Mercury(II) thiol­ate complexes of two flexible benzimidazole-based ligands

The structure of catena-poly[[{bis­[4-(trimethyl­ammonio)benzene­thiol­ate-κS]mercury(II)}-μ-1,1′-(ethane-1,2-di­yl)bis­(1H-benzimidazole)-κ²N³:N^3′] bis­(hexa­fluoridophosphate) 0.25-hydrate], {[Hg(C₁₆H₁₄N₄)(C₉H₁₃NS)₂](PF₆)₂·0.25H₂O}_n, contains a one-dimensional zigzag chain. The Hg^II cation is coordinated by two S atoms of two 4-(trimethyl­ammonio)­benzene­thiol­ate (Tab) ligands and by two N atoms from two different 1,1′-(ethane-1,2-di­yl)bis­(1H-benzimidazole) ligands, forming a distorted seesaw-shaped coordination geometry. The F atoms of the hexa­fluoridophosphate anion inter­act with the H atoms of the Tab ligand, generating a two-dimensional network. Furthermore, this layer is connected to neighbouring layers via H...π inter­actions, thereby forming a three-dimensional hydrogen-bonded structure. In catena-poly[[{[4-(trimethyl­ammonio)­benzene­thiol­ate-κS]mercury(II)}bis­[μ-4-(trimethyl­ammonio)­benzene­thiol­ate-κ²S:S]{[4-(trimethylammonio)­benzene­thiol­ate-κS]mercury(II)}-μ-1,1′-(hexane-1,6-di­yl)bis­(1H-benzimidazole)-κ²N³:N^3′] tetra­kis­(hexa­fluor­ido­phosphate)], {[Hg₂(C₂₀H₂₂N₄)(C₉H₁₃NS)₄](PF₆)₄}_n, each Hg^II cation is coordinated by two S atoms of two Tab ligands and one N atom of the 1,1′-(hexane-1,6-di­yl)bis­(1H-benzimidazole) (hbbm) ligand, forming a distorted T-shaped coordination geometry, while longer secondary Hg...S bonds join two such units across a centre of inversion to give the tetravalent cation. Adjacent {[Hg(Tab)₂]₂(μ-hbbm)}⁴⁺ cations are linked through the centrosymmetric hbbm ligands to afford a one-dimensional chain extending along the b axis. Several F atoms inter­act with the H atoms of the Tab and hbbm ligands, while the S atom inter­acts with an aromatic H atom of a different Tab ligand, to afford a complex intra- and inter­molecular hydrogen-bonding arrangement in a three-dimensional structure.

S1. Comment

In previous studies (Chen et al., 2006), we employed [Hg(Tab)₂](PF₆)₂ [Tab is 4-(trimethylammonio)benzenethiolate] as a potential model complex for mimicking the reactivity of unsaturated HgS₂ sites in the detoxification of mercury by metallothioneins (MTs) (Stillman et al., 1983; Cheesman et al., 1988; Fleischer et al., 2005; Baba et al., 2008; Vig et al., 2003), in DNA binding proteins (Patra & Goldberg, 2002; Henkel & Krebs, 2004), in mercury reductase and organomercury lyase (Bharara et al., 2005, 2006; Chan et al., 2002; Qian et al., 1998), and in metalloregulatory protein (MerR) (Moore et al., 1990; Ralston & O'Halloran, 1990; Gruff & Koch, 1990; Helmann et al., 1990; Govindaswamy et al., 1992). The chemistry of [Hg(Tab)₂](PF₆)₂ was analysed with some donor ligands (e.g. Tab, NCS^- and I^-), naturally encountered inorganic anions (e.g. Cl^-, NO₂^- and NO₃^-), organic amines and N-heterocyclic compounds (e.g. 1,2-diaminoethane, pyridine, 1,10-phenanthroline and N-methylimidazole) (Tang et al., 2009), and various carboxylic acids and amino acids (e.g. acetic, salicylic and oxalic acids) (Tang et al., 2011). However, most of these mercury thiolate compounds are monomeric and only a few are coordination polymers. As an extension of this work, we undertook reactions of [Hg(Tab)₂](PF₆)₂ with two bridging ligands, 1,1'-(ethane-1,2-diyl)bis(1H-benzimidazole) (ebbm) and 1,1'-(hexane-1,6-diyl)bis-(1H-benzimidazole) (hbbm), and the two title Hg–Tab coordination polymers, (I) and (II), were isolated therefrom. Here, we report the crystal structures of complexes (I) and (II).

The asymmetric unit of (I) contains an [Hg(Tab)₂(ebbm)]²⁺ dication (Fig. 1), two PF₆^- anions and a partial-occupancy (0.25) solvent water molecule. The Hg^II centre in this dication is coordinated by two S atoms from the Tab ligands and two N atoms from two different ebbm ligands, displaying a seesaw-shaped coordination geometry. Each [Hg(Tab)₂] unit is linked by a pair of ebbm ligands to form a one-dimensional zigzag chain extending along the c-axis direction (Fig. 2). Relative to the trans configuration of [Hg(Tab)₂](PF₆)₂, the two Tab ligands in (I) are oriented in the same direction, with a dihedral angle between the phenyl groups of 37.9 (3)°. The mean Hg—S bond length [2.3761 (17) Å; Table 1] is comparable with that in [Hg(Tab)₂(Ac)](PF₆).0.5H₂O [2.3752 (19) Å; Tang et al., 2011] but slightly longer than those in [Hg(Tab)₂](PF₆)₂ and [Hg(Tab)₂(phen)](PF₆)₂ [2.331 (3) and 2.344 (3) Å, respectively; Tang et al., 2009]. The average Hg—N bond length [2.543 (6) Å] is longer than those observed in [Hg(L)(SCN)₂] [2.421 (2) Å; L is 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene; Mahmoudi et al., 2007] and [HgI₂(L).1.5MeOH]_n [2.418 (7) Å; L is N,N'-bis(4-pyridyl)-1,4-benzenedicarboxamide; Li et al., 2005]. The S—Hg—S angle in (I) [160.72 (6)°] deviates significantly from the linear S—Hg—S angle of [Hg(Tab)₂](PF₆)₂. The N—Hg—N angle of 94.56 (18)° is comparable with that in [Hg(L)(SCN)₂]_n [93.76 (10)°; L is 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene; Mahmoudi et al., 2007].

In (I), the F atoms of the PF₆^- anions in one chain interact with the methyl H atoms of the Tab ligands in another chain to form four intramolecular hydrogen bonds [C8···F12, C9···F9, C17···F9 and C17···F4] and four intermolecular hydrogen bonds [C7···F10(x, -y + 1/2, z + 1/2), C9···F8(x, -y + 1/2, z + 1/2), C16···F2(-x + 2, y - 1/2, -z + 3/2) and C18···F12(-x + 2, y + 1/2, -z + 3/2)], affording a two-dimensional network (Table 2). Furthermore, this layer is connected to neighbouring ones via H···π interactions (H2A···Cg, where Cg is the centroid of the N5/C28/C33/N6/C34 ring), thereby forming a three-dimensional hydrogen-bonded network (Table 2).

The asymmetric unit of (II) comprisess half a {[Hg(Tab)₂]₂(µ-hbbm)}⁴⁺ tetracation and two PF₆^- anions. In the tetracation, two Hg(Tab)₂ units are bridged by one hbbm ligand via two Hg—N bonds (Fig. 3). There is a crystallographic inversion centre at the centre of the Hg1···Hg1ⁱ axis [symmetry code (i) -x + 2, -y + 1, -z + 1]. Each Hg^II cation is coordinated by two S atoms from two Tab ligands and one N atom from the hbbm ligand, displaying a distorted T-shaped coordination. Each tetracation is further connected via a secondary Hg···S interaction between the Hg^II center and the S atom of the Tab ligand of the adjacent one, forming a one-dimensional chain extending along the b-axis direction (Fig. 4). Therefore, the Hg^II centre in (II) may be viewed as having a pseudo-four-coordinated pinwheel-shaped geometry. Similar to (I), the two Tab ligands of (II) are also in a cis configuration, with a dihedral angle between the two Tab-ligand phenyl groups of 77.4 (3)°. The mean Hg—S bond length in (II) [2.3813 (16) Å] is slightly longer than that in (I), while the average Hg—N bond length [2.362 (14) Å] is much shorter than that observed in (I). The secondary Hg···S separation [3.1325 (16) Å] is intermediate between that observed in [Hg(Tab)₂(N-ⁱPrim)](PF₆)₂ [2.805 (5) Å; ⁱPrim is? Please define; Tang et al., 2009] and that in [Hg(SCH₂COOH)₂] [3.379 (3) Å; Bramlett et al., 2004]. The S—Hg—S angle [156.38 (6)°] is smaller than that of (I).

In (II), because the PF₆^- anions are located between the chains, several F atoms interact with the H atoms of the Tab and hbbm ligands to afford four intramolecular hydrogen bonds [C5···F7, C17···F12, C17···F12 and C17···F2] and three intermolecular hydrogen bonds [C8···F11(-x + 1, -y + 1, -z + 1), C17···F6(-x + 1, -y, -z + 1) and C26···F6(x + 1, y + 1, z + 1)]. In addition, the S atom of the Tab ligand interacts with a Tab-ligand H atom to form an intermolecular hydrogen bond [C3···S2(x + 1, y, z)]. These hydrogen-bonding interactions form a three-dimensional network (Table 3).

Related literature

For related literature, see: Baba et al. (2008); Bharara et al. (2005, 2006); Bramlett et al. (2004); Chan et al. (2002); Cheesman et al. (1988); Chen et al. (2006); Fleischer et al. (2005); Govindaswamy et al. (1992); Gruff & Koch (1990); Helmann et al. (1990); Henkel & Krebs (2004); Li et al. (2005); Mahmoudi et al. (2007); Moore et al. (1990); Patra & Goldberg (2002); Qian et al. (1998); Ralston & O'Halloran (1990); Stillman et al. (1983); Tang et al. (2009, 2011); Vig et al. (2003).

S2. Experimental

To a solution of [Hg(Tab)₂](PF₆)₂ (0.082 g, 0.1 mmol) in MeCN (5 ml) was added a solution of ebbm (0.013 g, 0.05 mmol) in MeOH (2 ml). The resulting mixture was stirred for 1 h to form a colourless solution and then filtered. Diethyl ether (20 ml) was layered onto the filtrate to form colourless prisms of [Hg(Tab)₂(ebbm)](PF₆)₂.0.25H₂O, (I), after several days. These were collected by filtration, washed with Et₂O and dried in vacuo (yield 0.092 g, 85.0% based on Hg). Analysis, found: C 37.32, H 3.70, N 7.58%; calculated for C₃₄H_40.5F₁₂HgN₆O_0.25P₂S₂: C 37.40, H 3.75, N 7.70%. IR (KBr, ν, cm^-1): 1615 (w), 1492 (m), 956 (m), 840 (s).

To a solution of [Hg(Tab)₂](PF₆)₂ (0.082 g, 0.1 mmol) in MeCN (5 ml) was added a solution of hbbm (0.016 g, 0.05 mmol) in MeOH (2 ml). The resulting mixture was stirred for 1 h to form a colourless solution and then filtered. Diethyl ether (20 ml) was layered onto the filtrate to form colourless prisms of {[Hg(Tab)₂]₂(µ-hbbm)}(PF₆)₄, (II), after several days. These were collected by filtration, washed with Et₂O and dried in vacuo (yield 0.044 g, 89.0% based on Hg). Analysis, found: C 34.45, H 3.72, N 5.43%; calculated for C₂₈H₃₇F₁₂HgN₄P₂S₂: C 34.17, H 3.80, N 5.69%. IR (KBr, ν, cm^-1): 1614 (w), 1490 (m), 958 (m), 837 (s).

S3. Refinement

For (I), the occupancy factor of a partial-occupancy solvent water molecule was fixed at 0.25. The two H atoms of this water molecule were not located. All other H atoms were placed in geometrically idealized positions, with C—H = 0.98 for methyl groups, 0.99 for methylene groups and 0.95 Å for phenyl groups, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for phenyl groups or U_iso(H) = 1.5U_eq(C) for methyl groups. [What was used for methylene groups?]

Computing details

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) x, -y + 3/2, z + 1/2.]
	Fig. 2. A view of a section of the one-dimensional chain of (I), extending along the c-axis direction.
	Fig. 3. The molecular structure of (II), with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 3, -y + 2, -z + 2.]
	Fig. 4. A view of a section of the one-dimensional chain in (II), extending along the b-axis direction, formed by secondary Hg···S interactions.

(I) catena-poly[[{bis[4-(trimethylammonio)benzenethiolate- κS]mercury(II)}-µ-1,1'-(ethane-1,2-diyl)bis(1H- benzimidazole)-κ²N³:N^3'] bis(hexafluoridophosphate) 0.25-hydrate

Crystal data

[Hg(C16H14N4)(C9H13NS)2](PF6)2·0.25H2O	F(000) = 2154
Mr = 1091.87	Dx = 1.797 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16698 reflections
a = 19.589 (4) Å	θ = 3.0–27.5°
b = 12.808 (3) Å	µ = 4.09 mm^−1
c = 16.207 (3) Å	T = 223 K
β = 97.14 (3)°	Chunk, colourless
V = 4034.9 (14) Å^3	0.30 × 0.15 × 0.10 mm
Z = 4

Data collection

Rigaku Mercury CCD area-detector diffractometer	9195 independent reflections
Radiation source: fine-focus sealed tube	7542 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −24→25
Tmin = 0.373, Tmax = 0.685	k = −16→15
22845 measured reflections	l = −21→16

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 9.2683P] where P = (Fo^2 + 2Fc^2)/3
9195 reflections	(Δ/σ)max = 0.001
523 parameters	Δρmax = 1.65 e Å^−3
0 restraints	Δρmin = −1.18 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	Occ. (<1)
Hg1	0.571852 (12)	0.457200 (17)	0.768166 (15)	0.03307 (9)
S1	0.55726 (9)	0.27444 (12)	0.75133 (10)	0.0363 (4)
S2	0.62578 (8)	0.62288 (12)	0.79261 (12)	0.0398 (4)
N1	0.8256 (3)	0.0435 (4)	0.8403 (3)	0.0402 (13)
N2	0.9281 (3)	0.5126 (5)	0.8394 (4)	0.0423 (13)
N3	0.4916 (3)	0.5149 (4)	0.6417 (3)	0.0373 (12)
N4	0.4615 (3)	0.6324 (4)	0.5418 (3)	0.0315 (11)
N5	0.4855 (3)	1.0079 (4)	0.3706 (3)	0.0369 (12)
N6	0.4324 (3)	0.8999 (4)	0.4505 (3)	0.0309 (11)
P1	0.90040 (10)	0.73258 (15)	0.59920 (13)	0.0467 (5)
P2	0.83318 (12)	0.22915 (18)	0.58846 (13)	0.0577 (5)
F1	0.8599 (4)	0.7376 (5)	0.6764 (4)	0.112 (2)
F2	0.8978 (3)	0.8563 (3)	0.5934 (4)	0.0816 (16)
F3	0.9393 (3)	0.7289 (5)	0.5202 (4)	0.111 (2)
F4	0.9028 (3)	0.6097 (4)	0.6059 (4)	0.0873 (17)
F5	0.8305 (3)	0.7263 (4)	0.5393 (4)	0.0817 (16)
F6	0.9708 (3)	0.7387 (5)	0.6564 (4)	0.111 (2)
F7	0.7715 (4)	0.2107 (9)	0.6370 (6)	0.177 (4)
F8	0.8943 (4)	0.2396 (6)	0.5355 (5)	0.130 (3)
F9	0.8802 (5)	0.2494 (6)	0.6703 (4)	0.146 (3)
F10	0.8208 (5)	0.3487 (5)	0.5785 (5)	0.155 (3)
F11	0.7843 (4)	0.2059 (8)	0.5085 (5)	0.165 (4)
F12	0.8510 (4)	0.1102 (5)	0.5980 (4)	0.116 (2)
C1	0.6381 (3)	0.2150 (5)	0.7815 (4)	0.0302 (13)
C2	0.6416 (3)	0.1079 (5)	0.7687 (4)	0.0369 (14)
H2A	0.6018	0.0723	0.7457	0.044*
C3	0.7018 (3)	0.0523 (4)	0.7889 (4)	0.0371 (15)
H3A	0.7027	−0.0205	0.7813	0.044*
C4	0.7612 (3)	0.1062 (5)	0.8206 (4)	0.0314 (13)
C5	0.7586 (3)	0.2101 (5)	0.8348 (4)	0.0444 (17)
H5A	0.7984	0.2458	0.8579	0.053*
C6	0.6973 (3)	0.2641 (5)	0.8154 (5)	0.0444 (17)
H6A	0.6962	0.3363	0.8257	0.053*
C7	0.8220 (4)	−0.0175 (7)	0.9184 (5)	0.068 (3)
H7A	0.8153	0.0298	0.9634	0.102*
H7B	0.8645	−0.0559	0.9324	0.102*
H7C	0.7838	−0.0661	0.9100	0.102*
C8	0.8361 (4)	−0.0308 (6)	0.7710 (5)	0.062 (2)
H8A	0.8387	0.0082	0.7202	0.093*
H8B	0.7979	−0.0793	0.7627	0.093*
H8C	0.8786	−0.0693	0.7855	0.093*
C9	0.8878 (4)	0.1103 (7)	0.8537 (6)	0.065 (2)
H9A	0.8914	0.1510	0.8040	0.098*
H9B	0.9282	0.0667	0.8657	0.098*
H9C	0.8843	0.1569	0.9002	0.098*
C10	0.7147 (3)	0.5899 (5)	0.8021 (4)	0.0363 (14)
C11	0.7417 (3)	0.5205 (6)	0.7500 (4)	0.0406 (16)
H11A	0.7124	0.4892	0.7066	0.049*
C12	0.8111 (3)	0.4958 (6)	0.7600 (4)	0.0411 (16)
H12A	0.8285	0.4467	0.7251	0.049*
C13	0.8535 (3)	0.5438 (5)	0.8214 (4)	0.0342 (14)
C14	0.8283 (4)	0.6151 (7)	0.8728 (5)	0.059 (2)
H14A	0.8580	0.6480	0.9149	0.071*
C15	0.7593 (4)	0.6383 (6)	0.8626 (5)	0.060 (2)
H15A	0.7422	0.6880	0.8974	0.072*
C16	0.9364 (4)	0.4455 (7)	0.9151 (5)	0.064 (2)
H16A	0.9078	0.3838	0.9053	0.096*
H16B	0.9226	0.4842	0.9617	0.096*
H16C	0.9842	0.4247	0.9275	0.096*
C17	0.9527 (4)	0.4530 (7)	0.7687 (5)	0.058 (2)
H17A	0.9245	0.3911	0.7572	0.087*
H17B	1.0003	0.4325	0.7839	0.087*
H17C	0.9491	0.4969	0.7196	0.087*
C18	0.9733 (4)	0.6074 (7)	0.8550 (6)	0.068 (2)
H18A	0.9588	0.6476	0.9004	0.103*
H18B	0.9696	0.6501	0.8052	0.103*
H18C	1.0207	0.5855	0.8693	0.103*
C19	0.4344 (3)	0.4785 (5)	0.5907 (4)	0.0302 (13)
C20	0.3982 (3)	0.3843 (5)	0.5943 (4)	0.0394 (15)
H20A	0.4105	0.3347	0.6363	0.047*
C21	0.3438 (4)	0.3681 (5)	0.5333 (5)	0.0472 (17)
H21A	0.3192	0.3050	0.5326	0.057*
C22	0.3243 (4)	0.4425 (6)	0.4728 (5)	0.0524 (19)
H22A	0.2862	0.4285	0.4331	0.063*
C23	0.3584 (4)	0.5362 (5)	0.4685 (4)	0.0413 (16)
H23A	0.3448	0.5864	0.4274	0.050*
C24	0.4144 (3)	0.5510 (4)	0.5294 (4)	0.0294 (12)
C25	0.5060 (3)	0.6046 (5)	0.6100 (4)	0.0348 (14)
H25A	0.5434	0.6462	0.6320	0.042*
C26	0.4696 (3)	0.7231 (4)	0.4900 (4)	0.0339 (14)
H26A	0.4631	0.7017	0.4315	0.041*
H26B	0.5166	0.7497	0.5027	0.041*
C27	0.4193 (3)	0.8102 (5)	0.5023 (4)	0.0370 (15)
H27A	0.3720	0.7854	0.4872	0.044*
H27B	0.4244	0.8310	0.5610	0.044*
C28	0.4216 (3)	1.0505 (4)	0.3836 (4)	0.0310 (13)
C29	0.3893 (4)	1.1427 (5)	0.3517 (4)	0.0416 (16)
H29A	0.4111	1.1885	0.3180	0.050*
C30	0.3251 (4)	1.1628 (5)	0.3718 (5)	0.0479 (18)
H30A	0.3021	1.2236	0.3513	0.057*
C31	0.2927 (4)	1.0959 (6)	0.4217 (5)	0.0482 (18)
H31A	0.2483	1.1130	0.4338	0.058*
C32	0.3229 (4)	1.0053 (5)	0.4544 (4)	0.0425 (16)
H32A	0.3006	0.9609	0.4888	0.051*
C33	0.3881 (3)	0.9833 (4)	0.4337 (4)	0.0311 (13)
C34	0.4888 (3)	0.9195 (5)	0.4121 (4)	0.0341 (14)
H34A	0.5267	0.8742	0.4150	0.041*
O1	0.9958 (13)	−0.088 (2)	0.9148 (18)	0.100 (11)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.03392 (14)	0.02958 (13)	0.03602 (14)	0.00245 (10)	0.00553 (10)	0.00140 (10)
S1	0.0377 (8)	0.0305 (8)	0.0404 (9)	0.0023 (7)	0.0032 (7)	−0.0024 (7)
S2	0.0315 (8)	0.0300 (8)	0.0573 (11)	0.0016 (7)	0.0031 (7)	0.0007 (8)
N1	0.037 (3)	0.042 (3)	0.042 (3)	0.012 (3)	0.007 (2)	0.003 (3)
N2	0.030 (3)	0.053 (3)	0.043 (3)	0.004 (3)	0.001 (2)	0.000 (3)
N3	0.041 (3)	0.032 (3)	0.040 (3)	0.003 (2)	0.007 (2)	0.005 (2)
N4	0.038 (3)	0.027 (2)	0.029 (3)	0.000 (2)	0.000 (2)	0.005 (2)
N5	0.039 (3)	0.028 (3)	0.043 (3)	−0.002 (2)	0.004 (3)	0.004 (2)
N6	0.034 (3)	0.028 (2)	0.033 (3)	−0.001 (2)	0.010 (2)	0.003 (2)
P1	0.0464 (11)	0.0402 (10)	0.0524 (11)	0.0005 (8)	0.0017 (9)	0.0041 (9)
P2	0.0656 (14)	0.0647 (13)	0.0434 (11)	0.0091 (11)	0.0094 (10)	0.0078 (10)
F1	0.158 (6)	0.107 (5)	0.083 (4)	0.006 (4)	0.061 (4)	−0.002 (4)
F2	0.074 (3)	0.039 (2)	0.128 (5)	−0.002 (2)	−0.003 (3)	0.007 (3)
F3	0.115 (5)	0.130 (5)	0.102 (5)	0.035 (4)	0.066 (4)	0.025 (4)
F4	0.114 (4)	0.044 (3)	0.099 (4)	0.008 (3)	−0.004 (4)	0.008 (3)
F5	0.069 (3)	0.071 (3)	0.097 (4)	−0.003 (3)	−0.024 (3)	−0.005 (3)
F6	0.078 (4)	0.090 (4)	0.145 (6)	0.004 (3)	−0.061 (4)	0.008 (4)
F7	0.133 (7)	0.266 (11)	0.150 (7)	0.026 (7)	0.096 (6)	0.043 (7)
F8	0.129 (6)	0.118 (5)	0.163 (7)	−0.012 (5)	0.089 (5)	0.005 (5)
F9	0.207 (8)	0.120 (6)	0.091 (5)	−0.045 (6)	−0.062 (5)	−0.016 (4)
F10	0.238 (10)	0.084 (5)	0.151 (7)	0.082 (6)	0.053 (7)	0.036 (5)
F11	0.149 (7)	0.237 (10)	0.092 (5)	−0.046 (7)	−0.051 (5)	0.041 (6)
F12	0.147 (6)	0.063 (4)	0.133 (6)	0.003 (4)	0.003 (5)	0.012 (4)
C1	0.033 (3)	0.034 (3)	0.024 (3)	−0.001 (3)	0.006 (2)	−0.004 (3)
C2	0.043 (4)	0.026 (3)	0.042 (4)	−0.003 (3)	0.006 (3)	−0.005 (3)
C3	0.046 (4)	0.020 (3)	0.046 (4)	0.004 (3)	0.009 (3)	0.000 (3)
C4	0.025 (3)	0.036 (3)	0.033 (3)	0.005 (3)	0.001 (2)	0.003 (3)
C5	0.036 (4)	0.044 (4)	0.051 (4)	0.002 (3)	−0.004 (3)	−0.016 (3)
C6	0.042 (4)	0.027 (3)	0.062 (5)	0.005 (3)	0.001 (3)	−0.011 (3)
C7	0.060 (5)	0.085 (6)	0.062 (5)	0.035 (5)	0.016 (4)	0.036 (5)
C8	0.054 (5)	0.067 (5)	0.065 (5)	0.024 (4)	0.011 (4)	−0.020 (4)
C9	0.042 (4)	0.062 (5)	0.094 (7)	0.006 (4)	0.016 (4)	0.008 (5)
C10	0.035 (3)	0.034 (3)	0.039 (4)	0.001 (3)	0.004 (3)	0.006 (3)
C11	0.030 (3)	0.056 (4)	0.034 (3)	−0.003 (3)	−0.002 (3)	−0.010 (3)
C12	0.038 (4)	0.050 (4)	0.035 (4)	0.004 (3)	0.004 (3)	−0.013 (3)
C13	0.023 (3)	0.042 (4)	0.037 (3)	0.002 (3)	0.002 (2)	−0.004 (3)
C14	0.041 (4)	0.078 (6)	0.053 (5)	0.002 (4)	−0.008 (3)	−0.036 (4)
C15	0.039 (4)	0.065 (5)	0.074 (6)	0.010 (4)	−0.004 (4)	−0.035 (4)
C16	0.050 (5)	0.091 (7)	0.050 (5)	0.018 (4)	−0.001 (4)	0.019 (5)
C17	0.041 (4)	0.077 (6)	0.057 (5)	0.019 (4)	0.008 (4)	−0.009 (4)
C18	0.038 (4)	0.067 (5)	0.099 (7)	−0.014 (4)	0.005 (4)	0.003 (5)
C19	0.031 (3)	0.032 (3)	0.028 (3)	0.002 (3)	0.006 (2)	0.002 (2)
C20	0.045 (4)	0.029 (3)	0.047 (4)	−0.001 (3)	0.015 (3)	0.005 (3)
C21	0.051 (4)	0.040 (4)	0.053 (4)	−0.015 (3)	0.018 (4)	−0.008 (3)
C22	0.047 (4)	0.063 (5)	0.046 (4)	−0.018 (4)	0.003 (3)	−0.012 (4)
C23	0.046 (4)	0.045 (4)	0.032 (3)	−0.004 (3)	0.000 (3)	0.005 (3)
C24	0.032 (3)	0.033 (3)	0.024 (3)	0.001 (3)	0.006 (2)	−0.005 (3)
C25	0.039 (3)	0.030 (3)	0.035 (3)	−0.001 (3)	0.005 (3)	0.003 (3)
C26	0.038 (3)	0.029 (3)	0.036 (3)	0.002 (3)	0.011 (3)	0.010 (3)
C27	0.041 (4)	0.036 (3)	0.037 (3)	0.004 (3)	0.018 (3)	0.011 (3)
C28	0.035 (3)	0.024 (3)	0.033 (3)	−0.002 (3)	0.001 (3)	−0.002 (3)
C29	0.051 (4)	0.033 (3)	0.040 (4)	−0.006 (3)	0.003 (3)	0.006 (3)
C30	0.055 (4)	0.031 (3)	0.056 (5)	0.013 (3)	0.001 (4)	0.002 (3)
C31	0.042 (4)	0.049 (4)	0.054 (5)	0.015 (3)	0.010 (3)	−0.001 (4)
C32	0.042 (4)	0.041 (4)	0.046 (4)	0.000 (3)	0.014 (3)	0.004 (3)
C33	0.035 (3)	0.026 (3)	0.033 (3)	0.000 (3)	0.007 (3)	0.002 (2)
C34	0.032 (3)	0.032 (3)	0.038 (3)	0.002 (3)	0.006 (3)	0.004 (3)
O1	0.069 (16)	0.12 (2)	0.13 (2)	0.055 (16)	0.061 (16)	0.098 (19)

Geometric parameters (Å, º)

Hg1—S1	2.3698 (16)	C8—H8B	0.9700
Hg1—S2	2.3816 (16)	C8—H8C	0.9700
Hg1—N3	2.533 (5)	C9—H9A	0.9700
Hg1—N5^i	2.554 (6)	C9—H9B	0.9700
S1—C1	1.770 (6)	C9—H9C	0.9700
S2—C10	1.781 (7)	C10—C15	1.376 (9)
N1—C4	1.496 (7)	C10—C11	1.376 (9)
N1—C7	1.496 (9)	C11—C12	1.384 (9)
N1—C8	1.507 (9)	C11—H11A	0.9400
N1—C9	1.482 (9)	C12—C13	1.361 (9)
N2—C13	1.508 (8)	C12—H12A	0.9400
N2—C16	1.491 (9)	C13—C14	1.369 (9)
N2—C17	1.504 (9)	C14—C15	1.374 (10)
N2—C18	1.506 (9)	C14—H14A	0.9400
N3—C19	1.388 (8)	C15—H15A	0.9400
N3—C25	1.304 (8)	C16—H16A	0.9700
N4—C24	1.389 (7)	C16—H16B	0.9700
N4—C25	1.367 (8)	C16—H16C	0.9700
N4—C26	1.454 (7)	C17—H17A	0.9700
N5—C34	1.314 (8)	C17—H17B	0.9700
N5—C28	1.404 (8)	C17—H17C	0.9700
N5—Hg1^ii	2.554 (6)	C18—H18A	0.9700
N6—C34	1.357 (8)	C18—H18B	0.9700
N6—C33	1.382 (7)	C18—H18C	0.9700
N6—C27	1.465 (7)	C19—C24	1.381 (8)
P1—F1	1.564 (6)	C19—C20	1.405 (8)
P1—F6	1.565 (5)	C20—C21	1.376 (10)
P1—F3	1.569 (6)	C20—H20A	0.9400
P1—F4	1.578 (5)	C21—C22	1.386 (10)
P1—F5	1.580 (5)	C21—H21A	0.9400
P1—F2	1.587 (5)	C22—C23	1.379 (9)
P2—F7	1.539 (7)	C22—H22A	0.9400
P2—F9	1.540 (6)	C23—C24	1.395 (9)
P2—F11	1.542 (7)	C23—H23A	0.9400
P2—F10	1.556 (7)	C25—H25A	0.9400
P2—F8	1.563 (7)	C26—C27	1.518 (8)
P2—F12	1.566 (6)	C26—H26A	0.9800
C1—C6	1.371 (9)	C26—H26B	0.9800
C1—C2	1.390 (8)	C27—H27A	0.9800
C2—C3	1.381 (9)	C27—H27B	0.9800
C2—H2A	0.9400	C28—C33	1.401 (8)
C3—C4	1.396 (9)	C28—C29	1.407 (8)
C3—H3A	0.9400	C29—C30	1.364 (10)
C4—C5	1.352 (9)	C29—H29A	0.9400
C5—C6	1.389 (9)	C30—C31	1.384 (10)
C5—H5A	0.9400	C30—H30A	0.9400
C6—H6A	0.9400	C31—C32	1.379 (10)
C7—H7A	0.9700	C31—H31A	0.9400
C7—H7B	0.9700	C32—C33	1.390 (9)
C7—H7C	0.9700	C32—H32A	0.9400
C8—H8A	0.9700	C34—H34A	0.9400
S1—Hg1—S2	160.72 (6)	H9A—C9—H9B	109.5
S1—Hg1—N3	98.10 (13)	N1—C9—H9C	109.5
S2—Hg1—N3	95.32 (13)	H9A—C9—H9C	109.5
S1—Hg1—N5^i	99.65 (12)	H9B—C9—H9C	109.5
S2—Hg1—N5^i	92.97 (12)	C15—C10—C11	118.0 (6)
N3—Hg1—N5^i	94.61 (17)	C15—C10—S2	118.8 (5)
C1—S1—Hg1	107.6 (2)	C11—C10—S2	123.1 (5)
C10—S2—Hg1	102.2 (2)	C10—C11—C12	121.4 (6)
C9—N1—C4	112.1 (5)	C10—C11—H11A	119.3
C9—N1—C7	107.6 (6)	C12—C11—H11A	119.3
C4—N1—C7	109.5 (5)	C13—C12—C11	119.0 (6)
C9—N1—C8	106.7 (6)	C13—C12—H12A	120.5
C4—N1—C8	111.7 (5)	C11—C12—H12A	120.5
C7—N1—C8	109.0 (6)	C12—C13—C14	120.8 (6)
C16—N2—C17	108.7 (6)	C12—C13—N2	120.7 (6)
C16—N2—C18	109.0 (6)	C14—C13—N2	118.3 (6)
C17—N2—C18	107.4 (6)	C13—C14—C15	119.7 (7)
C16—N2—C13	108.4 (5)	C13—C14—H14A	120.2
C17—N2—C13	112.5 (5)	C15—C14—H14A	120.2
C18—N2—C13	110.8 (6)	C14—C15—C10	121.1 (7)
C25—N3—C19	105.0 (5)	C14—C15—H15A	119.5
C25—N3—Hg1	115.7 (4)	C10—C15—H15A	119.5
C19—N3—Hg1	139.3 (4)	N2—C16—H16A	109.5
C25—N4—C24	105.5 (5)	N2—C16—H16B	109.5
C25—N4—C26	124.8 (5)	H16A—C16—H16B	109.5
C24—N4—C26	129.3 (5)	N2—C16—H16C	109.5
C34—N5—C28	104.3 (5)	H16A—C16—H16C	109.5
C34—N5—Hg1^ii	119.3 (4)	H16B—C16—H16C	109.5
C28—N5—Hg1^ii	134.7 (4)	N2—C17—H17A	109.5
C34—N6—C33	107.1 (5)	N2—C17—H17B	109.5
C34—N6—C27	128.3 (5)	H17A—C17—H17B	109.5
C33—N6—C27	124.7 (5)	N2—C17—H17C	109.5
F1—P1—F6	91.2 (4)	H17A—C17—H17C	109.5
F1—P1—F3	178.4 (4)	H17B—C17—H17C	109.5
F6—P1—F3	90.2 (4)	N2—C18—H18A	109.5
F1—P1—F4	90.0 (3)	N2—C18—H18B	109.5
F6—P1—F4	89.6 (3)	H18A—C18—H18B	109.5
F3—P1—F4	90.8 (4)	N2—C18—H18C	109.5
F1—P1—F5	90.3 (4)	H18A—C18—H18C	109.5
F6—P1—F5	178.4 (4)	H18B—C18—H18C	109.5
F3—P1—F5	88.2 (4)	C24—C19—N3	109.8 (5)
F4—P1—F5	90.4 (3)	C24—C19—C20	120.5 (6)
F1—P1—F2	89.4 (3)	N3—C19—C20	129.7 (6)
F6—P1—F2	90.2 (3)	C21—C20—C19	116.7 (6)
F3—P1—F2	89.8 (4)	C21—C20—H20A	121.6
F4—P1—F2	179.4 (4)	C19—C20—H20A	121.6
F5—P1—F2	89.8 (3)	C20—C21—C22	121.7 (6)
F7—P2—F9	90.5 (5)	C20—C21—H21A	119.2
F7—P2—F11	87.4 (5)	C22—C21—H21A	119.2
F9—P2—F11	177.6 (5)	C23—C22—C21	122.8 (7)
F7—P2—F10	94.7 (5)	C23—C22—H22A	118.6
F9—P2—F10	89.6 (5)	C21—C22—H22A	118.6
F11—P2—F10	91.7 (5)	C22—C23—C24	115.2 (6)
F7—P2—F8	175.5 (5)	C22—C23—H23A	122.4
F9—P2—F8	92.4 (5)	C24—C23—H23A	122.4
F11—P2—F8	89.6 (5)	C19—C24—N4	106.0 (5)
F10—P2—F8	88.8 (4)	C19—C24—C23	123.1 (6)
F7—P2—F12	88.8 (5)	N4—C24—C23	130.9 (6)
F9—P2—F12	88.7 (4)	N3—C25—N4	113.7 (6)
F11—P2—F12	90.1 (5)	N3—C25—H25A	123.2
F10—P2—F12	176.0 (5)	N4—C25—H25A	123.2
F8—P2—F12	87.8 (4)	N4—C26—C27	113.1 (5)
C6—C1—C2	117.2 (6)	N4—C26—H26A	109.0
C6—C1—S1	126.6 (5)	C27—C26—H26A	109.0
C2—C1—S1	116.3 (5)	N4—C26—H26B	109.0
C3—C2—C1	122.1 (6)	C27—C26—H26B	109.0
C3—C2—H2A	119.0	H26A—C26—H26B	107.8
C1—C2—H2A	119.0	N6—C27—C26	109.7 (5)
C2—C3—C4	118.6 (5)	N6—C27—H27A	109.7
C2—C3—H3A	120.7	C26—C27—H27A	109.7
C4—C3—H3A	120.7	N6—C27—H27B	109.7
C5—C4—C3	120.2 (6)	C26—C27—H27B	109.7
C5—C4—N1	122.7 (5)	H27A—C27—H27B	108.2
C3—C4—N1	117.0 (5)	C33—C28—N5	109.7 (5)
C4—C5—C6	120.1 (6)	C33—C28—C29	120.5 (6)
C4—C5—H5A	120.0	N5—C28—C29	129.7 (6)
C6—C5—H5A	120.0	C30—C29—C28	117.1 (6)
C1—C6—C5	121.8 (6)	C30—C29—H29A	121.4
C1—C6—H6A	119.1	C28—C29—H29A	121.4
C5—C6—H6A	119.1	C29—C30—C31	121.8 (6)
N1—C7—H7A	109.5	C29—C30—H30A	119.1
N1—C7—H7B	109.5	C31—C30—H30A	119.1
H7A—C7—H7B	109.5	C32—C31—C30	122.7 (7)
N1—C7—H7C	109.5	C32—C31—H31A	118.7
H7A—C7—H7C	109.5	C30—C31—H31A	118.7
H7B—C7—H7C	109.5	C31—C32—C33	116.2 (6)
N1—C8—H8A	109.5	C31—C32—H32A	121.9
N1—C8—H8B	109.5	C33—C32—H32A	121.9
H8A—C8—H8B	109.5	N6—C33—C32	133.0 (6)
N1—C8—H8C	109.5	N6—C33—C28	105.2 (5)
H8A—C8—H8C	109.5	C32—C33—C28	121.8 (6)
H8B—C8—H8C	109.5	N5—C34—N6	113.8 (5)
N1—C9—H9A	109.5	N5—C34—H34A	123.1
N1—C9—H9B	109.5	N6—C34—H34A	123.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N5^iii	0.94	2.59	3.479 (8)	157
C7—H7A···F10^iv	0.97	2.42	3.380 (12)	170
C9—H9C···F8^iv	0.97	2.55	3.508 (12)	169
C8—H8A···F12	0.97	2.41	3.379 (12)	177
C9—H9A···F9	0.97	2.49	3.452 (12)	171
C16—H16C···F2^v	0.97	2.53	3.462 (10)	160
C17—H17A···F9	0.97	2.39	3.286 (10)	153
C17—H17C···F4	0.97	2.43	3.363 (10)	162
C18—H18C···F12^vi	0.97	2.52	3.431 (11)	156

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+2, y−1/2, −z+3/2; (vi) −x+2, y+1/2, −z+3/2.

(II) catena-poly[[{[4-(trimethylammonio)benzenethiolate- κS]mercury(II)}bis[µ-4-(trimethylammonio)benzenethiolate- κ²S:S]{[4-(trimethylammonio)benzenethiolate- κS]mercury(II)}-µ-1,1'-(hexane-1,6-diyl)bis(1H- benzimidazole)-κ²N³:N^3'] tetrakis(hexafluoridophosphate)]

Crystal data

[Hg2(C20H22N4)(C9H13NS)4](PF6)4	Z = 1
Mr = 1968.58	F(000) = 966
Triclinic, P1	Dx = 1.811 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.871 (2) Å	Cell parameters from 8200 reflections
b = 10.364 (2) Å	θ = 3.0–27.5°
c = 18.078 (4) Å	µ = 4.56 mm^−1
α = 98.39 (3)°	T = 223 K
β = 97.85 (3)°	Prism, colourless
γ = 94.05 (3)°	0.45 × 0.20 × 0.15 mm
V = 1804.7 (6) Å^3

Data collection

Rigaku Mercury CCD area-detector diffractometer	6337 independent reflections
Radiation source: fine-focus sealed tube	5615 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (REQAB?; Jacobson, 1998)	h = −11→11
Tmin = 0.234, Tmax = 0.548	k = −12→11
15125 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0434P)^2] where P = (Fo^2 + 2Fc^2)/3
6337 reflections	(Δ/σ)max = 0.002
442 parameters	Δρmax = 1.04 e Å^−3
0 restraints	Δρmin = −0.85 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
Hg1	0.89148 (2)	0.62232 (2)	0.955548 (10)	0.04418 (10)
S1	0.67247 (15)	0.67404 (19)	0.98267 (8)	0.0609 (4)
S2	1.05378 (14)	0.49835 (15)	0.89525 (7)	0.0434 (3)
N1	0.3033 (5)	0.5693 (5)	0.6816 (2)	0.0465 (11)
N2	0.7996 (5)	0.1770 (4)	0.5987 (2)	0.0456 (11)
N3	1.0638 (5)	0.7776 (4)	1.0276 (2)	0.0448 (11)
N4	1.2681 (4)	0.8288 (5)	1.1002 (2)	0.0447 (11)
C1	0.5705 (5)	0.6414 (6)	0.8923 (3)	0.0425 (13)
C2	0.4469 (6)	0.5712 (7)	0.8845 (3)	0.0593 (17)
H2A	0.4193	0.5374	0.9261	0.071*
C3	0.3607 (6)	0.5485 (7)	0.8158 (3)	0.0567 (16)
H3A	0.2751	0.4998	0.8113	0.068*
C4	0.3990 (5)	0.5966 (5)	0.7548 (3)	0.0384 (12)
C5	0.5226 (6)	0.6670 (6)	0.7610 (3)	0.0464 (14)
H5A	0.5502	0.7005	0.7193	0.056*
C6	0.6070 (6)	0.6883 (6)	0.8304 (3)	0.0511 (15)
H6A	0.6926	0.7370	0.8349	0.061*
C7	0.3591 (7)	0.6249 (7)	0.6191 (3)	0.0651 (18)
H7A	0.3756	0.7193	0.6325	0.098*
H7B	0.2932	0.6032	0.5731	0.098*
H7C	0.4446	0.5883	0.6110	0.098*
C8	0.2785 (9)	0.4242 (7)	0.6576 (4)	0.085 (3)
H8A	0.3651	0.3881	0.6518	0.128*
H8B	0.2173	0.4052	0.6098	0.128*
H8C	0.2368	0.3853	0.6957	0.128*
C9	0.1710 (7)	0.6281 (9)	0.6914 (5)	0.090 (3)
H9A	0.1892	0.7221	0.7067	0.134*
H9B	0.1295	0.5904	0.7299	0.134*
H9C	0.1089	0.6099	0.6439	0.134*
C10	0.9631 (5)	0.3954 (5)	0.8150 (3)	0.0350 (11)
C11	0.8351 (6)	0.4184 (5)	0.7797 (3)	0.0450 (13)
H11A	0.7865	0.4839	0.8029	0.054*
C12	0.7786 (6)	0.3459 (5)	0.7110 (3)	0.0452 (13)
H12A	0.6918	0.3615	0.6873	0.054*
C13	0.8510 (6)	0.2496 (5)	0.6768 (3)	0.0389 (12)
C14	0.9749 (6)	0.2196 (6)	0.7131 (3)	0.0459 (13)
H14A	1.0209	0.1508	0.6912	0.055*
C15	1.0291 (5)	0.2923 (5)	0.7816 (3)	0.0414 (12)
H15A	1.1129	0.2722	0.8067	0.050*
C16	0.9012 (7)	0.2030 (7)	0.5473 (3)	0.069 (2)
H16A	0.9891	0.1749	0.5664	0.104*
H16B	0.9116	0.2960	0.5449	0.104*
H16C	0.8688	0.1549	0.4970	0.104*
C17	0.6639 (6)	0.2236 (6)	0.5651 (3)	0.0585 (16)
H17A	0.6766	0.3168	0.5635	0.088*
H17B	0.5940	0.2069	0.5962	0.088*
H17C	0.6353	0.1767	0.5142	0.088*
C18	0.7763 (8)	0.0337 (6)	0.6000 (4)	0.073 (2)
H18A	0.8610	0.0018	0.6209	0.109*
H18B	0.7468	−0.0118	0.5489	0.109*
H18C	0.7059	0.0179	0.6310	0.109*
C19	1.1933 (6)	0.7516 (6)	1.0406 (3)	0.0456 (13)
H19A	1.2298	0.6846	1.0106	0.055*
C20	1.0527 (6)	0.8836 (6)	1.0830 (3)	0.0442 (13)
C21	0.9400 (6)	0.9534 (6)	1.0974 (3)	0.0578 (16)
H21A	0.8543	0.9321	1.0666	0.069*
C22	0.9575 (8)	1.0523 (7)	1.1568 (4)	0.073 (2)
H22A	0.8836	1.1010	1.1671	0.088*
C23	1.0852 (8)	1.0824 (7)	1.2029 (4)	0.072 (2)
H23A	1.0944	1.1506	1.2442	0.087*
C24	1.1977 (7)	1.0158 (6)	1.1901 (3)	0.0545 (15)
H24A	1.2829	1.0376	1.2213	0.065*
C25	1.1799 (6)	0.9148 (6)	1.1287 (3)	0.0439 (13)
C26	1.4165 (6)	0.8296 (6)	1.1220 (3)	0.0538 (15)
H26A	1.4469	0.7469	1.0992	0.065*
H26B	1.4377	0.8365	1.1770	0.065*
C27	1.4936 (6)	0.9426 (6)	1.0966 (3)	0.0504 (15)
H27A	1.5923	0.9339	1.1068	0.060*
H27B	1.4757	1.0247	1.1265	0.060*
C28	1.4542 (5)	0.9500 (6)	1.0132 (3)	0.0474 (14)
H28A	1.4592	0.8639	0.9835	0.057*
H28B	1.3591	0.9721	1.0043	0.057*
P1	0.66344 (16)	−0.04237 (16)	0.33206 (9)	0.0495 (4)
F1	0.5833 (6)	0.0458 (5)	0.2822 (3)	0.131 (2)
F2	0.6100 (6)	0.0288 (6)	0.4031 (2)	0.132 (2)
F3	0.7913 (6)	0.0564 (6)	0.3513 (3)	0.141 (2)
F4	0.7485 (6)	−0.1317 (5)	0.3809 (3)	0.1178 (19)
F5	0.7157 (4)	−0.1148 (5)	0.2598 (2)	0.0985 (15)
F6	0.5362 (5)	−0.1442 (6)	0.3137 (3)	0.123 (2)
P2	0.78142 (18)	0.65473 (16)	0.58181 (9)	0.0540 (4)
F7	0.6997 (4)	0.7605 (4)	0.6268 (3)	0.0874 (13)
F8	0.8535 (6)	0.6172 (6)	0.6567 (3)	0.129 (2)
F9	0.9050 (6)	0.7586 (5)	0.5891 (4)	0.137 (2)
F10	0.8606 (5)	0.5474 (5)	0.5363 (3)	0.1109 (16)
F11	0.7127 (10)	0.6943 (8)	0.5099 (3)	0.217 (5)
F12	0.6641 (5)	0.5488 (5)	0.5824 (4)	0.150 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.03977 (14)	0.04984 (17)	0.03765 (14)	0.00091 (10)	0.00192 (9)	−0.00536 (10)
S1	0.0426 (8)	0.0975 (14)	0.0377 (8)	0.0111 (8)	0.0046 (6)	−0.0064 (8)
S2	0.0406 (7)	0.0520 (9)	0.0332 (7)	0.0008 (6)	0.0046 (6)	−0.0052 (6)
N1	0.048 (3)	0.049 (3)	0.039 (2)	−0.006 (2)	−0.001 (2)	0.006 (2)
N2	0.070 (3)	0.035 (3)	0.029 (2)	−0.007 (2)	0.007 (2)	−0.0033 (19)
N3	0.044 (3)	0.042 (3)	0.042 (2)	−0.008 (2)	0.006 (2)	−0.010 (2)
N4	0.042 (3)	0.047 (3)	0.041 (2)	−0.012 (2)	0.006 (2)	0.003 (2)
C1	0.039 (3)	0.052 (4)	0.033 (3)	0.005 (3)	0.003 (2)	−0.003 (2)
C2	0.050 (4)	0.086 (5)	0.040 (3)	−0.011 (3)	0.006 (3)	0.015 (3)
C3	0.041 (3)	0.080 (5)	0.047 (3)	−0.014 (3)	0.010 (3)	0.009 (3)
C4	0.038 (3)	0.041 (3)	0.034 (3)	0.001 (2)	0.001 (2)	0.003 (2)
C5	0.049 (3)	0.046 (4)	0.045 (3)	−0.003 (3)	0.006 (3)	0.014 (3)
C6	0.041 (3)	0.047 (4)	0.060 (4)	−0.008 (3)	−0.002 (3)	0.006 (3)
C7	0.083 (5)	0.071 (5)	0.041 (3)	−0.004 (4)	0.004 (3)	0.019 (3)
C8	0.136 (7)	0.049 (5)	0.055 (4)	−0.034 (4)	−0.011 (4)	0.003 (3)
C9	0.052 (4)	0.127 (8)	0.088 (5)	0.020 (5)	−0.005 (4)	0.019 (5)
C10	0.044 (3)	0.034 (3)	0.026 (2)	−0.002 (2)	0.009 (2)	0.002 (2)
C11	0.056 (3)	0.037 (3)	0.037 (3)	0.012 (3)	0.001 (3)	−0.009 (2)
C12	0.052 (3)	0.041 (4)	0.038 (3)	0.009 (3)	−0.003 (2)	−0.001 (2)
C13	0.059 (3)	0.028 (3)	0.027 (2)	−0.006 (2)	0.008 (2)	−0.002 (2)
C14	0.056 (4)	0.038 (3)	0.043 (3)	0.008 (3)	0.014 (3)	−0.002 (2)
C15	0.042 (3)	0.043 (3)	0.040 (3)	0.004 (2)	0.005 (2)	0.007 (2)
C16	0.081 (5)	0.089 (5)	0.036 (3)	−0.005 (4)	0.022 (3)	−0.002 (3)
C17	0.075 (4)	0.055 (4)	0.038 (3)	−0.008 (3)	−0.001 (3)	−0.002 (3)
C18	0.123 (6)	0.025 (4)	0.060 (4)	−0.008 (4)	−0.003 (4)	−0.005 (3)
C19	0.047 (3)	0.040 (3)	0.044 (3)	−0.005 (3)	0.006 (3)	−0.007 (2)
C20	0.052 (3)	0.042 (3)	0.036 (3)	−0.008 (3)	0.008 (2)	0.001 (2)
C21	0.053 (4)	0.059 (4)	0.057 (4)	0.000 (3)	0.007 (3)	−0.005 (3)
C22	0.072 (5)	0.067 (5)	0.075 (5)	0.006 (4)	0.019 (4)	−0.018 (4)
C23	0.089 (5)	0.057 (5)	0.062 (4)	−0.017 (4)	0.019 (4)	−0.017 (3)
C24	0.062 (4)	0.052 (4)	0.044 (3)	−0.018 (3)	0.009 (3)	−0.003 (3)
C25	0.051 (3)	0.048 (4)	0.031 (3)	−0.013 (3)	0.008 (2)	0.006 (2)
C26	0.047 (3)	0.061 (4)	0.048 (3)	−0.006 (3)	−0.004 (3)	0.005 (3)
C27	0.042 (3)	0.060 (4)	0.044 (3)	−0.011 (3)	0.004 (2)	0.001 (3)
C28	0.037 (3)	0.053 (4)	0.047 (3)	−0.004 (3)	0.001 (2)	−0.001 (3)
P1	0.0545 (9)	0.0429 (10)	0.0458 (8)	0.0039 (7)	0.0006 (7)	−0.0037 (7)
F1	0.194 (6)	0.087 (4)	0.090 (3)	0.065 (4)	−0.059 (3)	−0.008 (3)
F2	0.126 (4)	0.187 (6)	0.063 (3)	0.037 (4)	0.007 (3)	−0.057 (3)
F3	0.118 (4)	0.123 (5)	0.157 (5)	−0.068 (4)	−0.042 (4)	0.032 (4)
F4	0.186 (5)	0.080 (3)	0.079 (3)	0.034 (3)	−0.026 (3)	0.019 (3)
F5	0.084 (3)	0.141 (4)	0.069 (3)	0.029 (3)	0.022 (2)	−0.009 (3)
F6	0.109 (4)	0.157 (5)	0.083 (3)	−0.072 (3)	0.025 (3)	−0.022 (3)
P2	0.0709 (11)	0.0367 (9)	0.0517 (9)	0.0020 (8)	0.0097 (8)	−0.0015 (7)
F7	0.096 (3)	0.051 (2)	0.117 (3)	−0.005 (2)	0.056 (3)	−0.015 (2)
F8	0.149 (5)	0.138 (5)	0.098 (4)	0.007 (4)	−0.012 (3)	0.043 (4)
F9	0.123 (4)	0.068 (3)	0.238 (7)	−0.005 (3)	0.099 (5)	0.020 (4)
F10	0.119 (4)	0.074 (3)	0.129 (4)	0.033 (3)	0.022 (3)	−0.034 (3)
F11	0.352 (11)	0.257 (9)	0.062 (3)	0.216 (9)	0.006 (5)	0.029 (4)
F12	0.067 (3)	0.048 (3)	0.320 (9)	−0.008 (2)	0.020 (4)	−0.009 (4)

Geometric parameters (Å, º)

Hg1—S1	2.3617 (16)	C13—C14	1.384 (7)
Hg1—N3	2.362 (4)	C14—C15	1.370 (7)
Hg1—S2	2.4010 (16)	C14—H14A	0.9400
Hg1—S2^i	3.1325 (16)	C15—H15A	0.9400
Hg1—Hg1^i	3.8233 (12)	C16—H16A	0.9700
S1—C1	1.771 (5)	C16—H16B	0.9700
S2—C10	1.762 (5)	C16—H16C	0.9700
S2—Hg1^i	3.1325 (16)	C17—H17A	0.9700
N1—C4	1.496 (6)	C17—H17B	0.9700
N1—C7	1.492 (7)	C17—H17C	0.9700
N1—C8	1.496 (8)	C18—H18A	0.9700
N1—C9	1.500 (8)	C18—H18B	0.9700
N2—C18	1.491 (7)	C18—H18C	0.9700
N2—C16	1.495 (7)	C19—H19A	0.9400
N2—C13	1.503 (6)	C20—C25	1.394 (7)
N2—C17	1.534 (7)	C20—C21	1.402 (8)
N3—C19	1.322 (7)	C21—C22	1.355 (9)
N3—C20	1.395 (7)	C21—H21A	0.9400
N4—C19	1.339 (7)	C22—C23	1.400 (10)
N4—C25	1.384 (7)	C22—H22A	0.9400
N4—C26	1.464 (7)	C23—C24	1.377 (9)
C1—C2	1.355 (8)	C23—H23A	0.9400
C1—C6	1.366 (7)	C24—C25	1.393 (8)
C2—C3	1.385 (8)	C24—H24A	0.9400
C2—H2A	0.9400	C26—C27	1.512 (8)
C3—C4	1.362 (7)	C26—H26A	0.9800
C3—H3A	0.9400	C26—H26B	0.9800
C4—C5	1.359 (7)	C27—C28	1.518 (7)
C5—C6	1.387 (8)	C27—H27A	0.9800
C5—H5A	0.9400	C27—H27B	0.9800
C6—H6A	0.9400	C28—C28^ii	1.500 (10)
C7—H7A	0.9700	C28—H28A	0.9800
C7—H7B	0.9700	C28—H28B	0.9800
C7—H7C	0.9700	P1—F3	1.534 (5)
C8—H8A	0.9700	P1—F6	1.549 (5)
C8—H8B	0.9700	P1—F1	1.556 (4)
C8—H8C	0.9700	P1—F2	1.560 (4)
C9—H9A	0.9700	P1—F4	1.577 (4)
C9—H9B	0.9700	P1—F5	1.578 (4)
C9—H9C	0.9700	P2—F11	1.507 (5)
C10—C11	1.389 (7)	P2—F12	1.540 (5)
C10—C15	1.396 (7)	P2—F9	1.547 (5)
C11—C12	1.378 (7)	P2—F8	1.556 (5)
C11—H11A	0.9400	P2—F7	1.600 (4)
C12—C13	1.389 (7)	P2—F10	1.599 (4)
C12—H12A	0.9400
S1—Hg1—N3	110.36 (12)	N2—C16—H16B	109.5
S1—Hg1—S2	156.38 (6)	H16A—C16—H16B	109.5
N3—Hg1—S2	93.26 (12)	N2—C16—H16C	109.5
S1—Hg1—S2^i	90.69 (5)	H16A—C16—H16C	109.5
N3—Hg1—S2^i	79.17 (11)	H16B—C16—H16C	109.5
S2—Hg1—S2^i	93.66 (4)	N2—C17—H17A	109.5
S1—Hg1—Hg1^i	125.82 (5)	N2—C17—H17B	109.5
N3—Hg1—Hg1^i	83.21 (12)	H17A—C17—H17B	109.5
S2—Hg1—Hg1^i	54.85 (4)	N2—C17—H17C	109.5
S2^i—Hg1—Hg1^i	38.81 (3)	H17A—C17—H17C	109.5
C1—S1—Hg1	102.65 (18)	H17B—C17—H17C	109.5
C10—S2—Hg1	107.91 (18)	N2—C18—H18A	109.5
C10—S2—Hg1^i	117.05 (17)	N2—C18—H18B	109.5
Hg1—S2—Hg1^i	86.34 (4)	H18A—C18—H18B	109.5
C4—N1—C7	113.3 (4)	N2—C18—H18C	109.5
C4—N1—C8	108.6 (4)	H18A—C18—H18C	109.5
C7—N1—C8	107.2 (5)	H18B—C18—H18C	109.5
C4—N1—C9	109.6 (5)	N3—C19—N4	114.2 (5)
C7—N1—C9	107.4 (5)	N3—C19—H19A	122.9
C8—N1—C9	110.8 (6)	N4—C19—H19A	122.9
C18—N2—C16	110.4 (5)	C25—C20—N3	108.3 (5)
C18—N2—C13	110.6 (4)	C25—C20—C21	120.9 (5)
C16—N2—C13	109.5 (4)	N3—C20—C21	130.8 (5)
C18—N2—C17	108.0 (5)	C22—C21—C20	118.5 (6)
C16—N2—C17	106.5 (4)	C22—C21—H21A	120.8
C13—N2—C17	111.7 (4)	C20—C21—H21A	120.8
C19—N3—C20	104.9 (4)	C21—C22—C23	120.3 (7)
C19—N3—Hg1	121.8 (4)	C21—C22—H22A	119.8
C20—N3—Hg1	129.8 (3)	C23—C22—H22A	119.8
C19—N4—C25	105.8 (5)	C24—C23—C22	122.5 (6)
C19—N4—C26	125.1 (5)	C24—C23—H23A	118.7
C25—N4—C26	128.7 (5)	C22—C23—H23A	118.7
C2—C1—C6	117.8 (5)	C23—C24—C25	117.1 (6)
C2—C1—S1	118.7 (4)	C23—C24—H24A	121.5
C6—C1—S1	123.4 (4)	C25—C24—H24A	121.5
C1—C2—C3	120.8 (5)	N4—C25—C20	106.9 (5)
C1—C2—H2A	119.6	N4—C25—C24	132.4 (6)
C3—C2—H2A	119.6	C20—C25—C24	120.7 (6)
C4—C3—C2	120.4 (5)	N4—C26—C27	111.3 (5)
C4—C3—H3A	119.8	N4—C26—H26A	109.4
C2—C3—H3A	119.8	C27—C26—H26A	109.4
C3—C4—C5	120.0 (5)	N4—C26—H26B	109.4
C3—C4—N1	118.8 (5)	C27—C26—H26B	109.4
C5—C4—N1	121.2 (5)	H26A—C26—H26B	108.0
C4—C5—C6	118.4 (5)	C26—C27—C28	113.3 (5)
C4—C5—H5A	120.8	C26—C27—H27A	108.9
C6—C5—H5A	120.8	C28—C27—H27A	108.9
C1—C6—C5	122.5 (5)	C26—C27—H27B	108.9
C1—C6—H6A	118.7	C28—C27—H27B	108.9
C5—C6—H6A	118.7	H27A—C27—H27B	107.7
N1—C7—H7A	109.5	C28^ii—C28—C27	112.4 (6)
N1—C7—H7B	109.5	C28^ii—C28—H28A	109.1
H7A—C7—H7B	109.5	C27—C28—H28A	109.1
N1—C7—H7C	109.5	C28^ii—C28—H28B	109.1
H7A—C7—H7C	109.5	C27—C28—H28B	109.1
H7B—C7—H7C	109.5	H28A—C28—H28B	107.9
N1—C8—H8A	109.5	F3—P1—F6	178.7 (4)
N1—C8—H8B	109.5	F3—P1—F1	92.9 (3)
H8A—C8—H8B	109.5	F6—P1—F1	88.4 (3)
N1—C8—H8C	109.5	F3—P1—F2	88.0 (4)
H8A—C8—H8C	109.5	F6—P1—F2	92.1 (3)
H8B—C8—H8C	109.5	F1—P1—F2	89.8 (3)
N1—C9—H9A	109.5	F3—P1—F4	86.1 (3)
N1—C9—H9B	109.5	F6—P1—F4	92.6 (3)
H9A—C9—H9B	109.5	F1—P1—F4	178.1 (4)
N1—C9—H9C	109.5	F2—P1—F4	91.8 (3)
H9A—C9—H9C	109.5	F3—P1—F5	92.6 (3)
H9B—C9—H9C	109.5	F6—P1—F5	87.4 (3)
C11—C10—C15	118.5 (5)	F1—P1—F5	89.9 (3)
C11—C10—S2	123.3 (4)	F2—P1—F5	179.3 (3)
C15—C10—S2	117.9 (4)	F4—P1—F5	88.6 (3)
C12—C11—C10	120.4 (5)	F11—P2—F12	92.8 (5)
C12—C11—H11A	119.8	F11—P2—F9	92.9 (5)
C10—C11—H11A	119.8	F12—P2—F9	174.3 (4)
C11—C12—C13	119.5 (5)	F11—P2—F8	178.7 (5)
C11—C12—H12A	120.2	F12—P2—F8	88.3 (4)
C13—C12—H12A	120.2	F9—P2—F8	86.1 (4)
C14—C13—C12	121.0 (5)	F11—P2—F7	87.5 (3)
C14—C13—N2	117.7 (5)	F12—P2—F7	89.4 (3)
C12—C13—N2	121.3 (5)	F9—P2—F7	90.0 (3)
C15—C14—C13	118.6 (5)	F8—P2—F7	91.7 (3)
C15—C14—H14A	120.7	F11—P2—F10	92.2 (3)
C13—C14—H14A	120.7	F12—P2—F10	89.6 (3)
C14—C15—C10	121.8 (5)	F9—P2—F10	91.0 (3)
C14—C15—H15A	119.1	F8—P2—F10	88.6 (3)
C10—C15—H15A	119.1	F7—P2—F10	179.0 (3)
N2—C16—H16A	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···S2^iii	0.94	2.83	3.564 (5)	136
C5—H5A···F7	0.94	2.49	3.387 (6)	160
C7—H7C···F12	0.97	2.35	3.296 (8)	166
C17—H17A···F12	0.97	2.39	3.341 (8)	165
C17—H17C···F2	0.97	2.31	3.260 (7)	165
C8—H8B···F11^iv	0.97	2.46	3.112 (9)	124
C17—H17B···F6^v	0.97	2.34	3.294 (7)	167
C26—H26B···F6^vi	0.98	2.50	3.470 (7)	170

Symmetry codes: (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x+1, y+1, z+1.