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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 HgII centre in the complex component is a distorted T-shape. Bond-valence-sum calculations confirm the three-coordination mode of the HgII atom of the complex mol­ecule. The noncovalent nature of the Hg...Cl and Hg...O inter­actions in the structure are discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616002394/lg3182sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616002394/lg3182Isup2.hkl
Contains datablock I

CCDC reference: 1437491

Introduction top

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 HgII complex with a Cl2Hg—OP[N(C)(C)]3 segment; (ii) there are only two phospho­ric tri­amide HgII 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.

Experimental top

Synthesis and crystallization top

Synthesis of (C5H10N)3PO top

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.

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

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 top

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 Uiso(H) = 1.2Ueq(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?]

Results and discussion top

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 HgII 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 Sij = exp[(R0Rij)/bij], where Sij is the bond valence for atoms i and j, R0 is the standard value of the bond distance for atoms i and j, Rij is the actual bond distance between i and j, and bij 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 Rij 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 bij = 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 P1O1 bond length in complex (I) is longer than the PO 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 top

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 HgII complex with a Cl2Hg—OP[N(C)(C)]3 segment; (ii) there are only two phospho­ric tri­amide HgII 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 HgII 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 Sij = exp[(R0Rij)/bij], where Sij is the bond valence for atoms i and j, R0 is the standard value of the bond distance for atoms i and j, Rij is the actual bond distance between i and j, and bij 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 Rij 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 bij = 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 P1O1 bond length in complex (I) is longer than the PO 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 top

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 top

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 Uiso(H) = 1.2Ueq(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 top

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 top
[Figure 1] 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.]
[Figure 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.]
[Figure 3] 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) top
Crystal data top
[HgCl2(C15H30N3OP)][HgCl2]F(000) = 1340
Mr = 1413.25Dx = 2.072 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.1182 (15) ÅCell parameters from 19807 reflections
b = 10.5995 (8) Åθ = 1.1–25.6°
c = 19.338 (3) ŵ = 10.60 mm1
β = 96.337 (11)°T = 300 K
V = 2265.0 (5) Å3Block, less
Z = 20.23 × 0.16 × 0.10 mm
Data collection top
Stoe IPDS 2
diffractometer
4041 independent reflections
Radiation source: fine-focus sealed tube3336 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
Detector resolution: 6.67 pixels mm-1θmax = 25.2°, θmin = 2.0°
rotation method scansh = 1313
Absorption correction: integration
(X-SHAPE; Stoe & Cie, 2002)
k = 1212
Tmin = 0.066, Tmax = 0.133l = 2323
27440 measured reflections
Refinement top
Refinement on F231 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0217P)2 + 5.1731P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
4041 reflectionsΔρmax = 0.66 e Å3
223 parametersΔρmin = 0.79 e Å3
Crystal data top
[HgCl2(C15H30N3OP)][HgCl2]V = 2265.0 (5) Å3
Mr = 1413.25Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.1182 (15) ŵ = 10.60 mm1
b = 10.5995 (8) ÅT = 300 K
c = 19.338 (3) Å0.23 × 0.16 × 0.10 mm
β = 96.337 (11)°
Data collection top
Stoe IPDS 2
diffractometer
4041 independent reflections
Absorption correction: integration
(X-SHAPE; Stoe & Cie, 2002)
3336 reflections with I > 2σ(I)
Tmin = 0.066, Tmax = 0.133Rint = 0.061
27440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03631 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 1.05Δρmax = 0.66 e Å3
4041 reflectionsΔρmin = 0.79 e Å3
223 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.1911 (11)0.5083 (7)0.9128 (5)0.114 (4)
H1A0.12170.45990.92390.137*
H1B0.18860.51250.86260.137*
C20.3005 (10)0.4461 (10)0.9412 (6)0.114 (3)
H2A0.36930.48950.92550.137*
H2B0.30030.36040.92350.137*
C30.2957 (11)0.5713 (9)1.0499 (5)0.128 (4)
H3A0.28920.56221.09920.153*
H3B0.36520.62431.04450.153*
C40.3152 (10)0.4423 (9)1.0188 (6)0.129 (4)
H4A0.39580.41261.03520.155*
H4B0.25750.38311.03460.155*
C50.1835 (8)0.6340 (8)1.0157 (4)0.088 (2)
H5A0.11260.58891.02740.105*
H5B0.17920.71981.03260.105*
C60.4104 (8)0.7807 (10)0.8631 (5)0.101 (3)
H6A0.41350.83820.90230.121*
H6B0.45040.70310.87920.121*
C70.4737 (11)0.8352 (14)0.8102 (6)0.151 (5)
H7A0.55850.84340.82800.181*
H7B0.44240.91940.80030.181*
C80.4647 (10)0.7608 (12)0.7427 (5)0.123 (3)
H8A0.51020.68280.74950.148*
H8B0.49800.80960.70690.148*
C90.3312 (10)0.7319 (12)0.7207 (5)0.131 (4)
H9A0.29050.80940.70490.158*
H9B0.32530.67390.68160.158*
C100.2703 (10)0.6786 (12)0.7747 (5)0.125 (4)
H10A0.30190.59470.78510.150*
H10B0.18490.67050.75840.150*
C110.0250 (9)0.8724 (8)0.7978 (5)0.100 (3)
H11A0.09940.91090.78640.120*
H11B0.01720.93360.82370.120*
C120.0526 (11)0.8387 (12)0.7320 (5)0.130 (4)
H12A0.07360.91490.70570.156*
H12B0.00690.78470.70390.156*
C130.1650 (10)0.7727 (11)0.7461 (5)0.122 (4)
H13A0.20950.74650.70240.147*
H13B0.21590.83010.76900.147*
C140.1355 (9)0.6590 (11)0.7915 (5)0.117 (3)
H14A0.09260.59730.76650.141*
H14B0.20980.62050.80320.141*
C150.0569 (8)0.6978 (9)0.8585 (5)0.098 (3)
H15A0.10200.75490.88510.118*
H15B0.03610.62370.88670.118*
Cl10.44342 (18)1.12472 (19)0.93393 (12)0.0866 (6)
Cl20.2359 (2)0.9726 (2)1.10663 (10)0.0895 (6)
Cl30.08680 (18)1.17631 (17)0.95927 (11)0.0783 (5)
Hg10.32657 (3)1.02803 (3)1.00954 (2)0.07212 (11)
Hg20.00001.00001.00000.07027 (13)
O10.1987 (4)0.8749 (4)0.9383 (2)0.0708 (12)
P10.18104 (17)0.76084 (17)0.89264 (9)0.0635 (5)
N10.1848 (6)0.6350 (5)0.9408 (3)0.0774 (17)
N20.2835 (5)0.7536 (6)0.8382 (3)0.0714 (15)
N30.0539 (5)0.7600 (5)0.8414 (3)0.0689 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.192 (12)0.061 (5)0.084 (6)0.014 (6)0.010 (7)0.005 (4)
C20.123 (8)0.091 (6)0.128 (9)0.028 (6)0.009 (7)0.006 (6)
C30.180 (11)0.096 (7)0.089 (6)0.010 (7)0.060 (7)0.012 (5)
C40.127 (8)0.077 (6)0.165 (11)0.016 (6)0.065 (7)0.016 (6)
C50.109 (7)0.075 (5)0.082 (6)0.008 (5)0.019 (5)0.002 (4)
C60.086 (6)0.127 (8)0.092 (6)0.005 (5)0.017 (5)0.036 (5)
C70.122 (8)0.221 (13)0.114 (8)0.076 (8)0.033 (6)0.047 (7)
C80.113 (6)0.164 (10)0.099 (6)0.024 (7)0.039 (6)0.021 (6)
C90.133 (8)0.192 (11)0.070 (6)0.052 (8)0.014 (5)0.012 (6)
C100.115 (7)0.178 (10)0.086 (6)0.032 (7)0.030 (6)0.043 (6)
C110.106 (7)0.087 (6)0.100 (7)0.003 (5)0.023 (5)0.022 (5)
C120.137 (10)0.147 (10)0.099 (8)0.007 (8)0.020 (7)0.014 (7)
C130.110 (9)0.141 (10)0.105 (8)0.020 (7)0.037 (6)0.013 (7)
C140.105 (8)0.137 (9)0.103 (7)0.031 (7)0.021 (6)0.015 (6)
C150.085 (6)0.115 (7)0.091 (6)0.017 (5)0.003 (5)0.010 (5)
Cl10.0726 (12)0.0741 (12)0.1148 (16)0.0062 (10)0.0178 (11)0.0170 (11)
Cl20.0850 (13)0.1108 (16)0.0726 (12)0.0067 (12)0.0082 (10)0.0037 (11)
Cl30.0775 (12)0.0641 (10)0.0962 (14)0.0030 (9)0.0231 (10)0.0111 (9)
Hg10.06359 (18)0.06830 (18)0.0848 (2)0.00149 (14)0.00990 (14)0.00687 (14)
Hg20.0711 (3)0.0643 (2)0.0750 (3)0.01132 (18)0.0064 (2)0.00707 (18)
O10.083 (3)0.058 (3)0.071 (3)0.006 (2)0.006 (2)0.014 (2)
P10.0709 (12)0.0579 (10)0.0600 (11)0.0033 (9)0.0001 (9)0.0061 (8)
N10.113 (5)0.052 (3)0.063 (4)0.013 (3)0.008 (3)0.002 (3)
N20.069 (4)0.077 (4)0.067 (4)0.004 (3)0.004 (3)0.016 (3)
N30.065 (4)0.068 (4)0.071 (4)0.001 (3)0.001 (3)0.006 (3)
Geometric parameters (Å, º) top
C1—C21.438 (13)C10—N21.457 (10)
C1—N11.452 (9)C10—H10A0.9700
C1—H1A0.9700C10—H10B0.9700
C1—H1B0.9700C11—N31.475 (9)
C2—C41.493 (13)C11—C121.500 (12)
C2—H2A0.9700C11—H11A0.9700
C2—H2B0.9700C11—H11B0.9700
C3—C51.501 (12)C12—C131.483 (15)
C3—C41.518 (14)C12—H12A0.9700
C3—H3A0.9700C12—H12B0.9700
C3—H3B0.9700C13—C141.507 (14)
C4—H4A0.9700C13—H13A0.9700
C4—H4B0.9700C13—H13B0.9700
C5—N11.450 (9)C14—C151.536 (11)
C5—H5A0.9700C14—H14A0.9700
C5—H5B0.9700C14—H14B0.9700
C6—C71.426 (13)C15—N31.467 (10)
C6—N21.469 (10)C15—H15A0.9700
C6—H6A0.9700C15—H15B0.9700
C6—H6B0.9700Hg1—Cl12.301 (2)
C7—C81.519 (13)Hg1—Cl22.303 (2)
C7—H7A0.9700Hg1—O12.474 (4)
C7—H7B0.9700Hg2—Cl32.2829 (17)
C8—C91.530 (14)Hg2—Cl3i2.2829 (18)
C8—H8A0.9700P1—O11.497 (4)
C8—H8B0.9700P1—N11.625 (6)
C9—C101.423 (13)P1—N31.634 (6)
C9—H9A0.9700P1—N21.636 (6)
C9—H9B0.9700
C2—C1—N1110.8 (8)C9—C10—H10A109.0
C2—C1—H1A109.5N2—C10—H10A109.0
N1—C1—H1A109.5C9—C10—H10B109.0
C2—C1—H1B109.5N2—C10—H10B109.0
N1—C1—H1B109.5H10A—C10—H10B107.8
H1A—C1—H1B108.1N3—C11—C12111.2 (8)
C1—C2—C4113.0 (9)N3—C11—H11A109.4
C1—C2—H2A109.0C12—C11—H11A109.4
C4—C2—H2A109.0N3—C11—H11B109.4
C1—C2—H2B109.0C12—C11—H11B109.4
C4—C2—H2B109.0H11A—C11—H11B108.0
H2A—C2—H2B107.8C13—C12—C11112.0 (9)
C5—C3—C4111.9 (7)C13—C12—H12A109.2
C5—C3—H3A109.2C11—C12—H12A109.2
C4—C3—H3A109.2C13—C12—H12B109.2
C5—C3—H3B109.2C11—C12—H12B109.2
C4—C3—H3B109.2H12A—C12—H12B107.9
H3A—C3—H3B107.9C12—C13—C14110.5 (9)
C2—C4—C3111.6 (8)C12—C13—H13A109.6
C2—C4—H4A109.3C14—C13—H13A109.6
C3—C4—H4A109.3C12—C13—H13B109.6
C2—C4—H4B109.3C14—C13—H13B109.6
C3—C4—H4B109.3H13A—C13—H13B108.1
H4A—C4—H4B108.0C13—C14—C15110.1 (9)
N1—C5—C3110.1 (7)C13—C14—H14A109.6
N1—C5—H5A109.6C15—C14—H14A109.6
C3—C5—H5A109.6C13—C14—H14B109.6
N1—C5—H5B109.6C15—C14—H14B109.6
C3—C5—H5B109.6H14A—C14—H14B108.1
H5A—C5—H5B108.2N3—C15—C14110.2 (7)
C7—C6—N2112.1 (8)N3—C15—H15A109.6
C7—C6—H6A109.2C14—C15—H15A109.6
N2—C6—H6A109.2N3—C15—H15B109.6
C7—C6—H6B109.2C14—C15—H15B109.6
N2—C6—H6B109.2H15A—C15—H15B108.1
H6A—C6—H6B107.9Cl1—Hg1—Cl2163.79 (8)
C6—C7—C8114.5 (10)Cl1—Hg1—O1105.57 (13)
C6—C7—H7A108.6Cl2—Hg1—O190.58 (12)
C8—C7—H7A108.6Cl3i—Hg2—Cl3180.0
C6—C7—H7B108.6P1—O1—Hg1152.6 (3)
C8—C7—H7B108.6O1—P1—N1109.4 (3)
H7A—C7—H7B107.6N1—P1—N3108.0 (3)
C7—C8—C9108.2 (9)O1—P1—N2111.2 (3)
C7—C8—H8A110.0O1—P1—N3114.2 (3)
C9—C8—H8A110.0N1—P1—N2110.8 (3)
C7—C8—H8B110.0N3—P1—N2103.1 (3)
C9—C8—H8B110.0C5—N1—C1111.8 (6)
H8A—C8—H8B108.4C5—N1—P1125.2 (5)
C10—C9—C8113.6 (9)C1—N1—P1123.0 (5)
C10—C9—H9A108.8C10—N2—C6112.8 (7)
C8—C9—H9A108.8C10—N2—P1123.7 (6)
C10—C9—H9B108.8C6—N2—P1119.5 (5)
C8—C9—H9B108.8C15—N3—C11110.8 (6)
H9A—C9—H9B107.7C15—N3—P1123.9 (5)
C9—C10—N2113.0 (9)C11—N3—P1117.5 (5)
N1—C1—C2—C455.8 (13)N3—P1—N1—C166.0 (9)
C1—C2—C4—C349.4 (14)N2—P1—N1—C146.3 (9)
C5—C3—C4—C247.2 (14)C9—C10—N2—C653.4 (13)
C4—C3—C5—N152.2 (11)C9—C10—N2—P1149.3 (8)
N2—C6—C7—C852.8 (14)C7—C6—N2—C1052.7 (12)
C6—C7—C8—C950.3 (15)C7—C6—N2—P1149.0 (8)
C7—C8—C9—C1050.1 (15)O1—P1—N2—C10160.6 (8)
C8—C9—C10—N253.2 (15)N1—P1—N2—C1077.5 (8)
N3—C11—C12—C1355.9 (12)N3—P1—N2—C1037.8 (8)
C11—C12—C13—C1454.6 (13)O1—P1—N2—C643.6 (7)
C12—C13—C14—C1555.0 (13)N1—P1—N2—C678.3 (7)
C13—C14—C15—N357.4 (12)N3—P1—N2—C6166.4 (6)
Hg1—O1—P1—N183.1 (7)C14—C15—N3—C1158.7 (10)
Hg1—O1—P1—N3155.7 (6)C14—C15—N3—P1152.9 (7)
Hg1—O1—P1—N239.5 (7)C12—C11—N3—C1557.9 (11)
C3—C5—N1—C159.3 (10)C12—C11—N3—P1151.5 (7)
C3—C5—N1—P1120.2 (7)O1—P1—N3—C1594.5 (7)
C2—C1—N1—C561.4 (11)N1—P1—N3—C1527.4 (7)
C2—C1—N1—P1118.1 (8)N2—P1—N3—C15144.6 (7)
O1—P1—N1—C510.2 (8)O1—P1—N3—C1151.9 (7)
N3—P1—N1—C5114.6 (7)N1—P1—N3—C11173.8 (6)
N2—P1—N1—C5133.1 (7)N2—P1—N3—C1168.9 (7)
O1—P1—N1—C1169.2 (8)
Symmetry code: (i) x, y+2, z+2.

Experimental details

Crystal data
Chemical formula[HgCl2(C15H30N3OP)][HgCl2]
Mr1413.25
Crystal system, space groupMonoclinic, P21/n
Temperature (K)300
a, b, c (Å)11.1182 (15), 10.5995 (8), 19.338 (3)
β (°) 96.337 (11)
V3)2265.0 (5)
Z2
Radiation typeMo Kα
µ (mm1)10.60
Crystal size (mm)0.23 × 0.16 × 0.10
Data collection
DiffractometerStoe IPDS 2
Absorption correctionIntegration
(X-SHAPE; Stoe & Cie, 2002)
Tmin, Tmax0.066, 0.133
No. of measured, independent and
observed [I > 2σ(I)] reflections
27440, 4041, 3336
Rint0.061
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.074, 1.05
No. of reflections4041
No. of parameters223
No. of restraints31
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.66, 0.79

Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 1999) and ORTEP-3 for Windows (Farrugia, 2012).

Selected geometric parameters (Å, º) top
Hg1—Cl12.301 (2)P1—O11.497 (4)
Hg1—Cl22.303 (2)P1—N11.625 (6)
Hg1—O12.474 (4)P1—N31.634 (6)
Hg2—Cl32.2829 (17)P1—N21.636 (6)
Cl1—Hg1—Cl2163.79 (8)P1—O1—Hg1152.6 (3)
Cl1—Hg1—O1105.57 (13)O1—P1—N1109.4 (3)
Cl2—Hg1—O190.58 (12)O1—P1—N2111.2 (3)
Cl3i—Hg2—Cl3180.0O1—P1—N3114.2 (3)
Symmetry code: (i) x, y+2, z+2.
 

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