5-n-Butylpyridine-2-carboxylate-copper(II) and -iron(III) complexes

In trans-bis(5-n-butyl­pyridine-2-carboxyl­ato-[kappa]²N,O)­bis­(methanol-[kappa]O)copper(II), [Cu(C₁₀H₁₂NO₂)₂(CH₄O)₂], the Cu atom lies on a centre of symmetry and has a distorted octahedral coordination. The Cu-O(methanol) bond length in the axial direction is 2.596 (3) Å, which is much longer than the Cu-­O(carboxylate) and Cu-N distances in the equatorial plane [1.952 (2) and 1.977 (2) Å, respectively]. In mer-tris(5-n-bu­tyl­pyridine-2-carboxyl­ato-[kappa]²N,O)­iron(III), [Fe(C₁₀H₁₂NO₂)₃], the Fe atom also has a distorted octahedral geometry, with Fe-O and Fe-N bond-length ranges of 1.949 (4)-1.970 (4) and 2.116 (5)-2.161 (5) Å, respectively. Both crystals are stabilized by stacking interactions of the 5-n-butyl­pyridine-2-carboxyl­ate ligand, although hydrogen bonds also contribute to the stabilization of the copper(II) complex.

S1. Comment

Fusaric acid (5-butylpicolinic acid or 5-butylpyridine-2-carboxylic acid) is a well known fusarium mycotoxin produced by certain fungi which cause infections in cereal grains and other agricultural commodities (Nagatsu et al., 1970; Wang & Ng, 1999; D'Mello et al., 1999). It is a potent inhibitor of the copper enzyme dopamine β-hydroxylase, which catalyzes the biosynthesis of norepinephrine and lowers endogeneous levels of norepinephrine and epinephrine in brain, heart, spleen and adrenal glands. It is suggested that the inhibitory action of fusaric acid is due to complex interactions with the enzyme-substrate complex (Nagatsu et al., 1970). Fusaric acid also possesses a marked growth-inhibitory action on rice seedlings via the Fenton reaction, which produces reactive oxygen species such as hydroxyl radicals in the presence of reactive transition metals, such as copper, iron etc., and hydrogen peroxide (Iwahashi et al., 1999; Kasprzak, 2002). The formation of chelates of fusaric acid with the transition metals Fe^III, Cu^II, Co^II, Ni^II or Mn^II has been confirmed spectrophotometrically (Malini, 1966). These findings prompted us to clarify the structure of fusaric acid and the mode of interaction between fusaric acid and metal ions, and we have determined the crystal structures of the title Cu^II and Fe^III complexes, (I) and (II), respectively. \sch

The molecular structure of (I) is shown in Fig. 1. The Cu atom has a distorted octahedral coordination geometry in the trans form, defined by two N atoms and two O atoms of the bidentate ligand molecules in the equatorial plane, and two axial O atoms of the methanol molecules. The coordination bond length in the axial direction [Cu1—O3M 2.596 (3) Å] is longer than those in the equatorial plane (Table 1).

A similar coordination geometry was observed in hydrated bis(pyridine-2-carboxylato)copper(II), in which the corresponding Cu—O(aq) distance in the axial direction and Cu—O(carboxylate) bond length in the equatorial plane are 2.752 (2) and 1.940 (2) Å, respectively (Faure et al., 1973). These long bond lengths in the axial direction compared with those in the equatorial plane are usually observed in copper complexes of octahedral coordination geometry and are explained by a Jahn-Teller effect.

The butyl side chain of the fusaric acid ligands are in the fully extended trans zigzag conformation in (I), the zigzag plane nearly coinciding with the planes of the pyridine ring and the carboxylate [O2—C7—C2—N1 - 3.0 (4), C6—C5—C8—C9 - 17.5 (5) and C8—C9—C10—C11 - 179.6 (4)°].

In the crystal packing of (I), neighbouring molecules are stacked a mean distance of 3.403 (4) Å apart, and strong hydrogen bonds are formed between the coordinated methanol molecules and the carboxylate groups of neighbouring molecules (Table 2). The hydrocarbon side chains of the ligands and the coordinated methanol molecules form hydrophobic moieties by association.

The molecular structure of (II) is shown in Fig. 2. In this complex, the Fe atom has a distorted octahedral coordination geometry in the meridional form, bonded by three N and three O atoms from three bidentate ligands. The orientation of the hydrocarbon chains in (II) is very different from that in (I), with the chains roughly perpendicular to the pyridine ring plane [C14—C15—C18—C19 92.0 (7), C24—C25—C28—C29 80.0 (10) and C4—C5—C8—C9 - 76.7 (10)°]. The conformations of the three chains are different, being trans-gauche [C5—C8—C9—C10 - 179.3 (8) and C8—C9—C10—C11 - 63 (1)°], trans-trans [C15—C18—C19—C20 - 174.1 (7) and C18—C19—C20—C21 - 178.6 (7)°] and gauche-trans [C25—C28—C29—C30 68 (1) and C28—C29—C30—C31 166 (1)°].

The model of the coordination mode of the Fe^II complex of picolinic acid (pyridine-2-carboxylic acid) has been proposed from UV-visible absorption spectra (Iwahashi et al., 1999), in which the central Fe^II atom was expected to be coordinated by three N and three O atoms of the three ligands in the facial form. In this study, only the meridional isomer of the Fe^III complex was obtained, although there was a probability that both meridional and facial isomers were obtained in the preparation of compound (II). It is noted that the crystal structures of the Fe^II complexes of picolinic acid or fusaric acid have not yet been determined.

In the crystal packing of (II), one of the three pyridine rings (N1/C2—C6) stacks a mean distance of 3.681 (12) Å apart. Neighbouring carbohydrate side chains are associated, forming carbohydrate moieties.

In both (I) and (II), the central metal atom forms a five-membered ring with O and N atoms of the bidentate ligand, as also observed in the Cd^II complex of fusaric acid (Okabe, Wada & Muranishi, 2002), as well as in the analogous metal complexes, such as the Mo^V complex of picolinic acid (Okabe, Isomoto & Odoko, 2002) and the Ce^III complex of dipicolinic acid (pyridine-2,6-dicarboxylic acid; Okabe, Kyoyama & Fujimoto, 2002).

The major conformational differences found in the butyl side chain of fusaric acid in complexes (I) and (II) suggest that the conformational change of the butyl side chain occurs as required to accommodate the structure of its binding site on biological target molecules.

Parts of the text have been extensively rephrased - please check carefully to ensure the sense has not been altered.

S2. Experimental

Blue crystals of (I) were obtained by slow evaporation of a methanol-water solution (90:10 v/v) of a mixture of fusaric acid and CuSO₄·5H₂O (molar ratio 4:1). Colourless prismatic crystals of (II) were obtained by slow evaporation of an ethanol-water solution (30:70 v/v) of a mixture of fusaric acid and Fe(SO₄)₃.nH₂O (n = 6–9; molar ratio ca 4:1 assuming n = 7).

S3. Refinement

The reflection data for (I) were corrected for an intensity decay of 20.2%. The H atoms of (I) and (II) were treated by riding models. Only one H atom, H3M?, attached to the methanol hydroxy group in (I), was fixed at the position located from the difference Fourier map. The remaining H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å. Is this added text correct? The large atomic displacement parameters of the n-butyl groups of (II) suggest positional disorder.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation and Rigaku Corporation, 2000) for (I); MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, Rigaku Corporation, 2000) for (II). For both compounds, cell refinement: MSC/AFC Diffractometer Control Software. Data reduction: TEXSAN (Molecular Structure Corporation and Rigaku Corporation, 2000) for (I); TEXSAN (Molecular Structure Corporation, Rigaku Corporation, 2000) for (II). Program(s) used to solve structure: SIR88 (Burla et al., 1989) and DIRDIF94 (Beurskens et al., 1994) for (I); SIR92 (Altomare et al., 1999) and DIRDIF94 (Beurskens et al., 1994) for (II). For both compounds, 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; asterisks indicate symmetry-related atoms (symmetry code: 2 - x, 1 - y, 2 - z Is this the correct symmetry code?) Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. 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)

Crystal data

[Cu(C10H12NO2)2(CH4O)2]	F(000) = 510.0
Mr = 484.05	Dx = 1.359 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yn	Cell parameters from 23 reflections
a = 8.462 (4) Å	θ = 14.9–15.0°
b = 6.612 (4) Å	µ = 0.96 mm^−1
c = 21.456 (3) Å	T = 296 K
β = 99.88 (2)°	Plate, blue
V = 1182.7 (9) Å^3	0.5 × 0.4 × 0.2 mm
Z = 2

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.023
ω/2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = 0→10
Tmin = 0.636, Tmax = 0.825	k = 0→8
3139 measured reflections	l = −27→27
2707 independent reflections	3 standard reflections every 150 reflections
1998 reflections with I > 2σ(I)	intensity decay: 20.2%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.166	(Δ/σ)max < 0.001
S = 1.22	Δρmax = 0.34 e Å^−3
2707 reflections	Δρmin = −0.77 e Å^−3
145 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 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
Cu1	1.0000	0.5000	1.0000	0.0504 (2)
O1	1.2595 (3)	0.9717 (3)	0.9689 (2)	0.0656 (7)
O2	1.0586 (2)	0.7512 (3)	0.9619 (1)	0.0557 (6)
O3M	0.9219 (3)	0.7222 (3)	1.0898 (2)	0.0718 (7)
N1	1.2271 (3)	0.5014 (3)	1.0419 (1)	0.0433 (5)
C2	1.3026 (3)	0.6691 (4)	1.0272 (1)	0.0428 (6)
C3	1.4620 (3)	0.7025 (4)	1.0516 (2)	0.0508 (7)
C4	1.5427 (3)	0.5608 (5)	1.0924 (2)	0.0533 (7)
C5	1.4660 (3)	0.3876 (5)	1.1084 (2)	0.0505 (7)
C6	1.3051 (3)	0.3657 (4)	1.0814 (2)	0.0493 (7)
C7	1.2004 (3)	0.8104 (4)	0.9825 (2)	0.0480 (6)
C8	1.5542 (4)	0.2338 (6)	1.1530 (2)	0.0704 (10)
C9	1.4605 (4)	0.0864 (6)	1.1833 (2)	0.0639 (8)
C10	1.5649 (5)	−0.0517 (7)	1.2296 (2)	0.079 (1)
C11	1.4681 (7)	−0.2034 (9)	1.2602 (4)	0.128 (2)
C12	1.0385 (6)	0.8093 (7)	1.1356 (2)	0.090 (1)
H3	1.5140	0.8178	1.0408	0.0610*
H3M	0.8771	0.8108	1.0664	0.1078*
H4	1.6501	0.5817	1.1094	0.0640*
H6	1.2501	0.2518	1.0914	0.0592*
H8A	1.6237	0.1581	1.1300	0.0845*
H8B	1.6230	0.3068	1.1864	0.0845*
H9A	1.3967	0.0046	1.1508	0.0767*
H9B	1.3874	0.1590	1.2055	0.0767*
H10A	1.6385	−0.1237	1.2076	0.0945*
H10B	1.6281	0.0298	1.2624	0.0945*
H11A	1.3902	−0.1334	1.2798	0.1917*
H11B	1.5385	−0.2790	1.2916	0.1917*
H11C	1.4144	−0.2941	1.2285	0.1917*
H12A	1.0898	0.9180	1.1171	0.1355*
H12B	1.1170	0.7092	1.1519	0.1355*
H12C	0.9891	0.8609	1.1695	0.1355*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0314 (3)	0.0423 (3)	0.0728 (4)	−0.0144 (2)	−0.0046 (2)	0.0189 (2)
O1	0.045 (1)	0.041 (1)	0.110 (2)	−0.0130 (9)	0.009 (1)	0.021 (1)
O2	0.0363 (9)	0.045 (1)	0.082 (2)	−0.0116 (8)	−0.0015 (9)	0.0185 (10)
O3M	0.060 (1)	0.051 (1)	0.102 (2)	−0.006 (1)	0.005 (1)	0.008 (1)
N1	0.032 (1)	0.040 (1)	0.056 (1)	−0.0106 (8)	0.0022 (9)	0.0049 (9)
C2	0.034 (1)	0.035 (1)	0.060 (2)	−0.0096 (10)	0.010 (1)	−0.003 (1)
C3	0.037 (1)	0.045 (1)	0.070 (2)	−0.017 (1)	0.009 (1)	−0.002 (1)
C4	0.031 (1)	0.057 (2)	0.069 (2)	−0.014 (1)	−0.001 (1)	−0.001 (1)
C5	0.035 (1)	0.054 (2)	0.060 (2)	−0.006 (1)	0.002 (1)	0.004 (1)
C6	0.037 (1)	0.044 (1)	0.066 (2)	−0.010 (1)	0.004 (1)	0.008 (1)
C7	0.037 (1)	0.035 (1)	0.072 (2)	−0.008 (1)	0.012 (1)	0.004 (1)
C8	0.038 (1)	0.081 (2)	0.087 (3)	−0.003 (2)	−0.004 (2)	0.023 (2)
C9	0.051 (2)	0.065 (2)	0.073 (2)	0.005 (2)	0.002 (2)	0.013 (2)
C10	0.065 (2)	0.078 (2)	0.087 (3)	0.004 (2)	−0.005 (2)	0.027 (2)
C11	0.108 (4)	0.108 (4)	0.158 (5)	−0.014 (3)	−0.004 (4)	0.065 (4)
C12	0.094 (3)	0.086 (3)	0.086 (3)	−0.002 (2)	0.000 (2)	−0.011 (2)

Geometric parameters (Å, º)

Cu1—O2	1.952 (2)	C5—C6	1.392 (4)
Cu1—O2^i	1.952 (2)	C5—C8	1.504 (5)
Cu1—O3M	2.596 (3)	C6—H6	0.930
Cu1—O3M^i	2.596 (3)	C8—C9	1.477 (6)
Cu1—N1	1.977 (2)	C8—H8A	0.970
Cu1—N1^i	1.977 (2)	C8—H8B	0.970
O1—C7	1.234 (4)	C9—C10	1.516 (6)
O2—C7	1.268 (3)	C9—H9A	0.970
O3M—C12	1.393 (5)	C9—H9B	0.970
O3M—H3M	0.820	C10—C11	1.513 (8)
N1—C2	1.344 (3)	C10—H10A	0.970
N1—C6	1.329 (4)	C10—H10B	0.970
C2—C3	1.378 (4)	C11—H11A	0.960
C2—C7	1.502 (4)	C11—H11B	0.960
C3—C4	1.380 (4)	C11—H11C	0.960
C3—H3	0.930	C12—H12A	0.960
C4—C5	1.388 (4)	C12—H12B	0.960
C4—H4	0.930	C12—H12C	0.960
O2—Cu1—O2^i	180.0	N1—C6—H6	118.7
O2—Cu1—O3M	86.80 (9)	C5—C6—H6	118.7
O2—Cu1—O3M^i	93.20 (9)	O1—C7—O2	125.6 (3)
O2—Cu1—N1	83.66 (9)	O1—C7—C2	118.5 (2)
O2—Cu1—N1^i	96.34 (9)	O2—C7—C2	116.0 (2)
O2^i—Cu1—O3M	93.20 (9)	C5—C8—C9	118.8 (3)
O2^i—Cu1—O3M^i	86.80 (9)	C5—C8—H8A	107.6
O2^i—Cu1—N1	96.34 (9)	C5—C8—H8B	107.6
O2^i—Cu1—N1^i	83.66 (9)	C9—C8—H8A	107.6
O3M—Cu1—O3M^i	180.0	C9—C8—H8B	107.6
O3M—Cu1—N1	90.65 (9)	H8A—C8—H8B	107.1
O3M—Cu1—N1^i	89.35 (9)	C8—C9—C10	113.0 (3)
O3M^i—Cu1—N1	89.35 (9)	C8—C9—H9A	109.0
O3M^i—Cu1—N1^i	90.65 (9)	C8—C9—H9B	109.0
N1—Cu1—N1^i	180.0	C10—C9—H9A	109.0
Cu1—O2—C7	114.2 (2)	C10—C9—H9B	109.0
Cu1—O3M—C12	121.2 (3)	H9A—C9—H9B	107.8
Cu1—O3M—H3M	95.8	C9—C10—C11	112.7 (4)
C12—O3M—H3M	109.5	C9—C10—H10A	109.1
Cu1—N1—C2	111.2 (2)	C9—C10—H10B	109.1
Cu1—N1—C6	128.6 (2)	C11—C10—H10A	109.1
C2—N1—C6	120.2 (2)	C11—C10—H10B	109.1
N1—C2—C3	121.1 (2)	H10A—C10—H10B	107.8
N1—C2—C7	114.7 (2)	C10—C11—H11A	109.5
C3—C2—C7	124.2 (2)	C10—C11—H11B	109.5
C2—C3—C4	118.5 (3)	C10—C11—H11C	109.5
C2—C3—H3	120.7	H11A—C11—H11B	109.5
C4—C3—H3	120.7	H11A—C11—H11C	109.5
C3—C4—C5	121.0 (3)	H11B—C11—H11C	109.5
C3—C4—H4	119.5	O3M—C12—H12A	109.5
C5—C4—H4	119.5	O3M—C12—H12B	109.5
C4—C5—C6	116.7 (3)	O3M—C12—H12C	109.5
C4—C5—C8	120.8 (3)	H12A—C12—H12B	109.5
C6—C5—C8	122.5 (3)	H12A—C12—H12C	109.5
N1—C6—C5	122.5 (3)	H12B—C12—H12C	109.5
Cu1—O2—C7—O1	−174.4 (3)	O3M—Cu1—N1—C2	−83.5 (2)
Cu1—O2—C7—C2	5.7 (4)	O3M—Cu1—N1—C6	94.7 (3)
Cu1—O2^i—C7^i—O1^i	174.4 (3)	O3M—Cu1—N1^i—C2^i	−96.5 (2)
Cu1—O2^i—C7^i—C2^i	−5.7 (4)	O3M—Cu1—N1^i—C6^i	85.3 (3)
Cu1—N1—C2—C3	179.6 (2)	N1—Cu1—O2—C7	−5.1 (2)
Cu1—N1—C2—C7	−1.2 (3)	N1—Cu1—O2^i—C7^i	−174.9 (2)
Cu1—N1—C6—C5	−179.0 (2)	N1—Cu1—O3M—C12	9.0 (3)
Cu1—N1^i—C2^i—C3^i	−179.6 (2)	N1—Cu1—O3M^i—C12^i	171.0 (3)
Cu1—N1^i—C2^i—C7^i	1.2 (3)	N1—C2—C3—C4	−1.0 (5)
Cu1—N1^i—C6^i—C5^i	179.0 (2)	N1—C6—C5—C4	0.5 (5)
O1—C7—C2—N1	177.1 (3)	N1—C6—C5—C8	−179.9 (3)
O1—C7—C2—C3	−3.8 (5)	C2—N1—C6—C5	−1.0 (5)
O2—Cu1—O3M—C12	−74.6 (3)	C2—C3—C4—C5	0.4 (5)
O2—Cu1—O3M^i—C12^i	−105.4 (3)	C3—C2—N1—C6	1.2 (4)
O2—Cu1—N1—C2	3.2 (2)	C3—C4—C5—C6	−0.2 (5)
O2—Cu1—N1—C6	−178.6 (3)	C3—C4—C5—C8	−179.8 (3)
O2—Cu1—N1^i—C2^i	176.8 (2)	C4—C3—C2—C7	179.9 (3)
O2—Cu1—N1^i—C6^i	−1.4 (3)	C4—C5—C8—C9	162.1 (3)
O2—C7—C2—N1	−3.0 (4)	C5—C8—C9—C10	−177.0 (3)
O2—C7—C2—C3	176.2 (3)	C6—N1—C2—C7	−179.5 (3)
O3M—Cu1—O2—C7	85.9 (2)	C6—C5—C8—C9	−17.5 (5)
O3M—Cu1—O2^i—C7^i	94.1 (2)	C8—C9—C10—C11	−179.6 (4)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3M—H3M···O1^ii	0.82	1.92	2.716 (4)	164.0

Symmetry code: (ii) −x+2, −y+2, −z+2.

(II)

Crystal data

[Fe(C10H12NO2)3]	F(000) = 1244.0
Mr = 590.47	Dx = 1.272 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yn	Cell parameters from 24 reflections
a = 9.946 (5) Å	θ = 10.2–11.5°
b = 22.271 (5) Å	µ = 0.53 mm^−1
c = 14.072 (4) Å	T = 296 K
β = 98.40 (3)°	Prismatic, colourless
V = 3083.6 (19) Å^3	0.2 × 0.1 × 0.1 mm
Z = 4

Data collection

Rigaku AFC-5R diffractometer	θmax = 27.5°
ω/2θ scans	h = 0→12
7678 measured reflections	k = 0→28
7090 independent reflections	l = −18→18
2368 reflections with I > 2σ(I)	3 standard reflections every 150 reflections
Rint = 0.075	intensity decay: 0.7%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.225	(Δ/σ)max < 0.001
S = 0.93	Δρmax = 0.50 e Å^−3
7090 reflections	Δρmin = −0.55 e Å^−3
364 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
Fe1	0.17773 (7)	0.14451 (4)	0.37310 (6)	0.0500 (3)
O1	−0.1874 (4)	0.1029 (2)	0.2289 (4)	0.092 (2)
O2	0.0284 (4)	0.1301 (2)	0.2696 (3)	0.062 (1)
O3	0.4686 (4)	0.0223 (2)	0.3490 (3)	0.079 (1)
O4	0.2871 (4)	0.0705 (2)	0.3868 (3)	0.0564 (10)
O5	0.1690 (5)	0.3184 (2)	0.4514 (3)	0.083 (1)
O6	0.1352 (4)	0.2308 (2)	0.3748 (3)	0.058 (1)
N1	0.0275 (4)	0.1051 (2)	0.4506 (3)	0.050 (1)
N2	0.2962 (4)	0.1736 (2)	0.5060 (3)	0.051 (1)
N3	0.3114 (4)	0.1585 (2)	0.2712 (3)	0.050 (1)
C2	−0.0896 (5)	0.0930 (2)	0.3909 (4)	0.052 (1)
C3	−0.1997 (6)	0.0673 (3)	0.4243 (5)	0.066 (2)
C4	−0.1894 (6)	0.0537 (3)	0.5210 (5)	0.069 (2)
C5	−0.0705 (7)	0.0628 (3)	0.5818 (5)	0.064 (2)
C6	0.0350 (6)	0.0906 (3)	0.5434 (4)	0.061 (2)
C7	−0.0869 (6)	0.1092 (3)	0.2877 (5)	0.060 (2)
C8	−0.0484 (8)	0.0464 (4)	0.6887 (5)	0.088 (2)
C9	−0.109 (1)	0.0868 (5)	0.7468 (6)	0.144 (4)
C10	−0.084 (2)	0.0699 (7)	0.8565 (8)	0.180 (6)
C11	−0.136 (2)	0.019 (1)	0.881 (1)	0.28 (1)
C12	0.2806 (5)	0.2322 (3)	0.5227 (4)	0.052 (1)
C13	0.3425 (6)	0.2592 (3)	0.6052 (4)	0.063 (2)
C14	0.4159 (6)	0.2245 (3)	0.6756 (5)	0.069 (2)
C15	0.4326 (6)	0.1635 (3)	0.6593 (4)	0.060 (2)
C16	0.3728 (5)	0.1403 (3)	0.5725 (4)	0.053 (1)
C17	0.1895 (6)	0.2645 (3)	0.4450 (4)	0.057 (2)
C18	0.5005 (7)	0.1226 (3)	0.7358 (5)	0.074 (2)
C19	0.3902 (9)	0.0935 (4)	0.7927 (5)	0.106 (3)
C20	0.4459 (10)	0.0578 (4)	0.8748 (6)	0.120 (3)
C21	0.332 (1)	0.0303 (5)	0.9239 (8)	0.156 (4)
C22	0.4005 (5)	0.1134 (3)	0.2669 (4)	0.048 (1)
C23	0.4900 (6)	0.1128 (3)	0.2021 (4)	0.062 (2)
C24	0.4868 (6)	0.1598 (3)	0.1393 (5)	0.069 (2)
C25	0.3972 (6)	0.2069 (3)	0.1410 (5)	0.064 (2)
C26	0.3108 (6)	0.2043 (3)	0.2091 (4)	0.058 (2)
C27	0.3882 (6)	0.0636 (3)	0.3389 (4)	0.055 (1)
C28	0.3928 (9)	0.2584 (4)	0.0726 (6)	0.097 (3)
C29	0.318 (1)	0.2469 (6)	−0.0243 (9)	0.160 (5)
C30	0.180 (1)	0.2404 (8)	−0.0288 (10)	0.206 (7)
C31	0.107 (1)	0.2427 (7)	−0.127 (1)	0.246 (8)
H3	−0.2793	0.0594	0.3827	0.0788*
H4	−0.2643	0.0380	0.5451	0.0833*
H6	0.1146	0.0996	0.5843	0.0729*
H8A	−0.0851	0.0066	0.6961	0.1061*
H8B	0.0485	0.0448	0.7111	0.1061*
H9A	−0.2058	0.0880	0.7251	0.1724*
H9B	−0.0728	0.1267	0.7390	0.1724*
H10A	0.0136	0.0685	0.8772	0.2165*
H10B	−0.1198	0.1020	0.8919	0.2165*
H11A	−0.2193	0.0117	0.8394	0.4214*
H11B	−0.1530	0.0220	0.9463	0.4214*
H11C	−0.0729	−0.0127	0.8755	0.4214*
H13	0.3351	0.3005	0.6136	0.0757*
H14	0.4540	0.2417	0.7336	0.0827*
H16	0.3861	0.1000	0.5595	0.0636*
H18A	0.5660	0.1450	0.7799	0.0886*
H18B	0.5487	0.0912	0.7070	0.0886*
H19A	0.3356	0.1255	0.8144	0.1277*
H19B	0.3304	0.0684	0.7489	0.1277*
H20A	0.5034	0.0828	0.9204	0.1440*
H20B	0.5016	0.0260	0.8542	0.1440*
H21A	0.2903	0.0612	0.9570	0.2333*
H21B	0.3701	0.0003	0.9691	0.2333*
H21C	0.2656	0.0122	0.8764	0.2333*
H23	0.5514	0.0814	0.2008	0.0747*
H24	0.5465	0.1600	0.0942	0.0825*
H26	0.2496	0.2356	0.2122	0.0697*
H28A	0.3514	0.2925	0.1001	0.1169*
H28B	0.4854	0.2695	0.0663	0.1169*
H29A	0.3351	0.2799	−0.0659	0.1920*
H29B	0.3541	0.2108	−0.0495	0.1920*
H30A	0.1461	0.2719	0.0089	0.2468*
H30B	0.1616	0.2022	−0.0002	0.2468*
H31A	0.0153	0.2552	−0.1250	0.3685*
H31B	0.1077	0.2037	−0.1553	0.3685*
H31C	0.1512	0.2709	−0.1636	0.3685*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0417 (4)	0.0603 (5)	0.0485 (5)	−0.0039 (4)	0.0085 (3)	0.0002 (5)
O1	0.055 (3)	0.133 (5)	0.082 (3)	−0.025 (3)	−0.012 (3)	0.017 (3)
O2	0.049 (2)	0.084 (3)	0.051 (2)	−0.009 (2)	0.007 (2)	0.006 (2)
O3	0.070 (3)	0.067 (3)	0.103 (4)	0.015 (2)	0.025 (3)	0.011 (3)
O4	0.054 (2)	0.055 (2)	0.064 (2)	−0.003 (2)	0.018 (2)	0.000 (2)
O5	0.108 (4)	0.067 (3)	0.071 (3)	0.019 (3)	0.007 (3)	−0.004 (3)
O6	0.055 (2)	0.065 (3)	0.052 (2)	0.013 (2)	0.003 (2)	−0.002 (2)
N1	0.044 (3)	0.053 (3)	0.055 (3)	−0.001 (2)	0.010 (2)	0.000 (2)
N2	0.049 (3)	0.053 (3)	0.052 (3)	0.000 (2)	0.009 (2)	−0.005 (2)
N3	0.046 (2)	0.049 (3)	0.057 (3)	−0.006 (2)	0.011 (2)	−0.003 (2)
C2	0.042 (3)	0.048 (3)	0.066 (4)	0.001 (3)	0.008 (3)	0.006 (3)
C3	0.054 (4)	0.059 (4)	0.086 (5)	−0.010 (3)	0.016 (3)	0.005 (4)
C4	0.053 (4)	0.065 (4)	0.094 (5)	−0.008 (3)	0.025 (4)	0.009 (4)
C5	0.073 (4)	0.057 (4)	0.064 (4)	−0.005 (4)	0.022 (3)	0.004 (3)
C6	0.062 (4)	0.064 (4)	0.058 (4)	−0.004 (3)	0.016 (3)	0.000 (3)
C7	0.054 (4)	0.059 (4)	0.067 (4)	−0.007 (3)	0.008 (3)	0.008 (3)
C8	0.092 (5)	0.098 (6)	0.084 (5)	−0.001 (4)	0.042 (4)	0.009 (5)
C9	0.18 (1)	0.17 (1)	0.082 (6)	0.047 (8)	0.039 (7)	0.002 (7)
C10	0.21 (1)	0.25 (2)	0.094 (8)	0.05 (1)	0.059 (9)	0.031 (10)
C11	0.21 (2)	0.50 (4)	0.14 (1)	−0.01 (2)	0.06 (1)	0.11 (2)
C12	0.041 (3)	0.060 (4)	0.054 (4)	−0.001 (3)	0.007 (3)	−0.003 (3)
C13	0.066 (4)	0.054 (4)	0.069 (4)	0.001 (3)	0.008 (3)	−0.010 (3)
C14	0.065 (4)	0.072 (5)	0.067 (4)	−0.005 (4)	0.001 (3)	−0.013 (4)
C15	0.053 (3)	0.070 (4)	0.055 (4)	0.001 (3)	−0.003 (3)	−0.007 (3)
C16	0.047 (3)	0.046 (3)	0.065 (4)	0.003 (3)	0.005 (3)	0.003 (3)
C17	0.062 (4)	0.058 (4)	0.053 (4)	0.008 (3)	0.021 (3)	0.000 (3)
C18	0.073 (4)	0.075 (5)	0.067 (4)	0.002 (4)	−0.012 (4)	−0.009 (4)
C19	0.134 (7)	0.119 (7)	0.066 (5)	0.046 (6)	0.015 (5)	0.023 (5)
C20	0.150 (9)	0.095 (7)	0.108 (7)	0.003 (6)	−0.006 (6)	0.016 (6)
C21	0.153 (10)	0.16 (1)	0.17 (1)	−0.021 (8)	0.054 (8)	0.042 (8)
C22	0.044 (3)	0.050 (3)	0.051 (3)	−0.007 (3)	0.008 (3)	−0.003 (3)
C23	0.050 (3)	0.072 (4)	0.069 (4)	−0.002 (3)	0.021 (3)	−0.003 (4)
C24	0.069 (4)	0.082 (5)	0.062 (4)	−0.018 (4)	0.031 (3)	−0.004 (4)
C25	0.070 (4)	0.065 (4)	0.060 (4)	−0.009 (4)	0.024 (3)	−0.001 (3)
C26	0.056 (3)	0.055 (4)	0.065 (4)	−0.003 (3)	0.013 (3)	−0.002 (3)
C27	0.051 (3)	0.054 (4)	0.058 (4)	−0.005 (3)	0.003 (3)	−0.014 (3)
C28	0.103 (6)	0.106 (7)	0.089 (6)	0.000 (5)	0.036 (5)	0.029 (5)
C29	0.129 (10)	0.18 (1)	0.17 (1)	0.016 (8)	0.022 (9)	0.087 (9)
C30	0.13 (1)	0.30 (2)	0.19 (1)	0.04 (1)	0.027 (10)	0.10 (1)
C31	0.22 (2)	0.27 (2)	0.22 (2)	0.09 (1)	−0.04 (1)	0.09 (1)

Geometric parameters (Å, º)

Fe1—O2	1.949 (4)	C13—C14	1.379 (9)
Fe1—O4	1.970 (4)	C13—H13	0.930
Fe1—O6	1.969 (4)	C14—C15	1.392 (10)
Fe1—N1	2.161 (5)	C14—H14	0.930
Fe1—N2	2.159 (4)	C15—C16	1.379 (8)
Fe1—N3	2.116 (5)	C15—C18	1.494 (9)
O1—C7	1.209 (7)	C16—H16	0.930
O2—C7	1.296 (7)	C18—C19	1.59 (1)
O3—C27	1.214 (7)	C18—H18A	0.970
O4—C27	1.298 (7)	C18—H18B	0.970
O5—C17	1.223 (8)	C19—C20	1.44 (1)
O6—C17	1.293 (7)	C19—H19A	0.970
N1—C2	1.359 (7)	C19—H19B	0.970
N1—C6	1.336 (8)	C20—C21	1.53 (2)
N2—C12	1.339 (8)	C20—H20A	0.970
N2—C16	1.341 (7)	C20—H20B	0.970
N3—C22	1.347 (7)	C21—H21A	0.960
N3—C26	1.343 (8)	C21—H21B	0.960
C2—C3	1.377 (9)	C21—H21C	0.960
C2—C7	1.501 (9)	C22—C23	1.365 (8)
C3—C4	1.38 (1)	C22—C27	1.518 (8)
C3—H3	0.930	C23—C24	1.367 (9)
C4—C5	1.371 (9)	C23—H23	0.930
C4—H4	0.930	C24—C25	1.380 (9)
C5—C6	1.394 (9)	C24—H24	0.930
C5—C8	1.532 (9)	C25—C26	1.379 (9)
C6—H6	0.930	C25—C28	1.49 (1)
C8—C9	1.41 (1)	C26—H26	0.930
C8—H8A	0.970	C28—C29	1.48 (1)
C8—H8B	0.970	C28—H28A	0.970
C9—C10	1.57 (1)	C28—H28B	0.970
C9—H9A	0.970	C29—C30	1.37 (2)
C9—H9B	0.970	C29—H29A	0.970
C10—C11	1.30 (3)	C29—H29B	0.970
C10—H10A	0.970	C30—C31	1.46 (2)
C10—H10B	0.970	C30—H30A	0.970
C11—H11A	0.960	C30—H30B	0.970
C11—H11B	0.960	C31—H31A	0.960
C11—H11C	0.960	C31—H31B	0.960
C12—C13	1.372 (8)	C31—H31C	0.960
C12—C17	1.497 (8)
O1···C23^i	3.183 (7)	O4···C4^v	3.261 (8)
O1···C24^i	3.536 (8)	O4···C8^v	3.578 (8)
O1···C13^ii	3.563 (8)	O5···C24^vi	3.452 (8)
O3···C3^iii	3.463 (7)	O5···C18^ii	3.500 (8)
O3···C18^iv	3.470 (8)	O6···C14^ii	3.438 (7)
O2—Fe1—O4	106.5 (2)	C15—C14—H14	120.3
O2—Fe1—O6	91.6 (2)	C14—C15—C16	117.7 (5)
O2—Fe1—N1	78.6 (2)	C14—C15—C18	121.9 (5)
O2—Fe1—N2	163.1 (2)	C16—C15—C18	120.1 (6)
O2—Fe1—N3	90.2 (2)	N2—C16—C15	122.6 (6)
O4—Fe1—O6	158.9 (2)	N2—C16—H16	118.7
O4—Fe1—N1	91.4 (2)	C15—C16—H16	118.7
O4—Fe1—N2	86.7 (2)	O5—C17—O6	124.7 (5)
O4—Fe1—N3	78.3 (2)	O5—C17—C12	120.4 (5)
O6—Fe1—N1	103.0 (2)	O6—C17—C12	114.9 (5)
O6—Fe1—N2	77.7 (2)	C15—C18—C19	109.9 (5)
O6—Fe1—N3	91.3 (2)	C15—C18—H18A	109.7
N1—Fe1—N2	90.9 (2)	C15—C18—H18B	109.7
N1—Fe1—N3	162.0 (2)	C19—C18—H18A	109.7
N2—Fe1—N3	103.0 (2)	C19—C18—H18B	109.7
Fe1—O2—C7	120.8 (4)	H18A—C18—H18B	108.2
Fe1—O4—C27	120.4 (4)	C18—C19—C20	114.6 (7)
Fe1—O6—C17	120.6 (4)	C18—C19—H19A	108.6
Fe1—N1—C2	111.3 (4)	C18—C19—H19B	108.6
Fe1—N1—C6	130.3 (4)	C20—C19—H19A	108.6
C2—N1—C6	118.4 (5)	C20—C19—H19B	108.6
Fe1—N2—C12	112.4 (3)	H19A—C19—H19B	107.6
Fe1—N2—C16	128.4 (4)	C19—C20—C21	111.0 (8)
C12—N2—C16	119.1 (5)	C19—C20—H20A	109.4
Fe1—N3—C22	113.8 (4)	C19—C20—H20B	109.4
Fe1—N3—C26	127.5 (4)	C21—C20—H20A	109.4
C22—N3—C26	118.6 (5)	C21—C20—H20B	109.4
N1—C2—C3	121.6 (5)	H20A—C20—H20B	108.0
N1—C2—C7	114.5 (5)	C20—C21—H21A	109.5
C3—C2—C7	123.9 (5)	C20—C21—H21B	109.5
C2—C3—C4	118.6 (5)	C20—C21—H21C	109.5
C2—C3—H3	120.7	H21A—C21—H21B	109.5
C4—C3—H3	120.7	H21A—C21—H21C	109.5
C3—C4—C5	120.9 (6)	H21B—C21—H21C	109.5
C3—C4—H4	119.5	N3—C22—C23	122.3 (5)
C5—C4—H4	119.5	N3—C22—C27	113.4 (5)
C4—C5—C6	117.0 (6)	C23—C22—C27	124.3 (5)
C4—C5—C8	124.4 (6)	C22—C23—C24	118.0 (6)
C6—C5—C8	118.6 (5)	C22—C23—H23	121.0
N1—C6—C5	123.3 (5)	C24—C23—H23	121.0
N1—C6—H6	118.4	C23—C24—C25	121.7 (6)
C5—C6—H6	118.4	C23—C24—H24	119.2
O1—C7—O2	125.0 (6)	C25—C24—H24	119.2
O1—C7—C2	120.3 (6)	C24—C25—C26	116.7 (6)
O2—C7—C2	114.7 (5)	C24—C25—C28	122.1 (7)
C5—C8—C9	114.0 (7)	C26—C25—C28	121.2 (6)
C5—C8—H8A	108.8	N3—C26—C25	122.7 (5)
C5—C8—H8B	108.8	N3—C26—H26	118.6
C9—C8—H8A	108.8	C25—C26—H26	118.6
C9—C8—H8B	108.8	O3—C27—O4	125.1 (6)
H8A—C8—H8B	107.7	O3—C27—C22	121.0 (5)
C8—C9—C10	113.4 (9)	O4—C27—C22	113.9 (5)
C8—C9—H9A	108.9	C25—C28—C29	115.2 (8)
C8—C9—H9B	108.9	C25—C28—H28A	108.5
C10—C9—H9A	108.9	C25—C28—H28B	108.5
C10—C9—H9B	108.9	C29—C28—H28A	108.5
H9A—C9—H9B	107.7	C29—C28—H28B	108.5
C9—C10—C11	117 (1)	H28A—C28—H28B	107.5
C9—C10—H10A	108.0	C28—C29—C30	115 (1)
C9—C10—H10B	108.0	C28—C29—H29A	108.4
C11—C10—H10A	108.0	C28—C29—H29B	108.4
C11—C10—H10B	108.0	C30—C29—H29A	108.4
H10A—C10—H10B	107.3	C30—C29—H29B	108.5
C10—C11—H11A	109.5	H29A—C29—H29B	107.5
C10—C11—H11B	109.5	C29—C30—C31	113 (1)
C10—C11—H11C	109.5	C29—C30—H30A	108.9
H11A—C11—H11B	109.5	C29—C30—H30B	108.9
H11A—C11—H11C	109.5	C31—C30—H30A	108.9
H11B—C11—H11C	109.5	C31—C30—H30B	108.9
N2—C12—C13	121.8 (5)	H30A—C30—H30B	107.7
N2—C12—C17	114.4 (5)	C30—C31—H31A	109.5
C13—C12—C17	123.9 (6)	C30—C31—H31B	109.5
C12—C13—C14	119.2 (6)	C30—C31—H31C	109.5
C12—C13—H13	120.4	H31A—C31—H31B	109.5
C14—C13—H13	120.4	H31A—C31—H31C	109.5
C13—C14—C15	119.5 (6)	H31B—C31—H31C	109.5
C13—C14—H14	120.2
Fe1—O2—C7—O1	174.5 (5)	N1—Fe1—N3—C26	119.3 (6)
Fe1—O2—C7—C2	−4.8 (7)	N1—C2—C3—C4	−0.2 (9)
Fe1—O4—C27—O3	172.9 (4)	N1—C6—C5—C4	−4.0 (9)
Fe1—O4—C27—C22	−6.4 (6)	N1—C6—C5—C8	177.9 (6)
Fe1—O6—C17—O5	179.7 (5)	N2—Fe1—O2—C7	−48.6 (8)
Fe1—O6—C17—C12	−1.7 (7)	N2—Fe1—O4—C27	−99.9 (4)
Fe1—N1—C2—C3	179.6 (4)	N2—Fe1—O6—C17	0.5 (4)
Fe1—N1—C2—C7	0.2 (6)	N2—Fe1—N1—C2	164.7 (4)
Fe1—N1—C6—C5	−177.1 (4)	N2—Fe1—N1—C6	−17.0 (5)
Fe1—N2—C12—C13	177.2 (5)	N2—Fe1—N3—C22	83.0 (4)
Fe1—N2—C12—C17	−2.0 (6)	N2—Fe1—N3—C26	−101.0 (4)
Fe1—N2—C16—C15	−173.1 (4)	N2—C12—C13—C14	−4.1 (9)
Fe1—N3—C22—C23	176.5 (4)	N2—C16—C15—C14	−2.5 (9)
Fe1—N3—C22—C27	−2.1 (5)	N2—C16—C15—C18	171.5 (5)
Fe1—N3—C26—C25	−175.5 (4)	N3—Fe1—O2—C7	169.6 (4)
O1—C7—C2—N1	−176.6 (6)	N3—Fe1—O4—C27	4.2 (4)
O1—C7—C2—C3	4.0 (9)	N3—Fe1—O6—C17	−102.6 (4)
O2—Fe1—O4—C27	90.9 (4)	N3—Fe1—N1—C2	−54.3 (7)
O2—Fe1—O6—C17	167.2 (4)	N3—Fe1—N1—C6	123.9 (6)
O2—Fe1—N1—C2	−1.9 (3)	N3—Fe1—N2—C12	89.4 (4)
O2—Fe1—N1—C6	176.3 (5)	N3—Fe1—N2—C16	−94.9 (5)
O2—Fe1—N2—C12	−51.2 (8)	N3—C22—C23—C24	−0.7 (8)
O2—Fe1—N2—C16	124.5 (6)	N3—C26—C25—C24	−0.3 (9)
O2—Fe1—N3—C22	−107.6 (4)	N3—C26—C25—C28	179.5 (6)
O2—Fe1—N3—C26	68.3 (4)	C2—N1—C6—C5	1.0 (8)
O2—C7—C2—N1	2.8 (7)	C2—C3—C4—C5	−2.9 (10)
O2—C7—C2—C3	−176.7 (5)	C3—C2—N1—C6	1.2 (8)
O3—C27—C22—N3	−174.0 (5)	C3—C4—C5—C6	4.8 (9)
O3—C27—C22—C23	7.4 (8)	C3—C4—C5—C8	−177.2 (6)
O4—Fe1—O2—C7	91.8 (4)	C4—C3—C2—C7	179.2 (6)
O4—Fe1—O6—C17	−43.0 (7)	C4—C5—C8—C9	−76.7 (10)
O4—Fe1—N1—C2	−108.5 (4)	C5—C8—C9—C10	−179.3 (8)
O4—Fe1—N1—C6	69.7 (5)	C6—N1—C2—C7	−178.3 (5)
O4—Fe1—N2—C12	166.5 (4)	C6—C5—C8—C9	101.2 (8)
O4—Fe1—N2—C16	−17.7 (5)	C8—C9—C10—C11	−63 (1)
O4—Fe1—N3—C22	−0.8 (3)	C12—N2—C16—C15	2.3 (8)
O4—Fe1—N3—C26	175.2 (5)	C12—C13—C14—C15	3.8 (10)
O4—C27—C22—N3	5.3 (7)	C13—C12—N2—C16	1.1 (8)
O4—C27—C22—C23	−173.2 (5)	C13—C14—C15—C16	−0.7 (9)
O5—C17—C12—N2	−178.9 (6)	C13—C14—C15—C18	−174.5 (6)
O5—C17—C12—C13	2.0 (10)	C14—C13—C12—C17	175.0 (6)
O6—Fe1—O2—C7	−99.1 (4)	C14—C15—C18—C19	92.0 (7)
O6—Fe1—O4—C27	−57.5 (6)	C15—C18—C19—C20	−174.1 (7)
O6—Fe1—N1—C2	87.1 (4)	C16—N2—C12—C17	−178.1 (5)
O6—Fe1—N1—C6	−94.6 (5)	C16—C15—C18—C19	−81.8 (7)
O6—Fe1—N2—C12	0.9 (4)	C18—C19—C20—C21	−178.6 (7)
O6—Fe1—N2—C16	176.6 (5)	C22—N3—C26—C25	0.3 (8)
O6—Fe1—N3—C22	160.7 (3)	C22—C23—C24—C25	0.6 (9)
O6—Fe1—N3—C26	−23.3 (4)	C23—C22—N3—C26	0.2 (8)
O6—C17—C12—N2	2.4 (8)	C23—C24—C25—C26	−0.1 (9)
O6—C17—C12—C13	−176.7 (6)	C23—C24—C25—C28	−180.0 (6)
N1—Fe1—O2—C7	3.8 (4)	C24—C23—C22—C27	177.8 (5)
N1—Fe1—O4—C27	169.3 (4)	C24—C25—C28—C29	80.0 (10)
N1—Fe1—O6—C17	88.5 (4)	C25—C28—C29—C30	68 (1)
N1—Fe1—N2—C12	−102.2 (4)	C26—N3—C22—C27	−178.4 (5)
N1—Fe1—N2—C16	73.6 (5)	C26—C25—C28—C29	−99.8 (9)
N1—Fe1—N3—C22	−56.7 (7)	C28—C29—C30—C31	166 (1)

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