Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029971/ci6651sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029971/ci6651Isup2.hkl |
CCDC reference: 287516
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).
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 Uiso(H) = 1.2Ueq(carrier atom).
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.
Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. |
[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) Å3 | Block, brown |
Z = 4 | 0.22 × 0.16 × 0.14 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0127P)2] where P = (Fo2 + 2Fc2)/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) |
[Zn(C15H15N4)Cl3] | V = 1780.0 (4) Å3 |
Mr = 423.03 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.3222 (12) Å | µ = 1.83 mm−1 |
b = 13.3871 (18) Å | T = 294 K |
c = 15.977 (2) Å | 0.22 × 0.16 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 3615 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2630 reflections with I > 2σ(I) |
Tmin = 0.650, Tmax = 0.774 | Rint = 0.047 |
10139 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.062 | Δρmax = 0.34 e Å−3 |
S = 0.99 | Δρmin = −0.25 e Å−3 |
3615 reflections | Absolute structure: Flack (1983); 1529 Friedel pairs |
208 parameters | Absolute structure parameter: −0.015 (13) |
0 restraints |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cl2i | 0.93 | 2.83 | 3.608 (4) | 142 |
C4—H4A···Cl3i | 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. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C15H15N4)Cl3] |
Mr | 423.03 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 8.3222 (12), 13.3871 (18), 15.977 (2) |
V (Å3) | 1780.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.83 |
Crystal size (mm) | 0.22 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.650, 0.774 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10139, 3615, 2630 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.062, 0.99 |
No. of reflections | 3615 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.25 |
Absolute structure | Flack (1983); 1529 Friedel pairs |
Absolute structure parameter | −0.015 (13) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXTL (Bruker, 1999), SHELXTL.
Zn1—N3 | 2.099 (3) | Zn1—Cl1 | 2.2424 (11) |
Zn1—Cl2 | 2.2393 (11) | Zn1—Cl3 | 2.2548 (11) |
N3—Zn1—Cl2 | 107.64 (8) | N3—Zn1—Cl3 | 105.14 (8) |
N3—Zn1—Cl1 | 104.47 (8) | Cl2—Zn1—Cl3 | 113.48 (4) |
Cl2—Zn1—Cl1 | 114.22 (4) | Cl1—Zn1—Cl3 | 111.00 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cl2i | 0.93 | 2.83 | 3.608 (4) | 142 |
C4—H4A···Cl3i | 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. |
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 ZnII complex of 1,3-di(2-picolyl)imidazolium chloride, (I), is presented.
The ZnII 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.