Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616002394/lg3182sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616002394/lg3182Isup2.hkl |
CCDC reference: 1437491
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—O═P[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 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.
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?]
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[(R0–Rij)/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 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.
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—O═P[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[(R0–Rij)/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 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.
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.
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?]
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).
[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) Å3 | Block, less |
Z = 2 | 0.23 × 0.16 × 0.10 mm |
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 on F2 | 31 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-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 reflections | Δρmax = 0.66 e Å−3 |
223 parameters | Δρmin = −0.79 e Å−3 |
[HgCl2(C15H30N3OP)][HgCl2] | V = 2265.0 (5) Å3 |
Mr = 1413.25 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1182 (15) Å | µ = 10.60 mm−1 |
b = 10.5995 (8) Å | T = 300 K |
c = 19.338 (3) Å | 0.23 × 0.16 × 0.10 mm |
β = 96.337 (11)° |
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 = 0.133 | Rint = 0.061 |
27440 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 31 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.66 e Å−3 |
4041 reflections | Δρmin = −0.79 e Å−3 |
223 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—Cl3i | 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 | Cl3i—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. |
Experimental details
Crystal data | |
Chemical formula | [HgCl2(C15H30N3OP)][HgCl2] |
Mr | 1413.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 300 |
a, b, c (Å) | 11.1182 (15), 10.5995 (8), 19.338 (3) |
β (°) | 96.337 (11) |
V (Å3) | 2265.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 10.60 |
Crystal size (mm) | 0.23 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Integration (X-SHAPE; Stoe & Cie, 2002) |
Tmin, Tmax | 0.066, 0.133 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27440, 4041, 3336 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.074, 1.05 |
No. of reflections | 4041 |
No. of parameters | 223 |
No. of restraints | 31 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
Hg1—Cl1 | 2.301 (2) | P1—O1 | 1.497 (4) |
Hg1—Cl2 | 2.303 (2) | P1—N1 | 1.625 (6) |
Hg1—O1 | 2.474 (4) | P1—N3 | 1.634 (6) |
Hg2—Cl3 | 2.2829 (17) | P1—N2 | 1.636 (6) |
Cl1—Hg1—Cl2 | 163.79 (8) | P1—O1—Hg1 | 152.6 (3) |
Cl1—Hg1—O1 | 105.57 (13) | O1—P1—N1 | 109.4 (3) |
Cl2—Hg1—O1 | 90.58 (12) | O1—P1—N2 | 111.2 (3) |
Cl3i—Hg2—Cl3 | 180.0 | O1—P1—N3 | 114.2 (3) |
Symmetry code: (i) −x, −y+2, −z+2. |