Trichloro[1,3-bis(2-pyridylmethyl)imidazolium]zinc(II)

In the title compound, [Zn(C₁₅H₁₅N₄)Cl₃], the Zn^II atom is in a distorted tetra­hedral environment, coordinated by three Cl atoms and a pyridine N atom. In the crystal packing, the mol­ecules are linked by C—H...Cl hydrogen bonds into a sheet-like structure parallel to the ac plane.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.037
• wR factor = 0.062
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C15 H15 Cl3 N4 Zn1
            Atom count from _chemical_formula_moiety:
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.39
           From the CIF: _reflns_number_total               3615
           Count of symmetry unique reflns         2091
           Completeness (_total/calc)            172.88%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1524
           Fraction of Friedel pairs measured     0.729
           Are heavy atom types Z>Si present        yes

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

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

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S1. Comment

Since the discovery of stable imidazoline-2-ylenes by Arduengo in 1991 (Arduengo et al., 1991), much interest has been focused on the chemistry of N-heterocyclic carbenes (NHCs) and their metal complexes. In recent years, a number of metal complexes incorporating novel mono-, bi- and tridentate carbene ligands have been synthesized and structurally investigated. Transiton metal complexes of chelating carbene ligands containing pyridine units have received a lot of attention owing to their potential applications in organometallic chemistry and homogeneous catalysis (Chen & Lin,2000; Danopoulos et al., 2003; Poyatos et al., 2003). As a functionalized imidazolium salt, 1,3-di(2-picolyl)imidazolium chloride and its palladium carbene complexes have been prepared and structurally investigated (Magill et al., 2001). Recently, the structures of mono- and trinuclear silver, heteronuclear silver and gold, mononuclear mercury carbene complexes have been reported (Catalano et al., 2004). Here, the structure of a Zn^II complex of 1,3-di(2-picolyl)imidazolium chloride, (I), is presented.

The Zn^II atom is in a distorted tetrahedral environment with three Cl atoms and a pyridine N atom (Fig. 1). The bond angles around the metal atom range from 105.14 (8) to 114.22 (4)° (Table 1). The planes through the N3/C5–C9 and N4/C11–C15 pyridine rings form dihedral angles of 84.1 (1) and 70.8 (1)°, respectively, with the central five-membered ring. The crystal structure is stabilized by C—H···Cl hydrogen bonds (Table 2). The hydrogen bonds link the molecules into a sheet-like structure parallel to the ac plane.

S2. Experimental

1,3-di(2-picolyl)imidazolium chloride (0.286 g, 1.0 mmol) was added to a solution of anhydrous ZnCl₂ (0.136 g, 1.0 mmol) in methanol (20 ml), at room temperature to obtain compound (I) as pale brown powder (yield: 90%). Single crystals were grown by slow evaporation of methanol solution. Analysis calculated for C₁₅H₁₅Cl₃N₄Zn: C 42.59, H 3.57, N 13.24%; found: C 42.49, H 3.65, N 13.32%. ¹H NMR(δ, p.p.m.): 9.39 (s, 1H), 8.52 (s, 2H), 7.78–7.89 (m, 4H), 7.36–7.47 (m, 4H), 5.58–5.59 (d, 4H).

S3. Refinement

The H atoms were placed in calculated positions, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and included in the final cycles of refinement using a riding-model approximation, with U_iso(H) = 1.2U_eq(carrier atom).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.

(I)

Crystal data

[Zn(C15H15N4)Cl3]	F(000) = 856
Mr = 423.03	Dx = 1.579 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2564 reflections
a = 8.3222 (12) Å	θ = 2.8–22.6°
b = 13.3871 (18) Å	µ = 1.83 mm^−1
c = 15.977 (2) Å	T = 294 K
V = 1780.0 (4) Å^3	Block, brown
Z = 4	0.22 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3615 independent reflections
Radiation source: fine-focus sealed tube	2630 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.650, Tmax = 0.774	k = −11→16
10139 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.0127P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
3615 reflections	Δρmax = 0.34 e Å^−3
208 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Absolute structure: Flack (1983); 1529 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.015 (13)

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
Zn1	0.07466 (5)	0.66430 (3)	0.34702 (3)	0.03838 (12)
Cl1	0.18937 (13)	0.79383 (8)	0.28107 (7)	0.0584 (3)
Cl2	0.06791 (12)	0.67910 (8)	0.48658 (6)	0.0554 (3)
Cl3	−0.16608 (11)	0.62738 (7)	0.29015 (7)	0.0514 (3)
N1	0.5183 (3)	0.5658 (2)	0.4705 (2)	0.0392 (8)
N2	0.6904 (4)	0.5165 (2)	0.56160 (19)	0.0418 (8)
N3	0.2225 (3)	0.5421 (2)	0.31809 (17)	0.0342 (7)
N4	0.9282 (4)	0.4088 (2)	0.4814 (2)	0.0535 (8)
C1	0.6708 (4)	0.5712 (3)	0.4933 (2)	0.0411 (10)
H1	0.7507	0.6073	0.4660	0.049*
C2	0.4394 (5)	0.5048 (3)	0.5258 (3)	0.0540 (11)
H2	0.3308	0.4886	0.5246	0.065*
C3	0.5462 (5)	0.4733 (3)	0.5812 (3)	0.0539 (11)
H3	0.5267	0.4298	0.6254	0.065*
C4	0.4481 (4)	0.6128 (3)	0.3965 (2)	0.0423 (10)
H4A	0.5301	0.6503	0.3669	0.051*
H4B	0.3644	0.6590	0.4133	0.051*
C5	0.3784 (4)	0.5342 (2)	0.3394 (2)	0.0362 (9)
C6	0.4711 (4)	0.4553 (3)	0.3124 (3)	0.0470 (11)
H6	0.5780	0.4505	0.3288	0.056*
C7	0.4052 (5)	0.3840 (3)	0.2616 (3)	0.0532 (11)
H7	0.4673	0.3311	0.2422	0.064*
C8	0.2470 (5)	0.3918 (3)	0.2397 (3)	0.0553 (12)
H8	0.1992	0.3440	0.2056	0.066*
C9	0.1603 (5)	0.4715 (3)	0.2690 (2)	0.0456 (10)
H9	0.0527	0.4765	0.2539	0.055*
C10	0.8431 (4)	0.5002 (3)	0.6042 (2)	0.0461 (11)
H10A	0.8225	0.4819	0.6619	0.055*
H10B	0.9038	0.5621	0.6043	0.055*
C11	0.9428 (5)	0.4193 (3)	0.5633 (2)	0.0429 (10)
C12	1.0475 (5)	0.3641 (3)	0.6108 (3)	0.0606 (12)
H12	1.0527	0.3731	0.6684	0.073*
C13	1.1433 (6)	0.2961 (4)	0.5723 (4)	0.0850 (16)
H13	1.2149	0.2575	0.6032	0.102*
C14	1.1327 (5)	0.2850 (4)	0.4862 (4)	0.0777 (16)
H14	1.1989	0.2403	0.4580	0.093*
C15	1.0227 (5)	0.3413 (4)	0.4438 (3)	0.0646 (13)
H15	1.0129	0.3324	0.3863	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0305 (2)	0.0366 (2)	0.0480 (3)	0.0008 (2)	−0.0005 (2)	−0.0060 (2)
Cl1	0.0526 (7)	0.0502 (7)	0.0723 (8)	−0.0096 (5)	0.0019 (6)	0.0103 (6)
Cl2	0.0549 (6)	0.0620 (7)	0.0494 (6)	−0.0098 (6)	0.0096 (6)	−0.0156 (5)
Cl3	0.0333 (5)	0.0563 (7)	0.0647 (7)	−0.0006 (5)	−0.0071 (5)	−0.0126 (6)
N1	0.0315 (18)	0.043 (2)	0.044 (2)	−0.0023 (14)	−0.0033 (15)	−0.0010 (17)
N2	0.042 (2)	0.044 (2)	0.039 (2)	−0.0014 (16)	−0.0025 (17)	−0.0040 (17)
N3	0.0320 (17)	0.0343 (18)	0.0362 (19)	0.0023 (13)	−0.0003 (14)	−0.0040 (15)
N4	0.061 (2)	0.053 (2)	0.047 (2)	0.006 (2)	0.005 (2)	0.0003 (18)
C1	0.034 (2)	0.044 (2)	0.046 (2)	0.0008 (19)	−0.002 (2)	0.002 (2)
C2	0.036 (2)	0.072 (3)	0.055 (3)	−0.016 (2)	0.009 (3)	0.006 (2)
C3	0.056 (3)	0.068 (3)	0.038 (2)	−0.003 (2)	0.007 (3)	0.006 (2)
C4	0.032 (2)	0.039 (2)	0.056 (3)	−0.0009 (18)	−0.010 (2)	0.002 (2)
C5	0.035 (2)	0.034 (2)	0.040 (2)	−0.0009 (15)	0.0034 (18)	−0.001 (2)
C6	0.030 (2)	0.048 (3)	0.063 (3)	0.0090 (18)	0.0030 (19)	−0.002 (2)
C7	0.049 (3)	0.038 (2)	0.072 (3)	0.007 (2)	0.007 (2)	−0.011 (2)
C8	0.052 (3)	0.047 (3)	0.067 (3)	−0.005 (2)	−0.004 (2)	−0.019 (2)
C9	0.038 (2)	0.047 (3)	0.052 (3)	0.002 (2)	−0.010 (2)	−0.009 (2)
C10	0.047 (2)	0.057 (3)	0.034 (2)	0.002 (2)	−0.012 (2)	0.001 (2)
C11	0.044 (2)	0.039 (2)	0.046 (3)	−0.004 (2)	0.005 (2)	0.0031 (19)
C12	0.061 (3)	0.065 (3)	0.055 (3)	0.013 (2)	−0.010 (2)	0.003 (2)
C13	0.072 (3)	0.072 (4)	0.111 (5)	0.021 (3)	−0.015 (4)	0.008 (4)
C14	0.054 (3)	0.063 (3)	0.117 (5)	0.013 (2)	0.010 (3)	−0.014 (4)
C15	0.069 (3)	0.058 (3)	0.067 (3)	−0.005 (3)	0.013 (2)	−0.013 (3)

Geometric parameters (Å, º)

Zn1—N3	2.099 (3)	C4—H4B	0.97
Zn1—Cl2	2.2393 (11)	C5—C6	1.376 (4)
Zn1—Cl1	2.2424 (11)	C6—C7	1.368 (5)
Zn1—Cl3	2.2548 (11)	C6—H6	0.93
N1—C1	1.323 (4)	C7—C8	1.366 (5)
N1—C2	1.370 (4)	C7—H7	0.93
N1—C4	1.462 (4)	C8—C9	1.371 (5)
N2—C1	1.324 (4)	C8—H8	0.93
N2—C3	1.368 (4)	C9—H9	0.93
N2—C10	1.458 (4)	C10—C11	1.513 (5)
N3—C9	1.333 (4)	C10—H10A	0.97
N3—C5	1.346 (4)	C10—H10B	0.97
N4—C11	1.321 (5)	C11—C12	1.371 (5)
N4—C15	1.340 (5)	C12—C13	1.358 (6)
C1—H1	0.93	C12—H12	0.93
C2—C3	1.323 (5)	C13—C14	1.387 (7)
C2—H2	0.93	C13—H13	0.93
C3—H3	0.93	C14—C15	1.366 (6)
C4—C5	1.509 (5)	C14—H14	0.93
C4—H4A	0.97	C15—H15	0.93
N3—Zn1—Cl2	107.64 (8)	C7—C6—C5	119.8 (3)
N3—Zn1—Cl1	104.47 (8)	C7—C6—H6	120.1
Cl2—Zn1—Cl1	114.22 (4)	C5—C6—H6	120.1
N3—Zn1—Cl3	105.14 (8)	C8—C7—C6	119.0 (4)
Cl2—Zn1—Cl3	113.48 (4)	C8—C7—H7	120.5
Cl1—Zn1—Cl3	111.00 (4)	C6—C7—H7	120.5
C1—N1—C2	108.3 (3)	C7—C8—C9	118.6 (4)
C1—N1—C4	125.6 (3)	C7—C8—H8	120.7
C2—N1—C4	126.0 (3)	C9—C8—H8	120.7
C1—N2—C3	108.3 (3)	N3—C9—C8	123.3 (4)
C1—N2—C10	125.0 (3)	N3—C9—H9	118.4
C3—N2—C10	126.5 (3)	C8—C9—H9	118.4
C9—N3—C5	117.9 (3)	N2—C10—C11	112.5 (3)
C9—N3—Zn1	117.1 (2)	N2—C10—H10A	109.1
C5—N3—Zn1	124.8 (2)	C11—C10—H10A	109.1
C11—N4—C15	117.5 (4)	N2—C10—H10B	109.1
N1—C1—N2	108.3 (4)	C11—C10—H10B	109.1
N1—C1—H1	125.8	H10A—C10—H10B	107.8
N2—C1—H1	125.8	N4—C11—C12	123.4 (4)
C3—C2—N1	107.4 (4)	N4—C11—C10	116.9 (3)
C3—C2—H2	126.3	C12—C11—C10	119.6 (4)
N1—C2—H2	126.3	C13—C12—C11	118.9 (4)
C2—C3—N2	107.5 (4)	C13—C12—H12	120.5
C2—C3—H3	126.2	C11—C12—H12	120.5
N2—C3—H3	126.2	C12—C13—C14	118.9 (5)
N1—C4—C5	110.0 (3)	C12—C13—H13	120.6
N1—C4—H4A	109.7	C14—C13—H13	120.6
C5—C4—H4A	109.7	C15—C14—C13	118.5 (5)
N1—C4—H4B	109.7	C15—C14—H14	120.8
C5—C4—H4B	109.7	C13—C14—H14	120.8
H4A—C4—H4B	108.2	N4—C15—C14	122.9 (4)
N3—C5—C6	121.4 (3)	N4—C15—H15	118.6
N3—C5—C4	117.9 (3)	C14—C15—H15	118.6
C6—C5—C4	120.6 (3)
Cl2—Zn1—N3—C9	126.2 (2)	N1—C4—C5—N3	123.9 (3)
Cl1—Zn1—N3—C9	−112.0 (2)	N1—C4—C5—C6	−54.0 (5)
Cl3—Zn1—N3—C9	4.9 (3)	N3—C5—C6—C7	1.3 (6)
Cl2—Zn1—N3—C5	−59.8 (3)	C4—C5—C6—C7	179.2 (3)
Cl1—Zn1—N3—C5	62.0 (3)	C5—C6—C7—C8	−1.2 (6)
Cl3—Zn1—N3—C5	178.9 (3)	C6—C7—C8—C9	0.6 (7)
C2—N1—C1—N2	−0.6 (4)	C5—N3—C9—C8	0.2 (5)
C4—N1—C1—N2	−177.7 (3)	Zn1—N3—C9—C8	174.6 (3)
C3—N2—C1—N1	1.5 (4)	C7—C8—C9—N3	−0.1 (6)
C10—N2—C1—N1	177.5 (3)	C1—N2—C10—C11	−81.5 (4)
C1—N1—C2—C3	−0.5 (5)	C3—N2—C10—C11	93.8 (4)
C4—N1—C2—C3	176.6 (4)	C15—N4—C11—C12	−0.8 (6)
N1—C2—C3—N2	1.4 (5)	C15—N4—C11—C10	176.2 (3)
C1—N2—C3—C2	−1.8 (5)	N2—C10—C11—N4	31.7 (5)
C10—N2—C3—C2	−177.7 (3)	N2—C10—C11—C12	−151.1 (4)
C1—N1—C4—C5	119.3 (4)	N4—C11—C12—C13	1.0 (6)
C2—N1—C4—C5	−57.3 (5)	C10—C11—C12—C13	−175.9 (4)
C9—N3—C5—C6	−0.8 (5)	C11—C12—C13—C14	0.3 (7)
Zn1—N3—C5—C6	−174.7 (3)	C12—C13—C14—C15	−1.8 (7)
C9—N3—C5—C4	−178.7 (3)	C11—N4—C15—C14	−0.8 (6)
Zn1—N3—C5—C4	7.3 (4)	C13—C14—C15—N4	2.1 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2^i	0.93	2.83	3.608 (4)	142
C4—H4A···Cl3^i	0.97	2.83	3.638 (3)	142
C4—H4B···Cl2	0.97	2.74	3.588 (4)	146
C9—H9···Cl3	0.93	2.78	3.442 (4)	129
C10—H10B···Cl2	0.97	2.80	3.573 (4)	137

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