Dibromidobis(pyridine-3-carbonitrile-κN1)mercury(II)

Ghiasi, R.

doi:10.1107/S1600536811013274

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m595

doi:10.1107/S1600536811013274

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Dibromidobis(pyridine-3-carbonitrile-κN¹)mercury(II)

Reza Ghiasi ^a ^*

^aDepartment of Chemistry, Basic Science Faculty, East Tehran Branch, Islamic Azad University, Qiam Dasht, Tehran, Iran
^*Correspondence e-mail: rezaghiasi1975@gmail.com

(Received 6 April 2011; accepted 8 April 2011; online 16 April 2011)

In the crystal structure of the title compound, [HgBr₂(C₆H₄N₂)₂], the Hg atom is four coordinated by two pyridine N atoms and two Br⁻ anions in a considerably distorted tetrahedral environment. π–π interactions between adjacent pyridine rings [centroid–centroid distance of 3.648 (3) Å] stabilize the crystal structure.

Related literature

For related structures, see: Ghiasi (2011 ); Steffen & Palenik (1977 ); Li et al. (2004 ).

Experimental

Crystal data

[HgBr₂(C₆H₄N₂)₂]
M_r = 568.61
Triclinic, $[P \overline 1]$
a = 8.5823 (6) Å
b = 9.4069 (6) Å
c = 9.8562 (7) Å
α = 81.935 (5)°
β = 71.435 (6)°
γ = 80.508 (6)°
V = 740.70 (9) Å³
Z = 2
Mo Kα radiation
μ = 15.78 mm⁻¹
T = 120 K
0.45 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.033, T_max = 0.052
8486 measured reflections
3967 independent reflections
3751 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.18
3967 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −2.48 e Å⁻³

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013274/bt5511sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013274/bt5511Isup2.hkl

checkCIF report

Comment top

Recently, the crystal satructure of dibromozinc(II)-di-3-pyridine-carbonitrile have been reported, (Ghiasi, 2011). On the other hand there are several complexes, with formula, [MX₂L₂], such as [ZnCl₂(4-cypy)₂], (Steffen & Palenik, 1977), [CuBr₂(3-Cypy)₂], (Li et al. 2004), [where py is pyridine, 4-cypy is 4-cyanopyridine and 3-cypy is 3-cyanopyridine] have been synthesized and characterized by single-crystal X-ray diffraction methods. The molecular structure of the title compound is shown in Fig. 1. The Hg^II atom is four-coordinated in a slightly distorted tetrahedral configuration by two N atoms from two pyridine rings and two Br^- anions. The Hg—Br and Hg—N bond distances and angles (Table 1) are within normal ranges. π-π interactions between adjacent pyridine rings [centroid···centroid distance of 3.648 (3) Å, symmetry code: –x,1-y,1-z] stabilize the packing of the crystal structure.

Related literature top

For related structures, see: Ghiasi (2011); Steffen & Palenik (1977); Li et al. (2004).

Experimental top

Mercury(II) bromide (0.72 gr, 2 mmol) was disolved in methanol (12 ml) and the solution was mixed with a methanolic solution (10 ml) of 3-pyridinecarbonitrile (0.42 g, 4 mmol). This solution was left to evaporate slowly at room temperature. After one week, colorless prismatic crystals of the title compound were isolated (yield 0.64 g, 56.0%, m.p. < 570 K).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Unit-cell packing diagram for (I).

Dibromidobis(pyridine-3-carbonitrile-κN¹)mercury(II) top

Crystal data top

[HgBr₂(C₆H₄N₂)₂]	Z = 2
M_r = 568.61	F(000) = 516
Triclinic, P1	D_x = 2.549 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5823 (6) Å	Cell parameters from 8405 reflections
b = 9.4069 (6) Å	θ = 2.2–29.2°
c = 9.8562 (7) Å	µ = 15.78 mm⁻¹
α = 81.935 (5)°	T = 120 K
β = 71.435 (6)°	Prism, colorless
γ = 80.508 (6)°	0.45 × 0.22 × 0.2 mm
V = 740.70 (9) Å³

Data collection top

Bruker SMART CCD diffractometer	3751 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 29.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
T_min = 0.033, T_max = 0.052	k = −12→12
8486 measured reflections	l = −13→13
3967 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0481P)² + 0.8751P] where P = (F_o² + 2F_c²)/3
3967 reflections	(Δ/σ)_max = 0.013
172 parameters	Δρ_max = 1.13 e Å⁻³
0 restraints	Δρ_min = −2.48 e Å⁻³

Crystal data top

[HgBr₂(C₆H₄N₂)₂]	γ = 80.508 (6)°
M_r = 568.61	V = 740.70 (9) Å³
Triclinic, P1	Z = 2
a = 8.5823 (6) Å	Mo Kα radiation
b = 9.4069 (6) Å	µ = 15.78 mm⁻¹
c = 9.8562 (7) Å	T = 120 K
α = 81.935 (5)°	0.45 × 0.22 × 0.2 mm
β = 71.435 (6)°

Data collection top

Bruker SMART CCD diffractometer	3967 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3751 reflections with I > 2σ(I)
T_min = 0.033, T_max = 0.052	R_int = 0.043
8486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.18	Δρ_max = 1.13 e Å⁻³
3967 reflections	Δρ_min = −2.48 e Å⁻³
172 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
C1	0.0093 (6)	0.7134 (5)	0.4103 (5)	0.0225 (9)
H1	0.0187	0.784	0.4635	0.027*
C2	−0.1379 (6)	0.6544 (5)	0.4499 (6)	0.0239 (9)
H2	−0.2248	0.6851	0.5286	0.029*
C3	−0.1559 (7)	0.5491 (5)	0.3719 (5)	0.0241 (9)
H3	−0.2534	0.5073	0.3971	0.029*
C4	−0.0218 (6)	0.5089 (5)	0.2548 (5)	0.0224 (9)
C5	−0.0290 (6)	0.4010 (5)	0.1668 (6)	0.0241 (9)
C6	0.1248 (7)	0.5712 (5)	0.2222 (5)	0.0227 (9)
H6	0.2146	0.5409	0.1454	0.027*
C7	0.2284 (7)	1.0208 (6)	−0.0244 (6)	0.0277 (10)
H7	0.1906	1.0754	0.0541	0.033*
C8	0.1848 (9)	1.0747 (6)	−0.1468 (6)	0.0355 (13)
H8	0.1204	1.1641	−0.1508	0.043*
C9	0.2387 (8)	0.9933 (6)	−0.2636 (6)	0.0308 (11)
H9	0.2099	1.0259	−0.347	0.037*
C10	0.3368 (6)	0.8616 (5)	−0.2530 (5)	0.0221 (9)
C11	0.3959 (7)	0.7725 (6)	−0.3706 (6)	0.0265 (10)
C12	0.3758 (7)	0.8154 (5)	−0.1251 (5)	0.0237 (9)
H12	0.4413	0.7271	−0.118	0.028*
Br1	0.59621 (7)	0.60216 (6)	0.12550 (6)	0.02802 (12)
Br2	0.25093 (7)	1.02533 (5)	0.34027 (6)	0.02714 (12)
Hg1	0.38539 (2)	0.805335 (18)	0.216864 (18)	0.02106 (7)
N1	0.1397 (5)	0.6727 (5)	0.2979 (4)	0.0223 (8)
N2	−0.0327 (6)	0.3162 (5)	0.0956 (6)	0.0311 (10)
N3	0.3219 (6)	0.8943 (5)	−0.0129 (5)	0.0238 (8)
N4	0.4417 (7)	0.7012 (5)	−0.4646 (6)	0.0351 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.027 (2)	0.019 (2)	0.022 (2)	0.0020 (17)	−0.0076 (19)	−0.0081 (17)
C2	0.020 (2)	0.025 (2)	0.024 (2)	0.0023 (17)	−0.0048 (18)	−0.0038 (18)
C3	0.027 (2)	0.022 (2)	0.021 (2)	−0.0032 (18)	−0.0052 (19)	0.0010 (18)
C4	0.025 (2)	0.022 (2)	0.021 (2)	−0.0013 (18)	−0.0076 (18)	−0.0055 (17)
C5	0.024 (2)	0.024 (2)	0.025 (2)	−0.0017 (18)	−0.0073 (19)	−0.0041 (18)
C6	0.025 (2)	0.022 (2)	0.020 (2)	−0.0005 (17)	−0.0043 (18)	−0.0075 (17)
C7	0.035 (3)	0.024 (2)	0.025 (2)	0.002 (2)	−0.010 (2)	−0.0065 (19)
C8	0.055 (4)	0.025 (2)	0.026 (3)	0.010 (2)	−0.017 (3)	−0.007 (2)
C9	0.043 (3)	0.025 (2)	0.026 (2)	0.004 (2)	−0.016 (2)	−0.005 (2)
C10	0.025 (2)	0.021 (2)	0.020 (2)	−0.0017 (17)	−0.0062 (18)	−0.0037 (17)
C11	0.031 (3)	0.025 (2)	0.024 (2)	0.0001 (19)	−0.011 (2)	−0.0036 (19)
C12	0.027 (2)	0.021 (2)	0.024 (2)	−0.0018 (18)	−0.010 (2)	−0.0032 (18)
Br1	0.0268 (2)	0.0291 (2)	0.0289 (3)	0.00759 (19)	−0.0111 (2)	−0.01227 (19)
Br2	0.0334 (3)	0.0236 (2)	0.0239 (2)	0.00029 (19)	−0.0065 (2)	−0.01056 (18)
Hg1	0.02188 (10)	0.02100 (10)	0.02036 (10)	0.00031 (7)	−0.00584 (7)	−0.00698 (7)
N1	0.024 (2)	0.0245 (19)	0.0182 (18)	−0.0005 (15)	−0.0058 (16)	−0.0068 (15)
N2	0.030 (2)	0.029 (2)	0.034 (2)	−0.0031 (18)	−0.007 (2)	−0.0104 (19)
N3	0.023 (2)	0.0250 (19)	0.022 (2)	0.0014 (16)	−0.0068 (16)	−0.0052 (16)
N4	0.044 (3)	0.031 (2)	0.031 (2)	−0.001 (2)	−0.010 (2)	−0.009 (2)

Geometric parameters (Å, º) top

C1—N1	1.347 (6)	C7—H7	0.93
C1—C2	1.384 (7)	C8—C9	1.385 (8)
C1—H1	0.93	C8—H8	0.93
C2—C3	1.391 (7)	C9—C10	1.389 (7)
C2—H2	0.93	C9—H9	0.93
C3—C4	1.390 (7)	C10—C12	1.399 (7)
C3—H3	0.93	C10—C11	1.436 (7)
C4—C6	1.401 (7)	C11—N4	1.148 (7)
C4—C5	1.446 (7)	C12—N3	1.334 (7)
C5—N2	1.144 (7)	C12—H12	0.93
C6—N1	1.337 (6)	Br1—Hg1	2.4581 (5)
C6—H6	0.93	Br2—Hg1	2.4736 (5)
C7—N3	1.333 (7)	Hg1—N1	2.481 (4)
C7—C8	1.381 (8)	Hg1—N3	2.496 (4)

N1—C1—C2	122.7 (5)	C8—C9—C10	118.4 (5)
N1—C1—H1	118.7	C8—C9—H9	120.8
C2—C1—H1	118.7	C10—C9—H9	120.8
C1—C2—C3	120.0 (5)	C9—C10—C12	119.1 (5)
C1—C2—H2	120	C9—C10—C11	120.7 (5)
C3—C2—H2	120	C12—C10—C11	120.1 (4)
C4—C3—C2	117.1 (5)	N4—C11—C10	179.3 (6)
C4—C3—H3	121.4	N3—C12—C10	121.9 (5)
C2—C3—H3	121.4	N3—C12—H12	119
C3—C4—C6	120.0 (5)	C10—C12—H12	119
C3—C4—C5	121.2 (5)	Br1—Hg1—Br2	159.99 (2)
C6—C4—C5	118.8 (5)	Br1—Hg1—N1	98.01 (10)
N2—C5—C4	179.0 (6)	Br2—Hg1—N1	97.02 (10)
N1—C6—C4	122.1 (5)	Br1—Hg1—N3	97.22 (10)
N1—C6—H6	119	Br2—Hg1—N3	95.88 (10)
C4—C6—H6	119	N1—Hg1—N3	90.10 (14)
N3—C7—C8	123.4 (5)	C6—N1—C1	118.1 (4)
N3—C7—H7	118.3	C6—N1—Hg1	121.2 (3)
C8—C7—H7	118.3	C1—N1—Hg1	120.3 (3)
C7—C8—C9	118.7 (5)	C7—N3—C12	118.5 (5)
C7—C8—H8	120.6	C7—N3—Hg1	120.3 (3)
C9—C8—H8	120.6	C12—N3—Hg1	121.2 (3)

N1—C1—C2—C3	−0.3 (8)	C2—C1—N1—C6	0.0 (7)
C1—C2—C3—C4	−0.5 (7)	C2—C1—N1—Hg1	172.5 (4)
C2—C3—C4—C6	1.7 (7)	Br1—Hg1—N1—C6	−38.3 (4)
C2—C3—C4—C5	−179.7 (5)	Br2—Hg1—N1—C6	155.0 (4)
C3—C4—C5—N2	16E1 (4)	N3—Hg1—N1—C6	59.0 (4)
C6—C4—C5—N2	−2E1 (4)	Br1—Hg1—N1—C1	149.5 (4)
C3—C4—C6—N1	−2.1 (8)	Br2—Hg1—N1—C1	−17.2 (4)
C5—C4—C6—N1	179.3 (5)	N3—Hg1—N1—C1	−113.2 (4)
N3—C7—C8—C9	0.8 (10)	C8—C7—N3—C12	−0.2 (9)
C7—C8—C9—C10	−1.0 (10)	C8—C7—N3—Hg1	−178.2 (5)
C8—C9—C10—C12	0.7 (9)	C10—C12—N3—C7	−0.1 (8)
C8—C9—C10—C11	179.9 (6)	C10—C12—N3—Hg1	177.9 (4)
C9—C10—C11—N4	−6E1 (5)	Br1—Hg1—N3—C7	−169.9 (4)
C12—C10—C11—N4	12E1 (5)	Br2—Hg1—N3—C7	−5.0 (4)
C9—C10—C12—N3	−0.2 (8)	N1—Hg1—N3—C7	92.1 (4)
C11—C10—C12—N3	−179.3 (5)	Br1—Hg1—N3—C12	12.2 (4)
C4—C6—N1—C1	1.2 (7)	Br2—Hg1—N3—C12	177.1 (4)
C4—C6—N1—Hg1	−171.2 (4)	N1—Hg1—N3—C12	−85.9 (4)

Experimental details

Crystal data
Chemical formula	[HgBr₂(C₆H₄N₂)₂]
M_r	568.61
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.5823 (6), 9.4069 (6), 9.8562 (7)
α, β, γ (°)	81.935 (5), 71.435 (6), 80.508 (6)
V (Å³)	740.70 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	15.78
Crystal size (mm)	0.45 × 0.22 × 0.2

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.033, 0.052
No. of measured, independent and observed [I > 2σ(I)] reflections	8486, 3967, 3751
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.18
No. of reflections	3967
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.13, −2.48

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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Li, X.-H., Wu, H.-Y. & Hu, J.-G. (2004). Acta Cryst. E60, m1533–m1535. Web of Science CSD CrossRef IUCr Journals Google Scholar
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