Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048878/bh2127sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048878/bh2127Isup2.hkl |
CCDC reference: 667198
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.004 Å
- R factor = 0.030
- wR factor = 0.075
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - Cl2 .. 6.40 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - Cl3 .. 9.47 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N1 .. 6.10 su PLAT480_ALERT_4_C Long H...A H-Bond Reported H6C .. CL3 .. 2.87 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11B .. CL3 .. 2.84 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11C .. CL3 .. 2.85 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 1.97
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For details of the antitumour activity of pyrole [pyrazole?] containing complexes, see: Ciesielska et al. (2006). For the dimethylpyrazole derivative used as a ligand, see: Rüfenacht (1973). The title complex is isostructural with the Zn analogue (Cheng et al., 2006). For comparison with other complexes containing a [CuCl2N2] core, see: Allen (2002).
The title compound was obtained by reaction of N-hydroxymethyl-3,5-dimethylpyrazole (Rüfenacht, 1973) with CuCl2 (2:1 stoichiometric ratio) in ethanol at room temperature. Crystals were obtained by slow evaporation at room temperature. The product (green needles) was obtained in 52% yield.
The crystal used for data collection revealed to be twinned, and a twin-integration based on two orientations was done. A first refinement was carried out using HKLF 5 option in SHELXL97 (Sheldrick, 1997), resulting in a twin ratio 0.241 (2)/0.759 (2). Option LIST 6 was then applied in order to get a structure factors file containing merged data for a non-twinned model and the structure was refined to convergence. All H atoms were positioned geometrically and refined with a riding model; for methyl H atoms Uiso were constrained to be 1.5 times Ueq of the carrier atom and C—H = 0.98 Å; for others H atoms Uiso were constrained to be 1.2 times Ueq of the carrier atom and C—H = 0.97, 0.93, 0.86 or 0.82 Å for methylene, aromatic, amine and hydroxyl groups, respectively.
There have been numerous attempts to improve the effectiveness of antitumor agent cis-platin, through the modification of its structure. A number of pyrazole and its derivatives complexes were studied with respect to their cytotoxicity, apoptosis induction ability, and DNA damaging (Ciesielska et al., 2006). While searching for new complexes with ligands similar to previously studied ones, we synthesized a new CuII complex including a dimethylpyrazole derivative as ligand, (I).
Complex (I) is isostructural with the ZnII analogue, dichloro[(3,5-dimethyl-1H-pyrazol-1-yl)methane]zinc(II), reported by Cheng et al. (2006). Ionic radii for CuII and ZnII, 0.069 and 0.074 nm respectively, compare well, allowing isomorphous compounds to be formed.
In (I), the CuII ion is four coordinated by two N atoms and two Cl atoms (Fig. 1). This [CuCl2N2] coordination environment forms a distorted tetrahedral geometry with local non-crystallographic Cs symmetry. Angles around the CuII ion range from 115.28 (6) to 89.30 (8)°. These angles are comparable with those observed in other [CuCl2N2] coordination spheres (CSD, Version 5.28; Allen, 2002). The range of angles are 97.43–128.52° and 78.95–142.27° for Cl—Cu—Cl and N—Cu—N fragments, respectively (333 observations). The Cu—Cl and Cu—N bond lengths in (I) are also comparables with those observed in [CuCl2N2] moieties, which have averages of 2.22 and 2.05 Å, respectively, in the CSD.
In the crystal structure of (I) there are extensive C—H···Cl interactions (Table 2, Fig. 2). On the other hand, heterocyclic rings N1/N2/C2/C3/C4 in the asymmetric unit and N3/N4/C7/C8/C9 at position (1/2 - x, 1 - y, 1 - z) interact through π–π stacking interactions. The interplanar spacing is 3.531 (2) Å, while centroids of the rings are separated by 3.508 Å. The ring N3···C9 also interacts with a symmetry related N3···C9 ring at (1/2 - x, 1/2 - y, 2 - z). The interplanar spacing is 3.651 (2) Å, while the centroid to centroid separation is 3.650 Å.
For details of the antitumour activity of pyrole [pyrazole?] containing complexes, see: Ciesielska et al. (2006). For the dimethylpyrazole derivative used as a ligand, see: Rüfenacht (1973). The title complex is isostructural with the Zn analogue (Cheng et al., 2006). For comparison with other complexes containing a [CuCl2N2] core, see: Allen (2002).
Data collection: IPDS2 (Stoe & Cie, 2000); cell refinement: IPDS2 (Stoe & Cie, 2000); data reduction: IPDS2 (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PARST97 (Nardelli, 1996).
Fig. 1. Molecular structure and atomic numbering scheme showing 50% probability displacement ellipsoids in (I). | |
Fig. 2. Packing in the unit cell. |
[CuCl2(C11H16N4)] | F(000) = 1384 |
Mr = 338.72 | Dx = 1.585 Mg m−3 |
Monoclinic, C2/c | Melting point: 471 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.8120 (7) Å | Cell parameters from 2790 reflections |
b = 16.7384 (9) Å | θ = 1.0–26.2° |
c = 12.4943 (6) Å | µ = 1.90 mm−1 |
β = 113.58 (1)° | T = 193 K |
V = 2839.0 (3) Å3 | Needle, green |
Z = 8 | 0.2 × 0.1 × 0.1 mm |
Stoe IPDSII diffractometer | 2619 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.431 |
Graphite monochromator | θmax = 26.3°, θmin = 1.9° |
Detector resolution: 150 pixels mm-1 | h = −18→16 |
ω scans | k = 0→20 |
39701 measured reflections | l = 0→15 |
2790 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0335P)2 + 8.2559P] where P = (Fo2 + 2Fc2)/3 |
2790 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[CuCl2(C11H16N4)] | V = 2839.0 (3) Å3 |
Mr = 338.72 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.8120 (7) Å | µ = 1.90 mm−1 |
b = 16.7384 (9) Å | T = 193 K |
c = 12.4943 (6) Å | 0.2 × 0.1 × 0.1 mm |
β = 113.58 (1)° |
Stoe IPDSII diffractometer | 2619 reflections with I > 2σ(I) |
39701 measured reflections | Rint = 0.431 |
2790 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.49 e Å−3 |
2790 reflections | Δρmin = −0.37 e Å−3 |
167 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.22280 (2) | 0.382801 (16) | 0.73912 (2) | 0.01924 (10) | |
Cl2 | 0.38607 (4) | 0.38971 (4) | 0.81853 (6) | 0.03166 (15) | |
Cl3 | 0.15000 (4) | 0.50151 (3) | 0.70045 (5) | 0.02650 (14) | |
N4 | 0.18202 (15) | 0.22504 (12) | 0.81646 (18) | 0.0246 (4) | |
N2 | 0.18482 (15) | 0.22408 (12) | 0.62680 (18) | 0.0234 (4) | |
N1 | 0.17654 (15) | 0.30433 (12) | 0.60113 (18) | 0.0239 (4) | |
N3 | 0.17098 (15) | 0.30531 (12) | 0.83008 (18) | 0.0228 (4) | |
C1 | 0.23608 (18) | 0.20058 (15) | 0.7477 (2) | 0.0243 (5) | |
H1A | 0.3023 | 0.2253 | 0.7801 | 0.029* | |
H1B | 0.2446 | 0.1418 | 0.7524 | 0.029* | |
C2 | 0.12575 (18) | 0.30910 (15) | 0.4853 (2) | 0.0248 (5) | |
C9 | 0.13452 (18) | 0.18129 (16) | 0.8687 (2) | 0.0272 (5) | |
C4 | 0.14092 (17) | 0.17955 (15) | 0.5294 (2) | 0.0257 (5) | |
C10 | 0.1347 (2) | 0.09174 (17) | 0.8698 (3) | 0.0378 (6) | |
H10A | 0.1020 | 0.0718 | 0.7897 | 0.057* | |
H10B | 0.0995 | 0.0726 | 0.9166 | 0.057* | |
H10C | 0.2028 | 0.0723 | 0.9040 | 0.057* | |
C7 | 0.11546 (18) | 0.31124 (15) | 0.8915 (2) | 0.0243 (5) | |
C3 | 0.10333 (18) | 0.23234 (16) | 0.4379 (2) | 0.0265 (5) | |
H3 | 0.0687 | 0.2192 | 0.3578 | 0.032* | |
C8 | 0.09196 (19) | 0.23490 (16) | 0.9179 (2) | 0.0285 (5) | |
H8 | 0.0539 | 0.2225 | 0.9615 | 0.034* | |
C5 | 0.1358 (2) | 0.09069 (16) | 0.5300 (3) | 0.0354 (6) | |
H5A | 0.2010 | 0.0690 | 0.5777 | 0.053* | |
H5B | 0.1142 | 0.0706 | 0.4499 | 0.053* | |
H5C | 0.0887 | 0.0740 | 0.5628 | 0.053* | |
C11 | 0.0867 (2) | 0.39044 (16) | 0.9220 (2) | 0.0321 (6) | |
H11A | 0.1174 | 0.4329 | 0.8941 | 0.048* | |
H11B | 0.1089 | 0.3945 | 1.0070 | 0.048* | |
H11C | 0.0149 | 0.3961 | 0.8851 | 0.048* | |
C6 | 0.1003 (2) | 0.38793 (16) | 0.4253 (2) | 0.0323 (6) | |
H6A | 0.1371 | 0.4302 | 0.4795 | 0.048* | |
H6B | 0.0295 | 0.3976 | 0.3996 | 0.048* | |
H6C | 0.1177 | 0.3878 | 0.3574 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01992 (16) | 0.01714 (15) | 0.01992 (15) | 0.00007 (10) | 0.00719 (11) | −0.00023 (10) |
Cl2 | 0.0218 (3) | 0.0354 (3) | 0.0340 (3) | 0.0002 (2) | 0.0072 (2) | −0.0008 (3) |
Cl3 | 0.0277 (3) | 0.0202 (3) | 0.0299 (3) | 0.0015 (2) | 0.0096 (2) | 0.0004 (2) |
N4 | 0.0268 (10) | 0.0203 (10) | 0.0275 (11) | 0.0018 (8) | 0.0118 (9) | 0.0021 (8) |
N2 | 0.0260 (10) | 0.0191 (10) | 0.0253 (10) | 0.0023 (8) | 0.0105 (8) | 0.0002 (8) |
N1 | 0.0276 (10) | 0.0199 (10) | 0.0243 (10) | 0.0024 (8) | 0.0106 (8) | 0.0022 (8) |
N3 | 0.0249 (10) | 0.0185 (10) | 0.0237 (10) | 0.0014 (8) | 0.0083 (8) | −0.0004 (8) |
C1 | 0.0255 (12) | 0.0225 (12) | 0.0241 (12) | 0.0038 (9) | 0.0092 (10) | 0.0019 (9) |
C2 | 0.0231 (12) | 0.0283 (13) | 0.0230 (12) | 0.0007 (10) | 0.0093 (10) | 0.0001 (10) |
C9 | 0.0245 (12) | 0.0260 (13) | 0.0289 (12) | −0.0002 (10) | 0.0085 (10) | 0.0056 (10) |
C4 | 0.0212 (11) | 0.0249 (13) | 0.0300 (13) | 0.0001 (9) | 0.0091 (10) | −0.0058 (10) |
C10 | 0.0448 (17) | 0.0252 (14) | 0.0472 (17) | 0.0000 (12) | 0.0224 (14) | 0.0067 (12) |
C7 | 0.0245 (12) | 0.0279 (13) | 0.0195 (11) | 0.0018 (10) | 0.0076 (9) | −0.0011 (9) |
C3 | 0.0249 (12) | 0.0286 (13) | 0.0241 (12) | −0.0027 (10) | 0.0077 (10) | −0.0039 (10) |
C8 | 0.0291 (13) | 0.0322 (13) | 0.0271 (13) | 0.0005 (11) | 0.0142 (11) | 0.0024 (11) |
C5 | 0.0365 (15) | 0.0232 (13) | 0.0400 (15) | 0.0031 (11) | 0.0082 (12) | −0.0056 (11) |
C11 | 0.0354 (14) | 0.0339 (14) | 0.0314 (14) | 0.0034 (11) | 0.0181 (12) | −0.0033 (11) |
C6 | 0.0407 (15) | 0.0287 (14) | 0.0278 (13) | 0.0020 (11) | 0.0139 (12) | 0.0034 (11) |
Cu1—N1 | 2.055 (2) | C4—C3 | 1.374 (4) |
Cu1—N3 | 2.064 (2) | C4—C5 | 1.490 (4) |
Cu1—Cl2 | 2.2195 (9) | C10—H10A | 0.9800 |
Cu1—Cl3 | 2.2197 (7) | C10—H10B | 0.9800 |
N4—C9 | 1.351 (3) | C10—H10C | 0.9800 |
N4—N3 | 1.372 (3) | C7—C8 | 1.398 (4) |
N4—C1 | 1.448 (3) | C7—C11 | 1.488 (4) |
N2—C4 | 1.352 (3) | C3—H3 | 0.9500 |
N2—N1 | 1.375 (3) | C8—H8 | 0.9500 |
N2—C1 | 1.448 (3) | C5—H5A | 0.9800 |
N1—C2 | 1.340 (3) | C5—H5B | 0.9800 |
N3—C7 | 1.334 (3) | C5—H5C | 0.9800 |
C1—H1A | 0.9900 | C11—H11A | 0.9800 |
C1—H1B | 0.9900 | C11—H11B | 0.9800 |
C2—C3 | 1.398 (4) | C11—H11C | 0.9800 |
C2—C6 | 1.490 (4) | C6—H6A | 0.9800 |
C9—C8 | 1.375 (4) | C6—H6B | 0.9800 |
C9—C10 | 1.499 (4) | C6—H6C | 0.9800 |
N1—Cu1—N3 | 89.30 (8) | C9—C10—H10A | 109.5 |
N1—Cu1—Cl2 | 110.26 (7) | C9—C10—H10B | 109.5 |
N3—Cu1—Cl2 | 111.42 (6) | H10A—C10—H10B | 109.5 |
N1—Cu1—Cl3 | 114.82 (6) | C9—C10—H10C | 109.5 |
N3—Cu1—Cl3 | 115.28 (6) | H10A—C10—H10C | 109.5 |
Cl2—Cu1—Cl3 | 113.46 (3) | H10B—C10—H10C | 109.5 |
C9—N4—N3 | 111.1 (2) | N3—C7—C8 | 109.7 (2) |
C9—N4—C1 | 130.7 (2) | N3—C7—C11 | 121.3 (2) |
N3—N4—C1 | 118.2 (2) | C8—C7—C11 | 129.0 (2) |
C4—N2—N1 | 111.3 (2) | C4—C3—C2 | 106.9 (2) |
C4—N2—C1 | 130.7 (2) | C4—C3—H3 | 126.6 |
N1—N2—C1 | 118.00 (19) | C2—C3—H3 | 126.6 |
C2—N1—N2 | 105.6 (2) | C9—C8—C7 | 106.8 (2) |
C2—N1—Cu1 | 136.29 (17) | C9—C8—H8 | 126.6 |
N2—N1—Cu1 | 117.39 (15) | C7—C8—H8 | 126.6 |
C7—N3—N4 | 106.0 (2) | C4—C5—H5A | 109.5 |
C7—N3—Cu1 | 136.09 (17) | C4—C5—H5B | 109.5 |
N4—N3—Cu1 | 117.25 (15) | H5A—C5—H5B | 109.5 |
N2—C1—N4 | 111.01 (19) | C4—C5—H5C | 109.5 |
N2—C1—H1A | 109.4 | H5A—C5—H5C | 109.5 |
N4—C1—H1A | 109.4 | H5B—C5—H5C | 109.5 |
N2—C1—H1B | 109.4 | C7—C11—H11A | 109.5 |
N4—C1—H1B | 109.4 | C7—C11—H11B | 109.5 |
H1A—C1—H1B | 108.0 | H11A—C11—H11B | 109.5 |
N1—C2—C3 | 109.8 (2) | C7—C11—H11C | 109.5 |
N1—C2—C6 | 121.1 (2) | H11A—C11—H11C | 109.5 |
C3—C2—C6 | 129.2 (2) | H11B—C11—H11C | 109.5 |
N4—C9—C8 | 106.4 (2) | C2—C6—H6A | 109.5 |
N4—C9—C10 | 123.2 (2) | C2—C6—H6B | 109.5 |
C8—C9—C10 | 130.4 (2) | H6A—C6—H6B | 109.5 |
N2—C4—C3 | 106.5 (2) | C2—C6—H6C | 109.5 |
N2—C4—C5 | 123.6 (2) | H6A—C6—H6C | 109.5 |
C3—C4—C5 | 129.9 (2) | H6B—C6—H6C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl3i | 0.99 | 2.75 | 3.674 (2) | 155 |
C6—H6C···Cl3ii | 0.98 | 2.87 | 3.676 (3) | 140 |
C11—H11B···Cl3iii | 0.98 | 2.84 | 3.692 (3) | 146 |
C11—H11C···Cl3iv | 0.98 | 2.85 | 3.714 (2) | 147 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, −y+1, z−1/2; (iii) x, −y+1, z+1/2; (iv) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl2(C11H16N4)] |
Mr | 338.72 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 193 |
a, b, c (Å) | 14.8120 (7), 16.7384 (9), 12.4943 (6) |
β (°) | 113.58 (1) |
V (Å3) | 2839.0 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.90 |
Crystal size (mm) | 0.2 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Stoe IPDSII |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39701, 2790, 2619 |
Rint | 0.431 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.075, 1.11 |
No. of reflections | 2790 |
No. of parameters | 167 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Computer programs: IPDS2 (Stoe & Cie, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PARST97 (Nardelli, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl3i | 0.99 | 2.75 | 3.674 (2) | 155 |
C6—H6C···Cl3ii | 0.98 | 2.87 | 3.676 (3) | 140 |
C11—H11B···Cl3iii | 0.98 | 2.84 | 3.692 (3) | 146 |
C11—H11C···Cl3iv | 0.98 | 2.85 | 3.714 (2) | 147 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, −y+1, z−1/2; (iii) x, −y+1, z+1/2; (iv) −x, y, −z+3/2. |
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There have been numerous attempts to improve the effectiveness of antitumor agent cis-platin, through the modification of its structure. A number of pyrazole and its derivatives complexes were studied with respect to their cytotoxicity, apoptosis induction ability, and DNA damaging (Ciesielska et al., 2006). While searching for new complexes with ligands similar to previously studied ones, we synthesized a new CuII complex including a dimethylpyrazole derivative as ligand, (I).
Complex (I) is isostructural with the ZnII analogue, dichloro[(3,5-dimethyl-1H-pyrazol-1-yl)methane]zinc(II), reported by Cheng et al. (2006). Ionic radii for CuII and ZnII, 0.069 and 0.074 nm respectively, compare well, allowing isomorphous compounds to be formed.
In (I), the CuII ion is four coordinated by two N atoms and two Cl atoms (Fig. 1). This [CuCl2N2] coordination environment forms a distorted tetrahedral geometry with local non-crystallographic Cs symmetry. Angles around the CuII ion range from 115.28 (6) to 89.30 (8)°. These angles are comparable with those observed in other [CuCl2N2] coordination spheres (CSD, Version 5.28; Allen, 2002). The range of angles are 97.43–128.52° and 78.95–142.27° for Cl—Cu—Cl and N—Cu—N fragments, respectively (333 observations). The Cu—Cl and Cu—N bond lengths in (I) are also comparables with those observed in [CuCl2N2] moieties, which have averages of 2.22 and 2.05 Å, respectively, in the CSD.
In the crystal structure of (I) there are extensive C—H···Cl interactions (Table 2, Fig. 2). On the other hand, heterocyclic rings N1/N2/C2/C3/C4 in the asymmetric unit and N3/N4/C7/C8/C9 at position (1/2 - x, 1 - y, 1 - z) interact through π–π stacking interactions. The interplanar spacing is 3.531 (2) Å, while centroids of the rings are separated by 3.508 Å. The ring N3···C9 also interacts with a symmetry related N3···C9 ring at (1/2 - x, 1/2 - y, 2 - z). The interplanar spacing is 3.651 (2) Å, while the centroid to centroid separation is 3.650 Å.