(5,5′-Dimethyl-2,2′-bipyridine-κ²N,N′)diiodidomercury(II)

In the mol­ecule of the title compound, [HgI₂(C₁₂H₁₂N₂)], the Hg^II atom is four-coordinated in a distorted tetra­hedral configuration by two N atoms from 5,5′-dimethyl-2,2′-bipyridine and two I atoms. There is a π–π contact between pyridine rings of adjacent molecules [centroid–centroid distance = 3.723 (5) Å].

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.056
• wR factor = 0.124
• Data-to-parameter ratio = 28.0

checkCIF/PLATON results

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Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Hg1    --  I1      ..       7.56 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Hg1    --  I2      ..       7.62 su
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         13
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C11

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, we reported the syntheses and crystal structures of [Zn(5,5'-dmbpy)Cl₂], (II), (Khalighi et al., 2008), [Zn(6-mbpy)Cl₂], (III), (Ahmadi, Kalateh et al., 2008), [Cd(5,5'-dmbpy)(µ-Cl)₂]_n, (IV), (Ahmadi, Khalighi et al., 2008), [Cu(5,5'-dcbpy)(en)(H₂O)₂].2.5H₂O, (V), (Yousefi, Khalighi et al., 2008) and {[HgCl(dm4bt)]₂(µ-Cl)₂}, (VI), (Khavasi et al., 2008) [where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6-mbpy is 6-methyl-2,2' -bipyridine, 5,5'-dcbpy is 2,2'-bipyridine-5,5'-dicarboxylate, en is ethylene- diamine and dm4bt is 2,2'-dimethyl-4,4'-bithiazole]. There are several Hg^II complexes, with formula, [HgI₂(N—N)], such as [HgI₂(bipy)], (VII), [HgI₂(phen)], (VIII) and [HgI₂(2,9-dmphen)], (IX), (Freire et al., 1999), [HgI₂(bipy)][HgI₂], (X), (Chen et al., 2006), [HgI₂(4,4'-dmbpy)], (XI), (Yousefi, Tadayon Pour et al., 2008) and [HgI₂(TMDA)], (XII), (Htoon & Ladd, 1976) [where bipy is 2,2'-bipyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthroline, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine and TMDA is tetramethylethylene- diamine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

In the title compound, (Fig. 1), the Hg^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from 5,5'-dimethyl-2,2'-bi- pyridine and two I atoms. The Hg—I and Hg—N bond lengths and angles (Table 1) are within normal ranges, as in (VII), (VIII) and (XI).

In the crystal structure, the π-π contact (Fig. 2) between the pyridine rings, Cg2···Cg3ⁱ [symmetry code: (i) x, 1 - y, 1 - z, where Cg2 and Cg3 are centroids of the rings (N1/C1/C2/C4-C6) and (N2/C7-C10/C12), respectively] may stabilize the structure, with centroid-centroid distance of 3.723 (5) Å.

Related literature

For related literature, see: Ahmadi, Kalateh et al. (2008); Ahmadi, Khalighi et al. (2008); Chen et al. (2006); Freire et al. (1999); Htoon & Ladd (1976); Khalighi et al. (2008); Khavasi et al. (2008); Yousefi, Khalighi, et al. (2008); Yousefi, Tadayon Pour et al. (2008).

S2. Experimental

For the preparation of the title compound, (I), a solution of 5,5'-dimethyl -2,2'-bipyridine (0.25 g, 1.33 mmol) in methanol (10 ml) was added to a solution of HgI₂ (0.61 g, 1.33 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray analysis were isolated after one week by methanol diffusion to a colorless solution in DMSO (yield; 0.62 g, 72.9%).

S3. Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A packing diagram of the title compound.

(5,5'-Dimethyl-2,2'-bipyridine-κ²N,N')diiodidomercury(II)

Crystal data

[HgI2(C12H12N2)]	F(000) = 2272
Mr = 638.63	Dx = 2.665 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1768 reflections
a = 15.0325 (8) Å	θ = 2.4–29.3°
b = 15.0654 (8) Å	µ = 13.53 mm^−1
c = 14.0579 (10) Å	T = 298 K
V = 3183.7 (3) Å^3	Prism, colorless
Z = 8	0.35 × 0.31 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4306 independent reflections
Radiation source: fine-focus sealed tube	3418 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
ϕ and ω scans	θmax = 29.3°, θmin = 2.4°
Absorption correction: numerical shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)	h = −20→19
Tmin = 0.015, Tmax = 0.075	k = −20→17
23007 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0347P)^2 + 17.4498P] where P = (Fo^2 + 2Fc^2)/3
4306 reflections	(Δ/σ)max = 0.010
154 parameters	Δρmax = 1.44 e Å^−3
0 restraints	Δρmin = −1.51 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Hg1	0.11964 (2)	0.71065 (2)	0.60202 (3)	0.05197 (12)
I1	0.00810 (7)	0.80915 (5)	0.50004 (7)	0.0859 (3)
I2	0.25140 (5)	0.76000 (5)	0.71769 (6)	0.0687 (2)
N1	0.1696 (4)	0.5812 (5)	0.5214 (5)	0.0403 (14)
N2	0.0387 (4)	0.5836 (4)	0.6554 (5)	0.0381 (13)
C1	0.2371 (5)	0.5833 (6)	0.4598 (6)	0.0463 (18)
H1	0.2633	0.6377	0.4460	0.056*
C2	0.2697 (6)	0.5082 (7)	0.4155 (6)	0.049 (2)
C3	0.3485 (8)	0.5156 (9)	0.3481 (9)	0.077 (3)
H3A	0.3986	0.5399	0.3816	0.093*
H3B	0.3333	0.5538	0.2959	0.093*
H3C	0.3635	0.4578	0.3243	0.093*
C4	0.2299 (7)	0.4279 (7)	0.4391 (8)	0.063 (3)
H4	0.2506	0.3755	0.4121	0.076*
C5	0.1604 (7)	0.4257 (6)	0.5019 (7)	0.053 (2)
H5	0.1324	0.3723	0.5162	0.063*
C6	0.1322 (5)	0.5044 (5)	0.5440 (5)	0.0387 (16)
C7	0.0586 (5)	0.5057 (5)	0.6156 (5)	0.0378 (15)
C8	0.0140 (6)	0.4291 (6)	0.6412 (7)	0.054 (2)
H8	0.0270	0.3754	0.6118	0.065*
C9	−0.0503 (6)	0.4341 (6)	0.7113 (7)	0.054 (2)
H9	−0.0805	0.3829	0.7297	0.065*
C10	−0.0703 (6)	0.5135 (6)	0.7542 (6)	0.0477 (19)
C11	−0.1370 (7)	0.5206 (8)	0.8337 (8)	0.069 (3)
H11A	−0.1831	0.5615	0.8159	0.083*
H11B	−0.1078	0.5417	0.8901	0.083*
H11C	−0.1625	0.4633	0.8458	0.083*
C12	−0.0244 (5)	0.5873 (6)	0.7226 (6)	0.0465 (18)
H12	−0.0379	0.6422	0.7492	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.0544 (2)	0.04113 (17)	0.0603 (2)	0.00092 (15)	0.00422 (17)	−0.00082 (14)
I1	0.0978 (6)	0.0521 (4)	0.1078 (7)	0.0131 (4)	−0.0354 (5)	0.0050 (4)
I2	0.0660 (4)	0.0555 (4)	0.0845 (5)	0.0031 (3)	−0.0154 (4)	−0.0110 (3)
N1	0.039 (3)	0.044 (3)	0.037 (3)	0.001 (3)	0.003 (3)	−0.002 (3)
N2	0.035 (3)	0.039 (3)	0.041 (3)	0.002 (3)	0.000 (3)	0.001 (3)
C1	0.040 (4)	0.053 (5)	0.046 (4)	−0.002 (4)	0.009 (3)	−0.006 (4)
C2	0.041 (4)	0.072 (6)	0.035 (4)	0.012 (4)	0.000 (3)	−0.002 (4)
C3	0.061 (6)	0.098 (9)	0.073 (7)	0.016 (6)	0.029 (6)	−0.004 (6)
C4	0.070 (7)	0.058 (6)	0.062 (6)	0.019 (5)	0.001 (5)	−0.020 (5)
C5	0.058 (5)	0.045 (4)	0.056 (5)	0.003 (4)	0.004 (4)	−0.002 (4)
C6	0.038 (4)	0.038 (4)	0.040 (4)	0.001 (3)	−0.004 (3)	−0.002 (3)
C7	0.039 (4)	0.040 (4)	0.035 (4)	0.003 (3)	−0.009 (3)	−0.001 (3)
C8	0.057 (5)	0.047 (5)	0.058 (5)	−0.009 (4)	−0.004 (4)	−0.002 (4)
C9	0.051 (5)	0.051 (5)	0.062 (6)	−0.016 (4)	0.003 (4)	0.007 (4)
C10	0.038 (4)	0.057 (5)	0.048 (5)	−0.001 (4)	−0.005 (3)	0.010 (4)
C11	0.059 (6)	0.080 (7)	0.067 (6)	−0.001 (5)	0.031 (5)	0.000 (5)
C12	0.042 (4)	0.048 (4)	0.050 (5)	0.003 (4)	0.009 (4)	−0.003 (4)

Geometric parameters (Å, º)

Hg1—I1	2.6587 (9)	C6—N1	1.325 (10)
Hg1—I2	2.6684 (8)	C6—C7	1.496 (11)
Hg1—N1	2.377 (7)	C7—N2	1.335 (10)
Hg1—N2	2.389 (6)	C7—C8	1.382 (12)
C1—N1	1.335 (10)	C8—C9	1.384 (14)
C1—C2	1.380 (13)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.373 (13)
C2—C4	1.390 (15)	C9—H9	0.9300
C2—C3	1.521 (13)	C10—C12	1.382 (12)
C3—H3A	0.9600	C10—C11	1.505 (13)
C3—H3B	0.9600	C11—H11A	0.9600
C3—H3C	0.9600	C11—H11B	0.9600
C4—C5	1.368 (14)	C11—H11C	0.9600
C4—H4	0.9300	C12—N2	1.339 (10)
C5—C6	1.392 (11)	C12—H12	0.9300
C5—H5	0.9300
I1—Hg1—I2	129.89 (3)	C4—C5—C6	119.1 (9)
N1—Hg1—I1	113.59 (16)	C4—C5—H5	120.5
N1—Hg1—N2	69.7 (2)	C6—C5—H5	120.5
N1—Hg1—I2	106.53 (16)	N1—C6—C5	120.9 (8)
N2—Hg1—I1	107.15 (15)	N1—C6—C7	117.6 (7)
N2—Hg1—I2	114.22 (15)	C5—C6—C7	121.5 (7)
C1—N1—Hg1	122.0 (6)	N2—C7—C8	121.1 (8)
C6—N1—Hg1	117.9 (5)	N2—C7—C6	117.4 (7)
C6—N1—C1	119.9 (7)	C8—C7—C6	121.5 (7)
C7—N2—Hg1	117.3 (5)	C7—C8—C9	118.7 (9)
C7—N2—C12	119.4 (7)	C7—C8—H8	120.7
C12—N2—Hg1	123.3 (5)	C9—C8—H8	120.7
N1—C1—C2	122.9 (9)	C10—C9—C8	120.8 (8)
N1—C1—H1	118.5	C10—C9—H9	119.6
C2—C1—H1	118.5	C8—C9—H9	119.6
C1—C2—C4	116.9 (8)	C9—C10—C12	116.8 (8)
C1—C2—C3	119.9 (10)	C9—C10—C11	122.3 (9)
C4—C2—C3	123.2 (9)	C12—C10—C11	120.9 (9)
C2—C3—H3A	109.5	C10—C11—H11A	109.5
C2—C3—H3B	109.5	C10—C11—H11B	109.5
H3A—C3—H3B	109.5	H11A—C11—H11B	109.5
C2—C3—H3C	109.5	C10—C11—H11C	109.5
H3A—C3—H3C	109.5	H11A—C11—H11C	109.5
H3B—C3—H3C	109.5	H11B—C11—H11C	109.5
C5—C4—C2	120.3 (9)	N2—C12—C10	123.2 (8)
C5—C4—H4	119.8	N2—C12—H12	118.4
C2—C4—H4	119.8	C10—C12—H12	118.4
I1—Hg1—N1—C1	82.9 (6)	C5—C6—N1—C1	−2.1 (12)
I1—Hg1—N1—C6	−101.5 (5)	C7—C6—N1—C1	178.3 (7)
I2—Hg1—N1—C1	−66.4 (6)	C5—C6—N1—Hg1	−177.8 (6)
I2—Hg1—N1—C6	109.2 (5)	C7—C6—N1—Hg1	2.6 (9)
N2—Hg1—N1—C1	−176.7 (7)	N1—C6—C7—N2	−3.3 (11)
N2—Hg1—N1—C6	−1.1 (5)	C5—C6—C7—N2	177.1 (8)
I1—Hg1—N2—C7	108.7 (5)	N1—C6—C7—C8	178.0 (8)
I1—Hg1—N2—C12	−71.7 (6)	C5—C6—C7—C8	−1.6 (12)
I2—Hg1—N2—C7	−100.3 (5)	C8—C7—N2—C12	1.4 (12)
I2—Hg1—N2—C12	79.3 (6)	C6—C7—N2—C12	−177.3 (7)
N1—Hg1—N2—C7	−0.8 (5)	C8—C7—N2—Hg1	−179.0 (6)
N1—Hg1—N2—C12	178.9 (7)	C6—C7—N2—Hg1	2.3 (9)
C2—C1—N1—C6	1.5 (13)	N2—C7—C8—C9	−1.9 (13)
C2—C1—N1—Hg1	177.0 (6)	C6—C7—C8—C9	176.7 (8)
N1—C1—C2—C4	−1.1 (13)	C7—C8—C9—C10	0.6 (15)
N1—C1—C2—C3	−178.3 (9)	C8—C9—C10—C12	1.2 (14)
C1—C2—C4—C5	1.4 (14)	C8—C9—C10—C11	−177.2 (9)
C3—C2—C4—C5	178.5 (10)	C9—C10—C12—N2	−1.8 (13)
C2—C4—C5—C6	−2.1 (15)	C11—C10—C12—N2	176.6 (9)
C4—C5—C6—N1	2.5 (14)	C10—C12—N2—C7	0.6 (13)
C4—C5—C6—C7	−178.0 (8)	C10—C12—N2—Hg1	−179.1 (6)