Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113030163/sf3208sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113030163/sf3208Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113030163/sf3208IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113030163/sf3208IIIsup4.hkl |
CCDC references: 969907; 969908; 969909
Polymetric metal–organic complexes have attracted tremendous attention over recent decades because of their fascinating topologies (Eddaoudi et al., 2002; Chakrabary et al., 2011) and enormous potential for many practical applications, such as gas storage (Li & Yang, 2007; Kim et al., 2013), heterogeneous catalysis (Huang et al., 2013), drug delivery (Horcajada et al., 2008), ion exchange (Genna et al., 2013), luminescence (Liu et al., 2013) and chemical sensing (Yang et al., 2013). It is well known that fluorene is an excellent chromophore and has been widely studied in the field of organic luminescence (Yue et al., 2010; Peterson et al., 2011). Cuprous compounds have also been investigated as potential optical materials (Fang et al., 2011). Coordination polymers generated from fluorene-based ligands with CuCl could be expected to have good fluorescence properties. Based on this, we synthesized 2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene [L1 or (I)] and 2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene (L2), and two coordination polymers of L1 and L2, viz. [Cu2Cl2L1]n, (II), and [Cu4Cl4(L2)2]n. The structures of (I), (II) and (III) are reported here.
For the preparation of (I), a mixture of 2,7-dibromo-9,9-dimethylfluorene (3.52 g, 10 mmol), imidazole (1.90 g, 28 mmol), copper iodide (0.38 g, 2 mmol), caesium carbonate (13.04 g, 40 mmol) in dimethylformamide (DMF, 20 ml) was stirred under nitrogen at 393 K for 36 h. The reaction was monitored by thin-layer chromatography (TLC). The reaction product was poured into water, suction filtered and the residue purified by silica-gel column chromatography using dichloromethane and ethyl acetate (1:1 v/v) as eluent to afford (I) as a light-yellow solid (yield 2.48 g, 7.60 mmol, 76.1%). A solution of (I) (3.26 mg, 0.010 mmol) in tetrahydrofuran (THF, 10 ml) was left for about 2 d at room temperature, after which time colourless crystals of (I) were obtained (yield 2.34 mg, 71.7%). 1H NMR (300 MHz, CDCl3, 298 K, TMS): δ 8.05–7.12 (m, 6H, –C3H3N2; 6H, –C6H3), 1.59 (s, 6H, –CH3). IR (v, cm-1): 3087.68 (w), 2945.70 (w), 2917.33 (w), 2852.38 (w), 1613.55 (w), 1584.35 (w), 1490.72 (s), 1312.95 (m), 1250.46 (m), 1089.91 (w), 1052.59 (s), 976.15 (w), 903.13 (w), 813.96 (s), 763.38 (m), 732.23 (s), 655.92 (s), 627.12 (m). Elemental analysis (%) calculated for C21H18N4: C 77.30, H 5.52, N 17.18; found: C 77.40, H 5.42, N 17.18.
For the preparation of L2, a mixture of 2,7-dibromo-9,9-dipropylfluorene (3.82 g, 10 mmol), imidazole (1.90 g, 28 mmol), copper iodide (0.38 g, 2 mmol), caesium carbonate (13.04 g, 40 mmol) in DMF (20 ml) was stirred under nitrogen at 393 K for 36 h. The reaction was monitored by TLC. The reaction product was poured into water, suction filtered and the residue was purified by silica-gel column chromatography using dichloromethane and ethyl acetate (1:1 v/v) as eluent to afford L2 as a light-yellow solid (yield 2.80 g, 7.33 mmol, 73.3%). 1H NMR (300 MHz, CDCl3, 298 K, TMS): δ 8.25–7.45 (m, 6H, –C3H3N2; 6H, –C6H3), 2.07 (s, 4H, –CH2), 0.73 (m, 10H, –CH3CH2). IR (v, cm-1): 3107.50 (w), 2958.92 (w), 2924.25 (w), 2857.92 (w), 1614.06 (w), 1587.38 (w),1494.70 (s), 1294.67 (m), 1106.14 (m), 1052.35 (s), 901.77 (m), 796.91 (m), 708.67 (m), 694.07 (s). Elemental analysis (%) calculated for C25H26N4: C 78.53, H 6.81, N 14.66; found: C 78.43, H 6.91, N 14.66.
For the preparation of (II), a mixture of L1 (6.52 mg, 0.020 mmol), CuCl (19.8 mg, 0.20 mmol) and water (2 ml) was sealed in a 5 ml glass tube, heated at 423 K for 72 h and cooled slowly to room temperature over a period of 50 h. Yellow crystals of (II) were obtained (yield 8.11 mg, 0.016 mmol, 77.3%). IR (v, cm-1): 3117.34 (w), 2961.00 (w), 2925.92 (w), 1506.85 (s),1304.18 (m),1253.25 (m), 1118.08 (w), 1058.63 (m), 1052.35 (s), 810.94 (s), 734.45 (s), 644.07 (m), 607.56 (w).
For the preparation of (III), a mixture of L2 (7.64 mg, 0.020 mmol), CuCl (19.8 mg, 0.20 mmol) and water (2 ml) was sealed in a 5 ml glass tube, heated at 423 K for 72 h and cooled slowly to room temperature over a period of 50 h. Yellow crystals of (III) were obtained (yield 6.29 mg, 0.011 mmol, 54.3%). IR (v, cm-1): 3117.10 (w), 2923.92 (w), 2861.25 (w), 1506.02 (s), 1463.76 (m), 1300.25 (m), 1251.81 (m), 1104.75 (w), 1058.18 (m), 808.15 (s), 734.02 (m), 648.20 (m), 622.79 (w).
Crystal data, data collection and structure refinement details are summarized in Table 1. All non-hydrogen atoms were refined with anisotropic displacementparameters·Hydrogen atoms attached to anisotropically refined atoms were placed in geometrically idealized positions and included as riding atoms with C—H = 0.95 Å and Uiso(H) = 1.2*Ueq(C) (aromatic); C—H = 0.98 Å and Uiso(H) = 1.5*Ueq(C) (methyl).
Compound (I) crystallizes in a chiral monoclinic space group P21, with an independent molecule in the asymmetric unit (Fig. 1a). The dihedral angles between the planes of the imidazole rings and fluorene system are 35.0 (9) and 41.7 (9)°. The dihedral angle between the imidazole rings is 78.8 (7)°.
In the crystal structure, molecules of (I) are arranged in chiral chains via C1—H1···N4iii nonclassical hydrogen bonds along the b axis (see Table 2 for symmetry code and geometric details). The H1···N4 distance is shorter than published values of 2.9 Å (Jones et al., 2007) [what is this value for?]. The chains are stacked via two other hydrogen bonds (C5—H5···N4ii and C6—H6···N2i; Fig. 2 and Table 2) ino a two-dimensional network in the ab plane.
In compound (II), there are two crystallographically independent CuI centres (Fig. 1b and Table 3). Atom Cu1 lies in an approximately linear {CuN2} coordination environment consisting of two terminal imidazole N-atom donors (N1 and N4). Atom Cu2 lies in an approximately linear {CuCl2} coordination environment consisting of two cuprous ions (Cl1 and Cl2). Remarkably, complex (II) shows a short Cu···Cu contact [2.928 (5) Å] through which {[CuICl2]-} adheres to the undulating chain. Such close contacts can be interpreted in terms of a weak bonding interaction and compared with the results reported by Neumann et al. (1997), with a Cu···Cu contact of 2.810 (2) Å.
In the extended structure of (II), the chains are linked into a two-dimensional structure through π–π interactions and a C21—H21···Cl2iii hydrogen bond (see Table 4 for symmetry code and geometric details). The H21···Cl2iii distance is shorter than reported in the literature (3.31 Å [what is this value for?]; Bats et al., 2001) (Fig. 4). The π–π interactions between pairs of benzene rings of fluorene exhibit centroid–centroid distances of 3.783 (1) Å.
For (III), there are two CuI centres which are in different approximate trigonal coordination environments (Fig. 1c and Table 5). Atom Cu1 lies in a {CuN2Cl} coordination environment consisting of two terminal imidazole N-atom donors and one chloride ion from the {[CuI2Cl4]2-} unit. The Cu1 centre is deviates slightly (by 0.0615 Å) from the trigonal plane defined by the donor atoms N1, N4 and Cl1. Atom Cu2 lies in a {CuCl3} coordination environment consisting of three chloride ions from the {[CuI2Cl4]2-} unit. The Cu2 centre is deviates slightly (by 0.0188 Å) from the plane defined by the three donor atoms. The {[CuI2Cl4]2-} unit, acting as a bridging unit, links two different chains to a one-dimensional rope-ladder-type chain through a Cu1—Cl1 coordination interaction, and there are C23—H23···Cl1iii nonclassical hydrogen bonds in the chain (Fig. 5, and see Table 6 for symmetry code and geometric details).
In the extended structure of (III), the chains are linked into a two-dimensional net through C9—H9···Cl1iv and C13A–H13A···Cl2Bv hydrogen bonds (Fig. 6 and Table 6). The two-dimensional nets are packed into a three-dimensional framework through π–π interactions between parallel benzene rings of fluorene, with a centroid–centroid distance of 4.094 (4) Å, which is shorter than the value of 4.286 Å reported by Degtyarenko & Domasevitch (2013).
The photoluminescent properties of (II) and (III) were investigated in the solid state after excitation at 449 and 418 nm at room temperature. Complexes (II) and (III) exhibit emission maxima at 542 and 476 nm, respectively, with an obvious red shift for compound (II) (Fig. 7). This may be attributed to the difference of dihedral angles between terminal imidazole and fluorene ring. In compound (II), the dihedral angles are 7.8 (4) and 11.1 (7)°, while that in compound (III) are 25.6 (3) and 11.6 (1)°, which indicate that the terminal imidazole ring and and the fluorene system are more coplanar in (II) than in (III).
In summary, two new coordination polymers have been obtained from the assembly of fluorene-based ligands with cuprous chloride. In compound (II), the {[CuICl2]-} unit adheres to the undulating chain through a weak Cu···Cu interaction, and in (III), the {[CuI2Cl4]2-} unit connects two chains into a rope-ladder-type double chain. Meanwhile, the two compounds show different fluorescence properties. We can thus try to obtain complexes that present different fluorescence properties by controlling the structure formed by cuprous ions and chlorine ions with influence on the coplanarity of terminal imidazole and fluorene ring [not clear]. We are currently extending this study by preparing new symmetric fluorene-based ligands containing other coordination groups.
For related literature, see: Bats et al. (2001); Chakrabary et al. (2011); Degtyarenko & Domasevitch (2013); Eddaoudi et al. (2002); Fang et al. (2011); Genna et al. (2013); Horcajada et al. (2008); Huang et al. (2013); Jones et al. (2007); Kim et al. (2013); Li & Yang (2007); Liu et al. (2013); Neumann et al. (1997); Peterson et al. (2011); Yang et al. (2013); Yue et al. (2010).
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SMART (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 for (I); SHELXTL (Sheldrick, 2008) for (II), (III). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008 for (I); SHELXTL (Sheldrick, 2008) for (II), (III).
C21H18N4 | F(000) = 344 |
Mr = 326.39 | Dx = 1.286 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2yb | Cell parameters from 1540 reflections |
a = 6.616 (3) Å | θ = 3.5–22.4° |
b = 15.683 (6) Å | µ = 0.08 mm−1 |
c = 8.545 (4) Å | T = 298 K |
β = 108.037 (5)° | Block, colourless |
V = 843.1 (6) Å3 | 0.29 × 0.15 × 0.12 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1427 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 25.6°, θmin = 2.5° |
phi and ω scans | h = −7→8 |
4430 measured reflections | k = −9→19 |
1631 independent reflections | l = −10→10 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.0639P] where P = (Fo2 + 2Fc2)/3 |
1631 reflections | (Δ/σ)max = 0.001 |
228 parameters | Δρmax = 0.15 e Å−3 |
1 restraint | Δρmin = −0.23 e Å−3 |
C21H18N4 | V = 843.1 (6) Å3 |
Mr = 326.39 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.616 (3) Å | µ = 0.08 mm−1 |
b = 15.683 (6) Å | T = 298 K |
c = 8.545 (4) Å | 0.29 × 0.15 × 0.12 mm |
β = 108.037 (5)° |
Bruker SMART CCD area-detector diffractometer | 1427 reflections with I > 2σ(I) |
4430 measured reflections | Rint = 0.042 |
1631 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 1 restraint |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.15 e Å−3 |
1631 reflections | Δρmin = −0.23 e Å−3 |
228 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 | 0.4013 (6) | −0.1268 (3) | 1.0206 (5) | 0.0470 (10) | |
H1 | 0.4894 | −0.1641 | 0.9873 | 0.056* | |
C2 | 0.1669 (6) | −0.0773 (3) | 1.1154 (5) | 0.0539 (11) | |
H2 | 0.0573 | −0.0746 | 1.1620 | 0.065* | |
C3 | 0.2549 (6) | −0.0099 (3) | 1.0683 (4) | 0.0449 (10) | |
H3 | 0.2200 | 0.0470 | 1.0761 | 0.054* | |
C4 | 0.5468 (5) | 0.0075 (3) | 0.9427 (4) | 0.0375 (8) | |
C5 | 0.6168 (6) | 0.0862 (2) | 1.0140 (4) | 0.0408 (9) | |
H5 | 0.5719 | 0.1058 | 1.1005 | 0.049* | |
C6 | 0.7516 (6) | 0.1349 (3) | 0.9575 (4) | 0.0430 (9) | |
H6 | 0.7969 | 0.1879 | 1.0042 | 0.052* | |
C7 | 0.8198 (5) | 0.1043 (2) | 0.8299 (4) | 0.0366 (8) | |
C8 | 0.7452 (5) | 0.0263 (2) | 0.7564 (4) | 0.0359 (8) | |
C9 | 0.6089 (5) | −0.0227 (2) | 0.8118 (4) | 0.0393 (8) | |
H9 | 0.5595 | −0.0748 | 0.7628 | 0.047* | |
C10 | 0.8331 (5) | 0.0086 (2) | 0.6135 (4) | 0.0369 (8) | |
C11 | 0.6528 (6) | 0.0062 (3) | 0.4498 (4) | 0.0491 (10) | |
H11A | 0.5748 | 0.0588 | 0.4350 | 0.074* | |
H11B | 0.5591 | −0.0404 | 0.4509 | 0.074* | |
H11C | 0.7114 | −0.0014 | 0.3611 | 0.074* | |
C12 | 0.9605 (6) | −0.0743 (3) | 0.6366 (5) | 0.0478 (10) | |
H12A | 0.8684 | −0.1216 | 0.6367 | 0.072* | |
H12B | 1.0729 | −0.0726 | 0.7395 | 0.072* | |
H12C | 1.0200 | −0.0809 | 0.5482 | 0.072* | |
C13 | 0.9729 (5) | 0.0872 (2) | 0.6219 (4) | 0.0362 (8) | |
C14 | 0.9645 (5) | 0.1409 (2) | 0.7498 (4) | 0.0355 (8) | |
C15 | 1.0817 (6) | 0.2155 (2) | 0.7833 (4) | 0.0421 (9) | |
H15 | 1.0784 | 0.2501 | 0.8708 | 0.051* | |
C16 | 1.2034 (6) | 0.2376 (3) | 0.6847 (5) | 0.0447 (9) | |
H16 | 1.2808 | 0.2881 | 0.7040 | 0.054* | |
C17 | 1.2106 (5) | 0.1846 (2) | 0.5568 (4) | 0.0399 (9) | |
C18 | 1.0976 (6) | 0.1087 (2) | 0.5256 (4) | 0.0399 (9) | |
H18 | 1.1060 | 0.0729 | 0.4410 | 0.048* | |
C19 | 1.2812 (7) | 0.2047 (3) | 0.2898 (5) | 0.0522 (11) | |
H19 | 1.1535 | 0.1818 | 0.2239 | 0.063* | |
C20 | 1.5320 (6) | 0.2466 (3) | 0.5064 (5) | 0.0465 (10) | |
H20 | 1.6127 | 0.2594 | 0.6138 | 0.056* | |
C21 | 1.5856 (7) | 0.2603 (3) | 0.3694 (6) | 0.0559 (11) | |
H21 | 1.7137 | 0.2841 | 0.3676 | 0.067* | |
N1 | 0.4079 (5) | −0.0412 (2) | 1.0057 (3) | 0.0386 (7) | |
N2 | 0.2587 (6) | −0.1513 (2) | 1.0863 (5) | 0.0600 (10) | |
N3 | 1.3351 (5) | 0.21008 (19) | 0.4559 (4) | 0.0414 (7) | |
N4 | 1.4267 (6) | 0.2349 (2) | 0.2328 (4) | 0.0585 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.057 (3) | 0.040 (2) | 0.049 (2) | 0.006 (2) | 0.023 (2) | 0.0067 (18) |
C2 | 0.052 (2) | 0.061 (3) | 0.060 (3) | 0.004 (2) | 0.034 (2) | 0.004 (2) |
C3 | 0.045 (2) | 0.048 (3) | 0.042 (2) | 0.0056 (19) | 0.0141 (18) | −0.0040 (18) |
C4 | 0.0367 (19) | 0.0410 (19) | 0.0333 (17) | 0.0035 (18) | 0.0089 (15) | 0.0062 (17) |
C5 | 0.050 (2) | 0.040 (2) | 0.0347 (19) | 0.0005 (19) | 0.0154 (17) | −0.0030 (17) |
C6 | 0.052 (2) | 0.039 (2) | 0.039 (2) | −0.0011 (19) | 0.0141 (19) | −0.0068 (17) |
C7 | 0.0361 (19) | 0.034 (2) | 0.0349 (18) | 0.0025 (16) | 0.0044 (15) | 0.0031 (16) |
C8 | 0.0335 (18) | 0.038 (2) | 0.0315 (17) | 0.0035 (16) | 0.0041 (15) | 0.0012 (16) |
C9 | 0.0383 (19) | 0.0386 (19) | 0.0374 (18) | −0.0008 (17) | 0.0065 (16) | −0.0012 (16) |
C10 | 0.0395 (18) | 0.0370 (18) | 0.0328 (17) | −0.0012 (18) | 0.0091 (15) | −0.0040 (17) |
C11 | 0.054 (2) | 0.051 (2) | 0.0378 (19) | −0.007 (2) | 0.0076 (17) | −0.0022 (19) |
C12 | 0.055 (2) | 0.042 (2) | 0.048 (2) | 0.001 (2) | 0.0180 (19) | −0.0052 (18) |
C13 | 0.0327 (18) | 0.041 (2) | 0.0331 (18) | 0.0060 (17) | 0.0074 (15) | 0.0026 (16) |
C14 | 0.0348 (19) | 0.036 (2) | 0.0339 (19) | 0.0052 (17) | 0.0079 (16) | 0.0011 (16) |
C15 | 0.047 (2) | 0.041 (2) | 0.039 (2) | −0.0035 (18) | 0.0143 (18) | −0.0079 (17) |
C16 | 0.043 (2) | 0.041 (2) | 0.048 (2) | −0.009 (2) | 0.0107 (17) | −0.0049 (19) |
C17 | 0.036 (2) | 0.041 (2) | 0.043 (2) | −0.0001 (18) | 0.0138 (17) | 0.0036 (18) |
C18 | 0.043 (2) | 0.040 (2) | 0.0366 (19) | 0.0003 (18) | 0.0126 (17) | −0.0062 (16) |
C19 | 0.059 (2) | 0.055 (3) | 0.045 (2) | −0.005 (2) | 0.020 (2) | −0.006 (2) |
C20 | 0.039 (2) | 0.046 (2) | 0.051 (2) | −0.006 (2) | 0.0090 (18) | 0.0014 (19) |
C21 | 0.052 (2) | 0.046 (3) | 0.076 (3) | −0.007 (2) | 0.029 (2) | 0.003 (2) |
N1 | 0.0419 (18) | 0.0398 (17) | 0.0335 (16) | 0.0023 (15) | 0.0112 (14) | 0.0008 (14) |
N2 | 0.069 (2) | 0.054 (2) | 0.068 (2) | −0.002 (2) | 0.038 (2) | 0.0103 (19) |
N3 | 0.0432 (16) | 0.0375 (17) | 0.0441 (18) | 0.0009 (15) | 0.0145 (14) | −0.0010 (15) |
N4 | 0.072 (2) | 0.061 (2) | 0.055 (2) | −0.007 (2) | 0.036 (2) | −0.0046 (18) |
C1—N2 | 1.297 (5) | C11—H11B | 0.9600 |
C1—N1 | 1.352 (5) | C11—H11C | 0.9600 |
C1—H1 | 0.9300 | C12—H12A | 0.9600 |
C2—C3 | 1.328 (6) | C12—H12B | 0.9600 |
C2—N2 | 1.368 (6) | C12—H12C | 0.9600 |
C2—H2 | 0.9300 | C13—C18 | 1.376 (5) |
C3—N1 | 1.373 (4) | C13—C14 | 1.394 (5) |
C3—H3 | 0.9300 | C14—C15 | 1.383 (5) |
C4—C9 | 1.389 (5) | C15—C16 | 1.377 (5) |
C4—C5 | 1.391 (5) | C15—H15 | 0.9300 |
C4—N1 | 1.422 (4) | C16—C17 | 1.386 (5) |
C5—C6 | 1.371 (5) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | C17—C18 | 1.387 (5) |
C6—C7 | 1.388 (5) | C17—N3 | 1.422 (4) |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.394 (5) | C19—N4 | 1.296 (5) |
C7—C14 | 1.457 (5) | C19—N3 | 1.355 (5) |
C8—C9 | 1.375 (5) | C19—H19 | 0.9300 |
C8—C10 | 1.531 (5) | C20—C21 | 1.341 (6) |
C9—H9 | 0.9300 | C20—N3 | 1.365 (5) |
C10—C13 | 1.529 (5) | C20—H20 | 0.9300 |
C10—C12 | 1.530 (5) | C21—N4 | 1.366 (5) |
C10—C11 | 1.532 (5) | C21—H21 | 0.9300 |
C11—H11A | 0.9600 | ||
N2—C1—N1 | 112.6 (4) | C10—C12—H12B | 109.5 |
N2—C1—H1 | 123.7 | H12A—C12—H12B | 109.5 |
N1—C1—H1 | 123.7 | C10—C12—H12C | 109.5 |
C3—C2—N2 | 111.0 (3) | H12A—C12—H12C | 109.5 |
C3—C2—H2 | 124.5 | H12B—C12—H12C | 109.5 |
N2—C2—H2 | 124.5 | C18—C13—C14 | 119.8 (3) |
C2—C3—N1 | 106.2 (4) | C18—C13—C10 | 129.5 (3) |
C2—C3—H3 | 126.9 | C14—C13—C10 | 110.7 (3) |
N1—C3—H3 | 126.9 | C15—C14—C13 | 121.2 (3) |
C9—C4—C5 | 120.9 (3) | C15—C14—C7 | 130.1 (3) |
C9—C4—N1 | 120.6 (3) | C13—C14—C7 | 108.8 (3) |
C5—C4—N1 | 118.5 (3) | C16—C15—C14 | 118.8 (3) |
C6—C5—C4 | 120.4 (3) | C16—C15—H15 | 120.6 |
C6—C5—H5 | 119.8 | C14—C15—H15 | 120.6 |
C4—C5—H5 | 119.8 | C15—C16—C17 | 120.1 (3) |
C5—C6—C7 | 119.2 (4) | C15—C16—H16 | 120.0 |
C5—C6—H6 | 120.4 | C17—C16—H16 | 120.0 |
C7—C6—H6 | 120.4 | C16—C17—C18 | 121.2 (3) |
C6—C7—C8 | 120.1 (3) | C16—C17—N3 | 118.5 (3) |
C6—C7—C14 | 130.9 (3) | C18—C17—N3 | 120.3 (3) |
C8—C7—C14 | 109.0 (3) | C13—C18—C17 | 118.9 (3) |
C9—C8—C7 | 120.9 (3) | C13—C18—H18 | 120.6 |
C9—C8—C10 | 128.7 (3) | C17—C18—H18 | 120.6 |
C7—C8—C10 | 110.4 (3) | N4—C19—N3 | 112.7 (4) |
C8—C9—C4 | 118.4 (4) | N4—C19—H19 | 123.6 |
C8—C9—H9 | 120.8 | N3—C19—H19 | 123.6 |
C4—C9—H9 | 120.8 | C21—C20—N3 | 106.0 (4) |
C13—C10—C12 | 112.2 (3) | C21—C20—H20 | 127.0 |
C13—C10—C8 | 101.0 (3) | N3—C20—H20 | 127.0 |
C12—C10—C8 | 112.4 (3) | C20—C21—N4 | 110.9 (4) |
C13—C10—C11 | 110.6 (3) | C20—C21—H21 | 124.5 |
C12—C10—C11 | 109.8 (3) | N4—C21—H21 | 124.5 |
C8—C10—C11 | 110.6 (3) | C1—N1—C3 | 105.6 (3) |
C10—C11—H11A | 109.5 | C1—N1—C4 | 127.8 (3) |
C10—C11—H11B | 109.5 | C3—N1—C4 | 126.6 (3) |
H11A—C11—H11B | 109.5 | C1—N2—C2 | 104.6 (4) |
C10—C11—H11C | 109.5 | C19—N3—C20 | 105.8 (3) |
H11A—C11—H11C | 109.5 | C19—N3—C17 | 127.1 (3) |
H11B—C11—H11C | 109.5 | C20—N3—C17 | 127.0 (3) |
C10—C12—H12A | 109.5 | C19—N4—C21 | 104.5 (3) |
N2—C2—C3—N1 | 0.4 (5) | C6—C7—C14—C13 | −177.0 (4) |
C9—C4—C5—C6 | −1.0 (5) | C8—C7—C14—C13 | 2.4 (4) |
N1—C4—C5—C6 | 179.7 (3) | C13—C14—C15—C16 | 1.9 (5) |
C4—C5—C6—C7 | −0.9 (5) | C7—C14—C15—C16 | −177.9 (3) |
C5—C6—C7—C8 | 2.4 (5) | C14—C15—C16—C17 | −1.4 (5) |
C5—C6—C7—C14 | −178.3 (3) | C15—C16—C17—C18 | −0.3 (5) |
C6—C7—C8—C9 | −2.0 (5) | C15—C16—C17—N3 | 179.0 (3) |
C14—C7—C8—C9 | 178.5 (3) | C14—C13—C18—C17 | −0.9 (5) |
C6—C7—C8—C10 | 176.9 (3) | C10—C13—C18—C17 | 179.6 (3) |
C14—C7—C8—C10 | −2.6 (4) | C16—C17—C18—C13 | 1.5 (5) |
C7—C8—C9—C4 | 0.1 (5) | N3—C17—C18—C13 | −177.8 (3) |
C10—C8—C9—C4 | −178.6 (3) | N3—C20—C21—N4 | 1.0 (5) |
C5—C4—C9—C8 | 1.4 (5) | N2—C1—N1—C3 | 0.0 (5) |
N1—C4—C9—C8 | −179.3 (3) | N2—C1—N1—C4 | 178.5 (3) |
C9—C8—C10—C13 | −179.5 (3) | C2—C3—N1—C1 | −0.2 (4) |
C7—C8—C10—C13 | 1.7 (3) | C2—C3—N1—C4 | −178.8 (3) |
C9—C8—C10—C12 | −59.8 (5) | C9—C4—N1—C1 | 36.3 (5) |
C7—C8—C10—C12 | 121.4 (3) | C5—C4—N1—C1 | −144.4 (4) |
C9—C8—C10—C11 | 63.3 (5) | C9—C4—N1—C3 | −145.5 (3) |
C7—C8—C10—C11 | −115.5 (3) | C5—C4—N1—C3 | 33.8 (5) |
C12—C10—C13—C18 | 59.4 (4) | N1—C1—N2—C2 | 0.2 (5) |
C8—C10—C13—C18 | 179.3 (3) | C3—C2—N2—C1 | −0.4 (5) |
C11—C10—C13—C18 | −63.5 (5) | N4—C19—N3—C20 | −0.2 (5) |
C12—C10—C13—C14 | −120.0 (3) | N4—C19—N3—C17 | 178.6 (4) |
C8—C10—C13—C14 | −0.1 (3) | C21—C20—N3—C19 | −0.5 (4) |
C11—C10—C13—C14 | 117.0 (3) | C21—C20—N3—C17 | −179.3 (4) |
C18—C13—C14—C15 | −0.8 (5) | C16—C17—N3—C19 | −137.1 (4) |
C10—C13—C14—C15 | 178.8 (3) | C18—C17—N3—C19 | 42.1 (5) |
C18—C13—C14—C7 | 179.1 (3) | C16—C17—N3—C20 | 41.5 (5) |
C10—C13—C14—C7 | −1.3 (4) | C18—C17—N3—C20 | −139.2 (4) |
C6—C7—C14—C15 | 2.9 (6) | N3—C19—N4—C21 | 0.8 (5) |
C8—C7—C14—C15 | −177.7 (3) | C20—C21—N4—C19 | −1.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···N2i | 0.93 | 2.63 | 3.371 (6) | 137 |
C5—H5···N4ii | 0.93 | 2.64 | 3.460 (5) | 147 |
C1—H1···N4iii | 0.93 | 2.65 | 3.494 (5) | 152 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x−1, y, z+1; (iii) −x+2, y−1/2, −z+1. |
[Cu2Cl2(C21H18N4)] | F(000) = 1056 |
Mr = 524.37 | Dx = 1.700 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 3555 reflections |
a = 12.749 (9) Å | θ = 2.7–27.2° |
b = 17.215 (11) Å | µ = 2.35 mm−1 |
c = 9.489 (6) Å | T = 298 K |
β = 100.402 (9)° | Bar, pink |
V = 2048 (2) Å3 | 0.48 × 0.23 × 0.16 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3831 independent reflections |
Radiation source: fine-focus sealed tube | 2755 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
phi and ω scans | θmax = 25.6°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −13→15 |
Tmin = 0.398, Tmax = 0.705 | k = −20→18 |
10566 measured reflections | l = −11→11 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.099P)2] where P = (Fo2 + 2Fc2)/3 |
3831 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 0.91 e Å−3 |
0 restraints | Δρmin = −0.87 e Å−3 |
[Cu2Cl2(C21H18N4)] | V = 2048 (2) Å3 |
Mr = 524.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.749 (9) Å | µ = 2.35 mm−1 |
b = 17.215 (11) Å | T = 298 K |
c = 9.489 (6) Å | 0.48 × 0.23 × 0.16 mm |
β = 100.402 (9)° |
Bruker SMART CCD area-detector diffractometer | 3831 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2755 reflections with I > 2σ(I) |
Tmin = 0.398, Tmax = 0.705 | Rint = 0.069 |
10566 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.91 e Å−3 |
3831 reflections | Δρmin = −0.87 e Å−3 |
264 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 | 0.6949 (4) | 0.3358 (3) | 0.7449 (5) | 0.0547 (13) | |
H1 | 0.7418 | 0.3699 | 0.8002 | 0.066* | |
C2 | 0.6200 (4) | 0.3566 (3) | 0.6310 (6) | 0.0549 (14) | |
H2 | 0.6052 | 0.4066 | 0.5960 | 0.066* | |
C3 | 0.6160 (4) | 0.2320 (3) | 0.6638 (5) | 0.0434 (11) | |
H3 | 0.5967 | 0.1799 | 0.6525 | 0.052* | |
C4 | 0.4862 (3) | 0.2815 (2) | 0.4563 (4) | 0.0325 (9) | |
C5 | 0.4586 (3) | 0.2085 (2) | 0.3991 (5) | 0.0376 (10) | |
H5 | 0.4958 | 0.1652 | 0.4399 | 0.045* | |
C6 | 0.3782 (3) | 0.1990 (2) | 0.2843 (4) | 0.0339 (9) | |
H6 | 0.3584 | 0.1495 | 0.2502 | 0.041* | |
C7 | 0.3262 (3) | 0.2642 (2) | 0.2187 (4) | 0.0298 (8) | |
C8 | 0.3552 (3) | 0.3387 (2) | 0.2740 (4) | 0.0332 (9) | |
C9 | 0.4336 (3) | 0.3480 (2) | 0.3928 (4) | 0.0368 (10) | |
H9 | 0.4514 | 0.3971 | 0.4303 | 0.044* | |
C10 | 0.2905 (3) | 0.4015 (2) | 0.1815 (4) | 0.0358 (9) | |
C11 | 0.2225 (4) | 0.4498 (2) | 0.2671 (5) | 0.0432 (11) | |
H11A | 0.1886 | 0.4913 | 0.2082 | 0.065* | |
H11B | 0.2673 | 0.4711 | 0.3503 | 0.065* | |
H11C | 0.1691 | 0.4173 | 0.2961 | 0.065* | |
C12 | 0.3639 (4) | 0.4557 (3) | 0.1148 (5) | 0.0472 (11) | |
H12A | 0.4068 | 0.4254 | 0.0620 | 0.071* | |
H12B | 0.4093 | 0.4838 | 0.1894 | 0.071* | |
H12C | 0.3214 | 0.4917 | 0.0515 | 0.071* | |
C13 | 0.2203 (3) | 0.3512 (2) | 0.0691 (4) | 0.0322 (9) | |
C14 | 0.2410 (3) | 0.2727 (2) | 0.0954 (4) | 0.0301 (9) | |
C15 | 0.1829 (3) | 0.2170 (2) | 0.0049 (4) | 0.0344 (9) | |
H15 | 0.1952 | 0.1642 | 0.0214 | 0.041* | |
C16 | 0.1072 (3) | 0.2420 (2) | −0.1091 (5) | 0.0369 (9) | |
H16 | 0.0677 | 0.2056 | −0.1689 | 0.044* | |
C17 | 0.0892 (3) | 0.3200 (2) | −0.1355 (4) | 0.0314 (9) | |
C18 | 0.1445 (3) | 0.3764 (2) | −0.0449 (4) | 0.0351 (9) | |
H18 | 0.1308 | 0.4290 | −0.0608 | 0.042* | |
C19 | −0.0034 (4) | 0.4189 (3) | −0.3096 (6) | 0.0630 (16) | |
H19 | 0.0306 | 0.4635 | −0.2692 | 0.076* | |
C20 | −0.0774 (4) | 0.4156 (3) | −0.4282 (6) | 0.0613 (15) | |
H20 | −0.1043 | 0.4581 | −0.4840 | 0.074* | |
C21 | −0.0509 (3) | 0.2993 (3) | −0.3515 (5) | 0.0423 (11) | |
H21 | −0.0545 | 0.2456 | −0.3433 | 0.051* | |
Cl1 | 0.65855 (15) | 0.02121 (12) | 0.8299 (2) | 0.0946 (6) | |
Cl2 | 0.88472 (16) | 0.10157 (9) | 0.5935 (2) | 0.0916 (6) | |
Cu1 | 0.78789 (5) | 0.20173 (4) | 0.89997 (6) | 0.0511 (2) | |
Cu2 | 0.77042 (6) | 0.06509 (4) | 0.71334 (8) | 0.0729 (3) | |
N1 | 0.6917 (3) | 0.2586 (2) | 0.7663 (4) | 0.0431 (9) | |
N2 | 0.5701 (3) | 0.28965 (19) | 0.5776 (4) | 0.0352 (8) | |
N3 | 0.0134 (3) | 0.3451 (2) | −0.2583 (3) | 0.0351 (8) | |
N4 | −0.1078 (3) | 0.3396 (2) | −0.4553 (4) | 0.0424 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.059 (3) | 0.048 (3) | 0.043 (3) | −0.012 (2) | −0.027 (2) | 0.001 (2) |
C2 | 0.060 (3) | 0.033 (3) | 0.056 (3) | −0.009 (2) | −0.031 (2) | 0.013 (2) |
C3 | 0.049 (3) | 0.035 (2) | 0.035 (3) | 0.0092 (19) | −0.022 (2) | −0.0002 (19) |
C4 | 0.032 (2) | 0.037 (2) | 0.024 (2) | 0.0031 (16) | −0.0071 (16) | 0.0041 (16) |
C5 | 0.043 (2) | 0.033 (2) | 0.032 (2) | 0.0052 (18) | −0.0066 (18) | 0.0081 (17) |
C6 | 0.042 (2) | 0.026 (2) | 0.030 (2) | −0.0001 (16) | −0.0050 (18) | 0.0040 (16) |
C7 | 0.034 (2) | 0.029 (2) | 0.022 (2) | −0.0003 (15) | −0.0066 (16) | −0.0005 (15) |
C8 | 0.036 (2) | 0.031 (2) | 0.027 (2) | 0.0047 (16) | −0.0088 (17) | 0.0024 (17) |
C9 | 0.041 (2) | 0.028 (2) | 0.034 (2) | 0.0001 (16) | −0.0131 (18) | −0.0031 (17) |
C10 | 0.045 (2) | 0.025 (2) | 0.028 (2) | 0.0010 (17) | −0.0187 (18) | −0.0018 (16) |
C11 | 0.054 (3) | 0.031 (2) | 0.038 (3) | 0.0074 (19) | −0.011 (2) | −0.0027 (18) |
C12 | 0.053 (3) | 0.038 (2) | 0.042 (3) | −0.0038 (19) | −0.015 (2) | 0.004 (2) |
C13 | 0.037 (2) | 0.027 (2) | 0.027 (2) | −0.0002 (15) | −0.0103 (17) | −0.0042 (16) |
C14 | 0.037 (2) | 0.029 (2) | 0.021 (2) | 0.0012 (16) | −0.0042 (16) | −0.0014 (15) |
C15 | 0.041 (2) | 0.027 (2) | 0.030 (2) | −0.0021 (16) | −0.0068 (18) | −0.0033 (16) |
C16 | 0.038 (2) | 0.034 (2) | 0.033 (2) | −0.0038 (17) | −0.0088 (18) | −0.0073 (18) |
C17 | 0.028 (2) | 0.034 (2) | 0.025 (2) | 0.0020 (16) | −0.0115 (16) | −0.0034 (16) |
C18 | 0.038 (2) | 0.030 (2) | 0.029 (2) | 0.0028 (16) | −0.0139 (17) | −0.0051 (17) |
C19 | 0.079 (4) | 0.031 (3) | 0.059 (3) | 0.000 (2) | −0.042 (3) | 0.003 (2) |
C20 | 0.071 (4) | 0.041 (3) | 0.055 (3) | 0.001 (2) | −0.035 (3) | 0.003 (2) |
C21 | 0.045 (3) | 0.042 (3) | 0.031 (2) | −0.0057 (19) | −0.0160 (19) | −0.0025 (19) |
Cl1 | 0.0933 (12) | 0.1121 (14) | 0.0703 (11) | 0.0218 (10) | −0.0075 (9) | −0.0288 (10) |
Cl2 | 0.1080 (13) | 0.0503 (9) | 0.1051 (14) | −0.0130 (8) | −0.0111 (10) | −0.0052 (8) |
Cu1 | 0.0478 (4) | 0.0591 (4) | 0.0352 (4) | 0.0098 (3) | −0.0223 (3) | 0.0048 (3) |
Cu2 | 0.0828 (6) | 0.0565 (5) | 0.0644 (5) | 0.0184 (3) | −0.0272 (4) | −0.0178 (3) |
N1 | 0.041 (2) | 0.048 (2) | 0.032 (2) | 0.0064 (16) | −0.0149 (16) | 0.0019 (17) |
N2 | 0.038 (2) | 0.0344 (19) | 0.0277 (19) | 0.0014 (14) | −0.0098 (15) | 0.0038 (14) |
N3 | 0.0334 (18) | 0.0347 (19) | 0.0295 (19) | −0.0012 (14) | −0.0152 (14) | −0.0050 (14) |
N4 | 0.042 (2) | 0.047 (2) | 0.030 (2) | −0.0018 (16) | −0.0162 (15) | −0.0030 (16) |
C1—N1 | 1.346 (6) | C12—H12B | 0.9600 |
C1—C2 | 1.355 (6) | C12—H12C | 0.9600 |
C1—H1 | 0.9300 | C13—C18 | 1.383 (5) |
C2—N2 | 1.369 (6) | C13—C14 | 1.391 (6) |
C2—H2 | 0.9300 | C14—C15 | 1.406 (5) |
C3—N1 | 1.323 (6) | C15—C16 | 1.382 (6) |
C3—N2 | 1.351 (5) | C15—H15 | 0.9300 |
C3—H3 | 0.9300 | C16—C17 | 1.378 (6) |
C4—C5 | 1.389 (6) | C16—H16 | 0.9300 |
C4—C9 | 1.406 (6) | C17—C18 | 1.400 (5) |
C4—N2 | 1.430 (5) | C17—N3 | 1.440 (5) |
C5—C6 | 1.364 (6) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.333 (6) |
C6—C7 | 1.393 (5) | C19—N3 | 1.364 (6) |
C6—H6 | 0.9300 | C19—H19 | 0.9300 |
C7—C8 | 1.408 (6) | C20—N4 | 1.376 (6) |
C7—C14 | 1.453 (5) | C20—H20 | 0.9300 |
C8—C9 | 1.374 (5) | C21—N4 | 1.311 (6) |
C8—C10 | 1.536 (5) | C21—N3 | 1.347 (5) |
C9—H9 | 0.9300 | C21—H21 | 0.9300 |
C10—C13 | 1.531 (5) | Cl1—Cu2 | 2.097 (2) |
C10—C11 | 1.535 (6) | Cl2—Cu2 | 2.100 (2) |
C10—C12 | 1.535 (6) | Cu1—N4i | 1.871 (4) |
C11—H11A | 0.9600 | Cu1—N1 | 1.873 (4) |
C11—H11B | 0.9600 | Cu1—Cu2 | 2.9285 (17) |
C11—H11C | 0.9600 | N4—Cu1ii | 1.871 (4) |
C12—H12A | 0.9600 | ||
N1—C1—C2 | 110.2 (4) | C18—C13—C14 | 121.8 (4) |
N1—C1—H1 | 124.9 | C18—C13—C10 | 127.3 (4) |
C2—C1—H1 | 124.9 | C14—C13—C10 | 110.9 (3) |
C1—C2—N2 | 106.6 (4) | C13—C14—C15 | 119.5 (4) |
C1—C2—H2 | 126.7 | C13—C14—C7 | 109.4 (3) |
N2—C2—H2 | 126.7 | C15—C14—C7 | 131.1 (4) |
N1—C3—N2 | 111.7 (4) | C16—C15—C14 | 118.8 (4) |
N1—C3—H3 | 124.2 | C16—C15—H15 | 120.6 |
N2—C3—H3 | 124.2 | C14—C15—H15 | 120.6 |
C5—C4—C9 | 120.1 (4) | C17—C16—C15 | 121.0 (4) |
C5—C4—N2 | 120.2 (3) | C17—C16—H16 | 119.5 |
C9—C4—N2 | 119.7 (4) | C15—C16—H16 | 119.5 |
C6—C5—C4 | 121.4 (4) | C16—C17—C18 | 121.0 (4) |
C6—C5—H5 | 119.3 | C16—C17—N3 | 120.3 (3) |
C4—C5—H5 | 119.3 | C18—C17—N3 | 118.7 (3) |
C5—C6—C7 | 119.3 (4) | C13—C18—C17 | 117.8 (4) |
C5—C6—H6 | 120.4 | C13—C18—H18 | 121.1 |
C7—C6—H6 | 120.4 | C17—C18—H18 | 121.1 |
C6—C7—C8 | 119.7 (4) | C20—C19—N3 | 107.7 (4) |
C6—C7—C14 | 131.9 (4) | C20—C19—H19 | 126.2 |
C8—C7—C14 | 108.4 (3) | N3—C19—H19 | 126.2 |
C9—C8—C7 | 121.0 (4) | C19—C20—N4 | 109.3 (4) |
C9—C8—C10 | 128.4 (4) | C19—C20—H20 | 125.3 |
C7—C8—C10 | 110.5 (3) | N4—C20—H20 | 125.3 |
C8—C9—C4 | 118.4 (4) | N4—C21—N3 | 111.9 (4) |
C8—C9—H9 | 120.8 | N4—C21—H21 | 124.1 |
C4—C9—H9 | 120.8 | N3—C21—H21 | 124.1 |
C13—C10—C11 | 111.1 (3) | N4i—Cu1—N1 | 170.84 (17) |
C13—C10—C12 | 112.3 (4) | N4i—Cu1—Cu2 | 96.01 (13) |
C11—C10—C12 | 109.5 (3) | N1—Cu1—Cu2 | 92.38 (12) |
C13—C10—C8 | 100.7 (3) | Cl1—Cu2—Cl2 | 176.28 (7) |
C11—C10—C8 | 112.1 (3) | Cl1—Cu2—Cu1 | 87.43 (7) |
C12—C10—C8 | 111.0 (4) | Cl2—Cu2—Cu1 | 95.90 (6) |
C10—C11—H11A | 109.5 | C3—N1—C1 | 105.6 (4) |
C10—C11—H11B | 109.5 | C3—N1—Cu1 | 128.2 (3) |
H11A—C11—H11B | 109.5 | C1—N1—Cu1 | 125.8 (3) |
C10—C11—H11C | 109.5 | C3—N2—C2 | 105.9 (4) |
H11A—C11—H11C | 109.5 | C3—N2—C4 | 126.5 (4) |
H11B—C11—H11C | 109.5 | C2—N2—C4 | 127.7 (3) |
C10—C12—H12A | 109.5 | C21—N3—C19 | 105.8 (4) |
C10—C12—H12B | 109.5 | C21—N3—C17 | 126.6 (4) |
H12A—C12—H12B | 109.5 | C19—N3—C17 | 127.4 (3) |
C10—C12—H12C | 109.5 | C21—N4—C20 | 105.3 (4) |
H12A—C12—H12C | 109.5 | C21—N4—Cu1ii | 125.0 (3) |
H12B—C12—H12C | 109.5 | C20—N4—Cu1ii | 129.6 (3) |
N1—C1—C2—N2 | −1.5 (6) | C15—C16—C17—N3 | 177.2 (4) |
C9—C4—C5—C6 | −2.4 (6) | C14—C13—C18—C17 | −0.7 (6) |
N2—C4—C5—C6 | 179.4 (4) | C10—C13—C18—C17 | 179.9 (4) |
C4—C5—C6—C7 | 3.2 (6) | C16—C17—C18—C13 | 2.1 (6) |
C5—C6—C7—C8 | −1.7 (6) | N3—C17—C18—C13 | −177.2 (4) |
C5—C6—C7—C14 | 178.5 (4) | N3—C19—C20—N4 | −0.7 (7) |
C6—C7—C8—C9 | −0.7 (6) | N4i—Cu1—Cu2—Cl1 | 86.60 (14) |
C14—C7—C8—C9 | 179.2 (4) | N1—Cu1—Cu2—Cl1 | −97.09 (14) |
C6—C7—C8—C10 | 177.8 (4) | N4i—Cu1—Cu2—Cl2 | −91.74 (14) |
C14—C7—C8—C10 | −2.3 (5) | N1—Cu1—Cu2—Cl2 | 84.57 (14) |
C7—C8—C9—C4 | 1.5 (6) | N2—C3—N1—C1 | −0.3 (5) |
C10—C8—C9—C4 | −176.7 (4) | N2—C3—N1—Cu1 | −173.0 (3) |
C5—C4—C9—C8 | 0.0 (6) | C2—C1—N1—C3 | 1.1 (6) |
N2—C4—C9—C8 | 178.2 (4) | C2—C1—N1—Cu1 | 174.0 (4) |
C9—C8—C10—C13 | 179.3 (4) | N4i—Cu1—N1—C3 | −179.2 (9) |
C7—C8—C10—C13 | 1.0 (5) | Cu2—Cu1—N1—C3 | 24.5 (4) |
C9—C8—C10—C11 | −62.6 (6) | N4i—Cu1—N1—C1 | 9.5 (13) |
C7—C8—C10—C11 | 119.1 (4) | Cu2—Cu1—N1—C1 | −146.8 (4) |
C9—C8—C10—C12 | 60.2 (6) | N1—C3—N2—C2 | −0.6 (5) |
C7—C8—C10—C12 | −118.1 (4) | N1—C3—N2—C4 | 179.8 (4) |
C11—C10—C13—C18 | 61.4 (6) | C1—C2—N2—C3 | 1.3 (6) |
C12—C10—C13—C18 | −61.6 (6) | C1—C2—N2—C4 | −179.2 (4) |
C8—C10—C13—C18 | −179.8 (4) | C5—C4—N2—C3 | −13.3 (6) |
C11—C10—C13—C14 | −118.1 (4) | C9—C4—N2—C3 | 168.5 (4) |
C12—C10—C13—C14 | 118.9 (4) | C5—C4—N2—C2 | 167.2 (5) |
C8—C10—C13—C14 | 0.8 (5) | C9—C4—N2—C2 | −11.0 (7) |
C18—C13—C14—C15 | −0.6 (6) | N4—C21—N3—C19 | −1.2 (6) |
C10—C13—C14—C15 | 178.9 (4) | N4—C21—N3—C17 | −177.5 (4) |
C18—C13—C14—C7 | 178.3 (4) | C20—C19—N3—C21 | 1.2 (6) |
C10—C13—C14—C7 | −2.2 (5) | C20—C19—N3—C17 | 177.4 (5) |
C6—C7—C14—C13 | −177.3 (4) | C16—C17—N3—C21 | 4.8 (6) |
C8—C7—C14—C13 | 2.8 (4) | C18—C17—N3—C21 | −175.9 (4) |
C6—C7—C14—C15 | 1.5 (7) | C16—C17—N3—C19 | −170.8 (5) |
C8—C7—C14—C15 | −178.4 (4) | C18—C17—N3—C19 | 8.6 (7) |
C13—C14—C15—C16 | 0.6 (6) | N3—C21—N4—C20 | 0.8 (6) |
C7—C14—C15—C16 | −178.0 (4) | N3—C21—N4—Cu1ii | −176.4 (3) |
C14—C15—C16—C17 | 0.8 (6) | C19—C20—N4—C21 | 0.0 (7) |
C15—C16—C17—C18 | −2.2 (6) | C19—C20—N4—Cu1ii | 177.0 (4) |
Symmetry codes: (i) x+1, −y+1/2, z+3/2; (ii) x−1, −y+1/2, z−3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···Cl2iii | 0.93 | 2.63 | 3.519 (5) | 159 |
Symmetry code: (iii) x−1, y, z−1. |
[Cu2Cl2(C25H26N4)] | Z = 2 |
Mr = 580.48 | F(000) = 592 |
Triclinic, P1 | Dx = 1.557 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.205 (4) Å | Cell parameters from 1395 reflections |
b = 11.347 (4) Å | θ = 2.5–22.4° |
c = 11.652 (4) Å | µ = 1.95 mm−1 |
α = 66.157 (5)° | T = 298 K |
β = 66.036 (4)° | Block, colourless |
γ = 81.515 (5)° | 0.42 × 0.17 × 0.08 mm |
V = 1238.0 (7) Å3 |
Bruker SMART CCD area-detector diffractometer | 4577 independent reflections |
Radiation source: fine-focus sealed tube | 2525 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
phi and ω scans | θmax = 25.6°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −13→13 |
Tmin = 0.494, Tmax = 0.859 | k = −13→13 |
6627 measured reflections | l = −14→11 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.055P)2] where P = (Fo2 + 2Fc2)/3 |
4577 reflections | (Δ/σ)max = 0.001 |
320 parameters | Δρmax = 0.70 e Å−3 |
1 restraint | Δρmin = −0.55 e Å−3 |
[Cu2Cl2(C25H26N4)] | γ = 81.515 (5)° |
Mr = 580.48 | V = 1238.0 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.205 (4) Å | Mo Kα radiation |
b = 11.347 (4) Å | µ = 1.95 mm−1 |
c = 11.652 (4) Å | T = 298 K |
α = 66.157 (5)° | 0.42 × 0.17 × 0.08 mm |
β = 66.036 (4)° |
Bruker SMART CCD area-detector diffractometer | 4577 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2525 reflections with I > 2σ(I) |
Tmin = 0.494, Tmax = 0.859 | Rint = 0.030 |
6627 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 1 restraint |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.70 e Å−3 |
4577 reflections | Δρmin = −0.55 e Å−3 |
320 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Occ. (<1) | |
C1 | 1.1996 (5) | 0.9952 (5) | 0.1717 (5) | 0.0508 (13) | |
H1 | 1.2721 | 0.9775 | 0.1054 | 0.061* | |
C2 | 1.0775 (5) | 1.0702 (5) | 0.3211 (5) | 0.0553 (14) | |
H2 | 1.0500 | 1.1153 | 0.3783 | 0.066* | |
C3 | 0.9999 (5) | 0.9965 (5) | 0.3133 (5) | 0.0577 (15) | |
H3 | 0.9107 | 0.9814 | 0.3632 | 0.069* | |
C4 | 1.0379 (4) | 0.8685 (4) | 0.1694 (5) | 0.0389 (11) | |
C5 | 1.1103 (4) | 0.8755 (4) | 0.0381 (5) | 0.0481 (13) | |
H5 | 1.1847 | 0.9283 | −0.0149 | 0.058* | |
C6 | 1.0730 (4) | 0.8045 (4) | −0.0148 (5) | 0.0455 (12) | |
H6 | 1.1220 | 0.8074 | −0.1023 | 0.055* | |
C7 | 0.9598 (4) | 0.7287 (4) | 0.0668 (5) | 0.0390 (11) | |
C8 | 0.8892 (4) | 0.7196 (4) | 0.1999 (5) | 0.0406 (12) | |
C9 | 0.9265 (4) | 0.7898 (4) | 0.2539 (5) | 0.0451 (12) | |
H9 | 0.8794 | 0.7845 | 0.3425 | 0.054* | |
C10 | 0.7693 (5) | 0.6289 (5) | 0.2682 (5) | 0.0492 (14) | |
C11 | 0.6416 (5) | 0.7023 (7) | 0.3067 (6) | 0.071 (2) | |
H11A | 0.5687 | 0.6443 | 0.3411 | 0.086* | |
H11B | 0.6353 | 0.7263 | 0.3799 | 0.086* | |
C12 | 0.6284 (6) | 0.8198 (7) | 0.1949 (8) | 0.091 (2) | 0.42 (5) |
H12A | 0.6235 | 0.8016 | 0.1224 | 0.109* | 0.42 (5) |
H12B | 0.6963 | 0.8841 | 0.1583 | 0.109* | 0.42 (5) |
C13A | 0.495 (4) | 0.855 (5) | 0.285 (7) | 0.132 (13) | 0.42 (5) |
H13A | 0.4260 | 0.8203 | 0.2788 | 0.198* | 0.42 (5) |
H13B | 0.4884 | 0.9474 | 0.2546 | 0.198* | 0.42 (5) |
H13C | 0.4878 | 0.8204 | 0.3777 | 0.198* | 0.42 (5) |
C12' | 0.6284 (6) | 0.8198 (7) | 0.1949 (8) | 0.091 (2) | 0.58 (5) |
H12C | 0.6454 | 0.7947 | 0.1195 | 0.109* | 0.58 (5) |
H12D | 0.6993 | 0.8779 | 0.1666 | 0.109* | 0.58 (5) |
C13B | 0.4999 (19) | 0.903 (2) | 0.210 (3) | 0.080 (7) | 0.58 (5) |
H13D | 0.4262 | 0.8490 | 0.2405 | 0.120* | 0.58 (5) |
H13E | 0.5095 | 0.9702 | 0.1229 | 0.120* | 0.58 (5) |
H13F | 0.4864 | 0.9414 | 0.2739 | 0.120* | 0.58 (5) |
C14 | 0.7642 (7) | 0.5202 (7) | 0.3975 (6) | 0.090 (2) | |
H14A | 0.7444 | 0.5567 | 0.4652 | 0.108* | |
H14B | 0.6905 | 0.4647 | 0.4272 | 0.108* | |
C15 | 0.8676 (8) | 0.4449 (8) | 0.4001 (8) | 0.124 (3) | |
H15A | 0.9418 | 0.4997 | 0.3701 | 0.149* | |
H15B | 0.8870 | 0.4066 | 0.3337 | 0.149* | |
C16 | 0.8575 (8) | 0.3320 (8) | 0.5401 (7) | 0.143 (4) | |
H16A | 0.8321 | 0.3666 | 0.6093 | 0.215* | |
H16B | 0.9409 | 0.2920 | 0.5306 | 0.215* | |
H16C | 0.7935 | 0.2691 | 0.5651 | 0.215* | |
C17 | 0.7850 (4) | 0.5895 (4) | 0.1520 (5) | 0.0402 (11) | |
C18 | 0.8953 (4) | 0.6503 (4) | 0.0353 (5) | 0.0391 (11) | |
C19 | 0.9251 (4) | 0.6322 (5) | −0.0817 (5) | 0.0485 (13) | |
H19 | 0.9993 | 0.6717 | −0.1574 | 0.058* | |
C20 | 0.8451 (4) | 0.5551 (5) | −0.0883 (5) | 0.0460 (13) | |
H20 | 0.8639 | 0.5443 | −0.1688 | 0.055* | |
C21 | 0.7375 (4) | 0.4946 (4) | 0.0258 (5) | 0.0388 (11) | |
C22 | 0.7064 (4) | 0.5105 (4) | 0.1466 (5) | 0.0443 (12) | |
H22 | 0.6337 | 0.4685 | 0.2229 | 0.053* | |
C23 | 0.5576 (5) | 0.3388 (5) | 0.1157 (5) | 0.0592 (15) | |
H23 | 0.5321 | 0.3277 | 0.2061 | 0.071* | |
C24 | 0.6597 (5) | 0.4078 (6) | −0.0989 (6) | 0.0753 (19) | |
H24 | 0.7176 | 0.4519 | −0.1871 | 0.090* | |
C25 | 0.5641 (5) | 0.3242 (6) | −0.0605 (6) | 0.0736 (19) | |
H25 | 0.5454 | 0.3008 | −0.1193 | 0.088* | |
Cl1 | 1.27524 (14) | 1.23830 (15) | 0.39214 (14) | 0.0714 (5) | |
Cl2A | 1.3646 (9) | 0.9094 (12) | 0.6438 (11) | 0.108 (3) | 0.50 |
Cl2B | 1.3622 (12) | 0.8722 (13) | 0.6090 (12) | 0.124 (3) | 0.50 |
Cu1 | 1.34449 (6) | 1.17696 (6) | 0.18473 (7) | 0.0639 (3) | |
Cu2 | 1.40380 (10) | 1.08864 (10) | 0.46070 (9) | 0.1152 (4) | |
N1 | 1.2024 (4) | 1.0690 (4) | 0.2329 (4) | 0.0518 (11) | |
N2 | 1.0773 (4) | 0.9482 (4) | 0.2180 (4) | 0.0426 (10) | |
N3 | 0.6553 (3) | 0.4151 (4) | 0.0156 (4) | 0.0428 (10) | |
N4 | 0.4999 (4) | 0.2798 (4) | 0.0742 (4) | 0.0531 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.047 (3) | 0.054 (3) | 0.055 (3) | −0.019 (3) | −0.022 (3) | −0.016 (3) |
C2 | 0.060 (3) | 0.055 (3) | 0.054 (3) | −0.017 (3) | −0.017 (3) | −0.023 (3) |
C3 | 0.051 (3) | 0.067 (4) | 0.057 (3) | −0.022 (3) | −0.013 (3) | −0.026 (3) |
C4 | 0.045 (3) | 0.033 (3) | 0.045 (3) | −0.011 (2) | −0.024 (2) | −0.010 (2) |
C5 | 0.044 (3) | 0.041 (3) | 0.060 (4) | −0.015 (2) | −0.019 (3) | −0.015 (3) |
C6 | 0.044 (3) | 0.046 (3) | 0.043 (3) | −0.011 (2) | −0.011 (2) | −0.016 (2) |
C7 | 0.037 (3) | 0.033 (3) | 0.049 (3) | −0.006 (2) | −0.020 (2) | −0.011 (2) |
C8 | 0.044 (3) | 0.037 (3) | 0.041 (3) | −0.014 (2) | −0.018 (2) | −0.009 (2) |
C9 | 0.049 (3) | 0.051 (3) | 0.039 (3) | −0.015 (3) | −0.018 (2) | −0.014 (2) |
C10 | 0.063 (3) | 0.050 (3) | 0.036 (3) | −0.029 (3) | −0.023 (3) | −0.003 (2) |
C11 | 0.048 (3) | 0.112 (6) | 0.057 (4) | −0.044 (4) | 0.008 (3) | −0.048 (4) |
C12 | 0.052 (4) | 0.103 (6) | 0.135 (7) | −0.001 (4) | −0.034 (4) | −0.064 (6) |
C13A | 0.12 (2) | 0.16 (3) | 0.16 (4) | 0.08 (2) | −0.10 (3) | −0.09 (3) |
C12' | 0.052 (4) | 0.103 (6) | 0.135 (7) | −0.001 (4) | −0.034 (4) | −0.064 (6) |
C13B | 0.081 (9) | 0.090 (13) | 0.103 (14) | 0.030 (9) | −0.052 (10) | −0.061 (11) |
C14 | 0.101 (5) | 0.081 (5) | 0.091 (5) | −0.033 (4) | −0.053 (5) | −0.007 (4) |
C15 | 0.099 (6) | 0.102 (7) | 0.129 (7) | −0.015 (5) | −0.023 (6) | −0.017 (5) |
C16 | 0.158 (8) | 0.115 (7) | 0.092 (6) | 0.026 (6) | −0.049 (6) | 0.016 (5) |
C17 | 0.040 (3) | 0.035 (3) | 0.050 (3) | −0.008 (2) | −0.021 (2) | −0.013 (2) |
C18 | 0.043 (3) | 0.038 (3) | 0.046 (3) | −0.003 (2) | −0.022 (2) | −0.018 (2) |
C19 | 0.042 (3) | 0.053 (3) | 0.048 (3) | −0.015 (2) | −0.009 (2) | −0.020 (3) |
C20 | 0.043 (3) | 0.054 (3) | 0.041 (3) | −0.014 (2) | −0.008 (2) | −0.023 (3) |
C21 | 0.039 (3) | 0.039 (3) | 0.049 (3) | −0.003 (2) | −0.023 (2) | −0.018 (2) |
C22 | 0.039 (3) | 0.045 (3) | 0.046 (3) | −0.014 (2) | −0.013 (2) | −0.012 (2) |
C23 | 0.060 (3) | 0.072 (4) | 0.049 (3) | −0.030 (3) | −0.013 (3) | −0.024 (3) |
C24 | 0.074 (4) | 0.107 (5) | 0.052 (4) | −0.044 (4) | −0.008 (3) | −0.038 (4) |
C25 | 0.071 (4) | 0.102 (5) | 0.077 (4) | −0.022 (4) | −0.026 (4) | −0.055 (4) |
Cl1 | 0.0700 (9) | 0.0837 (11) | 0.0634 (9) | −0.0198 (8) | −0.0174 (8) | −0.0319 (8) |
Cl2A | 0.056 (3) | 0.121 (7) | 0.089 (5) | −0.020 (3) | −0.007 (3) | 0.003 (4) |
Cl2B | 0.105 (4) | 0.120 (7) | 0.107 (6) | −0.032 (4) | −0.038 (4) | 0.005 (4) |
Cu1 | 0.0633 (5) | 0.0590 (5) | 0.0775 (5) | −0.0270 (4) | −0.0286 (4) | −0.0225 (4) |
Cu2 | 0.1243 (8) | 0.1292 (9) | 0.0919 (7) | 0.0121 (7) | −0.0473 (6) | −0.0392 (6) |
N1 | 0.058 (3) | 0.049 (3) | 0.057 (3) | −0.022 (2) | −0.026 (2) | −0.016 (2) |
N2 | 0.047 (2) | 0.040 (2) | 0.046 (2) | −0.0133 (19) | −0.020 (2) | −0.013 (2) |
N3 | 0.039 (2) | 0.046 (2) | 0.049 (3) | −0.0109 (19) | −0.016 (2) | −0.021 (2) |
N4 | 0.056 (3) | 0.058 (3) | 0.052 (3) | −0.019 (2) | −0.018 (2) | −0.024 (2) |
C1—N1 | 1.310 (6) | C14—H14B | 0.9700 |
C1—N2 | 1.356 (5) | C15—C16 | 1.587 (10) |
C1—H1 | 0.9300 | C15—H15A | 0.9700 |
C2—C3 | 1.343 (6) | C15—H15B | 0.9700 |
C2—N1 | 1.360 (6) | C16—H16A | 0.9600 |
C2—H2 | 0.9300 | C16—H16B | 0.9600 |
C3—N2 | 1.362 (6) | C16—H16C | 0.9600 |
C3—H3 | 0.9300 | C17—C22 | 1.381 (5) |
C4—C5 | 1.385 (6) | C17—C18 | 1.408 (6) |
C4—C9 | 1.395 (5) | C18—C19 | 1.360 (6) |
C4—N2 | 1.438 (5) | C19—C20 | 1.383 (5) |
C5—C6 | 1.384 (6) | C19—H19 | 0.9300 |
C5—H5 | 0.9300 | C20—C21 | 1.378 (5) |
C6—C7 | 1.390 (6) | C20—H20 | 0.9300 |
C6—H6 | 0.9300 | C21—C22 | 1.387 (6) |
C7—C8 | 1.393 (6) | C21—N3 | 1.449 (5) |
C7—C18 | 1.455 (5) | C22—H22 | 0.9300 |
C8—C9 | 1.386 (6) | C23—N3 | 1.317 (5) |
C8—C10 | 1.542 (6) | C23—N4 | 1.322 (5) |
C9—H9 | 0.9300 | C23—H23 | 0.9300 |
C10—C14 | 1.497 (7) | C24—C25 | 1.348 (6) |
C10—C17 | 1.528 (6) | C24—N3 | 1.350 (6) |
C10—C11 | 1.539 (8) | C24—H24 | 0.9300 |
C11—C12 | 1.481 (9) | C25—N4 | 1.336 (6) |
C11—H11A | 0.9700 | C25—H25 | 0.9300 |
C11—H11B | 0.9700 | Cl1—Cu2 | 2.171 (2) |
C12—C13A | 1.55 (4) | Cl1—Cu1 | 2.5700 (17) |
C12—H12A | 0.9700 | Cl2A—Cu2 | 2.209 (13) |
C12—H12B | 0.9700 | Cl2A—Cu2i | 2.376 (9) |
C13A—H13A | 0.9600 | Cl2B—Cu2 | 2.342 (13) |
C13A—H13B | 0.9600 | Cl2B—Cu2i | 2.460 (11) |
C13A—H13C | 0.9600 | Cu1—N4ii | 1.901 (4) |
C13B—H13D | 0.9600 | Cu1—N1 | 1.910 (3) |
C13B—H13E | 0.9600 | Cu2—Cl2Ai | 2.376 (9) |
C13B—H13F | 0.9600 | Cu2—Cl2Bi | 2.460 (11) |
C14—C15 | 1.338 (9) | Cu2—Cu2i | 2.893 (2) |
C14—H14A | 0.9700 | N4—Cu1iii | 1.901 (4) |
N1—C1—N2 | 111.0 (5) | H16B—C16—H16C | 109.5 |
N1—C1—H1 | 124.5 | C22—C17—C18 | 119.1 (4) |
N2—C1—H1 | 124.5 | C22—C17—C10 | 129.7 (4) |
C3—C2—N1 | 109.9 (5) | C18—C17—C10 | 111.2 (3) |
C3—C2—H2 | 125.0 | C19—C18—C17 | 121.0 (4) |
N1—C2—H2 | 125.0 | C19—C18—C7 | 130.8 (4) |
C2—C3—N2 | 106.6 (4) | C17—C18—C7 | 108.3 (4) |
C2—C3—H3 | 126.7 | C18—C19—C20 | 120.1 (4) |
N2—C3—H3 | 126.7 | C18—C19—H19 | 119.9 |
C5—C4—C9 | 122.1 (4) | C20—C19—H19 | 119.9 |
C5—C4—N2 | 118.6 (4) | C21—C20—C19 | 119.2 (4) |
C9—C4—N2 | 119.3 (4) | C21—C20—H20 | 120.4 |
C6—C5—C4 | 120.6 (4) | C19—C20—H20 | 120.4 |
C6—C5—H5 | 119.7 | C20—C21—C22 | 121.6 (4) |
C4—C5—H5 | 119.7 | C20—C21—N3 | 117.9 (4) |
C5—C6—C7 | 117.9 (4) | C22—C21—N3 | 120.5 (4) |
C5—C6—H6 | 121.0 | C17—C22—C21 | 119.0 (4) |
C7—C6—H6 | 121.0 | C17—C22—H22 | 120.5 |
C6—C7—C8 | 121.2 (4) | C21—C22—H22 | 120.5 |
C6—C7—C18 | 129.4 (4) | N3—C23—N4 | 112.8 (4) |
C8—C7—C18 | 109.4 (4) | N3—C23—H23 | 123.6 |
C9—C8—C7 | 121.1 (4) | N4—C23—H23 | 123.6 |
C9—C8—C10 | 128.0 (4) | C25—C24—N3 | 106.6 (5) |
C7—C8—C10 | 110.8 (4) | C25—C24—H24 | 126.7 |
C8—C9—C4 | 117.0 (4) | N3—C24—H24 | 126.7 |
C8—C9—H9 | 121.5 | N4—C25—C24 | 110.3 (5) |
C4—C9—H9 | 121.5 | N4—C25—H25 | 124.8 |
C14—C10—C17 | 115.5 (5) | C24—C25—H25 | 124.8 |
C14—C10—C11 | 105.6 (5) | Cu2—Cl1—Cu1 | 86.93 (6) |
C17—C10—C11 | 110.7 (4) | Cu2—Cl2A—Cu2i | 78.2 (3) |
C14—C10—C8 | 113.9 (4) | Cu2—Cl2B—Cu2i | 74.0 (3) |
C17—C10—C8 | 100.4 (3) | N4ii—Cu1—N1 | 158.65 (17) |
C11—C10—C8 | 110.9 (4) | N4ii—Cu1—Cl1 | 98.40 (13) |
C12—C11—C10 | 115.3 (5) | N1—Cu1—Cl1 | 102.52 (13) |
C12—C11—H11A | 108.5 | Cl1—Cu2—Cl2A | 131.7 (3) |
C10—C11—H11A | 108.5 | Cl1—Cu2—Cl2B | 131.3 (3) |
C12—C11—H11B | 108.5 | Cl2A—Cu2—Cl2B | 17.5 (4) |
C10—C11—H11B | 108.5 | Cl1—Cu2—Cl2Ai | 126.3 (3) |
H11A—C11—H11B | 107.5 | Cl2A—Cu2—Cl2Ai | 101.8 (3) |
C11—C12—C13A | 94 (3) | Cl2B—Cu2—Cl2Ai | 100.7 (5) |
C11—C12—H12A | 112.9 | Cl1—Cu2—Cl2Bi | 122.7 (3) |
C13A—C12—H12A | 112.9 | Cl2A—Cu2—Cl2Bi | 102.0 (5) |
C11—C12—H12B | 112.9 | Cl2B—Cu2—Cl2Bi | 106.0 (3) |
C13A—C12—H12B | 112.9 | Cl2Ai—Cu2—Cl2Bi | 16.6 (4) |
H12A—C12—H12B | 110.3 | Cl1—Cu2—Cu2i | 173.74 (8) |
C15—C14—C10 | 120.0 (7) | Cl2A—Cu2—Cu2i | 53.5 (3) |
C15—C14—H14A | 107.3 | Cl2B—Cu2—Cu2i | 54.9 (3) |
C10—C14—H14A | 107.3 | Cl2Ai—Cu2—Cu2i | 48.3 (3) |
C15—C14—H14B | 107.3 | Cl2Bi—Cu2—Cu2i | 51.1 (3) |
C10—C14—H14B | 107.3 | C1—N1—C2 | 105.9 (4) |
H14A—C14—H14B | 106.9 | C1—N1—Cu1 | 126.7 (4) |
C14—C15—C16 | 118.0 (7) | C2—N1—Cu1 | 126.6 (3) |
C14—C15—H15A | 107.8 | C1—N2—C3 | 106.5 (4) |
C16—C15—H15A | 107.8 | C1—N2—C4 | 125.9 (4) |
C14—C15—H15B | 107.8 | C3—N2—C4 | 127.5 (4) |
C16—C15—H15B | 107.8 | C23—N3—C24 | 106.0 (4) |
H15A—C15—H15B | 107.2 | C23—N3—C21 | 126.9 (4) |
C15—C16—H16A | 109.5 | C24—N3—C21 | 127.1 (4) |
C15—C16—H16B | 109.5 | C23—N4—C25 | 104.2 (4) |
H16A—C16—H16B | 109.5 | C23—N4—Cu1iii | 125.3 (4) |
C15—C16—H16C | 109.5 | C25—N4—Cu1iii | 129.8 (3) |
H16A—C16—H16C | 109.5 | ||
N1—C2—C3—N2 | −0.2 (6) | C10—C17—C22—C21 | 176.5 (5) |
C9—C4—C5—C6 | 0.8 (7) | C20—C21—C22—C17 | 0.4 (7) |
N2—C4—C5—C6 | −177.4 (4) | N3—C21—C22—C17 | −178.3 (4) |
C4—C5—C6—C7 | 1.3 (7) | N3—C24—C25—N4 | 0.3 (7) |
C5—C6—C7—C8 | −2.9 (7) | Cu2—Cl1—Cu1—N4ii | −85.09 (15) |
C5—C6—C7—C18 | 176.7 (5) | Cu2—Cl1—Cu1—N1 | 99.16 (14) |
C6—C7—C8—C9 | 2.5 (7) | Cu1—Cl1—Cu2—Cl2A | −117.9 (3) |
C18—C7—C8—C9 | −177.1 (4) | Cu1—Cl1—Cu2—Cl2B | −94.5 (3) |
C6—C7—C8—C10 | −179.5 (4) | Cu1—Cl1—Cu2—Cl2Ai | 67.6 (3) |
C18—C7—C8—C10 | 0.9 (5) | Cu1—Cl1—Cu2—Cl2Bi | 87.3 (3) |
C7—C8—C9—C4 | −0.5 (7) | Cu1—Cl1—Cu2—Cu2i | 97.7 (6) |
C10—C8—C9—C4 | −178.1 (5) | Cu2i—Cl2A—Cu2—Cl1 | −175.47 (11) |
C5—C4—C9—C8 | −1.2 (7) | Cu2i—Cl2A—Cu2—Cl2B | 88.1 (19) |
N2—C4—C9—C8 | 177.0 (4) | Cu2i—Cl2A—Cu2—Cl2Ai | 0.0 |
C9—C8—C10—C14 | −58.1 (8) | Cu2i—Cl2A—Cu2—Cl2Bi | −17.0 (4) |
C7—C8—C10—C14 | 124.0 (5) | Cu2i—Cl2B—Cu2—Cl1 | −178.38 (10) |
C9—C8—C10—C17 | 177.8 (5) | Cu2i—Cl2B—Cu2—Cl2A | −79.2 (18) |
C7—C8—C10—C17 | 0.0 (5) | Cu2i—Cl2B—Cu2—Cl2Ai | 16.2 (4) |
C9—C8—C10—C11 | 60.8 (6) | Cu2i—Cl2B—Cu2—Cl2Bi | 0.0 |
C7—C8—C10—C11 | −117.1 (5) | N2—C1—N1—C2 | −0.3 (6) |
C14—C10—C11—C12 | 176.6 (4) | N2—C1—N1—Cu1 | −170.0 (3) |
C17—C10—C11—C12 | −57.7 (6) | C3—C2—N1—C1 | 0.3 (6) |
C8—C10—C11—C12 | 52.8 (6) | C3—C2—N1—Cu1 | 170.0 (4) |
C10—C11—C12—C13A | −177.9 (14) | N4ii—Cu1—N1—C1 | 24.0 (8) |
C17—C10—C14—C15 | 63.5 (8) | Cl1—Cu1—N1—C1 | −167.7 (4) |
C11—C10—C14—C15 | −173.8 (7) | N4ii—Cu1—N1—C2 | −143.7 (5) |
C8—C10—C14—C15 | −51.9 (9) | Cl1—Cu1—N1—C2 | 24.7 (4) |
C10—C14—C15—C16 | 179.4 (6) | N1—C1—N2—C3 | 0.2 (6) |
C14—C10—C17—C22 | 58.7 (7) | N1—C1—N2—C4 | 177.3 (4) |
C11—C10—C17—C22 | −61.2 (7) | C2—C3—N2—C1 | 0.0 (6) |
C8—C10—C17—C22 | −178.4 (5) | C2—C3—N2—C4 | −177.0 (4) |
C14—C10—C17—C18 | −123.8 (5) | C5—C4—N2—C1 | −25.1 (7) |
C11—C10—C17—C18 | 116.3 (4) | C9—C4—N2—C1 | 156.7 (5) |
C8—C10—C17—C18 | −0.9 (5) | C5—C4—N2—C3 | 151.3 (5) |
C22—C17—C18—C19 | 0.0 (7) | C9—C4—N2—C3 | −26.9 (7) |
C10—C17—C18—C19 | −177.8 (4) | N4—C23—N3—C24 | 1.5 (6) |
C22—C17—C18—C7 | 179.3 (4) | N4—C23—N3—C21 | 179.2 (4) |
C10—C17—C18—C7 | 1.5 (5) | C25—C24—N3—C23 | −1.0 (7) |
C6—C7—C18—C19 | −1.9 (9) | C25—C24—N3—C21 | −178.7 (5) |
C8—C7—C18—C19 | 177.7 (5) | C20—C21—N3—C23 | 171.9 (5) |
C6—C7—C18—C17 | 178.9 (5) | C22—C21—N3—C23 | −9.4 (7) |
C8—C7—C18—C17 | −1.4 (5) | C20—C21—N3—C24 | −10.9 (7) |
C17—C18—C19—C20 | 1.3 (7) | C22—C21—N3—C24 | 167.9 (5) |
C7—C18—C19—C20 | −177.8 (5) | N3—C23—N4—C25 | −1.2 (6) |
C18—C19—C20—C21 | −1.7 (7) | N3—C23—N4—Cu1iii | −172.9 (3) |
C19—C20—C21—C22 | 0.9 (7) | C24—C25—N4—C23 | 0.5 (7) |
C19—C20—C21—N3 | 179.6 (4) | C24—C25—N4—Cu1iii | 171.6 (4) |
C18—C17—C22—C21 | −0.9 (7) |
Symmetry codes: (i) −x+3, −y+2, −z+1; (ii) x+1, y+1, z; (iii) x−1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13A—H13C···Cl2Biv | 0.96 | 2.75 | 3.53 (6) | 139 |
C9—H9···Cl1v | 0.93 | 2.79 | 3.715 (5) | 176 |
C23—H23···Cl1iii | 0.93 | 2.83 | 3.392 (5) | 120 |
Symmetry codes: (iii) x−1, y−1, z; (iv) x−1, y, z; (v) −x+2, −y+2, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C21H18N4 | [Cu2Cl2(C21H18N4)] | [Cu2Cl2(C25H26N4)] |
Mr | 326.39 | 524.37 | 580.48 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 298 | 298 | 298 |
a, b, c (Å) | 6.616 (3), 15.683 (6), 8.545 (4) | 12.749 (9), 17.215 (11), 9.489 (6) | 11.205 (4), 11.347 (4), 11.652 (4) |
α, β, γ (°) | 90, 108.037 (5), 90 | 90, 100.402 (9), 90 | 66.157 (5), 66.036 (4), 81.515 (5) |
V (Å3) | 843.1 (6) | 2048 (2) | 1238.0 (7) |
Z | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 2.35 | 1.95 |
Crystal size (mm) | 0.29 × 0.15 × 0.12 | 0.48 × 0.23 × 0.16 | 0.42 × 0.17 × 0.08 |
Data collection | |||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | Multi-scan (SADABS; Bruker, 2003) | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | – | 0.398, 0.705 | 0.494, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4430, 1631, 1427 | 10566, 3831, 2755 | 6627, 4577, 2525 |
Rint | 0.042 | 0.069 | 0.030 |
(sin θ/λ)max (Å−1) | 0.608 | 0.608 | 0.608 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.112, 1.12 | 0.060, 0.172, 1.07 | 0.057, 0.143, 1.00 |
No. of reflections | 1631 | 3831 | 4577 |
No. of parameters | 228 | 264 | 320 |
No. of restraints | 1 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.23 | 0.91, −0.87 | 0.70, −0.55 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···N2i | 0.93 | 2.63 | 3.371 (6) | 137.2 |
C5—H5···N4ii | 0.93 | 2.64 | 3.460 (5) | 147.4 |
C1—H1···N4iii | 0.93 | 2.65 | 3.494 (5) | 152.0 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x−1, y, z+1; (iii) −x+2, y−1/2, −z+1. |
Cl1—Cu2 | 2.097 (2) | Cu1—N1 | 1.873 (4) |
Cl2—Cu2 | 2.100 (2) | Cu1—Cu2 | 2.9285 (17) |
Cu1—N4i | 1.871 (4) | N4—Cu1ii | 1.871 (4) |
N4i—Cu1—N1 | 170.84 (17) | Cl1—Cu2—Cl2 | 176.28 (7) |
Symmetry codes: (i) x+1, −y+1/2, z+3/2; (ii) x−1, −y+1/2, z−3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···Cl2iii | 0.93 | 2.63 | 3.519 (5) | 159.0 |
Symmetry code: (iii) x−1, y, z−1. |
Cl1—Cu2 | 2.171 (2) | Cu1—N4i | 1.901 (4) |
Cl1—Cu1 | 2.5700 (17) | Cu1—N1 | 1.910 (3) |
Cl2A—Cu2 | 2.209 (13) | Cu2—Cl2Aii | 2.376 (9) |
Cl2B—Cu2 | 2.342 (13) | Cu2—Cl2Bii | 2.460 (11) |
N4i—Cu1—N1 | 158.65 (17) | Cl1—Cu2—Cl2A | 131.7 (3) |
N4i—Cu1—Cl1 | 98.40 (13) | Cl1—Cu2—Cl2Bii | 122.7 (3) |
N1—Cu1—Cl1 | 102.52 (13) | Cl2B—Cu2—Cl2Bii | 106.0 (3) |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+3, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13A—H13C···Cl2Biii | 0.96 | 2.75 | 3.53 (6) | 138.8 |
C9—H9···Cl1iv | 0.93 | 2.79 | 3.715 (5) | 176.2 |
C23—H23···Cl1v | 0.93 | 2.83 | 3.392 (5) | 119.7 |
Symmetry codes: (iii) x−1, y, z; (iv) −x+2, −y+2, −z+1; (v) x−1, y−1, z. |
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