Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810403294X/av5023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010876810403294X/av50231sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010876810403294X/av50232gsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010876810403294X/av50232egsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010876810403294X/av50232osup5.hkl |
CCDC references: 268157; 268158; 268159; 268160
For all compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL, TOPOS 4.0 Standard; software used to prepare material for publication: local programs.
C16H16N4 | Dx = 1.245 Mg m−3 |
Mr = 264.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1009 reflections |
a = 19.499 (3) Å | θ = 2.5–22.1° |
b = 4.7884 (6) Å | µ = 0.08 mm−1 |
c = 15.106 (2) Å | T = 293 K |
V = 1410.5 (4) Å3 | Lath, colourless |
Z = 4 | 0.59 × 0.05 × 0.03 mm |
F(000) = 560 |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 885 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.083 |
Graphite monochromator | θmax = 30.6°, θmin = 2.5° |
Detector resolution: 25 pixels mm-1 | h = −27→27 |
π–scans | k = −3→6 |
9460 measured reflections | l = −21→21 |
2221 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.181 | w = 1/[σ2(Fo2) + (0.0847P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max < 0.001 |
2221 reflections | Δρmax = 0.14 e Å−3 |
182 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0 (10) |
C16H16N4 | V = 1410.5 (4) Å3 |
Mr = 264.33 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 19.499 (3) Å | µ = 0.08 mm−1 |
b = 4.7884 (6) Å | T = 293 K |
c = 15.106 (2) Å | 0.59 × 0.05 × 0.03 mm |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 885 reflections with I > 2σ(I) |
9460 measured reflections | Rint = 0.083 |
2221 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.181 | Δρmax = 0.14 e Å−3 |
S = 0.91 | Δρmin = −0.15 e Å−3 |
2221 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
182 parameters | Absolute structure parameter: 0 (10) |
1 restraint |
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 | ||
C3 | 0.8529 (2) | −0.3636 (9) | 0.3520 (3) | 0.0799 (12) | |
C4 | 0.9130 (2) | −0.3220 (9) | 0.4000 (3) | 0.0791 (11) | |
H4A | 0.9249 | −0.4103 | 0.4527 | 0.095* | |
C5 | 0.9513 (2) | −0.1272 (8) | 0.3556 (3) | 0.0727 (11) | |
C6 | 0.9255 (2) | 0.1327 (8) | 0.2136 (3) | 0.0625 (9) | |
C7 | 0.8773 (2) | 0.1804 (8) | 0.1472 (3) | 0.0716 (11) | |
H7A | 0.8356 | 0.0866 | 0.1455 | 0.086* | |
C8 | 0.8955 (2) | 0.3770 (9) | 0.0833 (3) | 0.0703 (11) | |
C9 | 0.9980 (2) | 0.4456 (8) | 0.1520 (3) | 0.0642 (10) | |
C10 | 1.0663 (2) | 0.5856 (8) | 0.1551 (3) | 0.0678 (10) | |
C11 | 1.0834 (3) | 0.7937 (9) | 0.0965 (3) | 0.0792 (12) | |
H11A | 1.0513 | 0.8554 | 0.0555 | 0.095* | |
C12 | 1.1484 (3) | 0.9130 (10) | 0.0981 (4) | 0.0869 (13) | |
H12A | 1.1594 | 1.0517 | 0.0573 | 0.104* | |
C13 | 1.1961 (2) | 0.8301 (10) | 0.1581 (4) | 0.0878 (14) | |
H13A | 1.2396 | 0.9101 | 0.1586 | 0.105* | |
C14 | 1.1788 (2) | 0.6243 (11) | 0.2185 (4) | 0.0919 (14) | |
H14A | 1.2108 | 0.5674 | 0.2606 | 0.110* | |
C15 | 1.1147 (2) | 0.5032 (9) | 0.2169 (3) | 0.0799 (12) | |
H15A | 1.1039 | 0.3645 | 0.2576 | 0.096* | |
C31 | 0.7947 (3) | −0.5540 (10) | 0.3735 (4) | 0.1005 (16) | |
H31A | 0.7976 | −0.6093 | 0.4344 | 0.121* | |
H31B | 0.7970 | −0.7165 | 0.3364 | 0.121* | |
H31C | 0.7521 | −0.4586 | 0.3634 | 0.19 (3)* | |
C51 | 1.0191 (2) | −0.0068 (11) | 0.3793 (4) | 0.0902 (13) | |
H51A | 1.0346 | −0.0866 | 0.4340 | 0.135* | |
H51B | 1.0149 | 0.1919 | 0.3858 | 0.135* | |
H51C | 1.0516 | −0.0477 | 0.3333 | 0.135* | |
C81 | 0.8477 (2) | 0.4494 (12) | 0.0097 (3) | 0.0950 (15) | |
H81A | 0.8063 | 0.3429 | 0.0156 | 0.143* | |
H81B | 0.8691 | 0.4070 | −0.0459 | 0.143* | |
H81C | 0.8371 | 0.6450 | 0.0122 | 0.143* | |
N1 | 0.85223 (17) | −0.2084 (7) | 0.2793 (2) | 0.0753 (9) | |
N2 | 0.91272 (17) | −0.0615 (7) | 0.2823 (2) | 0.0690 (9) | |
N3 | 0.95636 (17) | 0.5093 (7) | 0.0857 (2) | 0.0681 (9) | |
N4 | 0.98480 (16) | 0.2599 (7) | 0.2170 (2) | 0.0680 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.102 (3) | 0.059 (2) | 0.079 (3) | 0.011 (2) | 0.009 (3) | −0.010 (2) |
C4 | 0.104 (3) | 0.064 (2) | 0.070 (2) | 0.020 (2) | 0.007 (3) | −0.001 (2) |
C5 | 0.088 (3) | 0.071 (2) | 0.059 (2) | 0.024 (2) | 0.003 (2) | −0.006 (2) |
C6 | 0.072 (2) | 0.061 (2) | 0.055 (2) | 0.0179 (19) | 0.001 (2) | −0.0049 (18) |
C7 | 0.077 (3) | 0.072 (3) | 0.066 (3) | 0.0113 (19) | −0.003 (2) | −0.008 (2) |
C8 | 0.078 (3) | 0.077 (2) | 0.055 (2) | 0.019 (2) | −0.003 (2) | −0.008 (2) |
C9 | 0.080 (2) | 0.062 (2) | 0.051 (2) | 0.0166 (19) | −0.001 (2) | −0.0078 (19) |
C10 | 0.077 (3) | 0.064 (2) | 0.063 (2) | 0.010 (2) | −0.002 (2) | −0.014 (2) |
C11 | 0.096 (3) | 0.074 (3) | 0.068 (3) | 0.009 (2) | −0.008 (2) | −0.005 (2) |
C12 | 0.091 (3) | 0.083 (3) | 0.086 (3) | −0.006 (3) | 0.001 (3) | −0.004 (3) |
C13 | 0.085 (3) | 0.084 (3) | 0.095 (4) | −0.008 (2) | 0.003 (3) | −0.008 (3) |
C14 | 0.082 (3) | 0.099 (3) | 0.095 (3) | 0.008 (3) | −0.013 (3) | −0.001 (3) |
C15 | 0.081 (3) | 0.079 (3) | 0.081 (3) | 0.005 (2) | −0.008 (2) | 0.002 (3) |
C31 | 0.124 (4) | 0.068 (3) | 0.109 (4) | 0.004 (3) | 0.028 (3) | 0.000 (3) |
C51 | 0.091 (3) | 0.102 (3) | 0.077 (3) | 0.017 (3) | −0.011 (3) | 0.003 (2) |
C81 | 0.087 (3) | 0.125 (4) | 0.073 (3) | 0.023 (3) | −0.016 (2) | 0.010 (3) |
N1 | 0.084 (2) | 0.066 (2) | 0.076 (2) | 0.0082 (18) | 0.0038 (19) | −0.0034 (19) |
N2 | 0.077 (2) | 0.0668 (19) | 0.0629 (19) | 0.0123 (17) | 0.0027 (17) | −0.0018 (16) |
N3 | 0.070 (2) | 0.075 (2) | 0.0599 (18) | 0.0111 (17) | −0.0056 (17) | −0.0028 (17) |
N4 | 0.072 (2) | 0.0695 (19) | 0.0620 (19) | 0.0135 (16) | −0.0039 (18) | −0.0071 (19) |
C3—N1 | 1.325 (6) | C11—C12 | 1.391 (7) |
C3—C4 | 1.393 (6) | C11—H11A | 0.9300 |
C3—C31 | 1.491 (7) | C12—C13 | 1.358 (7) |
C4—C5 | 1.371 (6) | C12—H12A | 0.9300 |
C4—H4A | 0.9300 | C13—C14 | 1.386 (7) |
C5—N2 | 1.376 (5) | C13—H13A | 0.9300 |
C5—C51 | 1.485 (6) | C14—C15 | 1.378 (6) |
C6—N4 | 1.309 (5) | C14—H14A | 0.9300 |
C6—C7 | 1.393 (6) | C15—H15A | 0.9300 |
C6—N2 | 1.415 (5) | C31—H31A | 0.9600 |
C7—C8 | 1.394 (6) | C31—H31B | 0.9600 |
C7—H7A | 0.9300 | C31—H31C | 0.9600 |
C8—N3 | 1.347 (5) | C51—H51A | 0.9600 |
C8—C81 | 1.490 (6) | C51—H51B | 0.9600 |
C9—N3 | 1.325 (5) | C51—H51C | 0.9600 |
C9—N4 | 1.349 (5) | C81—H81A | 0.9600 |
C9—C10 | 1.491 (6) | C81—H81B | 0.9600 |
C10—C11 | 1.374 (6) | C81—H81C | 0.9600 |
C10—C15 | 1.385 (6) | N1—N2 | 1.374 (5) |
N1—C3—C4 | 111.1 (4) | C14—C13—H13A | 120.6 |
N1—C3—C31 | 121.0 (5) | C15—C14—C13 | 120.5 (5) |
C4—C3—C31 | 127.9 (5) | C15—C14—H14A | 119.7 |
C5—C4—C3 | 107.5 (5) | C13—C14—H14A | 119.7 |
C5—C4—H4A | 126.2 | C14—C15—C10 | 120.8 (5) |
C3—C4—H4A | 126.2 | C14—C15—H15A | 119.6 |
C4—C5—N2 | 104.6 (4) | C10—C15—H15A | 119.6 |
C4—C5—C51 | 129.2 (4) | C3—C31—H31A | 109.5 |
N2—C5—C51 | 126.3 (4) | C3—C31—H31B | 109.5 |
N4—C6—C7 | 123.2 (4) | H31A—C31—H31B | 109.5 |
N4—C6—N2 | 115.6 (4) | C3—C31—H31C | 109.5 |
C7—C6—N2 | 121.2 (4) | H31A—C31—H31C | 109.5 |
C6—C7—C8 | 116.0 (4) | H31B—C31—H31C | 109.5 |
C6—C7—H7A | 122.0 | C5—C51—H51A | 109.5 |
C8—C7—H7A | 122.0 | C5—C51—H51B | 109.5 |
N3—C8—C7 | 121.5 (4) | H51A—C51—H51B | 109.5 |
N3—C8—C81 | 117.5 (4) | C5—C51—H51C | 109.5 |
C7—C8—C81 | 121.0 (4) | H51A—C51—H51C | 109.5 |
N3—C9—N4 | 125.8 (4) | H51B—C51—H51C | 109.5 |
N3—C9—C10 | 117.8 (4) | C8—C81—H81A | 109.5 |
N4—C9—C10 | 116.3 (3) | C8—C81—H81B | 109.5 |
C11—C10—C15 | 118.3 (4) | H81A—C81—H81B | 109.5 |
C11—C10—C9 | 121.5 (4) | C8—C81—H81C | 109.5 |
C15—C10—C9 | 120.1 (4) | H81A—C81—H81C | 109.5 |
C10—C11—C12 | 120.6 (4) | H81B—C81—H81C | 109.5 |
C10—C11—H11A | 119.7 | C3—N1—N2 | 104.6 (4) |
C12—C11—H11A | 119.7 | N1—N2—C5 | 112.3 (3) |
C13—C12—C11 | 121.0 (5) | N1—N2—C6 | 117.6 (3) |
C13—C12—H12A | 119.5 | C5—N2—C6 | 130.1 (4) |
C11—C12—H12A | 119.5 | C9—N3—C8 | 116.9 (4) |
C12—C13—C14 | 118.8 (4) | C6—N4—C9 | 116.6 (3) |
C12—C13—H13A | 120.6 | ||
N1—N2—C6—N4 | −177.4 (3) | N4—C9—C10—C15 | 6.4 (5) |
C16H16Cl2CuN4 | F(000) = 812 |
Mr = 398.77 | Dx = 1.568 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2156 (3) Å | Cell parameters from 3896 reflections |
b = 11.6522 (4) Å | θ = 2.7–30.1° |
c = 20.3956 (8) Å | µ = 1.61 mm−1 |
β = 99.841 (1)° | T = 293 K |
V = 1689.58 (11) Å3 | Plate, clear green |
Z = 4 | 0.54 × 0.23 × 0.04 mm |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 5033 independent reflections |
Radiation source: fine-focus sealed tube | 3781 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 25 pixels mm-1 | θmax = 32.5°, θmin = 2.7° |
π–scans | h = −10→9 |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | k = −10→16 |
Tmin = 0.645, Tmax = 0.941 | l = −30→29 |
10578 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0633P)2 + 0.6674P] where P = (Fo2 + 2Fc2)/3 |
5033 reflections | (Δ/σ)max = 0.002 |
208 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C16H16Cl2CuN4 | V = 1689.58 (11) Å3 |
Mr = 398.77 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2156 (3) Å | µ = 1.61 mm−1 |
b = 11.6522 (4) Å | T = 293 K |
c = 20.3956 (8) Å | 0.54 × 0.23 × 0.04 mm |
β = 99.841 (1)° |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 5033 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | 3781 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.941 | Rint = 0.016 |
10578 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.49 e Å−3 |
5033 reflections | Δρmin = −0.31 e Å−3 |
208 parameters |
Experimental. none |
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 | 0.22177 (4) | 0.61122 (2) | 0.798820 (11) | 0.03757 (9) | |
Cl1 | 0.06612 (9) | 0.63934 (6) | 0.88209 (3) | 0.05440 (16) | |
Cl2 | 0.29307 (11) | 0.42863 (5) | 0.80839 (3) | 0.06331 (18) | |
C3 | 0.1279 (3) | 0.57142 (19) | 0.64365 (10) | 0.0403 (4) | |
C4 | 0.1072 (3) | 0.6472 (2) | 0.58965 (11) | 0.0495 (5) | |
H4A | 0.0722 | 0.6272 | 0.5451 | 0.059* | |
C5 | 0.1467 (3) | 0.75510 (19) | 0.61340 (10) | 0.0437 (5) | |
C6 | 0.2442 (3) | 0.82428 (16) | 0.73257 (9) | 0.0326 (4) | |
C7 | 0.2356 (3) | 0.94055 (18) | 0.72394 (10) | 0.0385 (4) | |
H7A | 0.1853 | 0.9733 | 0.6832 | 0.046* | |
C8 | 0.3059 (3) | 1.00788 (17) | 0.77918 (10) | 0.0372 (4) | |
C9 | 0.3798 (3) | 0.84661 (17) | 0.84216 (9) | 0.0338 (4) | |
C10 | 0.4668 (3) | 0.79601 (17) | 0.90664 (9) | 0.0365 (4) | |
C11 | 0.4598 (4) | 0.8576 (2) | 0.96475 (11) | 0.0475 (5) | |
H11A | 0.3997 | 0.9284 | 0.9625 | 0.057* | |
C12 | 0.5420 (4) | 0.8135 (2) | 1.02579 (11) | 0.0591 (6) | |
H12A | 0.5348 | 0.8543 | 1.0645 | 0.071* | |
C13 | 0.6345 (4) | 0.7098 (2) | 1.02971 (12) | 0.0612 (7) | |
H13A | 0.6915 | 0.6809 | 1.0707 | 0.073* | |
C14 | 0.6416 (4) | 0.6491 (2) | 0.97225 (13) | 0.0612 (7) | |
H14A | 0.7034 | 0.5788 | 0.9748 | 0.073* | |
C15 | 0.5587 (3) | 0.6909 (2) | 0.91101 (11) | 0.0484 (5) | |
H15A | 0.5643 | 0.6488 | 0.8727 | 0.058* | |
C31 | 0.1028 (4) | 0.4456 (2) | 0.64134 (12) | 0.0525 (5) | |
H31A | 0.2012 | 0.4111 | 0.6218 | 0.079* | |
H31B | −0.0170 | 0.4272 | 0.6151 | 0.079* | |
H31C | 0.1079 | 0.4167 | 0.6857 | 0.079* | |
C51 | 0.1549 (5) | 0.8643 (2) | 0.57589 (12) | 0.0645 (7) | |
H51A | 0.1370 | 0.8482 | 0.5291 | 0.097* | |
H51B | 0.2753 | 0.8999 | 0.5895 | 0.097* | |
H51C | 0.0576 | 0.9151 | 0.5849 | 0.097* | |
C81 | 0.3017 (4) | 1.13550 (19) | 0.77637 (12) | 0.0475 (5) | |
H81A | 0.2263 | 1.1642 | 0.8072 | 0.071* | |
H81B | 0.2486 | 1.1598 | 0.7322 | 0.071* | |
H81C | 0.4274 | 1.1648 | 0.7879 | 0.071* | |
N1 | 0.1767 (2) | 0.63092 (14) | 0.69990 (8) | 0.0359 (3) | |
N2 | 0.1861 (2) | 0.74406 (14) | 0.68144 (7) | 0.0343 (3) | |
N3 | 0.3823 (2) | 0.96011 (15) | 0.83758 (8) | 0.0382 (3) | |
N4 | 0.3073 (2) | 0.77576 (13) | 0.79207 (7) | 0.0316 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.05027 (16) | 0.02815 (15) | 0.03428 (13) | −0.00253 (10) | 0.00721 (10) | 0.00130 (8) |
Cl1 | 0.0670 (4) | 0.0582 (4) | 0.0416 (3) | −0.0201 (3) | 0.0195 (2) | −0.0094 (2) |
Cl2 | 0.0957 (5) | 0.0316 (3) | 0.0609 (4) | 0.0076 (3) | 0.0084 (3) | 0.0073 (2) |
C3 | 0.0404 (10) | 0.0406 (11) | 0.0401 (10) | −0.0012 (8) | 0.0072 (8) | −0.0105 (8) |
C4 | 0.0630 (13) | 0.0507 (13) | 0.0327 (10) | 0.0021 (11) | 0.0019 (9) | −0.0085 (9) |
C5 | 0.0571 (12) | 0.0446 (12) | 0.0280 (8) | 0.0041 (10) | 0.0032 (8) | −0.0006 (8) |
C6 | 0.0358 (8) | 0.0299 (9) | 0.0319 (8) | −0.0008 (7) | 0.0053 (7) | −0.0035 (7) |
C7 | 0.0453 (10) | 0.0344 (11) | 0.0344 (9) | 0.0028 (8) | 0.0030 (8) | 0.0041 (7) |
C8 | 0.0403 (9) | 0.0297 (10) | 0.0414 (10) | 0.0002 (8) | 0.0067 (8) | 0.0016 (7) |
C9 | 0.0363 (9) | 0.0313 (10) | 0.0329 (8) | −0.0010 (7) | 0.0031 (7) | −0.0013 (7) |
C10 | 0.0411 (9) | 0.0344 (10) | 0.0320 (8) | −0.0049 (8) | 0.0008 (7) | −0.0012 (7) |
C11 | 0.0638 (13) | 0.0390 (11) | 0.0370 (10) | 0.0001 (10) | 0.0007 (9) | −0.0060 (8) |
C12 | 0.0775 (16) | 0.0640 (16) | 0.0326 (10) | −0.0022 (13) | 0.0003 (10) | −0.0065 (10) |
C13 | 0.0712 (16) | 0.0657 (17) | 0.0400 (11) | 0.0013 (13) | −0.0099 (11) | 0.0083 (11) |
C14 | 0.0763 (17) | 0.0500 (14) | 0.0507 (13) | 0.0179 (13) | −0.0081 (12) | 0.0042 (11) |
C15 | 0.0601 (13) | 0.0437 (12) | 0.0382 (10) | 0.0093 (10) | −0.0009 (9) | −0.0029 (9) |
C31 | 0.0629 (14) | 0.0424 (13) | 0.0521 (13) | −0.0073 (11) | 0.0092 (11) | −0.0149 (10) |
C51 | 0.109 (2) | 0.0490 (14) | 0.0337 (11) | 0.0058 (14) | 0.0083 (12) | 0.0074 (9) |
C81 | 0.0573 (12) | 0.0302 (11) | 0.0530 (13) | −0.0036 (9) | 0.0040 (10) | 0.0004 (9) |
N1 | 0.0444 (8) | 0.0289 (8) | 0.0344 (8) | −0.0004 (6) | 0.0061 (6) | −0.0021 (6) |
N2 | 0.0439 (8) | 0.0283 (8) | 0.0296 (7) | 0.0008 (6) | 0.0031 (6) | −0.0008 (6) |
N3 | 0.0439 (8) | 0.0330 (9) | 0.0366 (8) | −0.0027 (7) | 0.0035 (7) | −0.0007 (6) |
N4 | 0.0367 (7) | 0.0280 (8) | 0.0291 (7) | −0.0016 (6) | 0.0034 (6) | 0.0005 (6) |
Cu1—N1 | 2.0011 (16) | C10—C15 | 1.388 (3) |
Cu1—N4 | 2.0259 (15) | C10—C11 | 1.394 (3) |
Cu1—Cl2 | 2.1898 (6) | C11—C12 | 1.383 (3) |
Cu1—Cl1 | 2.2147 (6) | C11—H11A | 0.9300 |
C3—N1 | 1.335 (2) | C12—C13 | 1.377 (4) |
C3—C4 | 1.399 (3) | C12—H12A | 0.9300 |
C3—C31 | 1.477 (3) | C13—C14 | 1.377 (4) |
C4—C5 | 1.360 (3) | C13—H13A | 0.9300 |
C4—H4A | 0.9300 | C14—C15 | 1.378 (3) |
C5—N2 | 1.374 (2) | C14—H14A | 0.9300 |
C5—C51 | 1.491 (3) | C15—H15A | 0.9300 |
C6—N4 | 1.346 (2) | C31—H31A | 0.9600 |
C6—C7 | 1.366 (3) | C31—H31B | 0.9600 |
C6—N2 | 1.410 (2) | C31—H31C | 0.9600 |
C7—C8 | 1.395 (3) | C51—H51A | 0.9600 |
C7—H7A | 0.9300 | C51—H51B | 0.9600 |
C8—N3 | 1.345 (3) | C51—H51C | 0.9600 |
C8—C81 | 1.488 (3) | C81—H81A | 0.9600 |
C9—N3 | 1.326 (3) | C81—H81B | 0.9600 |
C9—N4 | 1.348 (2) | C81—H81C | 0.9600 |
C9—C10 | 1.480 (3) | N1—N2 | 1.376 (2) |
N1—Cu1—N4 | 79.74 (6) | C12—C13—H13A | 120.4 |
N1—Cu1—Cl2 | 101.34 (5) | C14—C13—H13A | 120.4 |
N4—Cu1—Cl2 | 148.86 (5) | C13—C14—C15 | 121.1 (2) |
N1—Cu1—Cl1 | 137.72 (5) | C13—C14—H14A | 119.4 |
N4—Cu1—Cl1 | 96.45 (5) | C15—C14—H14A | 119.4 |
Cl2—Cu1—Cl1 | 102.57 (3) | C14—C15—C10 | 119.9 (2) |
N1—C3—C4 | 109.01 (19) | C14—C15—H15A | 120.1 |
N1—C3—C31 | 123.8 (2) | C10—C15—H15A | 120.1 |
C4—C3—C31 | 127.23 (19) | C3—C31—H31A | 109.5 |
C5—C4—C3 | 108.37 (18) | C3—C31—H31B | 109.5 |
C5—C4—H4A | 125.8 | H31A—C31—H31B | 109.5 |
C3—C4—H4A | 125.8 | C3—C31—H31C | 109.5 |
C4—C5—N2 | 105.53 (18) | H31A—C31—H31C | 109.5 |
C4—C5—C51 | 129.09 (19) | H31B—C31—H31C | 109.5 |
N2—C5—C51 | 125.3 (2) | C5—C51—H51A | 109.5 |
N4—C6—C7 | 122.26 (17) | C5—C51—H51B | 109.5 |
N4—C6—N2 | 113.61 (16) | H51A—C51—H51B | 109.5 |
C7—C6—N2 | 124.12 (17) | C5—C51—H51C | 109.5 |
C6—C7—C8 | 116.83 (18) | H51A—C51—H51C | 109.5 |
C6—C7—H7A | 121.6 | H51B—C51—H51C | 109.5 |
C8—C7—H7A | 121.6 | C8—C81—H81A | 109.5 |
N3—C8—C7 | 121.33 (18) | C8—C81—H81B | 109.5 |
N3—C8—C81 | 116.76 (19) | H81A—C81—H81B | 109.5 |
C7—C8—C81 | 121.91 (19) | C8—C81—H81C | 109.5 |
N3—C9—N4 | 124.45 (17) | H81A—C81—H81C | 109.5 |
N3—C9—C10 | 116.82 (16) | H81B—C81—H81C | 109.5 |
N4—C9—C10 | 118.72 (17) | C3—N1—N2 | 106.29 (16) |
C15—C10—C11 | 119.08 (19) | C3—N1—Cu1 | 141.28 (15) |
C15—C10—C9 | 122.27 (18) | N2—N1—Cu1 | 112.25 (11) |
C11—C10—C9 | 118.63 (19) | N1—N2—C5 | 110.77 (16) |
C12—C11—C10 | 120.1 (2) | N1—N2—C6 | 117.08 (15) |
C12—C11—H11A | 119.9 | C5—N2—C6 | 131.99 (17) |
C10—C11—H11A | 119.9 | C9—N3—C8 | 117.82 (17) |
C13—C12—C11 | 120.5 (2) | C6—N4—C9 | 116.99 (16) |
C13—C12—H12A | 119.8 | C6—N4—Cu1 | 113.51 (12) |
C11—C12—H12A | 119.8 | C9—N4—Cu1 | 127.70 (13) |
C12—C13—C14 | 119.3 (2) | ||
N1—N2—C6—N4 | 8.6 (2) | N4—C9—C10—C15 | 32.0 (3) |
C16H16Cl2CuN4 | Dx = 1.574 Mg m−3 |
Mr = 398.77 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 4601 reflections |
a = 11.6899 (6) Å | θ = 2.5–30.5° |
b = 14.9843 (8) Å | µ = 1.62 mm−1 |
c = 19.2115 (9) Å | T = 293 K |
V = 3365.2 (3) Å3 | Elongated prism, clear emerald green |
Z = 8 | 0.33 × 0.10 × 0.09 mm |
F(000) = 1624 |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 5379 independent reflections |
Radiation source: fine-focus sealed tube | 3611 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 25 pixels mm-1 | θmax = 32.4°, θmin = 2.1° |
π–scans | h = −16→17 |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | k = −17→22 |
Tmin = 0.657, Tmax = 0.86 | l = −26→15 |
17334 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | w = 1/[σ2(Fo2) + (0.053P)2 + 2.2199P] where P = (Fo2 + 2Fc2)/3 |
5379 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C16H16Cl2CuN4 | V = 3365.2 (3) Å3 |
Mr = 398.77 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.6899 (6) Å | µ = 1.62 mm−1 |
b = 14.9843 (8) Å | T = 293 K |
c = 19.2115 (9) Å | 0.33 × 0.10 × 0.09 mm |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 5379 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | 3611 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.86 | Rint = 0.024 |
17334 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | Δρmax = 0.49 e Å−3 |
5379 reflections | Δρmin = −0.44 e Å−3 |
208 parameters |
Experimental. none |
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 | 0.751430 (18) | 0.839560 (17) | 0.548815 (12) | 0.03193 (8) | |
Cl1 | 0.71694 (4) | 0.74685 (4) | 0.63721 (3) | 0.04276 (13) | |
Cl2 | 0.93311 (4) | 0.86988 (5) | 0.56060 (3) | 0.05205 (15) | |
C3 | 0.79496 (17) | 0.81698 (14) | 0.38867 (10) | 0.0364 (4) | |
C4 | 0.72127 (18) | 0.80284 (16) | 0.33277 (11) | 0.0403 (5) | |
H4A | 0.7428 | 0.7869 | 0.2879 | 0.048* | |
C5 | 0.61204 (17) | 0.81652 (13) | 0.35544 (10) | 0.0337 (4) | |
C6 | 0.54197 (15) | 0.86338 (12) | 0.47575 (9) | 0.0281 (3) | |
C7 | 0.42510 (15) | 0.86907 (13) | 0.46564 (10) | 0.0323 (4) | |
H7A | 0.3915 | 0.8540 | 0.4233 | 0.039* | |
C8 | 0.36002 (16) | 0.89850 (13) | 0.52199 (10) | 0.0330 (4) | |
C9 | 0.52140 (15) | 0.91422 (12) | 0.58829 (9) | 0.0297 (4) | |
C10 | 0.57579 (16) | 0.94086 (13) | 0.65468 (9) | 0.0321 (4) | |
C11 | 0.5195 (2) | 0.92555 (15) | 0.71717 (11) | 0.0450 (5) | |
H11A | 0.4460 | 0.9019 | 0.7172 | 0.054* | |
C12 | 0.5732 (3) | 0.94568 (18) | 0.77950 (12) | 0.0581 (6) | |
H12A | 0.5362 | 0.9342 | 0.8214 | 0.070* | |
C13 | 0.6811 (2) | 0.98264 (18) | 0.77971 (12) | 0.0563 (6) | |
H13A | 0.7169 | 0.9952 | 0.8218 | 0.068* | |
C14 | 0.7361 (2) | 1.00108 (16) | 0.71794 (13) | 0.0478 (5) | |
H14A | 0.8078 | 1.0280 | 0.7182 | 0.057* | |
C15 | 0.68394 (17) | 0.97928 (14) | 0.65567 (10) | 0.0368 (4) | |
H15A | 0.7217 | 0.9905 | 0.6139 | 0.044* | |
C31 | 0.92214 (18) | 0.81407 (19) | 0.38827 (12) | 0.0521 (6) | |
H31A | 0.9516 | 0.8724 | 0.3779 | 0.078* | |
H31B | 0.9477 | 0.7726 | 0.3535 | 0.078* | |
H31C | 0.9492 | 0.7954 | 0.4331 | 0.078* | |
C51 | 0.50499 (19) | 0.81183 (17) | 0.31405 (10) | 0.0452 (5) | |
H51A | 0.5229 | 0.7955 | 0.2670 | 0.068* | |
H51B | 0.4680 | 0.8690 | 0.3145 | 0.068* | |
H51C | 0.4549 | 0.7679 | 0.3339 | 0.068* | |
C81 | 0.23295 (17) | 0.90503 (17) | 0.51881 (13) | 0.0442 (5) | |
H81A | 0.2001 | 0.8721 | 0.5567 | 0.066* | |
H81B | 0.2064 | 0.8807 | 0.4755 | 0.066* | |
H81C | 0.2105 | 0.9665 | 0.5222 | 0.066* | |
N1 | 0.73495 (12) | 0.83749 (11) | 0.44553 (8) | 0.0316 (3) | |
N2 | 0.62136 (13) | 0.83753 (10) | 0.42500 (8) | 0.0295 (3) | |
N3 | 0.40850 (13) | 0.92337 (11) | 0.58266 (9) | 0.0348 (4) | |
N4 | 0.58950 (12) | 0.88237 (11) | 0.53781 (8) | 0.0282 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02606 (11) | 0.04428 (15) | 0.02545 (13) | 0.00235 (9) | −0.00037 (8) | 0.00186 (9) |
Cl1 | 0.0403 (2) | 0.0539 (3) | 0.0341 (3) | 0.0093 (2) | 0.00545 (19) | 0.0107 (2) |
Cl2 | 0.0298 (2) | 0.0792 (4) | 0.0471 (3) | −0.0078 (3) | −0.0035 (2) | −0.0021 (3) |
C3 | 0.0355 (9) | 0.0458 (11) | 0.0278 (9) | 0.0054 (8) | 0.0088 (8) | 0.0050 (8) |
C4 | 0.0449 (11) | 0.0511 (12) | 0.0248 (9) | 0.0053 (9) | 0.0065 (8) | 0.0002 (9) |
C5 | 0.0386 (10) | 0.0389 (10) | 0.0236 (9) | −0.0004 (8) | −0.0004 (7) | 0.0000 (7) |
C6 | 0.0290 (8) | 0.0304 (8) | 0.0247 (8) | 0.0004 (7) | 0.0013 (7) | 0.0022 (7) |
C7 | 0.0286 (8) | 0.0389 (10) | 0.0294 (9) | −0.0002 (7) | −0.0020 (7) | −0.0002 (8) |
C8 | 0.0284 (8) | 0.0382 (10) | 0.0323 (10) | 0.0006 (7) | 0.0004 (7) | 0.0015 (8) |
C9 | 0.0305 (8) | 0.0324 (9) | 0.0260 (8) | 0.0020 (7) | 0.0029 (7) | −0.0017 (7) |
C10 | 0.0358 (9) | 0.0360 (9) | 0.0244 (9) | 0.0053 (7) | 0.0011 (7) | −0.0023 (7) |
C11 | 0.0493 (12) | 0.0528 (13) | 0.0330 (11) | −0.0025 (10) | 0.0087 (9) | −0.0046 (9) |
C12 | 0.0818 (18) | 0.0668 (16) | 0.0257 (10) | −0.0018 (14) | 0.0073 (11) | −0.0009 (11) |
C13 | 0.0766 (17) | 0.0598 (15) | 0.0325 (11) | 0.0008 (13) | −0.0136 (11) | −0.0066 (10) |
C14 | 0.0492 (13) | 0.0523 (13) | 0.0419 (12) | −0.0002 (10) | −0.0119 (10) | −0.0059 (10) |
C15 | 0.0368 (9) | 0.0426 (10) | 0.0311 (10) | 0.0035 (8) | −0.0003 (8) | −0.0032 (8) |
C31 | 0.0365 (11) | 0.0822 (17) | 0.0378 (12) | 0.0125 (11) | 0.0109 (9) | 0.0074 (12) |
C51 | 0.0436 (11) | 0.0653 (14) | 0.0269 (10) | −0.0024 (10) | −0.0045 (8) | −0.0068 (10) |
C81 | 0.0298 (10) | 0.0566 (14) | 0.0461 (13) | 0.0012 (9) | 0.0020 (8) | −0.0020 (10) |
N1 | 0.0261 (7) | 0.0437 (9) | 0.0250 (8) | 0.0029 (6) | 0.0019 (5) | 0.0011 (6) |
N2 | 0.0257 (7) | 0.0402 (8) | 0.0225 (7) | 0.0021 (6) | 0.0012 (6) | −0.0015 (6) |
N3 | 0.0302 (8) | 0.0418 (9) | 0.0325 (8) | 0.0028 (6) | 0.0025 (6) | −0.0025 (7) |
N4 | 0.0268 (7) | 0.0344 (8) | 0.0233 (7) | 0.0016 (6) | −0.0003 (5) | −0.0011 (6) |
Cu1—N1 | 1.9938 (16) | C10—C15 | 1.389 (3) |
Cu1—N4 | 2.0098 (15) | C10—C11 | 1.388 (3) |
Cu1—Cl2 | 2.1836 (6) | C11—C12 | 1.385 (3) |
Cu1—Cl1 | 2.2307 (6) | C11—H11A | 0.9300 |
C3—N1 | 1.334 (2) | C12—C13 | 1.377 (4) |
C3—C4 | 1.393 (3) | C12—H12A | 0.9300 |
C3—C31 | 1.487 (3) | C13—C14 | 1.378 (3) |
C4—C5 | 1.365 (3) | C13—H13A | 0.9300 |
C4—H4A | 0.9300 | C14—C15 | 1.382 (3) |
C5—N2 | 1.377 (2) | C14—H14A | 0.9300 |
C5—C51 | 1.484 (3) | C15—H15A | 0.9300 |
C6—N4 | 1.346 (2) | C31—H31A | 0.9600 |
C6—C7 | 1.383 (2) | C31—H31B | 0.9600 |
C6—N2 | 1.401 (2) | C31—H31C | 0.9600 |
C7—C8 | 1.395 (3) | C51—H51A | 0.9600 |
C7—H7A | 0.9300 | C51—H51B | 0.9600 |
C8—N3 | 1.349 (3) | C51—H51C | 0.9600 |
C8—C81 | 1.490 (3) | C81—H81A | 0.9600 |
C9—N3 | 1.331 (2) | C81—H81B | 0.9600 |
C9—N4 | 1.342 (2) | C81—H81C | 0.9600 |
C9—C10 | 1.480 (3) | N1—N2 | 1.385 (2) |
N1—Cu1—N4 | 79.01 (6) | C12—C13—H13A | 119.8 |
N1—Cu1—Cl2 | 101.56 (5) | C14—C13—H13A | 119.8 |
N4—Cu1—Cl2 | 149.38 (5) | C13—C14—C15 | 119.4 (2) |
N1—Cu1—Cl1 | 136.93 (5) | C13—C14—H14A | 120.3 |
N4—Cu1—Cl1 | 96.23 (5) | C15—C14—H14A | 120.3 |
Cl2—Cu1—Cl1 | 103.09 (2) | C14—C15—C10 | 120.8 (2) |
N1—C3—C4 | 109.95 (17) | C14—C15—H15A | 119.6 |
N1—C3—C31 | 122.45 (19) | C10—C15—H15A | 119.6 |
C4—C3—C31 | 127.57 (18) | C3—C31—H31A | 109.5 |
C5—C4—C3 | 108.05 (18) | C3—C31—H31B | 109.5 |
C5—C4—H4A | 126.0 | H31A—C31—H31B | 109.5 |
C3—C4—H4A | 126.0 | C3—C31—H31C | 109.5 |
C4—C5—N2 | 105.66 (17) | H31A—C31—H31C | 109.5 |
C4—C5—C51 | 127.65 (18) | H31B—C31—H31C | 109.5 |
N2—C5—C51 | 126.68 (18) | C5—C51—H51A | 109.5 |
N4—C6—C7 | 121.29 (16) | C5—C51—H51B | 109.5 |
N4—C6—N2 | 113.68 (15) | H51A—C51—H51B | 109.5 |
C7—C6—N2 | 125.02 (17) | C5—C51—H51C | 109.5 |
C6—C7—C8 | 116.71 (17) | H51A—C51—H51C | 109.5 |
C6—C7—H7A | 121.6 | H51B—C51—H51C | 109.5 |
C8—C7—H7A | 121.6 | C8—C81—H81A | 109.5 |
N3—C8—C7 | 121.94 (17) | C8—C81—H81B | 109.5 |
N3—C8—C81 | 115.87 (18) | H81A—C81—H81B | 109.5 |
C7—C8—C81 | 122.19 (19) | C8—C81—H81C | 109.5 |
N3—C9—N4 | 124.47 (17) | H81A—C81—H81C | 109.5 |
N3—C9—C10 | 117.91 (16) | H81B—C81—H81C | 109.5 |
N4—C9—C10 | 117.62 (16) | C3—N1—N2 | 105.72 (16) |
C15—C10—C11 | 119.20 (19) | C3—N1—Cu1 | 140.14 (14) |
C15—C10—C9 | 120.97 (17) | N2—N1—Cu1 | 112.09 (11) |
C11—C10—C9 | 119.82 (18) | C5—N2—N1 | 110.61 (14) |
C12—C11—C10 | 119.8 (2) | C5—N2—C6 | 133.33 (16) |
C12—C11—H11A | 120.1 | N1—N2—C6 | 115.91 (14) |
C10—C11—H11A | 120.1 | C9—N3—C8 | 117.28 (16) |
C13—C12—C11 | 120.3 (2) | C9—N4—C6 | 118.05 (15) |
C13—C12—H12A | 119.8 | C9—N4—Cu1 | 126.59 (12) |
C11—C12—H12A | 119.8 | C6—N4—Cu1 | 114.49 (12) |
C12—C13—C14 | 120.4 (2) | ||
N1—N2—C6—N4 | −1.5 (2) | N4—C9—C10—C15 | 35.2 (3) |
C16H16Cl2CuN4 | Z = 4 |
Mr = 398.77 | F(000) = 812 |
Monoclinic, P21/n | Dx = 1.554 Mg m−3 |
a = 9.7652 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 18.7631 (10) Å | µ = 1.60 mm−1 |
c = 9.8115 (4) Å | T = 293 K |
β = 108.544 (1)° | Prism, clear orange |
V = 1704.38 (16) Å3 | 0.31 × 0.17 × 0.12 mm |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 3915 independent reflections |
Radiation source: fine-focus sealed tube | 3240 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 25 pixels mm-1 | θmax = 27.6°, θmin = 2.2° |
π–scans | h = −12→12 |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | k = −24→24 |
Tmin = 0.721, Tmax = 0.820 | l = −12→8 |
12988 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.2601P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.002 |
3915 reflections | Δρmax = 0.38 e Å−3 |
209 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0021 (6) |
C16H16Cl2CuN4 | V = 1704.38 (16) Å3 |
Mr = 398.77 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7652 (6) Å | µ = 1.60 mm−1 |
b = 18.7631 (10) Å | T = 293 K |
c = 9.8115 (4) Å | 0.31 × 0.17 × 0.12 mm |
β = 108.544 (1)° |
Bruker-Nonius X8Apex CCD area-detector diffractometer | 3915 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Bruker) | 3240 reflections with I > 2σ(I) |
Tmin = 0.721, Tmax = 0.820 | Rint = 0.019 |
12988 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.38 e Å−3 |
3915 reflections | Δρmin = −0.28 e Å−3 |
209 parameters |
Experimental. none |
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 | 0.35577 (2) | 0.953703 (11) | 0.63529 (2) | 0.03640 (10) | |
Cl1 | 0.26509 (5) | 0.85393 (2) | 0.69352 (5) | 0.04572 (14) | |
Cl2 | 0.26863 (6) | 0.95797 (3) | 0.39918 (5) | 0.04932 (14) | |
C3 | 0.2445 (2) | 1.10742 (10) | 0.6439 (2) | 0.0429 (4) | |
C4 | 0.2987 (2) | 1.16774 (11) | 0.7277 (2) | 0.0471 (5) | |
H4A | 0.2528 | 1.2117 | 0.7207 | 0.056* | |
C5 | 0.4302 (2) | 1.15061 (9) | 0.8209 (2) | 0.0406 (4) | |
C6 | 0.56506 (19) | 1.03183 (9) | 0.85684 (19) | 0.0342 (4) | |
C7 | 0.68466 (19) | 1.04774 (11) | 0.9723 (2) | 0.0423 (5) | |
H7A | 0.6963 | 1.0924 | 1.0157 | 0.051* | |
C8 | 0.7868 (2) | 0.99460 (12) | 1.0210 (2) | 0.0443 (5) | |
C9 | 0.65500 (18) | 0.91947 (10) | 0.84397 (19) | 0.0375 (4) | |
C10 | 0.6418 (2) | 0.84987 (10) | 0.7705 (2) | 0.0410 (4) | |
C11 | 0.6852 (3) | 0.78836 (12) | 0.8515 (3) | 0.0578 (6) | |
H11A | 0.7306 | 0.7917 | 0.9502 | 0.069* | |
C12 | 0.6613 (3) | 0.72257 (13) | 0.7865 (4) | 0.0756 (8) | |
H12A | 0.6879 | 0.6814 | 0.8414 | 0.091* | |
C13 | 0.5983 (3) | 0.71794 (13) | 0.6405 (4) | 0.0763 (8) | |
H13A | 0.5808 | 0.6733 | 0.5970 | 0.092* | |
C14 | 0.5605 (3) | 0.77812 (13) | 0.5572 (3) | 0.0624 (6) | |
H14A | 0.5204 | 0.7743 | 0.4579 | 0.075* | |
C15 | 0.5823 (2) | 0.84446 (11) | 0.6220 (2) | 0.0477 (5) | |
H15A | 0.5573 | 0.8854 | 0.5662 | 0.057* | |
C31 | 0.1050 (2) | 1.09956 (12) | 0.5253 (3) | 0.0616 (6) | |
H31A | 0.1136 | 1.1204 | 0.4391 | 0.092* | |
H31B | 0.0298 | 1.1233 | 0.5513 | 0.092* | |
H31C | 0.0818 | 1.0499 | 0.5093 | 0.092* | |
C51 | 0.5336 (2) | 1.19784 (11) | 0.9267 (2) | 0.0569 (6) | |
H51A | 0.4912 | 1.2441 | 0.9249 | 0.085* | |
H51B | 0.6209 | 1.2020 | 0.9021 | 0.085* | |
H51C | 0.5554 | 1.1778 | 1.0212 | 0.085* | |
C81 | 0.9208 (2) | 1.00655 (15) | 1.1464 (2) | 0.0600 (6) | |
H81A | 0.9661 | 0.9616 | 1.1793 | 0.090* | |
H81B | 0.8956 | 1.0293 | 1.2227 | 0.090* | |
H81C | 0.9863 | 1.0364 | 1.1172 | 0.090* | |
N1 | 0.33813 (17) | 1.05425 (8) | 0.68426 (18) | 0.0390 (4) | |
N2 | 0.45345 (15) | 1.07999 (8) | 0.79458 (15) | 0.0347 (3) | |
N3 | 0.77311 (17) | 0.93061 (10) | 0.95595 (18) | 0.0444 (4) | |
N4 | 0.54687 (15) | 0.96688 (8) | 0.79507 (16) | 0.0335 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03786 (15) | 0.02895 (14) | 0.03432 (15) | −0.00187 (8) | 0.00005 (10) | 0.00082 (8) |
Cl1 | 0.0478 (3) | 0.0376 (2) | 0.0470 (3) | −0.00841 (19) | 0.0084 (2) | 0.00478 (19) |
Cl2 | 0.0595 (3) | 0.0456 (3) | 0.0339 (3) | −0.0068 (2) | 0.0021 (2) | 0.00339 (19) |
C3 | 0.0396 (10) | 0.0349 (9) | 0.0474 (11) | 0.0041 (8) | 0.0040 (8) | 0.0022 (8) |
C4 | 0.0518 (11) | 0.0323 (9) | 0.0528 (12) | 0.0057 (8) | 0.0105 (9) | 0.0013 (8) |
C5 | 0.0471 (10) | 0.0319 (9) | 0.0418 (10) | −0.0038 (8) | 0.0129 (8) | −0.0032 (7) |
C6 | 0.0314 (8) | 0.0376 (9) | 0.0326 (9) | −0.0026 (7) | 0.0088 (7) | 0.0018 (7) |
C7 | 0.0336 (9) | 0.0495 (12) | 0.0394 (10) | −0.0036 (8) | 0.0054 (8) | −0.0087 (8) |
C8 | 0.0307 (9) | 0.0649 (13) | 0.0346 (10) | −0.0019 (8) | 0.0068 (7) | 0.0007 (9) |
C9 | 0.0318 (9) | 0.0424 (10) | 0.0366 (9) | 0.0008 (7) | 0.0088 (7) | 0.0076 (8) |
C10 | 0.0327 (9) | 0.0387 (10) | 0.0514 (11) | 0.0053 (7) | 0.0132 (8) | 0.0055 (8) |
C11 | 0.0554 (12) | 0.0485 (12) | 0.0692 (15) | 0.0161 (10) | 0.0196 (11) | 0.0142 (11) |
C12 | 0.0837 (19) | 0.0426 (13) | 0.107 (2) | 0.0169 (12) | 0.0389 (17) | 0.0165 (14) |
C13 | 0.0863 (19) | 0.0384 (13) | 0.119 (3) | −0.0027 (12) | 0.0530 (19) | −0.0159 (14) |
C14 | 0.0599 (14) | 0.0604 (15) | 0.0714 (16) | −0.0038 (11) | 0.0275 (12) | −0.0180 (12) |
C15 | 0.0475 (11) | 0.0422 (11) | 0.0539 (12) | 0.0044 (9) | 0.0170 (9) | −0.0004 (9) |
C31 | 0.0465 (12) | 0.0489 (12) | 0.0682 (15) | 0.0092 (10) | −0.0116 (11) | −0.0003 (11) |
C51 | 0.0603 (14) | 0.0404 (11) | 0.0605 (14) | −0.0071 (10) | 0.0058 (11) | −0.0121 (10) |
C81 | 0.0346 (11) | 0.0918 (18) | 0.0442 (12) | 0.0022 (11) | −0.0010 (9) | −0.0068 (12) |
N1 | 0.0359 (8) | 0.0322 (8) | 0.0392 (8) | 0.0001 (6) | −0.0017 (6) | −0.0030 (6) |
N2 | 0.0315 (7) | 0.0316 (7) | 0.0346 (8) | −0.0024 (6) | 0.0015 (6) | −0.0036 (6) |
N3 | 0.0322 (8) | 0.0555 (10) | 0.0412 (9) | 0.0061 (7) | 0.0058 (7) | 0.0051 (8) |
N4 | 0.0297 (7) | 0.0343 (7) | 0.0332 (8) | −0.0005 (6) | 0.0055 (6) | 0.0024 (6) |
Cu1—N1 | 1.9679 (15) | C10—C11 | 1.389 (3) |
Cu1—N4 | 2.0348 (14) | C10—C15 | 1.391 (3) |
Cu1—Cl2 | 2.2008 (5) | C11—C12 | 1.375 (4) |
Cu1—Cl1 | 2.2219 (5) | C11—H11A | 0.9300 |
C3—N1 | 1.326 (2) | C12—C13 | 1.371 (4) |
C3—C4 | 1.400 (3) | C12—H12A | 0.9300 |
C3—C31 | 1.491 (3) | C13—C14 | 1.374 (4) |
C4—C5 | 1.357 (3) | C13—H13A | 0.9300 |
C4—H4A | 0.9300 | C14—C15 | 1.383 (3) |
C5—N2 | 1.383 (2) | C14—H14A | 0.9300 |
C5—C51 | 1.488 (3) | C15—H15A | 0.9300 |
C6—N4 | 1.347 (2) | C31—H31A | 0.9600 |
C6—C7 | 1.376 (2) | C31—H31B | 0.9600 |
C6—N2 | 1.398 (2) | C31—H31C | 0.9600 |
C7—C8 | 1.384 (3) | C51—H51A | 0.9600 |
C7—H7A | 0.9300 | C51—H51B | 0.9600 |
C8—N3 | 1.346 (3) | C51—H51C | 0.9600 |
C8—C81 | 1.500 (3) | C81—H81A | 0.9600 |
C9—N3 | 1.332 (2) | C81—H81B | 0.9600 |
C9—N4 | 1.347 (2) | C81—H81C | 0.9600 |
C9—C10 | 1.477 (3) | N1—N2 | 1.378 (2) |
N1—Cu1—N4 | 79.95 (6) | C12—C13—H13A | 119.5 |
N1—Cu1—Cl2 | 100.81 (5) | C14—C13—H13A | 119.5 |
N4—Cu1—Cl2 | 139.41 (5) | C13—C14—C15 | 119.6 (2) |
N1—Cu1—Cl1 | 132.22 (5) | C13—C14—H14A | 120.2 |
N4—Cu1—Cl1 | 104.31 (4) | C15—C14—H14A | 120.2 |
Cl2—Cu1—Cl1 | 104.42 (2) | C14—C15—C10 | 119.9 (2) |
N1—C3—C4 | 109.70 (17) | C14—C15—H15A | 120.0 |
N1—C3—C31 | 122.06 (18) | C10—C15—H15A | 120.0 |
C4—C3—C31 | 128.24 (18) | C3—C31—H31A | 109.5 |
C5—C4—C3 | 107.71 (17) | C3—C31—H31B | 109.5 |
C5—C4—H4A | 126.1 | H31A—C31—H31B | 109.5 |
C3—C4—H4A | 126.1 | C3—C31—H31C | 109.5 |
C4—C5—N2 | 106.10 (16) | H31A—C31—H31C | 109.5 |
C4—C5—C51 | 127.99 (18) | H31B—C31—H31C | 109.5 |
N2—C5—C51 | 125.85 (18) | C5—C51—H51A | 109.5 |
N4—C6—C7 | 121.49 (17) | C5—C51—H51B | 109.5 |
N4—C6—N2 | 114.53 (15) | H51A—C51—H51B | 109.5 |
C7—C6—N2 | 123.99 (17) | C5—C51—H51C | 109.5 |
C6—C7—C8 | 117.25 (18) | H51A—C51—H51C | 109.5 |
C6—C7—H7A | 121.4 | H51B—C51—H51C | 109.5 |
C8—C7—H7A | 121.4 | C8—C81—H81A | 109.5 |
N3—C8—C7 | 121.79 (17) | C8—C81—H81B | 109.5 |
N3—C8—C81 | 116.82 (19) | H81A—C81—H81B | 109.5 |
C7—C8—C81 | 121.4 (2) | C8—C81—H81C | 109.5 |
N3—C9—N4 | 124.41 (18) | H81A—C81—H81C | 109.5 |
N3—C9—C10 | 117.35 (17) | H81B—C81—H81C | 109.5 |
N4—C9—C10 | 118.24 (16) | C3—N1—N2 | 106.54 (14) |
C11—C10—C15 | 119.2 (2) | C3—N1—Cu1 | 138.95 (13) |
C11—C10—C9 | 119.50 (19) | N2—N1—Cu1 | 114.50 (11) |
C15—C10—C9 | 121.23 (17) | N1—N2—C5 | 109.94 (14) |
C12—C11—C10 | 120.4 (2) | N1—N2—C6 | 116.47 (14) |
C12—C11—H11A | 119.8 | C5—N2—C6 | 133.58 (15) |
C10—C11—H11A | 119.8 | C9—N3—C8 | 117.41 (17) |
C13—C12—C11 | 119.7 (2) | C9—N4—C6 | 117.44 (15) |
C13—C12—H12A | 120.2 | C9—N4—Cu1 | 128.11 (13) |
C11—C12—H12A | 120.2 | C6—N4—Cu1 | 114.45 (11) |
C12—C13—C14 | 121.0 (2) | ||
N1—N2—C6—N4 | 2.8 (2) | N4—C9—C10—C15 | 38.6 (3) |
Experimental details
(1) | (2g) | (2eg) | (2o) | |
Crystal data | ||||
Chemical formula | C16H16N4 | C16H16Cl2CuN4 | C16H16Cl2CuN4 | C16H16Cl2CuN4 |
Mr | 264.33 | 398.77 | 398.77 | 398.77 |
Crystal system, space group | Orthorhombic, Pna21 | Monoclinic, P21/c | Orthorhombic, Pbca | Monoclinic, P21/n |
Temperature (K) | 293 | 293 | 293 | 293 |
a, b, c (Å) | 19.499 (3), 4.7884 (6), 15.106 (2) | 7.2156 (3), 11.6522 (4), 20.3956 (8) | 11.6899 (6), 14.9843 (8), 19.2115 (9) | 9.7652 (6), 18.7631 (10), 9.8115 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 99.841 (1), 90 | 90, 90, 90 | 90, 108.544 (1), 90 |
V (Å3) | 1410.5 (4) | 1689.58 (11) | 3365.2 (3) | 1704.38 (16) |
Z | 4 | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 1.61 | 1.62 | 1.60 |
Crystal size (mm) | 0.59 × 0.05 × 0.03 | 0.54 × 0.23 × 0.04 | 0.33 × 0.10 × 0.09 | 0.31 × 0.17 × 0.12 |
Data collection | ||||
Diffractometer | Bruker-Nonius X8Apex CCD area-detector diffractometer | Bruker-Nonius X8Apex CCD area-detector diffractometer | Bruker-Nonius X8Apex CCD area-detector diffractometer | Bruker-Nonius X8Apex CCD area-detector diffractometer |
Absorption correction | – | Empirical (using intensity measurements) SADABS (Bruker) | Empirical (using intensity measurements) SADABS (Bruker) | Empirical (using intensity measurements) SADABS (Bruker) |
Tmin, Tmax | – | 0.645, 0.941 | 0.657, 0.86 | 0.721, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9460, 2221, 885 | 10578, 5033, 3781 | 17334, 5379, 3611 | 12988, 3915, 3240 |
Rint | 0.083 | 0.016 | 0.024 | 0.019 |
(sin θ/λ)max (Å−1) | 0.715 | 0.757 | 0.753 | 0.651 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.181, 0.91 | 0.033, 0.107, 0.94 | 0.032, 0.098, 0.86 | 0.029, 0.088, 1.10 |
No. of reflections | 2221 | 5033 | 5379 | 3915 |
No. of parameters | 182 | 208 | 208 | 209 |
No. of restraints | 1 | 0 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 | 0.49, −0.31 | 0.49, −0.44 | 0.38, −0.28 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | ? | ? | ? |
Absolute structure parameter | 0 (10) | ? | ? | ? |
Computer programs: Bruker APEX2, Bruker SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Bruker SHELXTL, TOPOS 4.0 Standard, local programs.