Aqua­(phthalocyaninato-κ⁴N)­magnesium(II) 3-chloro­pyridine disolvate

The structure of the title compound, [Mg(C₃₂H₁₆N₈)(H₂O)]·2C₅H₄ClN, comprises MgPcH₂O [Pc is phthalocyaninate(2−)] and 3-chloro­pyridine solvent mol­ecules inter­acting via O—H...N hydrogen bonds and π–π inter­actions. The central Mg atom is (4+1)-coordinated by four equatorial isoindole N atoms of the macrocycle and by the O atom of an axial water mol­ecule. The MgPcH₂O mol­ecule is not planar, the Mg atom being displaced by 0.496 (2) Å from the isoindole N₄ plane towards the water O atom. MgPcH₂O mol­ecules related by a twofold screw axis inter­act via O—H...N_azamethine hydrogen bonds, forming a polymeric chain along the b axis, while those related by inversion centres form π–π inter­acting dimers.

S1. Comment

Our interest in magnesium phthalocyanine (Pc) and its complexes exhibiting (4 + 1)-coordination of the central Mg atom (Kubiak et al., 1995; Janczak & Kubiak, 2001; Janczak & Idemori, 2002) arises from their similarities to chlorophyll (Clayton, 1966; Sauer et al., 1968; Balischmiter & Katz, 1969; Larkum & Kühl, 2005), as they possess a similar coordination environment of the central Mg atom, as well as from their solid-state optical properties (especially the `X-phase'). However, the origin and the nature of the near-IR broad absorption are not completely understood, though a few possible explanations are found in the literature. Endo et al. (1999) assigned the MgPc(H<sub>2</sub>O)<sub>2</sub> composition to the `X-phase' and suggested that the near-IR broad absorption band arises from exciton coupling effects. Janczak & Idemori (2003) studied the solid-state near-IR absorption spectra of MgPc and the triclinic modification of MgPc(H₂O), suggesting that the origin of this near-IR absorption arises from the specific molecular arrangement in the crystal structures. In both structures, a similar arrangement of the structural motif is present, i.e. face-to-face dimers of π–π stacked molecules (Janczak & Kubiak, 2001; Janczak & Idemori, 2003). Furthermore, the monoclinic modification of MgPc(H₂O) does not exhibit near-IR absorption, since the molecular arrangement is different from that in the active triclinic form (Mizuguchi, 2002). This hypothesis is supported by work reporting the solid-state spectra of titanyl phthalocyanine (TiOPc) and vanadyl phthalocyanine (VOPc), which analogously to MgPc(H₂O) appear in two crystallographic modifications, i.e. in monoclinic and triclinic forms (Ziolo et al., 1980; Yamada et al., 1996; Hiller et al., 1982; Oka et al., 1992). However, only the triclinic form is near-IR active (Saito et al., 1993, 1994; Naleva et al., 1993; Mizuguchi et al., 1995). Thus, the electronic spectra vary significantly as a result of molecular interactions and, especially, of the molecular arrangement in the crystals. The present structure analysis has been carried out in order to study the correlation between the crystal and electronic structures in the title compound, (I).

The asymmetric unit in (I) consists of an aqua(phthalocyaninato)magnesium(II) and two 3-chloropyridine (A and B) molecules (Fig. 1). The geometry of the MgPcH₂O unit is not planar and the central Mg atom exhibits (4 + 1) geometry, coordinated equatorially by four N-isoindole atoms of the Pc macrocycle and by the O atom of an axial water molecule (Table 1). This coordination environment of the central Mg atom is similar to that found in several chlorophyll derivatives (Kratky & Dunitz, 1975; Chow et al., 1975; Serlin et al., 1975). Owing to the interaction with the axially coordinated water O atom, the central Mg atom is significantly displaced [0.496 (2) Å] from the weighted least-squares plane defined by the four isoindole N atoms. The displacement of the Mg atom from the N₄ plane is comparable to that observed in other aqua–magnesium–phthalocyanine complexes solvated by pyridine (Fischer et al., 1971; Mizuguchi & Mochizuki, 2002), diethylamine (Kinzhybalo & Janczak, 2007a), n-propylamine (Kinzhybalo & Janczak, 2007b) or 2-methoxyethylamine (Kinzhybalo & Janczak, 2007c), as well as in the triclinic and monoclinic modifications of MgPcH₂O (Janczak & Idemori, 2003; Mizuguchi, 2002). In all cases, the Mg atom displacement from the N₄ plane lies between 0.442 (2) and 0.502 (2) Å.

The displacement of Mg from the N₄ plane in magnesium–phthalocyaninate complexes is significantly greater (by about 0.15 Å) than that in aqua–magnesium–porphyrinate complexes (Choon et al., 1986; McKee & Rodley, 1988; Yang & Jacobson, 1991; Timkovich or??? Timkovitch & Tulinsky, 1969; Velazquez et al., 1992; Barkigia et al. 1983) and in chlorophyll derivatives (Kratky & Dunitz, 1975; Chow et al., 1975; Serlin et al., 1975) owing to the greater flexibilty of the porphyrinate ring, as well as to the larger central hole in comparison with the Pc macroring. The saucer-shape geometry of MgPcH₂O in (I) results from the interaction of the positively charged central Mg atom of about +0.5 (Zerner et al. 1966) with the negatively charged O atom of the water molecule and is comparable to that in the gas phase obtained by molecular orbital calculations (Janczak & Idemori, 2003). However, the ab-initio calculated axial Mg—O bond (2.142 Å) is significantly longer than that in (I) [2.029 (2) Å].

The electron-rich N atom of one 3-chloropyridine (3-Clpyr) molecule (A) accepts the O donor atom of the water molecule and forms an O—H···N hydrogen bond (Fig. 1 and Table 2). Molecule A is almost parallel to the mean Pc plane [~6.1 (2)°]. The second 3-Clpyr molecule (B) is also almost parallel to the Pc plane, although it is not hydrogen bonded with the MgPcH₂O molecule; rign atom N51 is oriented towards H46/C46 of the 3-Clpyr molecule (A). The C···N distance between these halopyridines [the ring plane dihedral angle is 7.7 (2)°] is long [C46···N51 = 3.343 (3) Å] but important, as shown by the molecular orbital calculations (Frisch et al., 1998) on 3-Clpyr dimers with geometry similar to that of A and B in (I). The electrostatic potential calculated for the 3-Clpyr molecules has an opposite sign around the interacting N51···H46 atoms. The lone electron pair on atom N51 is oriented towards H46/C46 of the other 3-Clpyr molecule (A), and between the N51 and H46 atoms the (3,-1) critical point characterizing the interaction between N51 and H46 can be localized (Bader, 1990). Molecules A and B are essentially parallel to the Pc macroring, at 1.1 (2) and 3.8 (2)° to their closest Pc C₆ rings; however, owing to the saucer shape of the ring, the distances are slightly longer (by about 0.1 Å) but indicate significant π–π overlaps between the aromatic ring π clouds (the ring centroid distances are 3.4–3.6 Å). As a result of the π–π interactions, the C18–C23 and C26–C31 phenyl rings are less distorted from the Pc N₄ plane than the other half of the Pc macrocycle. The average deviations of the C atoms of these two C₆ aromatic rings are 0.269 and 0.143 Å, while the average deviations of the C atoms of the C2–C7 and C10–C15 rings are 0.569 and 0.324 Å, respectively.

MgPcH₂O–3-chloropyridine systems related by a twofold screw axes interact via O—H···N_azamethine hydrogen bonds, forming pseudo-one-dimensional chains along the b axis (Fig. 2). MgPcH₂O molecules related by an inversion interact via π–π interactions in a back-to-back fashion [the interplanar N₄ distance is 3.392 (3) Å]. The overlap of the Pc ligands in this manner in (I) is characteristic of five-coordinate (4 + 1) Mg–phthalocyaninate(2-) complexes (Fig. 3). Scheidt & Lee (1987) examined the overlap in neutral, structurally characterized, sterically unhindered metal–porphyrinate complexes and discovered that the distribution of the lateral shift of the ligands is trimodal rather than continuous. The values appear to cluster at ~1.5 Å for dimers with strong π–π overlap, at ~3.5 Å with intermediate π–π overlap and at ~6.5 Å with weak overlap. The Pc ligands in the dimers of (I) [with an N₄ interplanar distance of 3.392 (3) Å] represent an intermediate overlap between the ligand π-systems. However, owing to the saucer shape of the Pc ligands, the mean interplanar separation between the dimer 40-atom rings (~3.22 Å) is nearly midway between the sum of the C atom van der Waals radii of the π-ring system (~3.4 Å) and the distance at which the steric interactions between the π-aromatic ring system becomes predominantly repulsive (~3.08 Å; Pauling, 1960). Thus, a degree of π–π stabilization in (I) is evident, and the O—H···N hydrogen bonds play an important role in the molecular packing pattern. Besides these dimers, π–π interactions between the 3-chloropyridine molecules and half of the Pc macroring add to the energetically favourable molecular arrangement, and yield to greater planarity in half of the Pc ligand (as noted above).

In (I), chains of MgPcH₂O and 3-chloropyridine molecules related by inversion centres interact via the π–π clouds, forming a hole at the (1/2, 1/2, 1/2) site and symmetrically equivalent positions in which the 3-chloropyridine molecules are located (Fig. 3). Since the molecular arrangement of the MgPcH₂O and 3-Clpyr molecules is different from that of the triclinic modification of MgPcH₂O (Janczak & Idemori, 2003) and MgPcH₂O·MPA (MPA is 2-methoxyethylamine; Kinzhybalo & Janczak, 2007b), both being near-IR active, the present crystal does not show near-IR broad absorption bands. Instead, it exhibits characteristic absorption bands caused by the molecular distortion. In 3-chloropyridine solution, this compound has a UV–vis spectrum that is quite similiar to that of MgPcH₂O in pyridine solution (Janczak & Idemori, 2003). In the solid state, a slight broadening of the bands was observed, since upon crystallization the double degeneracy of the excited state is lifted because of the molecular distortion (approximately C_4v in solution and C₁ in the solid state).

Thermogravimetric analysis shows three characteristic steps, the first at ca 400 K, the second at ca 440 K and the third at ca 478 K, and these correspond exactly to the successive weight loss of one 3-Clpyr molecule (14.51%), the second 3-Clpyr molecule and the water molecule (3.25%). The third step, at 478 K, correlates well with the loss of water in the MgPcH₂O complex (Janczak & Idemori, 2003). Finally, above 478 K, the sample transforms into the β-modification of MgPc (Kubiak et al., 1995).

Related literature

For related literature, see: Bader (1990); Balischmiter & Katz (1969); Barkigia et al. (1983); Choon et al. (1986); Chow et al. (1975); Clayton (1966); Endo et al. (1999); Fischer et al. (1971); Frisch et al. (1998); Hiller et al. (1982); Janczak & Idemori (2002, 2003); Janczak & Kubiak (2001); Kinzhybalo & Janczak (2007a, 2007b, 2007c); Kratky & Dunitz (1975); Kubiak et al. (1995); Larkum & Kühl (2005); McKee & Rodley (1988); Mizuguchi (2002); Mizuguchi & Mochizuki (2002); Mizuguchi et al. (1995); Naleva et al. (1993); Oka et al. (1992); Pauling (1960); Saito et al. (1993, 1994); Sauer et al. (1968); Scheidt & Lee (1987); Serlin et al. (1975); Timkovitch & Tulinsky (1969); Velazquez et al. (1992); Yamada et al. (1996); Yang & Jacobson (1991); Zerner et al. (1966); Ziolo et al. (1980).

S2. Experimental

Violet crystals of (I) were obtained by recrystallization of MgPc crystals obtained as described elsewhere (Janczak & Kubiak, 2001) in 3-chloropyridine. MgPc (about 1 g) was added to 20 ml of 3-Clpyr. The suspension was degassed and sealed into a glass ampoule. The ampoule was heated at 433 K over a period of 15 h. Crystals of (I) were formed during the cooling process (at about 363–368 K). The presence of water in these crystals results from the high affinity of water to MgPc (Janczak & Idemori, 2003).

S3. Refinement

H atoms bonded to C atoms were positioned geometrically and treated as riding, with U_iso(H) values of 1.2U_eq(C). H atoms of the coordinated water molecules were located in difference Fourier syntheses and in the final refinement cycles were constrained to O—H distances of 0.82 Å, with U_iso(H) equal to 1.5U_eq(O).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELTXL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of (I), with the atom labelling; displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the hydrogen-bonded polymeric structure of (I); H atoms, except those of water molecules, have been omitted for clarity. [Symmetry code: (i) -x + 3/2, y + 1/2, -z + 1/2.]
	Fig. 3. The molecular packing of (I), with the π–π interaction between the MgPcH2O molecules; H atoms, except those of water molecules, have been omitted for clarity. [Symmetry code: (i) -x + 3/2, y + 1/2, -z + 1/2.]

Aqua(phthalocyaninato-κ⁴N)magnesium(II) 3-chloropyridine disolvate

Crystal data

[Mg(C32H16N8)(H2O)]·2C5H4ClN	F(000) = 1608
Mr = 781.94	Dx = 1.410 Mg m^−3 Dm = 1.41 Mg m^−3 Dm measured by floatation
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1452 reflections
a = 14.981 (3) Å	θ = 3.1–28.0°
b = 13.956 (2) Å	µ = 0.24 mm^−1
c = 18.309 (3) Å	T = 295 K
β = 105.80 (1)°	Paralellepiped, violet
V = 3683.3 (11) Å^3	0.38 × 0.27 × 0.24 mm
Z = 4

Data collection

Kuma KM-4 CCD area-detector diffractometer	8890 independent reflections
Radiation source: fine-focus sealed tube	5340 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 28.0°, θmin = 3.1°
ω scans	h = −19→19
Absorption correction: analytical [face-indexed (SHELXTL; Sheldrick, 1990)]	k = −18→18
Tmin = 0.929, Tmax = 0.947	l = −24→22
39524 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0319P)^2] where P = (Fo^2 + 2Fc^2)/3
8890 reflections	(Δ/σ)max = 0.002
511 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Mg1	0.62169 (6)	0.03543 (5)	0.18097 (4)	0.0547 (2)
O1	0.72046 (13)	0.12833 (10)	0.23786 (9)	0.0654 (5)
H1O	0.734	0.1076	0.2814	0.098*
H2O	0.7234	0.1864	0.2322	0.098*
N1	0.49933 (14)	0.08370 (12)	0.19572 (12)	0.0619 (6)
N2	0.44368 (14)	0.18068 (13)	0.08241 (12)	0.0564 (6)
N3	0.57503 (14)	0.08185 (13)	0.07250 (12)	0.0551 (6)
N4	0.68184 (15)	0.00287 (13)	0.01283 (11)	0.0579 (6)
N5	0.69979 (13)	−0.06165 (12)	0.14174 (11)	0.0517 (5)
N6	0.74722 (13)	−0.16814 (11)	0.24922 (11)	0.0484 (5)
N7	0.62365 (14)	−0.06268 (12)	0.26326 (11)	0.0535 (5)
N8	0.49858 (16)	0.00134 (12)	0.31276 (11)	0.0634 (6)
C1	0.46631 (19)	0.06281 (17)	0.25586 (15)	0.0614 (7)
C2	0.38220 (19)	0.11853 (17)	0.24924 (16)	0.0669 (7)
C3	0.3188 (2)	0.1181 (2)	0.29476 (16)	0.0752 (9)
H3	0.3258	0.0781	0.3366	0.102*
C4	0.2452 (2)	0.1827 (3)	0.2714 (2)	0.1126 (12)
H4	0.2061	0.1912	0.3027	0.135*
C5	0.2275 (2)	0.2331 (2)	0.2069 (2)	0.1094 (13)
H5	0.1733	0.2690	0.1916	0.143*
C6	0.2920 (2)	0.2318 (2)	0.16113 (18)	0.0851 (10)
H6	0.2842	0.2710	0.1188	0.101*
C7	0.36432 (18)	0.17098 (18)	0.18290 (15)	0.0629 (7)
C8	0.43741 (18)	0.14804 (17)	0.14921 (15)	0.0600 (7)
C9	0.5040 (2)	0.14912 (16)	0.04720 (15)	0.0608 (7)
C10	0.50284 (18)	0.17982 (16)	−0.03049 (15)	0.0650 (7)
C11	0.4497 (2)	0.24579 (17)	−0.08059 (18)	0.0691 (8)
H11	0.4035	0.2798	−0.0667	0.081*
C12	0.4639 (2)	0.26106 (19)	−0.14831 (18)	0.0796 (9)
H12	0.4291	0.3057	−0.1819	0.095*
C13	0.5349 (3)	0.2061 (2)	−0.16743 (15)	0.0675 (11)
H13	0.5445	0.2166	−0.2149	0.081*
C14	0.59074 (19)	0.13823 (17)	−0.12091 (17)	0.0606 (8)
H14	0.6367	0.1043	−0.1352	0.073*
C15	0.57188 (19)	0.12536 (16)	−0.05090 (15)	0.0584 (7)
C16	0.61587 (18)	0.06479 (16)	0.01351 (14)	0.0560 (7)
C17	0.71758 (17)	−0.05499 (15)	0.07196 (15)	0.0533 (6)
C18	0.78908 (18)	−0.12552 (16)	0.06830 (14)	0.0607 (7)
C19	0.8345 (2)	−0.14733 (19)	0.01586 (16)	0.0682 (9)
H19	0.8202	−0.1140	−0.0298	0.082*
C20	0.8990 (2)	−0.2152 (2)	0.02813 (17)	0.0890 (10)
H20	0.9283	−0.2304	−0.0091	0.107*
C21	0.9224 (2)	−0.2636 (2)	0.09782 (18)	0.0801 (11)
H21	0.9696	−0.3091	0.1070	0.091*
C22	0.87883 (18)	−0.24658 (17)	0.15230 (15)	0.0696 (8)
H22	0.8921	−0.2820	0.1970	0.084*
C23	0.81326 (17)	−0.17367 (15)	0.13814 (13)	0.0578 (7)
C24	0.75169 (16)	−0.13523 (15)	0.18163 (14)	0.0526 (6)
C25	0.68733 (17)	−0.13498 (16)	0.28590 (13)	0.0528 (6)
C26	0.68006 (17)	−0.17477 (15)	0.35770 (13)	0.0509 (6)
C27	0.72911 (18)	−0.24348 (16)	0.40789 (13)	0.0629 (7)
H27	0.7772	−0.2776	0.3969	0.075*
C28	0.70477 (19)	−0.26005 (19)	0.47490 (15)	0.0650 (8)
H28	0.7383	−0.3046	0.5093	0.078*
C29	0.6331 (2)	−0.2128 (2)	0.49156 (15)	0.0704 (9)
H29	0.6158	−0.2299	0.5349	0.085*
C30	0.58555 (18)	−0.1402 (2)	0.44588 (15)	0.0624 (8)
H30	0.5403	−0.1044	0.4595	0.072*
C31	0.60948 (19)	−0.12291 (16)	0.37647 (15)	0.0627 (7)
C32	0.57514 (19)	−0.05527 (16)	0.31673 (15)	0.0616 (7)
Cl1	0.76872 (10)	0.02373 (8)	0.57342 (7)	0.0907 (5)
N41	0.8139 (2)	0.0462 (2)	0.37421 (16)	0.0986 (9)
C42	0.7800 (3)	0.0583 (2)	0.4303 (2)	0.0873 (12)
H42	0.7328	0.1027	0.4273	0.129*
C43	0.8160 (3)	0.0017 (3)	0.49960 (17)	0.0945 (12)
C44	0.8833 (3)	−0.0613 (3)	0.5016 (2)	0.1132 (13)
H44	0.9101	−0.0962	0.5454	0.136*
C45	0.9118 (3)	−0.0732 (3)	0.4371 (3)	0.1110 (16)
H45	0.9532	−0.1220	0.4347	0.135*
C46	0.8822 (3)	−0.0180 (3)	0.3809 (2)	0.1078 (12)
H46	0.9099	−0.0223	0.3413	0.129*
Cl2	1.17661 (11)	−0.07811 (11)	0.13922 (9)	0.1194 (7)
N51	0.9870 (5)	0.0064 (6)	0.2424 (4)	0.124 (3)
C52	1.0608 (4)	−0.0476 (4)	0.2258 (4)	0.1172 (19)
H52	1.0918	−0.0955	0.2582	0.141*
C53	1.0833 (3)	−0.0257 (3)	0.1611 (3)	0.1147 (13)
C54	1.0233 (5)	0.0240 (5)	0.1054 (3)	0.130 (2)
H54	1.0287	0.0270	0.0560	0.166*
C55	0.9557 (6)	0.0684 (5)	0.1269 (7)	0.111 (5)
H55	0.9164	0.1092	0.0926	0.133*
C56	0.9425 (5)	0.0578 (5)	0.1911 (5)	0.116 (3)
H56	0.8940	0.0925	0.2008	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mg1	0.0646 (6)	0.0359 (4)	0.0656 (5)	0.0027 (4)	0.0213 (4)	0.0048 (4)
O1	0.0717 (13)	0.0436 (9)	0.0854 (13)	0.0022 (10)	0.0195 (12)	0.0040 (9)
N1	0.0607 (16)	0.0457 (11)	0.0758 (15)	0.0067 (11)	0.0141 (13)	0.0107 (11)
N2	0.0609 (15)	0.0409 (12)	0.0724 (15)	0.0102 (10)	0.0065 (13)	0.0054 (11)
N3	0.0637 (15)	0.0406 (12)	0.0688 (16)	0.0126 (11)	0.0119 (13)	0.0007 (11)
N4	0.0711 (16)	0.0396 (11)	0.0617 (14)	0.0069 (11)	0.0161 (12)	0.0113 (10)
N5	0.0531 (13)	0.0434 (12)	0.0599 (13)	0.0055 (10)	0.0177 (11)	0.0088 (10)
N6	0.0609 (14)	0.0293 (10)	0.0607 (13)	0.0055 (10)	0.0261 (11)	0.0003 (9)
N7	0.0516 (13)	0.0427 (11)	0.0717 (14)	0.0032 (10)	0.0262 (12)	0.0028 (10)
N8	0.0919 (18)	0.0343 (11)	0.0766 (15)	0.0043 (12)	0.0441 (13)	0.0022 (10)
C1	0.073 (2)	0.0472 (15)	0.0580 (17)	0.0006 (14)	0.0085 (16)	0.0015 (13)
C2	0.062 (2)	0.0528 (16)	0.087 (2)	0.0011 (15)	0.0101 (17)	0.0011 (15)
C3	0.079 (2)	0.081 (2)	0.083 (2)	0.0022 (19)	0.011 (2)	0.0106 (17)
C4	0.096 (3)	0.133 (3)	0.121 (3)	0.038 (2)	0.049 (2)	0.009 (3)
C5	0.092 (3)	0.115 (3)	0.138 (4)	0.049 (2)	0.043 (3)	0.010 (3)
C6	0.073 (2)	0.082 (2)	0.087 (2)	0.0352 (19)	0.002 (2)	0.0089 (18)
C7	0.0563 (18)	0.0637 (17)	0.0703 (19)	0.0093 (15)	0.0020 (16)	0.0024 (15)
C8	0.0637 (19)	0.0484 (15)	0.0669 (19)	0.0108 (14)	0.0103 (16)	0.0051 (14)
C9	0.0646 (19)	0.0324 (14)	0.0717 (19)	0.0154 (14)	0.0049 (16)	0.0039 (13)
C10	0.067 (2)	0.0539 (13)	0.063 (2)	0.0061 (14)	0.0015 (17)	0.0090 (14)
C11	0.065 (2)	0.0575 (16)	0.076 (2)	0.0075 (16)	0.0101 (19)	0.0088 (16)
C12	0.078 (3)	0.0707 (17)	0.085 (2)	−0.0097 (17)	0.014 (2)	0.0102 (16)
C13	0.066 (3)	0.059 (2)	0.0706 (19)	−0.011 (2)	0.013 (2)	0.0101 (19)
C14	0.061 (2)	0.0539 (15)	0.065 (2)	−0.0011 (15)	0.0111 (18)	0.0097 (15)
C15	0.060 (2)	0.0528 (13)	0.0607 (17)	0.0016 (14)	0.0100 (15)	0.0075 (13)
C16	0.0697 (19)	0.0403 (14)	0.0581 (17)	0.0129 (14)	0.0113 (16)	0.0010 (13)
C17	0.0616 (17)	0.0417 (13)	0.0611 (18)	0.0070 (12)	0.0158 (15)	0.0013 (13)
C18	0.063 (2)	0.0599 (14)	0.0603 (17)	0.0081 (14)	0.0182 (16)	0.0061 (13)
C19	0.082 (2)	0.0682 (19)	0.071 (2)	0.0114 (18)	0.0233 (19)	0.0096 (16)
C20	0.099 (3)	0.083 (2)	0.084 (2)	0.031 (2)	0.0235 (19)	0.0032 (18)
C21	0.091 (3)	0.073 (2)	0.082 (2)	0.027 (2)	0.022 (2)	0.0031 (18)
C22	0.082 (2)	0.0585 (16)	0.0845 (19)	0.0247 (15)	0.0225 (17)	0.0030 (14)
C23	0.0606 (19)	0.0474 (13)	0.0652 (17)	0.0086 (13)	0.0180 (15)	0.0009 (12)
C24	0.0589 (17)	0.0378 (12)	0.0625 (18)	0.0072 (12)	0.0205 (15)	0.0018 (12)
C25	0.0559 (17)	0.0425 (13)	0.0541 (17)	0.0103 (13)	0.0117 (14)	0.0011 (12)
C26	0.0535 (17)	0.0438 (13)	0.0547 (16)	0.0064 (13)	0.0140 (13)	0.0057 (12)
C27	0.081 (2)	0.0455 (14)	0.0585 (16)	0.0001 (14)	0.0131 (15)	0.0108 (13)
C28	0.075 (2)	0.063 (2)	0.0639 (19)	0.0104 (17)	0.0236 (17)	0.0148 (16)
C29	0.078 (3)	0.066 (2)	0.069 (2)	0.0080 (19)	0.0258 (18)	0.0181 (17)
C30	0.0653 (19)	0.068 (2)	0.0645 (19)	0.0058 (17)	0.0367 (17)	0.0093 (16)
C31	0.065 (2)	0.0631 (13)	0.0651 (19)	0.0063 (14)	0.0290 (17)	0.0080 (13)
C32	0.0635 (19)	0.0535 (14)	0.063 (2)	0.0018 (13)	0.0183 (16)	0.0018 (13)
Cl1	0.1053 (14)	0.0834 (10)	0.0888 (10)	−0.0118 (9)	0.0101 (9)	0.0086 (8)
N41	0.102 (3)	0.099 (2)	0.085 (2)	−0.0089 (19)	0.0079 (19)	0.0048 (17)
C42	0.104 (3)	0.060 (2)	0.086 (3)	−0.016 (2)	0.014 (3)	−0.003 (2)
C43	0.105 (4)	0.083 (2)	0.085 (2)	−0.011 (2)	0.011 (2)	0.010 (2)
C44	0.117 (3)	0.088 (3)	0.120 (3)	0.003 (2)	0.008 (3)	0.031 (2)
C45	0.113 (4)	0.092 (3)	0.113 (4)	−0.002 (3)	0.015 (4)	0.016 (3)
C46	0.098 (3)	0.080 (3)	0.132 (4)	−0.004 (2)	0.009 (3)	0.013 (2)
Cl2	0.1022 (15)	0.1222 (15)	0.1432 (15)	0.0098 (12)	0.0114 (12)	0.0119 (12)
N51	0.123 (7)	0.117 (8)	0.126 (6)	0.004 (5)	0.044 (5)	0.010 (5)
C52	0.103 (5)	0.115 (5)	0.118 (6)	0.001 (4)	0.016 (4)	0.017 (4)
C53	0.113 (4)	0.115 (3)	0.118 (3)	0.001 (3)	0.019 (3)	0.011 (3)
C54	0.143 (5)	0.113 (6)	0.121 (5)	0.018 (4)	0.019 (5)	0.049 (5)
C55	0.124 (8)	0.135 (6)	0.115 (16)	0.016 (5)	0.028 (10)	0.040 (8)
C56	0.113 (6)	0.128 (7)	0.123 (7)	0.011 (5)	0.024 (5)	0.035 (6)

Geometric parameters (Å, º)

Mg1—O1	2.029 (2)	C17—C18	1.470 (3)
Mg1—N1	2.039 (2)	C18—C19	1.354 (3)
Mg1—N3	2.024 (2)	C18—C23	1.402 (3)
Mg1—N5	2.044 (2)	C19—C20	1.328 (3)
Mg1—N7	2.030 (2)	C19—H19	0.9300
O1—H1O	0.8200	C20—C21	1.401 (3)
O1—H2O	0.8200	C20—H20	0.9300
N1—C1	1.356 (3)	C21—C22	1.354 (3)
N1—C8	1.401 (3)	C21—H21	0.9300
N2—C9	1.320 (3)	C22—C23	1.389 (3)
N2—C8	1.332 (3)	C22—H22	0.9300
N3—C16	1.399 (3)	C23—C24	1.474 (3)
N3—C9	1.400 (3)	C25—C26	1.458 (3)
N4—C16	1.315 (3)	C26—C27	1.391 (3)
N4—C17	1.340 (3)	C26—C31	1.399 (3)
N5—C24	1.372 (3)	C27—C28	1.391 (3)
N5—C17	1.377 (3)	C27—H27	0.9300
N6—C24	1.339 (3)	C28—C29	1.363 (3)
N6—C25	1.341 (3)	C28—H28	0.9300
N7—C32	1.373 (3)	C29—C30	1.381 (3)
N7—C25	1.373 (3)	C29—H29	0.9300
N8—C1	1.334 (3)	C30—C31	1.432 (3)
N8—C32	1.378 (3)	C30—H30	0.9300
C1—C2	1.457 (3)	C31—C32	1.430 (3)
C2—C7	1.380 (3)	Cl1—C43	1.716 (3)
C2—C3	1.424 (3)	N41—C42	1.276 (4)
C3—C4	1.399 (3)	N41—C46	1.339 (4)
C3—H3	0.9300	C42—C43	1.467 (4)
C4—C5	1.337 (3)	C42—H42	0.9300
C4—H4	0.9300	C43—C44	1.330 (4)
C5—C6	1.442 (3)	C44—C45	1.371 (5)
C5—H5	0.9300	C44—H44	0.9300
C6—C7	1.348 (3)	C45—C46	1.266 (4)
C6—H6	0.9300	C45—H45	0.9300
C7—C8	1.432 (3)	C46—H46	0.9300
C9—C10	1.481 (3)	Cl2—C53	1.719 (3)
C10—C11	1.388 (3)	N51—C56	1.225 (7)
C10—C15	1.413 (3)	N51—C52	1.438 (6)
C11—C12	1.331 (3)	C52—C53	1.351 (5)
C11—H11	0.9300	C52—H52	0.9300
C12—C13	1.430 (3)	C53—C54	1.354 (5)
C12—H12	0.9300	C54—C55	1.335 (6)
C13—C14	1.391 (3)	C54—H54	0.9300
C13—H13	0.9300	C55—C56	1.252 (8)
C14—C15	1.397 (3)	C55—H55	0.9300
C14—H14	0.9300	C56—H56	0.9300
C15—C16	1.455 (3)
O1—Mg1—N1	106.09 (8)	N5—C17—C18	108.9 (2)
O1—Mg1—N3	107.94 (7)	C19—C18—C23	118.9 (2)
O1—Mg1—N5	101.35 (8)	C19—C18—C17	134.1 (2)
O1—Mg1—N7	100.88 (8)	C23—C18—C17	106.9 (2)
N1—Mg1—N3	86.64 (9)	C20—C19—C18	121.6 (3)
N1—Mg1—N5	152.49 (8)	C20—C19—H19	119.2
N1—Mg1—N7	87.50 (9)	C18—C19—H19	119.2
N3—Mg1—N5	86.86 (8)	C19—C20—C21	119.2 (3)
N3—Mg1—N7	151.10 (8)	C19—C20—H20	120.4
N5—Mg1—N7	85.40 (8)	C21—C20—H20	120.4
Mg1—O1—H1O	103	C22—C21—C20	122.3 (3)
Mg1—O1—H2O	129	C22—C21—H21	118.8
H1O—O1—H2O	118	C20—C21—H21	118.8
C1—N1—C8	107.7 (2)	C21—C22—C23	116.7 (3)
C1—N1—Mg1	125.20 (17)	C21—C22—H22	121.6
C8—N1—Mg1	127.00 (18)	C23—C22—H22	121.6
C9—N2—C8	124.3 (2)	C22—C23—C18	121.0 (2)
C16—N3—C9	108.1 (2)	C22—C23—C24	132.9 (2)
C16—N3—Mg1	126.60 (17)	C18—C23—C24	105.9 (2)
C9—N3—Mg1	124.59 (18)	N6—C24—N5	125.8 (2)
C16—N4—C17	121.6 (2)	N6—C24—C23	124.8 (2)
C24—N5—C17	108.63 (19)	N5—C24—C23	109.4 (2)
C24—N5—Mg1	127.20 (16)	N6—C25—N7	127.4 (2)
C17—N5—Mg1	123.71 (15)	N6—C25—C26	123.0 (2)
C24—N6—C25	123.59 (19)	N7—C25—C26	109.6 (2)
C32—N7—C25	107.4 (2)	C27—C26—C31	119.5 (2)
C32—N7—Mg1	125.09 (16)	C27—C26—C25	134.6 (2)
C25—N7—Mg1	126.03 (16)	C31—C26—C25	105.7 (2)
C1—N8—C32	121.9 (2)	C28—C27—C26	118.6 (2)
N8—C1—N1	129.6 (2)	C28—C27—H27	120.7
N8—C1—C2	122.0 (3)	C26—C27—H27	120.7
N1—C1—C2	108.4 (2)	C29—C28—C27	121.9 (2)
C7—C2—C3	121.1 (3)	C29—C28—H28	119.1
C7—C2—C1	108.2 (3)	C27—C28—H28	119.1
C3—C2—C1	130.4 (3)	C28—C29—C30	121.8 (3)
C4—C3—C2	114.5 (3)	C28—C29—H29	119.1
C4—C3—H3	122.7	C30—C29—H29	119.1
C2—C3—H3	122.7	C29—C30—C31	116.7 (3)
C5—C4—C3	123.9 (3)	C29—C30—H30	121.7
C5—C4—H4	118.0	C31—C30—H30	121.7
C3—C4—H4	118.0	C26—C31—C32	107.0 (2)
C4—C5—C6	120.3 (3)	C26—C31—C30	121.3 (2)
C4—C5—H5	119.9	C32—C31—C30	131.7 (3)
C6—C5—H5	119.9	N7—C32—N8	126.9 (2)
C7—C6—C5	116.6 (3)	N7—C32—C31	110.2 (2)
C7—C6—H6	121.7	N8—C32—C31	122.7 (3)
C5—C6—H6	121.7	C42—N41—C46	118.5 (3)
C6—C7—C2	122.8 (3)	N41—C42—C43	119.4 (4)
C6—C7—C8	131.3 (3)	N41—C42—H42	120.3
C2—C7—C8	105.8 (2)	C43—C42—H42	120.3
N2—C8—N1	125.2 (2)	C44—C43—C42	118.5 (3)
N2—C8—C7	124.9 (2)	C44—C43—Cl1	124.7 (4)
N1—C8—C7	109.8 (2)	C42—C43—Cl1	116.8 (4)
N2—C9—N3	128.4 (2)	C43—C44—C45	117.9 (4)
N2—C9—C10	122.8 (2)	C43—C44—H44	121.1
N3—C9—C10	108.7 (3)	C45—C44—H44	121.1
C11—C10—C15	120.8 (3)	C46—C45—C44	120.3 (5)
C11—C10—C9	133.0 (3)	C46—C45—H45	119.9
C15—C10—C9	106.3 (2)	C44—C45—H45	119.9
C12—C11—C10	120.9 (3)	C45—C46—N41	124.9 (5)
C12—C11—H11	119.6	C45—C46—H46	117.6
C10—C11—H11	119.6	N41—C46—H46	117.6
C11—C12—C13	117.4 (3)	C56—N51—C52	115.7 (8)
C11—C12—H12	121.3	C53—C52—N51	117.2 (5)
C13—C12—H12	121.3	C53—C52—H52	121.4
C14—C13—C12	125.4 (3)	N51—C52—H52	121.4
C14—C13—H13	117.3	C52—C53—C54	120.3 (4)
C12—C13—H13	117.3	C52—C53—Cl2	121.4 (5)
C13—C14—C15	114.3 (3)	C54—C53—Cl2	117.2 (6)
C13—C14—H14	122.9	C55—C54—C53	114.6 (7)
C15—C14—H14	122.9	C55—C54—H54	122.7
C14—C15—C10	121.2 (2)	C53—C54—H54	122.7
C14—C15—C16	131.2 (3)	C56—C55—C54	123.3 (10)
C10—C15—C16	107.5 (2)	C56—C55—H55	118.3
N4—C16—N3	127.3 (2)	C54—C55—H55	118.3
N4—C16—C15	123.4 (2)	N51—C56—C55	126.6 (10)
N3—C16—C15	109.3 (2)	N51—C56—H56	116.7
N4—C17—N5	130.9 (2)	C55—C56—H56	116.7
N4—C17—C18	120.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N41	0.82	1.99	2.758 (3)	156
O1—H2O···N6^i	0.82	2.09	2.880 (2)	163
C46—H46···N51	0.93	2.43	3.344 (8)	167

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.