Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112045362/sk3456sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112045362/sk3456Isup2.hkl |
CCDC reference: 821945
For related literature, see: Aakeröy & Beatty (2001); Aakeröy & Seddon (1993); Beatty (2003); Braga & Grepioni (2000); Cruzan et al. (1996); Desiraju (2002); Ding et al. (2009); Fourmigue & Batail (2004); Guo (2010); Janiak (2000); Jian et al. (2003, 2004); Long et al. (2004); Metrangolo et al. (2005, 2006); Moulton & Zaworotko (2001); Politzer et al. (2007); Steiner (2002); Xantheas (1994, 1995).
NH4SCN (7.6 mg, 0.1 mmol) was added to an acetonitrile solution of the ligand L (25.6 mg, 0.1 mmol) with stirring. The resulting mixture was then added to a solution of CuCl2.2H2O (17.0 mg, 0.1 mmol) in acetonitrile–H2O (10 ml, 1:1 v/v) with vigorous stirring for ca 30 min. The reaction solution was filtered and left to stand at room temperature. Green crystals of (I) suitable for X-ray diffraction were obtained by evaporation of the filtrate (yield 40%, based on CuII). Analysis, calculated for C44H44Cl2CuN12O4.6H2O: C 50.45, H 5.39, N 16.05%; found: C 50.31, H 5.32, N 16.19%.
Although all H atoms were visible in difference maps, they were finally placed in calculated positions, with C—H and O—H distances of 0.93–0.97 and 0.85 Å, respectively, and included in the final refinement in a riding-model approximation, with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms, or Uiso(H) = 1.5Ueq(C) for water H atoms.
Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[CuCl2(C11H11N3O)4]·6H2O | F(000) = 1094 |
Mr = 1047.45 | Dx = 1.393 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4452 reflections |
a = 7.9853 (6) Å | θ = 2.4–25.4° |
b = 10.8365 (7) Å | µ = 0.61 mm−1 |
c = 28.974 (2) Å | T = 293 K |
β = 95.123 (1)° | Block, green |
V = 2497.2 (3) Å3 | 0.32 × 0.28 × 0.22 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 5891 independent reflections |
Radiation source: fine-focus sealed tube | 4473 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 27.9°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −10→10 |
Tmin = 0.828, Tmax = 0.877 | k = −14→12 |
16593 measured reflections | l = −38→35 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.6416P] where P = (Fo2 + 2Fc2)/3 |
5891 reflections | (Δ/σ)max < 0.001 |
313 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
[CuCl2(C11H11N3O)4]·6H2O | V = 2497.2 (3) Å3 |
Mr = 1047.45 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9853 (6) Å | µ = 0.61 mm−1 |
b = 10.8365 (7) Å | T = 293 K |
c = 28.974 (2) Å | 0.32 × 0.28 × 0.22 mm |
β = 95.123 (1)° |
Bruker APEXII CCD area-detector diffractometer | 5891 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 4473 reflections with I > 2σ(I) |
Tmin = 0.828, Tmax = 0.877 | Rint = 0.023 |
16593 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.36 e Å−3 |
5891 reflections | Δρmin = −0.29 e Å−3 |
313 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 | ||
Cu1 | 0.0000 | 0.5000 | 0.0000 | 0.03106 (9) | |
Cl1 | −0.18258 (6) | 0.34110 (4) | 0.051372 (15) | 0.04099 (12) | |
O1 | −0.2697 (2) | 0.65408 (13) | 0.17904 (6) | 0.0686 (5) | |
O2 | 0.6076 (2) | 0.15005 (13) | 0.19332 (5) | 0.0613 (4) | |
O3 | 0.0150 (2) | 0.09050 (14) | 0.07526 (6) | 0.0724 (5) | |
H3A | −0.0329 | 0.0206 | 0.0720 | 0.087* | |
H3B | −0.0467 | 0.1517 | 0.0665 | 0.087* | |
O4 | 0.5432 (3) | 0.17508 (19) | −0.00309 (7) | 0.0943 (7) | |
H4A | 0.6111 | 0.2276 | 0.0099 | 0.113* | |
H4B | 0.5175 | 0.1130 | 0.0130 | 0.113* | |
O5 | 0.3414 (3) | 0.0316 (2) | 0.05056 (8) | 0.1026 (7) | |
H5A | 0.3201 | −0.0154 | 0.0277 | 0.123* | |
H5B | 0.2587 | 0.0709 | 0.0592 | 0.123* | |
N1 | −0.07581 (18) | 0.64617 (12) | 0.03713 (5) | 0.0320 (3) | |
N2 | −0.1027 (2) | 0.84014 (14) | 0.06113 (6) | 0.0463 (4) | |
N3 | −0.21651 (18) | 0.76593 (13) | 0.07922 (5) | 0.0344 (3) | |
N4 | 0.20256 (17) | 0.47475 (12) | 0.04594 (5) | 0.0322 (3) | |
N5 | 0.38467 (18) | 0.39148 (13) | 0.09646 (5) | 0.0340 (3) | |
N6 | 0.4476 (2) | 0.50480 (14) | 0.08814 (6) | 0.0455 (4) | |
C1 | −0.1986 (2) | 0.65168 (16) | 0.06465 (6) | 0.0341 (4) | |
H1 | −0.2632 | 0.5848 | 0.0726 | 0.041* | |
C2 | −0.0212 (3) | 0.76395 (17) | 0.03612 (6) | 0.0425 (4) | |
H2 | 0.0665 | 0.7888 | 0.0192 | 0.051* | |
C3 | −0.3371 (2) | 0.81892 (19) | 0.10882 (6) | 0.0452 (5) | |
H3A' | −0.4219 | 0.7577 | 0.1142 | 0.054* | |
H3B' | −0.3931 | 0.8886 | 0.0931 | 0.054* | |
C4 | −0.2517 (2) | 0.86114 (17) | 0.15501 (6) | 0.0401 (4) | |
H4A' | −0.1432 | 0.8966 | 0.1501 | 0.048* | |
H4B' | −0.3192 | 0.9253 | 0.1676 | 0.048* | |
C5 | −0.2267 (2) | 0.75801 (17) | 0.18972 (6) | 0.0406 (4) | |
C6 | −0.1487 (2) | 0.78626 (17) | 0.23705 (6) | 0.0385 (4) | |
C7 | −0.0823 (3) | 0.90101 (19) | 0.24902 (7) | 0.0482 (5) | |
H7 | −0.0880 | 0.9646 | 0.2274 | 0.058* | |
C8 | −0.0069 (3) | 0.9209 (2) | 0.29354 (7) | 0.0596 (6) | |
H8 | 0.0383 | 0.9979 | 0.3016 | 0.072* | |
C9 | 0.0011 (3) | 0.8283 (3) | 0.32547 (7) | 0.0624 (6) | |
H9 | 0.0519 | 0.8422 | 0.3552 | 0.075* | |
C10 | −0.0654 (3) | 0.7147 (2) | 0.31406 (8) | 0.0635 (6) | |
H10 | −0.0602 | 0.6519 | 0.3360 | 0.076* | |
C11 | −0.1397 (3) | 0.6935 (2) | 0.27019 (7) | 0.0536 (5) | |
H11 | −0.1844 | 0.6161 | 0.2626 | 0.064* | |
C12 | 0.3340 (2) | 0.55063 (18) | 0.05777 (6) | 0.0424 (4) | |
H12 | 0.3427 | 0.6292 | 0.0453 | 0.051* | |
C13 | 0.2404 (2) | 0.37564 (17) | 0.07120 (6) | 0.0371 (4) | |
H13 | 0.1748 | 0.3047 | 0.0712 | 0.045* | |
C14 | 0.4767 (2) | 0.30298 (17) | 0.12726 (6) | 0.0395 (4) | |
H14A | 0.5840 | 0.2850 | 0.1155 | 0.047* | |
H14B | 0.4134 | 0.2266 | 0.1274 | 0.047* | |
C15 | 0.5066 (2) | 0.35133 (16) | 0.17636 (6) | 0.0380 (4) | |
H15A | 0.5793 | 0.4231 | 0.1768 | 0.046* | |
H15B | 0.4004 | 0.3763 | 0.1873 | 0.046* | |
C16 | 0.5870 (2) | 0.25317 (17) | 0.20801 (6) | 0.0383 (4) | |
C17 | 0.6397 (2) | 0.28372 (17) | 0.25732 (6) | 0.0381 (4) | |
C18 | 0.7150 (3) | 0.1921 (2) | 0.28553 (7) | 0.0530 (5) | |
H18 | 0.7290 | 0.1135 | 0.2735 | 0.064* | |
C19 | 0.7694 (3) | 0.2165 (3) | 0.33131 (8) | 0.0642 (6) | |
H19 | 0.8209 | 0.1549 | 0.3499 | 0.077* | |
C20 | 0.7471 (3) | 0.3318 (3) | 0.34914 (7) | 0.0625 (6) | |
H20 | 0.7839 | 0.3484 | 0.3799 | 0.075* | |
C21 | 0.6713 (3) | 0.4224 (2) | 0.32215 (7) | 0.0596 (6) | |
H21 | 0.6557 | 0.5003 | 0.3346 | 0.072* | |
C22 | 0.6172 (3) | 0.39892 (19) | 0.27614 (7) | 0.0477 (5) | |
H22 | 0.5655 | 0.4611 | 0.2579 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03373 (16) | 0.03098 (16) | 0.02706 (15) | 0.00256 (12) | −0.00507 (11) | −0.00742 (11) |
Cl1 | 0.0458 (3) | 0.0407 (2) | 0.0371 (2) | −0.00502 (19) | 0.00724 (19) | −0.00097 (18) |
O1 | 0.0981 (13) | 0.0392 (9) | 0.0639 (10) | −0.0081 (8) | −0.0183 (9) | −0.0068 (7) |
O2 | 0.0895 (12) | 0.0385 (8) | 0.0522 (9) | 0.0086 (8) | −0.0145 (8) | −0.0008 (7) |
O3 | 0.0804 (12) | 0.0396 (9) | 0.0962 (13) | −0.0028 (8) | 0.0024 (10) | −0.0011 (8) |
O4 | 0.1078 (16) | 0.0795 (13) | 0.0904 (14) | −0.0414 (12) | −0.0204 (12) | 0.0056 (10) |
O5 | 0.0930 (16) | 0.1017 (16) | 0.1142 (18) | −0.0024 (12) | 0.0147 (13) | 0.0027 (13) |
N1 | 0.0364 (8) | 0.0310 (7) | 0.0282 (7) | −0.0015 (6) | 0.0018 (6) | −0.0060 (6) |
N2 | 0.0634 (11) | 0.0322 (8) | 0.0446 (9) | −0.0036 (7) | 0.0125 (8) | −0.0075 (7) |
N3 | 0.0374 (8) | 0.0367 (8) | 0.0288 (7) | 0.0023 (6) | 0.0014 (6) | −0.0054 (6) |
N4 | 0.0333 (8) | 0.0321 (8) | 0.0301 (7) | −0.0028 (6) | −0.0026 (6) | −0.0016 (6) |
N5 | 0.0348 (8) | 0.0349 (8) | 0.0313 (7) | −0.0027 (6) | −0.0031 (6) | 0.0035 (6) |
N6 | 0.0415 (9) | 0.0406 (9) | 0.0513 (9) | −0.0109 (7) | −0.0125 (7) | 0.0092 (7) |
C1 | 0.0351 (9) | 0.0320 (9) | 0.0346 (9) | −0.0019 (7) | −0.0003 (7) | −0.0045 (7) |
C2 | 0.0526 (12) | 0.0358 (10) | 0.0410 (10) | −0.0086 (8) | 0.0144 (9) | −0.0081 (8) |
C3 | 0.0415 (11) | 0.0567 (12) | 0.0368 (10) | 0.0155 (9) | 0.0006 (8) | −0.0094 (9) |
C4 | 0.0468 (11) | 0.0397 (10) | 0.0339 (9) | 0.0076 (8) | 0.0040 (8) | −0.0078 (8) |
C5 | 0.0409 (10) | 0.0395 (10) | 0.0414 (10) | 0.0041 (8) | 0.0025 (8) | −0.0069 (8) |
C6 | 0.0389 (10) | 0.0411 (10) | 0.0360 (9) | 0.0041 (8) | 0.0059 (8) | −0.0024 (8) |
C7 | 0.0565 (13) | 0.0494 (12) | 0.0379 (10) | −0.0070 (10) | 0.0008 (9) | −0.0019 (9) |
C8 | 0.0597 (14) | 0.0709 (16) | 0.0470 (12) | −0.0109 (12) | −0.0020 (10) | −0.0140 (11) |
C9 | 0.0534 (13) | 0.098 (2) | 0.0346 (11) | 0.0095 (13) | −0.0035 (9) | −0.0055 (12) |
C10 | 0.0773 (17) | 0.0725 (16) | 0.0406 (12) | 0.0171 (13) | 0.0053 (11) | 0.0105 (11) |
C11 | 0.0666 (14) | 0.0477 (12) | 0.0467 (12) | 0.0037 (10) | 0.0067 (10) | 0.0045 (9) |
C12 | 0.0454 (11) | 0.0352 (10) | 0.0441 (10) | −0.0090 (8) | −0.0096 (9) | 0.0068 (8) |
C13 | 0.0366 (10) | 0.0367 (9) | 0.0368 (9) | −0.0061 (7) | −0.0038 (7) | 0.0007 (7) |
C14 | 0.0421 (10) | 0.0395 (10) | 0.0356 (9) | 0.0049 (8) | −0.0033 (8) | 0.0046 (8) |
C15 | 0.0392 (10) | 0.0377 (10) | 0.0358 (9) | 0.0001 (8) | −0.0028 (7) | 0.0038 (7) |
C16 | 0.0383 (10) | 0.0360 (10) | 0.0396 (10) | −0.0027 (8) | −0.0024 (8) | 0.0044 (8) |
C17 | 0.0332 (9) | 0.0443 (10) | 0.0363 (9) | −0.0023 (8) | 0.0010 (7) | 0.0077 (8) |
C18 | 0.0589 (14) | 0.0539 (13) | 0.0452 (11) | 0.0064 (10) | −0.0011 (10) | 0.0108 (9) |
C19 | 0.0633 (15) | 0.0847 (18) | 0.0428 (12) | 0.0104 (13) | −0.0059 (10) | 0.0190 (12) |
C20 | 0.0528 (13) | 0.099 (2) | 0.0347 (11) | 0.0012 (13) | −0.0029 (9) | 0.0019 (12) |
C21 | 0.0611 (14) | 0.0706 (16) | 0.0461 (12) | 0.0019 (12) | −0.0008 (10) | −0.0115 (11) |
C22 | 0.0503 (12) | 0.0498 (12) | 0.0418 (11) | 0.0040 (9) | −0.0031 (9) | 0.0022 (9) |
Cu1—N4 | 2.0196 (13) | C4—H4B' | 0.9700 |
Cu1—N4i | 2.0196 (13) | C5—C6 | 1.486 (2) |
Cu1—N1 | 2.0370 (13) | C6—C7 | 1.384 (3) |
Cu1—N1i | 2.0370 (13) | C6—C11 | 1.388 (3) |
Cu1—Cl1 | 2.7738 (5) | C7—C8 | 1.391 (3) |
Cu1—Cl1i | 2.7738 (5) | C7—H7 | 0.9300 |
O1—C5 | 1.210 (2) | C8—C9 | 1.363 (3) |
O2—C16 | 1.212 (2) | C8—H8 | 0.9300 |
O3—H3A | 0.8504 | C9—C10 | 1.369 (3) |
O3—H3B | 0.8506 | C9—H9 | 0.9300 |
O4—H4A | 0.8500 | C10—C11 | 1.373 (3) |
O4—H4B | 0.8544 | C10—H10 | 0.9300 |
O5—H5A | 0.8407 | C11—H11 | 0.9300 |
O5—H5B | 0.8418 | C12—H12 | 0.9300 |
N1—C1 | 1.319 (2) | C13—H13 | 0.9300 |
N1—C2 | 1.350 (2) | C14—C15 | 1.515 (2) |
N2—C2 | 1.309 (2) | C14—H14A | 0.9700 |
N2—N3 | 1.354 (2) | C14—H14B | 0.9700 |
N3—C1 | 1.320 (2) | C15—C16 | 1.510 (2) |
N3—C3 | 1.463 (2) | C15—H15A | 0.9700 |
N4—C13 | 1.319 (2) | C15—H15B | 0.9700 |
N4—C12 | 1.353 (2) | C16—C17 | 1.490 (2) |
N5—C13 | 1.320 (2) | C17—C22 | 1.380 (3) |
N5—N6 | 1.3566 (19) | C17—C18 | 1.389 (3) |
N5—C14 | 1.462 (2) | C18—C19 | 1.384 (3) |
N6—C12 | 1.304 (2) | C18—H18 | 0.9300 |
C1—H1 | 0.9300 | C19—C20 | 1.370 (3) |
C2—H2 | 0.9300 | C19—H19 | 0.9300 |
C3—C4 | 1.517 (2) | C20—C21 | 1.363 (3) |
C3—H3A' | 0.9700 | C20—H20 | 0.9300 |
C3—H3B' | 0.9700 | C21—C22 | 1.388 (3) |
C4—C5 | 1.505 (3) | C21—H21 | 0.9300 |
C4—H4A' | 0.9700 | C22—H22 | 0.9300 |
N4—Cu1—N4i | 180 | C9—C8—H8 | 119.8 |
N4—Cu1—N1 | 90.89 (5) | C7—C8—H8 | 119.8 |
N4i—Cu1—N1 | 89.11 (5) | C8—C9—C10 | 120.3 (2) |
N4—Cu1—N1i | 89.11 (5) | C8—C9—H9 | 119.8 |
N4i—Cu1—N1i | 90.89 (5) | C10—C9—H9 | 119.8 |
N1—Cu1—N1i | 180 | C9—C10—C11 | 120.0 (2) |
H3A—O3—H3B | 114.8 | C9—C10—H10 | 120.0 |
H4A—O4—H4B | 117.3 | C11—C10—H10 | 120.0 |
H5A—O5—H5B | 115.5 | C10—C11—C6 | 120.7 (2) |
C1—N1—C2 | 103.27 (14) | C10—C11—H11 | 119.6 |
C1—N1—Cu1 | 128.79 (11) | C6—C11—H11 | 119.6 |
C2—N1—Cu1 | 127.71 (12) | N6—C12—N4 | 114.62 (16) |
C2—N2—N3 | 102.93 (14) | N6—C12—H12 | 122.7 |
C1—N3—N2 | 109.75 (14) | N4—C12—H12 | 122.7 |
C1—N3—C3 | 130.63 (16) | N4—C13—N5 | 110.30 (15) |
N2—N3—C3 | 119.59 (15) | N4—C13—H13 | 124.8 |
C13—N4—C12 | 102.72 (14) | N5—C13—H13 | 124.8 |
C13—N4—Cu1 | 127.31 (12) | N5—C14—C15 | 112.01 (15) |
C12—N4—Cu1 | 129.95 (12) | N5—C14—H14A | 109.2 |
C13—N5—N6 | 109.76 (14) | C15—C14—H14A | 109.2 |
C13—N5—C14 | 128.26 (15) | N5—C14—H14B | 109.2 |
N6—N5—C14 | 121.88 (14) | C15—C14—H14B | 109.2 |
C12—N6—N5 | 102.60 (14) | H14A—C14—H14B | 107.9 |
N1—C1—N3 | 110.06 (15) | C16—C15—C14 | 110.45 (15) |
N1—C1—H1 | 125.0 | C16—C15—H15A | 109.6 |
N3—C1—H1 | 125.0 | C14—C15—H15A | 109.6 |
N2—C2—N1 | 113.98 (17) | C16—C15—H15B | 109.6 |
N2—C2—H2 | 123.0 | C14—C15—H15B | 109.6 |
N1—C2—H2 | 123.0 | H15A—C15—H15B | 108.1 |
N3—C3—C4 | 111.58 (15) | O2—C16—C17 | 120.38 (16) |
N3—C3—H3A' | 109.3 | O2—C16—C15 | 120.02 (17) |
C4—C3—H3A' | 109.3 | C17—C16—C15 | 119.61 (16) |
N3—C3—H3B' | 109.3 | C22—C17—C18 | 118.62 (18) |
C4—C3—H3B' | 109.3 | C22—C17—C16 | 122.96 (16) |
H3A'—C3—H3B' | 108.0 | C18—C17—C16 | 118.41 (18) |
C5—C4—C3 | 112.82 (16) | C19—C18—C17 | 120.6 (2) |
C5—C4—H4A' | 109.0 | C19—C18—H18 | 119.7 |
C3—C4—H4A' | 109.0 | C17—C18—H18 | 119.7 |
C5—C4—H4B' | 109.0 | C20—C19—C18 | 119.7 (2) |
C3—C4—H4B' | 109.0 | C20—C19—H19 | 120.1 |
H4A'—C4—H4B' | 107.8 | C18—C19—H19 | 120.1 |
O1—C5—C6 | 120.91 (18) | C21—C20—C19 | 120.5 (2) |
O1—C5—C4 | 120.19 (17) | C21—C20—H20 | 119.8 |
C6—C5—C4 | 118.90 (16) | C19—C20—H20 | 119.8 |
C7—C6—C11 | 118.84 (18) | C20—C21—C22 | 120.2 (2) |
C7—C6—C5 | 122.40 (17) | C20—C21—H21 | 119.9 |
C11—C6—C5 | 118.75 (18) | C22—C21—H21 | 119.9 |
C6—C7—C8 | 119.8 (2) | C17—C22—C21 | 120.35 (19) |
C6—C7—H7 | 120.1 | C17—C22—H22 | 119.8 |
C8—C7—H7 | 120.1 | C21—C22—H22 | 119.8 |
C9—C8—C7 | 120.4 (2) | ||
N4—Cu1—N1—C1 | −104.33 (15) | C6—C7—C8—C9 | −0.3 (3) |
N4i—Cu1—N1—C1 | 75.67 (15) | C7—C8—C9—C10 | −0.2 (4) |
N4—Cu1—N1—C2 | 82.13 (15) | C8—C9—C10—C11 | 0.4 (4) |
N4i—Cu1—N1—C2 | −97.87 (15) | C9—C10—C11—C6 | −0.2 (4) |
C2—N2—N3—C1 | 0.0 (2) | C7—C6—C11—C10 | −0.3 (3) |
C2—N2—N3—C3 | −178.24 (16) | C5—C6—C11—C10 | 178.6 (2) |
N1—Cu1—N4—C13 | 119.76 (15) | N5—N6—C12—N4 | −0.1 (2) |
N1i—Cu1—N4—C13 | −60.24 (15) | C13—N4—C12—N6 | 0.0 (2) |
N1—Cu1—N4—C12 | −62.34 (17) | Cu1—N4—C12—N6 | −178.30 (13) |
N1i—Cu1—N4—C12 | 117.66 (17) | C12—N4—C13—N5 | 0.1 (2) |
C13—N5—N6—C12 | 0.1 (2) | Cu1—N4—C13—N5 | 178.45 (11) |
C14—N5—N6—C12 | 176.73 (17) | N6—N5—C13—N4 | −0.1 (2) |
C2—N1—C1—N3 | 0.03 (19) | C14—N5—C13—N4 | −176.48 (16) |
Cu1—N1—C1—N3 | −174.73 (11) | C13—N5—C14—C15 | −122.42 (19) |
N2—N3—C1—N1 | 0.0 (2) | N6—N5—C14—C15 | 61.6 (2) |
C3—N3—C1—N1 | 177.98 (16) | N5—C14—C15—C16 | 174.65 (15) |
N3—N2—C2—N1 | 0.0 (2) | C14—C15—C16—O2 | −5.0 (3) |
C1—N1—C2—N2 | 0.0 (2) | C14—C15—C16—C17 | 175.35 (16) |
Cu1—N1—C2—N2 | 174.81 (13) | O2—C16—C17—C22 | −179.0 (2) |
C1—N3—C3—C4 | 112.7 (2) | C15—C16—C17—C22 | 0.6 (3) |
N2—N3—C3—C4 | −69.5 (2) | O2—C16—C17—C18 | 1.0 (3) |
N3—C3—C4—C5 | −83.5 (2) | C15—C16—C17—C18 | −179.31 (18) |
C3—C4—C5—O1 | 1.7 (3) | C22—C17—C18—C19 | −1.3 (3) |
C3—C4—C5—C6 | −178.31 (16) | C16—C17—C18—C19 | 178.6 (2) |
O1—C5—C6—C7 | 173.1 (2) | C17—C18—C19—C20 | 0.7 (4) |
C4—C5—C6—C7 | −6.9 (3) | C18—C19—C20—C21 | 0.2 (4) |
O1—C5—C6—C11 | −5.7 (3) | C19—C20—C21—C22 | −0.6 (4) |
C4—C5—C6—C11 | 174.27 (18) | C18—C17—C22—C21 | 0.9 (3) |
C11—C6—C7—C8 | 0.5 (3) | C16—C17—C22—C21 | −179.01 (19) |
C5—C6—C7—C8 | −178.3 (2) | C20—C21—C22—C17 | 0.0 (3) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2ii | 0.85 | 2.05 | 2.888 (2) | 169 |
O3—H3B···Cl1 | 0.85 | 2.34 | 3.1853 (17) | 170 |
O4—H4A···Cl1iii | 0.85 | 2.31 | 3.1469 (18) | 170 |
O4—H4B···O5 | 0.85 | 2.05 | 2.807 (3) | 147 |
O5—H5A···O4iv | 0.84 | 2.20 | 2.825 (3) | 131 |
O5—H5B···O3 | 0.84 | 2.05 | 2.837 (3) | 155 |
C9—H9···Cl1v | 0.93 | 2.81 | 3.732 (2) | 169 |
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y, −z; (v) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl2(C11H11N3O)4]·6H2O |
Mr | 1047.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.9853 (6), 10.8365 (7), 28.974 (2) |
β (°) | 95.123 (1) |
V (Å3) | 2497.2 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.32 × 0.28 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.828, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16593, 5891, 4473 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.05 |
No. of reflections | 5891 |
No. of parameters | 313 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.29 |
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 2005), SHELXTL (Sheldrick, 2008).
Cu1—N4 | 2.0196 (13) | Cu1—Cl1 | 2.7738 (5) |
Cu1—N1 | 2.0370 (13) | ||
N4—Cu1—N1 | 90.89 (5) | N4i—Cu1—N1 | 89.11 (5) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2ii | 0.85 | 2.05 | 2.888 (2) | 169 |
O3—H3B···Cl1 | 0.85 | 2.34 | 3.1853 (17) | 170 |
O4—H4A···Cl1iii | 0.85 | 2.31 | 3.1469 (18) | 170 |
O4—H4B···O5 | 0.85 | 2.05 | 2.807 (3) | 147 |
O5—H5A···O4iv | 0.84 | 2.20 | 2.825 (3) | 131 |
O5—H5B···O3 | 0.84 | 2.05 | 2.837 (3) | 155 |
C9—H9···Cl1v | 0.93 | 2.81 | 3.732 (2) | 169 |
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y, −z; (v) −x, y+1/2, −z+1/2. |
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Noncovalent interactions have received much interest in crystal engineering of supramolecular architecture. A convenient and efficient approach to crystal engineering is the synthesis of reliable synthons that can control the dimensionality of the molecular architecture. Classical hydrogen-bonding interactions have played an important role in crystal engineering and have been investigated in much detail (Moulton & Zaworotko, 2001; Desiraju, 2002; Steiner, 2002; Beatty, 2003; Aakeröy & Seddon, 1993; Aakeröy & Beatty, 2001; Janiak, 2000; Braga & Grepioni, 2000), while the studies of other weak interactions, such as halogen-bond contacts, have received attention only in more recent years (Fourmigue & Batail, 2004; Metrangolo et al., 2005; Metrangolo et al., 2006; Politzer et al., 2007). Neutral organic ligands containing rigid or flexible triazole-like spacers, such as 1,4-bis(triazol-1-ylmethyl)benzene, have been used to generate a rich variety of metal–organic architectures with different metal ions by various reaction procedures (Ding et al., 2009). In our recent research, the 1-phenyl-3-(1H-1,2,4-triazol-1-yl)propan-1-one (L) ligand, with two methylene Csp3 atoms, is highly flexible and can assume a variable dihedral angle. These ligands can produce architectures quite different from those obtained from triazole-based ligands. For the L ligand, a variety of nickel and cobalt compounds have been reported (Jian et al., 2003, 2004; Guo, 2010), while for CuII fewer compounds have been reported.
As a continuation of this work, we report here the title mononuclear copper(II) complex [CuCl2L4].6H2O, (I), which is located on an inversion centre (Fig. 1). The CuII ion is six-coordinated by four N atoms [N1, N4, N1i and N4i; symmetry code: (i) -x, -y + 1, -z] from four L ligands and by two chloride atoms (Cl1 and Cl1i). The structure is completed by three independent solvent water molecules (O3, O4 and O5). The axial Cu—Cl distances [2.7738 (5) Å] are much longer than the Cu—N distances [2.0364 (15) and 2.0206 (15) Å], indicative of a distorted octahedral environment with [Which?] axis elongated. The triazole and phenyl rings of L are not coplanar: the corresponding dihedral angles formed by the least-squares planes of the phenyl and triazole rings are 69.27 (11) and 52.74 (11)°, respectively.
All water H atoms could be located in the Fourier difference map and all are involved in hydrogen bonds; the geometric parameters of the hydrogen bonding are collected in Table 2. It is interesting that a cyclic water tetramer is located in between and parallel to two Cu atoms, formed by hydrogen bonding between atoms O3, Cl1iii, O5 and O4 and their symmetry-related counterparts [Revised text OK?] [O5—H5B···O3 = 2.837 (3) Å and O4—H4A···Cl1iii = 3.1469 (18) Å; symmetry code: x + 1, y, z]. The coordination environment of the water tetramers is shown in Fig. 2. Each water molecule in the cluster is involved in the formation of three hydrogen bonds, two from a water–water interaction and one from a water–host interaction. Within the cluster, the four water molecules are fully coplanar and each water monomer acts as both a single hydrogen-bond donor and acceptor. Such an arrangement results in the formation of an irregular up–up–down–down (uudd) water tetramer that was also reported by Long et al. (2004). The hydrogen-bond distances and angles within the water tetramer are as follows: O4···O5 = 2.808 (3) Å, O5···O4iv = 2.826 (3) Å, O4—H4B···O5 = 147° and O5—H5A···O4iv = 131°. The average hydrogen-bond distance within the water tetramer is 2.816 Å, significantly longer than the value of 2.78 Å found in the udud water tetramer of (D2O)4 in the gas phase (Cruzan et al., 1996) and the value of 2.743 Å calculated in the discrete udud water tetramer (Xantheas, 1994, 1995).
There are two chloride anions in the asymmetric unit of (I), each with the same supramolecular contacts and function. Atom Cl1 links the tetramers into a one-dimensional chain (Fig. 3). Each Cl atom forms two hydrogen bonds with an average (O)H···Cl1 distance of 2.325 Å. As shown in Fig. 4, the O atoms of the solvent water molecules, the Cl atoms and the N atoms from the ligands generate the intermolecular hydrogen bonding and form a novel two-dimensional layer in the ab plane. Intermolecular C9—H9···Cl1v (see Table 2 for details) hydrogen bonds extend these two-dimensional layers to generate a three-dimensional supramolecular network in the bc plane, as shown in Fig. 5.
In summary, weak C—H···Cl hydrogen-bond interactions are quite important for the assembly of three-dimensional supramolecular architectures. Subtle changes inthese weak interactions, such as the formation of water clusters, may be helpful for a deeper understanding of similar weak interactions as important driving forces in biological systems.