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

Manjare, S.T.; Singh, H.B.; Butcher, R.J.

doi:10.1107/S1600536814017516

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Volume 70| Part 9| September 2014| Pages 118-120

doi:10.1107/S1600536814017516

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

Sudesh T. Manjare,^a Harkesh B. Singh ^a and Ray J. Butcher ^b ^*

^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 Hg^II 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].

Keywords: crystal structure; mercury complex; tertiary amine donors.

CCDC reference: 1016995

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 Hg^II, 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 Hg^II complexes in solution, greatly enhancing the meaningfulness of NMR characterization. Significantly, under conditions of slow intermolecular exchange the rates of intramolecular isomerization processes for Hg^II 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).

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

2. Structural commentary

In the structure of (3), the Hg^II 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 Hg^II attached to tertiary N donors (Choi et al., 2005 ; Niu et al., 2004 ), only one has Hg^II 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].

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 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 π–π interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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
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) for structures of Hg^II 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.

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.

6. Refinement

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 U_iso(H) = 1.2U_eq(C), and C—H = 0.98 Å for methyl H atoms, with U_iso(H) = 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₂H₂₀N₂)]
M_r	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)
V (Å³)	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 ) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 )]
T_min, T_max	0.026, 0.339
No. of measured, independent and observed [I > 2σ(I)] reflections	13173, 5125, 3248
R_int	0.067
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	1.54, −1.61
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ), WinGX (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1016995

Crystal structure: contains datablock 3. DOI: 10.1107/S1600536814017516/wm5031sup1.cif

Structure factors: contains datablock 3. DOI: 10.1107/S1600536814017516/wm50313sup2.hkl

checkCIF report

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 Hg^II, 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 Hg^II complexes in solution, greatly enhancing the meaningfulness of NMR characterization. Significantly, under conditions of slow intermolecular exchange the rates of intramolecular isomerization processes for Hg^II 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).

Structural commentary top

In the structure of (3), the Hg^II 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 Hg^II attached to tertiary N donors (Choi et al., 2005; Niu et al., 2004), only one has Hg^II 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 π–π interactions.

Database survey top

Synthesis and crystallization top

Refinement top

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

	Fig. 1. Reaction scheme showing the synthesis of the title compound.
	Fig. 2. The molecular structure of [HgCl₂(C₁₂H₂₀N₂)], showing the atom labelling and displacement ellipsoids at the 30% probability level.
	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
M_r = 463.79	D_x = 1.991 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1518 reflections
a = 9.0839 (3) Å	θ = 5.3–30.8°
b = 15.5367 (6) Å	µ = 10.27 mm⁻¹
c = 11.3161 (5) Å	T = 200 K
β = 104.324 (4)°	Plate, colorless
V = 1547.43 (10) Å³	0.79 × 0.23 × 0.05 mm
Z = 4

Data collection top

Agilent Xcalibur diffractometer	5125 independent reflections
Radiation source: fine-focus sealed tube	3248 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.6°, θ_min = 5.1°
ω scans	h = −13→11
Absorption correction: analytical [CrysAlis PRO (Agilent, 2014) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −16→23
T_min = 0.026, T_max = 0.339	l = −16→16
13173 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0132P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
5125 reflections	Δρ_max = 1.54 e Å⁻³
158 parameters	Δρ_min = −1.61 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00248 (16)

Crystal data top

[HgCl₂(C₁₂H₂₀N₂)]	V = 1547.43 (10) Å³
M_r = 463.79	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0839 (3) Å	µ = 10.27 mm⁻¹
b = 15.5367 (6) Å	T = 200 K
c = 11.3161 (5) Å	0.79 × 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)
T_min = 0.026, T_max = 0.339	R_int = 0.067
13173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 0.96	Δρ_max = 1.54 e Å⁻³
5125 reflections	Δρ_min = −1.61 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Hg	0.11248 (2)	0.279066 (14)	0.55937 (2)	0.03718 (9)
Cl1	0.24245 (15)	0.15445 (9)	0.51432 (13)	0.0476 (4)
Cl2	−0.08589 (15)	0.34782 (10)	0.40263 (13)	0.0502 (4)
N1	0.0504 (5)	0.3190 (3)	0.7420 (4)	0.0402 (11)
N2	0.2991 (5)	0.3891 (3)	0.6352 (4)	0.0423 (11)
C1	−0.0894 (5)	0.1816 (4)	0.7510 (5)	0.0368 (13)
C2	−0.0412 (6)	0.1163 (4)	0.6876 (5)	0.0431 (14)
H2A	0.0635	0.1125	0.6885	0.052*
C3	−0.1412 (7)	0.0563 (4)	0.6228 (5)	0.0511 (16)
H3A	−0.1059	0.0123	0.5784	0.061*
C4	−0.2928 (7)	0.0605 (4)	0.6231 (5)	0.0531 (16)
H4A	−0.3624	0.0194	0.5788	0.064*
C5	−0.3428 (6)	0.1239 (4)	0.6871 (6)	0.0552 (17)
H5A	−0.4470	0.1263	0.6879	0.066*
C6	−0.2417 (6)	0.1853 (4)	0.7516 (5)	0.0481 (15)
H6A	−0.2773	0.2294	0.7957	0.058*
C7	0.0218 (6)	0.2459 (4)	0.8187 (5)	0.0455 (14)
H7A	0.1193	0.2163	0.8541	0.055*
H7B	−0.0163	0.2691	0.8870	0.055*
C8	0.1829 (7)	0.3687 (4)	0.8088 (6)	0.0572 (18)
H8A	0.2647	0.3280	0.8471	0.069*
H8B	0.1540	0.4009	0.8752	0.069*
C9	0.2449 (7)	0.4314 (4)	0.7321 (6)	0.0574 (17)
H9A	0.1644	0.4732	0.6950	0.069*
H9B	0.3298	0.4638	0.7852	0.069*
C10	0.3076 (7)	0.4511 (4)	0.5401 (6)	0.0597 (18)
H10A	0.3811	0.4962	0.5747	0.090*
H10B	0.2074	0.4770	0.5077	0.090*
H10C	0.3401	0.4216	0.4743	0.090*
C11	0.4498 (6)	0.3478 (4)	0.6837 (7)	0.064 (2)
H11A	0.5219	0.3906	0.7281	0.095*
H11B	0.4871	0.3247	0.6158	0.095*
H11C	0.4398	0.3008	0.7390	0.095*
C12	−0.0886 (6)	0.3744 (4)	0.7088 (6)	0.0575 (17)
H12A	−0.1164	0.3928	0.7833	0.086*
H12B	−0.1725	0.3415	0.6575	0.086*
H12C	−0.0679	0.4251	0.6641	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg	0.03850 (13)	0.03097 (13)	0.04205 (14)	−0.00121 (10)	0.00990 (8)	−0.00793 (11)
Cl1	0.0585 (9)	0.0360 (8)	0.0541 (9)	0.0049 (7)	0.0249 (7)	−0.0088 (7)
Cl2	0.0470 (8)	0.0549 (10)	0.0448 (9)	0.0077 (7)	0.0037 (6)	−0.0001 (8)
N1	0.050 (3)	0.032 (3)	0.041 (3)	−0.001 (2)	0.017 (2)	−0.006 (2)
N2	0.047 (3)	0.031 (3)	0.046 (3)	−0.004 (2)	0.007 (2)	−0.001 (2)
C1	0.034 (3)	0.039 (3)	0.037 (3)	0.007 (2)	0.008 (2)	0.012 (3)
C2	0.044 (3)	0.033 (3)	0.057 (4)	0.008 (3)	0.021 (3)	0.010 (3)
C3	0.069 (4)	0.040 (4)	0.048 (4)	0.003 (3)	0.022 (3)	0.009 (3)
C4	0.068 (4)	0.050 (4)	0.039 (4)	−0.013 (3)	0.009 (3)	0.009 (3)
C5	0.038 (3)	0.072 (5)	0.055 (4)	0.002 (3)	0.009 (3)	0.010 (4)
C6	0.046 (3)	0.055 (4)	0.047 (4)	0.003 (3)	0.018 (3)	0.006 (3)
C7	0.051 (3)	0.045 (4)	0.045 (4)	0.006 (3)	0.020 (3)	0.006 (3)
C8	0.076 (4)	0.050 (4)	0.046 (4)	−0.023 (3)	0.015 (3)	−0.018 (3)
C9	0.068 (4)	0.042 (4)	0.064 (4)	−0.018 (3)	0.020 (3)	−0.021 (3)
C10	0.075 (4)	0.043 (4)	0.061 (4)	−0.008 (3)	0.018 (3)	−0.001 (3)
C11	0.035 (3)	0.058 (5)	0.089 (5)	−0.006 (3)	−0.001 (3)	0.000 (4)
C12	0.062 (4)	0.048 (4)	0.069 (5)	0.026 (3)	0.029 (3)	0.003 (3)

Geometric parameters (Å, º) top

Hg—N1	2.355 (4)	C5—C6	1.398 (8)
Hg—Cl1	2.3875 (14)	C5—H5A	0.9500
Hg—N2	2.411 (4)	C6—H6A	0.9500
Hg—Cl2	2.4397 (13)	C7—H7A	0.9900
N1—C8	1.472 (6)	C7—H7B	0.9900
N1—C7	1.491 (7)	C8—C9	1.503 (9)
N1—C12	1.497 (6)	C8—H8A	0.9900
N2—C10	1.460 (7)	C8—H8B	0.9900
N2—C9	1.465 (8)	C9—H9A	0.9900
N2—C11	1.489 (7)	C9—H9B	0.9900
C1—C2	1.375 (7)	C10—H10A	0.9800
C1—C6	1.386 (7)	C10—H10B	0.9800
C1—C7	1.491 (8)	C10—H10C	0.9800
C2—C3	1.379 (8)	C11—H11A	0.9800
C2—H2A	0.9500	C11—H11B	0.9800
C3—C4	1.380 (8)	C11—H11C	0.9800
C3—H3A	0.9500	C12—H12A	0.9800
C4—C5	1.364 (8)	C12—H12B	0.9800
C4—H4A	0.9500	C12—H12C	0.9800

N1—Hg—Cl1	129.73 (12)	C1—C7—N1	113.9 (5)
N1—Hg—N2	78.51 (16)	C1—C7—H7A	108.8
Cl1—Hg—N2	108.04 (12)	N1—C7—H7A	108.8
N1—Hg—Cl2	103.21 (11)	C1—C7—H7B	108.8
Cl1—Hg—Cl2	121.01 (5)	N1—C7—H7B	108.8
N2—Hg—Cl2	106.03 (11)	H7A—C7—H7B	107.7
C8—N1—C7	109.8 (4)	N1—C8—C9	114.7 (5)
C8—N1—C12	111.0 (5)	N1—C8—H8A	108.6
C7—N1—C12	109.0 (4)	C9—C8—H8A	108.6
C8—N1—Hg	104.3 (3)	N1—C8—H8B	108.6
C7—N1—Hg	115.1 (3)	C9—C8—H8B	108.6
C12—N1—Hg	107.6 (3)	H8A—C8—H8B	107.6
C10—N2—C9	110.1 (5)	N2—C9—C8	112.6 (5)
C10—N2—C11	110.1 (5)	N2—C9—H9A	109.1
C9—N2—C11	111.5 (5)	C8—C9—H9A	109.1
C10—N2—Hg	111.5 (3)	N2—C9—H9B	109.1
C9—N2—Hg	104.4 (3)	C8—C9—H9B	109.1
C11—N2—Hg	109.1 (3)	H9A—C9—H9B	107.8
C2—C1—C6	118.7 (5)	N2—C10—H10A	109.5
C2—C1—C7	119.9 (5)	N2—C10—H10B	109.5
C6—C1—C7	121.3 (5)	H10A—C10—H10B	109.5
C1—C2—C3	121.5 (5)	N2—C10—H10C	109.5
C1—C2—H2A	119.2	H10A—C10—H10C	109.5
C3—C2—H2A	119.2	H10B—C10—H10C	109.5
C2—C3—C4	119.5 (6)	N2—C11—H11A	109.5
C2—C3—H3A	120.2	N2—C11—H11B	109.5
C4—C3—H3A	120.2	H11A—C11—H11B	109.5
C5—C4—C3	119.9 (6)	N2—C11—H11C	109.5
C5—C4—H4A	120.0	H11A—C11—H11C	109.5
C3—C4—H4A	120.0	H11B—C11—H11C	109.5
C4—C5—C6	120.5 (6)	N1—C12—H12A	109.5
C4—C5—H5A	119.7	N1—C12—H12B	109.5
C6—C5—H5A	119.7	H12A—C12—H12B	109.5
C1—C6—C5	119.8 (6)	N1—C12—H12C	109.5
C1—C6—H6A	120.1	H12A—C12—H12C	109.5
C5—C6—H6A	120.1	H12B—C12—H12C	109.5

Cl1—Hg—N1—C8	89.5 (4)	C7—C1—C2—C3	−179.3 (5)
N2—Hg—N1—C8	−14.5 (4)	C1—C2—C3—C4	−1.2 (9)
Cl2—Hg—N1—C8	−118.5 (3)	C2—C3—C4—C5	0.0 (9)
Cl1—Hg—N1—C7	−30.9 (4)	C3—C4—C5—C6	0.7 (9)
N2—Hg—N1—C7	−134.9 (4)	C2—C1—C6—C5	−0.9 (8)
Cl2—Hg—N1—C7	121.2 (3)	C7—C1—C6—C5	−179.9 (5)
Cl1—Hg—N1—C12	−152.6 (3)	C4—C5—C6—C1	−0.3 (9)
N2—Hg—N1—C12	103.4 (4)	C2—C1—C7—N1	85.1 (6)
Cl2—Hg—N1—C12	−0.6 (4)	C6—C1—C7—N1	−95.8 (6)
N1—Hg—N2—C10	−132.3 (4)	C8—N1—C7—C1	−168.4 (5)
Cl1—Hg—N2—C10	99.4 (4)	C12—N1—C7—C1	69.8 (6)
Cl2—Hg—N2—C10	−31.7 (4)	Hg—N1—C7—C1	−51.1 (5)
N1—Hg—N2—C9	−13.4 (4)	C7—N1—C8—C9	166.8 (5)
Cl1—Hg—N2—C9	−141.7 (3)	C12—N1—C8—C9	−72.6 (7)
Cl2—Hg—N2—C9	87.2 (4)	Hg—N1—C8—C9	43.0 (6)
N1—Hg—N2—C11	105.9 (4)	C10—N2—C9—C8	160.3 (5)
Cl1—Hg—N2—C11	−22.4 (4)	C11—N2—C9—C8	−77.1 (6)
Cl2—Hg—N2—C11	−153.5 (4)	Hg—N2—C9—C8	40.5 (6)
C6—C1—C2—C3	1.6 (8)	N1—C8—C9—N2	−61.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl2ⁱ	0.99	2.78	3.748 (6)	165

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl2ⁱ	0.99	2.78	3.748 (6)	165.2

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₂H₂₀N₂)]
M_r	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)
V (Å³)	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 diffractometer
Absorption correction	Analytical [CrysAlis PRO (Agilent, 2014) using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.026, 0.339
No. of measured, independent and observed [I > 2σ(I)] reflections	13173, 5125, 3248
R_int	0.067
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	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

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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Volume 70| Part 9| September 2014| Pages 118-120

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