Why magnesium is five-coordinate in methanol(phthalocyaninato)magnesium(II)

The square-pyramidal Mg center in the title compound, [Mg(C₃₂H₁₆N₈)(CH₄O)], is five-coordinate due to the formation of back-to-back [pi]-[pi] dimers that saturate the vacant apical site of the metal coordination sphere. Each complex is a member of a back-to-back and a face-to-face dimer; the latter are tethered by two strong O-H...N hydrogen bonds. The dimers form columns that likely determine the solid-state packing. The phthalocyaninate ligands are essentially planar, with a slight `hat visor' conformation character.

S1. Comment

For several years we have been interested in the synthesis and structures of metallophthalocyanine complexes. As a broad class of compounds, the metallophthalocyanines exhibit a wide array of optical, electronic, magnetic and chemical/photochemical properties that can be profoundly affected by subtle modifications to their solid-state and/or solution structures (McKeown, 1998, and references therein; Schultz et al., 1990, and references therein; Leznoff & Lever, 1989–1996, and references therein). We have recently broadened our ongoing investigations involving solvothermal (solventothermal) reactions of transition metal starting materials with 1,2-dicyanobenzene, which result in modified metallophthalocyanine derivatives, to include main group metals, in hopes that we may compare and contrast their reactivity. As a part of these efforts, we carried out the reaction of 1,2-dicyanobenzene with magnesium acetate tetrahydrate and found that the title compound, (I), was produced.

Apart from the more subtle aspects of the structure of (I) discussed later in this paper, it is interesting from a chemical standpoint that the compound possesses a (flat) unsubstituted phthalocyaninate (Pc) ligand, in contrast to the saddle-shaped alkoxy-modified Pc moieties observed in complexes that form in similar reactions involving Ni^II that we have reported elsewhere, even as the reaction and crystallization conditions were essentially identical (Molek et al., 2001).

Methanol(phthalocyaninato)magnesium(II) (Fig. 1) is one of the five crystallographically characterized complexes in which the magnesium center is bound to a κ⁴N₄-type ligand with a delocalized π system and one or two alcohol ligands, and the first example of such a complex with a Pc ligand.

The only other structurally characterized complex with five-coordinate magnesium is 2-propanol(tetraphenylporphinato)magnesium, (II) (Byrn et al., 1993), which crystallizes as a 2-propanol clathrate. Unfortunately, the position of the hydroxy H atom of the ligated propanol is chemically unreasonable, as reported to the Cambridge Structural Database (CSD; Version 5.26, updated May 2005; Allen, 2002) and confirmed by the authors; hence, in the following discussion, we will ignore this error. The Mg—O and Mg—N bond lengths in (I) [2.0331 (14) and average 2.0336 (17) Å, respectively] are appreciably shorter than the corresponding distances in (II) [2.076 and average 2.087 (5) Å, respectively], but all values are in the typical range. In the three relevant octahedral Mg complexes with κ⁴N₄ ligands and two identical alcohols in the apical positions, viz. dimethanol(tetraphenylporphinato)magnesium(II), (III), dimethanol(tetraphenylporphinato)magnesium(II) acetone solvate, (IV) (both by McKee and Rodley, 1988), and bis(2-methoxyethanol-O)(phthalocyaninato)magnesium(II), (V) (Matsumoto et al., 2000), all Mg—O distances are substantially longer at 2.220, 2.187 and 2.245 Å, respectively. The Mg—N distances would be expected to be shorter since the Mg atom resides in the plane of the four ligating N atoms, but the shortening is not observed in the cases of (III) (2.069 Å) and (IV) (2.075 Å). However, in the case of the Pc ligand in (V), the two symmetry independent Mg—N distances average 2.002 (14) Å.

There are many examples of radical and non-radical five-coordinate Mg complexes with large porphinate-like κ⁴N₄ ligands, but in most cases the ligand in the apical position is water and we will not discuss compounds with aqua ligands here. The non-radical compounds include Mg(Pc)(Ph₃P═O), Mg(Pc)(Ph₃P═O)·CH₂Cl₂, Mg(Pc)(Ph₃P═O).pyridine, Mg(Pc)(Ph₃P=O).tetrahydrofuran (all four by Huckstadt et al., 2000), cis-[2,3,7,8-tetrakis(N,N-dimethylamino)- 12,13:17,18-dibenzoporphyrazinato-N,N',N'',N'''](dimethylsulfoxide-O)magnesium(II), and [2,3-bis(N,N-dimethylamino)norphthalocyaninate-N,N',N'',N''')(dimethylsulfoxide-O)magnesium(II) (both by Montalban et al., 2000). In all of these structures the metal center is essentially square pyramidal with Mg—O and Mg—N distances comparable to those in (I).

Several aspects of the solid-state geometry of (I) are noteworthy. One aspect is the absence of a second alcohol molecule in the sixth coordination position about the Mg center, the second is the mutual arrangement of molecules of (I) in the lattice, and the third is the conformation of the Pc ring.

The Mg center in (I) is square pyramidal with a very slightly distorted C_4v symmetry (Fig. 1). The Mg—N distances differ by less than 0.0037 Å, the Mg—O vector forms an 89.5 (2)° angle to the plane defined by atoms N1, N3, N5 and N7, and the Mg atom is displaced toward the O atom from this plane by 0.4369 (10) Å. Four equatorial coordination sites about the central metal are occupied by the Pc ligand, which shields 65.07 (2)% of the Mg coordination sphere (Solid-G; Guzei & Wendt, 2004). The MeOH ligand shields an additional 16.80 (2)% and thus there is room [18.14 (2)%] to accommodate an additional ligand (Fig. 2). Our density functional theory computations at the pbe1pbe/6–31+G* level of theory (GAUSSIAN03; Frisch et al., 2004) on a simplified Mg complex (VI) (Fig. 3) indicate that a reaction between (VI) and MeOH is favored by −16.78 kcal mol⁻¹, while coordinating the second methanol is favored by a considerably smaller −3.25 kcal mol⁻¹. Apparently, there are two ways of saturating the magnesium coordination sphere, viz. (1) introduction of another ligand with a solid angle less than 0.8π (or shielding percentage of ~20%), and (2) mutual back-to-back arrangement of molecules of (I) in the lattice in order to compensate for the small `sixth ligand' coordination energy by forming favorable van der Waals interactions between the π systems of the Pc ligands (see below). A review of relevant structures reported to the CSD reveals that in the magnesium complexes with a large κ⁴N₄ ligand the five-coordinate complexes outnumber six-coordinate systems at a ~2:1 ratio. This may be an indication that expansive van der Waals contacts between large planar ligands are more favorable than saturating the metal coordination sphere with a lone ligand.

The overlap of the Pc ligands in the back-to-back π–π dimers of (I) is a characteristic of this structure type (Fig. 4). Scheidt & Lee (1987) examined the overlap in all neutral structurally characterized sterically unhindered metal porphinate complexes and discovered that the distribution of the lateral shift of the ligands is trimodal rather than continuous. The values seemed to cluster at ~1.5 Å for dimers with strong overlaps, at ~3.5 Å with intermediate overlaps and at ~6.5 Å with weak overlaps. The Pc ligands in the π–π dimers of (I) are laterally offset by 1.612 (2) Å, which according to the above classification represents a strong overlap between the ligand π systems. The mean interplanar separation between the dimer 40-atom rings, 3.33 (4) Å, is approximately half way between the sum of the C-atom van der Waals radii (3.650 Å) and the distance at which the steric interaction becomes predominantly repulsive (3.078 Å). Thus, a degree of π–π stabilization in (I) is evident and plays a role in the molecular packing pattern.

While the formation of back-to-back dimers explains the five-coordinate nature of the Mg center, bonding in the face-to-face dimers deserves separate scrutiny. (−x, 1 − y, 1 − z)-Centrosymmetrically related molecules of (I) form strongly bonded face-to-face dimers in which molecules are held together by two identical hydrogen-bonding interactions between the hydroxyl group and an `outer' N atom of the Pc ring, viz. O1—H1···N6 with an O1···N6 separation of 2.698 (2) Å and an O1—H1···N6 angle of 177 (2)°. The 6.030 (2) Å offset between the participating molecules allows for energetically favorable molecular arrangement. Because of the significant lateral displacement, only half of the Pc ligand including atoms C17—C32 overlaps with the other Pc ligand, but the π systems are in very close proximity [3.32 (4) Å]. Thus, each molecule of (I) is a member of a strongly hydrogen-bonded cofacial dimer and a π–π back-to-back dimer that form columns in the lattice (Fig. 4). The mutual arrangement of the dimers is likely to govern the solid-state packing pattern rather than vice versa. It is also possible that there are weaker hydrogen-bonding interactions of the C—H···π type between dimer columns related by a crystallographic c-glide plane, but our examination shows that they must be very weak and it is not clear how much they affect the crystal structure of (I).

A useful way of describing the conformation of the Pc ligand is by looking at the signs of the net r.m.s. displacements of the four quadrants of the ligand (e.g. Ph rings) from the plane of the four ligating N atoms. To each quadrant either a `+' or a `-' is assigned. A dome or concave conformation is characterized by a `+ + + +' combination of the four signs (C<sub>4v</sub> symmetry), a `+ + - -' sequence yields a waving conformation (C_2h), a `+ - + -' arrangement is a saddle conformation (D<sub>2d</sub>), and a `+ + + -' series is a `hat visor' conformation (C<sub>s</sub>). Of course, the planar Pc ligand complies with the D<sub>4h</sub> symmetry and in chemical praxis numerous examples of deviations from the idealized geometries are expected. Huckstadt et al. (2000) studied the conformation of the Pc ring in several aforementioned Mg complexes and concluded that the ring has a `concave' (+ + + + in our classification) conformation when the ring overlap within back-to-back π–π dimers in monoclinic systems is weak, and a `waving' (+ + - -) conformation when the overlap is good in triclinic systems. The r.m.s. deviation of atoms from the 40-atom π system in (I) is 0.036 Å, and thus the ruffling of the system is slight. On the other hand, the analysis of atomic displacements from the plane defined by atoms N1, N3, N5 and N7 indicates that the ligand conformation in (I) is closer to the `hat visor' (+ + + -) symmetry (Fig. 5). The crystal system of (I) is monoclinic and the ligand overlap is strong, which makes us conclude that the crystal system is inconsequential for ligand conformation. Additionally, the `hat visor' geometry of the Pc moiety in (I) with good overlap contrasts with the findings of Huckstadt et al. (2000). Perhaps the scarcity of five-coordinate Mg complexes with Pc ligands does not currently allow for reliable generalizations in this area.

S2. Experimental

All reagents were obtained from commercial sources and used as received. Magnesium acetate tetrahydrate (41.5 mg, 0.194 mmol) and 1,2-dicyanobenzene (99.3 mg, 0.775 mmol) were combined with methanol (4 ml) in a PTFE-lined autoclave and heated at 343 K for one week. Thin purple needles of (I) were observed upon opening the autoclave.

S3. Refinement

All H atoms bound to C atoms were placed in idealized locations and refined as riding with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic C atoms, and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl groups. Atom H1 attached to atom O was refined with U_iso(H) = 1.5U_eq(O); the O—H1 distance was allowed to refine.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Figure 1. The molecular structure of (I), drawn with 50% probability ellipsoids, showing a near-perfect square-pyramidal geometry at magnesium. Figure 2. (a) The projection of (I) viewed from the side of the methanol ligand. The solid angles corresponding to each ligand are represented by the shadows cast by the ligands onto a sphere with a 12 Å radius from an imaginary light bulb placed at the Mg center. The light grey shadow is for the methanol ligand and dark shadows belong to the Pc moiety. (b) The projection of (I) viewed from the opposite side. The white space indicates room about the Mg atom available for an incoming ligand. These diagrams are combined into an animated feature in the on-line version of the journal. Figure 3. The magnesium complex (VI) used for our theoretical studies. Figure 4. The co-facial and back-to-back stacking of the centrosymmetrically related molecules results in the formation of columns in the crystal structure. All H atoms except the hydroxy H atoms participating in hydrogen-bonding interactions have been omitted for clarity. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) −x, 1 − y, −z; (iii) x, y, z − 1.] Figure 5. Perpendicular atomic displacements (in 0.01 Å units) in (I) from the least-squares plane defined by the four coordinating N atoms.

(I)

Crystal data

[Mg(C32H16N8)(CH4O)]	F(000) = 1176
Mr = 568.88	Dx = 1.493 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5952 reflections
a = 13.1896 (10) Å	θ = 1.8–26.4°
b = 24.3104 (18) Å	µ = 0.12 mm^−1
c = 8.0185 (6) Å	T = 100 K
β = 100.103 (2)°	Block, purple
V = 2531.2 (3) Å^3	0.46 × 0.27 × 0.20 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	5168 independent reflections
Radiation source: fine-focus sealed tube	3871 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
0.30° ω scans	θmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −16→16
Tmin = 0.948, Tmax = 0.977	k = −30→30
20390 measured reflections	l = −10→9

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0688P)^2 + 0.9057P] where P = (Fo^2 + 2Fc^2)/3
5168 reflections	(Δ/σ)max = 0.001
392 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.25 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	0.01263 (4)	0.42395 (2)	0.17324 (7)	0.01181 (16)
O1	0.00808 (10)	0.37909 (6)	0.38578 (17)	0.0178 (3)
H1	0.0052 (16)	0.3999 (9)	0.467 (3)	0.021*
N1	0.12493 (12)	0.38546 (6)	0.07293 (19)	0.0143 (3)
N2	0.02388 (12)	0.31752 (6)	−0.10717 (19)	0.0151 (3)
N3	−0.08887 (12)	0.38388 (6)	−0.00637 (19)	0.0145 (3)
N4	−0.24471 (12)	0.43209 (6)	0.03072 (19)	0.0149 (3)
N5	−0.09741 (12)	0.48191 (6)	0.18377 (19)	0.0140 (3)
N6	0.00312 (12)	0.55100 (6)	0.35670 (19)	0.0142 (3)
N7	0.11588 (12)	0.48373 (6)	0.26114 (19)	0.0143 (3)
N8	0.27234 (12)	0.43687 (6)	0.21665 (19)	0.0147 (3)
C1	0.22766 (14)	0.39533 (8)	0.1219 (2)	0.0147 (4)
C2	0.28603 (15)	0.35287 (8)	0.0514 (2)	0.0158 (4)
C3	0.39146 (15)	0.34428 (8)	0.0607 (2)	0.0173 (4)
H3	0.4407	0.3682	0.1241	0.021*
C4	0.42155 (15)	0.29966 (8)	−0.0257 (2)	0.0200 (4)
H4	0.4929	0.2927	−0.0209	0.024*
C5	0.34946 (16)	0.26449 (8)	−0.1202 (3)	0.0213 (4)
H5	0.3727	0.2340	−0.1774	0.026*
C6	0.24449 (16)	0.27332 (8)	−0.1317 (2)	0.0199 (4)
H6	0.1954	0.2498	−0.1971	0.024*
C7	0.21381 (14)	0.31792 (8)	−0.0438 (2)	0.0156 (4)
C8	0.11232 (14)	0.33995 (8)	−0.0296 (2)	0.0150 (4)
C9	−0.06861 (15)	0.33875 (8)	−0.0969 (2)	0.0151 (4)
C10	−0.16595 (15)	0.31526 (8)	−0.1838 (2)	0.0160 (4)
C11	−0.19071 (15)	0.27026 (8)	−0.2905 (2)	0.0191 (4)
H11	−0.1384	0.2480	−0.3236	0.023*
C12	−0.29409 (16)	0.25890 (8)	−0.3468 (3)	0.0223 (5)
H12	−0.3128	0.2280	−0.4180	0.027*
C13	−0.37175 (15)	0.29219 (8)	−0.3008 (3)	0.0216 (4)
H13	−0.4420	0.2833	−0.3407	0.026*
C14	−0.34733 (15)	0.33761 (8)	−0.1982 (2)	0.0179 (4)
H14	−0.3996	0.3605	−0.1683	0.021*
C15	−0.24385 (15)	0.34872 (8)	−0.1403 (2)	0.0155 (4)
C16	−0.19309 (14)	0.39184 (8)	−0.0306 (2)	0.0148 (4)
C17	−0.20031 (14)	0.47316 (8)	0.1270 (2)	0.0146 (4)
C18	−0.25977 (15)	0.51609 (8)	0.1907 (2)	0.0150 (4)
C19	−0.36562 (15)	0.52409 (8)	0.1716 (2)	0.0173 (4)
H19	−0.4127	0.5000	0.1044	0.021*
C20	−0.39955 (15)	0.56858 (8)	0.2545 (2)	0.0186 (4)
H20	−0.4714	0.5750	0.2444	0.022*
C21	−0.33024 (15)	0.60408 (8)	0.3524 (2)	0.0192 (4)
H21	−0.3558	0.6342	0.4081	0.023*
C22	−0.22441 (15)	0.59628 (8)	0.3703 (2)	0.0173 (4)
H22	−0.1776	0.6208	0.4363	0.021*
C23	−0.18919 (14)	0.55145 (8)	0.2884 (2)	0.0148 (4)
C24	−0.08638 (14)	0.52854 (7)	0.2797 (2)	0.0136 (4)
C25	0.09687 (14)	0.53015 (8)	0.3460 (2)	0.0139 (4)
C26	0.19466 (14)	0.55515 (8)	0.4270 (2)	0.0142 (4)
C27	0.22174 (15)	0.60054 (8)	0.5311 (2)	0.0169 (4)
H27	0.1704	0.6238	0.5628	0.020*
C28	0.32541 (15)	0.61099 (8)	0.5873 (2)	0.0193 (4)
H28	0.3450	0.6413	0.6606	0.023*
C29	0.40196 (15)	0.57780 (8)	0.5384 (2)	0.0190 (4)
H29	0.4725	0.5863	0.5772	0.023*
C30	0.37577 (15)	0.53276 (8)	0.4339 (2)	0.0164 (4)
H30	0.4273	0.5102	0.3998	0.020*
C31	0.27202 (14)	0.52153 (8)	0.3805 (2)	0.0148 (4)
C32	0.22076 (14)	0.47703 (8)	0.2781 (2)	0.0145 (4)
C33	0.01175 (16)	0.32099 (8)	0.4149 (3)	0.0234 (5)
H33A	0.0257	0.3021	0.3134	0.035*
H33B	−0.0545	0.3085	0.4406	0.035*
H33C	0.0666	0.3126	0.5107	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mg1	0.0087 (3)	0.0149 (3)	0.0121 (3)	0.0009 (2)	0.0027 (2)	−0.0034 (2)
O1	0.0218 (7)	0.0168 (7)	0.0156 (7)	0.0002 (6)	0.0059 (6)	−0.0024 (6)
N1	0.0152 (8)	0.0155 (8)	0.0130 (8)	0.0003 (6)	0.0046 (6)	−0.0009 (6)
N2	0.0172 (9)	0.0159 (8)	0.0132 (8)	0.0014 (6)	0.0053 (6)	0.0003 (6)
N3	0.0138 (8)	0.0169 (8)	0.0136 (8)	0.0015 (6)	0.0043 (6)	−0.0009 (6)
N4	0.0149 (8)	0.0185 (9)	0.0115 (8)	0.0018 (6)	0.0031 (6)	0.0005 (6)
N5	0.0147 (8)	0.0163 (8)	0.0113 (8)	0.0003 (6)	0.0033 (6)	−0.0002 (6)
N6	0.0146 (8)	0.0170 (8)	0.0115 (8)	0.0001 (6)	0.0040 (6)	0.0000 (6)
N7	0.0151 (8)	0.0161 (8)	0.0123 (8)	0.0014 (6)	0.0040 (6)	0.0008 (6)
N8	0.0150 (8)	0.0167 (8)	0.0133 (8)	0.0009 (6)	0.0052 (6)	0.0004 (6)
C1	0.0136 (9)	0.0175 (10)	0.0136 (9)	0.0009 (7)	0.0040 (7)	0.0029 (7)
C2	0.0191 (10)	0.0170 (10)	0.0125 (9)	0.0021 (8)	0.0064 (7)	0.0035 (7)
C3	0.0178 (10)	0.0218 (10)	0.0131 (9)	0.0016 (8)	0.0049 (7)	0.0048 (8)
C4	0.0165 (10)	0.0240 (11)	0.0213 (10)	0.0052 (8)	0.0082 (8)	0.0056 (8)
C5	0.0259 (11)	0.0201 (11)	0.0208 (11)	0.0052 (8)	0.0122 (8)	0.0000 (8)
C6	0.0237 (11)	0.0177 (10)	0.0197 (10)	−0.0008 (8)	0.0076 (8)	−0.0010 (8)
C7	0.0171 (10)	0.0165 (10)	0.0146 (9)	0.0012 (8)	0.0067 (7)	0.0037 (8)
C8	0.0182 (10)	0.0166 (9)	0.0116 (9)	0.0001 (8)	0.0063 (7)	0.0015 (7)
C9	0.0190 (10)	0.0151 (9)	0.0115 (9)	−0.0002 (8)	0.0038 (7)	0.0025 (7)
C10	0.0194 (10)	0.0167 (10)	0.0122 (9)	−0.0005 (8)	0.0035 (7)	0.0024 (7)
C11	0.0226 (11)	0.0183 (10)	0.0167 (10)	0.0022 (8)	0.0042 (8)	−0.0002 (8)
C12	0.0240 (11)	0.0198 (11)	0.0215 (11)	−0.0034 (8)	−0.0004 (8)	−0.0052 (8)
C13	0.0163 (10)	0.0252 (11)	0.0216 (10)	−0.0035 (8)	−0.0018 (8)	−0.0013 (9)
C14	0.0155 (10)	0.0210 (10)	0.0169 (10)	0.0013 (8)	0.0024 (8)	0.0016 (8)
C15	0.0192 (10)	0.0154 (10)	0.0115 (9)	0.0008 (8)	0.0019 (7)	0.0031 (7)
C16	0.0150 (10)	0.0190 (10)	0.0106 (9)	−0.0007 (8)	0.0023 (7)	0.0027 (7)
C17	0.0152 (10)	0.0185 (10)	0.0109 (9)	0.0021 (8)	0.0047 (7)	0.0031 (7)
C18	0.0176 (10)	0.0168 (10)	0.0112 (9)	0.0015 (8)	0.0044 (7)	0.0043 (7)
C19	0.0157 (10)	0.0194 (10)	0.0170 (10)	0.0022 (8)	0.0038 (8)	0.0038 (8)
C20	0.0149 (10)	0.0228 (11)	0.0195 (10)	0.0055 (8)	0.0067 (8)	0.0058 (8)
C21	0.0229 (11)	0.0193 (10)	0.0173 (10)	0.0074 (8)	0.0085 (8)	0.0034 (8)
C22	0.0206 (10)	0.0187 (10)	0.0131 (9)	0.0025 (8)	0.0041 (8)	0.0015 (8)
C23	0.0149 (10)	0.0194 (10)	0.0107 (9)	0.0038 (8)	0.0037 (7)	0.0048 (7)
C24	0.0162 (10)	0.0153 (9)	0.0102 (9)	0.0021 (7)	0.0043 (7)	0.0012 (7)
C25	0.0177 (10)	0.0149 (9)	0.0101 (9)	0.0005 (7)	0.0049 (7)	0.0020 (7)
C26	0.0159 (10)	0.0169 (9)	0.0103 (9)	−0.0001 (8)	0.0039 (7)	0.0031 (7)
C27	0.0204 (10)	0.0158 (10)	0.0158 (10)	0.0002 (8)	0.0068 (8)	0.0013 (8)
C28	0.0228 (11)	0.0200 (10)	0.0154 (10)	−0.0043 (8)	0.0040 (8)	−0.0021 (8)
C29	0.0148 (10)	0.0243 (11)	0.0178 (10)	−0.0041 (8)	0.0026 (8)	0.0011 (8)
C30	0.0145 (10)	0.0190 (10)	0.0164 (9)	0.0013 (8)	0.0049 (7)	0.0009 (8)
C31	0.0164 (10)	0.0171 (10)	0.0118 (9)	0.0006 (8)	0.0046 (7)	0.0035 (7)
C32	0.0146 (10)	0.0184 (10)	0.0110 (9)	0.0007 (7)	0.0039 (7)	0.0038 (7)
C33	0.0258 (12)	0.0178 (10)	0.0264 (11)	−0.0006 (9)	0.0040 (9)	−0.0007 (9)

Geometric parameters (Å, º)

Mg1—N7	2.0315 (17)	C10—C15	1.402 (3)
Mg1—O1	2.0331 (14)	C11—C12	1.387 (3)
Mg1—N1	2.0333 (16)	C11—H11	0.9500
Mg1—N3	2.0345 (17)	C12—C13	1.405 (3)
Mg1—N5	2.0352 (16)	C12—H12	0.9500
O1—C33	1.431 (2)	C13—C14	1.381 (3)
O1—H1	0.83 (2)	C13—H13	0.9500
N1—C1	1.364 (2)	C14—C15	1.389 (3)
N1—C8	1.371 (2)	C14—H14	0.9500
N2—C8	1.338 (2)	C15—C16	1.454 (3)
N2—C9	1.340 (2)	C17—C18	1.451 (3)
N3—C9	1.368 (2)	C18—C19	1.391 (3)
N3—C16	1.368 (2)	C18—C23	1.401 (3)
N4—C17	1.333 (2)	C19—C20	1.384 (3)
N4—C16	1.334 (2)	C19—H19	0.9500
N5—C24	1.363 (2)	C20—C21	1.395 (3)
N5—C17	1.370 (2)	C20—H20	0.9500
N6—C24	1.348 (2)	C21—C22	1.391 (3)
N6—C25	1.353 (2)	C21—H21	0.9500
N7—C25	1.363 (2)	C22—C23	1.393 (3)
N7—C32	1.376 (2)	C22—H22	0.9500
N8—C32	1.333 (2)	C23—C24	1.479 (2)
N8—C1	1.337 (2)	C25—C26	1.470 (3)
C1—C2	1.459 (3)	C26—C27	1.392 (3)
C2—C3	1.395 (3)	C26—C31	1.408 (3)
C2—C7	1.399 (3)	C27—C28	1.386 (3)
C3—C4	1.382 (3)	C27—H27	0.9500
C3—H3	0.9500	C28—C29	1.401 (3)
C4—C5	1.399 (3)	C28—H28	0.9500
C4—H4	0.9500	C29—C30	1.385 (3)
C5—C6	1.388 (3)	C29—H29	0.9500
C5—H5	0.9500	C30—C31	1.387 (3)
C6—C7	1.391 (3)	C30—H30	0.9500
C6—H6	0.9500	C31—C32	1.452 (3)
C7—C8	1.465 (3)	C33—H33A	0.9800
C9—C10	1.465 (3)	C33—H33B	0.9800
C10—C11	1.391 (3)	C33—H33C	0.9800
N7—Mg1—O1	102.09 (6)	C14—C13—H13	119.6
N7—Mg1—N1	88.62 (7)	C12—C13—H13	119.6
O1—Mg1—N1	102.44 (6)	C13—C14—C15	117.89 (18)
N7—Mg1—N3	154.96 (7)	C13—C14—H14	121.1
O1—Mg1—N3	102.94 (6)	C15—C14—H14	121.1
N1—Mg1—N3	86.23 (6)	C14—C15—C10	121.59 (18)
N7—Mg1—N5	85.98 (7)	C14—C15—C16	131.60 (18)
O1—Mg1—N5	102.15 (6)	C10—C15—C16	106.81 (16)
N1—Mg1—N5	155.41 (7)	N4—C16—N3	128.07 (17)
N3—Mg1—N5	88.59 (7)	N4—C16—C15	122.75 (17)
C33—O1—Mg1	131.39 (12)	N3—C16—C15	109.18 (16)
C33—O1—H1	118.4 (15)	N4—C17—N5	128.15 (17)
Mg1—O1—H1	110.2 (15)	N4—C17—C18	122.19 (17)
C1—N1—C8	108.93 (15)	N5—C17—C18	109.65 (16)
C1—N1—Mg1	124.11 (12)	C19—C18—C23	122.08 (17)
C8—N1—Mg1	126.04 (13)	C19—C18—C17	130.98 (18)
C8—N2—C9	122.89 (16)	C23—C18—C17	106.92 (16)
C9—N3—C16	108.86 (15)	C20—C19—C18	117.35 (18)
C9—N3—Mg1	126.46 (13)	C20—C19—H19	121.3
C16—N3—Mg1	123.56 (12)	C18—C19—H19	121.3
C17—N4—C16	124.18 (17)	C19—C20—C21	121.24 (18)
C24—N5—C17	108.55 (15)	C19—C20—H20	119.4
C24—N5—Mg1	126.35 (13)	C21—C20—H20	119.4
C17—N5—Mg1	123.41 (12)	C22—C21—C20	121.35 (18)
C24—N6—C25	123.77 (16)	C22—C21—H21	119.3
C25—N7—C32	108.59 (15)	C20—C21—H21	119.3
C25—N7—Mg1	126.47 (13)	C21—C22—C23	118.01 (18)
C32—N7—Mg1	123.42 (12)	C21—C22—H22	121.0
C32—N8—C1	124.10 (16)	C23—C22—H22	121.0
N8—C1—N1	127.81 (17)	C22—C23—C18	119.97 (17)
N8—C1—C2	122.97 (17)	C22—C23—C24	134.51 (18)
N1—C1—C2	109.20 (16)	C18—C23—C24	105.50 (16)
C3—C2—C7	121.00 (17)	N6—C24—N5	126.40 (17)
C3—C2—C1	132.36 (18)	N6—C24—C23	124.22 (17)
C7—C2—C1	106.61 (16)	N5—C24—C23	109.38 (16)
C4—C3—C2	117.51 (18)	N6—C25—N7	126.30 (17)
C4—C3—H3	121.2	N6—C25—C26	123.90 (17)
C2—C3—H3	121.2	N7—C25—C26	109.80 (16)
C3—C4—C5	121.57 (18)	C27—C26—C31	119.83 (18)
C3—C4—H4	119.2	C27—C26—C25	134.90 (18)
C5—C4—H4	119.2	C31—C26—C25	105.27 (16)
C6—C5—C4	121.11 (18)	C28—C27—C26	118.37 (18)
C6—C5—H5	119.4	C28—C27—H27	120.8
C4—C5—H5	119.4	C26—C27—H27	120.8
C5—C6—C7	117.54 (18)	C27—C28—C29	121.43 (18)
C5—C6—H6	121.2	C27—C28—H28	119.3
C7—C6—H6	121.2	C29—C28—H28	119.3
C6—C7—C2	121.26 (18)	C30—C29—C28	120.60 (18)
C6—C7—C8	132.48 (18)	C30—C29—H29	119.7
C2—C7—C8	106.23 (16)	C28—C29—H29	119.7
N2—C8—N1	127.73 (17)	C29—C30—C31	118.05 (18)
N2—C8—C7	123.28 (17)	C29—C30—H30	121.0
N1—C8—C7	108.99 (16)	C31—C30—H30	121.0
N2—C9—N3	127.32 (17)	C30—C31—C26	121.69 (17)
N2—C9—C10	123.49 (17)	C30—C31—C32	131.13 (17)
N3—C9—C10	109.19 (16)	C26—C31—C32	107.18 (16)
C11—C10—C15	120.40 (18)	N8—C32—N7	128.32 (17)
C11—C10—C9	133.66 (18)	N8—C32—C31	122.53 (17)
C15—C10—C9	105.94 (16)	N7—C32—C31	109.15 (16)
C12—C11—C10	117.91 (19)	O1—C33—H33A	109.5
C12—C11—H11	121.0	O1—C33—H33B	109.5
C10—C11—H11	121.0	H33A—C33—H33B	109.5
C11—C12—C13	121.35 (18)	O1—C33—H33C	109.5
C11—C12—H12	119.3	H33A—C33—H33C	109.5
C13—C12—H12	119.3	H33B—C33—H33C	109.5
C14—C13—C12	120.84 (19)
N7—Mg1—O1—C33	−133.99 (16)	C11—C12—C13—C14	0.3 (3)
N1—Mg1—O1—C33	−42.72 (17)	C12—C13—C14—C15	−1.0 (3)
N3—Mg1—O1—C33	46.22 (17)	C13—C14—C15—C10	0.1 (3)
N5—Mg1—O1—C33	137.57 (16)	C13—C14—C15—C16	−178.95 (19)
N7—Mg1—N1—C1	18.76 (15)	C11—C10—C15—C14	1.4 (3)
O1—Mg1—N1—C1	−83.33 (15)	C9—C10—C15—C14	−178.60 (16)
N3—Mg1—N1—C1	174.24 (15)	C11—C10—C15—C16	−179.32 (17)
N5—Mg1—N1—C1	96.0 (2)	C9—C10—C15—C16	0.68 (19)
N7—Mg1—N1—C8	−173.40 (15)	C17—N4—C16—N3	1.3 (3)
O1—Mg1—N1—C8	84.52 (15)	C17—N4—C16—C15	−177.74 (17)
N3—Mg1—N1—C8	−17.92 (15)	C9—N3—C16—N4	−177.87 (18)
N5—Mg1—N1—C8	−96.2 (2)	Mg1—N3—C16—N4	13.5 (3)
N7—Mg1—N3—C9	96.4 (2)	C9—N3—C16—C15	1.3 (2)
O1—Mg1—N3—C9	−84.05 (15)	Mg1—N3—C16—C15	−167.31 (12)
N1—Mg1—N3—C9	17.86 (15)	C14—C15—C16—N4	−2.8 (3)
N5—Mg1—N3—C9	173.81 (15)	C10—C15—C16—N4	177.99 (17)
N7—Mg1—N3—C16	−97.0 (2)	C14—C15—C16—N3	177.93 (19)
O1—Mg1—N3—C16	82.53 (15)	C10—C15—C16—N3	−1.2 (2)
N1—Mg1—N3—C16	−175.56 (15)	C16—N4—C17—N5	−1.4 (3)
N5—Mg1—N3—C16	−19.61 (15)	C16—N4—C17—C18	179.95 (17)
N7—Mg1—N5—C24	−21.46 (15)	C24—N5—C17—N4	−179.41 (18)
O1—Mg1—N5—C24	80.06 (15)	Mg1—N5—C17—N4	−13.4 (3)
N1—Mg1—N5—C24	−99.2 (2)	C24—N5—C17—C18	−0.6 (2)
N3—Mg1—N5—C24	−177.00 (15)	Mg1—N5—C17—C18	165.40 (12)
N7—Mg1—N5—C17	175.07 (14)	N4—C17—C18—C19	0.8 (3)
O1—Mg1—N5—C17	−83.41 (14)	N5—C17—C18—C19	−178.12 (18)
N1—Mg1—N5—C17	97.3 (2)	N4—C17—C18—C23	178.97 (16)
N3—Mg1—N5—C17	19.53 (14)	N5—C17—C18—C23	0.1 (2)
O1—Mg1—N7—C25	−80.20 (15)	C23—C18—C19—C20	−0.4 (3)
N1—Mg1—N7—C25	177.37 (15)	C17—C18—C19—C20	177.55 (18)
N3—Mg1—N7—C25	99.3 (2)	C18—C19—C20—C21	0.3 (3)
N5—Mg1—N7—C25	21.38 (15)	C19—C20—C21—C22	0.2 (3)
O1—Mg1—N7—C32	84.06 (14)	C20—C21—C22—C23	−0.6 (3)
N1—Mg1—N7—C32	−18.37 (14)	C21—C22—C23—C18	0.5 (3)
N3—Mg1—N7—C32	−96.4 (2)	C21—C22—C23—C24	−177.89 (19)
N5—Mg1—N7—C32	−174.36 (14)	C19—C18—C23—C22	0.0 (3)
C32—N8—C1—N1	−1.0 (3)	C17—C18—C23—C22	−178.37 (16)
C32—N8—C1—C2	177.85 (17)	C19—C18—C23—C24	178.83 (16)
C8—N1—C1—N8	177.28 (18)	C17—C18—C23—C24	0.42 (19)
Mg1—N1—C1—N8	−13.1 (3)	C25—N6—C24—N5	1.3 (3)
C8—N1—C1—C2	−1.7 (2)	C25—N6—C24—C23	−179.01 (16)
Mg1—N1—C1—C2	167.91 (12)	C17—N5—C24—N6	−179.42 (17)
N8—C1—C2—C3	−0.1 (3)	Mg1—N5—C24—N6	15.1 (3)
N1—C1—C2—C3	179.00 (19)	C17—N5—C24—C23	0.9 (2)
N8—C1—C2—C7	−178.07 (17)	Mg1—N5—C24—C23	−164.61 (12)
N1—C1—C2—C7	1.0 (2)	C22—C23—C24—N6	−2.0 (3)
C7—C2—C3—C4	−0.8 (3)	C18—C23—C24—N6	179.48 (17)
C1—C2—C3—C4	−178.59 (19)	C22—C23—C24—N5	177.72 (19)
C2—C3—C4—C5	0.4 (3)	C18—C23—C24—N5	−0.8 (2)
C3—C4—C5—C6	0.5 (3)	C24—N6—C25—N7	−1.5 (3)
C4—C5—C6—C7	−0.9 (3)	C24—N6—C25—C26	178.75 (16)
C5—C6—C7—C2	0.6 (3)	C32—N7—C25—N6	178.93 (17)
C5—C6—C7—C8	178.63 (19)	Mg1—N7—C25—N6	−14.9 (3)
C3—C2—C7—C6	0.3 (3)	C32—N7—C25—C26	−1.3 (2)
C1—C2—C7—C6	178.61 (17)	Mg1—N7—C25—C26	164.92 (12)
C3—C2—C7—C8	−178.19 (16)	N6—C25—C26—C27	2.2 (3)
C1—C2—C7—C8	0.09 (19)	N7—C25—C26—C27	−177.6 (2)
C9—N2—C8—N1	1.7 (3)	N6—C25—C26—C31	−178.50 (16)
C9—N2—C8—C7	−178.28 (16)	N7—C25—C26—C31	1.7 (2)
C1—N1—C8—N2	−178.20 (17)	C31—C26—C27—C28	−0.5 (3)
Mg1—N1—C8—N2	12.4 (3)	C25—C26—C27—C28	178.65 (19)
C1—N1—C8—C7	1.8 (2)	C26—C27—C28—C29	1.5 (3)
Mg1—N1—C8—C7	−167.60 (12)	C27—C28—C29—C30	−1.1 (3)
C6—C7—C8—N2	0.6 (3)	C28—C29—C30—C31	−0.3 (3)
C2—C7—C8—N2	178.85 (17)	C29—C30—C31—C26	1.3 (3)
C6—C7—C8—N1	−179.42 (19)	C29—C30—C31—C32	−177.27 (18)
C2—C7—C8—N1	−1.1 (2)	C27—C26—C31—C30	−0.9 (3)
C8—N2—C9—N3	−1.9 (3)	C25—C26—C31—C30	179.73 (16)
C8—N2—C9—C10	178.77 (17)	C27—C26—C31—C32	178.00 (16)
C16—N3—C9—N2	179.71 (17)	C25—C26—C31—C32	−1.41 (19)
Mg1—N3—C9—N2	−12.1 (3)	C1—N8—C32—N7	1.2 (3)
C16—N3—C9—C10	−0.9 (2)	C1—N8—C32—C31	−179.95 (17)
Mg1—N3—C9—C10	167.33 (12)	C25—N7—C32—N8	179.28 (18)
N2—C9—C10—C11	−0.5 (3)	Mg1—N7—C32—N8	12.6 (3)
N3—C9—C10—C11	−179.9 (2)	C25—N7—C32—C31	0.35 (19)
N2—C9—C10—C15	179.52 (17)	Mg1—N7—C32—C31	−166.34 (12)
N3—C9—C10—C15	0.1 (2)	C30—C31—C32—N8	0.4 (3)
C15—C10—C11—C12	−2.0 (3)	C26—C31—C32—N8	−178.28 (16)
C9—C10—C11—C12	178.00 (19)	C30—C31—C32—N7	179.44 (18)
C10—C11—C12—C13	1.2 (3)	C26—C31—C32—N7	0.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N6^i	0.83 (2)	1.87 (2)	2.698 (2)	177 (2)

Symmetry code: (i) −x, −y+1, −z+1.