Dichlorido[(1R,2R)-N-(pyridin-2-yl­methyl)cyclo­hexane-1,2-diamine-κ3N,N′,N′′]mercury(II)

Gao, C.-Z.; Zhang, X.-Y.; Cheng, L.

doi:10.1107/S1600536812003340

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m235

doi:10.1107/S1600536812003340

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Dichlorido[(1R,2R)-N-(pyridin-2-ylmethyl)cyclohexane-1,2-diamine-κ³N,N′,N′′]mercury(II)

Chuan-Zhu Gao,^a Xiu-Ying Zhang ^a and Lin Cheng ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 6 January 2012; accepted 26 January 2012; online 4 February 2012)

In the title compound, [HgCl₂(C₁₂H₁₉N₃)], the Hg^II ion is coordinated by three N atoms of the (1R,2R)-N-(pyridin-2-ylmethyl)cyclohexane-1,2-diamine ligand and by a Cl atom in the basal plane, and by a second Cl atom in the apical position, within a distorted square-pyramidal geometry. The coordination of the enantiopure ligand to the metal atom renders the central N atom chiral with an S configuration, so the complex is enantiomerically pure and corresponds to the S,R,R diastereoisomer. Molecules are linked via weak N—H⋯Cl hydrogen bonds into a one-dimensional hydrogen-bonding supramolecular chain along the crystallographic b axis.

Related literature

For related structures, see: Cheng et al. (2011 ); Yin et al. (2011 ). For nonlinear optical applications and luminescence properties, see: He et al. (2010 ).

Experimental

Crystal data

[HgCl₂(C₁₂H₁₉N₃)]
M_r = 476.79
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.5319 (12) Å
b = 8.8244 (12) Å
c = 19.688 (3) Å
V = 1482.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 10.73 mm⁻¹
T = 123 K
0.08 × 0.06 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.481, T_max = 0.565
11063 measured reflections
2902 independent reflections
2796 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.045
S = 1.06
2902 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.68 e Å⁻³
Absolute structure: Flack (1983 ), 1206 Friedel pairs
Flack parameter: 0.009 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯Cl2ⁱ	0.87	2.83	3.527 (5)	138
N3—H3C⋯Cl1ⁱⁱ	0.87	2.45	3.316 (5)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812003340/rk2329sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003340/rk2329Isup2.hkl

checkCIF report

Comment top

Recently, there has been current significant interest in the rational design and synthesis of chiral coordination polymers due to their potential utility in enantiomerically selective catalysis and separations, second–order non–linear optical applications and luminescence (He et al. 2010). A basic design route for this kind of polymers is to appropriately organize the metal ions into ordered architectures by use of chiral ligands. Herein, we report a new chiral complex, Hg(2–Amp)Cl₂, where 2–Amp = 2–(((1R,2R)–2–aminocyclohexylamino)methyl)phenol, as a chiral ligand.

The title compound is a mononuclear complex, in which the coordination environment of Hg^II can be described as distorted square–pyramidal, being surrounded by one tridentate ligand and two chlorine anions (Fig. 1).

The molecules are linked to each other, via weak N—H···Cl hydrogen bonds, into a one–dimensional hydrogen bonding network (Table 1, Fig. 2).

Related literature top

For related structures, see: Cheng et al. (2011); Yin et al. (2011). For nonlinear optical applications and luminescence properties, see: He et al. (2010).

Experimental top

(1R,2R)-N¹-(pyridin-2-yl-methyl)cyclohexane-1,2-diamine (0.041 g, 0.2 mmol) dissolved in water (8 ml) was added to a methanol solution (10 ml) of HgCl₂ (0.054 g, 0.2 mmol). The mixture solution was stirred for 1 h at room temperature and then filtered. The filtrate was allowed to evaporate slowly at room temperature. After 2 weeks, colourless block crystals were obtained with 58.7% yield (0.056 g).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the weak N—H···Cl hydrogen bonding chain. Symmetry codes: (i) 1-x, 1/2+y, 1/2-z; (ii) 1-x, -1/2+y, 1/2-z; (iii) x, 1+y, z; (iv) 1-x, 3/2+y, 1/2-z

Dichlorido[(1R,2R)-N-(pyridin-2-ylmethyl)cyclohexane- 1,2-diamine-κ³N,N',N'']mercury(II) top

Crystal data top

[HgCl₂(C₁₂H₁₉N₃)]	F(000) = 904
M_r = 476.79	D_x = 2.136 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 791 reflections
a = 8.5319 (12) Å	θ = 2.4–28.0°
b = 8.8244 (12) Å	µ = 10.73 mm⁻¹
c = 19.688 (3) Å	T = 123 K
V = 1482.3 (4) Å³	Block, colourless
Z = 4	0.08 × 0.06 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2902 independent reflections
Radiation source: fine–focus sealed tube	2796 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.481, T_max = 0.565	k = −10→10
11063 measured reflections	l = −24→24

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.0101P)² + 0.1P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2902 reflections	Δρ_max = 1.08 e Å⁻³
163 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with 1206 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.009 (7)

Crystal data top

[HgCl₂(C₁₂H₁₉N₃)]	V = 1482.3 (4) Å³
M_r = 476.79	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5319 (12) Å	µ = 10.73 mm⁻¹
b = 8.8244 (12) Å	T = 123 K
c = 19.688 (3) Å	0.08 × 0.06 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2902 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2796 reflections with I > 2σ(I)
T_min = 0.481, T_max = 0.565	R_int = 0.028
11063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.045	Δρ_max = 1.08 e Å⁻³
S = 1.06	Δρ_min = −0.68 e Å⁻³
2902 reflections	Absolute structure: Flack (1983), with 1206 Friedel pairs
163 parameters	Absolute structure parameter: 0.009 (7)
0 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Hg1	0.26613 (2)	0.88923 (2)	0.290676 (8)	0.03034 (6)
Cl1	0.29943 (16)	1.16949 (14)	0.31668 (6)	0.0395 (3)
Cl2	0.35752 (15)	0.69726 (14)	0.37081 (6)	0.0377 (3)
C1	−0.0295 (7)	0.8653 (6)	0.4070 (3)	0.0438 (14)
H1A	0.0532	0.8345	0.4362	0.053*
C2	−0.1777 (7)	0.8749 (6)	0.4328 (3)	0.0492 (15)
H2A	−0.1975	0.8543	0.4794	0.059*
C3	−0.2978 (7)	0.9151 (7)	0.3897 (3)	0.0567 (17)
H3A	−0.4025	0.9204	0.4059	0.068*
C4	−0.2644 (7)	0.9477 (6)	0.3223 (3)	0.0473 (13)
H4A	−0.3461	0.9749	0.2918	0.057*
C5	−0.1117 (6)	0.9401 (5)	0.3000 (2)	0.0322 (11)
C6	−0.0662 (6)	0.9816 (6)	0.2286 (2)	0.0384 (13)
H6A	−0.1586	0.9713	0.1985	0.046*
H6B	−0.0320	1.0888	0.2274	0.046*
C7	0.1322 (6)	0.9362 (5)	0.1386 (2)	0.0282 (11)
H7A	0.1457	1.0486	0.1412	0.034*
C8	0.0268 (6)	0.9017 (7)	0.0780 (2)	0.0379 (12)
H8A	−0.0722	0.9592	0.0829	0.045*
H8B	0.0005	0.7924	0.0782	0.045*
C9	0.1023 (7)	0.9418 (6)	0.0101 (2)	0.0433 (14)
H9A	0.0328	0.9087	−0.0273	0.052*
H9B	0.1146	1.0532	0.0069	0.052*
C10	0.2604 (6)	0.8673 (5)	0.0025 (2)	0.0418 (12)
H10A	0.3092	0.9004	−0.0407	0.050*
H10B	0.2469	0.7559	0.0006	0.050*
C11	0.3670 (6)	0.9082 (7)	0.0615 (2)	0.0379 (13)
H11A	0.3895	1.0182	0.0604	0.046*
H11B	0.4676	0.8533	0.0569	0.046*
C12	0.2906 (5)	0.8671 (5)	0.1300 (2)	0.0211 (10)
H12A	0.2757	0.7547	0.1301	0.025*
N1	0.0037 (5)	0.8977 (5)	0.34230 (19)	0.0347 (10)
N2	0.0605 (4)	0.8849 (5)	0.20324 (18)	0.0277 (8)
H2B	0.0364	0.7922	0.1924	0.033*
N3	0.3965 (4)	0.9033 (6)	0.18723 (18)	0.0312 (10)
H3B	0.4219	0.9987	0.1891	0.037*
H3C	0.4701	0.8351	0.1867	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.02454 (9)	0.03805 (10)	0.02844 (9)	0.00119 (9)	−0.00319 (9)	0.00272 (8)
Cl1	0.0418 (8)	0.0354 (6)	0.0412 (6)	−0.0061 (6)	0.0044 (5)	0.0003 (5)
Cl2	0.0344 (7)	0.0393 (7)	0.0393 (6)	0.0026 (6)	−0.0101 (6)	0.0055 (6)
C1	0.048 (3)	0.044 (4)	0.039 (3)	−0.004 (3)	0.010 (3)	0.000 (3)
C2	0.060 (4)	0.041 (3)	0.047 (3)	−0.014 (3)	0.023 (3)	−0.015 (3)
C3	0.044 (4)	0.054 (4)	0.072 (4)	−0.019 (3)	0.030 (3)	−0.026 (3)
C4	0.026 (3)	0.063 (3)	0.053 (3)	−0.001 (3)	0.000 (3)	−0.023 (3)
C5	0.024 (2)	0.031 (3)	0.042 (3)	−0.0020 (19)	−0.001 (2)	−0.009 (2)
C6	0.029 (3)	0.035 (3)	0.051 (3)	0.009 (2)	−0.006 (2)	−0.006 (2)
C7	0.031 (3)	0.027 (3)	0.026 (2)	−0.002 (2)	−0.003 (2)	0.0041 (19)
C8	0.038 (3)	0.042 (3)	0.035 (3)	0.005 (3)	−0.013 (2)	−0.002 (3)
C9	0.057 (4)	0.043 (3)	0.030 (3)	0.002 (3)	−0.011 (3)	0.002 (2)
C10	0.049 (3)	0.046 (3)	0.031 (2)	−0.003 (3)	0.002 (2)	−0.003 (2)
C11	0.039 (3)	0.043 (3)	0.031 (3)	0.000 (3)	0.006 (2)	−0.003 (2)
C12	0.024 (2)	0.022 (2)	0.0181 (18)	−0.0105 (19)	−0.0011 (18)	0.0004 (17)
N1	0.026 (2)	0.040 (3)	0.038 (2)	−0.005 (2)	0.0040 (18)	−0.001 (2)
N2	0.0269 (19)	0.025 (2)	0.031 (2)	0.0037 (17)	−0.0025 (17)	−0.001 (2)
N3	0.026 (2)	0.035 (2)	0.033 (2)	0.001 (2)	−0.0007 (16)	−0.0011 (19)

Geometric parameters (Å, º) top

Hg1—N3	2.324 (4)	C7—C12	1.492 (6)
Hg1—Cl2	2.4426 (12)	C7—C8	1.524 (6)
Hg1—N2	2.458 (3)	C7—H7A	1.0000
Hg1—N1	2.460 (4)	C8—C9	1.525 (7)
Hg1—Cl1	2.5415 (13)	C8—H8A	0.9900
C1—N1	1.336 (6)	C8—H8B	0.9900
C1—C2	1.364 (8)	C9—C10	1.508 (7)
C1—H1A	0.9500	C9—H9A	0.9900
C2—C3	1.378 (9)	C9—H9B	0.9900
C2—H2A	0.9500	C10—C11	1.519 (7)
C3—C4	1.387 (8)	C10—H10A	0.9900
C3—H3A	0.9500	C10—H10B	0.9900
C4—C5	1.376 (7)	C11—C12	1.541 (6)
C4—H4A	0.9500	C11—H11A	0.9900
C5—N1	1.342 (6)	C11—H11B	0.9900
C5—C6	1.505 (7)	C12—N3	1.479 (5)
C6—N2	1.465 (6)	C12—H12A	1.0000
C6—H6A	0.9900	N2—H2B	0.8700
C6—H6B	0.9900	N3—H3B	0.8700
C7—N2	1.483 (6)	N3—H3C	0.8700

N3—Hg1—Cl2	116.76 (12)	C9—C8—H8B	109.0
N3—Hg1—N2	74.25 (13)	H8A—C8—H8B	107.8
Cl2—Hg1—N2	132.01 (10)	C10—C9—C8	111.3 (4)
N3—Hg1—N1	142.75 (13)	C10—C9—H9A	109.4
Cl2—Hg1—N1	92.57 (11)	C8—C9—H9A	109.4
N2—Hg1—N1	68.91 (12)	C10—C9—H9B	109.4
N3—Hg1—Cl1	94.08 (13)	C8—C9—H9B	109.4
Cl2—Hg1—Cl1	120.60 (4)	H9A—C9—H9B	108.0
N2—Hg1—Cl1	103.66 (10)	C9—C10—C11	110.8 (4)
N1—Hg1—Cl1	89.37 (11)	C9—C10—H10A	109.5
N1—C1—C2	122.5 (6)	C11—C10—H10A	109.5
N1—C1—H1A	118.7	C9—C10—H10B	109.5
C2—C1—H1A	118.7	C11—C10—H10B	109.5
C1—C2—C3	118.4 (5)	H10A—C10—H10B	108.1
C1—C2—H2A	120.8	C10—C11—C12	111.1 (4)
C3—C2—H2A	120.8	C10—C11—H11A	109.4
C2—C3—C4	119.3 (5)	C12—C11—H11A	109.4
C2—C3—H3A	120.3	C10—C11—H11B	109.4
C4—C3—H3A	120.3	C12—C11—H11B	109.4
C5—C4—C3	119.3 (6)	H11A—C11—H11B	108.0
C5—C4—H4A	120.4	N3—C12—C7	112.2 (3)
C3—C4—H4A	120.4	N3—C12—C11	111.0 (3)
N1—C5—C4	120.7 (5)	C7—C12—C11	112.7 (4)
N1—C5—C6	117.3 (4)	N3—C12—H12A	106.8
C4—C5—C6	122.0 (5)	C7—C12—H12A	106.8
N2—C6—C5	111.5 (4)	C11—C12—H12A	106.8
N2—C6—H6A	109.3	C1—N1—C5	119.7 (5)
C5—C6—H6A	109.3	C1—N1—Hg1	125.5 (4)
N2—C6—H6B	109.3	C5—N1—Hg1	114.8 (3)
C5—C6—H6B	109.3	C6—N2—C7	114.7 (4)
H6A—C6—H6B	108.0	C6—N2—Hg1	106.2 (3)
N2—C7—C12	110.3 (3)	C7—N2—Hg1	107.6 (3)
N2—C7—C8	111.6 (4)	C6—N2—H2B	117.2
C12—C7—C8	111.3 (4)	C7—N2—H2B	100.0
N2—C7—H7A	107.8	Hg1—N2—H2B	110.9
C12—C7—H7A	107.8	C12—N3—Hg1	111.3 (3)
C8—C7—H7A	107.8	C12—N3—H3B	113.1
C7—C8—C9	113.0 (4)	Hg1—N3—H3B	97.7
C7—C8—H8A	109.0	C12—N3—H3C	106.4
C9—C8—H8A	109.0	Hg1—N3—H3C	108.7
C7—C8—H8B	109.0	H3B—N3—H3C	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl2ⁱ	0.87	2.83	3.527 (5)	138
N3—H3C···Cl1ⁱⁱ	0.87	2.45	3.316 (5)	173

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₂H₁₉N₃)]
M_r	476.79
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	123
a, b, c (Å)	8.5319 (12), 8.8244 (12), 19.688 (3)
V (Å³)	1482.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.73
Crystal size (mm)	0.08 × 0.06 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.481, 0.565
No. of measured, independent and observed [I > 2σ(I)] reflections	11063, 2902, 2796
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.045, 1.06
No. of reflections	2902
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.68
Absolute structure	Flack (1983), with 1206 Friedel pairs
Absolute structure parameter	0.009 (7)

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl2ⁱ	0.87	2.83	3.527 (5)	138.4
N3—H3C···Cl1ⁱⁱ	0.87	2.45	3.316 (5)	172.9

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (grant No. 21001024), the Natural Science Foundation of Jiangsu Province (grant No. BK2011587) and Southeast University (grants No. 4007041121 and No. 9207040016).

References

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