The first phospho­ramide–mercury(II) complex with a Cl₂Hg–OP[N(C)(C)]₃ segment

Mercury(II) exhibits a strong preference for linear coordination which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization. If the two ligands attached to the mercury(II) ion are weak donors, the metal ion can act as a good Lewis acid and expand its coordination number. Moreover, mercury has a special affinity for softer bases, such as S and N atoms, and has much less affinity for hard bases, such as those including an O atom. The asymmetric unit of di­chlorido­[tris­(piperidin-1-yl)phos­phane oxide-κO]mercury(II)–di­chlorido­mercury(II) (2/1), [HgCl₂{(C₅H₁₀N)₃PO}]₂·[HgCl₂], is composed of one HgCl₂{(C₅H₁₀N)₃PO} complex and one half of a discrete HgCl₂ entity located on an inversion centre. The coordination environment around the Hg^II centre in the complex component is a distorted T-shape. Bond-valence-sum calculations confirm the three-coordination mode of the Hg^II atom of the complex mol­ecule. The noncovalent nature of the Hg...Cl and Hg...O inter­actions in the structure are discussed.

S1. Introduction

Mercuric coordination compounds including ligands with different donor atoms (typically, sulfur, nitro­gen and oxygen) have been investigated (Lippard, 1990). The oxidation state +2 is the most common for Hg and is also the main oxidation state in nature. The coordination chemistry of mercury(II) differs from most other transition metals due to d¹⁰ configuration and its large size (Sahebalzamani et al., 2010).

Mercury(II) exhibits a strong preference for linear coordination (Canty & Marker, 1976) which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization (Thomas & Gaillard, 2015). It should be noted that if the two ligands attached to the mercury(II) ion are weak donors, e.g. C1⁻ as in HgC1₂, the metal ion can act as a good Lewis acid and expand its coordination number (Fisher & Drago, 1975). Moreover, mercury has a special affinity for softer bases such as S and N atoms and has much less affinity for hard bases, such as those including an O atom (Meyer & Nockemann, 2003).

In this paper, we describe the synthesis and structural characterization of a new three-coordinated mercury(II) complex with a tris­(piperidin-1-yl)phosphane oxide O-donor ligand. Using the Cambridge Structural Database (CSD, Version 5.36, with updates to November 2014; Groom & Allen, 2014), the highlights concerning this new complex are as follows: (i) the structure of (I) is the first example of a three-coordinated Hg^II complex with a Cl₂Hg—O═P[N(C)(C)]₃ segment; (ii) there are only two phospho­ric tri­amide Hg^II structures present, namely bis­(dimesyl­amide-κN)(hexa­methyl­phospho­ramide-κO)mercury(II) (CSD refcode JUWNOE; Blaschette et al., 1993) and bis­(µ₃-hexa­methyl­phospho­ramide)­tris­(µ₂-perfluoro-o-phenyl­ene)trimercury(II) (CAMFEC; Tikhonova et al., 2002), in which the commercial material [(CH₃)₂N]₃P(O) was used for the preparation of these complexes, and (iii) the [C₅H₁₀N]₃PO ligand was used only in two complex structures, namely tris­(tripiperidinylphosphine oxide)tris­(iso­thio­cyanato)­praseodymium(III) (MALMAO; da Silva et al., 2005) and bis­(nitrato-κ²O,O')dioxidobis(tripiperidinylphosphine oxide-κO)uranium (LOPVUH; de Aquino et al., 2000), so far.

S2. Experimental

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of (C5H10N)3PO

The preparation of the tris­(piperidin-1-yl)phosphane oxide ligand was reported previously as the by-product of the synthesis of [(C₅H₁₀N)₄P]Br (Schiemenz et al., 2001). The synthesis of (C₅H₁₀N)₃PO was performed in a different way. A dry aceto­nitrile solution of piperidine (1.2 M, 10 ml) was added dropwise to a solution of P(O)Cl₃ (2 mmol) in the same solvent (30 ml) at 273 K. After stirring for 4 h, the precipitated amine hydro­chloride salt (C₅H₁₀NH·HCl) was filtered off, and the aceto­nitrile solution of the tris­(piperidin-1-yl)phosphane oxide ligand was used in the complex reaction.

S2.1.2. Synthesis of [HgC2{PO(NC5H10)3}]2.HgCl2 (I)

A solution of HgCl₂ (1 mmol) in methanol (10 ml) was added dropwise to the aceto­nitrile solution of (C₅H₁₀N)₃PO (2 mmol, 50 ml) and stirred for 48 h under reflux. After cooling to room temperature, colourless block-shaped crystals of (I) were obtained within a few days.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). DELU and SIMU instructions in SHELXL2014 (Sheldrick, 2015) were applied to atoms C6, C7, C8, C9 and C10 in order to limit the disorder in the corresponding ring. Splitting of the ring into two different parts did not solve the problems of displacement of some atoms in the ring. With these two instructions, the problem is not solved but limited. [Please descrive what the instructions do?]

S3. Results and discussion

The asymmetric unit of (I) is composed of one HgCl₂{PO(C₅H₁₀N)₃} complex and one half of a HgCl₂ component (Fig. 1). In the discrete HgCl₂ component, the Hg2 atom is located at the inversion centre and hence shows an ideal linear coordination environment.

The Hg1—Cl bond lengths in the present mercury(II)–phospho­ramide complex are consistent with those reported for other complexes of Hg^II chloride (Li et al., 2012; Kubo et al., 2000) and are longer than the two equal Hg—Cl bond lengths in the discrete HgCl₂ entity (Table 2). The Hg1—O1 bond length is comparable to similar bonds in analogous structures (Yang et al., 2010).

In the HgCl₂{PO(C₅H₁₀N)₃} complex, the Cl1—Hg1—Cl2 segment shows a distortion of about 16° from a linear bonding arrangement, due to the presence of the coordinated phospho­ric tri­amide molecule. The coordinated O atom forms Cl1—Hg1—O1 and Cl2—Hg1—O1 angles of close to 90° (Table 2).

Khavasi and Azhdari Tehrani (2013) introduced a simple equation of τ₃ = |[(α + β + γ)/360] - |(α − 120)/60|| for the geometry index τ₃ of three-coordinated compounds. In this equation, α is the largest angle in the three-coordinated compound and the values of τ₃ will range from 1.00 for a perfect trigonal planar geometry to zero for a perfect T-shaped geometry. The τ₃ index for three coordinated Hg1 complex is 0.27, which implies a distorted T-shape geometry (Tiekink, 1987).

Using a van der Waals radius of 1.70 Å for mercury, 1.75 Å for chlorine and 1.50 Å for oxygen (Batsanov, 2001), four different noncovalent inter­actions are considered in (I), namely Hg1···Cl3 [3.154 (2) Å], Hg2···Cl2 [3.166 (2) Å], Hg2···O1 [2.940 (5) Å] and Hg1···Cl1ⁱⁱ [3.121 (2) Å; symmetry code: (ii) −x + 1, −y + 2, −z + 2]. The two last inter­actions take part in forming a chain along the a direction (Fig. 2) and the other two help to stabilize the aggregation with no effect on the pattern of extended structure formed. Such simultaneously close and distant bonded atoms are usual for mercury(II) (Canty, 1980). A view of linear chains in the crystal is shown in Fig. 3.

In order to prove the noncovalent nature of the Hg···Cl inter­action involving atom Hg1 in the three-coordinate complex, bond-valence calculations were performed using the equation S_ij = exp[(R₀–R_ij)/b_ij], where S_ij is the bond valence for atoms i and j, R₀ is the standard value of the bond distance for atoms i and j, R_ij is the actual bond distance between i and j, and b_ij is a constant (Brown & Altermatt, 1985). Such a calculation for the Hg[Cl]₂[O] segment provides a bond-valence sum (BVS) value of 2.142 v.u. for Hg, considering two Hg—Cl and one Hg—O bond (with R_ij as given in Table 2 for the Hg1—Cl1, Hg1—Cl2 and Hg1—O1 bond lengths, R₀ = 2.28 Å for Hg—Cl and 1.972 Å for Hg—O, and b_ij = 0.37; Brown, https://www.iucr.org/resources/data/datasets/bond-valence-parameters). Considering the Hg1···Cl1ⁱⁱ and Hg1···Cl3 inter­actions, the BVSs are calculated as 2.245 and 2.339 v.u. respectively, confirming the noncovalent nature of these inter­actions.

The P atom in the phospho­ric tri­amide ligand adopts a slightly distorted P[O][N]₃ tetra­hedral environment and the Hg1—O1—P1 unit is significantly bent, with an angle of 152.6 (3)°. Moreover, the P1═O1 bond length in complex (I) is longer than the P═O double-bond length in phospho­ric tri­amide compounds, for example, compared with tris­(morpholino)­phosphine oxide (BIVYAG; Romming & Songstad, 1982), which is the closest structure to the free ligand discussed here.

The six-membered piperidine rings in the phospho­ric tri­amide ligand adopt a near chair conformation on the base of puckering parameters calculated according to Cremer & Pople (1975), which are Q = 0.537 (10), θ = 7.9 (11)° and Φ = 6(9)° for the ring containing atom N1, Q = 0.507 (11), θ = 180.0 (14)° and Φ = 90 (308)° for the ring containing atom N2, and Q = 0.569 (10), θ = 2.4 (11)° and Φ = 307 (23)° for the ring containing atom N3.

Structure description

Mercuric coordination compounds including ligands with different donor atoms (typically, sulfur, nitro­gen and oxygen) have been investigated (Lippard, 1990). The oxidation state +2 is the most common for Hg and is also the main oxidation state in nature. The coordination chemistry of mercury(II) differs from most other transition metals due to d¹⁰ configuration and its large size (Sahebalzamani et al., 2010).

Mercury(II) exhibits a strong preference for linear coordination (Canty & Marker, 1976) which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization (Thomas & Gaillard, 2015). It should be noted that if the two ligands attached to the mercury(II) ion are weak donors, e.g. C1⁻ as in HgC1₂, the metal ion can act as a good Lewis acid and expand its coordination number (Fisher & Drago, 1975). Moreover, mercury has a special affinity for softer bases such as S and N atoms and has much less affinity for hard bases, such as those including an O atom (Meyer & Nockemann, 2003).

In this paper, we describe the synthesis and structural characterization of a new three-coordinated mercury(II) complex with a tris­(piperidin-1-yl)phosphane oxide O-donor ligand. Using the Cambridge Structural Database (CSD, Version 5.36, with updates to November 2014; Groom & Allen, 2014), the highlights concerning this new complex are as follows: (i) the structure of (I) is the first example of a three-coordinated Hg^II complex with a Cl₂Hg—O═P[N(C)(C)]₃ segment; (ii) there are only two phospho­ric tri­amide Hg^II structures present, namely bis­(dimesyl­amide-κN)(hexa­methyl­phospho­ramide-κO)mercury(II) (CSD refcode JUWNOE; Blaschette et al., 1993) and bis­(µ₃-hexa­methyl­phospho­ramide)­tris­(µ₂-perfluoro-o-phenyl­ene)trimercury(II) (CAMFEC; Tikhonova et al., 2002), in which the commercial material [(CH₃)₂N]₃P(O) was used for the preparation of these complexes, and (iii) the [C₅H₁₀N]₃PO ligand was used only in two complex structures, namely tris­(tripiperidinylphosphine oxide)tris­(iso­thio­cyanato)­praseodymium(III) (MALMAO; da Silva et al., 2005) and bis­(nitrato-κ²O,O')dioxidobis(tripiperidinylphosphine oxide-κO)uranium (LOPVUH; de Aquino et al., 2000), so far.

The asymmetric unit of (I) is composed of one HgCl₂{PO(C₅H₁₀N)₃} complex and one half of a HgCl₂ component (Fig. 1). In the discrete HgCl₂ component, the Hg2 atom is located at the inversion centre and hence shows an ideal linear coordination environment.

The Hg1—Cl bond lengths in the present mercury(II)–phospho­ramide complex are consistent with those reported for other complexes of Hg^II chloride (Li et al., 2012; Kubo et al., 2000) and are longer than the two equal Hg—Cl bond lengths in the discrete HgCl₂ entity (Table 2). The Hg1—O1 bond length is comparable to similar bonds in analogous structures (Yang et al., 2010).

In the HgCl₂{PO(C₅H₁₀N)₃} complex, the Cl1—Hg1—Cl2 segment shows a distortion of about 16° from a linear bonding arrangement, due to the presence of the coordinated phospho­ric tri­amide molecule. The coordinated O atom forms Cl1—Hg1—O1 and Cl2—Hg1—O1 angles of close to 90° (Table 2).

Khavasi and Azhdari Tehrani (2013) introduced a simple equation of τ₃ = |[(α + β + γ)/360] - |(α − 120)/60|| for the geometry index τ₃ of three-coordinated compounds. In this equation, α is the largest angle in the three-coordinated compound and the values of τ₃ will range from 1.00 for a perfect trigonal planar geometry to zero for a perfect T-shaped geometry. The τ₃ index for three coordinated Hg1 complex is 0.27, which implies a distorted T-shape geometry (Tiekink, 1987).

Using a van der Waals radius of 1.70 Å for mercury, 1.75 Å for chlorine and 1.50 Å for oxygen (Batsanov, 2001), four different noncovalent inter­actions are considered in (I), namely Hg1···Cl3 [3.154 (2) Å], Hg2···Cl2 [3.166 (2) Å], Hg2···O1 [2.940 (5) Å] and Hg1···Cl1ⁱⁱ [3.121 (2) Å; symmetry code: (ii) −x + 1, −y + 2, −z + 2]. The two last inter­actions take part in forming a chain along the a direction (Fig. 2) and the other two help to stabilize the aggregation with no effect on the pattern of extended structure formed. Such simultaneously close and distant bonded atoms are usual for mercury(II) (Canty, 1980). A view of linear chains in the crystal is shown in Fig. 3.

In order to prove the noncovalent nature of the Hg···Cl inter­action involving atom Hg1 in the three-coordinate complex, bond-valence calculations were performed using the equation S_ij = exp[(R₀–R_ij)/b_ij], where S_ij is the bond valence for atoms i and j, R₀ is the standard value of the bond distance for atoms i and j, R_ij is the actual bond distance between i and j, and b_ij is a constant (Brown & Altermatt, 1985). Such a calculation for the Hg[Cl]₂[O] segment provides a bond-valence sum (BVS) value of 2.142 v.u. for Hg, considering two Hg—Cl and one Hg—O bond (with R_ij as given in Table 2 for the Hg1—Cl1, Hg1—Cl2 and Hg1—O1 bond lengths, R₀ = 2.28 Å for Hg—Cl and 1.972 Å for Hg—O, and b_ij = 0.37; Brown, https://www.iucr.org/resources/data/datasets/bond-valence-parameters). Considering the Hg1···Cl1ⁱⁱ and Hg1···Cl3 inter­actions, the BVSs are calculated as 2.245 and 2.339 v.u. respectively, confirming the noncovalent nature of these inter­actions.

The P atom in the phospho­ric tri­amide ligand adopts a slightly distorted P[O][N]₃ tetra­hedral environment and the Hg1—O1—P1 unit is significantly bent, with an angle of 152.6 (3)°. Moreover, the P1═O1 bond length in complex (I) is longer than the P═O double-bond length in phospho­ric tri­amide compounds, for example, compared with tris­(morpholino)­phosphine oxide (BIVYAG; Romming & Songstad, 1982), which is the closest structure to the free ligand discussed here.

The six-membered piperidine rings in the phospho­ric tri­amide ligand adopt a near chair conformation on the base of puckering parameters calculated according to Cremer & Pople (1975), which are Q = 0.537 (10), θ = 7.9 (11)° and Φ = 6(9)° for the ring containing atom N1, Q = 0.507 (11), θ = 180.0 (14)° and Φ = 90 (308)° for the ring containing atom N2, and Q = 0.569 (10), θ = 2.4 (11)° and Φ = 307 (23)° for the ring containing atom N3.

Synthesis and crystallization

The preparation of the tris­(piperidin-1-yl)phosphane oxide ligand was reported previously as the by-product of the synthesis of [(C₅H₁₀N)₄P]Br (Schiemenz et al., 2001). The synthesis of (C₅H₁₀N)₃PO was performed in a different way. A dry aceto­nitrile solution of piperidine (1.2 M, 10 ml) was added dropwise to a solution of P(O)Cl₃ (2 mmol) in the same solvent (30 ml) at 273 K. After stirring for 4 h, the precipitated amine hydro­chloride salt (C₅H₁₀NH·HCl) was filtered off, and the aceto­nitrile solution of the tris­(piperidin-1-yl)phosphane oxide ligand was used in the complex reaction.

A solution of HgCl₂ (1 mmol) in methanol (10 ml) was added dropwise to the aceto­nitrile solution of (C₅H₁₀N)₃PO (2 mmol, 50 ml) and stirred for 48 h under reflux. After cooling to room temperature, colourless block-shaped crystals of (I) were obtained within a few days.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). DELU and SIMU instructions in SHELXL2014 (Sheldrick, 2015) were applied to atoms C6, C7, C8, C9 and C10 in order to limit the disorder in the corresponding ring. Splitting of the ring into two different parts did not solve the problems of displacement of some atoms in the ring. With these two instructions, the problem is not solved but limited. [Please descrive what the instructions do?]

Computing details

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 1999) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. Displacement ellipsoid plot (30% probability level) for the [HgCl2{PO(C5H10N)3}] and HgCl2 components in structure (I), showing the atom-labelling scheme. H atoms have been omitted for clarity. [Symmetry code: (i) −x, −y + 2, z + 2.]
	Fig. 2. A view of linear arrangement of components parallel to [100] built from Hg···Cl and Hg···O interactions. H atoms have been omitted for clarity. [Symmetry codes: (i) −x, −y + 2, −z + 2; (ii) −x + 1, −y + 2, −z + 2.]
	Fig. 3. A view of the crystal packing, viewed along the b axis, showing adjacent linear chains. The Hg···Cl and Hg···O interactions have been shown as dashed lines. H atoms have been omitted for clarity.

Dichlorido[tris(piperidin-1-yl)phosphane oxide-κO]mercury(II)–dichloridomercury(II) (2/1)

Crystal data

[HgCl2(C15H30N3OP)][HgCl2]	F(000) = 1340
Mr = 1413.25	Dx = 2.072 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.1182 (15) Å	Cell parameters from 19807 reflections
b = 10.5995 (8) Å	θ = 1.1–25.6°
c = 19.338 (3) Å	µ = 10.60 mm^−1
β = 96.337 (11)°	T = 300 K
V = 2265.0 (5) Å^3	Block, less
Z = 2	0.23 × 0.16 × 0.10 mm

Data collection

Stoe IPDS 2 diffractometer	4041 independent reflections
Radiation source: fine-focus sealed tube	3336 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
Detector resolution: 6.67 pixels mm^-1	θmax = 25.2°, θmin = 2.0°
rotation method scans	h = −13→13
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2002)	k = −12→12
Tmin = 0.066, Tmax = 0.133	l = −23→23
27440 measured reflections

Refinement

Refinement on F^2	31 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0217P)^2 + 5.1731P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
4041 reflections	Δρmax = 0.66 e Å^−3
223 parameters	Δρmin = −0.79 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. DELU and SIME instructions in SHELXL97 (Sheldrick, 2008) were applied to C6, C7, C8, C9, and C10 in order to limit the disorder in the corresponding ring. A splitting of the ring in two different parts was not solving the problems of displacement of some atoms in the ring. With these two instructions, the problem is not solved but limited.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1911 (11)	0.5083 (7)	0.9128 (5)	0.114 (4)
H1A	0.1217	0.4599	0.9239	0.137*
H1B	0.1886	0.5125	0.8626	0.137*
C2	0.3005 (10)	0.4461 (10)	0.9412 (6)	0.114 (3)
H2A	0.3693	0.4895	0.9255	0.137*
H2B	0.3003	0.3604	0.9235	0.137*
C3	0.2957 (11)	0.5713 (9)	1.0499 (5)	0.128 (4)
H3A	0.2892	0.5622	1.0992	0.153*
H3B	0.3652	0.6243	1.0445	0.153*
C4	0.3152 (10)	0.4423 (9)	1.0188 (6)	0.129 (4)
H4A	0.3958	0.4126	1.0352	0.155*
H4B	0.2575	0.3831	1.0346	0.155*
C5	0.1835 (8)	0.6340 (8)	1.0157 (4)	0.088 (2)
H5A	0.1126	0.5889	1.0274	0.105*
H5B	0.1792	0.7198	1.0326	0.105*
C6	0.4104 (8)	0.7807 (10)	0.8631 (5)	0.101 (3)
H6A	0.4135	0.8382	0.9023	0.121*
H6B	0.4504	0.7031	0.8792	0.121*
C7	0.4737 (11)	0.8352 (14)	0.8102 (6)	0.151 (5)
H7A	0.5585	0.8434	0.8280	0.181*
H7B	0.4424	0.9194	0.8003	0.181*
C8	0.4647 (10)	0.7608 (12)	0.7427 (5)	0.123 (3)
H8A	0.5102	0.6828	0.7495	0.148*
H8B	0.4980	0.8096	0.7069	0.148*
C9	0.3312 (10)	0.7319 (12)	0.7207 (5)	0.131 (4)
H9A	0.2905	0.8094	0.7049	0.158*
H9B	0.3253	0.6739	0.6816	0.158*
C10	0.2703 (10)	0.6786 (12)	0.7747 (5)	0.125 (4)
H10A	0.3019	0.5947	0.7851	0.150*
H10B	0.1849	0.6705	0.7584	0.150*
C11	0.0250 (9)	0.8724 (8)	0.7978 (5)	0.100 (3)
H11A	0.0994	0.9109	0.7864	0.120*
H11B	−0.0172	0.9336	0.8237	0.120*
C12	−0.0526 (11)	0.8387 (12)	0.7320 (5)	0.130 (4)
H12A	−0.0736	0.9149	0.7057	0.156*
H12B	−0.0069	0.7847	0.7039	0.156*
C13	−0.1650 (10)	0.7727 (11)	0.7461 (5)	0.122 (4)
H13A	−0.2095	0.7465	0.7024	0.147*
H13B	−0.2159	0.8301	0.7690	0.147*
C14	−0.1355 (9)	0.6590 (11)	0.7915 (5)	0.117 (3)
H14A	−0.0926	0.5973	0.7665	0.141*
H14B	−0.2098	0.6205	0.8032	0.141*
C15	−0.0569 (8)	0.6978 (9)	0.8585 (5)	0.098 (3)
H15A	−0.1020	0.7549	0.8851	0.118*
H15B	−0.0361	0.6237	0.8867	0.118*
Cl1	0.44342 (18)	1.12472 (19)	0.93393 (12)	0.0866 (6)
Cl2	0.2359 (2)	0.9726 (2)	1.10663 (10)	0.0895 (6)
Cl3	0.08680 (18)	1.17631 (17)	0.95927 (11)	0.0783 (5)
Hg1	0.32657 (3)	1.02803 (3)	1.00954 (2)	0.07212 (11)
Hg2	0.0000	1.0000	1.0000	0.07027 (13)
O1	0.1987 (4)	0.8749 (4)	0.9383 (2)	0.0708 (12)
P1	0.18104 (17)	0.76084 (17)	0.89264 (9)	0.0635 (5)
N1	0.1848 (6)	0.6350 (5)	0.9408 (3)	0.0774 (17)
N2	0.2835 (5)	0.7536 (6)	0.8382 (3)	0.0714 (15)
N3	0.0539 (5)	0.7600 (5)	0.8414 (3)	0.0689 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.192 (12)	0.061 (5)	0.084 (6)	0.014 (6)	−0.010 (7)	−0.005 (4)
C2	0.123 (8)	0.091 (6)	0.128 (9)	0.028 (6)	0.009 (7)	0.006 (6)
C3	0.180 (11)	0.096 (7)	0.089 (6)	−0.010 (7)	−0.060 (7)	0.012 (5)
C4	0.127 (8)	0.077 (6)	0.165 (11)	0.016 (6)	−0.065 (7)	0.016 (6)
C5	0.109 (7)	0.075 (5)	0.082 (6)	0.008 (5)	0.019 (5)	0.002 (4)
C6	0.086 (6)	0.127 (8)	0.092 (6)	−0.005 (5)	0.017 (5)	−0.036 (5)
C7	0.122 (8)	0.221 (13)	0.114 (8)	−0.076 (8)	0.033 (6)	−0.047 (7)
C8	0.113 (6)	0.164 (10)	0.099 (6)	−0.024 (7)	0.039 (6)	−0.021 (6)
C9	0.133 (8)	0.192 (11)	0.070 (6)	−0.052 (8)	0.014 (5)	−0.012 (6)
C10	0.115 (7)	0.178 (10)	0.086 (6)	−0.032 (7)	0.030 (6)	−0.043 (6)
C11	0.106 (7)	0.087 (6)	0.100 (7)	0.003 (5)	−0.023 (5)	0.022 (5)
C12	0.137 (10)	0.147 (10)	0.099 (8)	0.007 (8)	−0.020 (7)	0.014 (7)
C13	0.110 (9)	0.141 (10)	0.105 (8)	0.020 (7)	−0.037 (6)	−0.013 (7)
C14	0.105 (8)	0.137 (9)	0.103 (7)	−0.031 (7)	−0.021 (6)	−0.015 (6)
C15	0.085 (6)	0.115 (7)	0.091 (6)	−0.017 (5)	−0.003 (5)	0.010 (5)
Cl1	0.0726 (12)	0.0741 (12)	0.1148 (16)	0.0062 (10)	0.0178 (11)	0.0170 (11)
Cl2	0.0850 (13)	0.1108 (16)	0.0726 (12)	0.0067 (12)	0.0082 (10)	−0.0037 (11)
Cl3	0.0775 (12)	0.0641 (10)	0.0962 (14)	−0.0030 (9)	0.0231 (10)	0.0111 (9)
Hg1	0.06359 (18)	0.06830 (18)	0.0848 (2)	0.00149 (14)	0.00990 (14)	−0.00687 (14)
Hg2	0.0711 (3)	0.0643 (2)	0.0750 (3)	−0.01132 (18)	0.0064 (2)	0.00707 (18)
O1	0.083 (3)	0.058 (3)	0.071 (3)	−0.006 (2)	0.006 (2)	−0.014 (2)
P1	0.0709 (12)	0.0579 (10)	0.0600 (11)	0.0033 (9)	−0.0001 (9)	−0.0061 (8)
N1	0.113 (5)	0.052 (3)	0.063 (4)	0.013 (3)	−0.008 (3)	−0.002 (3)
N2	0.069 (4)	0.077 (4)	0.067 (4)	−0.004 (3)	0.004 (3)	−0.016 (3)
N3	0.065 (4)	0.068 (4)	0.071 (4)	−0.001 (3)	−0.001 (3)	0.006 (3)

Geometric parameters (Å, º)

C1—C2	1.438 (13)	C10—N2	1.457 (10)
C1—N1	1.452 (9)	C10—H10A	0.9700
C1—H1A	0.9700	C10—H10B	0.9700
C1—H1B	0.9700	C11—N3	1.475 (9)
C2—C4	1.493 (13)	C11—C12	1.500 (12)
C2—H2A	0.9700	C11—H11A	0.9700
C2—H2B	0.9700	C11—H11B	0.9700
C3—C5	1.501 (12)	C12—C13	1.483 (15)
C3—C4	1.518 (14)	C12—H12A	0.9700
C3—H3A	0.9700	C12—H12B	0.9700
C3—H3B	0.9700	C13—C14	1.507 (14)
C4—H4A	0.9700	C13—H13A	0.9700
C4—H4B	0.9700	C13—H13B	0.9700
C5—N1	1.450 (9)	C14—C15	1.536 (11)
C5—H5A	0.9700	C14—H14A	0.9700
C5—H5B	0.9700	C14—H14B	0.9700
C6—C7	1.426 (13)	C15—N3	1.467 (10)
C6—N2	1.469 (10)	C15—H15A	0.9700
C6—H6A	0.9700	C15—H15B	0.9700
C6—H6B	0.9700	Hg1—Cl1	2.301 (2)
C7—C8	1.519 (13)	Hg1—Cl2	2.303 (2)
C7—H7A	0.9700	Hg1—O1	2.474 (4)
C7—H7B	0.9700	Hg2—Cl3	2.2829 (17)
C8—C9	1.530 (14)	Hg2—Cl3^i	2.2829 (18)
C8—H8A	0.9700	P1—O1	1.497 (4)
C8—H8B	0.9700	P1—N1	1.625 (6)
C9—C10	1.423 (13)	P1—N3	1.634 (6)
C9—H9A	0.9700	P1—N2	1.636 (6)
C9—H9B	0.9700
C2—C1—N1	110.8 (8)	C9—C10—H10A	109.0
C2—C1—H1A	109.5	N2—C10—H10A	109.0
N1—C1—H1A	109.5	C9—C10—H10B	109.0
C2—C1—H1B	109.5	N2—C10—H10B	109.0
N1—C1—H1B	109.5	H10A—C10—H10B	107.8
H1A—C1—H1B	108.1	N3—C11—C12	111.2 (8)
C1—C2—C4	113.0 (9)	N3—C11—H11A	109.4
C1—C2—H2A	109.0	C12—C11—H11A	109.4
C4—C2—H2A	109.0	N3—C11—H11B	109.4
C1—C2—H2B	109.0	C12—C11—H11B	109.4
C4—C2—H2B	109.0	H11A—C11—H11B	108.0
H2A—C2—H2B	107.8	C13—C12—C11	112.0 (9)
C5—C3—C4	111.9 (7)	C13—C12—H12A	109.2
C5—C3—H3A	109.2	C11—C12—H12A	109.2
C4—C3—H3A	109.2	C13—C12—H12B	109.2
C5—C3—H3B	109.2	C11—C12—H12B	109.2
C4—C3—H3B	109.2	H12A—C12—H12B	107.9
H3A—C3—H3B	107.9	C12—C13—C14	110.5 (9)
C2—C4—C3	111.6 (8)	C12—C13—H13A	109.6
C2—C4—H4A	109.3	C14—C13—H13A	109.6
C3—C4—H4A	109.3	C12—C13—H13B	109.6
C2—C4—H4B	109.3	C14—C13—H13B	109.6
C3—C4—H4B	109.3	H13A—C13—H13B	108.1
H4A—C4—H4B	108.0	C13—C14—C15	110.1 (9)
N1—C5—C3	110.1 (7)	C13—C14—H14A	109.6
N1—C5—H5A	109.6	C15—C14—H14A	109.6
C3—C5—H5A	109.6	C13—C14—H14B	109.6
N1—C5—H5B	109.6	C15—C14—H14B	109.6
C3—C5—H5B	109.6	H14A—C14—H14B	108.1
H5A—C5—H5B	108.2	N3—C15—C14	110.2 (7)
C7—C6—N2	112.1 (8)	N3—C15—H15A	109.6
C7—C6—H6A	109.2	C14—C15—H15A	109.6
N2—C6—H6A	109.2	N3—C15—H15B	109.6
C7—C6—H6B	109.2	C14—C15—H15B	109.6
N2—C6—H6B	109.2	H15A—C15—H15B	108.1
H6A—C6—H6B	107.9	Cl1—Hg1—Cl2	163.79 (8)
C6—C7—C8	114.5 (10)	Cl1—Hg1—O1	105.57 (13)
C6—C7—H7A	108.6	Cl2—Hg1—O1	90.58 (12)
C8—C7—H7A	108.6	Cl3^i—Hg2—Cl3	180.0
C6—C7—H7B	108.6	P1—O1—Hg1	152.6 (3)
C8—C7—H7B	108.6	O1—P1—N1	109.4 (3)
H7A—C7—H7B	107.6	N1—P1—N3	108.0 (3)
C7—C8—C9	108.2 (9)	O1—P1—N2	111.2 (3)
C7—C8—H8A	110.0	O1—P1—N3	114.2 (3)
C9—C8—H8A	110.0	N1—P1—N2	110.8 (3)
C7—C8—H8B	110.0	N3—P1—N2	103.1 (3)
C9—C8—H8B	110.0	C5—N1—C1	111.8 (6)
H8A—C8—H8B	108.4	C5—N1—P1	125.2 (5)
C10—C9—C8	113.6 (9)	C1—N1—P1	123.0 (5)
C10—C9—H9A	108.8	C10—N2—C6	112.8 (7)
C8—C9—H9A	108.8	C10—N2—P1	123.7 (6)
C10—C9—H9B	108.8	C6—N2—P1	119.5 (5)
C8—C9—H9B	108.8	C15—N3—C11	110.8 (6)
H9A—C9—H9B	107.7	C15—N3—P1	123.9 (5)
C9—C10—N2	113.0 (9)	C11—N3—P1	117.5 (5)
N1—C1—C2—C4	55.8 (13)	N3—P1—N1—C1	66.0 (9)
C1—C2—C4—C3	−49.4 (14)	N2—P1—N1—C1	−46.3 (9)
C5—C3—C4—C2	47.2 (14)	C9—C10—N2—C6	−53.4 (13)
C4—C3—C5—N1	−52.2 (11)	C9—C10—N2—P1	149.3 (8)
N2—C6—C7—C8	−52.8 (14)	C7—C6—N2—C10	52.7 (12)
C6—C7—C8—C9	50.3 (15)	C7—C6—N2—P1	−149.0 (8)
C7—C8—C9—C10	−50.1 (15)	O1—P1—N2—C10	−160.6 (8)
C8—C9—C10—N2	53.2 (15)	N1—P1—N2—C10	77.5 (8)
N3—C11—C12—C13	55.9 (12)	N3—P1—N2—C10	−37.8 (8)
C11—C12—C13—C14	−54.6 (13)	O1—P1—N2—C6	43.6 (7)
C12—C13—C14—C15	55.0 (13)	N1—P1—N2—C6	−78.3 (7)
C13—C14—C15—N3	−57.4 (12)	N3—P1—N2—C6	166.4 (6)
Hg1—O1—P1—N1	83.1 (7)	C14—C15—N3—C11	58.7 (10)
Hg1—O1—P1—N3	−155.7 (6)	C14—C15—N3—P1	−152.9 (7)
Hg1—O1—P1—N2	−39.5 (7)	C12—C11—N3—C15	−57.9 (11)
C3—C5—N1—C1	59.3 (10)	C12—C11—N3—P1	151.5 (7)
C3—C5—N1—P1	−120.2 (7)	O1—P1—N3—C15	−94.5 (7)
C2—C1—N1—C5	−61.4 (11)	N1—P1—N3—C15	27.4 (7)
C2—C1—N1—P1	118.1 (8)	N2—P1—N3—C15	144.6 (7)
O1—P1—N1—C5	10.2 (8)	O1—P1—N3—C11	51.9 (7)
N3—P1—N1—C5	−114.6 (7)	N1—P1—N3—C11	173.8 (6)
N2—P1—N1—C5	133.1 (7)	N2—P1—N3—C11	−68.9 (7)
O1—P1—N1—C1	−169.2 (8)

Symmetry code: (i) −x, −y+2, −z+2.