Aqua­(phthalocyaninato)magnesium n-propyl­amine disolvate

The crystals of the title compound, [Mg(C₃₂H₁₆N₈)(H₂O)]·2C₃H₉N, are built up from MgPc(H₂O) [Pc is phthalo­cyaninate(2−)] and n-propyl­amine mol­ecules that inter­act via O—H...N hydrogen bonds. The MgPc(H₂O) mol­ecule is non-planar. The central Mg atom is coordinated by the four equatorial isoindole N atoms of the Pc ring system and by the O atom of an axial water mol­ecule. The Mg atom is displaced by 0.509 (1) Å from the N₄ plane towards the water O atom. MgPc(H₂O)·2(n-propyl­amine) mol­ecules related by the inversion centre are linked by N—H...O hydrogen bonds to form a dimeric aggregate.

S1. Comment

Our interest in magnesium phthalocyanine and its complexes exhibiting (4 + 1)-coordination (Kubiak et al., 1995; Janczak & Kubiak, 2001; Janczak & Idemori, 2002) is due to their similarities to chlorophyll (Clayton, 1966), since they possess a coordination environment of the central Mg atom analogous to that in chlorophyll, as well as due to their optical properties in the solid state, especially the `X-phase'. However, the origin and the nature of the near-IR broad absorption are not completely clear, though several possible explanations can be found in the literature. Endo et al. (1999) suggested that the near-IR broad absorption band arises from the exciton coupling effects and assigned the composition MgPc(H<sub>2</sub>O)<sub>2</sub> [Pc is phthalocyaninate(2-)] to the `X-phase'.

Janczak & Idemori (2003) studied the solid-state near-IR absorption spectra of MgPc and the triclinic modification of MgPcH₂O, and suggested that this near-IR absorption arises from the specific molecular arrangement in the crystals. In both near-IR active crystals a similar arrangement of the structural motif can be found, i.e. face-to-face dimers of π–π stacked molecules (Janczak & Kubiak, 2001; Janczak & Idemori, 2003). Furthermore, the monoclinic modification of MgPcH₂O does not show the near-IR absorption, since the molecular arrangement is quite different from that in the active triclinic form of MgPcH₂O (Mizuguchi, 2002). Thus, the electronic spectra vary significantly as a result of the molecular interactions and, especially, because of the molecular arrangement in the crystals. Therefore, 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 of (I) consists of aqua(phthalocyaninato)magnesium and two n-propylamine molecules (Fig. 1) linked via O—H···N hydrogen bonds. The MgPcH₂O unit is not planar. The central Mg atom exhibits (4 + 1)-coordination by four equatorial isoindole N atoms of the phthalocyaninate(2-) ring and by an axial water molecule. This coordination of Mg 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 O atom of the water molecule, the central Mg atom is significantly displaced [0.509 (1) 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) or diethylamine (Kinzhybalo & Janczak, 2007a), as well as in the triclinic and monoclinic modifications of MgPcH₂O (Janczak & Idemori, 2003; Mizuguchi, 2002).

In all cases, the displacement of the Mg atom from the N₄ plane ranges from 0.442 (2) to 0.496 (2) Å. The displacement of Mg from the N₄ plane is significantly smaller (by about 0.15 Å) in the 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 system and to the larger central hole in relation to the phthalocyaninate(2-) macroring. The geometry of the MgPcH₂O molecule in (I) is comparable to that in the gas phase obtained from molecular orbital calculations (Janczak & Idemori, 2003). However, the ab-initio calculated axial Mg—O bond is significantly longer (2.142 Å) than that found in this crystal [1.9712 (15) Å]. The shortening of this bond is probably due to the interaction with the two n-propylamine molecules and to intermolecular interactions present in the crystal.

The electron-rich N atoms of the n-propylamine molecules each accept an O—H···N hydrogen bond from the water molecule (Fig. 1 and Table 2). Two MgPcH₂O.2(n-propylamine) units related by inversion interact via two additional N—H···O hydrogen bonds, forming a dimeric structure. In the dimer, one of the two n-propylamine molecules acts as a bridge (as a donor and as an acceptor) between two MgPcH₂O molecules, while the other n-propylamine molecule is involved as an acceptor in a single hydrogen bond (see Fig. 2). However, the orientation of the former n-propylamine molecule in relation to the Pc ring brings one of the H atoms of the amine group close to the C2–C7(1 - x, -y, -z) ring. This orientation results in an N—H···π interaction with the phenyl ring (Table 2), but this interaction is rather weak and therefore plays an insignificant role in the molecular arrangement.

In the crystal structure of (I), the dimeric aggregates, [MgPcH₂O.2(n-propylamine)]₂, are stacked along the [110] direction in a herringbone fashion, forming layers that are parallel to the (001) crystallographic plane. The dimeric aggregates are arranged in the stack in a back-to-back fashion, with a distance of 3.386 (3) Å between the phthalocyaninato(2-) macrocycles (Fig. 3). This value indicates a strong π–π interaction between the π-clouds of the Pc(2-) ring, since this value is comparable to the typical distance of 3.4 Å between aromatic ring systems involved in such interactions (Pauling, 1960). Since the molecular arrangement of MgPcH₂O.2(n-propylamine) is different from that of the triclinic modification of MgPcH₂O (Janczak & Idemori, 2003) and MgPcH₂O·MPA, where MPA = 2-methoxyethylamine (Kinzhybalo & Janczak, 2007b), which are both near-IR active, the present crystal does not show a near-IR broad absorption band. Instead, it exhibits charactristic absorption bands caused by the molecular distortion. In n-propylamine solution this compound has a UV–Vis spectrum quite similar to that of MgPcH₂O in 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 as a result of the molecular distortion (approximately C_4v in solution and C₁ in the solid state).

The thermogravimetric analysis shows two characteristic steps, the first at about 368 K and the second at about 478 K. These steps correspond exactly to the weight loss of both n-propylamine molecules (17.57%) and the water molecule (2.67%). The second step at 478 K correlate well with the loss of water in the MgPcH₂O complex (Janczak & Idemori, 2003). Finally, above 278 K, the sample transforms into the β-modification of MgPc (Kubiak et al., 1995).

Related literature

For related literature, see: Barkigia et al. (1983); Choon et al. (1986); Chow et al. (1975); Clayton (1966); Endo et al. (1999); Fischer et al. (1971); Janczak & Idemori (2002, 2003); Janczak & Kubiak (2001); Kinzhybalo & Janczak (2007a, 2007b); Kratky & Dunitz (1975); Kubiak et al. (1995); McKee & Rodley (1988); Mizuguchi (2002); Mizuguchi & Mochizuki (2002); Pauling (1960); Serlin et al. (1975); Timkovitch & Tulinsky (1969); Velazquez et al. (1992); Yang & Jacobson (1991).

S2. Experimental

Violet crystals of the title compound were obtained by recrystallization of MgPc crystals obtained as described elsewhere (Janczak & Kubiak, 2001) from n-propylamine. MgPc (about 1 g) was added to n-propylamine (20 ml). The suspension was degassed and sealed into a glass ampoule. The ampoule was heated at 423 K for 10–12 h. During the cooling process, the title crystals were formed (from a hot solution, at about 353–363 K). The presence of water in the crystals is governed by the high affinity of MgPc for water (Janczak & Idemori, 2003).

S3. Refinement

C-bound H atoms were placed in their geometric positions with C—H distances of 0.93–0.97 Å and treated as riding, with U_iso(H) values of 1.2U_eq(C) (for aromatic) and 1.5U_eq(C) (for aliphatic H atoms) [please check U_iso(H) treatment for non-methyl propylamine atoms]. The H atoms of the coordinated water molecule and amine groups were located in difference Fourier syntheses, but in the final refinement they were constrained, with O—H distances of 0.80 Å and N—H of 0.86–0.90 Å, and with U_iso(H) values of 1.2U_eq(O) and 1.5U_eq(N). Refinement of the occupancy factors for the two independent propylamine units gave values of 0.998 (4) and 0.996 (4); thereafter these occupancies were fixed at unity.

Computing details

Data collection: KM-4 CCD Software (Kuma, 2004); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of (I), with the atom-labelling scheme. Displacment ellipsoids are drawn at the 50% probability level.
	Fig. 2. The hydrogen-bonded dimeric structure of (I). All H atoms attached to C atoms have been omitted for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z.]
	Fig. 3. The molecular packing of (I) in the unit cell showing the back-to-back π–π interaction between the dimeric [MgPcH2O.2(n-propylamine)]2 aggregates. H atoms attached to C atoms have been omitted for clarity.

Aqua(phthalocyaninato)magnesium n-propylamine disolvate

Crystal data

[Mg(C32H16N8)(H2O)]·2C3H9N	F(000) = 2832
Mr = 673.08	Dx = 1.281 Mg m^−3 Dm = 1.28 Mg m^−3 Dm measured by floatation
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2565 reflections
a = 23.227 (5) Å	θ = 3.0–28.0°
b = 14.526 (3) Å	µ = 0.10 mm^−1
c = 20.765 (4) Å	T = 295 K
β = 94.99 (2)°	Paralellepiped, violet
V = 6979 (2) Å^3	0.50 × 0.24 × 0.14 mm
Z = 8

Data collection

Kuma KM-4 with CCD area-detector diffractometer	8356 independent reflections
Radiation source: fine-focus sealed tube	4307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 28.0°, θmin = 3.0°
ω scans	h = −30→30
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1991)	k = −19→18
Tmin = 0.949, Tmax = 0.984	l = −26→27
38071 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0342P)^2] where P = (Fo^2 + 2Fc^2)/3
8356 reflections	(Δ/σ)max = 0.002
457 parameters	Δρmax = 0.32 e Å^−3
11 restraints	Δρmin = −0.26 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	0.37154 (3)	0.34965 (5)	0.00661 (3)	0.0508 (2)
O1	0.40394 (6)	0.46001 (10)	−0.03204 (8)	0.0793 (5)
H1O	0.3925	0.5119	−0.0307	0.095*
H2O	0.4343	0.4632	−0.0476	0.095*
N1	0.44252 (8)	0.36053 (12)	0.15861 (7)	0.0549 (5)
N2	0.44256 (7)	0.28903 (11)	0.05251 (7)	0.0540 (5)
N3	0.47048 (8)	0.18766 (11)	−0.03231 (8)	0.0590 (5)
N4	0.37449 (7)	0.24826 (11)	−0.06132 (7)	0.0529 (5)
N5	0.27973 (8)	0.26608 (11)	−0.11769 (7)	0.0533 (5)
N6	0.28508 (7)	0.35449 (11)	−0.01852 (7)	0.0496 (4)
N7	0.25535 (8)	0.45126 (11)	0.06781 (8)	0.0556 (5)
N8	0.35225 (7)	0.39321 (11)	0.09599 (7)	0.0518 (4)
C1	0.46560 (9)	0.30721 (14)	0.11489 (9)	0.0529 (5)
C2	0.51977 (10)	0.25828 (14)	0.12726 (10)	0.0557 (6)
C3	0.55900 (10)	0.25021 (16)	0.18087 (11)	0.0695 (7)
H3	0.5538	0.2815	0.2190	0.083*
C4	0.60595 (12)	0.19409 (18)	0.17566 (12)	0.0868 (8)
H4	0.6328	0.1877	0.2113	0.104*
C5	0.61518 (11)	0.14654 (18)	0.11968 (12)	0.0893 (8)
H5	0.6479	0.1101	0.1181	0.107*
C6	0.57576 (10)	0.15327 (16)	0.06636 (11)	0.0756 (7)
H6	0.5811	0.1211	0.0286	0.091*
C7	0.52788 (10)	0.20924 (15)	0.07034 (10)	0.0593 (6)
C8	0.47843 (9)	0.22891 (14)	0.02556 (9)	0.0543 (6)
C9	0.42200 (10)	0.19561 (14)	−0.07089 (9)	0.0522 (5)
C10	0.41064 (10)	0.14382 (14)	−0.13084 (9)	0.0567 (6)
C11	0.44369 (11)	0.08086 (16)	−0.16204 (10)	0.0727 (7)
H11	0.4810	0.0656	−0.1455	0.087*
C12	0.41916 (13)	0.04198 (17)	−0.21819 (12)	0.0861 (8)
H12	0.4406	0.0010	−0.2408	0.103*
C13	0.36337 (13)	0.06264 (18)	−0.24161 (11)	0.0849 (8)
H13	0.3479	0.0344	−0.2794	0.102*
C14	0.32987 (10)	0.12374 (16)	−0.21082 (10)	0.0708 (7)
H14	0.2922	0.1373	−0.2268	0.085*
C15	0.35504 (10)	0.16413 (14)	−0.15487 (9)	0.0572 (6)
C16	0.33294 (10)	0.23112 (13)	−0.11003 (9)	0.0500 (5)
C17	0.25756 (9)	0.32278 (13)	−0.07523 (9)	0.0476 (5)
C18	0.19927 (9)	0.35937 (14)	−0.08350 (9)	0.0525 (5)
C19	0.15503 (10)	0.34999 (16)	−0.13226 (10)	0.0652 (6)
H19	0.1593	0.3137	−0.1685	0.078*
C20	0.10457 (11)	0.39672 (18)	−0.12475 (12)	0.0791 (8)
H20	0.0744	0.3928	−0.1571	0.095*
C21	0.09744 (11)	0.44936 (17)	−0.07045 (14)	0.0815 (8)
H21	0.0625	0.4794	−0.0669	0.098*
C22	0.14070 (11)	0.45792 (15)	−0.02210 (11)	0.0702 (7)
H22	0.1357	0.4929	0.0145	0.084*
C23	0.19195 (10)	0.41314 (14)	−0.02921 (10)	0.0548 (6)
C24	0.24653 (9)	0.40860 (14)	0.01148 (9)	0.0505 (5)
C25	0.30361 (10)	0.44254 (13)	0.10704 (9)	0.0504 (5)
C26	0.31217 (10)	0.48651 (14)	0.16981 (9)	0.0572 (6)
C27	0.27845 (10)	0.54686 (15)	0.20243 (10)	0.0715 (7)
H27	0.2418	0.5642	0.1851	0.086*
C28	0.30131 (13)	0.58008 (17)	0.26138 (11)	0.0878 (8)
H28	0.2800	0.6218	0.2835	0.105*
C29	0.35456 (13)	0.55321 (18)	0.28812 (11)	0.0883 (8)
H29	0.3683	0.5767	0.3282	0.106*
C30	0.38883 (11)	0.49161 (16)	0.25689 (10)	0.0746 (7)
H30	0.4249	0.4733	0.2754	0.090*
C31	0.36664 (10)	0.45869 (14)	0.19684 (9)	0.0549 (6)
C32	0.39083 (10)	0.39934 (13)	0.14931 (9)	0.0500 (5)
N9	0.51568 (13)	0.4520 (2)	−0.07758 (14)	0.1452 (12)
H91	0.4995	0.4794	−0.1131	0.218*
H92	0.5392	0.4926	−0.0559	0.218*
C33	0.5517 (2)	0.3754 (3)	−0.0977 (2)	0.181 (2)
H331	0.5530	0.3278	−0.0648	0.213*
H332	0.5908	0.3976	−0.1003	0.213*
C34	0.53080 (19)	0.3344 (3)	−0.1606 (2)	0.200 (3)
H341	0.5304	0.3821	−0.1934	0.264*
H342	0.4912	0.3143	−0.1581	0.264*
C35	0.56552 (18)	0.2535 (3)	−0.1826 (2)	0.216 (2)
H351	0.5742	0.2122	−0.1470	0.324*
H352	0.6009	0.2755	−0.1979	0.324*
H353	0.5434	0.2216	−0.2170	0.324*
N10	0.3500 (2)	0.6137 (2)	−0.0773 (2)	0.1996 (16)
H10A	0.3562	0.5850	−0.1124	0.299*
H10B	0.3558	0.6727	−0.0793	0.299*
C36	0.2917 (2)	0.6079 (4)	−0.0760 (3)	0.241 (3)
H361	0.2831	0.6014	−0.0313	0.277*
H362	0.2786	0.5522	−0.0985	0.277*
C37	0.2568 (3)	0.6880 (5)	−0.1053 (4)	0.301 (4)
H371	0.2745	0.7460	−0.0915	0.362*
H372	0.2546	0.6851	−0.1522	0.362*
C38	0.1972 (3)	0.6795 (5)	−0.0817 (4)	0.382 (5)
H381	0.1740	0.6392	−0.1100	0.574*
H382	0.1794	0.7391	−0.0816	0.574*
H383	0.2004	0.6547	−0.0387	0.574*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mg1	0.0575 (5)	0.0541 (4)	0.0407 (3)	0.0071 (4)	0.0027 (3)	−0.0008 (3)
O1	0.0757 (13)	0.0707 (11)	0.0927 (12)	−0.0025 (9)	0.0147 (10)	0.0196 (9)
N1	0.0674 (13)	0.0539 (11)	0.0430 (9)	0.0052 (10)	0.0025 (9)	0.0014 (8)
N2	0.0645 (12)	0.0561 (11)	0.0411 (9)	0.0114 (9)	0.0017 (9)	−0.0002 (8)
N3	0.0656 (14)	0.0648 (12)	0.0473 (10)	0.0129 (10)	0.0079 (10)	−0.0016 (9)
N4	0.0596 (13)	0.0565 (11)	0.0422 (9)	0.0069 (10)	0.0011 (9)	0.0023 (8)
N5	0.0615 (13)	0.0546 (11)	0.0442 (10)	−0.0036 (10)	0.0061 (9)	0.0043 (8)
N6	0.0536 (12)	0.0525 (11)	0.0428 (9)	0.0018 (9)	0.0043 (8)	0.0019 (8)
N7	0.0631 (13)	0.0543 (11)	0.0502 (10)	0.0076 (10)	0.0098 (10)	−0.0008 (9)
N8	0.0555 (12)	0.0555 (11)	0.0444 (9)	0.0088 (9)	0.0053 (9)	0.0016 (8)
C1	0.0616 (16)	0.0515 (13)	0.0455 (12)	0.0025 (12)	0.0035 (11)	0.0033 (11)
C2	0.0597 (16)	0.0532 (14)	0.0529 (13)	0.0061 (12)	−0.0022 (12)	0.0078 (11)
C3	0.0710 (18)	0.0724 (17)	0.0629 (15)	0.0099 (14)	−0.0065 (13)	0.0042 (12)
C4	0.087 (2)	0.094 (2)	0.0743 (17)	0.0201 (17)	−0.0209 (15)	0.0073 (15)
C5	0.083 (2)	0.094 (2)	0.0867 (18)	0.0309 (16)	−0.0161 (16)	0.0038 (16)
C6	0.0749 (18)	0.0775 (17)	0.0728 (15)	0.0259 (15)	−0.0022 (14)	−0.0041 (13)
C7	0.0611 (16)	0.0595 (15)	0.0563 (13)	0.0167 (12)	−0.0009 (12)	0.0065 (11)
C8	0.0621 (16)	0.0559 (14)	0.0448 (12)	0.0135 (12)	0.0051 (11)	0.0035 (11)
C9	0.0576 (16)	0.0538 (14)	0.0459 (12)	0.0086 (12)	0.0083 (11)	0.0003 (11)
C10	0.0704 (17)	0.0539 (14)	0.0478 (12)	0.0033 (13)	0.0158 (12)	−0.0020 (11)
C11	0.0885 (19)	0.0706 (17)	0.0606 (14)	0.0058 (14)	0.0162 (14)	−0.0091 (13)
C12	0.098 (2)	0.0820 (19)	0.0817 (18)	0.0059 (17)	0.0265 (17)	−0.0292 (15)
C13	0.104 (2)	0.085 (2)	0.0665 (15)	−0.0122 (18)	0.0118 (16)	−0.0298 (14)
C14	0.0783 (18)	0.0788 (18)	0.0565 (13)	−0.0089 (14)	0.0124 (13)	−0.0195 (13)
C15	0.0751 (18)	0.0527 (14)	0.0455 (12)	−0.0053 (13)	0.0153 (12)	−0.0005 (11)
C16	0.0574 (16)	0.0511 (14)	0.0417 (12)	−0.0018 (12)	0.0051 (11)	0.0045 (10)
C17	0.0548 (15)	0.0491 (13)	0.0390 (11)	−0.0025 (11)	0.0039 (11)	0.0093 (10)
C18	0.0547 (16)	0.0502 (13)	0.0521 (12)	−0.0010 (12)	0.0013 (12)	0.0117 (11)
C19	0.0579 (17)	0.0708 (16)	0.0652 (14)	−0.0040 (14)	−0.0044 (13)	0.0157 (12)
C20	0.0625 (19)	0.085 (2)	0.0855 (19)	−0.0088 (15)	−0.0103 (15)	0.0079 (16)
C21	0.0622 (19)	0.0767 (19)	0.103 (2)	0.0134 (15)	−0.0053 (17)	0.0157 (16)
C22	0.0637 (17)	0.0703 (17)	0.0757 (16)	0.0111 (14)	0.0014 (14)	0.0083 (13)
C23	0.0533 (16)	0.0492 (14)	0.0620 (14)	0.0084 (12)	0.0007 (12)	0.0098 (11)
C24	0.0567 (15)	0.0483 (13)	0.0474 (12)	0.0077 (11)	0.0086 (11)	0.0082 (10)
C25	0.0586 (16)	0.0493 (13)	0.0441 (12)	0.0040 (12)	0.0088 (11)	−0.0011 (10)
C26	0.0710 (17)	0.0518 (14)	0.0499 (12)	0.0028 (12)	0.0121 (12)	−0.0044 (11)
C27	0.0741 (18)	0.0744 (17)	0.0663 (15)	0.0129 (14)	0.0074 (13)	−0.0151 (13)
C28	0.102 (2)	0.093 (2)	0.0701 (17)	0.0165 (18)	0.0157 (16)	−0.0288 (15)
C29	0.116 (2)	0.093 (2)	0.0557 (14)	0.0083 (18)	0.0068 (16)	−0.0291 (14)
C30	0.097 (2)	0.0759 (17)	0.0504 (13)	0.0025 (15)	0.0031 (13)	−0.0085 (12)
C31	0.0699 (17)	0.0515 (14)	0.0442 (12)	−0.0010 (12)	0.0102 (12)	−0.0038 (10)
C32	0.0593 (16)	0.0482 (13)	0.0423 (12)	0.0022 (12)	0.0026 (11)	0.0010 (10)
N9	0.145 (3)	0.141 (3)	0.156 (2)	−0.013 (2)	0.052 (2)	−0.051 (2)
C33	0.204 (7)	0.164 (5)	0.168 (4)	−0.114 (5)	−0.018 (4)	0.074 (4)
C34	0.226 (6)	0.191 (5)	0.169 (4)	−0.120 (5)	−0.051 (4)	0.072 (4)
C35	0.195 (5)	0.152 (4)	0.310 (6)	0.031 (3)	0.071 (4)	−0.091 (4)
N10	0.218 (4)	0.122 (3)	0.258 (4)	0.022 (3)	0.016 (4)	0.047 (3)
C36	0.202 (6)	0.225 (5)	0.305 (7)	0.012 (5)	0.070 (6)	0.097 (5)
C37	0.204 (7)	0.375 (11)	0.327 (9)	−0.015 (8)	0.028 (7)	0.026 (7)
C38	0.412 (13)	0.377 (11)	0.350 (10)	0.037 (10)	−0.020 (10)	0.026 (8)

Geometric parameters (Å, º)

Mg1—O1	1.9712 (15)	C18—C19	1.385 (3)
Mg1—N6	2.0316 (17)	C18—C23	1.394 (3)
Mg1—N2	2.0327 (18)	C19—C20	1.375 (3)
Mg1—N4	2.0446 (17)	C19—H19	0.9300
Mg1—N8	2.0471 (16)	C20—C21	1.384 (3)
O1—H1O	0.80	C20—H20	0.9300
O1—H2O	0.80	C21—C22	1.363 (3)
N1—C32	1.325 (2)	C21—H21	0.9300
N1—C1	1.340 (2)	C22—C23	1.376 (3)
N2—C8	1.360 (2)	C22—H22	0.9300
N2—C1	1.383 (2)	C23—C24	1.463 (3)
N3—C9	1.329 (2)	C25—C26	1.450 (3)
N3—C8	1.341 (2)	C26—C27	1.390 (3)
N4—C16	1.359 (2)	C26—C31	1.398 (3)
N4—C9	1.371 (2)	C27—C28	1.378 (3)
N5—C16	1.333 (2)	C27—H27	0.9300
N5—C17	1.341 (2)	C28—C29	1.368 (3)
N6—C17	1.370 (2)	C28—H28	0.9300
N6—C24	1.380 (2)	C29—C30	1.395 (3)
N7—C24	1.324 (2)	C29—H29	0.9300
N7—C25	1.333 (2)	C30—C31	1.392 (3)
N8—C32	1.365 (2)	C30—H30	0.9300
N8—C25	1.374 (2)	C31—C32	1.459 (3)
C1—C2	1.448 (3)	N9—C33	1.475 (5)
C2—C3	1.381 (3)	N9—H91	0.89
C2—C7	1.407 (3)	N9—H92	0.90
C3—C4	1.373 (3)	C33—C34	1.479 (3)
C3—H3	0.9300	C33—H331	0.9700
C4—C5	1.385 (3)	C33—H332	0.9700
C4—H4	0.9300	C34—C35	1.518 (3)
C5—C6	1.378 (3)	C34—H341	0.9700
C5—H5	0.9300	C34—H342	0.9700
C6—C7	1.386 (3)	C35—H351	0.9600
C6—H6	0.9300	C35—H352	0.9600
C7—C8	1.442 (3)	C35—H353	0.9600
C9—C10	1.459 (3)	N10—C36	1.359 (5)
C10—C15	1.375 (3)	N10—H10A	0.86
C10—C11	1.390 (3)	N10—H10B	0.87
C11—C12	1.374 (3)	C36—C37	1.515 (9)
C11—H11	0.9300	C36—H361	0.9700
C12—C13	1.377 (3)	C36—H362	0.9700
C12—H12	0.9300	C37—C38	1.513 (10)
C13—C14	1.374 (3)	C37—H371	0.9700
C13—H13	0.9300	C37—H372	0.9700
C14—C15	1.385 (3)	C38—H381	0.9600
C14—H14	0.9300	C38—H382	0.9600
C15—C16	1.470 (3)	C38—H383	0.9600
C17—C18	1.451 (3)
O1—Mg1—N6	105.74 (7)	C20—C19—H19	121.5
O1—Mg1—N2	102.72 (7)	C18—C19—H19	121.5
N6—Mg1—N2	151.54 (7)	C19—C20—C21	121.9 (2)
O1—Mg1—N4	105.55 (7)	C19—C20—H20	119.0
N6—Mg1—N4	86.53 (7)	C21—C20—H20	119.0
N2—Mg1—N4	86.38 (7)	C22—C21—C20	121.2 (2)
O1—Mg1—N8	103.84 (7)	C22—C21—H21	119.4
N6—Mg1—N8	86.15 (7)	C20—C21—H21	119.4
N2—Mg1—N8	86.64 (7)	C21—C22—C23	117.9 (2)
N4—Mg1—N8	150.61 (7)	C21—C22—H22	121.1
Mg1—O1—H1O	128	C23—C22—H22	121.1
Mg1—O1—H2O	126	C22—C23—C18	121.3 (2)
H1O—O1—H2O	105	C22—C23—C24	132.4 (2)
C32—N1—C1	123.90 (17)	C18—C23—C24	106.35 (19)
C8—N2—C1	107.88 (17)	N7—C24—N6	127.51 (19)
C8—N2—Mg1	125.88 (13)	N7—C24—C23	123.31 (19)
C1—N2—Mg1	126.05 (14)	N6—C24—C23	109.18 (17)
C9—N3—C8	123.00 (18)	N7—C25—N8	127.41 (17)
C16—N4—C9	108.57 (17)	N7—C25—C26	123.3 (2)
C16—N4—Mg1	125.53 (14)	N8—C25—C26	109.24 (19)
C9—N4—Mg1	125.27 (14)	C27—C26—C31	121.00 (19)
C16—N5—C17	124.09 (17)	C27—C26—C25	132.6 (2)
C17—N6—C24	107.88 (17)	C31—C26—C25	106.38 (19)
C17—N6—Mg1	125.88 (14)	C28—C27—C26	117.6 (2)
C24—N6—Mg1	124.70 (14)	C28—C27—H27	121.2
C24—N7—C25	123.55 (18)	C26—C27—H27	121.2
C32—N8—C25	108.77 (16)	C29—C28—C27	121.7 (2)
C32—N8—Mg1	125.13 (14)	C29—C28—H28	119.2
C25—N8—Mg1	124.09 (13)	C27—C28—H28	119.2
N1—C1—N2	126.85 (19)	C28—C29—C30	121.8 (2)
N1—C1—C2	123.77 (18)	C28—C29—H29	119.1
N2—C1—C2	109.37 (18)	C30—C29—H29	119.1
C3—C2—C7	120.5 (2)	C31—C30—C29	117.1 (2)
C3—C2—C1	133.4 (2)	C31—C30—H30	121.5
C7—C2—C1	106.09 (18)	C29—C30—H30	121.5
C4—C3—C2	117.4 (2)	C30—C31—C26	120.8 (2)
C4—C3—H3	121.3	C30—C31—C32	132.4 (2)
C2—C3—H3	121.3	C26—C31—C32	106.71 (17)
C3—C4—C5	123.0 (2)	N1—C32—N8	127.79 (18)
C3—C4—H4	118.5	N1—C32—C31	123.37 (18)
C5—C4—H4	118.5	N8—C32—C31	108.83 (18)
C6—C5—C4	119.9 (2)	C33—N9—H91	108.2
C6—C5—H5	120.0	C33—N9—H92	107.6
C4—C5—H5	120.0	H91—N9—H92	108.4
C5—C6—C7	118.3 (2)	N9—C33—C34	113.8 (4)
C5—C6—H6	120.8	N9—C33—H331	108.8
C7—C6—H6	120.8	C34—C33—H331	108.8
C6—C7—C2	120.9 (2)	N9—C33—H332	108.8
C6—C7—C8	132.5 (2)	C34—C33—H332	108.8
C2—C7—C8	106.51 (19)	H331—C33—H332	107.7
N3—C8—N2	127.88 (19)	C33—C34—C35	115.8 (5)
N3—C8—C7	121.9 (2)	C33—C34—H341	108.3
N2—C8—C7	110.10 (17)	C35—C34—H341	108.3
N3—C9—N4	127.70 (18)	C33—C34—H342	108.3
N3—C9—C10	123.4 (2)	C35—C34—H342	108.3
N4—C9—C10	108.86 (19)	H341—C34—H342	107.4
C15—C10—C11	120.7 (2)	C34—C35—H351	109.5
C15—C10—C9	107.06 (19)	C34—C35—H352	109.5
C11—C10—C9	132.1 (2)	H351—C35—H352	109.5
C12—C11—C10	117.5 (2)	C34—C35—H353	109.5
C12—C11—H11	121.3	H351—C35—H353	109.5
C10—C11—H11	121.3	H352—C35—H353	109.5
C11—C12—C13	121.2 (2)	C36—N10—H10A	103.2
C11—C12—H12	119.4	C36—N10—H10B	102.7
C13—C12—H12	119.4	H10A—N10—H10B	113.6
C14—C13—C12	122.0 (2)	N10—C36—C37	116.3 (5)
C14—C13—H13	119.0	N10—C36—H361	108.2
C12—C13—H13	119.0	C37—C36—H361	108.2
C13—C14—C15	116.7 (2)	N10—C36—H362	108.2
C13—C14—H14	121.7	C37—C36—H362	108.2
C15—C14—H14	121.7	H361—C36—H362	107.4
C10—C15—C14	121.9 (2)	C38—C37—C36	106.2 (3)
C10—C15—C16	106.31 (19)	C38—C37—H371	110.5
C14—C15—C16	131.8 (2)	C36—C37—H371	110.5
N5—C16—N4	127.60 (19)	C38—C37—H372	110.5
N5—C16—C15	123.23 (19)	C36—C37—H372	110.5
N4—C16—C15	109.16 (19)	H371—C37—H372	108.7
N5—C17—N6	126.46 (19)	C37—C38—H381	109.5
N5—C17—C18	123.70 (18)	C37—C38—H382	109.5
N6—C17—C18	109.84 (18)	H381—C38—H382	109.5
C19—C18—C23	120.8 (2)	C37—C38—H383	109.5
C19—C18—C17	132.5 (2)	H381—C38—H383	109.5
C23—C18—C17	106.73 (18)	H382—C38—H383	109.5
C20—C19—C18	117.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O···N9	0.80	2.05	2.841 (3)	170
O1—H1O···N10	0.80	1.99	2.689 (4)	147
N9—H92···O1^i	0.90	2.26	3.092 (3)	153
N10—H10B···Cg^i	0.87	2.76	3.478 (4)	141

Symmetry code: (i) −x+1, −y+1, −z.