Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030449/xu2279sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030449/xu2279Isup2.hkl |
CCDC reference: 654821
A methanol solution (5 ml) of 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) (Xie et al., 2000) (55.6 mg, 0.2 mmol) was added to methanol solution (5 ml) of copper(II) dichloride dihydrate (17.1 mg, 0.1 mmol). The clear solution was set aside for a week for the growth of crystals. The yellow copper(I) chloride adduct is air stable.
The carbon-bound H atoms were placed in calculated positions [C—H = 0.93 to 0.97 Å], and were included in the refinement in the riding model approximation with Uiso(H) = 1.2Ueq(C).
The 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) heterocycle binds to two copper(I) atoms in the 1:1 adduct with copper(I) chloride to furnish a linear chain structure. The copper atom shows tetrahedral coordination (Table 1) as is covalently bonded to one chlorine atom and datively bonded to the adjacent one (Borsting & Steel, 2004). The present compound is a 1:1 adduct but the compound exists as a monomeric dinculear molecule as the heterocycle functions instead as a bidentate chelate (Fig. 1). However, bond dimensions involving the copper atom are not significantly difference, so that the different architectures reflect the flexible nature of the ligand, which possess three methylene linkages separating the fused-rings.
For the isomeric chain structure, see Borsting & Steel (2004). For related literature, see: Xie et al. (2000).
Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. Thermal ellipsoid plot of (C15H14N6)2Cl2Cu2; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. Symmetry code i: 1 – x, 1 – y, 1 – z. |
[Cu2Cl2(C15H14N6)2] | F(000) = 768 |
Mr = 754.62 | Dx = 1.655 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3803 reflections |
a = 9.886 (3) Å | θ = 2.1–27.9° |
b = 10.055 (3) Å | µ = 1.63 mm−1 |
c = 15.876 (4) Å | T = 295 K |
β = 106.401 (4)° | Prism, yellow |
V = 1514.0 (7) Å3 | 0.23 × 0.20 × 0.19 mm |
Z = 2 |
Rigaku Saturn diffractometer | 3592 independent reflections |
Radiation source: fine-focus sealed tube | 3425 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 27.9°, θmin = 2.8° |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006) | h = −13→12 |
Tmin = 0.592, Tmax = 0.748 | k = −12→13 |
17855 measured reflections | l = −20→20 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.7057P] where P = (Fo2 + 2Fc2)/3 |
3592 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
[Cu2Cl2(C15H14N6)2] | V = 1514.0 (7) Å3 |
Mr = 754.62 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.886 (3) Å | µ = 1.63 mm−1 |
b = 10.055 (3) Å | T = 295 K |
c = 15.876 (4) Å | 0.23 × 0.20 × 0.19 mm |
β = 106.401 (4)° |
Rigaku Saturn diffractometer | 3592 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006) | 3425 reflections with I > 2σ(I) |
Tmin = 0.592, Tmax = 0.748 | Rint = 0.033 |
17855 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.59 e Å−3 |
3592 reflections | Δρmin = −0.81 e Å−3 |
208 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.37039 (3) | 0.44465 (3) | 0.431367 (18) | 0.04155 (11) | |
Cl1 | 0.53996 (5) | 0.58239 (5) | 0.40490 (3) | 0.03700 (13) | |
N1 | 0.16588 (17) | 0.50352 (17) | 0.40525 (10) | 0.0339 (3) | |
N2 | 0.06485 (18) | 0.42252 (17) | 0.41610 (11) | 0.0364 (4) | |
N3 | −0.06712 (19) | 0.4634 (2) | 0.38526 (13) | 0.0444 (4) | |
N4 | 0.38999 (18) | 0.25130 (16) | 0.39053 (11) | 0.0352 (3) | |
N5 | 0.29088 (18) | 0.16622 (17) | 0.34729 (10) | 0.0366 (3) | |
N6 | 0.3327 (2) | 0.04471 (17) | 0.33617 (13) | 0.0431 (4) | |
C1 | 0.0923 (2) | 0.6102 (2) | 0.36354 (12) | 0.0348 (4) | |
C2 | 0.1380 (2) | 0.7295 (2) | 0.33471 (13) | 0.0412 (4) | |
H2 | 0.2333 | 0.7481 | 0.3440 | 0.049* | |
C3 | 0.0357 (3) | 0.8171 (2) | 0.29235 (15) | 0.0504 (5) | |
H3 | 0.0623 | 0.8968 | 0.2719 | 0.060* | |
C4 | −0.1112 (3) | 0.7899 (3) | 0.27846 (16) | 0.0568 (6) | |
H4 | −0.1773 | 0.8517 | 0.2484 | 0.068* | |
C5 | −0.1564 (3) | 0.6767 (3) | 0.30800 (16) | 0.0537 (6) | |
H5 | −0.2518 | 0.6605 | 0.3002 | 0.064* | |
C6 | −0.0523 (2) | 0.5844 (2) | 0.35115 (14) | 0.0401 (4) | |
C7 | 0.0958 (2) | 0.2884 (2) | 0.45160 (13) | 0.0398 (4) | |
H7A | 0.0414 | 0.2703 | 0.4925 | 0.048* | |
H7B | 0.1951 | 0.2816 | 0.4832 | 0.048* | |
C8 | 0.0595 (2) | 0.1869 (2) | 0.37756 (14) | 0.0425 (4) | |
H8A | −0.0402 | 0.1937 | 0.3471 | 0.051* | |
H8B | 0.0767 | 0.0984 | 0.4026 | 0.051* | |
C9 | 0.1437 (2) | 0.2046 (2) | 0.31134 (13) | 0.0398 (4) | |
H9A | 0.1014 | 0.1511 | 0.2598 | 0.048* | |
H9B | 0.1391 | 0.2970 | 0.2931 | 0.048* | |
C10 | 0.4737 (2) | 0.04905 (19) | 0.37568 (14) | 0.0390 (4) | |
C11 | 0.5774 (3) | −0.0498 (2) | 0.38292 (17) | 0.0509 (6) | |
H11 | 0.5546 | −0.1354 | 0.3613 | 0.061* | |
C12 | 0.7128 (3) | −0.0132 (3) | 0.42332 (16) | 0.0509 (5) | |
H12 | 0.7843 | −0.0754 | 0.4286 | 0.061* | |
C13 | 0.7485 (2) | 0.1159 (2) | 0.45750 (16) | 0.0474 (5) | |
H13 | 0.8425 | 0.1354 | 0.4850 | 0.057* | |
C14 | 0.6498 (2) | 0.2130 (2) | 0.45152 (15) | 0.0429 (4) | |
H14 | 0.6740 | 0.2978 | 0.4742 | 0.052* | |
C15 | 0.5096 (2) | 0.17771 (19) | 0.40924 (12) | 0.0348 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03493 (17) | 0.03753 (17) | 0.04959 (18) | −0.00308 (9) | 0.00770 (12) | −0.00336 (10) |
Cl1 | 0.0374 (2) | 0.0393 (2) | 0.0299 (2) | −0.01079 (18) | 0.00249 (17) | 0.00473 (17) |
N1 | 0.0309 (8) | 0.0358 (8) | 0.0344 (8) | −0.0022 (6) | 0.0080 (6) | −0.0020 (6) |
N2 | 0.0313 (8) | 0.0411 (9) | 0.0367 (8) | −0.0042 (7) | 0.0093 (6) | −0.0022 (7) |
N3 | 0.0321 (9) | 0.0526 (11) | 0.0486 (10) | −0.0010 (8) | 0.0115 (8) | −0.0040 (8) |
N4 | 0.0374 (8) | 0.0316 (8) | 0.0344 (8) | −0.0036 (6) | 0.0064 (6) | −0.0065 (6) |
N5 | 0.0399 (9) | 0.0339 (8) | 0.0335 (7) | −0.0058 (7) | 0.0063 (6) | −0.0061 (6) |
N6 | 0.0503 (11) | 0.0310 (8) | 0.0444 (9) | −0.0062 (7) | 0.0073 (8) | −0.0058 (7) |
C1 | 0.0350 (9) | 0.0379 (10) | 0.0295 (8) | 0.0014 (8) | 0.0060 (7) | −0.0053 (7) |
C2 | 0.0478 (11) | 0.0374 (10) | 0.0380 (10) | 0.0001 (9) | 0.0115 (8) | −0.0031 (8) |
C3 | 0.0694 (16) | 0.0388 (11) | 0.0416 (11) | 0.0080 (10) | 0.0134 (10) | −0.0009 (9) |
C4 | 0.0585 (14) | 0.0567 (14) | 0.0488 (12) | 0.0221 (12) | 0.0049 (11) | −0.0015 (11) |
C5 | 0.0389 (11) | 0.0632 (15) | 0.0533 (13) | 0.0137 (11) | 0.0038 (10) | −0.0044 (11) |
C6 | 0.0341 (10) | 0.0472 (11) | 0.0374 (10) | 0.0032 (8) | 0.0077 (8) | −0.0065 (8) |
C7 | 0.0425 (11) | 0.0401 (10) | 0.0370 (9) | −0.0067 (8) | 0.0114 (8) | 0.0033 (8) |
C8 | 0.0383 (10) | 0.0421 (11) | 0.0445 (10) | −0.0086 (9) | 0.0076 (8) | −0.0023 (9) |
C9 | 0.0382 (10) | 0.0445 (11) | 0.0317 (9) | −0.0064 (8) | 0.0019 (7) | −0.0062 (8) |
C10 | 0.0486 (12) | 0.0297 (9) | 0.0366 (9) | −0.0023 (8) | 0.0088 (8) | −0.0011 (7) |
C11 | 0.0640 (15) | 0.0319 (10) | 0.0518 (13) | 0.0067 (10) | 0.0082 (11) | −0.0037 (9) |
C12 | 0.0564 (14) | 0.0431 (12) | 0.0510 (12) | 0.0149 (11) | 0.0112 (11) | 0.0020 (10) |
C13 | 0.0411 (11) | 0.0490 (13) | 0.0496 (12) | 0.0023 (10) | 0.0086 (9) | −0.0012 (10) |
C14 | 0.0416 (11) | 0.0369 (10) | 0.0471 (11) | −0.0024 (8) | 0.0073 (9) | −0.0069 (8) |
C15 | 0.0403 (10) | 0.0323 (9) | 0.0314 (8) | −0.0011 (8) | 0.0093 (7) | −0.0026 (7) |
Cu1—N1 | 2.034 (2) | C4—H4 | 0.9300 |
Cu1—N4 | 2.076 (2) | C5—C6 | 1.411 (3) |
Cu1—Cl1 | 2.3028 (7) | C5—H5 | 0.9300 |
Cu1—Cl1i | 2.5131 (8) | C7—C8 | 1.521 (3) |
Cl1—Cu1i | 2.5131 (8) | C7—H7A | 0.9700 |
N1—N2 | 1.337 (2) | C7—H7B | 0.9700 |
N1—C1 | 1.359 (3) | C8—C9 | 1.524 (3) |
N2—N3 | 1.323 (3) | C8—H8A | 0.9700 |
N2—C7 | 1.460 (3) | C8—H8B | 0.9700 |
N3—C6 | 1.356 (3) | C9—H9A | 0.9700 |
N4—N5 | 1.335 (2) | C9—H9B | 0.9700 |
N4—C15 | 1.355 (3) | C10—C15 | 1.406 (3) |
N5—N6 | 1.318 (2) | C10—C11 | 1.409 (3) |
N5—C9 | 1.457 (3) | C11—C12 | 1.361 (4) |
N6—C10 | 1.358 (3) | C11—H11 | 0.9300 |
C1—C2 | 1.404 (3) | C12—C13 | 1.413 (4) |
C1—C6 | 1.411 (3) | C12—H12 | 0.9300 |
C2—C3 | 1.366 (3) | C13—C14 | 1.365 (3) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.433 (4) | C14—C15 | 1.405 (3) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.354 (4) | ||
N1—Cu1—N4 | 112.58 (7) | C1—C6—C5 | 121.2 (2) |
N1—Cu1—Cl1 | 121.38 (5) | N2—C7—C8 | 110.08 (17) |
N1—Cu1—Cl1i | 106.40 (5) | N2—C7—H7A | 109.6 |
N4—Cu1—Cl1 | 111.68 (5) | C8—C7—H7A | 109.6 |
N4—Cu1—Cl1i | 100.66 (5) | N2—C7—H7B | 109.6 |
Cl1—Cu1—Cl1i | 101.04 (2) | C8—C7—H7B | 109.6 |
Cu1—Cl1—Cu1i | 78.957 (19) | H7A—C7—H7B | 108.2 |
N2—N1—C1 | 103.12 (16) | C7—C8—C9 | 113.52 (17) |
N2—N1—Cu1 | 122.15 (13) | C7—C8—H8A | 108.9 |
C1—N1—Cu1 | 133.93 (14) | C9—C8—H8A | 108.9 |
N3—N2—N1 | 117.21 (17) | C7—C8—H8B | 108.9 |
N3—N2—C7 | 120.49 (17) | C9—C8—H8B | 108.9 |
N1—N2—C7 | 121.96 (17) | H8A—C8—H8B | 107.7 |
N2—N3—C6 | 102.74 (17) | N5—C9—C8 | 112.22 (17) |
N5—N4—C15 | 103.35 (16) | N5—C9—H9A | 109.2 |
N5—N4—Cu1 | 129.87 (13) | C8—C9—H9A | 109.2 |
C15—N4—Cu1 | 126.57 (13) | N5—C9—H9B | 109.2 |
N6—N5—N4 | 116.77 (17) | C8—C9—H9B | 109.2 |
N6—N5—C9 | 120.65 (17) | H9A—C9—H9B | 107.9 |
N4—N5—C9 | 122.56 (17) | N6—C10—C15 | 108.71 (18) |
N5—N6—C10 | 103.20 (16) | N6—C10—C11 | 130.0 (2) |
N1—C1—C2 | 131.01 (19) | C15—C10—C11 | 121.2 (2) |
N1—C1—C6 | 107.76 (18) | C12—C11—C10 | 116.3 (2) |
C2—C1—C6 | 121.2 (2) | C12—C11—H11 | 121.9 |
C3—C2—C1 | 116.7 (2) | C10—C11—H11 | 121.9 |
C3—C2—H2 | 121.6 | C11—C12—C13 | 122.4 (2) |
C1—C2—H2 | 121.6 | C11—C12—H12 | 118.8 |
C2—C3—C4 | 122.0 (2) | C13—C12—H12 | 118.8 |
C2—C3—H3 | 119.0 | C14—C13—C12 | 122.3 (2) |
C4—C3—H3 | 119.0 | C14—C13—H13 | 118.8 |
C5—C4—C3 | 121.8 (2) | C12—C13—H13 | 118.8 |
C5—C4—H4 | 119.1 | C13—C14—C15 | 116.2 (2) |
C3—C4—H4 | 119.1 | C13—C14—H14 | 121.9 |
C4—C5—C6 | 117.0 (2) | C15—C14—H14 | 121.9 |
C4—C5—H5 | 121.5 | N4—C15—C14 | 130.47 (19) |
C6—C5—H5 | 121.5 | N4—C15—C10 | 107.97 (18) |
N3—C6—C1 | 109.17 (19) | C14—C15—C10 | 121.54 (19) |
N3—C6—C5 | 129.6 (2) | ||
N1—Cu1—Cl1—Cu1i | 117.13 (6) | C2—C3—C4—C5 | 1.1 (4) |
N4—Cu1—Cl1—Cu1i | −106.28 (5) | C3—C4—C5—C6 | −1.7 (4) |
Cl1i—Cu1—Cl1—Cu1i | 0.0 | N2—N3—C6—C1 | 0.2 (2) |
N4—Cu1—N1—N2 | 40.36 (16) | N2—N3—C6—C5 | 179.3 (2) |
Cl1—Cu1—N1—N2 | 176.60 (12) | N1—C1—C6—N3 | 0.3 (2) |
Cl1i—Cu1—N1—N2 | −68.98 (14) | C2—C1—C6—N3 | −179.66 (18) |
N4—Cu1—N1—C1 | −127.53 (17) | N1—C1—C6—C5 | −178.99 (19) |
Cl1—Cu1—N1—C1 | 8.7 (2) | C2—C1—C6—C5 | 1.1 (3) |
Cl1i—Cu1—N1—C1 | 123.13 (17) | C4—C5—C6—N3 | −178.5 (2) |
C1—N1—N2—N3 | 0.7 (2) | C4—C5—C6—C1 | 0.6 (3) |
Cu1—N1—N2—N3 | −170.33 (14) | N3—N2—C7—C8 | 72.4 (2) |
C1—N1—N2—C7 | 174.18 (17) | N1—N2—C7—C8 | −100.8 (2) |
Cu1—N1—N2—C7 | 3.1 (2) | N2—C7—C8—C9 | 61.2 (2) |
N1—N2—N3—C6 | −0.6 (2) | N6—N5—C9—C8 | 93.2 (2) |
C7—N2—N3—C6 | −174.12 (18) | N4—N5—C9—C8 | −88.6 (2) |
N1—Cu1—N4—N5 | 3.63 (19) | C7—C8—C9—N5 | 71.6 (2) |
Cl1—Cu1—N4—N5 | −136.92 (15) | N5—N6—C10—C15 | −0.1 (2) |
Cl1i—Cu1—N4—N5 | 116.54 (16) | N5—N6—C10—C11 | −177.7 (2) |
N1—Cu1—N4—C15 | −170.15 (15) | N6—C10—C11—C12 | 176.9 (2) |
Cl1—Cu1—N4—C15 | 49.30 (17) | C15—C10—C11—C12 | −0.5 (3) |
Cl1i—Cu1—N4—C15 | −57.23 (16) | C10—C11—C12—C13 | 0.9 (4) |
C15—N4—N5—N6 | 0.4 (2) | C11—C12—C13—C14 | −0.7 (4) |
Cu1—N4—N5—N6 | −174.49 (14) | C12—C13—C14—C15 | 0.0 (4) |
C15—N4—N5—C9 | −177.89 (17) | N5—N4—C15—C14 | 177.8 (2) |
Cu1—N4—N5—C9 | 7.2 (3) | Cu1—N4—C15—C14 | −7.1 (3) |
N4—N5—N6—C10 | −0.2 (2) | N5—N4—C15—C10 | −0.4 (2) |
C9—N5—N6—C10 | 178.15 (17) | Cu1—N4—C15—C10 | 174.66 (13) |
N2—N1—C1—C2 | 179.3 (2) | C13—C14—C15—N4 | −177.6 (2) |
Cu1—N1—C1—C2 | −11.2 (3) | C13—C14—C15—C10 | 0.4 (3) |
N2—N1—C1—C6 | −0.6 (2) | N6—C10—C15—N4 | 0.4 (2) |
Cu1—N1—C1—C6 | 168.93 (14) | C11—C10—C15—N4 | 178.2 (2) |
N1—C1—C2—C3 | 178.5 (2) | N6—C10—C15—C14 | −178.04 (19) |
C6—C1—C2—C3 | −1.7 (3) | C11—C10—C15—C14 | −0.2 (3) |
C1—C2—C3—C4 | 0.6 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Cl2(C15H14N6)2] |
Mr | 754.62 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 9.886 (3), 10.055 (3), 15.876 (4) |
β (°) | 106.401 (4) |
V (Å3) | 1514.0 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.63 |
Crystal size (mm) | 0.23 × 0.20 × 0.19 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2006) |
Tmin, Tmax | 0.592, 0.748 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17855, 3592, 3425 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.104, 1.06 |
No. of reflections | 3592 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.81 |
Computer programs: CrystalClear (Rigaku/MSC, 2006), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
Cu1—N1 | 2.034 (2) | Cu1—Cl1 | 2.3028 (7) |
Cu1—N4 | 2.076 (2) | Cu1—Cl1i | 2.5131 (8) |
N1—Cu1—N4 | 112.58 (7) | N4—Cu1—Cl1 | 111.68 (5) |
N1—Cu1—Cl1 | 121.38 (5) | N4—Cu1—Cl1i | 100.66 (5) |
N1—Cu1—Cl1i | 106.40 (5) | Cl1—Cu1—Cl1i | 101.04 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) heterocycle binds to two copper(I) atoms in the 1:1 adduct with copper(I) chloride to furnish a linear chain structure. The copper atom shows tetrahedral coordination (Table 1) as is covalently bonded to one chlorine atom and datively bonded to the adjacent one (Borsting & Steel, 2004). The present compound is a 1:1 adduct but the compound exists as a monomeric dinculear molecule as the heterocycle functions instead as a bidentate chelate (Fig. 1). However, bond dimensions involving the copper atom are not significantly difference, so that the different architectures reflect the flexible nature of the ligand, which possess three methylene linkages separating the fused-rings.