Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810034537/lh5106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536810034537/lh5106Isup2.hkl |
CCDC reference: 797596
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.010 Å
- R factor = 0.074
- wR factor = 0.147
- Data-to-parameter ratio = 20.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 10 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.90 eA-3 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.71 eA-3 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.62 eA-3 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.54 eA-3 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.51 eA-3 PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density -1.63 eA-3
Alert level G PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 10.83 PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c ....... P21/n
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
N1,N1,N4,N4-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine. An amount of 1.00 g (11.34 mmol) 1,4-diaminobutane was dissolved in 30 ml anhydrous dichloroethane under an inert atmosphere (argon) followed by the addition of 4.55 ml (47.65 mmol) pyridine-2-carboxaldehyde. The mixture was stirred for 15 min at r.t. and then cooled with an ice bath prior to the portionwise addition of 14.43 g (68.06 mmol) sodium triacetoxyborohydride (gas evolution, exothermic reaction). The reaction was stirred overnight allowing the temperature slowly to rise to room temperature. The reaction was quenched by the dropwise addition of saturated sodium bicarbonate solution and stirring was continued until the gas evolution ceased. The mixture was separated and the organic layer was further washed with saturated sodium bicarbonate solution, water and brine. The organic phase was dried with anhydrous sodium sulfate, filtered and the solvent removed under reduced pressure. The crude reaction mixture was then purified by silica gel column chromatography starting with chloroform and increasing gradient to chloroform:methanol 10:1 (v/v). Yield: 4.02 g (78%). 1H NMR (CDCl3): δ = 8.40 (m, 4H), 7.51 (m, 4H), 7.39 (d, J = 7.81 Hz, 4H), 7.02 (m, 4H), 3.67 (s, 8H), 2.39 (m, 4H), 1.42 (m, 4H) p.p.m..
Synthesis of metal complex. To 2 ml of an aqueous solution of copper bromide, two equivalents (50 mg, 0.11 mmol) of N1,N1,N4,N4-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine in 2 ml methanol were added followed by the addition of 2 ml N,N-dimethylformamide. Single crystals were obtained after a week by slow evaporation of the solvents at room temperature.
All the H atoms were placed in idealized positions and refined in a riding-model approximation with C—Haryl = 0.95 Å, C—Hmethyl = 0.98Å and C—Hmethylene = 0.99Å and Uiso(H) = 1.5Ueq(Cmethyl) and 1.2Ueq(Cmethylene/aryl).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu2Br4(C28H32N6)] | F(000) = 880 |
Mr = 899.32 | Dx = 2.002 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2666 reflections |
a = 8.8613 (6) Å | θ = 2.7–27.2° |
b = 14.249 (1) Å | µ = 6.81 mm−1 |
c = 11.9488 (9) Å | T = 90 K |
β = 98.588 (2)° | Plates, green |
V = 1491.80 (18) Å3 | 0.18 × 0.12 × 0.08 mm |
Z = 2 |
Bruker APEX CCD diffractometer | 3623 independent reflections |
Radiation source: fine-focus sealed tube | 3171 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 512 pixels mm-1 | θmax = 28.1°, θmin = 2.2° |
ϕ and ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −18→18 |
Tmin = 0.374, Tmax = 0.612 | l = −15→15 |
14513 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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.38 | w = 1/[σ2(Fo2) + (0.042P)2 + 10.8322P] where P = (Fo2 + 2Fc2)/3 |
3623 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 1.38 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
[Cu2Br4(C28H32N6)] | V = 1491.80 (18) Å3 |
Mr = 899.32 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.8613 (6) Å | µ = 6.81 mm−1 |
b = 14.249 (1) Å | T = 90 K |
c = 11.9488 (9) Å | 0.18 × 0.12 × 0.08 mm |
β = 98.588 (2)° |
Bruker APEX CCD diffractometer | 3623 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3171 reflections with I > 2σ(I) |
Tmin = 0.374, Tmax = 0.612 | Rint = 0.052 |
14513 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.38 | w = 1/[σ2(Fo2) + (0.042P)2 + 10.8322P] where P = (Fo2 + 2Fc2)/3 |
3623 reflections | Δρmax = 1.38 e Å−3 |
181 parameters | Δρmin = −0.85 e Å−3 |
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 | 0.35669 (10) | 0.75522 (6) | 0.35899 (7) | 0.0111 (2) | |
Br1 | 0.21437 (9) | 0.82045 (5) | 0.15805 (6) | 0.01711 (19) | |
Br2 | 0.29274 (9) | 0.87831 (5) | 0.48204 (6) | 0.01847 (19) | |
N1 | 0.4360 (6) | 0.6374 (4) | 0.2878 (5) | 0.0087 (11) | |
N2 | 0.1789 (7) | 0.6693 (4) | 0.3702 (5) | 0.0101 (11) | |
N3 | 0.5695 (6) | 0.8000 (4) | 0.3456 (5) | 0.0099 (11) | |
C1 | 0.2983 (8) | 0.5899 (5) | 0.2279 (6) | 0.0138 (14) | |
H1A | 0.3214 | 0.5230 | 0.2157 | 0.017* | |
H1B | 0.2676 | 0.6195 | 0.1530 | 0.017* | |
C2 | 0.1707 (8) | 0.5972 (5) | 0.2964 (6) | 0.0118 (13) | |
C3 | 0.0522 (8) | 0.5333 (5) | 0.2869 (6) | 0.0161 (15) | |
H3 | 0.0470 | 0.4837 | 0.2334 | 0.019* | |
C4 | −0.0587 (9) | 0.5423 (5) | 0.3564 (7) | 0.0208 (16) | |
H4 | −0.1415 | 0.4994 | 0.3507 | 0.025* | |
C5 | −0.0474 (9) | 0.6153 (6) | 0.4350 (7) | 0.0214 (16) | |
H5 | −0.1201 | 0.6219 | 0.4854 | 0.026* | |
C6 | 0.0718 (8) | 0.6775 (5) | 0.4377 (6) | 0.0159 (14) | |
H6 | 0.0784 | 0.7284 | 0.4896 | 0.019* | |
C7 | 0.5359 (8) | 0.6749 (5) | 0.2094 (6) | 0.0136 (14) | |
H7A | 0.4729 | 0.7002 | 0.1406 | 0.016* | |
H7B | 0.6010 | 0.6242 | 0.1863 | 0.016* | |
C8 | 0.6340 (8) | 0.7514 (5) | 0.2682 (6) | 0.0132 (14) | |
C9 | 0.7788 (9) | 0.7733 (5) | 0.2435 (6) | 0.0169 (15) | |
H9 | 0.8206 | 0.7398 | 0.1866 | 0.020* | |
C10 | 0.8606 (8) | 0.8445 (5) | 0.3033 (6) | 0.0167 (15) | |
H10 | 0.9603 | 0.8600 | 0.2890 | 0.020* | |
C11 | 0.7950 (9) | 0.8930 (5) | 0.3845 (6) | 0.0186 (15) | |
H11 | 0.8492 | 0.9421 | 0.4267 | 0.022* | |
C12 | 0.6489 (9) | 0.8689 (5) | 0.4032 (6) | 0.0147 (14) | |
H12 | 0.6041 | 0.9024 | 0.4587 | 0.018* | |
C13 | 0.5282 (8) | 0.5732 (5) | 0.3704 (6) | 0.0111 (13) | |
H13A | 0.6209 | 0.6073 | 0.4052 | 0.013* | |
H13B | 0.5620 | 0.5193 | 0.3281 | 0.013* | |
C14 | 0.4471 (7) | 0.5353 (4) | 0.4650 (5) | 0.0096 (13) | |
H14A | 0.3506 | 0.5042 | 0.4323 | 0.011* | |
H14B | 0.4224 | 0.5875 | 0.5139 | 0.011* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0124 (4) | 0.0090 (4) | 0.0126 (4) | 0.0003 (3) | 0.0041 (3) | −0.0005 (3) |
Br1 | 0.0196 (4) | 0.0162 (4) | 0.0155 (3) | 0.0032 (3) | 0.0024 (3) | 0.0062 (3) |
Br2 | 0.0249 (4) | 0.0131 (3) | 0.0198 (4) | −0.0001 (3) | 0.0110 (3) | −0.0037 (3) |
N1 | 0.009 (3) | 0.008 (3) | 0.011 (3) | −0.002 (2) | 0.004 (2) | 0.000 (2) |
N2 | 0.014 (3) | 0.009 (3) | 0.008 (2) | −0.002 (2) | 0.003 (2) | 0.003 (2) |
N3 | 0.010 (3) | 0.009 (3) | 0.011 (3) | 0.002 (2) | 0.003 (2) | 0.004 (2) |
C1 | 0.018 (4) | 0.012 (3) | 0.012 (3) | −0.003 (3) | 0.003 (3) | −0.006 (3) |
C2 | 0.013 (3) | 0.010 (3) | 0.011 (3) | 0.003 (3) | −0.003 (3) | 0.005 (2) |
C3 | 0.017 (4) | 0.010 (3) | 0.018 (3) | −0.002 (3) | −0.006 (3) | −0.002 (3) |
C4 | 0.013 (4) | 0.019 (4) | 0.032 (4) | −0.002 (3) | 0.005 (3) | 0.005 (3) |
C5 | 0.014 (4) | 0.027 (4) | 0.025 (4) | 0.001 (3) | 0.007 (3) | 0.009 (3) |
C6 | 0.014 (4) | 0.018 (4) | 0.015 (3) | 0.003 (3) | 0.003 (3) | 0.001 (3) |
C7 | 0.014 (4) | 0.016 (3) | 0.013 (3) | 0.001 (3) | 0.009 (3) | −0.004 (3) |
C8 | 0.019 (4) | 0.011 (3) | 0.010 (3) | −0.001 (3) | 0.003 (3) | 0.005 (3) |
C9 | 0.018 (4) | 0.019 (4) | 0.016 (3) | 0.003 (3) | 0.007 (3) | 0.005 (3) |
C10 | 0.011 (3) | 0.015 (3) | 0.024 (4) | −0.004 (3) | 0.002 (3) | 0.009 (3) |
C11 | 0.019 (4) | 0.015 (3) | 0.020 (4) | −0.001 (3) | −0.002 (3) | 0.001 (3) |
C12 | 0.021 (4) | 0.008 (3) | 0.016 (3) | 0.002 (3) | 0.003 (3) | 0.007 (3) |
C13 | 0.010 (3) | 0.010 (3) | 0.015 (3) | 0.002 (3) | 0.005 (3) | 0.004 (2) |
C14 | 0.007 (3) | 0.008 (3) | 0.013 (3) | 0.000 (2) | 0.001 (2) | 0.005 (2) |
Cu1—N2 | 2.015 (6) | C5—C6 | 1.375 (11) |
Cu1—N3 | 2.019 (6) | C5—H5 | 0.9500 |
Cu1—N1 | 2.053 (5) | C6—H6 | 0.9500 |
Cu1—Br2 | 2.4099 (11) | C7—C8 | 1.502 (10) |
Cu1—Br1 | 2.7045 (11) | C7—H7A | 0.9900 |
N1—C7 | 1.482 (8) | C7—H7B | 0.9900 |
N1—C1 | 1.482 (9) | C8—C9 | 1.394 (10) |
N1—C13 | 1.495 (8) | C9—C10 | 1.382 (11) |
N2—C6 | 1.340 (9) | C9—H9 | 0.9500 |
N2—C2 | 1.349 (9) | C10—C11 | 1.388 (11) |
N3—C12 | 1.337 (9) | C10—H10 | 0.9500 |
N3—C8 | 1.349 (9) | C11—C12 | 1.389 (11) |
C1—C2 | 1.496 (10) | C11—H11 | 0.9500 |
C1—H1A | 0.9900 | C12—H12 | 0.9500 |
C1—H1B | 0.9900 | C13—C14 | 1.526 (9) |
C2—C3 | 1.381 (10) | C13—H13A | 0.9900 |
C3—C4 | 1.384 (11) | C13—H13B | 0.9900 |
C3—H3 | 0.9500 | C14—C14i | 1.536 (12) |
C4—C5 | 1.395 (12) | C14—H14A | 0.9900 |
C4—H4 | 0.9500 | C14—H14B | 0.9900 |
N2—Cu1—N3 | 161.0 (2) | C6—C5—H5 | 120.8 |
N2—Cu1—N1 | 81.4 (2) | C4—C5—H5 | 120.8 |
N3—Cu1—N1 | 81.0 (2) | N2—C6—C5 | 122.7 (7) |
N2—Cu1—Br2 | 98.29 (16) | N2—C6—H6 | 118.7 |
N3—Cu1—Br2 | 97.22 (16) | C5—C6—H6 | 118.7 |
N1—Cu1—Br2 | 166.96 (16) | N1—C7—C8 | 109.0 (5) |
N2—Cu1—Br1 | 90.12 (16) | N1—C7—H7A | 109.9 |
N3—Cu1—Br1 | 97.95 (15) | C8—C7—H7A | 109.9 |
N1—Cu1—Br1 | 93.22 (16) | N1—C7—H7B | 109.9 |
Br2—Cu1—Br1 | 99.82 (4) | C8—C7—H7B | 109.9 |
C7—N1—C1 | 112.7 (5) | H7A—C7—H7B | 108.3 |
C7—N1—C13 | 108.6 (5) | N3—C8—C9 | 121.9 (7) |
C1—N1—C13 | 111.7 (5) | N3—C8—C7 | 114.7 (6) |
C7—N1—Cu1 | 103.9 (4) | C9—C8—C7 | 123.4 (6) |
C1—N1—Cu1 | 105.4 (4) | C10—C9—C8 | 118.9 (7) |
C13—N1—Cu1 | 114.4 (4) | C10—C9—H9 | 120.6 |
C6—N2—C2 | 119.0 (6) | C8—C9—H9 | 120.6 |
C6—N2—Cu1 | 128.2 (5) | C9—C10—C11 | 119.0 (7) |
C2—N2—Cu1 | 112.7 (4) | C9—C10—H10 | 120.5 |
C12—N3—C8 | 119.0 (6) | C11—C10—H10 | 120.5 |
C12—N3—Cu1 | 128.1 (5) | C10—C11—C12 | 119.2 (7) |
C8—N3—Cu1 | 112.9 (5) | C10—C11—H11 | 120.4 |
N1—C1—C2 | 109.8 (5) | C12—C11—H11 | 120.4 |
N1—C1—H1A | 109.7 | N3—C12—C11 | 122.0 (7) |
C2—C1—H1A | 109.7 | N3—C12—H12 | 119.0 |
N1—C1—H1B | 109.7 | C11—C12—H12 | 119.0 |
C2—C1—H1B | 109.7 | N1—C13—C14 | 115.7 (5) |
H1A—C1—H1B | 108.2 | N1—C13—H13A | 108.4 |
N2—C2—C3 | 121.5 (7) | C14—C13—H13A | 108.4 |
N2—C2—C1 | 116.0 (6) | N1—C13—H13B | 108.4 |
C3—C2—C1 | 122.5 (6) | C14—C13—H13B | 108.4 |
C2—C3—C4 | 119.2 (7) | H13A—C13—H13B | 107.4 |
C2—C3—H3 | 120.4 | C13—C14—C14i | 108.6 (7) |
C4—C3—H3 | 120.4 | C13—C14—H14A | 110.0 |
C3—C4—C5 | 119.2 (7) | C14i—C14—H14A | 110.0 |
C3—C4—H4 | 120.4 | C13—C14—H14B | 110.0 |
C5—C4—H4 | 120.4 | C14i—C14—H14B | 110.0 |
C6—C5—C4 | 118.3 (7) | H14A—C14—H14B | 108.3 |
N2—Cu1—N1—C7 | 151.6 (4) | Cu1—N2—C2—C3 | −176.6 (5) |
N3—Cu1—N1—C7 | −35.6 (4) | C6—N2—C2—C1 | −177.1 (6) |
Br2—Cu1—N1—C7 | −118.9 (7) | Cu1—N2—C2—C1 | 4.5 (7) |
Br1—Cu1—N1—C7 | 62.0 (4) | N1—C1—C2—N2 | 24.0 (8) |
N2—Cu1—N1—C1 | 32.9 (4) | N1—C1—C2—C3 | −154.9 (6) |
N3—Cu1—N1—C1 | −154.3 (4) | N2—C2—C3—C4 | −1.4 (10) |
Br2—Cu1—N1—C1 | 122.4 (7) | C1—C2—C3—C4 | 177.4 (7) |
Br1—Cu1—N1—C1 | −56.7 (4) | C2—C3—C4—C5 | −0.5 (11) |
N2—Cu1—N1—C13 | −90.2 (4) | C3—C4—C5—C6 | 2.1 (11) |
N3—Cu1—N1—C13 | 82.6 (4) | C2—N2—C6—C5 | −0.2 (10) |
Br2—Cu1—N1—C13 | −0.7 (10) | Cu1—N2—C6—C5 | 178.0 (5) |
Br1—Cu1—N1—C13 | −179.8 (4) | C4—C5—C6—N2 | −1.7 (11) |
N3—Cu1—N2—C6 | 137.8 (7) | C1—N1—C7—C8 | 158.0 (6) |
N1—Cu1—N2—C6 | 160.1 (6) | C13—N1—C7—C8 | −77.8 (7) |
Br2—Cu1—N2—C6 | −6.7 (6) | Cu1—N1—C7—C8 | 44.4 (6) |
Br1—Cu1—N2—C6 | −106.7 (6) | C12—N3—C8—C9 | −2.4 (10) |
N3—Cu1—N2—C2 | −44.0 (9) | Cu1—N3—C8—C9 | 177.9 (5) |
N1—Cu1—N2—C2 | −21.7 (4) | C12—N3—C8—C7 | 179.3 (6) |
Br2—Cu1—N2—C2 | 171.5 (4) | Cu1—N3—C8—C7 | −0.3 (7) |
Br1—Cu1—N2—C2 | 71.6 (4) | N1—C7—C8—N3 | −30.7 (8) |
N2—Cu1—N3—C12 | −136.2 (7) | N1—C7—C8—C9 | 151.1 (6) |
N1—Cu1—N3—C12 | −158.5 (6) | N3—C8—C9—C10 | 2.5 (10) |
Br2—Cu1—N3—C12 | 8.4 (6) | C7—C8—C9—C10 | −179.4 (7) |
Br1—Cu1—N3—C12 | 109.4 (5) | C8—C9—C10—C11 | −1.1 (10) |
N2—Cu1—N3—C8 | 43.4 (9) | C9—C10—C11—C12 | −0.2 (10) |
N1—Cu1—N3—C8 | 21.0 (4) | C8—N3—C12—C11 | 1.1 (10) |
Br2—Cu1—N3—C8 | −172.0 (4) | Cu1—N3—C12—C11 | −179.4 (5) |
Br1—Cu1—N3—C8 | −71.0 (4) | C10—C11—C12—N3 | 0.2 (10) |
C7—N1—C1—C2 | −151.4 (6) | C7—N1—C13—C14 | 174.3 (6) |
C13—N1—C1—C2 | 86.1 (7) | C1—N1—C13—C14 | −60.8 (7) |
Cu1—N1—C1—C2 | −38.8 (6) | Cu1—N1—C13—C14 | 58.8 (7) |
C6—N2—C2—C3 | 1.8 (10) | N1—C13—C14—C14i | 175.1 (6) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Br4(C28H32N6)] |
Mr | 899.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 8.8613 (6), 14.249 (1), 11.9488 (9) |
β (°) | 98.588 (2) |
V (Å3) | 1491.80 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.81 |
Crystal size (mm) | 0.18 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.374, 0.612 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14513, 3623, 3171 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.147, 1.38 |
No. of reflections | 3623 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.042P)2 + 10.8322P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.38, −0.85 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 1999), SHELXTL (Sheldrick, 2008).
Cu1—N2 | 2.015 (6) | Cu1—Br2 | 2.4099 (11) |
Cu1—N3 | 2.019 (6) | Cu1—Br1 | 2.7045 (11) |
Cu1—N1 | 2.053 (5) |
The described ligand N1,N1,N4,N4-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine has been used as starting material for hydrothermal synthesis of metal-organic transition metal/molybdateoxide frameworks in the principal author's laboratory (Bartholomä, unpublished results). The dipicolylamine moiety has originally been used in our laboratory as metal chelating entity for binding of the M(CO)3 core (M = Re,99mTc) for radiopharmaceutical purposes. A different coordination mode has been observed for the M(CO)3 core in which the dipicolylamine metal chelate is coordinated in a facial manner (Bartholomä, 2009).
The title complex was prepared as part of a series with different cadmium and copper salts to study the coordination properties of the ligand with these metals without the interaction of metaloxide clusters (Bartholomä, 2010a,b,c). The crystalline sample obtained with copper chloride as metal source and N1,N1,N5,N5-tetrakis(pyridin-2-ylmethyl)pentane-1,5-diamine gave a structurally similar compound with a distorted square pyramidal coordination geometry of the copper atoms as observed for the described complex. The Cu—Npy distances of 1.986 (4) Å and 1.996 (4), and a Cu—Ntert distance of 2.076 (4) Å (Bartholomä, 2010d).
Crystal structures of the ligands N1,N1,N3,N3-tetrakis(2-pyridiniomethyl)-1,3-diaminopropane and N1,N1,N4,N4-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine have been described recently (Fujihara, 2004; Mambanda, 2007). Superoxide dismutase activity of iron(II) complexes of N1,N1,N3,N3-tetrakis(2-pyridiniomethyl)-1,3-diaminopropane and related ligands has been investigated by Tamura et al. (2000). Studies on the thermodynamic and kinetic behaviour of the reaction of platinum(II) complexes of higher ligand homologues with chloride have been performed by Ertürk et al. (2007).