The structures of three Hg₂X₄L₂ macrocycles {X = Cl, Br and I, and L = 1,2-bis­[4-(pyridin-3-yl)phen­oxy]ethane} assembled from ether-bridged dipyridyl ligands

The new ether-bridged dipyridyl ligand 1,2-bis­[4-(pyridin-3-yl)phen­oxy]ethane (L) has been used to synthesize three isostructural centrosymmetric binuclear Hg^II macrocycles, namely bis­{μ-1,2-bis­[4-(pyridin-3-yl)phen­oxy]ethane-κ²N:N′}­bis­[dichloridomercury(II)], [Hg₂Cl₄(C₂₄H₂₀N₂O₂)₂], and the bromido, [Hg₂Br₄(C₂₄H₂₀N₂O₂)₂], and iodido, [Hg₂I₄(C₂₄H₂₀N₂O₂)₂], analogues. The Hg atoms adopt a highly distorted tetra­hedral coordination environment consisting of two halides and two pyridine N-donor atoms from two bridging ligands. In the solid state, the macrocycles form two-dimensional sheets in the bc plane through noncovalent Hg...X and X...X (X = Cl, Br and I) inter­actions.

S1. Comment

Numerous supramolecular compounds designed and constructed through crystal engineering have attracted significant attention because of their fascinating structural topologies (Chae et al., 2001) and functional applications (Wang et al., 2011). It is well known that the selection of appropriate ligands as building blocks is a key point in the design and synthesis of functional supramolecular compounds. Compared with rigid ligands, flexible ligands can adopt different conformations under varying conditions resulting in potentially novel topologies (Chuang et al., 2010). N-donor ligands, such as those containing pyridyl groups, are good candidates for the assembly of versatile structures (Fujita et al., 2007). Recently, our group has reported several compounds generated from flexible ether-bridged ligands containing dicyanomethylene groups (Dong et al., 2007), carboxylic acid groups (Jiang et al., 2009) and terminal indoline-2,3-dione groups (Fang et al., 2011) and terminal imidazole groups (Yuan et al., 2011). There are few reports on flexible ether-bridged dipyridyl ligands. In order to investigate further the influence of factors such as the terminal groups of the ligand and the coordinated metal ions on the topologies and properties of supramolecular compounds, we studied the design and synthesis of a new flexible ether-bridged dipyridyl ligand 1,2-bis[4-(pyridin-3-yl)phenoxy]ethane (L). Three new macrocycles have been synthesized based on L and the inorganic salts HgX₂ (X = Cl, Br and I), viz. [Hg₂Cl₄L₂], (I), [Hg₂Br₄L₂], (II), and [Hg₂I₄L₂], (III). The X-ray crystal structures show that they are isostructural. We report the intermolecular interactions in the lattices of the three compounds.

The three isostructural compounds crystallize in the triclinic space group P1. The unit cells have been chosen in a similar fashion in order to facilitate the structural comparison. The unit cell of (III) became nonstandard (cell setting I, but b > c > a). As shown in Fig. 1, each compound contains macrocycles comprised of two ligands bridging two HgX₂ moieties. The Hg^II centre lies in a highly distorted tetrahedral coordination environment defined by two N-atom donors from two pyridine ligands and two coordinated X^- (X = Cl, Br and I). The corresponding metal–ligand interatomic bond distances and the bond angles exhibit some differences in (I), (II) and (III) (Tables 1–3), but are comparable to those of reported related Hg^II complexes (Masciocchi et al., 2009). The diameters of the cavities in the middle of the macrocycles are 3.269 (7), 3.811 (7) and 2.770 (6) Å for the Cl, Br and I derivatives, respectively.

The flexible L ligand can adopt different conformations under different conditions. In our previous study, the flexible ether-bridged organic ligand with terminal indoline-2,3-dione groups adopts a trans conformation about its central core in the free state, but a gauche conformation after coordinating to the Ag^I centre (Fang et al., 2011). Here in (I), the O1—C12—C13—O2 torsion angle of the central ether group is 108.5 (1)° (Fig. 1a). In (II), the torsion angle has changed to 109.9 (1)° (Fig. 1b), and in (III), the corresponding torsion angle is 77.9 (7)° (Fig. 1c). The sign of the torsion angle in (III) is opposite to that in (I) and (II), indicating a difference of some 150° between these torsion angles in the structures, so the ethylene bridge is oriented quite differently in (III) to the corresponding bridges in (I) and (II), as can be seen in Fig. 1. Additionally, the dihedral angle between the terminal N1-pyridine plane and the adjacent C6-benzene plane is 24.7 (2)° in (I) and 21.2 (2)° in (II). In contrast, the terminal N2-pyridine plane and the adjacent C17-benzene plane are nearly coplanar, with a dihedral angle of 9.8 (3)° in (I) and 6.8 (2)° in (II). In (III), the dihedral angles of the relative pyridine rings and benzene rings are 15.0 (2) and 18.5 (2)°.

In the solid state, as shown in Fig. 2, compounds (I)–(III) have the same packing motif. Herein, the representative structure of (I) is described in detail. As shown in Fig. 3, the one-dimensional Hg—Cl chains are formed along the [021] direction through noncovalent Hg···Cl interactions [Hg1···Cl2ⁱⁱ; symmetry code: (ii) -x+1, -y-1 -z+2]. If three different Cl···Cl interactions [Cl2···Cl1ⁱⁱ, Cl2···Cl2ⁱⁱ and Cl1···Cl1ⁱⁱⁱ; symmetry code: ((iii) -x+1, -y, -z+2] are taken into consideration, a network parallel to the bc plane if formed. Fig. 4 shows the chains of Hg—Br moieties in (II) and the chains of Hg—I moieties in (III) with noncovalent interactions emphasized. The important noncovalent interactions in (I)–(III) are compared in Table 4. These two-dimensional sheets driven by noncovalent Hg···X and X···X (X = Cl, Br and I) interactions are both arranged in an ···AA··· parallel fashion in the a direction. The Hg—X distances, in the range 3.369 (2)–3.9819 (9) Å, are shorter than their van der Waals contact distances, the X···X distances are all beyond the sums of van der Waals radii (van der Waals radii: Hg = 2.15 Å, Cl = 1.80 Å, Br = 1.95 Å and I = 2.15 Å; Batsanov, 2001). Weak Cl···Cl interactions as long as 3.72 Å, which is longer than the van der Waals contact of 3.60 Å, have been reported for hexachlorobenzene (Sarma & Desiraju, 1986). The X···X (X = Cl, Br and I) distances in (I), (II) and (III) are a little longer than the sums of the van der Waals radii. The Hg—X and the weak X···X interactions are important for assisting in the lattice formation.

In summary, three macrocycles have been synthesized based on the flexible ether-bridged dipyridyl ligand. We anticipate this approach may be useful in constructing novel supramolecular compounds with the flexible ether-bridged dipyridyl ligand.

Related literature

For related literature, see: Batsanov (2001); Chae et al. (2001); Chuang et al. (2010); Dong et al. (2007); Fang et al. (2011); Fujita et al. (2007); Jiang et al. (2009); Masciocchi et al. (2009); Sarma, Jagarlapudi & Desiraju (1986); Wang et al. (2011); Yuan et al. (2011).

S2. Experimental

For the preparation of 1,2-bis[4-(pyridin-3-yl)phenoxy]ethane (L), sodium hydroxide (0.44 g, 11 mmol) was added with stirring to a solution of 1,2-bis(p-tolylsulfonyl)ethane (1.85 g, 5 mmol) and 4-(pyridin-3-yl)phenol (1.71 g, 10 mmol) in anhydrous N,N-dimethylformamide (50 ml). The mixture was stirred for 24 h at 358 K, and monitored by thin-layer chromatography (TLC). After removal of the solvent, the compound was purified by column chromatography using silica gel and CH₂Cl₂–MeOH (20:1 v/v) to afford L as a white crystalline solid (yield 1.54 g, 4.18 mmol, 83.7%). Elemental analysis calculated for C₂₄H₂₀N₂O₂: C 78.24, H 5.47, N 7.60%; found: C 78.17, H 5.38, N 7.73%.

For the preparation of (I), a solution of HgCl₂(5.97 mg, 0.022 mmol) in methanol (8 ml) was layered onto a solution of L (8.10 mg, 0.022 mmol) in CH₂Cl₂ (8 ml). The system was left for about 1 week at room temperature and colourless crystals of (I) were obtained (yield 11.11 mg, 79%). IR (KBr pellet, cm^-1): 3417(m), 3128 (m), 2925 (w), 2873 (w), 1605 (s), 1580 (w), 1515 (s), 1476 (s), 1452 (m), 1435 (m), 1399 (s), 1315 (w), 1282 (s), 1246 (s), 1200 (w), 1181 (s), 1131 (w), 1072 (m), 1026 (w), 1002 (w), 944 (m), 840 (m), 802 (s), 738 (w), 698 (m), 646 (w), 632 (m), 556 (m), 490 (w).

For the preparation of (II), a solution of HgBr₂ (7.93 mg, 0.022 mmol) in methanol (8 ml) was layered onto a solution of L (8.10 mg, 0.022 mmol) in CH₂Cl₂ (8 ml). The system was left for about 1 week at room temperature and colourless crystals of (II) were obtained (yield 10.10 mg, 63%). IR (KBr pellet, cm^-1): 3415 (m), 3128 (m), 2925 (w), 2873 (w), 1605 (s), 1516 (s), 1476 (s), 1452 (m), 1436 (m), 1400 (s), 1282 (s), 1246 (s), 1181 (s), 1130 (w), 1072 (m), 1026 (w), 1001 (w), 944 (m), 837 (m), 802 (s), 738 (w), 698 (m), 646 (w), 632( m), 555 (m).

For the preparation of (III), a solution of HgI₂ (10.00 mg, 0.022 mmol) in methanol (7 ml) was layered onto a solution of L (8.10 mg, 0.022 mmol) in CH₂Cl₂ (7 ml). The system was left for about 1 week at room temperature and colourless crystals of (III) were obtained (yield 10.67 mg, 59%). IR (KBr pellet, cm^-1): 3417 (m), 3128 (m), 2919 (w), 1605 (s), 1517 (s), 1475 (s), 1450 (m), 1436 (m), 1399 (s), 1313 (w), 1280 (s), 1246 (s), 1180 (s), 1130 (w), 1073 (m), 1024 (w), 1001 (w), 950 (s), 836 (s), 801 (s), 738 (w), 700 (m), 646 (w), 630 (m), 553 (m).

S3. Refinement

H atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) (aromatic) and C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) (methylene). Atoms O1, O2, C12 and C13 in (I) are statistically disordered because of the rotation about the C—O bond, Attempts to model the disorder were not successful. The ratio of the disorder part is less than 20%; the minor component is not included in the refinement. In the C6–C11 benzene ring of (III), the bond lengths except for the C6—C11 bond range from 1.358 to 1.378 Å; a restraint of 1.37 (1) Å was applied to the longer C6—C11 bond to keep the rationality of the ring. As a result, the C6—C11 bond length is 1.388 Å.

Computing details

For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (a) (I), (b) (II) and (c) (III), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry code: (i) -x+1, -y+1, -z+1.]
	Fig. 2. The packing feature of compound (I). H atoms have been omitted for clarity.
	Fig. 3. The two-dimensional sheet parallel to the bc plane and the ···AA··· parallel fashion of the two-dimensional sheet in the a direction. The one-dimensional Hg—Cl chains are formed along the b direction through noncovalent Hg···Cl interactions (Hg1···Cl2^ii) and three different Cl···Cl interactions (Cl2···Cl1^ii, Cl2···Cl2^ii and Cl1···Cl1^iii). H atoms have been omitted for clarity. [Symmetry codes: (ii) -x+1, -y-1, -z+2; (iii) -x+1, -y, -z+2.]
	Fig. 4. The Hg—X fragments and the chains formed by Hg···X and X···X interactions in (II) and (III) analogous to those shown in Fig. 3. [Symmetry codes: (ii) -x+1, -y-1, -z+2; (iii) -x+1, -y, -z+2.]

(I) bis{µ-1,2-bis[4-(pyridin-3-yl)phenoxy]ethane- κ²N:N'}bis[dichloridomercury(II)]

Crystal data

[Hg2Cl4(C24H20N2O2)2]	Z = 1
Mr = 1279.82	F(000) = 616
Triclinic, P1	Dx = 1.927 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7822 (15) Å	Cell parameters from 3326 reflections
b = 10.6904 (18) Å	θ = 2.4–26.0°
c = 12.044 (2) Å	µ = 7.25 mm^−1
α = 86.662 (2)°	T = 298 K
β = 78.930 (2)°	Block, colourless
γ = 84.014 (2)°	0.20 × 0.15 × 0.15 mm
V = 1102.8 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4066 independent reflections
Radiation source: fine-focus sealed tube	3708 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕand ω scans	θmax = 25.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.325, Tmax = 0.410	k = −9→12
5867 measured reflections	l = −14→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0783P)^2 + 0.1498P] where P = (Fo^2 + 2Fc^2)/3
4066 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 1.99 e Å^−3
0 restraints	Δρmin = −1.68 e Å^−3

Special details

Experimental. Spectroscopic data for (I): IR (KBr pellet, cm^-1): 3453 (s), 2948 (w), 2931 (w), 1635 (s), 1610 (s), 1517 (s), 1474 (s), 1454 (s), 1428 (w), 1384 (s), 1338 (w), 1311 (w), 1283 (m), 1243 (s), 1180 (m), 1116 (w), 1102 (w), 1079 (s), 1069 (s), 997 (m), 938 (m), 841 (s), 801 (s), 713 (s), 629 (s), 554 (m), 512 (w); ¹H NMR (300 MHz, DMSO, 25°, TMS): δ 8.85 (s, 1H, -C₅H₄N), 8.51 (d, 1H, -C₅H₄N), 8.03 (d, 1H, -C₅H₄N), 7.46 (t, 1H, -C₅H₄N), 7.46-7.11 (aabb, 4H, -C₆H₄-), 4.40 (s, 2H, -CH₂-).

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
C1	0.5273 (11)	−0.4072 (9)	0.7328 (7)	0.066 (2)
H1	0.4942	−0.4835	0.7643	0.080*
C2	0.6001 (12)	−0.4014 (9)	0.6195 (7)	0.073 (2)
H2	0.6212	−0.4736	0.5775	0.087*
C3	0.6396 (10)	−0.2886 (8)	0.5718 (6)	0.059 (2)
H3	0.6825	−0.2827	0.4951	0.071*
C4	0.6170 (7)	−0.1811 (7)	0.6356 (6)	0.0447 (15)
C5	0.5488 (8)	−0.2015 (7)	0.7505 (6)	0.0464 (16)
H5	0.5350	−0.1330	0.7969	0.056*
C6	0.6608 (7)	−0.0570 (7)	0.5892 (5)	0.0434 (15)
C7	0.7768 (9)	−0.0447 (7)	0.4944 (6)	0.0544 (18)
H7	0.8263	−0.1170	0.4590	0.065*
C8	0.8210 (9)	0.0695 (8)	0.4512 (6)	0.0559 (19)
H8	0.8995	0.0736	0.3874	0.067*
C9	0.7507 (9)	0.1790 (7)	0.5010 (6)	0.0498 (16)
C10	0.6316 (9)	0.1695 (7)	0.5935 (6)	0.0565 (19)
H10	0.5803	0.2422	0.6270	0.068*
C11	0.5879 (9)	0.0545 (7)	0.6368 (6)	0.0518 (17)
H11	0.5077	0.0508	0.6994	0.062*
C12	0.9080 (14)	0.3037 (9)	0.3653 (8)	0.087 (3)
H12A	0.8650	0.2888	0.2994	0.105*
H12B	0.9932	0.2394	0.3703	0.105*
C13	0.9697 (13)	0.4351 (13)	0.3523 (11)	0.096 (3)
H13A	0.9947	0.4580	0.4231	0.115*
H13B	1.0629	0.4355	0.2941	0.115*
C14	0.8966 (10)	0.6362 (8)	0.2860 (7)	0.058 (2)
C15	1.0303 (10)	0.6899 (9)	0.2961 (7)	0.066 (2)
H15	1.1053	0.6450	0.3317	0.079*
C16	1.0509 (8)	0.8119 (8)	0.2524 (7)	0.0565 (19)
H16	1.1410	0.8470	0.2594	0.068*
C17	0.9437 (7)	0.8829 (6)	0.1992 (5)	0.0394 (14)
C18	0.8096 (8)	0.8235 (7)	0.1906 (6)	0.0479 (16)
H18	0.7342	0.8674	0.1549	0.057*
C19	0.7872 (9)	0.7043 (8)	0.2330 (7)	0.0557 (18)
H19	0.6974	0.6688	0.2260	0.067*
C20	0.9645 (7)	1.0120 (6)	0.1525 (5)	0.0381 (14)
C21	1.1045 (8)	1.0660 (7)	0.1440 (6)	0.0473 (16)
H21	1.1892	1.0198	0.1674	0.057*
C22	1.1176 (8)	1.1862 (8)	0.1015 (6)	0.0523 (17)
H22	1.2109	1.2221	0.0958	0.063*
C23	0.9917 (7)	1.2540 (7)	0.0671 (6)	0.0452 (15)
H23	1.0009	1.3363	0.0390	0.054*
C24	0.8465 (7)	1.0885 (7)	0.1143 (6)	0.0419 (14)
H24	0.7518	1.0552	0.1182	0.050*
Cl1	0.4617 (2)	−0.1547 (2)	1.0667 (2)	0.0679 (6)
Cl2	0.2783 (2)	−0.52263 (19)	1.0097 (2)	0.0712 (6)
Hg1	0.36668 (3)	−0.32236 (2)	0.99358 (2)	0.04437 (13)
N1	0.5032 (7)	−0.3086 (6)	0.7976 (5)	0.0481 (14)
N2	0.8577 (6)	1.2051 (5)	0.0729 (5)	0.0424 (12)
O1	0.7901 (7)	0.2962 (5)	0.4652 (4)	0.0649 (15)
O2	0.8583 (10)	0.5138 (7)	0.3240 (6)	0.099 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.080 (6)	0.056 (5)	0.063 (5)	−0.027 (4)	−0.006 (4)	0.010 (4)
C2	0.106 (7)	0.051 (5)	0.058 (5)	−0.017 (5)	0.002 (5)	−0.013 (4)
C3	0.076 (5)	0.055 (5)	0.042 (4)	−0.015 (4)	0.002 (3)	−0.003 (3)
C4	0.041 (3)	0.051 (4)	0.042 (3)	−0.005 (3)	−0.006 (3)	−0.004 (3)
C5	0.050 (4)	0.043 (4)	0.046 (4)	−0.005 (3)	−0.008 (3)	−0.002 (3)
C6	0.042 (3)	0.052 (4)	0.037 (3)	−0.007 (3)	−0.009 (3)	0.005 (3)
C7	0.066 (4)	0.044 (4)	0.045 (4)	0.000 (3)	0.008 (3)	−0.001 (3)
C8	0.065 (4)	0.051 (5)	0.044 (4)	−0.012 (4)	0.010 (3)	0.004 (3)
C9	0.068 (4)	0.046 (4)	0.037 (3)	−0.012 (3)	−0.011 (3)	0.007 (3)
C10	0.070 (5)	0.039 (4)	0.055 (4)	0.002 (4)	0.000 (4)	−0.005 (3)
C11	0.055 (4)	0.049 (5)	0.048 (4)	−0.008 (3)	0.001 (3)	0.000 (3)
C12	0.137 (9)	0.044 (5)	0.068 (6)	−0.021 (6)	0.018 (6)	0.006 (4)
C13	0.082 (7)	0.106 (10)	0.099 (8)	−0.021 (7)	−0.017 (6)	0.012 (7)
C14	0.074 (5)	0.039 (4)	0.053 (4)	−0.004 (4)	0.006 (4)	0.004 (3)
C15	0.066 (5)	0.057 (5)	0.069 (5)	0.004 (4)	−0.015 (4)	0.021 (4)
C16	0.043 (4)	0.053 (5)	0.071 (5)	−0.002 (3)	−0.012 (3)	0.013 (4)
C17	0.041 (3)	0.038 (4)	0.036 (3)	0.002 (3)	−0.003 (2)	−0.001 (3)
C18	0.050 (4)	0.045 (4)	0.048 (4)	−0.011 (3)	−0.008 (3)	0.004 (3)
C19	0.056 (4)	0.049 (5)	0.061 (4)	−0.016 (4)	−0.004 (3)	0.001 (4)
C20	0.037 (3)	0.042 (4)	0.033 (3)	−0.003 (3)	−0.002 (2)	−0.003 (3)
C21	0.037 (3)	0.053 (5)	0.052 (4)	−0.004 (3)	−0.009 (3)	0.001 (3)
C22	0.040 (3)	0.054 (5)	0.063 (4)	−0.011 (3)	−0.011 (3)	0.006 (4)
C23	0.047 (4)	0.042 (4)	0.048 (4)	−0.009 (3)	−0.010 (3)	0.006 (3)
C24	0.032 (3)	0.044 (4)	0.049 (3)	−0.008 (3)	−0.005 (3)	0.002 (3)
Cl1	0.0470 (9)	0.0656 (14)	0.0960 (15)	−0.0068 (9)	−0.0162 (9)	−0.0325 (12)
Cl2	0.0617 (11)	0.0361 (11)	0.1196 (18)	−0.0200 (9)	−0.0248 (12)	0.0203 (11)
Hg1	0.04736 (18)	0.03537 (19)	0.05181 (19)	−0.01233 (12)	−0.01111 (12)	0.00770 (12)
N1	0.054 (3)	0.044 (4)	0.045 (3)	−0.015 (3)	−0.005 (3)	0.007 (3)
N2	0.040 (3)	0.038 (3)	0.048 (3)	−0.010 (2)	−0.006 (2)	0.005 (2)
O1	0.103 (4)	0.042 (3)	0.047 (3)	−0.019 (3)	−0.002 (3)	0.001 (2)
O2	0.117 (6)	0.071 (5)	0.083 (5)	0.019 (4)	0.016 (4)	0.035 (4)

Geometric parameters (Å, º)

C1—N1	1.322 (11)	C13—H13B	0.9700
C1—C2	1.392 (12)	C14—C19	1.377 (12)
C1—H1	0.9300	C14—C15	1.388 (12)
C2—C3	1.355 (12)	C14—O2	1.414 (11)
C2—H2	0.9300	C15—C16	1.395 (12)
C3—C4	1.395 (11)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.378 (10)
C4—C5	1.413 (10)	C16—H16	0.9300
C4—C6	1.469 (10)	C17—C18	1.418 (9)
C5—N1	1.314 (9)	C17—C20	1.475 (10)
C5—H5	0.9300	C18—C19	1.364 (11)
C6—C7	1.387 (9)	C18—H18	0.9300
C6—C11	1.392 (10)	C19—H19	0.9300
C7—C8	1.364 (11)	C20—C24	1.384 (9)
C7—H7	0.9300	C20—C21	1.396 (9)
C8—C9	1.378 (11)	C21—C22	1.362 (11)
C8—H8	0.9300	C21—H21	0.9300
C9—O1	1.358 (9)	C22—C23	1.376 (10)
C9—C10	1.381 (11)	C22—H22	0.9300
C10—C11	1.370 (11)	C23—N2	1.326 (8)
C10—H10	0.9300	C23—H23	0.9300
C11—H11	0.9300	C24—N2	1.322 (9)
C12—O1	1.433 (10)	C24—H24	0.9300
C12—C13	1.547 (15)	Cl1—Hg1	2.337 (2)
C12—H12A	0.9700	Cl2—Hg1	2.338 (2)
C12—H12B	0.9700	Hg1—N1	2.438 (6)
C13—O2	1.306 (13)	Hg1—N2^i	2.463 (5)
C13—H13A	0.9700	N2—Hg1^i	2.463 (5)
N1—C1—C2	122.8 (8)	C19—C14—O2	114.0 (8)
N1—C1—H1	118.6	C15—C14—O2	126.6 (8)
C2—C1—H1	118.6	C14—C15—C16	119.2 (7)
C3—C2—C1	118.6 (8)	C14—C15—H15	120.4
C3—C2—H2	120.7	C16—C15—H15	120.4
C1—C2—H2	120.7	C17—C16—C15	123.0 (8)
C2—C3—C4	121.3 (7)	C17—C16—H16	118.5
C2—C3—H3	119.4	C15—C16—H16	118.5
C4—C3—H3	119.4	C16—C17—C18	115.6 (7)
C3—C4—C5	114.2 (7)	C16—C17—C20	123.4 (6)
C3—C4—C6	123.7 (6)	C18—C17—C20	121.0 (6)
C5—C4—C6	122.1 (6)	C19—C18—C17	122.3 (7)
N1—C5—C4	125.7 (7)	C19—C18—H18	118.8
N1—C5—H5	117.2	C17—C18—H18	118.8
C4—C5—H5	117.2	C18—C19—C14	120.5 (7)
C7—C6—C11	116.3 (7)	C18—C19—H19	119.8
C7—C6—C4	121.5 (6)	C14—C19—H19	119.8
C11—C6—C4	122.2 (6)	C24—C20—C21	115.1 (6)
C8—C7—C6	122.4 (7)	C24—C20—C17	122.5 (6)
C8—C7—H7	118.8	C21—C20—C17	122.4 (6)
C6—C7—H7	118.8	C22—C21—C20	120.3 (6)
C7—C8—C9	120.7 (7)	C22—C21—H21	119.8
C7—C8—H8	119.7	C20—C21—H21	119.8
C9—C8—H8	119.7	C21—C22—C23	119.5 (7)
O1—C9—C8	124.5 (7)	C21—C22—H22	120.3
O1—C9—C10	117.5 (7)	C23—C22—H22	120.3
C8—C9—C10	118.0 (7)	N2—C23—C22	121.7 (7)
C11—C10—C9	121.1 (7)	N2—C23—H23	119.1
C11—C10—H10	119.5	C22—C23—H23	119.1
C9—C10—H10	119.5	N2—C24—C20	125.2 (6)
C10—C11—C6	121.5 (7)	N2—C24—H24	117.4
C10—C11—H11	119.2	C20—C24—H24	117.4
C6—C11—H11	119.2	Cl1—Hg1—Cl2	152.25 (10)
O1—C12—C13	110.2 (8)	Cl1—Hg1—N1	100.05 (16)
O1—C12—H12A	109.6	Cl2—Hg1—N1	103.08 (16)
C13—C12—H12A	109.6	Cl1—Hg1—N2^i	98.41 (14)
O1—C12—H12B	109.6	Cl2—Hg1—N2^i	98.11 (14)
C13—C12—H12B	109.6	N1—Hg1—N2^i	86.50 (19)
H12A—C12—H12B	108.1	C5—N1—C1	117.4 (6)
O2—C13—C12	106.3 (10)	C5—N1—Hg1	121.2 (5)
O2—C13—H13A	110.5	C1—N1—Hg1	121.3 (5)
C12—C13—H13A	110.5	C24—N2—C23	118.1 (6)
O2—C13—H13B	110.5	C24—N2—Hg1^i	119.5 (4)
C12—C13—H13B	110.5	C23—N2—Hg1^i	122.3 (5)
H13A—C13—H13B	108.7	C9—O1—C12	116.2 (6)
C19—C14—C15	119.5 (8)	C13—O2—C14	117.0 (10)
N1—C1—C2—C3	−4.1 (15)	C16—C17—C20—C24	−170.3 (6)
C1—C2—C3—C4	3.9 (15)	C18—C17—C20—C24	10.3 (9)
C2—C3—C4—C5	−0.9 (12)	C16—C17—C20—C21	9.4 (10)
C2—C3—C4—C6	178.5 (8)	C18—C17—C20—C21	−170.0 (6)
C3—C4—C5—N1	−2.2 (11)	C24—C20—C21—C22	0.5 (9)
C6—C4—C5—N1	178.3 (7)	C17—C20—C21—C22	−179.2 (6)
C3—C4—C6—C7	−24.7 (11)	C20—C21—C22—C23	0.0 (11)
C5—C4—C6—C7	154.7 (7)	C21—C22—C23—N2	−0.8 (11)
C3—C4—C6—C11	154.7 (7)	C21—C20—C24—N2	−0.5 (9)
C5—C4—C6—C11	−25.9 (10)	C17—C20—C24—N2	179.2 (6)
C11—C6—C7—C8	1.7 (11)	C4—C5—N1—C1	2.2 (11)
C4—C6—C7—C8	−178.9 (7)	C4—C5—N1—Hg1	−174.5 (5)
C6—C7—C8—C9	−0.1 (13)	C2—C1—N1—C5	1.1 (13)
C7—C8—C9—O1	178.3 (8)	C2—C1—N1—Hg1	177.8 (7)
C7—C8—C9—C10	−1.8 (12)	Cl1—Hg1—N1—C5	−26.4 (5)
O1—C9—C10—C11	−178.1 (7)	Cl2—Hg1—N1—C5	169.1 (5)
C8—C9—C10—C11	2.0 (12)	N2^i—Hg1—N1—C5	71.6 (5)
C9—C10—C11—C6	−0.3 (12)	Cl1—Hg1—N1—C1	157.1 (6)
C7—C6—C11—C10	−1.5 (11)	Cl2—Hg1—N1—C1	−7.5 (6)
C4—C6—C11—C10	179.1 (7)	N2^i—Hg1—N1—C1	−105.0 (6)
O1—C12—C13—O2	−71.5 (12)	C20—C24—N2—C23	−0.2 (10)
C19—C14—C15—C16	0.1 (12)	C20—C24—N2—Hg1^i	178.8 (5)
O2—C14—C15—C16	179.1 (8)	C22—C23—N2—C24	0.9 (10)
C14—C15—C16—C17	0.2 (13)	C22—C23—N2—Hg1^i	−178.1 (5)
C15—C16—C17—C18	−0.4 (11)	C8—C9—O1—C12	3.2 (12)
C15—C16—C17—C20	−179.9 (7)	C10—C9—O1—C12	−176.7 (8)
C16—C17—C18—C19	0.5 (10)	C13—C12—O1—C9	−165.7 (8)
C20—C17—C18—C19	180.0 (6)	C12—C13—O2—C14	−168.2 (8)
C17—C18—C19—C14	−0.3 (11)	C19—C14—O2—C13	165.6 (9)
C15—C14—C19—C18	0.0 (11)	C15—C14—O2—C13	−13.5 (14)
O2—C14—C19—C18	−179.1 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) bis{µ-1,2-bis[4-(pyridin-3-yl)phenoxy]ethane- κ²N:N'}bis[dibromidomercury(II)]

Crystal data

[Hg2Br4(C24H20N2O2)2]	Z = 1
Mr = 1457.66	F(000) = 688
Triclinic, P1	Dx = 2.106 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.021 (4) Å	Cell parameters from 2261 reflections
b = 11.096 (4) Å	θ = 2.3–23.2°
c = 11.914 (5) Å	µ = 10.20 mm^−1
α = 81.812 (5)°	T = 298 K
β = 78.764 (5)°	Block, colourless
γ = 81.635 (5)°	0.15 × 0.14 × 0.13 mm
V = 1149.1 (8) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4234 independent reflections
Radiation source: fine-focus sealed tube	3491 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 25.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→9
Tmin = 0.310, Tmax = 0.351	k = −13→7
6112 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0448P)^2 + 0.1447P] where P = (Fo^2 + 2Fc^2)/3
4234 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 1.19 e Å^−3
0 restraints	Δρmin = −1.04 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
Br1	0.46032 (8)	−0.16667 (8)	1.06539 (8)	0.0674 (2)
Br2	0.25820 (11)	−0.52762 (8)	1.02646 (10)	0.0853 (3)
C1	0.4994 (10)	−0.3976 (8)	0.7275 (8)	0.080 (3)
H1	0.4598	−0.4703	0.7590	0.095*
C2	0.5734 (12)	−0.3894 (9)	0.6154 (8)	0.088 (3)
H2	0.5876	−0.4555	0.5728	0.105*
C3	0.6271 (11)	−0.2775 (9)	0.5671 (7)	0.079 (3)
H3	0.6766	−0.2681	0.4908	0.095*
C4	0.6066 (7)	−0.1812 (7)	0.6325 (6)	0.0527 (17)
C5	0.5342 (8)	−0.2045 (7)	0.7467 (6)	0.0540 (17)
H5	0.5224	−0.1422	0.7935	0.065*
C6	0.6596 (8)	−0.0593 (7)	0.5874 (6)	0.0516 (17)
C7	0.7724 (9)	−0.0468 (7)	0.4912 (6)	0.063 (2)
H7	0.8144	−0.1155	0.4543	0.076*
C8	0.8246 (9)	0.0643 (8)	0.4482 (6)	0.068 (2)
H8	0.9004	0.0698	0.3831	0.082*
C9	0.7647 (8)	0.1669 (7)	0.5013 (6)	0.0555 (18)
C10	0.6499 (9)	0.1575 (8)	0.5974 (6)	0.063 (2)
H10	0.6076	0.2262	0.6343	0.075*
C11	0.5987 (8)	0.0439 (7)	0.6380 (6)	0.0586 (19)
H11	0.5207	0.0383	0.7016	0.070*
C12	0.9231 (10)	0.2928 (7)	0.3664 (7)	0.074 (2)
H12A	0.8797	0.2843	0.3000	0.089*
H12B	1.0077	0.2287	0.3718	0.089*
C13	0.9791 (10)	0.4190 (8)	0.3523 (8)	0.084 (3)
H13A	1.0066	0.4339	0.4235	0.101*
H13B	1.0677	0.4235	0.2916	0.101*
C14	0.8920 (8)	0.6250 (8)	0.2874 (6)	0.061 (2)
C15	1.0254 (9)	0.6680 (8)	0.2959 (7)	0.068 (2)
H15	1.1008	0.6165	0.3283	0.082*
C16	1.0450 (8)	0.7904 (8)	0.2547 (7)	0.065 (2)
H16	1.1337	0.8198	0.2621	0.078*
C17	0.9381 (7)	0.8686 (6)	0.2037 (5)	0.0466 (16)
C18	0.8060 (8)	0.8216 (7)	0.1966 (7)	0.0589 (19)
H18	0.7306	0.8722	0.1633	0.071*
C19	0.7842 (8)	0.7028 (7)	0.2373 (7)	0.0609 (19)
H19	0.6946	0.6742	0.2309	0.073*
C20	0.9624 (7)	0.9977 (6)	0.1582 (5)	0.0420 (15)
C21	1.0991 (8)	1.0437 (7)	0.1515 (7)	0.0598 (19)
H21	1.1804	0.9932	0.1773	0.072*
C22	1.1160 (8)	1.1646 (7)	0.1064 (7)	0.062 (2)
H22	1.2079	1.1953	0.1016	0.074*
C23	0.9955 (8)	1.2374 (7)	0.0694 (6)	0.0563 (18)
H23	1.0065	1.3186	0.0403	0.068*
C24	0.8515 (8)	1.0791 (7)	0.1161 (6)	0.0531 (17)
H24	0.7593	1.0504	0.1170	0.064*
Hg1	0.35219 (3)	−0.32686 (2)	0.99462 (2)	0.05355 (13)
N1	0.4807 (7)	−0.3094 (6)	0.7936 (5)	0.0601 (15)
N2	0.8637 (6)	1.1967 (5)	0.0734 (5)	0.0515 (14)
O1	0.8105 (6)	0.2816 (5)	0.4685 (4)	0.0705 (15)
O2	0.8578 (6)	0.5059 (5)	0.3240 (5)	0.0792 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0517 (4)	0.0724 (5)	0.0860 (6)	−0.0108 (4)	−0.0146 (4)	−0.0296 (5)
Br2	0.0754 (5)	0.0491 (5)	0.1318 (9)	−0.0217 (4)	−0.0170 (5)	0.0004 (5)
C1	0.095 (7)	0.067 (5)	0.084 (7)	−0.038 (5)	−0.011 (5)	−0.008 (5)
C2	0.118 (8)	0.082 (6)	0.072 (6)	−0.040 (6)	−0.002 (5)	−0.028 (5)
C3	0.094 (6)	0.095 (7)	0.051 (5)	−0.021 (6)	−0.002 (4)	−0.020 (5)
C4	0.044 (4)	0.061 (5)	0.054 (4)	−0.005 (3)	−0.010 (3)	−0.011 (4)
C5	0.056 (4)	0.058 (4)	0.048 (4)	−0.010 (4)	−0.004 (3)	−0.008 (4)
C6	0.049 (4)	0.062 (5)	0.045 (4)	−0.008 (3)	−0.012 (3)	−0.004 (3)
C7	0.074 (5)	0.063 (5)	0.043 (4)	0.001 (4)	0.008 (3)	−0.014 (4)
C8	0.072 (5)	0.084 (6)	0.039 (4)	−0.011 (5)	0.014 (3)	−0.003 (4)
C9	0.059 (4)	0.069 (5)	0.036 (4)	−0.007 (4)	−0.005 (3)	−0.002 (4)
C10	0.069 (5)	0.068 (5)	0.048 (4)	−0.008 (4)	−0.001 (4)	−0.011 (4)
C11	0.054 (4)	0.072 (5)	0.047 (4)	−0.016 (4)	0.005 (3)	−0.007 (4)
C12	0.092 (6)	0.061 (5)	0.056 (5)	−0.004 (5)	0.007 (4)	0.003 (4)
C13	0.077 (6)	0.088 (7)	0.074 (6)	−0.004 (5)	−0.005 (5)	0.021 (5)
C14	0.056 (4)	0.076 (5)	0.046 (4)	−0.005 (4)	0.001 (3)	−0.003 (4)
C15	0.058 (5)	0.071 (5)	0.068 (5)	−0.003 (4)	−0.016 (4)	0.018 (4)
C16	0.047 (4)	0.083 (6)	0.064 (5)	−0.009 (4)	−0.017 (3)	0.005 (4)
C17	0.037 (3)	0.060 (4)	0.041 (4)	0.002 (3)	−0.002 (3)	−0.015 (3)
C18	0.050 (4)	0.055 (4)	0.075 (5)	−0.002 (4)	−0.018 (4)	−0.013 (4)
C19	0.057 (4)	0.065 (5)	0.065 (5)	−0.014 (4)	−0.019 (4)	−0.005 (4)
C20	0.038 (3)	0.056 (4)	0.033 (3)	−0.006 (3)	−0.003 (3)	−0.014 (3)
C21	0.037 (4)	0.069 (5)	0.073 (5)	0.003 (3)	−0.009 (3)	−0.015 (4)
C22	0.038 (4)	0.069 (5)	0.082 (6)	−0.005 (4)	−0.015 (4)	−0.015 (4)
C23	0.046 (4)	0.054 (4)	0.068 (5)	−0.011 (3)	−0.001 (3)	−0.010 (4)
C24	0.044 (4)	0.061 (5)	0.058 (4)	−0.013 (3)	−0.013 (3)	−0.007 (4)
Hg1	0.05616 (19)	0.04413 (18)	0.0619 (2)	−0.01459 (13)	−0.01151 (13)	−0.00151 (13)
N1	0.065 (4)	0.060 (4)	0.056 (4)	−0.017 (3)	−0.011 (3)	−0.003 (3)
N2	0.045 (3)	0.056 (4)	0.054 (4)	−0.010 (3)	−0.006 (3)	−0.007 (3)
O1	0.086 (4)	0.069 (4)	0.050 (3)	−0.017 (3)	0.001 (3)	0.004 (3)
O2	0.073 (4)	0.069 (4)	0.085 (4)	−0.010 (3)	−0.009 (3)	0.021 (3)

Geometric parameters (Å, º)

C1—N1	1.314 (10)	C13—H13B	0.9700
C1—C2	1.369 (13)	C14—C19	1.373 (10)
C1—H1	0.9300	C14—C15	1.384 (10)
C2—C3	1.404 (12)	C14—O2	1.390 (9)
C2—H2	0.9300	C15—C16	1.401 (11)
C3—C4	1.380 (11)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.374 (9)
C4—C5	1.396 (10)	C16—H16	0.9300
C4—C6	1.492 (10)	C17—C18	1.390 (9)
C5—N1	1.331 (9)	C17—C20	1.489 (9)
C5—H5	0.9300	C18—C19	1.366 (10)
C6—C11	1.364 (10)	C18—H18	0.9300
C6—C7	1.382 (10)	C19—H19	0.9300
C7—C8	1.378 (11)	C20—C24	1.369 (9)
C7—H7	0.9300	C20—C21	1.385 (9)
C8—C9	1.371 (10)	C21—C22	1.391 (10)
C8—H8	0.9300	C21—H21	0.9300
C9—O1	1.376 (9)	C22—C23	1.363 (10)
C9—C10	1.389 (10)	C22—H22	0.9300
C10—C11	1.394 (10)	C23—N2	1.322 (8)
C10—H10	0.9300	C23—H23	0.9300
C11—H11	0.9300	C24—N2	1.343 (9)
C12—O1	1.428 (9)	C24—H24	0.9300
C12—C13	1.533 (12)	Br1—Hg1	2.4644 (10)
C12—H12A	0.9700	Br2—Hg1	2.4512 (12)
C12—H12B	0.9700	Hg1—N1	2.443 (6)
C13—O2	1.410 (9)	Hg1—N2^i	2.449 (5)
C13—H13A	0.9700	N2—Hg1^i	2.449 (5)
N1—C1—C2	124.3 (8)	C19—C14—O2	115.9 (7)
N1—C1—H1	117.9	C15—C14—O2	125.0 (7)
C2—C1—H1	117.9	C14—C15—C16	118.9 (7)
C1—C2—C3	117.5 (8)	C14—C15—H15	120.6
C1—C2—H2	121.3	C16—C15—H15	120.6
C3—C2—H2	121.3	C17—C16—C15	122.4 (7)
C4—C3—C2	120.2 (8)	C17—C16—H16	118.8
C4—C3—H3	119.9	C15—C16—H16	118.8
C2—C3—H3	119.9	C16—C17—C18	116.9 (7)
C3—C4—C5	115.8 (7)	C16—C17—C20	121.6 (6)
C3—C4—C6	123.5 (7)	C18—C17—C20	121.5 (6)
C5—C4—C6	120.7 (6)	C19—C18—C17	121.6 (7)
N1—C5—C4	124.8 (7)	C19—C18—H18	119.2
N1—C5—H5	117.6	C17—C18—H18	119.2
C4—C5—H5	117.6	C18—C19—C14	121.2 (7)
C11—C6—C7	117.3 (7)	C18—C19—H19	119.4
C11—C6—C4	121.9 (6)	C14—C19—H19	119.4
C7—C6—C4	120.8 (7)	C24—C20—C21	114.9 (6)
C8—C7—C6	122.1 (7)	C24—C20—C17	121.9 (6)
C8—C7—H7	119.0	C21—C20—C17	123.2 (6)
C6—C7—H7	119.0	C20—C21—C22	120.6 (7)
C9—C8—C7	120.0 (7)	C20—C21—H21	119.7
C9—C8—H8	120.0	C22—C21—H21	119.7
C7—C8—H8	120.0	C23—C22—C21	118.9 (7)
C8—C9—O1	125.3 (6)	C23—C22—H22	120.5
C8—C9—C10	119.2 (7)	C21—C22—H22	120.5
O1—C9—C10	115.5 (7)	N2—C23—C22	122.3 (7)
C9—C10—C11	119.3 (7)	N2—C23—H23	118.8
C9—C10—H10	120.4	C22—C23—H23	118.8
C11—C10—H10	120.4	N2—C24—C20	125.9 (6)
C6—C11—C10	122.1 (7)	N2—C24—H24	117.1
C6—C11—H11	119.0	C20—C24—H24	117.1
C10—C11—H11	119.0	Br1—Hg1—Br2	150.17 (4)
O1—C12—C13	108.9 (7)	Br1—Hg1—N1	100.18 (15)
O1—C12—H12A	109.9	Br2—Hg1—N1	104.22 (15)
C13—C12—H12A	109.9	N2^i—Hg1—Br1	97.82 (14)
O1—C12—H12B	109.9	N2^i—Hg1—Br2	100.51 (14)
C13—C12—H12B	109.9	N1—Hg1—N2^i	86.53 (19)
H12A—C12—H12B	108.3	C1—N1—C5	117.3 (7)
O2—C13—C12	106.5 (7)	C1—N1—Hg1	123.8 (5)
O2—C13—H13A	110.4	C5—N1—Hg1	118.9 (5)
C12—C13—H13A	110.4	C23—N2—C24	117.4 (6)
O2—C13—H13B	110.4	C23—N2—Hg1^i	122.4 (5)
C12—C13—H13B	110.4	C24—N2—Hg1^i	120.2 (4)
H13A—C13—H13B	108.6	C9—O1—C12	115.5 (6)
C19—C14—C15	119.0 (7)	C14—O2—C13	116.2 (6)
N1—C1—C2—C3	−2.7 (16)	C16—C17—C20—C24	−174.5 (7)
C1—C2—C3—C4	0.9 (14)	C18—C17—C20—C24	5.5 (10)
C2—C3—C4—C5	1.4 (12)	C16—C17—C20—C21	7.9 (10)
C2—C3—C4—C6	−179.7 (8)	C18—C17—C20—C21	−172.2 (7)
C3—C4—C5—N1	−2.4 (11)	C24—C20—C21—C22	1.1 (10)
C6—C4—C5—N1	178.7 (6)	C17—C20—C21—C22	178.9 (7)
C3—C4—C6—C11	158.8 (8)	C20—C21—C22—C23	0.2 (12)
C5—C4—C6—C11	−22.3 (10)	C21—C22—C23—N2	−0.9 (12)
C3—C4—C6—C7	−20.7 (11)	C21—C20—C24—N2	−2.0 (10)
C5—C4—C6—C7	158.2 (7)	C17—C20—C24—N2	−179.9 (6)
C11—C6—C7—C8	1.1 (12)	C2—C1—N1—C5	1.8 (14)
C4—C6—C7—C8	−179.4 (7)	C2—C1—N1—Hg1	−178.9 (8)
C6—C7—C8—C9	0.2 (13)	C4—C5—N1—C1	0.8 (11)
C7—C8—C9—O1	178.0 (7)	C4—C5—N1—Hg1	−178.5 (5)
C7—C8—C9—C10	−0.9 (12)	N2^i—Hg1—N1—C1	−104.7 (7)
C8—C9—C10—C11	0.3 (11)	Br2—Hg1—N1—C1	−4.7 (7)
O1—C9—C10—C11	−178.7 (7)	Br1—Hg1—N1—C1	158.0 (6)
C7—C6—C11—C10	−1.7 (11)	N2^i—Hg1—N1—C5	74.6 (5)
C4—C6—C11—C10	178.8 (7)	Br2—Hg1—N1—C5	174.5 (5)
C9—C10—C11—C6	1.1 (12)	Br1—Hg1—N1—C5	−22.8 (5)
O1—C12—C13—O2	−70.1 (9)	C22—C23—N2—C24	0.1 (10)
C19—C14—C15—C16	1.1 (12)	C22—C23—N2—Hg1^i	−179.4 (6)
O2—C14—C15—C16	179.6 (7)	C20—C24—N2—C23	1.5 (10)
C14—C15—C16—C17	−1.6 (12)	C20—C24—N2—Hg1^i	−179.0 (5)
C15—C16—C17—C18	1.3 (11)	C8—C9—O1—C12	4.1 (11)
C15—C16—C17—C20	−178.7 (7)	C10—C9—O1—C12	−177.0 (7)
C16—C17—C18—C19	−0.7 (11)	C13—C12—O1—C9	−171.3 (6)
C20—C17—C18—C19	179.4 (7)	C19—C14—O2—C13	166.8 (7)
C17—C18—C19—C14	0.3 (12)	C15—C14—O2—C13	−11.8 (11)
C15—C14—C19—C18	−0.5 (12)	C12—C13—O2—C14	−169.1 (7)
O2—C14—C19—C18	−179.1 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

(III) bis{µ-1,2-bis[4-(pyridin-3-yl)phenoxy]ethane- κ²N:N'}bis[iodidomercury(II)]

Crystal data

[Hg2I4(C24H20N2O2)2]	Z = 1
Mr = 1645.62	F(000) = 760
Triclinic, P1	Dx = 2.252 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9444 (16) Å	Cell parameters from 3275 reflections
b = 12.352 (2) Å	θ = 2.4–27.0°
c = 12.052 (2) Å	µ = 8.91 mm^−1
α = 72.641 (2)°	T = 298 K
β = 74.882 (2)°	Block, colourless
γ = 77.620 (2)°	0.20 × 0.15 × 0.15 mm
V = 1213.3 (4) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4426 independent reflections
Radiation source: fine-focus sealed tube	3740 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.269, Tmax = 0.348	k = −14→14
6387 measured reflections	l = −12→14

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0445P)^2] where P = (Fo^2 + 2Fc^2)/3
4426 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 1.11 e Å^−3
1 restraint	Δρmin = −1.10 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
C1	0.5421 (7)	−0.3617 (6)	0.7284 (6)	0.0512 (15)
H1	0.5164	−0.4354	0.7611	0.061*
C2	0.6406 (9)	−0.3372 (6)	0.6195 (7)	0.065 (2)
H2	0.6806	−0.3936	0.5784	0.079*
C3	0.6801 (8)	−0.2287 (6)	0.5709 (7)	0.065 (2)
H3	0.7487	−0.2123	0.4974	0.078*
C4	0.6187 (6)	−0.1437 (5)	0.6303 (5)	0.0406 (13)
C5	0.5236 (7)	−0.1789 (5)	0.7401 (5)	0.0481 (15)
H5	0.4844	−0.1253	0.7846	0.058*
C6	0.6549 (6)	−0.0249 (5)	0.5844 (5)	0.0405 (13)
C7	0.7775 (7)	0.0037 (6)	0.4901 (6)	0.0534 (16)
H7	0.8399	−0.0537	0.4562	0.064*
C8	0.8113 (8)	0.1142 (6)	0.4440 (6)	0.0560 (17)
H8	0.8942	0.1306	0.3795	0.067*
C9	0.7217 (7)	0.1999 (5)	0.4939 (5)	0.0432 (14)
C10	0.6013 (7)	0.1732 (6)	0.5879 (6)	0.0523 (16)
H10	0.5412	0.2305	0.6228	0.063*
C11	0.5664 (7)	0.0638 (5)	0.6322 (6)	0.0532 (16)
H11	0.4818	0.0486	0.6956	0.064*
C12	0.8457 (8)	0.3461 (6)	0.3417 (6)	0.0526 (16)
H12A	0.8244	0.3121	0.2856	0.063*
H12B	0.9538	0.3193	0.3487	0.063*
C13	0.8204 (8)	0.4731 (6)	0.2980 (6)	0.0553 (16)
H13A	0.8616	0.4955	0.2129	0.066*
H13B	0.7092	0.5018	0.3130	0.066*
C14	0.9126 (7)	0.6343 (5)	0.3114 (5)	0.0425 (14)
C15	1.0155 (7)	0.6758 (5)	0.3514 (6)	0.0491 (15)
H15	1.0703	0.6270	0.4076	0.059*
C16	1.0365 (7)	0.7884 (5)	0.3084 (5)	0.0447 (14)
H16	1.1066	0.8143	0.3360	0.054*
C17	0.9571 (6)	0.8658 (5)	0.2248 (5)	0.0365 (12)
C18	0.8547 (7)	0.8219 (5)	0.1869 (5)	0.0440 (14)
H18	0.7997	0.8707	0.1309	0.053*
C19	0.8311 (7)	0.7097 (6)	0.2285 (6)	0.0508 (16)
H19	0.7605	0.6839	0.2012	0.061*
C20	0.9810 (6)	0.9871 (5)	0.1800 (5)	0.0373 (13)
C21	1.1090 (6)	1.0272 (5)	0.1905 (6)	0.0454 (14)
H21	1.1860	0.9765	0.2268	0.054*
C22	1.1218 (7)	1.1427 (6)	0.1467 (6)	0.0504 (16)
H22	1.2082	1.1694	0.1529	0.061*
C23	1.0089 (7)	1.2176 (5)	0.0946 (6)	0.0460 (14)
H23	1.0189	1.2950	0.0657	0.055*
C24	0.8729 (7)	1.0703 (5)	0.1249 (5)	0.0451 (14)
H24	0.7862	1.0462	0.1156	0.054*
Hg1	0.33105 (3)	−0.31840 (2)	0.99668 (2)	0.04913 (10)
I1	0.45290 (5)	−0.18407 (5)	1.07191 (5)	0.06595 (16)
I2	0.23304 (5)	−0.51441 (4)	1.03272 (5)	0.06082 (15)
N1	0.4828 (6)	−0.2833 (4)	0.7883 (5)	0.0491 (12)
N2	0.8836 (5)	1.1814 (4)	0.0843 (4)	0.0425 (11)
O1	0.7450 (5)	0.3123 (4)	0.4541 (4)	0.0538 (11)
O2	0.8984 (5)	0.5213 (4)	0.3581 (4)	0.0547 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.055 (4)	0.045 (4)	0.056 (4)	−0.014 (3)	−0.020 (3)	−0.006 (3)
C2	0.083 (5)	0.047 (4)	0.066 (5)	−0.008 (4)	−0.009 (4)	−0.020 (4)
C3	0.073 (5)	0.061 (5)	0.055 (4)	−0.014 (4)	0.007 (4)	−0.022 (4)
C4	0.038 (3)	0.040 (3)	0.046 (3)	−0.001 (2)	−0.018 (3)	−0.009 (3)
C5	0.047 (3)	0.046 (4)	0.045 (3)	−0.008 (3)	0.001 (3)	−0.010 (3)
C6	0.038 (3)	0.048 (4)	0.038 (3)	−0.005 (3)	−0.014 (3)	−0.009 (3)
C7	0.055 (4)	0.044 (4)	0.056 (4)	−0.004 (3)	0.002 (3)	−0.019 (3)
C8	0.050 (4)	0.053 (4)	0.055 (4)	−0.018 (3)	0.011 (3)	−0.011 (3)
C9	0.044 (3)	0.052 (4)	0.040 (3)	−0.010 (3)	−0.015 (3)	−0.013 (3)
C10	0.057 (4)	0.052 (4)	0.048 (4)	−0.005 (3)	−0.005 (3)	−0.021 (3)
C11	0.049 (4)	0.055 (4)	0.047 (4)	−0.008 (3)	0.005 (3)	−0.013 (3)
C12	0.063 (4)	0.056 (4)	0.043 (3)	−0.019 (3)	−0.004 (3)	−0.017 (3)
C13	0.067 (4)	0.057 (4)	0.048 (4)	−0.019 (3)	−0.020 (3)	−0.010 (3)
C14	0.044 (3)	0.044 (4)	0.044 (3)	−0.007 (3)	−0.012 (3)	−0.016 (3)
C15	0.053 (4)	0.048 (4)	0.052 (4)	−0.001 (3)	−0.026 (3)	−0.013 (3)
C16	0.039 (3)	0.049 (4)	0.051 (4)	−0.005 (3)	−0.020 (3)	−0.011 (3)
C17	0.031 (3)	0.040 (3)	0.037 (3)	−0.001 (2)	−0.004 (2)	−0.012 (2)
C18	0.047 (3)	0.039 (3)	0.049 (3)	−0.004 (3)	−0.022 (3)	−0.008 (3)
C19	0.052 (4)	0.052 (4)	0.060 (4)	−0.010 (3)	−0.030 (3)	−0.014 (3)
C20	0.030 (3)	0.047 (3)	0.035 (3)	0.000 (2)	−0.005 (2)	−0.016 (3)
C21	0.035 (3)	0.048 (4)	0.060 (4)	−0.003 (3)	−0.019 (3)	−0.018 (3)
C22	0.038 (3)	0.055 (4)	0.065 (4)	−0.009 (3)	−0.012 (3)	−0.022 (3)
C23	0.045 (3)	0.043 (4)	0.052 (4)	−0.010 (3)	−0.013 (3)	−0.011 (3)
C24	0.038 (3)	0.049 (4)	0.049 (3)	−0.009 (3)	−0.014 (3)	−0.007 (3)
Hg1	0.05209 (16)	0.04490 (16)	0.05199 (16)	−0.01471 (11)	−0.01592 (12)	−0.00525 (11)
I1	0.0506 (3)	0.0845 (4)	0.0802 (4)	−0.0097 (2)	−0.0164 (2)	−0.0450 (3)
I2	0.0608 (3)	0.0435 (3)	0.0802 (3)	−0.0167 (2)	−0.0315 (2)	0.0018 (2)
N1	0.048 (3)	0.045 (3)	0.053 (3)	−0.008 (2)	−0.011 (2)	−0.010 (3)
N2	0.036 (2)	0.039 (3)	0.051 (3)	−0.007 (2)	−0.010 (2)	−0.006 (2)
O1	0.066 (3)	0.046 (3)	0.052 (3)	−0.014 (2)	−0.005 (2)	−0.019 (2)
O2	0.073 (3)	0.049 (3)	0.051 (3)	−0.018 (2)	−0.026 (2)	−0.009 (2)

Geometric parameters (Å, º)

C1—N1	1.318 (7)	C13—H13B	0.9700
C1—C2	1.366 (10)	C14—O2	1.362 (7)
C1—H1	0.9300	C14—C15	1.387 (8)
C2—C3	1.375 (10)	C14—C19	1.390 (9)
C2—H2	0.9300	C15—C16	1.367 (9)
C3—C4	1.384 (8)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.393 (8)
C4—C5	1.375 (8)	C16—H16	0.9300
C4—C6	1.479 (8)	C17—C18	1.387 (8)
C5—N1	1.333 (8)	C17—C20	1.475 (8)
C5—H5	0.9300	C18—C19	1.367 (9)
C6—C7	1.378 (9)	C18—H18	0.9300
C6—C11	1.388 (6)	C19—H19	0.9300
C7—C8	1.378 (9)	C20—C21	1.388 (7)
C7—H7	0.9300	C20—C24	1.391 (8)
C8—C9	1.375 (8)	C21—C22	1.385 (9)
C8—H8	0.9300	C21—H21	0.9300
C9—C10	1.358 (8)	C22—C23	1.362 (9)
C9—O1	1.369 (7)	C22—H22	0.9300
C10—C11	1.368 (9)	C23—N2	1.338 (7)
C10—H10	0.9300	C23—H23	0.9300
C11—H11	0.9300	C24—N2	1.328 (7)
C12—O1	1.416 (7)	C24—H24	0.9300
C12—C13	1.485 (9)	I1—Hg1	2.6365 (6)
C12—H12A	0.9700	I2—Hg1	2.6272 (6)
C12—H12B	0.9700	Hg1—N1	2.482 (5)
C13—O2	1.437 (7)	Hg1—N2^i	2.471 (5)
C13—H13A	0.9700	N2—Hg1^i	2.471 (5)
N1—C1—C2	121.5 (6)	O2—C14—C19	124.8 (5)
N1—C1—H1	119.2	C15—C14—C19	118.6 (6)
C2—C1—H1	119.2	C16—C15—C14	120.1 (6)
C1—C2—C3	119.6 (6)	C16—C15—H15	120.0
C1—C2—H2	120.2	C14—C15—H15	120.0
C3—C2—H2	120.2	C15—C16—C17	122.6 (5)
C2—C3—C4	120.6 (7)	C15—C16—H16	118.7
C2—C3—H3	119.7	C17—C16—H16	118.7
C4—C3—H3	119.7	C18—C17—C16	115.9 (5)
C5—C4—C3	114.5 (6)	C18—C17—C20	122.3 (5)
C5—C4—C6	121.4 (5)	C16—C17—C20	121.7 (5)
C3—C4—C6	124.1 (6)	C19—C18—C17	122.8 (6)
N1—C5—C4	125.7 (6)	C19—C18—H18	118.6
N1—C5—H5	117.1	C17—C18—H18	118.6
C4—C5—H5	117.1	C18—C19—C14	120.0 (5)
C7—C6—C11	116.4 (6)	C18—C19—H19	120.0
C7—C6—C4	121.4 (5)	C14—C19—H19	120.0
C11—C6—C4	122.2 (5)	C21—C20—C24	115.2 (6)
C6—C7—C8	122.5 (5)	C21—C20—C17	123.5 (5)
C6—C7—H7	118.8	C24—C20—C17	121.3 (5)
C8—C7—H7	118.8	C22—C21—C20	119.8 (6)
C9—C8—C7	119.6 (6)	C22—C21—H21	120.1
C9—C8—H8	120.2	C20—C21—H21	120.1
C7—C8—H8	120.2	C23—C22—C21	120.5 (6)
C10—C9—O1	117.2 (5)	C23—C22—H22	119.8
C10—C9—C8	118.8 (6)	C21—C22—H22	119.8
O1—C9—C8	124.0 (6)	N2—C23—C22	120.9 (6)
C9—C10—C11	121.5 (6)	N2—C23—H23	119.6
C9—C10—H10	119.3	C22—C23—H23	119.6
C11—C10—H10	119.3	N2—C24—C20	125.1 (5)
C10—C11—C6	121.2 (6)	N2—C24—H24	117.4
C10—C11—H11	119.4	C20—C24—H24	117.4
C6—C11—H11	119.4	I1—Hg1—I2	149.69 (2)
O1—C12—C13	109.6 (5)	I1—Hg1—N1	98.91 (12)
O1—C12—H12A	109.8	I2—Hg1—N1	103.46 (12)
C13—C12—H12A	109.8	N2^i—Hg1—I1	100.74 (11)
O1—C12—H12B	109.8	N2^i—Hg1—I2	100.93 (11)
C13—C12—H12B	109.8	N2^i—Hg1—N1	86.14 (16)
H12A—C12—H12B	108.2	C1—N1—C5	117.9 (6)
O2—C13—C12	109.3 (5)	C1—N1—Hg1	125.7 (4)
O2—C13—H13A	109.8	C5—N1—Hg1	115.7 (4)
C12—C13—H13A	109.8	C24—N2—C23	118.5 (5)
O2—C13—H13B	109.8	C24—N2—Hg1^i	120.4 (4)
C12—C13—H13B	109.8	C23—N2—Hg1^i	121.1 (4)
H13A—C13—H13B	108.3	C9—O1—C12	117.6 (4)
O2—C14—C15	116.6 (5)	C14—O2—C13	116.1 (5)
N1—C1—C2—C3	0.5 (11)	C18—C17—C20—C21	−162.3 (5)
C1—C2—C3—C4	−1.3 (12)	C16—C17—C20—C21	17.8 (8)
C2—C3—C4—C5	2.5 (10)	C18—C17—C20—C24	18.6 (8)
C2—C3—C4—C6	−179.9 (7)	C16—C17—C20—C24	−161.3 (6)
C3—C4—C5—N1	−3.2 (9)	C24—C20—C21—C22	−0.3 (8)
C6—C4—C5—N1	179.1 (6)	C17—C20—C21—C22	−179.5 (5)
C5—C4—C6—C7	163.9 (6)	C20—C21—C22—C23	0.7 (9)
C3—C4—C6—C7	−13.6 (9)	C21—C22—C23—N2	−0.1 (9)
C5—C4—C6—C11	−17.2 (9)	C21—C20—C24—N2	−0.7 (9)
C3—C4—C6—C11	165.4 (7)	C17—C20—C24—N2	178.5 (5)
C11—C6—C7—C8	−0.5 (10)	C2—C1—N1—C5	−1.1 (9)
C4—C6—C7—C8	178.5 (6)	C2—C1—N1—Hg1	−171.6 (5)
C6—C7—C8—C9	0.9 (11)	C4—C5—N1—C1	2.6 (9)
C7—C8—C9—C10	−0.1 (10)	C4—C5—N1—Hg1	174.1 (5)
C7—C8—C9—O1	−179.5 (6)	N2^i—Hg1—N1—C1	−120.7 (5)
O1—C9—C10—C11	178.4 (6)	I2—Hg1—N1—C1	−20.4 (5)
C8—C9—C10—C11	−1.0 (10)	I1—Hg1—N1—C1	139.0 (5)
C9—C10—C11—C6	1.4 (10)	N2^i—Hg1—N1—C5	68.6 (4)
C7—C6—C11—C10	−0.6 (10)	I2—Hg1—N1—C5	168.9 (4)
C4—C6—C11—C10	−179.6 (6)	I1—Hg1—N1—C5	−31.7 (4)
O1—C12—C13—O2	77.9 (7)	C20—C24—N2—C23	1.3 (9)
O2—C14—C15—C16	179.8 (5)	C20—C24—N2—Hg1^i	−175.1 (4)
C19—C14—C15—C16	−0.8 (9)	C22—C23—N2—C24	−0.8 (9)
C14—C15—C16—C17	0.4 (10)	C22—C23—N2—Hg1^i	175.5 (4)
C15—C16—C17—C18	−0.2 (9)	C10—C9—O1—C12	−166.3 (6)
C15—C16—C17—C20	179.7 (5)	C8—C9—O1—C12	13.1 (9)
C16—C17—C18—C19	0.3 (9)	C13—C12—O1—C9	163.3 (5)
C20—C17—C18—C19	−179.6 (5)	C15—C14—O2—C13	−166.5 (5)
C17—C18—C19—C14	−0.6 (10)	C19—C14—O2—C13	14.1 (9)
O2—C14—C19—C18	−179.8 (6)	C12—C13—O2—C14	167.4 (5)
C15—C14—C19—C18	0.8 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.