A novel two-dimensional metal-organic supra­molecular framework including [pi]-[pi] stacking and hydrogen-bond inter­actions

[[mu]-N,N'-Bis­(pyridin-3-yl)benzene-1,4-dicarboxamide-1:2[kappa]²N:N']bis­{[N,N'-bis­(pyridin-3-yl)benzene-1,4-dicarboxamide-[kappa]N]di­iodidomercury(II)}, [Hg₂I₄(C₁₈H₁₄N₄O₂)₃], is an S-shaped dinuclear mol­ecule, composed of two HgI₂ units and three N,N'-bis­(pyridin-3-yl)benzene-1,4-di­car­boxamide (L) ligands. The central L ligand is centrosymmetric and coordinated to two Hg^II cations via two pyridine N atoms, in a syn-syn conformation. The two terminal L ligands are monodentate, with one uncoordinated pyridine N atom, and each adopts a syn-anti conformation. The HgI₂ units show highly distorted tetra­hedral (sawhorse) geometry, as the Hg^II centres lie only 0.34 (2) or 0.32 (2) Å from the planes defined by the I and pyridine N atoms. Supra­molecular inter­actions, thermal stability and solid-state luminescence properties were also measured.

S1. Comment

In the past decade, metal–organic frameworks (MOFs) have attracted wide attention due to their potential applications in catalysis, gas storage, electronics, luminescence, molecular sensing, porous materials, magnetic devices and nanosized materials (Luo et al., 2012; Zeng et al., 2010; PrakashaReddy & Pedireddi, 2007; Wei et al., 2006). They often have inherently varied structures, for instance polyrotaxane or interpenetrating nets or polycatenane topological matrices (Adarsh & Dastidar, 2011), and many combinations of metals or metal clusters and organic ligands can make MOFs (Sun, Luo et al., 2012). Therefore, the proper choice of organic ligands with different functionalities and of the metal ion may result in specific supramolecular structures containing one-, two- or three-dimensional networks (Tsai et al., 2010). The linear rigid ligand N,N'-bis(pyridin-3-yl)benzene-1,4-dicarboxamide (L) has recently been synthesized and reacted with metal salts that result in the formation of one-, two- and even three-dimensional coordination networks (Tsai et al., 2010). The L ligand coordinates to the metal centre through its pyridyl N atoms and interacts with other ligand molecules via hydrogen bonds involving the amide groups, which are significant for molecular recognition and building supramolecular frameworks (Rajput & Biradha, 2009; Adarsh et al., 2009). Against this background, we report here the title complex, (I), formed from the L ligand and iodine ligands coordinated to the Hg^II metal centre. In addition, we also discuss the synthesis, structure, thermostability and solid-state photoluminescence properties of (I).

Compound (I) is a centrosymmetric S-shaped molecule. It contains two Hg^II cations, one bridging L ligand, two terminal L ligands and four I^- anions. The bridging L ligand is located about a crystallographic inversion centre, so there is only one crystallographically independent Hg^II centre, which is four-coordinated by two terminal I atoms and two pyridyl N atoms from two L ligands (one bridging L ligand and one terminal L ligand) (see Fig. 1). The coordination geometry is not a typical tetrahedron, in that the I1—Hg1—I2 and N1—Hg1—N5 angles are 151.070 (18) and 80.97 (16)°, respectively, very different from the regular tetrahedral angle. Moreover, the Hg^II centre lies only ca 0.34 or 0.32 Å from the planes defined by atoms I1/I2/N1 and I1/I2/N5, respectively. The bond lengths and angles involving atom Hg1 are summerized in Table 1. The Hg—I bonds are longer than the Hg—N bonds, due to the different ratios of atom radii. The bond lengths in (I) are comparable with those observed in other Hg-containing compounds, such as [HgI₂(X)]_n [X is N,N'-bis(4-pyridylformamide)-1,4-benzene, 4,4'-azopyridine, 4,4'-trimethylene dipyridine or N,N'-bis(pyridin-3-ylformyl)piperazine; Li et al., 2005].

As shown in Fig. 1, there are two coordination modes for the L ligand. The centrosymmetric L ligand plays a bridging role between to two Hg^II cations through an Hg—N coordination bond, whereas the other L ligands are only connected to one Hg^II cation and act as terminal ligands. Interestingly, the conformations of these L ligands are also different. The central L ligand adopts a cis–cis conformation, where cis means that the pyridyl N atom and acylamide N—H group are located on the same side. In contrast, the two terminal L ligands adopt cis–anti conformations, where anti means that the pyridyl N atoms and acylamide N—H groups are located on opposite sides. The C═O bond length in the acylamide group of the L ligand is 1.227 (7) Å. The torsion angles of the acylamide group of the L ligand are H6M—N6—C24—O3 = 174.69°, H2M—N2—C6—O1 = 168.57° and H3M—N3—C13—O2 = 177.72°. The dihedral angles between the pyridyl and phenyl planes for the L ligand are ca 7.62° (central ligand), and ca 2.44 and 7.68° (terminal ligand) [Which value for which end of the ligand?].

Atoms Hg1 and symmetry-related Hg1ⁱ [symmetry code: (i) 1 - x, 2 - y, 1 - z] are bridged by one L ligand, creating a dinuclear structure with a large metal-to-metal span of ca 18.25 Å. Taking the two terminal L ligands into account, a clear S-like shape is observed.

As shown in Fig. 1, typical N—H···O hydrogen bonds are observed between the amide groups in this S-shaped molecule. All the N—H and C═O groups in the central L ligand act as hydrogen-bond donors and acceptors, respectively, whereas the terminal L ligands only contribute parts of the N—H and C═O groups to form hydrogen bonds. Interestingly, those N—H groups that do not form hydrogen bonds within the dinuclear molecule of (I) can act as donors to form hydrogen bonds with uncoordinated pyridyl N atoms from other adjacent dinuclear molecules. Conversely, the uncoordinated pyridyl N atoms from one dinuclear molecule of (I) act as acceptors to generate hydrogen bonds with the N—H groups from other adjacent dinuclear molecules. Thus, each dinuclear molecule will connect to four adjacent dinuclear molecules through typical N—H···N hydrogen bonds (Fig. 2). Extended in the bc plane, this connectivity will construct an overall two-dimensional supramolecular brick-wall net (Fig. 3). Within this, obvious π–π interactions with a centroid-to-centroid distance of ca. 3.72Å are observed. All of the N—H···O and N—H···N hydrogen-bond parameters are summarized in Table 2. Finally, as shown in Fig. 4, these layers lead to a three-dimensional structure with AA packing along the a direction, and I···I contacts of 4.34 Å between the layers further enhance the structure.

A search of the Cambridge Structural Database (CSD, February 2013 release; Allen, 2002) reveals 13 compounds containing the ligand L, involving eight Cu-based, three Zn-based and two Co-based compounds (Adarsh et al., 2010; Adarsh & Dastidar, 2011; Tsai et al., 2010; Rajput & Biradha, 2009). In these compounds, the L ligands play a bridging role to link two metal centers through the pyridyl N atoms. Typical N—H···O hydrogen bonds were also found in those compounds. By contrast, our case should present the first L-containing Hg^II-based compound. Interestingly, in our case there are two kinds of L ligand, bridging and terminal. The uncoordinated N atoms of the terminal L ligands of (I) provide a potential acceptor for constructing hydrogen bonds with the N—H groups, resulting in the overall two-dimensional supramolecular brick-wall net.

Related literature

For related literature, see: Adarsh & Dastidar (2011); Adarsh et al. (2009, 2010); Allen (2002); Li et al. (2005); Luo et al. (2008, 2012); PrakashaReddy & Pedireddi (2007); Rajput & Biradha (2009); Sun, Luo, Song, Tian, Huang, Zhu, Yuan, Feng, Luo, Liu & Xu (2012); Tsai et al. (2010); Wei et al. (2006); Zeng et al. (2010).

S2. Experimental

For the synthesis of (I), a CH₃CN solution (4 ml) of HgI₂ (0.2 mmol) and L (0.2 mmmol) in a ratio of 1:1 was sealed in a Teflon reactor and heated at 433 K for 3 d, and then cooled to room temperature at 3 K h^-1. Red block crystals of (I) were obtained in 63% yield based on HgI₂.

To evaluate its thermostability, a sample of (I) was heated in a nitrogen atmosphere from 308 to 1073 K at a heating rate of 10 K min^-1. As shown in Fig. 5, compound (I) is heat-stable to over 443 K, but displays a sharp weight loss at around 483 K, indicating decomposition.

In addition, the solid-state photoluminescence properties of (I) were measured. As shown in Fig. 6, an intense emission occurs at 440 nm with an excitation wavelength of 322 nm. As we know, the emission is mainly derived from the π–π* transition. Meanwhile, the free L ligand exhibits a 465 nm blue emission under 320 nm excitation, which indicates that the emission of (I) originates from the L ligand, and the blue shift (25 nm) is mainly due to a metal-to-ligand or ligand-to-metal charge transfer (Luo et al., 2008).

S3. Refinement

C-bound H atoms of the benzene and pyridine rings were placed in calculated positions, with C—H = 0.93 Å, and treated using a riding-model approximation, with U_iso(H) = 1.2U_eq(C). N-bound H atoms were found through residual Q peaks, and refined with N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The zero-dimensional S-shaped structure of (I), showing the atom-numbering scheme. The coordination environment of the Hg^II cations can be seen, together with the N—H···O hydrogen-bond interactions (dashed lines) between the three segments of the compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]
	Fig. 2. A view of the N—H···N hydrogen-bond interactions (dashed lines) of each dinuclear molecule with four adjacent identical dinuclear molecules. C-bound H atoms have been omitted for clarity. [Added text OK?] (In the electronic version of the journal, Hg atoms are coloured lavender, C green, N blue, O red, H pink and I yellow.)
	Fig. 3. A view of the two-dimensional structure of (I), along the a direction. N—H···N hydrogen bonds are shown as black dashed lines. One of the π–π interactions is highlighted as a dashed line in the inset on the right-hand side. (In the electronic version of the journal, Hg atoms are coloured lavender, C green, N blue, O red, H pink and I yellow.)
	Fig. 4. A view of the three-dimensional packing for (I), along the a direction. [According to the axes, this view is along the b direction. Please clarify]
	Fig. 5. The thermogravimetric curve of (I).
	Fig. 6. The solid-state photoluminescence spectrum of (I).

[µ-N,N'-Bis(pyridin-3-yl)benzene-1,4-dicarboxamide-1:2κ²N:N']bis{[N,N'-bis(pyridin-3-yl)benzene-1,4-dicarboxamide-κN]diiodidomercury(II)}

Crystal data

[Hg2I4(C18N4H14O2)3]	F(000) = 1740
Mr = 1863.78	Dx = 2.251 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.416 (3) Å	Cell parameters from 4787 reflections
b = 9.2907 (17) Å	θ = 2.2–25.1°
c = 16.229 (3) Å	µ = 7.89 mm^−1
β = 98.059 (5)°	T = 296 K
V = 2749.3 (8) Å^3	Block, red
Z = 2	0.21 × 0.18 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5397 independent reflections
Radiation source: fine-focus sealed tube	4213 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ϕ and ω scans	θmax = 26.0°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
Tmin = 0.288, Tmax = 0.451	k = −10→11
21841 measured reflections	l = −17→20

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0424P)^2] where P = (Fo^2 + 2Fc^2)/3
5397 reflections	(Δ/σ)max = 0.002
361 parameters	Δρmax = 0.68 e Å^−3
3 restraints	Δρmin = −1.11 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.8957 (3)	0.4349 (7)	0.3839 (4)	0.0498 (16)
H1	0.9340	0.4374	0.3522	0.060*
C2	0.8476 (4)	0.3208 (8)	0.3732 (5)	0.0548 (18)
H2	0.8543	0.2464	0.3367	0.066*
C3	0.7891 (3)	0.3199 (7)	0.4182 (4)	0.0450 (16)
H3	0.7548	0.2457	0.4114	0.054*
C4	0.7823 (3)	0.4298 (6)	0.4728 (3)	0.0345 (13)
C5	0.8347 (3)	0.5373 (6)	0.4822 (4)	0.0351 (13)
H5	0.8315	0.6094	0.5212	0.042*
C6	0.6792 (3)	0.5446 (6)	0.5278 (3)	0.0319 (13)
C7	0.6140 (3)	0.5124 (6)	0.5705 (3)	0.0277 (12)
C8	0.5929 (3)	0.6119 (6)	0.6259 (3)	0.0323 (12)
H8	0.6207	0.6947	0.6380	0.039*
C9	0.5309 (3)	0.5900 (6)	0.6638 (3)	0.0339 (13)
H9	0.5179	0.6562	0.7022	0.041*
C10	0.4878 (3)	0.4670 (6)	0.6436 (3)	0.0262 (11)
C11	0.5096 (3)	0.3667 (6)	0.5884 (3)	0.0317 (12)
H11	0.4825	0.2830	0.5766	0.038*
C12	0.5714 (3)	0.3908 (6)	0.5510 (3)	0.0325 (12)
H12	0.5845	0.3249	0.5125	0.039*
C13	0.4225 (3)	0.4352 (6)	0.6841 (3)	0.0298 (12)
C14	0.3281 (3)	0.6662 (6)	0.8123 (4)	0.0353 (13)
H14	0.3618	0.7403	0.8104	0.042*
C15	0.3302 (3)	0.5505 (6)	0.7581 (3)	0.0287 (12)
C16	0.2807 (3)	0.4406 (7)	0.7618 (4)	0.0447 (15)
H16	0.2800	0.3617	0.7264	0.054*
C17	0.2322 (3)	0.4498 (7)	0.8190 (4)	0.0517 (17)
H17	0.1987	0.3762	0.8229	0.062*
C18	0.2334 (3)	0.5673 (7)	0.8700 (4)	0.0469 (16)
H18	0.2004	0.5715	0.9083	0.056*
C19	0.8551 (3)	0.9105 (7)	0.2905 (4)	0.0393 (14)
H19	0.8964	0.8998	0.2640	0.047*
C20	0.7931 (3)	0.9691 (7)	0.2468 (4)	0.0432 (15)
H20	0.7930	0.9990	0.1921	0.052*
C21	0.7303 (3)	0.9835 (6)	0.2845 (3)	0.0358 (13)
H21	0.6874	1.0221	0.2558	0.043*
C22	0.7335 (3)	0.9388 (6)	0.3662 (3)	0.0288 (12)
C23	0.7986 (3)	0.8838 (7)	0.4054 (3)	0.0353 (13)
H23	0.8010	0.8555	0.4607	0.042*
C24	0.6165 (3)	1.0375 (6)	0.3999 (3)	0.0282 (12)
C25	0.5570 (3)	1.0144 (5)	0.4525 (3)	0.0267 (12)
C26	0.4857 (3)	1.0538 (6)	0.4201 (3)	0.0303 (12)
H26	0.4761	1.0903	0.3663	0.036*
C27	0.5705 (3)	0.9609 (6)	0.5330 (3)	0.0313 (13)
H27	0.6179	0.9347	0.5554	0.038*
Hg1	0.971813 (12)	0.75840 (3)	0.449105 (15)	0.04003 (9)
I1	0.95304 (2)	0.85421 (5)	0.59730 (3)	0.05171 (14)
I2	1.05662 (2)	0.69367 (5)	0.33796 (3)	0.05282 (14)
N1	0.8902 (2)	0.5404 (5)	0.4365 (3)	0.0396 (12)
N2	0.7227 (2)	0.4295 (5)	0.5198 (3)	0.0335 (11)
H2M	0.718 (3)	0.349 (3)	0.545 (3)	0.040*
N3	0.3838 (3)	0.5535 (5)	0.7044 (3)	0.0348 (11)
H3M	0.397 (3)	0.638 (3)	0.691 (4)	0.042*
N4	0.2805 (3)	0.6767 (6)	0.8668 (3)	0.0399 (12)
N5	0.8585 (2)	0.8687 (5)	0.3689 (3)	0.0386 (12)
N6	0.6730 (2)	0.9421 (5)	0.4109 (3)	0.0312 (10)
H6M	0.669 (3)	0.871 (4)	0.444 (3)	0.037*
O1	0.6918 (2)	0.6658 (4)	0.5033 (3)	0.0473 (11)
O2	0.4054 (2)	0.3127 (4)	0.6992 (3)	0.0426 (10)
O3	0.6137 (2)	1.1375 (4)	0.3504 (3)	0.0471 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.047 (4)	0.045 (4)	0.062 (4)	0.004 (3)	0.024 (3)	−0.004 (3)
C2	0.048 (4)	0.049 (4)	0.073 (5)	−0.004 (3)	0.027 (3)	−0.026 (4)
C3	0.038 (3)	0.033 (4)	0.066 (5)	−0.004 (3)	0.017 (3)	−0.007 (3)
C4	0.034 (3)	0.034 (3)	0.036 (3)	0.007 (2)	0.007 (2)	0.005 (3)
C5	0.039 (3)	0.026 (3)	0.041 (3)	0.001 (2)	0.011 (3)	−0.003 (3)
C6	0.028 (3)	0.035 (4)	0.034 (3)	0.000 (2)	0.010 (2)	0.003 (3)
C7	0.027 (3)	0.027 (3)	0.029 (3)	0.001 (2)	0.001 (2)	0.005 (2)
C8	0.032 (3)	0.027 (3)	0.038 (3)	0.000 (2)	0.006 (2)	−0.001 (3)
C9	0.038 (3)	0.028 (3)	0.037 (3)	−0.002 (2)	0.009 (2)	−0.005 (3)
C10	0.027 (3)	0.023 (3)	0.030 (3)	0.000 (2)	0.007 (2)	0.002 (2)
C11	0.034 (3)	0.024 (3)	0.036 (3)	−0.002 (2)	0.000 (2)	0.001 (2)
C12	0.035 (3)	0.030 (3)	0.034 (3)	0.006 (2)	0.008 (2)	−0.006 (2)
C13	0.034 (3)	0.027 (3)	0.028 (3)	0.003 (2)	0.004 (2)	0.005 (2)
C14	0.038 (3)	0.024 (3)	0.046 (4)	−0.001 (2)	0.015 (3)	0.001 (3)
C15	0.023 (3)	0.028 (3)	0.036 (3)	0.000 (2)	0.008 (2)	0.003 (2)
C16	0.045 (4)	0.042 (4)	0.050 (4)	−0.007 (3)	0.017 (3)	−0.011 (3)
C17	0.044 (4)	0.039 (4)	0.078 (5)	−0.008 (3)	0.029 (3)	−0.012 (4)
C18	0.041 (3)	0.049 (4)	0.055 (4)	0.007 (3)	0.024 (3)	0.006 (3)
C19	0.033 (3)	0.044 (4)	0.043 (4)	0.000 (3)	0.013 (3)	0.003 (3)
C20	0.046 (3)	0.059 (4)	0.026 (3)	0.003 (3)	0.010 (3)	0.006 (3)
C21	0.034 (3)	0.042 (4)	0.031 (3)	0.005 (3)	0.002 (2)	0.003 (3)
C22	0.026 (3)	0.023 (3)	0.038 (3)	−0.001 (2)	0.007 (2)	−0.002 (2)
C23	0.028 (3)	0.047 (4)	0.033 (3)	0.008 (3)	0.010 (2)	0.007 (3)
C24	0.024 (3)	0.019 (3)	0.041 (3)	−0.004 (2)	0.004 (2)	0.002 (2)
C25	0.025 (3)	0.015 (3)	0.040 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)
C26	0.031 (3)	0.026 (3)	0.034 (3)	0.002 (2)	0.003 (2)	0.003 (2)
C27	0.021 (3)	0.030 (3)	0.041 (3)	0.004 (2)	0.002 (2)	0.000 (3)
Hg1	0.03217 (13)	0.05026 (18)	0.03984 (15)	0.00487 (10)	0.01274 (10)	−0.00294 (11)
I1	0.0488 (3)	0.0657 (3)	0.0425 (3)	0.0053 (2)	0.01285 (19)	−0.0128 (2)
I2	0.0480 (3)	0.0638 (3)	0.0523 (3)	0.0018 (2)	0.0269 (2)	−0.0081 (2)
N1	0.033 (3)	0.036 (3)	0.052 (3)	0.002 (2)	0.016 (2)	0.000 (2)
N2	0.035 (2)	0.027 (3)	0.041 (3)	0.004 (2)	0.014 (2)	0.006 (2)
N3	0.041 (3)	0.023 (3)	0.043 (3)	−0.003 (2)	0.016 (2)	0.003 (2)
N4	0.040 (3)	0.039 (3)	0.044 (3)	0.003 (2)	0.018 (2)	0.001 (2)
N5	0.029 (2)	0.047 (3)	0.041 (3)	0.009 (2)	0.010 (2)	0.009 (2)
N6	0.030 (2)	0.025 (3)	0.041 (3)	0.0007 (19)	0.012 (2)	0.006 (2)
O1	0.046 (2)	0.028 (3)	0.073 (3)	0.0072 (19)	0.028 (2)	0.018 (2)
O2	0.048 (2)	0.026 (2)	0.057 (3)	−0.0001 (19)	0.020 (2)	0.006 (2)
O3	0.044 (2)	0.035 (3)	0.067 (3)	0.0122 (19)	0.027 (2)	0.021 (2)

Geometric parameters (Å, º)

C1—N1	1.314 (8)	C16—H16	0.9300
C1—C2	1.376 (9)	C17—C18	1.368 (9)
C1—H1	0.9300	C17—H17	0.9300
C2—C3	1.385 (8)	C18—N4	1.342 (8)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.369 (8)	C19—N5	1.323 (7)
C3—H3	0.9300	C19—C20	1.370 (8)
C4—C5	1.382 (8)	C19—H19	0.9300
C4—N2	1.422 (7)	C20—C21	1.389 (8)
C5—N1	1.343 (7)	C20—H20	0.9300
C5—H5	0.9300	C21—C22	1.383 (7)
C6—O1	1.227 (7)	C21—H21	0.9300
C6—N2	1.353 (7)	C22—C23	1.375 (7)
C6—C7	1.499 (7)	C22—N6	1.413 (6)
C7—C8	1.383 (7)	C23—N5	1.331 (7)
C7—C12	1.386 (7)	C23—H23	0.9300
C8—C9	1.385 (7)	C24—O3	1.224 (6)
C8—H8	0.9300	C24—N6	1.359 (7)
C9—C10	1.403 (7)	C24—C25	1.497 (7)
C9—H9	0.9300	C25—C27	1.388 (7)
C10—C11	1.391 (7)	C25—C26	1.392 (7)
C10—C13	1.479 (7)	C26—C27^i	1.375 (7)
C11—C12	1.380 (7)	C26—H26	0.9300
C11—H11	0.9300	C27—C26^i	1.375 (7)
C12—H12	0.9300	C27—H27	0.9300
C13—O2	1.215 (6)	Hg1—N1	2.514 (5)
C13—N3	1.375 (7)	Hg1—N5	2.517 (4)
C14—N4	1.333 (7)	Hg1—I2	2.6162 (6)
C14—C15	1.393 (8)	Hg1—I1	2.6324 (6)
C14—H14	0.9300	N2—H2M	0.858 (10)
C15—C16	1.376 (8)	N3—H3M	0.860 (10)
C15—N3	1.406 (7)	N6—H6M	0.859 (10)
C16—C17	1.378 (8)
N1—C1—C2	123.3 (6)	N4—C18—H18	118.7
N1—C1—H1	118.3	C17—C18—H18	118.7
C2—C1—H1	118.3	N5—C19—C20	122.5 (5)
C1—C2—C3	118.2 (6)	N5—C19—H19	118.7
C1—C2—H2	120.9	C20—C19—H19	118.7
C3—C2—H2	120.9	C19—C20—C21	119.8 (5)
C4—C3—C2	119.0 (6)	C19—C20—H20	120.1
C4—C3—H3	120.5	C21—C20—H20	120.1
C2—C3—H3	120.5	C22—C21—C20	117.8 (5)
C3—C4—C5	119.0 (5)	C22—C21—H21	121.1
C3—C4—N2	119.5 (5)	C20—C21—H21	121.1
C5—C4—N2	121.5 (5)	C23—C22—C21	118.2 (5)
N1—C5—C4	121.9 (5)	C23—C22—N6	118.1 (5)
N1—C5—H5	119.1	C21—C22—N6	123.7 (5)
C4—C5—H5	119.1	N5—C23—C22	123.8 (5)
O1—C6—N2	123.5 (5)	N5—C23—H23	118.1
O1—C6—C7	122.2 (5)	C22—C23—H23	118.1
N2—C6—C7	114.2 (5)	O3—C24—N6	122.8 (5)
C8—C7—C12	119.4 (5)	O3—C24—C25	121.1 (5)
C8—C7—C6	118.9 (5)	N6—C24—C25	116.1 (5)
C12—C7—C6	121.5 (5)	C27—C25—C26	119.1 (5)
C7—C8—C9	121.0 (5)	C27—C25—C24	122.6 (4)
C7—C8—H8	119.5	C26—C25—C24	118.3 (5)
C9—C8—H8	119.5	C27^i—C26—C25	120.5 (5)
C8—C9—C10	119.3 (5)	C27^i—C26—H26	119.7
C8—C9—H9	120.3	C25—C26—H26	119.7
C10—C9—H9	120.3	C26^i—C27—C25	120.4 (5)
C11—C10—C9	119.4 (5)	C26^i—C27—H27	119.8
C11—C10—C13	118.6 (5)	C25—C27—H27	119.8
C9—C10—C13	121.8 (5)	N1—Hg1—N5	80.97 (16)
C12—C11—C10	120.3 (5)	N1—Hg1—I2	99.61 (11)
C12—C11—H11	119.8	N5—Hg1—I2	105.58 (11)
C10—C11—H11	119.8	N1—Hg1—I1	101.12 (11)
C11—C12—C7	120.4 (5)	N5—Hg1—I1	97.44 (11)
C11—C12—H12	119.8	I2—Hg1—I1	151.070 (18)
C7—C12—H12	119.8	C1—N1—C5	118.5 (5)
O2—C13—N3	122.9 (5)	C1—N1—Hg1	123.6 (4)
O2—C13—C10	121.8 (5)	C5—N1—Hg1	117.7 (4)
N3—C13—C10	115.3 (5)	C6—N2—C4	124.2 (5)
N4—C14—C15	123.7 (5)	C6—N2—H2M	122 (4)
N4—C14—H14	118.2	C4—N2—H2M	113 (4)
C15—C14—H14	118.2	C13—N3—C15	124.4 (5)
C16—C15—C14	117.9 (5)	C13—N3—H3M	119 (4)
C16—C15—N3	124.7 (5)	C15—N3—H3M	116 (4)
C14—C15—N3	117.4 (5)	C14—N4—C18	117.3 (5)
C15—C16—C17	118.6 (6)	C19—N5—C23	117.8 (5)
C15—C16—H16	120.7	C19—N5—Hg1	122.8 (3)
C17—C16—H16	120.7	C23—N5—Hg1	119.4 (4)
C18—C17—C16	120.0 (6)	C24—N6—C22	126.2 (5)
C18—C17—H17	120.0	C24—N6—H6M	117 (4)
C16—C17—H17	120.0	C22—N6—H6M	117 (4)
N4—C18—C17	122.5 (6)
N1—C1—C2—C3	2.3 (11)	N6—C24—C25—C26	−148.7 (5)
C1—C2—C3—C4	−1.6 (11)	C27—C25—C26—C27^i	−0.3 (9)
C2—C3—C4—C5	−0.9 (9)	C24—C25—C26—C27^i	−177.9 (5)
C2—C3—C4—N2	−179.5 (6)	C26—C25—C27—C26^i	0.3 (9)
C3—C4—C5—N1	3.1 (9)	C24—C25—C27—C26^i	177.8 (5)
N2—C4—C5—N1	−178.3 (5)	C2—C1—N1—C5	−0.2 (10)
O1—C6—C7—C8	−38.8 (8)	C2—C1—N1—Hg1	−175.3 (5)
N2—C6—C7—C8	140.5 (5)	C4—C5—N1—C1	−2.5 (9)
O1—C6—C7—C12	136.4 (6)	C4—C5—N1—Hg1	172.8 (4)
N2—C6—C7—C12	−44.3 (7)	N5—Hg1—N1—C1	103.2 (5)
C12—C7—C8—C9	1.6 (8)	I2—Hg1—N1—C1	−1.2 (5)
C6—C7—C8—C9	176.9 (5)	I1—Hg1—N1—C1	−160.9 (5)
C7—C8—C9—C10	−1.9 (8)	N5—Hg1—N1—C5	−71.9 (4)
C8—C9—C10—C11	2.5 (8)	I2—Hg1—N1—C5	−176.3 (4)
C8—C9—C10—C13	177.8 (5)	I1—Hg1—N1—C5	24.0 (4)
C9—C10—C11—C12	−2.8 (8)	O1—C6—N2—C4	−8.7 (9)
C13—C10—C11—C12	−178.3 (5)	C7—C6—N2—C4	172.0 (5)
C10—C11—C12—C7	2.5 (8)	C3—C4—N2—C6	−132.2 (6)
C8—C7—C12—C11	−1.9 (8)	C5—C4—N2—C6	49.2 (8)
C6—C7—C12—C11	−177.1 (5)	O2—C13—N3—C15	12.9 (8)
C11—C10—C13—O2	30.4 (8)	C10—C13—N3—C15	−166.0 (5)
C9—C10—C13—O2	−145.0 (6)	C16—C15—N3—C13	−37.8 (8)
C11—C10—C13—N3	−150.7 (5)	C14—C15—N3—C13	141.0 (5)
C9—C10—C13—N3	33.9 (7)	C15—C14—N4—C18	1.5 (9)
N4—C14—C15—C16	−0.6 (9)	C17—C18—N4—C14	−1.2 (9)
N4—C14—C15—N3	−179.5 (5)	C20—C19—N5—C23	0.6 (9)
C14—C15—C16—C17	−0.5 (9)	C20—C19—N5—Hg1	179.3 (5)
N3—C15—C16—C17	178.3 (6)	C22—C23—N5—C19	0.7 (9)
C15—C16—C17—C18	0.7 (10)	C22—C23—N5—Hg1	−178.0 (4)
C16—C17—C18—N4	0.2 (11)	N1—Hg1—N5—C19	−110.9 (5)
N5—C19—C20—C21	−1.3 (10)	I2—Hg1—N5—C19	−13.4 (5)
C19—C20—C21—C22	0.7 (9)	I1—Hg1—N5—C19	149.0 (5)
C20—C21—C22—C23	0.5 (8)	N1—Hg1—N5—C23	67.8 (5)
C20—C21—C22—N6	−177.4 (5)	I2—Hg1—N5—C23	165.3 (4)
C21—C22—C23—N5	−1.2 (9)	I1—Hg1—N5—C23	−32.4 (5)
N6—C22—C23—N5	176.8 (5)	O3—C24—N6—C22	−3.0 (9)
O3—C24—C25—C27	−145.8 (6)	C25—C24—N6—C22	177.3 (5)
N6—C24—C25—C27	33.8 (7)	C23—C22—N6—C24	151.7 (5)
O3—C24—C25—C26	31.6 (8)	C21—C22—N6—C24	−30.3 (8)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I2	0.93	3.31	3.967 (7)	129
C5—H5···I1	0.93	3.31	3.971 (6)	130
C17—H17···I1^ii	0.93	3.25	3.946 (6)	134
C21—H21···O3	0.93	2.44	2.905 (7)	111
C23—H23···I1	0.93	3.32	3.921 (5)	125
N2—H2M···N4^ii	0.86 (1)	2.15 (2)	2.989 (7)	166 (6)
N3—H3M···O3^i	0.86 (1)	2.19 (2)	3.008 (6)	158 (5)
N6—H6M···O1	0.86 (1)	2.15 (2)	2.969 (6)	159 (5)

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