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Crystal structure of (N1-benzyl-N1,N2,N2-tri­methyl­ethane-1,2-di­amine-κ2N,N′)di­chloridomercury(II)

aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India, and bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 27 June 2014; accepted 30 July 2014; online 6 August 2014)

In the structure of the title compound, [HgCl2(C12H20N2)], the HgII atom has a distorted tetra­hedral coordination sphere defined by two tertiary amine N-atom donors, as well as two Cl anions [the dihedral angle between the N—Hg—N and Cl—Hg—Cl planes is 82.80 (9)°]. The five-membered chelate ring adopts an envelope conformation, with puckering parameters of Q(2) = 0.446 (6) Å and φ(2) = 88.8 (6)°, with the two amine CH3 substituents on opposite sides of the ring. In the crystal, the mol­ecules are linked by C—H⋯Cl inter­actions into a zigzag chain parallel to [101].

1. Chemical context

The chemistry of mercuric compounds with multidentate amine ligands is of inter­est due to the low coordination number and geometry preferences of HgII, which facilitates extraordinarily rapid exchange of simple ligands (Bebout et al., 2013[Bebout, D. C., Bowers, E. V., Freer, R. E., Kastner, M. E., Parrish, D. A., Raymond, J. & Butcher, R. J. (2013). J. Chem. Crystallogr. 43, 108-115.]; Carra et al., 2013[Carra, B. J., Berry, S. M., Pike, R. D., Deborah, C. & Bebout, D. C. (2013). Dalton Trans. 42, 14424-14431.]). The enhanced binding thermodynamics of these multidentate ligands has been used to suppress inter­molecular ligand-exchange rates for a variety of HgII complexes in solution, greatly enhancing the meaningfulness of NMR characterization. Significantly, under conditions of slow inter­molecular exchange the rates of intra­molecular isomerization processes for HgII can still exceed both the chemical shift and coupling constant time scale, particularly when bond cleavage is unnecessary and structures of these complexes have been determined (Bebout et al., 2013[Bebout, D. C., Bowers, E. V., Freer, R. E., Kastner, M. E., Parrish, D. A., Raymond, J. & Butcher, R. J. (2013). J. Chem. Crystallogr. 43, 108-115.]; Carra et al., 2013[Carra, B. J., Berry, S. M., Pike, R. D., Deborah, C. & Bebout, D. C. (2013). Dalton Trans. 42, 14424-14431.]).

[Scheme 1]

In view of this inter­est in the coordination chemistry of mercury with multidentate amine ligands, and the lack of such structures involving tertiary amine donors, we report here the structure of the HgCl2 adduct of N1-benzyl-N1,N2,N2-tri­methyl­ethane-1,2-di­amine. The o-di­amine-substituted aryl bromide, N1-(2-bromo­benz­yl)-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, can be prepared by the reaction of N1,N1,N2-tri­methyl­ethane-1,2-di­amine and ortho-bromo­benzyl bromide. The ligand is moisture sensitive and is difficult to purify by column chromatography. However, it could easily be purified by vacuum distillation. The moisture-sensitive ligand, when treated with n-BuLi in tetra­hydro­furan (THF) and mercuric chloride, afforded the title compound, [HgCl2(C12H20N2)], (3) (Fig. 1[link]).

[Figure 1]
Figure 1
Reaction scheme showing the synthesis of the title compound.

2. Structural commentary

In the structure of (3), the HgII atom is four-coordinated by two tertiary amine N-atom donors, as well as two Cl anions to give a distorted tetra­hedral coordination environment (Fig. 2[link]). The distortion from ideal values can be seen by the dihedral angle between the N1—Hg—N2 and Cl1—Hg—Cl2 planes of 82.80 (9)°. The Hg—N and Hg—Cl bond lengths are in the normal ranges for such bonds (Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]). The five-membered chelate ring adopts an envelope conformation with puckering parameters of Q(2) = 0.446 (6)Å and φ(2) = 88.8 (6)° (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]), with the two amine CH3 substituents on opposite sides of the ring. Of the two reported structures which contain HgII attached to tertiary N donors (Choi et al., 2005[Choi, S.-N., Kim, S.-Y., Ryu, H.-W. & Lee, Y.-M. (2005). Acta Cryst. C61, m504-m506.]; Niu et al., 2004[Niu, W., Wong, E. H., Hill, D. C., Tranchemontage, D. J., Lam, K.-C., Sommer, R. D., Zakharov, L. N. & Rheingold, A. L. (2004). Dalton Trans. pp. 3536-3547.]), only one has HgII in an N2Cl2 coordination environment (Choi et al., 2005[Choi, S.-N., Kim, S.-Y., Ryu, H.-W. & Lee, Y.-M. (2005). Acta Cryst. C61, m504-m506.]) and thus provides the best comparison. The Hg—Cl [2.3875 (14) and 2.4397 (13) Å] and Hg—N bond lengths [2.355 (4) and 2.411 (4) Å] in (3) agree well with those found in the previous example [Hg—Cl = 2.397 (3) and 2.374 (2) Å; Hg—N = 2.353 (7) and 2.391 (6) Å].

[Figure 2]
Figure 2
The mol­ecular structure of [HgCl2(C12H20N2)], showing the atom labelling and displacement ellipsoids at the 30% probability level.

3. Supra­molecular features

The mol­ecular adducts are linked by C—H⋯Cl inter­actions (Table 1[link] and Fig. 3[link]) into a zigzag chain parallel to [101]. As a result of the bulky nature of the complex, with the two amine CH3 substituents on opposite sides of the chelate ring, there is no evidence of any ππ inter­actions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C7—H7A⋯Cl2i 0.99 2.78 3.748 (6) 165
Symmetry code: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].
[Figure 3]
Figure 3
The mol­ecular packing for [HgCl2(C12H20N2)] viewed along the c axis. C—H⋯Cl inter­actions are shown as dashed lines.

4. Database survey

In view of the inter­est in the coordination chemistry of mercury, it is surprising that a search of the Cambridge Structural Database (Version 5.35, November 2013 with one update; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) for structures of HgII with an N2Cl2 coordination sphere gave 96 hits, but the vast majority of these involved aromatic N donors such as pyridine and imidazole. There were only six hits involving aliphatic amine N-atom donors and only two (Choi et al., 2005[Choi, S.-N., Kim, S.-Y., Ryu, H.-W. & Lee, Y.-M. (2005). Acta Cryst. C61, m504-m506.]; Niu et al., 2004[Niu, W., Wong, E. H., Hill, D. C., Tranchemontage, D. J., Lam, K.-C., Sommer, R. D., Zakharov, L. N. & Rheingold, A. L. (2004). Dalton Trans. pp. 3536-3547.]) where the N atoms involved were both from tertiary amine functionalities.

5. Synthesis and crystallization

A stirred solution of N1-(2-bromo­benz­yl)-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, (1), (1.10 ml, 5.34 mmol) in dry THF (15 ml) was treated dropwise with a 1.6 M solution of n-BuLi in hexane (3.80 ml, 6.15 mmol) via syringe under N2 at 273 K. On stirring the reaction mixture for 2 h at this temperature, the li­thia­ted product (2) was obtained. Mercuric chloride (1.55 g, 5.70 mmol) was added to the reaction mixture under a brisk flow of N2 gas and stirring was continued for an additional 6 h at room temperature. The reaction mixture was then removed from the N2 line and evaporated to dryness to give a colourless hygroscopic solid. The solid was extracted with dry chloro­form. The organic phase was separated, dried over Na2SO4, and filtered. The filtrate was evaporated to dryness to give a colourless crystalline solid of the HgCl2 adduct of N1-benzyl-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, (3) (yield 1.25 g, 51%). The reaction scheme is shown in Fig. 1[link].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. H atoms were placed in geom­etric­ally idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (methyl­ene), with Uiso(H) = 1.2Ueq(C), and C—H = 0.98 Å for methyl H atoms, with Uiso(H) = 1.5Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula [HgCl2(C12H20N2)]
Mr 463.79
Crystal system, space group Monoclinic, P21/n
Temperature (K) 200
a, b, c (Å) 9.0839 (3), 15.5367 (6), 11.3161 (5)
β (°) 104.324 (4)
V3) 1547.43 (10)
Z 4
Radiation type Mo Kα
μ (mm−1) 10.27
Crystal size (mm) 0.79 × 0.23 × 0.05
 
Data collection
Diffractometer Agilent Xcalibur
Absorption correction Analytical [CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995[Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.])]
Tmin, Tmax 0.026, 0.339
No. of measured, independent and observed [I > 2σ(I)] reflections 13173, 5125, 3248
Rint 0.067
(sin θ/λ)max−1) 0.758
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.074, 0.96
No. of reflections 5125
No. of parameters 158
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 1.54, −1.61
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

The chemistry of mercuric compounds with multidentate amine ligands is of inter­est due to the low coordination number and geometry preferences of HgII, which facilitates extraordinarily rapid exchange of simple ligands (Bebout et al., 2013; Carra et al., 2013). The enhanced binding thermodynamics of these multidentate ligands has been used to suppress inter­molecular ligand-exchange rates for a variety of HgII complexes in solution, greatly enhancing the meaningfulness of NMR characterization. Significantly, under conditions of slow inter­molecular exchange the rates of intra­molecular isomerization processes for HgII can still exceed both the chemical shift and coupling constant time scale, particularly when bond cleavage is unnecessary and structures of these complexes have been determined (Bebout et al., 2013; Carra et al., 2013).

In view of this inter­est in the coordination chemistry of mercury with multidentate amine ligands, and the lack of such structures involving tertiary amine donors, we report here the structure of the HgCl2 adduct of N1-benzyl-N1,N2,N2-tri­methyl­ethane-1,2-di­amine. The o-di­amine-substituted aryl bromide, N1-(2-bromo­benzyl)-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, can be prepared by the reaction of N1,N1,N2-tri­methyl­ethane-1,2-di­amine and ortho-bromo­benzyl bromide. The ligand is moisture sensitive and is difficult to purify by column chromatography. However, it could easily be purified by vacuum distillation. The moisture-sensitive ligand, when treated with n-BuLi in tetra­hydro­furan (THF) and mercuric chloride, afforded the title compound, [HgCl2(C12H20N2)], (3) (Fig. 1).

Structural commentary top

In the structure of (3), the HgII atom is four-coordinated by two tertiary amine N-atom donors, as well as two Cl- anions to give a distorted tetra­hedral coordination environment (Fig. 2). The distortion from ideal values can be seen by the dihedral angle between the N1—Hg—N2 and Cl1—Hg—Cl2 planes of 82.80 (9)°. The Hg—N and Hg—Cl bond lengths are in the normal ranges for such bonds (Allen, 2002). The five-membered chelate ring adopts an envelope conformation with puckering parameters of Q(2) = 0.446 (6)Å and ϕ(2) = 88.8 (6)° (Cremer & Pople, 1975), with the two amine CH3 substituents on opposite sides of the ring. Of the two reported structures which contain HgII attached to tertiary N donors (Choi et al., 2005; Niu et al., 2004), only one has HgII in an N2Cl2 coordination environment (Choi et al., 2005) and thus provides the best comparison. The Hg—Cl [2.3875 (14) and 2.4397 (13) Å] and Hg—N bond lengths [2.355 (4) and 2.411 (4) Å] in (3) agree well with those found in the previous example [Hg—Cl = 2.397 (3) and 2.374 (2) Å; Hg—N = 2.353 (7) and 2.391 (6) Å].

Supra­molecular features top

The molecular adducts are linked by C—H···Cl inter­actions (Table 1 and Fig. 3) into a zigzag chain parallel to [101]. As a result of the bulky nature of the complex, with the two amine CH3 substituents on opposite sides of the chelate ring, there is no evidence of any ππ inter­actions.

Database survey top

In view of the inter­est in the coordination chemistry of mercury, it is surprising that a search of the Cambridge Structural Database (Version 5.35, November 2013 with one update; Allen, 2002) for structures of HgII with an N2Cl2 coordination sphere gave 96 hits, but the vast majority of these involved aromatic N donors such as pyridine and imidazole. There were only six hits involving aliphatic amine N-atom donors and only two (Choi et al., 2005; Niu et al., 2004) where the N atoms involved were both from tertiary amine functionalities.

Synthesis and crystallization top

A stirred solution of N1-(2-bromo­benzyl)-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, (1), (1.10 ml, 5.34 mmol) in dry THF (15 ml) was treated dropwise with a 1.6 M solution of n-BuLi in hexane (3.80 ml, 6.15 mmol) via syringe under N2 at 273 K. On stirring the reaction mixture for 2 h at this temperature, the li­thia­ted product (2) was obtained. Mercuric chloride (1.55 g, 5.70 mmol) was added to the reaction mixture under a brisk flow of N2 gas and stirring was continued for an additional 6 h at room temperature. The reaction mixture was then removed from the N2 line and evaporated to dryness to give a colourless hygroscopic solid. The solid was extracted with dry chloro­form. The organic phase was separated, dried over Na2SO4, and filtered. The filtrate was evaporated to dryness to give a colourless crystalline solid of the HgCl2 adduct of N1-benzyl-N1,N2,N2-tri­methyl­ethane-1,2-di­amine, (3) (yield 1.25 g, 51%). The reaction scheme is shown in Fig. 1.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (methyl­ene), with Uiso(H) = 1.2Ueq(C), and C—H = 0.98 Å for methyl H atoms, with Uiso(H) = 1.5Ueq(C).

Related literature top

For related literature, see: Allen (2002); Bebout et al. (2013); Carra et al. (2013); Choi et al. (2005); Cremer & Pople (1975); Niu et al. (2004).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Reaction scheme showing the synthesis of the title compound.
[Figure 2] Fig. 2. The molecular structure of [HgCl2(C12H20N2)], showing the atom labelling and displacement ellipsoids at the 30% probability level.
[Figure 3] Fig. 3. The molecular packing for [HgCl2(C12H20N2)] viewed along the c axis. C—H···Cl interactions are shown as dashed lines.
(N1-Benzyl-N1,N2,N2-trimethylethane-1,2-diamine-κ2N,N')dichloridomercury(II) top
Crystal data top
[HgCl2(C12H20N2)]F(000) = 880
Mr = 463.79Dx = 1.991 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1518 reflections
a = 9.0839 (3) Åθ = 5.3–30.8°
b = 15.5367 (6) ŵ = 10.27 mm1
c = 11.3161 (5) ÅT = 200 K
β = 104.324 (4)°Plate, colorless
V = 1547.43 (10) Å30.79 × 0.23 × 0.05 mm
Z = 4
Data collection top
Agilent Xcalibur
diffractometer
5125 independent reflections
Radiation source: fine-focus sealed tube3248 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
Detector resolution: 10.5081 pixels mm-1θmax = 32.6°, θmin = 5.1°
ω scansh = 1311
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2014) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
k = 1623
Tmin = 0.026, Tmax = 0.339l = 1616
13173 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0132P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
5125 reflectionsΔρmax = 1.54 e Å3
158 parametersΔρmin = 1.61 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00248 (16)
Crystal data top
[HgCl2(C12H20N2)]V = 1547.43 (10) Å3
Mr = 463.79Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.0839 (3) ŵ = 10.27 mm1
b = 15.5367 (6) ÅT = 200 K
c = 11.3161 (5) Å0.79 × 0.23 × 0.05 mm
β = 104.324 (4)°
Data collection top
Agilent Xcalibur
diffractometer
5125 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2014) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
3248 reflections with I > 2σ(I)
Tmin = 0.026, Tmax = 0.339Rint = 0.067
13173 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 0.96Δρmax = 1.54 e Å3
5125 reflectionsΔρmin = 1.61 e Å3
158 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. 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 (Å2) top
xyzUiso*/Ueq
Hg0.11248 (2)0.279066 (14)0.55937 (2)0.03718 (9)
Cl10.24245 (15)0.15445 (9)0.51432 (13)0.0476 (4)
Cl20.08589 (15)0.34782 (10)0.40263 (13)0.0502 (4)
N10.0504 (5)0.3190 (3)0.7420 (4)0.0402 (11)
N20.2991 (5)0.3891 (3)0.6352 (4)0.0423 (11)
C10.0894 (5)0.1816 (4)0.7510 (5)0.0368 (13)
C20.0412 (6)0.1163 (4)0.6876 (5)0.0431 (14)
H2A0.06350.11250.68850.052*
C30.1412 (7)0.0563 (4)0.6228 (5)0.0511 (16)
H3A0.10590.01230.57840.061*
C40.2928 (7)0.0605 (4)0.6231 (5)0.0531 (16)
H4A0.36240.01940.57880.064*
C50.3428 (6)0.1239 (4)0.6871 (6)0.0552 (17)
H5A0.44700.12630.68790.066*
C60.2417 (6)0.1853 (4)0.7516 (5)0.0481 (15)
H6A0.27730.22940.79570.058*
C70.0218 (6)0.2459 (4)0.8187 (5)0.0455 (14)
H7A0.11930.21630.85410.055*
H7B0.01630.26910.88700.055*
C80.1829 (7)0.3687 (4)0.8088 (6)0.0572 (18)
H8A0.26470.32800.84710.069*
H8B0.15400.40090.87520.069*
C90.2449 (7)0.4314 (4)0.7321 (6)0.0574 (17)
H9A0.16440.47320.69500.069*
H9B0.32980.46380.78520.069*
C100.3076 (7)0.4511 (4)0.5401 (6)0.0597 (18)
H10A0.38110.49620.57470.090*
H10B0.20740.47700.50770.090*
H10C0.34010.42160.47430.090*
C110.4498 (6)0.3478 (4)0.6837 (7)0.064 (2)
H11A0.52190.39060.72810.095*
H11B0.48710.32470.61580.095*
H11C0.43980.30080.73900.095*
C120.0886 (6)0.3744 (4)0.7088 (6)0.0575 (17)
H12A0.11640.39280.78330.086*
H12B0.17250.34150.65750.086*
H12C0.06790.42510.66410.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg0.03850 (13)0.03097 (13)0.04205 (14)0.00121 (10)0.00990 (8)0.00793 (11)
Cl10.0585 (9)0.0360 (8)0.0541 (9)0.0049 (7)0.0249 (7)0.0088 (7)
Cl20.0470 (8)0.0549 (10)0.0448 (9)0.0077 (7)0.0037 (6)0.0001 (8)
N10.050 (3)0.032 (3)0.041 (3)0.001 (2)0.017 (2)0.006 (2)
N20.047 (3)0.031 (3)0.046 (3)0.004 (2)0.007 (2)0.001 (2)
C10.034 (3)0.039 (3)0.037 (3)0.007 (2)0.008 (2)0.012 (3)
C20.044 (3)0.033 (3)0.057 (4)0.008 (3)0.021 (3)0.010 (3)
C30.069 (4)0.040 (4)0.048 (4)0.003 (3)0.022 (3)0.009 (3)
C40.068 (4)0.050 (4)0.039 (4)0.013 (3)0.009 (3)0.009 (3)
C50.038 (3)0.072 (5)0.055 (4)0.002 (3)0.009 (3)0.010 (4)
C60.046 (3)0.055 (4)0.047 (4)0.003 (3)0.018 (3)0.006 (3)
C70.051 (3)0.045 (4)0.045 (4)0.006 (3)0.020 (3)0.006 (3)
C80.076 (4)0.050 (4)0.046 (4)0.023 (3)0.015 (3)0.018 (3)
C90.068 (4)0.042 (4)0.064 (4)0.018 (3)0.020 (3)0.021 (3)
C100.075 (4)0.043 (4)0.061 (4)0.008 (3)0.018 (3)0.001 (3)
C110.035 (3)0.058 (5)0.089 (5)0.006 (3)0.001 (3)0.000 (4)
C120.062 (4)0.048 (4)0.069 (5)0.026 (3)0.029 (3)0.003 (3)
Geometric parameters (Å, º) top
Hg—N12.355 (4)C5—C61.398 (8)
Hg—Cl12.3875 (14)C5—H5A0.9500
Hg—N22.411 (4)C6—H6A0.9500
Hg—Cl22.4397 (13)C7—H7A0.9900
N1—C81.472 (6)C7—H7B0.9900
N1—C71.491 (7)C8—C91.503 (9)
N1—C121.497 (6)C8—H8A0.9900
N2—C101.460 (7)C8—H8B0.9900
N2—C91.465 (8)C9—H9A0.9900
N2—C111.489 (7)C9—H9B0.9900
C1—C21.375 (7)C10—H10A0.9800
C1—C61.386 (7)C10—H10B0.9800
C1—C71.491 (8)C10—H10C0.9800
C2—C31.379 (8)C11—H11A0.9800
C2—H2A0.9500C11—H11B0.9800
C3—C41.380 (8)C11—H11C0.9800
C3—H3A0.9500C12—H12A0.9800
C4—C51.364 (8)C12—H12B0.9800
C4—H4A0.9500C12—H12C0.9800
N1—Hg—Cl1129.73 (12)C1—C7—N1113.9 (5)
N1—Hg—N278.51 (16)C1—C7—H7A108.8
Cl1—Hg—N2108.04 (12)N1—C7—H7A108.8
N1—Hg—Cl2103.21 (11)C1—C7—H7B108.8
Cl1—Hg—Cl2121.01 (5)N1—C7—H7B108.8
N2—Hg—Cl2106.03 (11)H7A—C7—H7B107.7
C8—N1—C7109.8 (4)N1—C8—C9114.7 (5)
C8—N1—C12111.0 (5)N1—C8—H8A108.6
C7—N1—C12109.0 (4)C9—C8—H8A108.6
C8—N1—Hg104.3 (3)N1—C8—H8B108.6
C7—N1—Hg115.1 (3)C9—C8—H8B108.6
C12—N1—Hg107.6 (3)H8A—C8—H8B107.6
C10—N2—C9110.1 (5)N2—C9—C8112.6 (5)
C10—N2—C11110.1 (5)N2—C9—H9A109.1
C9—N2—C11111.5 (5)C8—C9—H9A109.1
C10—N2—Hg111.5 (3)N2—C9—H9B109.1
C9—N2—Hg104.4 (3)C8—C9—H9B109.1
C11—N2—Hg109.1 (3)H9A—C9—H9B107.8
C2—C1—C6118.7 (5)N2—C10—H10A109.5
C2—C1—C7119.9 (5)N2—C10—H10B109.5
C6—C1—C7121.3 (5)H10A—C10—H10B109.5
C1—C2—C3121.5 (5)N2—C10—H10C109.5
C1—C2—H2A119.2H10A—C10—H10C109.5
C3—C2—H2A119.2H10B—C10—H10C109.5
C2—C3—C4119.5 (6)N2—C11—H11A109.5
C2—C3—H3A120.2N2—C11—H11B109.5
C4—C3—H3A120.2H11A—C11—H11B109.5
C5—C4—C3119.9 (6)N2—C11—H11C109.5
C5—C4—H4A120.0H11A—C11—H11C109.5
C3—C4—H4A120.0H11B—C11—H11C109.5
C4—C5—C6120.5 (6)N1—C12—H12A109.5
C4—C5—H5A119.7N1—C12—H12B109.5
C6—C5—H5A119.7H12A—C12—H12B109.5
C1—C6—C5119.8 (6)N1—C12—H12C109.5
C1—C6—H6A120.1H12A—C12—H12C109.5
C5—C6—H6A120.1H12B—C12—H12C109.5
Cl1—Hg—N1—C889.5 (4)C7—C1—C2—C3179.3 (5)
N2—Hg—N1—C814.5 (4)C1—C2—C3—C41.2 (9)
Cl2—Hg—N1—C8118.5 (3)C2—C3—C4—C50.0 (9)
Cl1—Hg—N1—C730.9 (4)C3—C4—C5—C60.7 (9)
N2—Hg—N1—C7134.9 (4)C2—C1—C6—C50.9 (8)
Cl2—Hg—N1—C7121.2 (3)C7—C1—C6—C5179.9 (5)
Cl1—Hg—N1—C12152.6 (3)C4—C5—C6—C10.3 (9)
N2—Hg—N1—C12103.4 (4)C2—C1—C7—N185.1 (6)
Cl2—Hg—N1—C120.6 (4)C6—C1—C7—N195.8 (6)
N1—Hg—N2—C10132.3 (4)C8—N1—C7—C1168.4 (5)
Cl1—Hg—N2—C1099.4 (4)C12—N1—C7—C169.8 (6)
Cl2—Hg—N2—C1031.7 (4)Hg—N1—C7—C151.1 (5)
N1—Hg—N2—C913.4 (4)C7—N1—C8—C9166.8 (5)
Cl1—Hg—N2—C9141.7 (3)C12—N1—C8—C972.6 (7)
Cl2—Hg—N2—C987.2 (4)Hg—N1—C8—C943.0 (6)
N1—Hg—N2—C11105.9 (4)C10—N2—C9—C8160.3 (5)
Cl1—Hg—N2—C1122.4 (4)C11—N2—C9—C877.1 (6)
Cl2—Hg—N2—C11153.5 (4)Hg—N2—C9—C840.5 (6)
C6—C1—C2—C31.6 (8)N1—C8—C9—N261.6 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Cl2i0.992.783.748 (6)165
Symmetry code: (i) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Cl2i0.992.783.748 (6)165.2
Symmetry code: (i) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[HgCl2(C12H20N2)]
Mr463.79
Crystal system, space groupMonoclinic, P21/n
Temperature (K)200
a, b, c (Å)9.0839 (3), 15.5367 (6), 11.3161 (5)
β (°) 104.324 (4)
V3)1547.43 (10)
Z4
Radiation typeMo Kα
µ (mm1)10.27
Crystal size (mm)0.79 × 0.23 × 0.05
Data collection
DiffractometerAgilent Xcalibur
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Agilent, 2014) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
Tmin, Tmax0.026, 0.339
No. of measured, independent and
observed [I > 2σ(I)] reflections
13173, 5125, 3248
Rint0.067
(sin θ/λ)max1)0.758
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.074, 0.96
No. of reflections5125
No. of parameters158
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.54, 1.61

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

 

Acknowledgements

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

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