	102.6 (6)	C30—C29—C28	120.6 (9)
C11—C10—C9	114.3 (6)	C30—C29—H29	119.7
N2—C10—H10	109.5	C28—C29—H29	119.7
C11—C10—H10	109.5	C29—C30—C31	120.6 (8)
C9—C10—H10	109.5	C29—C30—H30	119.7
O1—C11—N3	128.6 (6)	C31—C30—H30	119.7
O1—C11—C10	119.2 (6)	C30—C31—C32	120.2 (8)
N3—C11—C10	112.2 (5)	C30—C31—H31	119.9
C17—C12—N3	122.1 (5)	C32—C31—H31	119.9
C17—C12—C13	118.3 (6)	C31—C32—C27	120.2 (8)
N3—C12—C13	119.4 (6)	C31—C32—H32	119.9
C14—C13—C12	120.5 (7)	C27—C32—H32	119.9
C14—C13—H13	119.8	O3—C33—O2	125.4 (6)
C12—C13—H13	119.8	O3—C33—C25	119.4 (6)
C15—C14—C13	120.8 (7)	O2—C33—C25	115.1 (5)