Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103002956/av1127sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103002956/av1127Isup2.hkl |
CCDC reference: 185488
The crude 2-chloro-5-methylpyridine contained 2-chloro-5-methylpyridine (79.4%), 2-chloro-3-methylpyridine (13.6%) and 3-methylpyridine (5.2%) (determined by peak area % with GC—MS). Crude 2-chloro-5- methylpyridine (12.0 g) in absolute ethanol (30 ml) was mixed with CuCl2·2H2O (5.0 g, 0.029 mol, in 20 ml) in a round-bottom flask. The blue precipitate appeared immediately. More ethanol (50 ml) was added to the mixture, and it was refluxed for 15 min. The precipitate changed from blue to dark violet. After suction filtration, the precipitate was washed with absolute ethanol and dried to obtain a dark-violet crystalline precipitate (10.5 g; 73.6% recycle yield of 2-chloro-5-methyl pyridine). The product was recrystallized in absolute ethanol, and a single-crystal was obtained from the refined product mother solution.
A melting-point determination was performed on XRC1 melting-point apparatus (Science Instrument Company, Sichuan University). The crystal melted at 413 K (decomposed).
CHN analysis was obtained with an Eger 2000 elemental analyzer. Analysis; calculated for C12H12Cl4CuN2: C 37.02, H 3.08, N 7.19%; found: C 37.05, H 3.39, N 7.60%.
H atoms were added at calculated positions and refined using a riding model. H atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl H atoms) times the equivalent isotropic displacement parameters of their parent atoms, and C—H distances were restrained to 0.95 Å for H atoms bonded to C2, C3 and C5, and 0.98 Å for methyl H.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: DATARED, Enraf-Nonius; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
[CuCl2(C6H6ClN)2] | F(000) = 390 |
Mr = 389.58 | Dx = 1.676 Mg m−3 |
Monoclinic, P21/c | Melting point: 140 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.862 (1) Å | Cell parameters from 25 reflections |
b = 12.941 (4) Å | θ = 2.6–30.2° |
c = 10.538 (4) Å | µ = 2.09 mm−1 |
β = 105.12 (3)° | T = 293 K |
V = 771.7 (4) Å3 | Prism, dark violet |
Z = 2 | 0.35 × 0.3 × 0.2 mm |
CAD-4 diffractometer | Rint = 0.028 |
ω/2θ scans | θmax = 30.2°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) North, Phillips & Mathews, 1968 | h = −8→8 |
Tmin = 0.528, Tmax = 0.680 | k = −1→18 |
2585 measured reflections | l = 0→14 |
2284 independent reflections | 3 standard reflections every 100 reflections |
1352 reflections with I > 2σ(I) |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0684P)2 + 0.0962P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.037 | (Δ/σ)max = 0.023 |
wR(F2) = 0.116 | Δρmax = 0.54 e Å−3 |
S = 0.98 | Δρmin = −0.64 e Å−3 |
2284 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
90 parameters | Extinction coefficient: 0.053 (4) |
0 restraints |
[CuCl2(C6H6ClN)2] | V = 771.7 (4) Å3 |
Mr = 389.58 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.862 (1) Å | µ = 2.09 mm−1 |
b = 12.941 (4) Å | T = 293 K |
c = 10.538 (4) Å | 0.35 × 0.3 × 0.2 mm |
β = 105.12 (3)° |
CAD-4 diffractometer | 2284 independent reflections |
Absorption correction: empirical (using intensity measurements) North, Phillips & Mathews, 1968 | 1352 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.680 | Rint = 0.028 |
2585 measured reflections | 3 standard reflections every 100 reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.54 e Å−3 |
2284 reflections | Δρmin = −0.64 e Å−3 |
90 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0 | 0.5 | 0.5 | 0.03760 (17) | |
Cl2 | 0.30697 (13) | 0.55558 (6) | 0.66244 (8) | 0.0532 (2) | |
Cl1 | −0.19362 (18) | 0.36842 (10) | 0.69258 (10) | 0.0771 (3) | |
N | 0.0948 (4) | 0.35446 (18) | 0.5451 (2) | 0.0401 (5) | |
C1 | −0.0024 (5) | 0.3008 (3) | 0.6239 (3) | 0.0501 (7) | |
C5 | 0.2460 (5) | 0.3056 (2) | 0.4889 (3) | 0.0444 (6) | |
H5 | 0.3186 | 0.3434 | 0.4354 | 0.053* | |
C4 | 0.2983 (6) | 0.2019 (2) | 0.5072 (3) | 0.0548 (8) | |
C2 | 0.0416 (7) | 0.1966 (3) | 0.6489 (3) | 0.0669 (10) | |
H2 | −0.0292 | 0.1606 | 0.7049 | 0.08* | |
C3 | 0.1919 (7) | 0.1485 (3) | 0.5888 (4) | 0.0668 (10) | |
H3 | 0.223 | 0.0784 | 0.6033 | 0.08* | |
C6 | 0.4637 (7) | 0.1515 (3) | 0.4385 (5) | 0.0821 (13) | |
H6A | 0.5806 | 0.1125 | 0.5009 | 0.123* | |
H6B | 0.5402 | 0.2036 | 0.3995 | 0.123* | |
H6C | 0.3761 | 0.1061 | 0.3712 | 0.123* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0379 (3) | 0.0379 (3) | 0.0384 (3) | 0.0041 (2) | 0.01251 (18) | −0.0019 (2) |
Cl2 | 0.0491 (4) | 0.0521 (4) | 0.0529 (4) | 0.0019 (3) | 0.0033 (3) | −0.0072 (3) |
Cl1 | 0.0654 (5) | 0.1123 (9) | 0.0649 (5) | −0.0084 (5) | 0.0371 (5) | −0.0050 (5) |
N | 0.0399 (11) | 0.0398 (12) | 0.0403 (11) | −0.0009 (10) | 0.0099 (10) | 0.0009 (10) |
C1 | 0.0479 (16) | 0.0586 (19) | 0.0414 (15) | −0.0052 (14) | 0.0075 (12) | 0.0062 (14) |
C5 | 0.0441 (14) | 0.0411 (15) | 0.0475 (15) | 0.0037 (12) | 0.0113 (12) | −0.0024 (12) |
C4 | 0.0504 (17) | 0.0439 (16) | 0.0604 (19) | 0.0062 (14) | −0.0026 (15) | −0.0062 (14) |
C2 | 0.074 (2) | 0.064 (2) | 0.055 (2) | −0.0200 (19) | 0.0025 (18) | 0.0207 (17) |
C3 | 0.072 (2) | 0.0463 (18) | 0.071 (2) | 0.0009 (17) | −0.002 (2) | 0.0107 (18) |
C6 | 0.066 (2) | 0.068 (3) | 0.104 (3) | 0.023 (2) | 0.008 (2) | −0.030 (2) |
Cu—N | 1.986 (2) | C5—H5 | 0.93 |
Cu—Ni | 1.986 (2) | C4—C3 | 1.373 (5) |
Cu—Cl2i | 2.2536 (11) | C4—C6 | 1.503 (5) |
Cu—Cl2 | 2.2536 (11) | C2—C3 | 1.363 (6) |
Cl1—C1 | 1.723 (4) | C2—H2 | 0.93 |
N—C1 | 1.321 (4) | C3—H3 | 0.93 |
N—C5 | 1.345 (4) | C6—H6A | 0.96 |
C1—C2 | 1.385 (5) | C6—H6B | 0.96 |
C5—C4 | 1.378 (4) | C6—H6C | 0.96 |
N—Cu—Ni | 180.0000 | C3—C4—C5 | 117.2 (3) |
N—Cu—Cl2i | 89.84 (7) | C3—C4—C6 | 122.6 (3) |
Ni—Cu—Cl2i | 90.16 (7) | C5—C4—C6 | 120.2 (3) |
N—Cu—Cl2 | 90.16 (7) | C3—C2—C1 | 117.9 (3) |
Ni—Cu—Cl2 | 89.84 (7) | C3—C2—H2 | 121.1 |
Cl2i—Cu—Cl2 | 180 | C1—C2—H2 | 121.1 |
C1—N—C5 | 118.1 (3) | C2—C3—C4 | 121.0 (3) |
C1—N—Cu | 120.6 (2) | C2—C3—H3 | 119.5 |
C5—N—Cu | 121.09 (19) | C4—C3—H3 | 119.5 |
N—C1—C2 | 122.8 (3) | C4—C6—H6A | 109.5 |
N—C1—Cl1 | 115.6 (2) | C4—C6—H6B | 109.5 |
C2—C1—Cl1 | 121.6 (3) | H6A—C6—H6B | 109.5 |
N—C5—C4 | 123.0 (3) | C4—C6—H6C | 109.5 |
N—C5—H5 | 118.5 | H6A—C6—H6C | 109.5 |
C4—C5—H5 | 118.5 | H6B—C6—H6C | 109.5 |
Cl2i—Cu—N—C1 | −84.8 (2) | Cu—N—C5—C4 | −173.3 (2) |
Cl2—Cu—N—C1 | 95.2 (2) | N—C5—C4—C3 | −1.2 (5) |
Cl2i—Cu—N—C5 | 90.3 (2) | N—C5—C4—C6 | 178.3 (3) |
Cl2—Cu—N—C5 | −89.7 (2) | N—C1—C2—C3 | 0.0 (5) |
C5—N—C1—C2 | −1.2 (4) | Cl1—C1—C2—C3 | 178.9 (3) |
Cu—N—C1—C2 | 174.0 (2) | C1—C2—C3—C4 | 0.7 (5) |
C5—N—C1—Cl1 | 179.9 (2) | C5—C4—C3—C2 | −0.1 (5) |
Cu—N—C1—Cl1 | −4.9 (3) | C6—C4—C3—C2 | −179.6 (4) |
C1—N—C5—C4 | 1.9 (4) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl2ii | 0.93 | 2.76 | 3.685 (4) | 171 |
C5—H5···Cl2iii | 0.93 | 2.96 | 3.850 (3) | 160 |
C6—H6C···Cl2iv | 0.96 | 2.99 | 3.885 (4) | 156 |
Symmetry codes: (ii) −x, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl2(C6H6ClN)2] |
Mr | 389.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.862 (1), 12.941 (4), 10.538 (4) |
β (°) | 105.12 (3) |
V (Å3) | 771.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.09 |
Crystal size (mm) | 0.35 × 0.3 × 0.2 |
Data collection | |
Diffractometer | CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) North, Phillips & Mathews, 1968 |
Tmin, Tmax | 0.528, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2585, 2284, 1352 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.707 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.116, 0.98 |
No. of reflections | 2284 |
No. of parameters | 90 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.64 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, DATARED, Enraf-Nonius, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
Cu—N | 1.986 (2) | Cu—Cl2 | 2.2536 (11) |
N—Cu—Ni | 180.0000 | Cl2i—Cu—Cl2 | 180 |
Cl2—Cu—N—C1 | 95.2 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl2ii | 0.93 | 2.76 | 3.685 (4) | 170.5 |
C5—H5···Cl2iii | 0.93 | 2.96 | 3.850 (3) | 160.3 |
C6—H6C···Cl2iv | 0.96 | 2.99 | 3.885 (4) | 156.4 |
Symmetry codes: (ii) −x, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+1/2, z−1/2. |
2-Chloro-5-methylpyridine is a very important intermediate for the preparation of biological activity compounds, especially insecticides (Guenth, 1991) (e.g. imidacloprid; Diehr, 1990). 2-Chloro-5-methylpyridine is usually manufactured from 3-methylpyridine-N-oxide, but ?the product also contains 3-methylpyridine and its isomer 2-chloro-3-methylpyridine?? (Kaufmann et al., 1991). Because the properties of isomers are similar, it is difficult to separate them by ordinary methods, such as distillation. We have found that the crystalline complex of 2-chloro-5-methylpyridine can be formed easily when crude 2-chloro-5-methylpyridine is mixed with CuCl2·2H2O in absolute ethanol and hence can be isolated with over 99% purity. In order to look for specific structural features, we have performed an X-ray structural analysis of the title compound, (I).
The molecular structure of (I) is shown in Fig.1. The Cu atom lies on a crystallographic inversion center so that the angles N—Cu—N and Cl—Cu—Cl are 180°. The two pyridine rings are coplanar in the complex molecule because of crystallographic symmetry, but they twist from the CuN2Cl2 coordination plane with a torsion angle Cl2—Cu—N—C1 of 95.2 (2)°. The bond distances Cu—N and Cu—Cl [1.986 (2) and 2.2536 (11) Å, respectively (Table 1)] agree with the corresponding values for other Cu(II) complexes (Silva et al., 2001; Zavalij et al., 2002). The bond lengths and angles in the complex molecule are largely common.
A further analysis of the short intermolecular contacts shows that there are three kinds of C—H···Cl interactions (Table. 2). In the first type, the H···Cl distance is 2.76 Å, which is obviously shorter than the sum of the van der Waals radii of these two atoms (2.95 Å). The angle C—H···Cl is 170.5°, which is close to 180°. These parameters indicate a hydrogen bonding interaction (Aullon et al., 1998). In the other types of interaction, the H···Cl distances are very close to 2.95 Å. If the C—H···Cl distances and angles are normalized (Jeffrey & Lewis, 1978; Taylor & Kennard, 1983), the H···Cl distances are 2.82 and 2.87 Å, and the angles are 159.3 and 155.4°, respectively. These values suggest that the second and third C—H···Cl interactions can also be considered as hydrogen-bonding interactions. Among these three kinds of interactions, the first one is the strongest, the second is less strong and the third is weak.
A detailed analysis of the crystal packing shows that the hydrogen bonds involving the first and the third C—H···Cl interactions [i.e. C2 to Cl2(-x, y − 1/2, −z + 3/2) and C6 to Cl2(x, −y + 1/2, z − 1/2), respectively] generate two-dimensional networks when viewed in the direction of the α axis (Fig.2). The molecular networks are stacked one upon another. Because the centroid distances between neighbouring pyridine rings in adjacent molecular networks are 5.862 Å, any intermolecular forces between these rings should be very weak (Panda et al., 2001). The C5—H···Cl2(-x + 1, −y + 1, −z + 1) interactions (Fig.3) enforce the connection between adjacent molecular networks. Therefore, the C—H···Cl interactions are likely to be the major intermolecular forces, which cause complex molecules to be packed compactly and be isolated from the reactant mixture.
All three kinds of C—H···Cl interactions acting on the same pyridine ring in the complex molecule force the pyridine ring to rotate around the N—Cu bond, so that the pyridine ring twists from the CuN2Cl2 coordination plane with a Cl2—Cu—N—C1 torsion angle of 95.2 (2)° rather than 90°.
The crystal packing diagram also shows that although each Cl atom in a Cu—Cl interaction can form all three kinds of C—H···Cl connection, ??the interaction does not fully fit the concept of a hydrogen bond.?? Moreover, the H···Cl distances in the second and third C—H···Cl interactions, before normalizing, are 2.96 and 2.99 Å, respectively, which are a little longer than 2.95 Å. It would be better to describe these three kinds of C—H···Cl interactions as hydrogen bridges (Desiraju, 2002). The complex molecules form a supramolecular structure in the crystals via these hydrogen bridges.