Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057686/cf2155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057686/cf2155Isup2.hkl |
CCDC reference: 672690
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.006 Å
- R factor = 0.058
- wR factor = 0.127
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.22 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Bencini et al. (1987); Garcia et al. (1997); Kahn & Martinez (1998); Klingele & Brooker (2003); Klingele et al. (2005); Koningsbruggen (2004); Koningsbruggen et al. (1995); Lavrenova & Larionov (1998); Matouzenko et al. (2004); Moliner et al. (1998, 2001).
The title compound was prepared by reaction of 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole with copper(II) perchlorate in acetonitrile and water. To a warm solution of 1.06 grams of 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole (4.0 mmol) in 20 ml acetonitrile-water (V/V = 1:1), 0.52 grams of copper(II) perchlorate (2.0 mmol) was added. The filtrate was left to stand at room temperature for several days, and single crystals suitable for X-ray diffraction were collected.
All H atoms were located in a difference Fourier map and allowed to ride on their parent atoms at distances of 0.93Å (aromatic), 0.96Å (methyl) and 0.97Å (methylene), and with Uiso(H) values of 1.2 or 1.5 times Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
Fig. 1. The molecular structure of the title compound with the atomic labelling. Displacement ellipsoids are shown at the 30% probability level. |
[Cu(C16H16N4)2](ClO4)2 | Z = 1 |
Mr = 791.10 | F(000) = 407 |
Triclinic, P1 | Dx = 1.534 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0113 (14) Å | Cell parameters from 1954 reflections |
b = 8.3126 (14) Å | θ = 2.6–25.9° |
c = 14.215 (3) Å | µ = 0.86 mm−1 |
α = 99.374 (3)° | T = 291 K |
β = 102.689 (3)° | Block, blue |
γ = 107.041 (2)° | 0.26 × 0.20 × 0.18 mm |
V = 856.4 (3) Å3 |
Bruker SMART APEX CCD diffractometer | 3294 independent reflections |
Radiation source: sealed tube | 2297 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.808, Tmax = 0.861 | k = −10→4 |
4686 measured reflections | l = −17→17 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0658P)2] where P = (Fo2 + 2Fc2)/3 |
3294 reflections | (Δ/σ)max < 0.001 |
234 parameters | Δρmax = 0.82 e Å−3 |
1 restraint | Δρmin = −0.47 e Å−3 |
[Cu(C16H16N4)2](ClO4)2 | γ = 107.041 (2)° |
Mr = 791.10 | V = 856.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.0113 (14) Å | Mo Kα radiation |
b = 8.3126 (14) Å | µ = 0.86 mm−1 |
c = 14.215 (3) Å | T = 291 K |
α = 99.374 (3)° | 0.26 × 0.20 × 0.18 mm |
β = 102.689 (3)° |
Bruker SMART APEX CCD diffractometer | 3294 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2297 reflections with I > 2σ(I) |
Tmin = 0.808, Tmax = 0.861 | Rint = 0.031 |
4686 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 1 restraint |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.82 e Å−3 |
3294 reflections | Δρmin = −0.47 e Å−3 |
234 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. |
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 | ||
C1 | 0.2672 (5) | 0.8169 (5) | 0.4734 (3) | 0.0436 (8) | |
H1 | 0.2871 | 0.8753 | 0.4242 | 0.052* | |
C2 | 0.3614 (5) | 0.7036 (5) | 0.4944 (3) | 0.0464 (9) | |
H2 | 0.4479 | 0.6920 | 0.4620 | 0.056* | |
C3 | 0.3255 (6) | 0.6094 (5) | 0.5632 (3) | 0.0517 (10) | |
H3 | 0.3800 | 0.5269 | 0.5741 | 0.062* | |
C4 | 0.2066 (5) | 0.6394 (5) | 0.6158 (3) | 0.0439 (8) | |
H4 | 0.1849 | 0.5829 | 0.6655 | 0.053* | |
C5 | 0.1218 (4) | 0.7550 (4) | 0.5924 (2) | 0.0346 (7) | |
C6 | −0.0067 (5) | 0.8021 (4) | 0.6396 (2) | 0.0331 (7) | |
C7 | −0.1790 (6) | 0.8482 (5) | 0.7319 (3) | 0.0514 (9) | |
C8 | −0.2685 (6) | 0.8364 (6) | 0.8112 (3) | 0.0594 (11) | |
H8A | −0.1771 | 0.8451 | 0.8711 | 0.071* | |
H8B | −0.3578 | 0.7206 | 0.7938 | 0.071* | |
C9 | −0.3609 (7) | 0.9592 (7) | 0.8374 (4) | 0.0722 (14) | |
H9A | −0.3116 | 1.0153 | 0.9070 | 0.108* | |
H9B | −0.4889 | 0.8975 | 0.8232 | 0.108* | |
H9C | −0.3425 | 1.0448 | 0.7993 | 0.108* | |
C10 | 0.0172 (5) | 0.6772 (5) | 0.7884 (2) | 0.0405 (7) | |
C11 | 0.1746 (6) | 0.7618 (6) | 0.8615 (3) | 0.0551 (10) | |
H11 | 0.2371 | 0.8783 | 0.8674 | 0.066* | |
C12 | 0.2433 (6) | 0.6748 (6) | 0.9279 (3) | 0.0574 (11) | |
H12 | 0.3485 | 0.7346 | 0.9800 | 0.069* | |
C13 | 0.1561 (6) | 0.5013 (5) | 0.9166 (3) | 0.0473 (9) | |
C14 | 0.0003 (6) | 0.4204 (6) | 0.8422 (3) | 0.0560 (10) | |
H14 | −0.0582 | 0.3025 | 0.8342 | 0.067* | |
C15 | −0.0762 (6) | 0.5021 (5) | 0.7780 (3) | 0.0563 (11) | |
H15 | −0.1862 | 0.4431 | 0.7293 | 0.068* | |
C16 | 0.2347 (6) | 0.4050 (6) | 0.9865 (4) | 0.0607 (11) | |
H16A | 0.3107 | 0.3535 | 0.9581 | 0.091* | |
H16B | 0.1373 | 0.3158 | 0.9965 | 0.091* | |
H16C | 0.3057 | 0.4848 | 1.0492 | 0.091* | |
Cl1 | −0.35945 (13) | 0.75087 (13) | 0.28048 (7) | 0.0529 (3) | |
Cu1 | 0.0000 | 1.0000 | 0.5000 | 0.03407 (19) | |
N1 | 0.1517 (4) | 0.8428 (4) | 0.5214 (2) | 0.0366 (6) | |
N2 | −0.0939 (4) | 0.8995 (4) | 0.6031 (2) | 0.0387 (6) | |
N3 | −0.2055 (5) | 0.9288 (5) | 0.6598 (2) | 0.0503 (8) | |
N4 | −0.0578 (4) | 0.7672 (4) | 0.7204 (2) | 0.0428 (7) | |
O11 | −0.4876 (4) | 0.8173 (4) | 0.3132 (2) | 0.0591 (8) | |
O12 | −0.2782 (4) | 0.8561 (4) | 0.2241 (2) | 0.0564 (7) | |
O13 | −0.2264 (4) | 0.7560 (4) | 0.3667 (2) | 0.0594 (8) | |
O14 | −0.4462 (4) | 0.5766 (4) | 0.2267 (2) | 0.0740 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (2) | 0.050 (2) | 0.0445 (19) | 0.0306 (18) | 0.0273 (18) | 0.0285 (17) |
C2 | 0.055 (2) | 0.057 (2) | 0.050 (2) | 0.0327 (19) | 0.0264 (17) | 0.0321 (18) |
C3 | 0.066 (3) | 0.060 (2) | 0.060 (2) | 0.046 (2) | 0.029 (2) | 0.036 (2) |
C4 | 0.0469 (19) | 0.047 (2) | 0.055 (2) | 0.0257 (17) | 0.0234 (17) | 0.0300 (18) |
C5 | 0.0441 (17) | 0.0351 (17) | 0.0335 (15) | 0.0162 (15) | 0.0167 (14) | 0.0193 (14) |
C6 | 0.0402 (15) | 0.0269 (15) | 0.0345 (16) | 0.0145 (13) | 0.0089 (13) | 0.0101 (12) |
C7 | 0.066 (2) | 0.054 (2) | 0.061 (2) | 0.034 (2) | 0.037 (2) | 0.0349 (19) |
C8 | 0.060 (2) | 0.073 (3) | 0.049 (2) | 0.017 (2) | 0.026 (2) | 0.024 (2) |
C9 | 0.075 (3) | 0.074 (3) | 0.069 (3) | 0.021 (3) | 0.033 (3) | 0.015 (3) |
C10 | 0.0628 (18) | 0.0398 (18) | 0.0293 (14) | 0.0239 (16) | 0.0186 (12) | 0.0169 (13) |
C11 | 0.059 (2) | 0.050 (2) | 0.056 (2) | 0.0147 (18) | 0.0140 (14) | 0.0198 (18) |
C12 | 0.058 (2) | 0.067 (3) | 0.052 (2) | 0.026 (2) | 0.0083 (19) | 0.029 (2) |
C13 | 0.060 (2) | 0.055 (2) | 0.0360 (18) | 0.0219 (19) | 0.0214 (17) | 0.0206 (17) |
C14 | 0.066 (2) | 0.051 (2) | 0.057 (2) | 0.024 (2) | 0.012 (2) | 0.028 (2) |
C15 | 0.066 (2) | 0.041 (2) | 0.056 (2) | 0.0145 (19) | 0.0016 (19) | 0.0248 (19) |
C16 | 0.068 (3) | 0.058 (3) | 0.071 (3) | 0.032 (2) | 0.024 (2) | 0.031 (2) |
Cl1 | 0.0524 (5) | 0.0504 (6) | 0.0511 (5) | 0.0100 (4) | 0.0129 (4) | 0.0157 (4) |
Cu1 | 0.0445 (3) | 0.0388 (3) | 0.0348 (3) | 0.0229 (3) | 0.0183 (2) | 0.0261 (3) |
N1 | 0.0407 (15) | 0.0344 (14) | 0.0394 (15) | 0.0156 (13) | 0.0090 (12) | 0.0198 (12) |
N2 | 0.0468 (15) | 0.0495 (18) | 0.0299 (13) | 0.0191 (13) | 0.0173 (12) | 0.0234 (12) |
N3 | 0.065 (2) | 0.066 (2) | 0.0453 (18) | 0.0412 (18) | 0.0238 (16) | 0.0341 (16) |
N4 | 0.0607 (18) | 0.0420 (16) | 0.0392 (15) | 0.0266 (14) | 0.0190 (14) | 0.0224 (13) |
O11 | 0.0631 (17) | 0.0517 (17) | 0.0564 (17) | 0.0120 (14) | 0.0141 (14) | 0.0147 (14) |
O12 | 0.0551 (15) | 0.0517 (17) | 0.0565 (16) | 0.0090 (13) | 0.0131 (13) | 0.0177 (14) |
O13 | 0.0586 (16) | 0.0471 (16) | 0.0525 (18) | 0.0096 (13) | 0.0075 (14) | 0.0152 (14) |
O14 | 0.068 (2) | 0.0549 (19) | 0.066 (2) | −0.0070 (16) | 0.0069 (17) | −0.0063 (16) |
C1—N1 | 1.310 (5) | C10—N4 | 1.449 (4) |
C1—C2 | 1.398 (5) | C11—C12 | 1.395 (5) |
C1—H1 | 0.930 | C11—H11 | 0.930 |
C2—C3 | 1.376 (5) | C12—C13 | 1.371 (6) |
C2—H2 | 0.930 | C12—H12 | 0.930 |
C3—C4 | 1.387 (5) | C13—C14 | 1.351 (6) |
C3—H3 | 0.930 | C13—C16 | 1.518 (5) |
C4—C5 | 1.372 (4) | C14—C15 | 1.367 (5) |
C4—H4 | 0.930 | C14—H14 | 0.930 |
C5—N1 | 1.361 (4) | C15—H15 | 0.930 |
C5—C6 | 1.456 (4) | C16—H16A | 0.960 |
C6—N2 | 1.312 (4) | C16—H16B | 0.960 |
C6—N4 | 1.348 (4) | C16—H16C | 0.960 |
C7—N3 | 1.325 (4) | Cl1—O12 | 1.398 (3) |
C7—N4 | 1.356 (5) | Cl1—O14 | 1.407 (3) |
C7—C8 | 1.464 (5) | Cl1—O13 | 1.422 (3) |
C8—C9 | 1.474 (6) | Cl1—O11 | 1.426 (3) |
C8—H8A | 0.970 | Cl1—Cu1 | 3.5736 (11) |
C8—H8B | 0.970 | Cu1—N2 | 1.982 (3) |
C9—H9A | 0.960 | Cu1—N2i | 1.982 (3) |
C9—H9B | 0.960 | Cu1—N1i | 2.043 (3) |
C9—H9C | 0.960 | Cu1—N1 | 2.043 (3) |
C10—C11 | 1.353 (6) | N2—N3 | 1.374 (4) |
C10—C15 | 1.394 (5) | ||
N1—C1—C2 | 121.6 (3) | C14—C13—C16 | 121.7 (4) |
N1—C1—H1 | 119.2 | C12—C13—C16 | 120.1 (4) |
C2—C1—H1 | 119.2 | C13—C14—C15 | 123.7 (4) |
C3—C2—C1 | 119.6 (3) | C13—C14—H14 | 118.1 |
C3—C2—H2 | 120.2 | C15—C14—H14 | 118.1 |
C1—C2—H2 | 120.2 | C14—C15—C10 | 117.4 (4) |
C2—C3—C4 | 118.8 (3) | C14—C15—H15 | 121.3 |
C2—C3—H3 | 120.6 | C10—C15—H15 | 121.3 |
C4—C3—H3 | 120.6 | C13—C16—H16A | 109.5 |
C5—C4—C3 | 118.0 (3) | C13—C16—H16B | 109.5 |
C5—C4—H4 | 121.0 | H16A—C16—H16B | 109.5 |
C3—C4—H4 | 121.0 | C13—C16—H16C | 109.5 |
N1—C5—C4 | 123.0 (3) | H16A—C16—H16C | 109.5 |
N1—C5—C6 | 111.5 (3) | H16B—C16—H16C | 109.5 |
C4—C5—C6 | 125.5 (3) | O12—Cl1—O14 | 112.3 (2) |
N2—C6—N4 | 108.3 (3) | O12—Cl1—O13 | 110.27 (18) |
N2—C6—C5 | 119.5 (3) | O14—Cl1—O13 | 108.0 (2) |
N4—C6—C5 | 132.2 (3) | O12—Cl1—O11 | 108.75 (19) |
N3—C7—N4 | 109.7 (3) | O14—Cl1—O11 | 110.0 (2) |
N3—C7—C8 | 127.6 (4) | O13—Cl1—O11 | 107.42 (19) |
N4—C7—C8 | 122.7 (3) | O12—Cl1—Cu1 | 90.71 (12) |
C7—C8—C9 | 120.8 (4) | O14—Cl1—Cu1 | 138.86 (16) |
C7—C8—H8A | 107.1 | O11—Cl1—Cu1 | 92.63 (13) |
C9—C8—H8A | 107.1 | N2—Cu1—N2i | 180 |
C7—C8—H8B | 107.1 | N2—Cu1—N1i | 99.18 (12) |
C9—C8—H8B | 107.1 | N2i—Cu1—N1i | 80.82 (12) |
H8A—C8—H8B | 106.8 | N2—Cu1—N1 | 80.82 (12) |
C8—C9—H9A | 109.5 | N2i—Cu1—N1 | 99.18 (12) |
C8—C9—H9B | 109.5 | N1i—Cu1—N1 | 180 |
H9A—C9—H9B | 109.5 | N2—Cu1—Cl1 | 101.05 (9) |
C8—C9—H9C | 109.5 | N2i—Cu1—Cl1 | 78.95 (9) |
H9A—C9—H9C | 109.5 | N1i—Cu1—Cl1 | 76.99 (8) |
H9B—C9—H9C | 109.5 | N1—Cu1—Cl1 | 103.01 (8) |
C11—C10—C15 | 120.4 (4) | C1—N1—C5 | 118.7 (3) |
C11—C10—N4 | 120.6 (3) | C1—N1—Cu1 | 127.2 (2) |
C15—C10—N4 | 119.0 (3) | C5—N1—Cu1 | 114.1 (2) |
C10—C11—C12 | 120.1 (4) | C6—N2—N3 | 109.5 (3) |
C10—C11—H11 | 120.0 | C6—N2—Cu1 | 113.3 (2) |
C12—C11—H11 | 120.0 | N3—N2—Cu1 | 136.0 (2) |
C13—C12—C11 | 120.1 (4) | C7—N3—N2 | 105.7 (3) |
C13—C12—H12 | 120.0 | C6—N4—C7 | 106.8 (3) |
C11—C12—H12 | 120.0 | C6—N4—C10 | 126.5 (3) |
C14—C13—C12 | 118.2 (4) | C7—N4—C10 | 126.3 (3) |
Symmetry code: (i) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C16H16N4)2](ClO4)2 |
Mr | 791.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 8.0113 (14), 8.3126 (14), 14.215 (3) |
α, β, γ (°) | 99.374 (3), 102.689 (3), 107.041 (2) |
V (Å3) | 856.4 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.26 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.808, 0.861 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4686, 3294, 2297 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.127, 1.03 |
No. of reflections | 3294 |
No. of parameters | 234 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.82, −0.47 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
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The coordination chemistry of 1,2,4-triazole derivatives has attracted great attention in recent years (Bencini et al., 1987; Koningsbruggen et al., 1995; Moliner et al., 1998; Moliner et al., 2001; Klingele & Brooker 2003; Klingele et al., 2005). Some spin-crossover complexes of 1,2,4-triazoles with iron(II) salts have been reported, which could be used as molecular-based memory devices, displays and optical switches (Garcia et al., 1997; Lavrenova & Larionov, 1998; Kahn & Martinez, 1998; Koningsbruggen, 2004; Matouzenko et al., 2004). We report here the crystal structure analysis of the title compound, (I).
The structure of (I) is shown in Fig.1. In the crystal structure, the CuII atom lies on an inversion centre and is coordinated by two 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole ligands in a distorted square-planar geometry. In each ligand, the dihedral angle between the triazole and pyridine rings is 9.1 (3)°, and that between the triazole and benzene rings is 85.01 (14)°.