Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010302198X/av1150sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010302198X/av1150Isup2.hkl |
CCDC reference: 209476
2-Chloro-5-methylpyridine (0.8 g; 7.8 mmol) in absolute ethanol (5 ml) was mixed with Cu(NO3)2·3H2O (0.7 g; 3.3 mmol) in What? (5 ml) in a round-bottomed flask. The solution appeared cloudy in a short time. It was heated until it became clear, cooled to room temperature and filtered. A single-crystal of (I) was obtained in the filtrate in 3 d (m.p 463 K, decomposed). Analysis calculated for C12H12O6CuN4: C 32.55, H 2.738, N 12.66%; found: C 32.55, H 2.778, N 12.55%.
H atoms were added at calculated positions, refined using a riding model and given Uiso parameters equal to 1.2 (or 1.5 for methyl H atoms) times the Ueq parameters of their parent atoms. C—H distances were restrained to 0.98 Å for methyl H and 0.95 Å for H atoms bonded to atoms C2, C3 and C5.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku, 2002); 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 (Farrugia, 1999).
[Cu(NO3)2(C6H6ClN)2] | F(000) = 446 |
Mr = 442.7 | Dx = 1.717 Mg m−3 |
Monoclinic, P21/c | Melting point: 190 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6855 (2) Å | Cell parameters from 6378 reflections |
b = 13.2221 (3) Å | θ = 2.6–27.4° |
c = 9.9254 (3) Å | µ = 1.62 mm−1 |
β = 102.5430 (8)° | T = 293 K |
V = 856.43 (4) Å3 | Prism, dark violet |
Z = 2 | 0.40 × 0.25 × 0.23 mm |
Rigaku R-AXIS Rapid diffractometer | 1743 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.019 |
ω scans | θmax = 27.4°, θmin = 2.6° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
Tmin = 0.621, Tmax = 0.688 | k = −16→17 |
7866 measured reflections | l = −12→12 |
1945 independent reflections |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0342P)2 + 0.4423P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.028 | (Δ/σ)max = 0.013 |
wR(F2) = 0.072 | Δρmax = 0.40 e Å−3 |
S = 1.08 | Δρmin = −0.26 e Å−3 |
1945 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
117 parameters | Extinction coefficient: 0.0063 (12) |
0 restraints |
[Cu(NO3)2(C6H6ClN)2] | V = 856.43 (4) Å3 |
Mr = 442.7 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.6855 (2) Å | µ = 1.62 mm−1 |
b = 13.2221 (3) Å | T = 293 K |
c = 9.9254 (3) Å | 0.40 × 0.25 × 0.23 mm |
β = 102.5430 (8)° |
Rigaku R-AXIS Rapid diffractometer | 1945 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1743 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.688 | Rint = 0.019 |
7866 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.40 e Å−3 |
1945 reflections | Δρmin = −0.26 e Å−3 |
117 parameters |
Experimental. Melting point determination was performed on XRC1 melting-point apparatus (made by Science Instrument Company of Sichuan University). The crystal melted at 463k(decomposed). CHN analysis was obtained by using Eger 2000 elemental analyzer. |
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 | 0.5 | 0.0 | 0.03203 (12) | |
Cl | 0.18862 (9) | 0.68108 (5) | −0.15480 (6) | 0.05497 (17) | |
N1 | −0.0808 (2) | 0.64536 (12) | −0.00593 (15) | 0.0330 (3) | |
N2 | 0.2899 (3) | 0.53765 (14) | 0.22194 (19) | 0.0460 (4) | |
C1 | 0.0049 (3) | 0.71822 (15) | −0.06730 (19) | 0.0362 (4) | |
C2 | −0.0475 (3) | 0.81897 (16) | −0.0637 (2) | 0.0447 (5) | |
H2 | 0.0163 | 0.8679 | −0.107 | 0.054* | |
O1 | 0.1014 (2) | 0.51426 (12) | 0.20667 (17) | 0.0502 (4) | |
C4 | −0.2912 (3) | 0.77128 (14) | 0.06954 (19) | 0.0354 (4) | |
C5 | −0.2282 (3) | 0.67275 (14) | 0.06107 (19) | 0.0343 (4) | |
H5 | −0.2901 | 0.6226 | 0.1035 | 0.041* | |
O3 | 0.3605 (3) | 0.53783 (16) | 0.1163 (2) | 0.0721 (5) | |
O2 | 0.3874 (3) | 0.55805 (16) | 0.3365 (2) | 0.0804 (6) | |
C6 | −0.4564 (3) | 0.79613 (17) | 0.1459 (2) | 0.0475 (5) | |
H6A | −0.5212 | 0.7348 | 0.1659 | 0.071* | |
H6B | −0.5564 | 0.8393 | 0.0899 | 0.071* | |
H6C | −0.3968 | 0.8301 | 0.2306 | 0.071* | |
C3 | −0.1970 (3) | 0.84501 (15) | 0.0059 (2) | 0.0431 (5) | |
H3 | −0.2349 | 0.9124 | 0.0103 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.03108 (17) | 0.03316 (18) | 0.03294 (18) | 0.00107 (12) | 0.00932 (12) | −0.00547 (12) |
Cl | 0.0486 (3) | 0.0697 (4) | 0.0555 (3) | −0.0076 (3) | 0.0309 (2) | −0.0052 (3) |
N1 | 0.0330 (7) | 0.0345 (8) | 0.0333 (8) | −0.0018 (6) | 0.0111 (6) | −0.0021 (6) |
N2 | 0.0518 (10) | 0.0330 (8) | 0.0484 (10) | −0.0019 (8) | 0.0003 (8) | −0.0042 (7) |
C1 | 0.0333 (9) | 0.0449 (10) | 0.0323 (9) | −0.0049 (8) | 0.0112 (7) | −0.0010 (8) |
C2 | 0.0494 (11) | 0.0416 (11) | 0.0444 (11) | −0.0076 (9) | 0.0131 (9) | 0.0082 (9) |
O1 | 0.0488 (9) | 0.0484 (9) | 0.0536 (9) | 0.0022 (7) | 0.0115 (7) | −0.0049 (7) |
C4 | 0.0331 (9) | 0.0377 (10) | 0.0345 (9) | 0.0013 (7) | 0.0057 (7) | −0.0041 (7) |
C5 | 0.0334 (8) | 0.0350 (9) | 0.0368 (10) | −0.0037 (7) | 0.0128 (7) | −0.0018 (7) |
O3 | 0.0772 (13) | 0.0680 (12) | 0.0792 (13) | −0.0161 (10) | 0.0349 (11) | −0.0069 (10) |
O2 | 0.0865 (14) | 0.0665 (12) | 0.0676 (12) | −0.0090 (11) | −0.0282 (10) | −0.0114 (10) |
C6 | 0.0433 (11) | 0.0466 (12) | 0.0557 (12) | 0.0058 (9) | 0.0174 (9) | −0.0097 (10) |
C3 | 0.0487 (11) | 0.0324 (10) | 0.0469 (11) | 0.0027 (8) | 0.0072 (9) | 0.0015 (8) |
Cu—N1i | 1.9939 (16) | C1—C2 | 1.380 (3) |
Cu—N1 | 1.9939 (16) | C2—C3 | 1.376 (3) |
Cu—O1 | 2.0246 (16) | C2—H2 | 0.93 |
Cu—O3 | 2.4866 (19) | C4—C5 | 1.377 (3) |
Cu—O1i | 2.0246 (16) | C4—C3 | 1.385 (3) |
Cl—C1 | 1.7224 (19) | C4—C6 | 1.505 (3) |
N1—C1 | 1.334 (2) | C5—H5 | 0.93 |
N1—C5 | 1.352 (2) | C6—H6A | 0.96 |
N2—O2 | 1.211 (2) | C6—H6B | 0.96 |
N2—O3 | 1.240 (3) | C6—H6C | 0.96 |
N2—O1 | 1.274 (2) | C3—H3 | 0.93 |
N1i—Cu—N1 | 180 | C3—C2—H2 | 121 |
N1i—Cu—O1 | 91.77 (6) | C1—C2—H2 | 121 |
N1—Cu—O1 | 88.23 (6) | N2—O1—Cu | 104.37 (13) |
N1—Cu—O3 | 92.80 (7) | C5—C4—C3 | 117.53 (17) |
O1—Cu—O3 | 55.49 (7) | C5—C4—C6 | 120.33 (18) |
N1i—Cu—O1i | 88.23 (6) | C3—C4—C6 | 122.14 (18) |
N1—Cu—O1i | 91.77 (6) | N1—C5—C4 | 123.27 (17) |
O1—Cu—O1i | 180.00 (9) | N1—C5—H5 | 118.4 |
C1—N1—C5 | 117.54 (16) | C4—C5—H5 | 118.4 |
C1—N1—Cu | 124.69 (13) | C4—C6—H6A | 109.5 |
C5—N1—Cu | 117.73 (12) | C4—C6—H6B | 109.5 |
O2—N2—O3 | 124.5 (2) | H6A—C6—H6B | 109.5 |
O2—N2—O1 | 118.8 (2) | C4—C6—H6C | 109.5 |
O3—N2—O1 | 116.63 (18) | H6A—C6—H6C | 109.5 |
N1—C1—C2 | 123.27 (18) | H6B—C6—H6C | 109.5 |
N1—C1—Cl | 116.65 (15) | C2—C3—C4 | 120.30 (19) |
C2—C1—Cl | 120.08 (15) | C2—C3—H3 | 119.9 |
C3—C2—C1 | 118.08 (18) | C4—C3—H3 | 119.9 |
O1—Cu—N1—C1 | 113.70 (15) | O3—N2—O1—Cu | −5.1 (2) |
O1i—Cu—N1—C1 | −66.30 (15) | N1i—Cu—O1—N2 | 88.12 (13) |
O1—Cu—N1—C5 | −63.90 (14) | N1—Cu—O1—N2 | −91.88 (13) |
O1i—Cu—N1—C5 | 116.10 (14) | C1—N1—C5—C4 | −0.6 (3) |
C5—N1—C1—C2 | 1.0 (3) | Cu—N1—C5—C4 | 177.18 (14) |
Cu—N1—C1—C2 | −176.65 (15) | C3—C4—C5—N1 | −0.2 (3) |
C5—N1—C1—Cl | −178.76 (13) | C6—C4—C5—N1 | 179.98 (18) |
Cu—N1—C1—Cl | 3.6 (2) | C1—C2—C3—C4 | −0.3 (3) |
N1—C1—C2—C3 | −0.5 (3) | C5—C4—C3—C2 | 0.6 (3) |
Cl—C1—C2—C3 | 179.16 (16) | C6—C4—C3—C2 | −179.6 (2) |
O2—N2—O1—Cu | 174.87 (17) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2ii | 0.93 | 2.83 | 3.651 (3) | 147 |
C2—H2···O1ii | 0.93 | 2.57 | 3.469 (3) | 162 |
C3—H3···O2iii | 0.93 | 2.78 | 3.587 (3) | 146 |
C5—H5···O3iv | 0.93 | 2.62 | 3.420 (3) | 145 |
C6—H6B···O2v | 0.96 | 2.81 | 3.584 (3) | 138 |
C5—H5···O1 | 0.93 | 2.96 | 3.155 (2) | 93 |
C3—H3···O2v | 0.93 | 2.76 | 3.188 (3) | 109 |
Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) −x, y+1/2, −z+1/2; (iv) x−1, y, z; (v) x−1, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NO3)2(C6H6ClN)2] |
Mr | 442.7 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.6855 (2), 13.2221 (3), 9.9254 (3) |
β (°) | 102.5430 (8) |
V (Å3) | 856.43 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.62 |
Crystal size (mm) | 0.40 × 0.25 × 0.23 |
Data collection | |
Diffractometer | Rigaku R-AXIS Rapid diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.621, 0.688 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7866, 1945, 1743 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.072, 1.08 |
No. of reflections | 1945 |
No. of parameters | 117 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.26 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Molecular Structure Corporation & Rigaku, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu—N1 | 1.9939 (16) | N2—O2 | 1.211 (2) |
Cu—O1 | 2.0246 (16) | N2—O3 | 1.240 (3) |
Cu—O3 | 2.4866 (19) | N2—O1 | 1.274 (2) |
N1—Cu—O1 | 88.23 (6) | O1—Cu—O3 | 55.49 (7) |
N1—Cu—O3 | 92.80 (7) | ||
O1—Cu—N1—C1 | 113.70 (15) | N1—Cu—O1—N2 | −91.88 (13) |
O3—N2—O1—Cu | −5.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.93 | 2.83 | 3.651 (3) | 147 |
C2—H2···O1i | 0.93 | 2.57 | 3.469 (3) | 162 |
C3—H3···O2ii | 0.93 | 2.78 | 3.587 (3) | 146 |
C5—H5···O3iii | 0.93 | 2.62 | 3.420 (3) | 145 |
C6—H6B···O2iv | 0.96 | 2.81 | 3.584 (3) | 138 |
C5—H5···O1 | 0.93 | 2.96 | 3.155 (2) | 93 |
C3—H3···O2iv | 0.93 | 2.76 | 3.188 (3) | 109 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) x−1, −y+3/2, z−1/2. |
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2-Chloro-5-methylpyridine can form a complex with CuCl2·2H2O [dichlorobis(2-chloro-5-methylpyridine-κN)copper(II); Xuan et al.,2003]. In recent work, we have found that it can also form a complex with Cu(NO3)2, but the melting point of this complex is much higher than that of the former. In order to study the specific structural features of this latter copper complex, (I), we have performed an X-ray structral analysis, and the results are presented here. \sch
The molecular structure of (I) is shown in Fig.1. The Cu atom lies on a crystallographic inversion centre, so the N1—Cu—N1i, O2—Cu—O2i and O3—Cu—O3i angles are 180° [symmetry code:(i)-x, 1 − y, −z]. The two pyridine rings are coplanar in the molecule of (I) because of crystallographic symmetry, but they are twisted from the Cu/N1/O2 plane, with an O1—Cu—N1—C1 torsion angle of 113.70 (15)°. The title complex forms a distorted octahedral structure, with Cu—N1, Cu—O1 and Cu—O3 distances of 1.9939 (16), 2.0246 (16) and 2.4866 (19) Å, respectively, N1—Cu—O1 and N1—Cu—O3 angles of 88.23 (6) and 92.80 (7)°, respectively, and O3—N2—O1—Cu and N1—Cu—O1—N2 torsion angles of −5.1 (2) and −91.88 (33)°, respectively. The Cu—N1 and Cu—O1 bond distances (Table 1) agree with the corresponding values for other CuII complexes (Zavalij et al., 2002), but Cu—O3 is 0.46 Å longer than Cu—O1. The N2—O1 bond is longer than N2—O3, so the nitrate is unsymmetrical. The nitrate groups act as bidentate ligands, just as they do in other metal complexes (Eleonora et al., 2001; Yoshida et al., 2001; Sommerer et al., 1994), but in (I) they are unsymmetrical bidentate ligands. The nitrate bite angle is 55.49 (7)°.
Analysis of the short intermolecular contacts (Nardelli, 1995; Desiraju, 1996) in (I) shows that there are five types of C—H···O hydrogen-bonding interactions (Table 2), and the nitrate group acts as a C—H···O acceptor. A detailed analysis of the crystal packing shows that two types of hydrogen bonds [C2···O2(x, 3/2 − y, z − 1/2) and C2···O1(x, 3/2 − y, z − 1/2)] generate two-dimensional networks in the direction of the a axis (Fig. 2), and these molecular networks are stacked on top of each other. Three other types of hydrogen bonds [C3···O2(-x, y + 1/2, 1/2 − z), C5···O3(x − 1, y, z) and C6···O2(x − 1, 3/2 − y, z − 1/2)] (Fig. 3) enforce the connection between adjacent molecular networks. Because the centroid-centroid distance between pyridine rings in adjacent molecular networks is 6.6855 Å, any intermolecular forces between these rings should be very weak (Panda et al., 2001). Thus, the C—H···O interactions are likely to be the major intermolecular forces, causing the complex molecules to pack in a compact fashion.
In the crystal of (I), every single complex molecule can form 10 C—H···O hydrogen bonds with neighbouring molecules, but dichlorobis(2-chloro-5-methylpyridine-κN)copper(II) can only form six C—H···Cl hydrogen bonds. This maybe why the melting point of the title complex is much higher than that of the latter.
Table 2. Hydrogen-bonding and short-contact geometry