8-Hydroxyquinaldinic acid and its nickel(II) complex

The molecules of 8-hydroxy­quinolinium-2-carboxyl­ate, C₁₀H₇NO₃, have a planar structure, in which the carboxyl group is ionized and the ring N atom is protonated. The derived nickel(II) complex, bis(8-hydroxy­quinoline-2-carboxyl­ato-[kappa]³O²,N,O⁸)­nickel(II) trihydrate, [Ni(C₁₀H₆NO₃)₂]·3H₂O, contains an octahedral central Ni^II ion coordinated by the hydroxyl O atom, the ring N atom and the carboxyl­ate O atom of each of the two tridentate ligands, with a perpendicular orientation of the quinoline rings.

S1. Comment

8-Hydroxyquinaldic acid (8-hydroxyquinoline-2-carboxylic acid), (I), is one of the tryptophan metabolites formed through the kynurenine metabolic pathway (Rodwell, 1983). This compound is known as a tridentate chelating agent with three ligand atoms, the hydroxyl O atom, the quinoline ring N atom, and the carboxyl O atom (Irving & Pinnington, 1954; Moberg & Weber, 1984). The physiological role of this compound or of its metal complexes are as yet unclear, but the analogous compound 8-hydroxyquinoline and its metal complexes have various biological properties, such as antimicrobial or fungicidal activity (Okide et al., 2000; Patel et al., 1999) or antitumour activity (Smith et al., 1998). These findings drive structural research of various quinoline derivatives because of their therapeutic value.

Until now, the solid-state structures of 8-hydroxyquinaldinic acid and its metal complexes have not been determined, apart from the structure of the cobalt(II) complex which we reported recently (Okabe & Muranishi; 2002). Therefore, it is of interest to clarify the detailed structure of this compound and the coordinating behaviour of its metal complexes in connection with their physiological role, as well as their use as selective chelating reagents for metal ions (Högberg et al. 1985). In this study, the structure of (I) and of its nickel(II) complex, (II), have been determined and the results are presented here. \sch

The structure of (I) is shown in Fig. 1. It is planar, with a slight torsion of the carboxylate group [O2—C10—C1—N1 - 4.2 (3)°]. The carboxyl group is ionized, the ring N atom is protonated, and the hydroxyl group remains unchanged. The net charge of the molecule is kept neutral by this H-atom transfer. Bifurcated hydrogen bonds are formed intramolecularly between the protonated NH⁺ group and the carboxyl O atom, and between NH⁺ and the hydroxyl O atoms (Table 2). Neighbouring molecules are linked together by intermolecular hydrogen bonds between the carboxylate and hydroxyl groups along the c axis (Fig. 2). The quinoline rings are stacked together along the a axis, with a mean distance between the rings of 3.380 (5) Å.

The molecular structure of complex (II) is shown in Fig. 3. In this complex, two tridentate ligand molecules coordinate to the central Ni^II ion in a bisected octahedral coordination geometry, in which two quinoline rings are oriented perpendicularly. The two carboxyl groups of the two ligand molecules are ionized and are essentially coplanar with the quinoline ring planes, as shown by the relevant torsion angles [O2—C10—C1—N1 - 4.2 (3)° and O5—C20—C11—N2 - 8.2 (4)°].

The overall structure of (II) is the same as the cobalt(II) complex (Okabe & Muranishi, 2002). Three ligand atoms (the hydroxyl O, the quinoline N and the carboxyl O atoms) and the central Ni^II ion form five-membered rings. The distances between Ni^II and the carboxylato O atoms, [2.080 (3)–2.124 (2) Å] are shorter than those between Ni^II and the hydroxyl O atoms [2.227 (2)–2.290 (3) Å]. The Ni—N distance is the shortest of those involving the three coordinated ligand atoms.

In an NMR study of the manganese(II) complex of quinaldinic acid derivatives (Moberg & Weber, 1984), a bisected octahedral structure with a perpendicular orientation of the quinoline rings was postulated as one of the possible coordination modes around the central metal ion. However, the manganese(II) complex of 8-hydroxyquinaldinic acid could not be clearly deduced as a bisected octahedral structure from the NMR study. The bisected octahedral coordination mode of the cobalt(II) complex (Okabe & Muranishi, 2002) and the nickel(II) complex, (II), may be a common feature of the metal complexes of 8-hydroxyquinaldinic acid, although further structural studies are needed for confirmation.

In the crystal packing of (II), stacking interactions are present between the C1—C9/N1 quinoline rings and between the C11—C19/N2 rings. The mean distances are 3.454 (4) Å for the C1—C9/N1 rings and 3.378 (4) Å for the C11—C19/N2 rings. Neighbouring nickel(II) complex molecules are also connected together by a hydrogen-bonding network through the water molecules (Table 4).

S2. Experimental

Yellow plate crystals of (I) and light-yellow prismatic crystals of (II) were obtained by, respectively, slow evaporation of an ethanol-water solution (ca 70% does this mean 70:30 v/v?), and of an ethanol-water solution (ca 70% does this mean 70:30 v/v?) of a mixture of 8-hydroxyquinaldinic acid and nickel(II) acetate tetrahydrate (molar ratio 4:1).

S3. Refinement

For compound (I), all H atoms were initially located from the difference Fourier maps, and then they were refined at their ideal positions by a riding model, using the SHELXL97 HFIX instruction (Sheldrick, 1997) with C—H = 0.93, O—H = 0.82 and N—H = 0.86 Å. Is this added text OK? For complex (II), all H atoms were also initially located from the difference Fourier maps, and then all except those of the 8-hydroxyl groups were refined at their ideal positions by riding models using the SHELXL97 HFIX instruction, with C—H = 0.93 Å. Is this added text OK? The H atoms of the 8-hydroxyl groups were fixed in the positions located from the Fourier maps. The water H atoms were idealized using the SHELXL97 SADI restriction.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation & Rigaku Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. A view of the molecule of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I) showing the hydrogen-bonding scheme.
	Fig. 3. A view of the molecule of (II), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) 8-hydroxyquinolinium-2-carboxylate

Crystal data

C10H7NO3	F(000) = 784.0
Mr = 189.17	Dx = 1.583 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2yc	Cell parameters from 16 reflections
a = 12.748 (2) Å	θ = 10.2–12.9°
b = 7.476 (3) Å	µ = 0.12 mm^−1
c = 16.657 (2) Å	T = 296 K
β = 90.68 (1)°	Plate, yellow
V = 1587.3 (7) Å^3	0.20 × 0.10 × 0.05 mm
Z = 8

Data collection

Rigaku AFC-5R diffractometer	θmax = 27.5°
ω/2θ scans	h = 12→16
2068 measured reflections	k = 0→9
1838 independent reflections	l = −21→21
691 reflections with I > 2σ(I)	3 standard reflections every 150 reflections
Rint = 0.066	intensity decay: 0.8%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.197	(Δ/σ)max < 0.001
S = 0.87	Δρmax = 0.28 e Å^−3
1838 reflections	Δρmin = −0.27 e Å^−3
128 parameters

Special details

Refinement. Refinement using reflections with F² > -10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3802 (2)	0.1005 (4)	0.7905 (2)	0.0381 (8)
O2	0.3821 (3)	−0.1027 (4)	0.6906 (2)	0.0443 (9)
O3E	0.4069 (3)	0.0399 (4)	0.4296 (2)	0.0347 (8)
N1	0.3840 (3)	0.1568 (4)	0.5812 (2)	0.0248 (8)
C1	0.3718 (3)	0.2025 (5)	0.6578 (2)	0.0268 (9)
C2	0.3518 (4)	0.3799 (5)	0.6771 (2)	0.033 (1)
C3	0.3478 (4)	0.5061 (5)	0.6176 (2)	0.035 (1)
C4	0.3621 (3)	0.4587 (5)	0.5368 (2)	0.0263 (9)
C5	0.3606 (3)	0.5821 (6)	0.4732 (2)	0.034 (1)
C6	0.3749 (4)	0.5240 (6)	0.3965 (3)	0.038 (1)
C7	0.3908 (4)	0.3418 (6)	0.3786 (2)	0.035 (1)
C8	0.3927 (3)	0.2162 (5)	0.4383 (2)	0.0257 (9)
C9	0.3799 (3)	0.2773 (5)	0.5195 (2)	0.0230 (9)
C10	0.3792 (3)	0.0492 (6)	0.7188 (2)	0.0288 (10)
H1	0.3950	0.0461	0.5700	0.0297*
H2	0.3412	0.4128	0.7302	0.0396*
H3	0.3355	0.6250	0.6308	0.0419*
H3E	0.4021	0.0136	0.3819	0.0521*
H5	0.3499	0.7030	0.4833	0.0409*
H6	0.3742	0.6069	0.3548	0.0454*
H7	0.4002	0.3066	0.3256	0.0416*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.061 (2)	0.035 (2)	0.018 (1)	0.006 (2)	0.002 (1)	0.004 (1)
O2	0.075 (3)	0.027 (2)	0.031 (2)	−0.002 (2)	−0.003 (2)	−0.001 (1)
O3E	0.056 (2)	0.030 (2)	0.018 (1)	0.012 (2)	−0.002 (1)	−0.003 (1)
N1	0.034 (2)	0.020 (2)	0.020 (1)	0.000 (1)	−0.002 (1)	−0.005 (1)
C1	0.032 (2)	0.027 (2)	0.022 (2)	0.000 (2)	−0.002 (2)	0.001 (2)
C2	0.056 (3)	0.024 (2)	0.020 (2)	0.002 (2)	−0.001 (2)	−0.002 (2)
C3	0.050 (3)	0.025 (2)	0.030 (2)	0.003 (2)	−0.002 (2)	−0.006 (2)
C4	0.030 (2)	0.025 (2)	0.025 (2)	−0.001 (2)	−0.002 (2)	−0.004 (2)
C5	0.046 (3)	0.026 (2)	0.030 (2)	0.002 (2)	−0.003 (2)	0.003 (2)
C6	0.061 (3)	0.032 (3)	0.020 (2)	−0.002 (2)	−0.007 (2)	0.006 (2)
C7	0.050 (3)	0.038 (3)	0.016 (2)	0.001 (2)	−0.002 (2)	−0.001 (2)
C8	0.030 (2)	0.026 (2)	0.021 (2)	0.004 (2)	−0.002 (2)	0.000 (2)
C9	0.026 (2)	0.026 (2)	0.016 (2)	−0.003 (2)	−0.003 (2)	0.000 (2)
C10	0.032 (2)	0.033 (3)	0.021 (2)	−0.002 (2)	0.003 (2)	0.004 (2)

Geometric parameters (Å, º)

O1—C10	1.255 (4)	C3—C4	1.405 (6)
O2—C10	1.230 (5)	C3—H3	0.930
O3E—C8	1.338 (5)	C4—C5	1.405 (6)
O3E—H3E	0.820	C4—C9	1.406 (6)
N1—C1	1.332 (4)	C5—C6	1.364 (6)
N1—C9	1.367 (5)	C5—H5	0.930
N1—H1	0.860	C6—C7	1.409 (6)
C1—C2	1.388 (6)	C6—H6	0.930
C1—C10	1.533 (5)	C7—C8	1.368 (6)
C2—C3	1.369 (6)	C7—H7	0.930
C2—H2	0.930	C8—C9	1.438 (5)
O1···O3E^i	2.562 (4)	O3E···C4^vii	3.480 (5)
O1···C10^ii	3.098 (5)	O3E···C5^v	3.549 (5)
O1···C6^iii	3.317 (5)	O3E···C10^viii	3.587 (4)
O1···O1^ii	3.354 (6)	N1···C7^vii	3.574 (6)
O1···C1^ii	3.355 (5)	N1···C6^vii	3.590 (6)
O1···C3^iv	3.375 (5)	C1···C7^vii	3.411 (6)
O1···O2^ii	3.401 (5)	C3···C7^ix	3.520 (6)
O1···C8^i	3.418 (5)	C3···C6^ix	3.552 (7)
O1···C2^iv	3.435 (5)	C4···C6^ix	3.522 (6)
O2···C3^v	3.195 (5)	C4···C8^vii	3.530 (6)
O2···O3E^vi	3.404 (4)	C4···C5^ix	3.554 (6)
O2···C10^ii	3.567 (5)	C5···C9^ix	3.472 (6)
O2···O2^ii	3.580 (7)	C8···C9^vii	3.553 (5)
O3E···N1^vi	3.052 (4)	C9···C9^vii	3.391 (7)
O3E···C3^vii	3.349 (5)	C10···C10^ii	3.240 (8)
O3E···O3E^vi	3.371 (6)
C8—O3E—H3E	109.5	C4—C5—H5	120.1
C1—N1—C9	123.2 (3)	C6—C5—H5	120.1
C1—N1—H1	118.4	C5—C6—C7	121.8 (4)
C9—N1—H1	118.4	C5—C6—H6	119.1
N1—C1—C2	119.3 (3)	C7—C6—H6	119.1
N1—C1—C10	115.8 (3)	C6—C7—C8	120.8 (4)
C2—C1—C10	124.8 (3)	C6—C7—H7	119.6
C1—C2—C3	119.8 (4)	C8—C7—H7	119.6
C1—C2—H2	120.1	O3E—C8—C7	126.7 (3)
C3—C2—H2	120.1	O3E—C8—C9	115.6 (3)
C2—C3—C4	121.0 (4)	C7—C8—C9	117.7 (4)
C2—C3—H3	119.5	N1—C9—C4	119.1 (3)
C4—C3—H3	119.5	N1—C9—C8	119.6 (3)
C3—C4—C5	123.8 (4)	C4—C9—C8	121.3 (3)
C3—C4—C9	117.6 (3)	O1—C10—O2	130.2 (4)
C5—C4—C9	118.6 (3)	O1—C10—C1	113.7 (3)
C4—C5—C6	119.8 (4)	O2—C10—C1	116.0 (3)
O1—C10—C1—N1	171.7 (4)	C2—C1—N1—C9	1.3 (6)
O1—C10—C1—C2	−9.5 (6)	C2—C3—C4—C5	−178.9 (4)
O2—C10—C1—N1	−9.0 (5)	C2—C3—C4—C9	0.4 (6)
O2—C10—C1—C2	169.8 (4)	C3—C2—C1—C10	179.5 (4)
O3E—C8—C7—C6	179.9 (4)	C3—C4—C5—C6	−179.9 (4)
O3E—C8—C9—N1	0.8 (5)	C3—C4—C9—C8	178.4 (4)
O3E—C8—C9—C4	−178.6 (3)	C4—C5—C6—C7	0.4 (7)
N1—C1—C2—C3	−1.8 (6)	C4—C9—C8—C7	2.4 (6)
N1—C9—C4—C3	−0.9 (5)	C5—C4—C9—C8	−2.2 (6)
N1—C9—C4—C5	178.4 (4)	C5—C6—C7—C8	−0.2 (7)
N1—C9—C8—C7	−178.3 (4)	C6—C5—C4—C9	0.9 (6)
C1—N1—C9—C4	0.1 (5)	C6—C7—C8—C9	−1.1 (6)
C1—N1—C9—C8	−179.3 (4)	C9—N1—C1—C10	−179.8 (3)
C1—C2—C3—C4	1.0 (7)	C9—N1—C1—C10	−179.8 (3)

Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1, y, −z+3/2; (iii) x, −y+1, z+1/2; (iv) −x+1/2, y−1/2, −z+3/2; (v) x, y−1, z; (vi) −x+1, −y, −z+1; (vii) −x+1/2, −y+1/2, −z+1; (viii) x, −y, z−1/2; (ix) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.30	2.662 (4)	105
N1—H1···O3E	0.86	2.35	2.692 (4)	104
O3E—H3E···O1^viii	0.82	1.76	2.562 (4)	164

Symmetry code: (viii) x, −y, z−1/2.

(II) bis(8-hydroxyquinoline-2-carboxylato-κ³O²,N,O⁸)nickel(II) trihydrate

Crystal data

[Ni(C10H6NO3)2](H2O)3	Z = 2
Mr = 489.05	F(000) = 504.0
Triclinic, P1	Dx = 1.681 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 9.237 (1) Å	Cell parameters from 25 reflections
b = 15.865 (3) Å	θ = 14.5–15.0°
c = 7.200 (1) Å	µ = 1.06 mm^−1
α = 97.63 (1)°	T = 296 K
β = 106.95 (1)°	Prismatic, yellow
γ = 101.90 (1)°	0.25 × 0.10 × 0.10 mm
V = 966.4 (3) Å^3

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.024
ω/2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = 0→11
Tmin = 0.880, Tmax = 0.899	k = −20→20
4703 measured reflections	l = −9→8
4434 independent reflections	3 standard reflections every 150 reflections
3202 reflections with I > 2σ(I)	intensity decay: 0.3%

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.134	(Δ/σ)max < 0.001
S = 0.90	Δρmax = 0.64 e Å^−3
4434 reflections	Δρmin = −0.32 e Å^−3
307 parameters

Special details

Refinement. Refinement using reflections with F² > -10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.35159 (4)	0.24765 (2)	0.51613 (5)	0.0330 (1)
O1	0.5238 (3)	0.1381 (2)	0.1118 (3)	0.0476 (5)
O2	0.4618 (3)	0.2384 (1)	0.3029 (3)	0.0419 (5)
O3E	0.2416 (3)	0.1921 (2)	0.7356 (3)	0.0445 (5)
O4	−0.0255 (3)	0.3462 (2)	0.2899 (4)	0.0510 (6)
O5	0.1311 (2)	0.2542 (1)	0.3279 (3)	0.0405 (5)
O6E	0.5855 (2)	0.3045 (1)	0.7478 (3)	0.0381 (4)
O7	0.7305 (3)	0.2340 (2)	0.9998 (3)	0.0458 (5)
O8	0.8476 (5)	0.3037 (3)	0.6064 (6)	0.098 (1)
O9	1.0476 (4)	0.2373 (3)	0.8940 (5)	0.082 (1)
N1	0.3338 (3)	0.1197 (2)	0.4607 (3)	0.0316 (5)
N2	0.3606 (3)	0.3735 (1)	0.5880 (3)	0.0288 (4)
C1	0.3830 (3)	0.0892 (2)	0.3185 (4)	0.0331 (6)
C2	0.3643 (4)	−0.0018 (2)	0.2550 (5)	0.0396 (6)
C3	0.2938 (4)	−0.0592 (2)	0.3487 (5)	0.0435 (7)
C4	0.2408 (3)	−0.0275 (2)	0.5046 (5)	0.0392 (7)
C5	0.1645 (4)	−0.0811 (2)	0.6087 (5)	0.0489 (8)
C6	0.1160 (4)	−0.0429 (2)	0.7510 (6)	0.0531 (9)
C7	0.1387 (4)	0.0485 (2)	0.8018 (5)	0.0472 (8)
C8	0.2131 (3)	0.1029 (2)	0.7056 (4)	0.0381 (6)
C9	0.2641 (3)	0.0642 (2)	0.5559 (4)	0.0340 (6)
C10	0.4623 (3)	0.1605 (2)	0.2346 (4)	0.0352 (6)
C11	0.2379 (3)	0.4020 (2)	0.5028 (4)	0.0300 (5)
C12	0.2383 (4)	0.4909 (2)	0.5395 (4)	0.0364 (6)
C13	0.3726 (4)	0.5507 (2)	0.6685 (4)	0.0357 (6)
C14	0.5050 (3)	0.5216 (2)	0.7618 (4)	0.0313 (5)
C15	0.6481 (4)	0.5766 (2)	0.8961 (4)	0.0385 (6)
C16	0.7667 (4)	0.5399 (2)	0.9789 (4)	0.0400 (7)
C17	0.7528 (3)	0.4483 (2)	0.9352 (4)	0.0372 (6)
C18	0.6158 (3)	0.3931 (2)	0.8057 (4)	0.0311 (5)
C19	0.4924 (3)	0.4307 (2)	0.7181 (4)	0.0285 (5)
C20	0.1018 (3)	0.3284 (2)	0.3616 (4)	0.0340 (6)
H2	0.3989	−0.0222	0.1528	0.0475*
H3	0.2805	−0.1194	0.3099	0.0522*
H3E	0.1891	0.2136	0.7843	0.0609*
H5	0.1479	−0.1419	0.5795	0.0586*
H6	0.0655	−0.0786	0.8178	0.0637*
H6E	0.6261	0.2801	0.8322	0.0609*
H7	0.1036	0.0722	0.9004	0.0566*
H7A	0.672 (4)	0.202 (2)	1.050 (6)	0.0687*
H7B	0.798 (4)	0.271 (2)	1.099 (5)	0.0687*
H8A	0.756 (5)	0.304 (5)	0.532 (8)	0.1463*
H8B	0.893 (7)	0.293 (5)	0.519 (8)	0.1463*
H9A	0.982 (6)	0.257 (4)	0.814 (7)	0.1233*
H9B	1.018 (7)	0.236 (4)	0.994 (6)	0.1233*
H12	0.1502	0.5094	0.4785	0.0436*
H13	0.3758	0.6102	0.6939	0.0428*
H15	0.6613	0.6370	0.9279	0.0462*
H16	0.8603	0.5766	1.0673	0.0480*
H17	0.8361	0.4257	0.9942	0.0447*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0366 (2)	0.0275 (2)	0.0335 (2)	0.0076 (1)	0.0102 (1)	0.0060 (1)
O1	0.052 (1)	0.048 (1)	0.046 (1)	0.009 (1)	0.026 (1)	0.0056 (10)
O2	0.054 (1)	0.030 (1)	0.045 (1)	0.0055 (9)	0.024 (1)	0.0081 (9)
O3E	0.053 (1)	0.043 (1)	0.045 (1)	0.014 (1)	0.024 (1)	0.0122 (10)
O4	0.034 (1)	0.056 (1)	0.053 (1)	0.012 (1)	0.0004 (10)	0.011 (1)
O5	0.037 (1)	0.033 (1)	0.042 (1)	0.0043 (9)	0.0029 (9)	0.0048 (9)
O6E	0.036 (1)	0.034 (1)	0.036 (1)	0.0102 (8)	0.0013 (8)	0.0051 (8)
O7	0.050 (1)	0.047 (1)	0.035 (1)	0.006 (1)	0.0074 (9)	0.0126 (9)
O8	0.093 (3)	0.121 (3)	0.120 (3)	0.055 (3)	0.069 (3)	0.041 (3)
O9	0.064 (2)	0.096 (2)	0.081 (2)	0.012 (2)	0.037 (2)	−0.020 (2)
N1	0.030 (1)	0.029 (1)	0.033 (1)	0.0055 (9)	0.0063 (9)	0.0083 (9)
N2	0.030 (1)	0.029 (1)	0.025 (1)	0.0053 (9)	0.0077 (9)	0.0061 (8)
C1	0.031 (1)	0.032 (1)	0.031 (1)	0.006 (1)	0.005 (1)	0.007 (1)
C2	0.042 (2)	0.033 (1)	0.037 (1)	0.008 (1)	0.007 (1)	0.001 (1)
C3	0.043 (2)	0.029 (1)	0.050 (2)	0.008 (1)	0.004 (1)	0.007 (1)
C4	0.032 (1)	0.031 (1)	0.044 (2)	0.003 (1)	−0.001 (1)	0.011 (1)
C5	0.043 (2)	0.040 (2)	0.055 (2)	0.001 (1)	0.005 (1)	0.023 (1)
C6	0.045 (2)	0.052 (2)	0.058 (2)	0.000 (2)	0.011 (2)	0.034 (2)
C7	0.040 (2)	0.063 (2)	0.042 (2)	0.010 (1)	0.015 (1)	0.024 (2)
C8	0.034 (1)	0.042 (2)	0.038 (1)	0.009 (1)	0.009 (1)	0.016 (1)
C9	0.027 (1)	0.033 (1)	0.038 (1)	0.005 (1)	0.003 (1)	0.013 (1)
C10	0.037 (1)	0.035 (1)	0.029 (1)	0.005 (1)	0.007 (1)	0.006 (1)
C11	0.030 (1)	0.031 (1)	0.028 (1)	0.005 (1)	0.011 (1)	0.005 (1)
C12	0.038 (1)	0.038 (1)	0.040 (1)	0.015 (1)	0.016 (1)	0.014 (1)
C13	0.047 (2)	0.027 (1)	0.037 (1)	0.011 (1)	0.018 (1)	0.007 (1)
C14	0.038 (1)	0.029 (1)	0.028 (1)	0.005 (1)	0.016 (1)	0.0057 (10)
C15	0.048 (2)	0.028 (1)	0.035 (1)	−0.001 (1)	0.017 (1)	0.002 (1)
C16	0.037 (2)	0.041 (2)	0.031 (1)	−0.006 (1)	0.008 (1)	0.001 (1)
C17	0.031 (1)	0.043 (2)	0.032 (1)	0.004 (1)	0.007 (1)	0.006 (1)
C18	0.034 (1)	0.032 (1)	0.026 (1)	0.006 (1)	0.009 (1)	0.005 (1)
C19	0.032 (1)	0.031 (1)	0.023 (1)	0.006 (1)	0.011 (1)	0.0051 (10)
C20	0.031 (1)	0.038 (1)	0.030 (1)	0.006 (1)	0.006 (1)	0.008 (1)

Geometric parameters (Å, º)

Ni1—O2	2.080 (3)	C2—H2	0.930
Ni1—O3E	2.290 (3)	C3—C4	1.423 (5)
Ni1—O5	2.124 (2)	C3—H3	0.930
Ni1—O6E	2.227 (2)	C4—C5	1.418 (5)
Ni1—N1	1.979 (2)	C4—C9	1.408 (4)
Ni1—N2	1.972 (2)	C5—C6	1.354 (6)
O1—C10	1.234 (4)	C5—H5	0.930
O2—C10	1.269 (4)	C6—C7	1.403 (5)
O3E—C8	1.360 (4)	C6—H6	0.930
O3E—H3E	0.781	C7—C8	1.374 (5)
O4—C20	1.245 (4)	C7—H7	0.930
O5—C20	1.270 (4)	C8—C9	1.415 (5)
O6E—C18	1.358 (3)	C11—C12	1.401 (4)
O6E—H6E	0.806	C11—C20	1.520 (3)
O7—H7A	0.85 (4)	C12—C13	1.382 (3)
O7—H7B	0.85 (3)	C12—H12	0.930
O8—H8A	0.86 (6)	C13—C14	1.413 (4)
O8—H8B	0.87 (6)	C13—H13	0.930
O9—H9A	0.85 (6)	C14—C15	1.413 (3)
O9—H9B	0.84 (5)	C14—C19	1.407 (4)
N1—C1	1.311 (4)	C15—C16	1.367 (5)
N1—C9	1.358 (4)	C15—H15	0.930
N2—C11	1.321 (4)	C16—C17	1.417 (4)
N2—C19	1.356 (3)	C16—H16	0.930
C1—C2	1.414 (4)	C17—C18	1.370 (3)
C1—C10	1.510 (4)	C17—H17	0.930
C2—C3	1.372 (5)	C18—C19	1.419 (4)
O1···O7^i	2.576 (4)	O9···C3^ii	3.576 (4)
O1···C8^i	3.334 (3)	N2···C14^iii	3.569 (4)
O1···C5^ii	3.368 (4)	N2···C13^iii	3.599 (4)
O1···C7^i	3.478 (4)	C1···C3^ii	3.406 (4)
O1···O3E^i	3.505 (3)	C2···C3^ii	3.435 (4)
O2···C13^iii	3.332 (3)	C2···C4^ii	3.453 (4)
O3E···O9^iv	2.556 (5)	C2···C6^i	3.572 (4)
O4···O7^v	2.689 (3)	C4···C7^vi	3.476 (4)
O4···O8^iv	2.943 (6)	C5···C8^vi	3.478 (4)
O4···O9^v	3.444 (5)	C6···C9^vi	3.481 (4)
O4···C17^v	3.572 (4)	C7···C10^vii	3.565 (4)
O5···O9^v	2.952 (4)	C11···C15^iii	3.369 (5)
O5···C6^vi	3.515 (4)	C11···C14^iii	3.578 (4)
O7···C3^ii	3.406 (4)	C12···C16^xi	3.578 (5)
O7···C10^vii	3.482 (4)	C13···C17^xi	3.377 (5)
O7···C20^viii	3.526 (3)	C13···C19^iii	3.388 (5)
O8···C20^ix	3.315 (6)	C13···C16^xi	3.505 (5)
O9···C8^ix	3.242 (6)	C14···C15^xi	3.554 (5)
O9···C7^ix	3.311 (6)	C14···C16^xi	3.598 (5)
O9···C20^viii	3.332 (5)	C15···C19^xi	3.397 (5)
O9···C15^x	3.438 (4)	C15···C20^iii	3.586 (5)
O9···C16^x	3.463 (5)
O2—Ni1—O3E	153.13 (9)	C6—C5—H5	120.3
O2—Ni1—O5	97.86 (9)	C5—C6—C7	122.7 (4)
O2—Ni1—O6E	89.13 (8)	C5—C6—H6	118.7
O2—Ni1—N1	78.96 (10)	C7—C6—H6	118.7
O2—Ni1—N2	105.83 (9)	C6—C7—C8	119.9 (4)
O3E—Ni1—O5	91.84 (9)	C6—C7—H7	120.1
O3E—Ni1—O6E	93.02 (8)	C8—C7—H7	120.1
O3E—Ni1—N1	74.6 (1)	O3E—C8—C7	126.8 (3)
O3E—Ni1—N2	100.67 (10)	O3E—C8—C9	114.9 (3)
O5—Ni1—O6E	154.03 (8)	C7—C8—C9	118.3 (3)
O5—Ni1—N1	101.60 (8)	N1—C9—C4	121.5 (3)
O5—Ni1—N2	78.10 (8)	N1—C9—C8	116.7 (3)
O6E—Ni1—N1	104.29 (8)	C4—C9—C8	121.8 (3)
O6E—Ni1—N2	75.93 (8)	O1—C10—O2	126.7 (3)
N1—Ni1—N2	175.2 (1)	O1—C10—C1	117.6 (3)
Ni1—O2—C10	114.3 (2)	O2—C10—C1	115.7 (3)
Ni1—O3E—C8	111.8 (2)	N2—C11—C12	122.3 (2)
Ni1—O3E—H3E	125.0	N2—C11—C20	112.6 (2)
C8—O3E—H3E	117.0	C12—C11—C20	125.1 (3)
Ni1—O5—C20	113.9 (1)	C11—C12—C13	118.5 (3)
Ni1—O6E—C18	111.9 (2)	C11—C12—H12	120.8
Ni1—O6E—H6E	124.9	C13—C12—H12	120.8
C18—O6E—H6E	114.8	C12—C13—C14	120.1 (3)
H7A—O7—H7B	104 (3)	C12—C13—H13	119.9
H8A—O8—H8B	102 (5)	C14—C13—H13	119.9
H9A—O9—H9B	105 (6)	C13—C14—C15	125.1 (3)
Ni1—N1—C1	117.3 (2)	C13—C14—C19	117.2 (2)
Ni1—N1—C9	121.8 (2)	C15—C14—C19	117.7 (3)
C1—N1—C9	120.7 (3)	C14—C15—C16	119.4 (3)
Ni1—N2—C11	119.1 (1)	C14—C15—H15	120.3
Ni1—N2—C19	120.7 (2)	C16—C15—H15	120.3
C11—N2—C19	120.1 (2)	C15—C16—C17	122.6 (2)
N1—C1—C2	122.2 (3)	C15—C16—H16	118.7
N1—C1—C10	113.4 (2)	C17—C16—H16	118.7
C2—C1—C10	124.4 (3)	C16—C17—C18	119.6 (3)
C1—C2—C3	118.1 (3)	C16—C17—H17	120.2
C1—C2—H2	121.0	C18—C17—H17	120.2
C3—C2—H2	121.0	O6E—C18—C17	126.4 (3)
C2—C3—C4	120.6 (3)	O6E—C18—C19	115.5 (2)
C2—C3—H3	119.7	C17—C18—C19	118.1 (3)
C4—C3—H3	119.7	N2—C19—C14	121.7 (2)
C3—C4—C5	125.2 (3)	N2—C19—C18	115.7 (2)
C3—C4—C9	116.9 (3)	C14—C19—C18	122.6 (2)
C5—C4—C9	118.0 (3)	O4—C20—O5	126.5 (2)
C4—C5—C6	119.4 (3)	O4—C20—C11	117.9 (3)
C4—C5—H5	120.3	O5—C20—C11	115.6 (2)
Ni1—O2—C10—O1	−177.8 (2)	O6E—Ni1—N2—C19	4.3 (2)
Ni1—O2—C10—C1	0.3 (3)	O6E—C18—C17—C16	179.2 (3)
Ni1—O3E—C8—C7	−175.3 (2)	O6E—C18—C19—N2	−0.1 (4)
Ni1—O3E—C8—C9	3.3 (3)	O6E—C18—C19—C14	−179.9 (3)
Ni1—O5—C20—O4	−170.6 (3)	N1—Ni1—O2—C10	2.2 (2)
Ni1—O5—C20—C11	9.9 (3)	N1—Ni1—O3E—C8	−3.9 (2)
Ni1—O6E—C18—C17	−175.4 (3)	N1—Ni1—O5—C20	168.2 (2)
Ni1—O6E—C18—C19	3.3 (3)	N1—Ni1—O6E—C18	−179.1 (2)
Ni1—N1—C1—C2	−174.7 (2)	N1—C1—C2—C3	−0.9 (4)
Ni1—N1—C1—C10	6.2 (3)	N1—C9—C4—C3	0.1 (4)
Ni1—N1—C9—C4	174.9 (2)	N1—C9—C4—C5	−178.8 (3)
Ni1—N1—C9—C8	−3.7 (3)	N1—C9—C8—C7	178.5 (3)
Ni1—N2—C11—C12	−177.0 (2)	N2—Ni1—O2—C10	−177.9 (2)
Ni1—N2—C11—C20	2.0 (3)	N2—Ni1—O3E—C8	175.9 (2)
Ni1—N2—C19—C14	175.9 (2)	N2—Ni1—O5—C20	−7.0 (2)
Ni1—N2—C19—C18	−3.9 (4)	N2—Ni1—O6E—C18	−4.0 (2)
O1—C10—C1—N1	174.1 (2)	N2—C11—C12—C13	0.5 (5)
O1—C10—C1—C2	−5.0 (4)	N2—C19—C14—C13	1.7 (5)
O2—Ni1—O3E—C8	−13.9 (3)	N2—C19—C14—C15	−178.7 (3)
O2—Ni1—O5—C20	−111.6 (2)	N2—C19—C18—C17	178.7 (3)
O2—Ni1—O6E—C18	102.5 (2)	C1—N1—C9—C4	−0.7 (4)
O2—Ni1—N1—C1	−4.8 (2)	C1—N1—C9—C8	−179.3 (2)
O2—Ni1—N1—C9	179.5 (2)	C1—C2—C3—C4	0.2 (4)
O2—Ni1—N2—C11	97.2 (2)	C2—C1—N1—C9	1.1 (4)
O2—Ni1—N2—C19	−80.7 (2)	C2—C3—C4—C5	179.0 (3)
O2—C10—C1—N1	−4.2 (3)	C2—C3—C4—C9	0.1 (4)
O2—C10—C1—C2	176.7 (3)	C3—C2—C1—C10	178.1 (3)
O3E—Ni1—O2—C10	12.0 (3)	C3—C4—C5—C6	−178.3 (3)
O3E—Ni1—O5—C20	93.6 (2)	C3—C4—C9—C8	178.6 (3)
O3E—Ni1—O6E—C18	−104.3 (2)	C4—C5—C6—C7	−0.4 (5)
O3E—Ni1—N1—C1	179.8 (2)	C4—C9—C8—C7	−0.1 (4)
O3E—Ni1—N1—C9	4.0 (2)	C5—C4—C9—C8	−0.3 (4)
O3E—Ni1—N2—C11	−87.4 (2)	C5—C6—C7—C8	−0.1 (5)
O3E—Ni1—N2—C19	94.8 (2)	C6—C5—C4—C9	0.5 (4)
O3E—C8—C7—C6	178.9 (3)	C6—C7—C8—C9	0.3 (4)
O3E—C8—C9—N1	−0.3 (4)	C9—N1—C1—C10	−178.0 (2)
O3E—C8—C9—C4	−178.9 (2)	C11—N2—C19—C14	−2.0 (4)
O4—C20—C11—N2	172.3 (3)	C11—N2—C19—C18	178.2 (3)
O4—C20—C11—C12	−8.7 (5)	C11—C12—C13—C14	−0.7 (5)
O5—Ni1—O2—C10	−98.1 (2)	C12—C11—N2—C19	0.9 (5)
O5—Ni1—O3E—C8	97.6 (2)	C12—C13—C14—C15	−179.9 (3)
O5—Ni1—O6E—C18	−3.8 (3)	C12—C13—C14—C19	−0.3 (5)
O5—Ni1—N1—C1	91.1 (2)	C13—C12—C11—C20	−178.4 (3)
O5—Ni1—N1—C9	−84.7 (2)	C13—C14—C15—C16	179.0 (3)
O5—Ni1—N2—C11	2.3 (2)	C13—C14—C19—C18	−178.5 (3)
O5—Ni1—N2—C19	−175.6 (2)	C14—C15—C16—C17	0.1 (5)
O5—C20—C11—N2	−8.2 (4)	C14—C19—C18—C17	−1.1 (5)
O5—C20—C11—C12	170.8 (3)	C15—C14—C19—C18	1.1 (5)
O6E—Ni1—O2—C10	107.0 (2)	C15—C16—C17—C18	−0.1 (5)
O6E—Ni1—O3E—C8	−107.9 (2)	C16—C15—C14—C19	−0.6 (5)
O6E—Ni1—O5—C20	−7.2 (4)	C16—C17—C18—C19	0.5 (5)
O6E—Ni1—N1—C1	−91.0 (2)	C19—N2—C11—C20	179.8 (3)
O6E—Ni1—N1—C9	93.2 (2)	C19—N2—C11—C20	179.8 (3)
O6E—Ni1—N2—C11	−177.8 (2)

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) x−1, y, z−1; (vi) −x, −y, −z+1; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x+1, y, z; (x) −x+2, −y+1, −z+2; (xi) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3E—H3E···O9^iv	0.78	1.79	2.556 (4)	167
O6E—H6E···O7	0.81	1.66	2.465 (3)	173
O7—H7A···O1^vii	0.85 (2)	1.73 (2)	2.576 (3)	169 (4)
O7—H7A···O2^vii	0.85 (2)	3.10 (3)	3.757 (3)	135 (3)
O7—H7B···O4^viii	0.85 (2)	1.85 (2)	2.689 (3)	168 (4)
O7—H7B···O5^viii	0.85 (2)	3.12 (4)	3.687 (3)	126 (3)
O8—H8B···O4^ix	0.87 (3)	2.20 (5)	2.943 (4)	144 (7)
O8—H8B···O5^ix	0.87 (3)	3.03 (7)	3.872 (4)	162 (5)
O8—H8A···O6E	0.87 (3)	2.51 (6)	2.888 (4)	107 (5)
O8—H8A···O2	0.87 (3)	2.63 (4)	3.447 (5)	157 (7)
O9—H9A···O8	0.85 (6)	1.98 (5)	2.821 (6)	172 (6)
O9—H9B···O5^viii	0.84 (5)	2.27 (4)	2.952 (4)	138 (5)

Symmetry codes: (iv) x−1, y, z; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x+1, y, z.