Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041669/hb2515sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041669/hb2515Isup2.hkl |
CCDC reference: 660173
2,4-Dibromo-6-((pyridine-2-ylmethylamino)methyl)phenol (0.372 g, 1 mmol) was added to a methanol solution (20 ml) of CuCl2·2H2O (0.170 g, 1 mmol) with stirring. The resulting solution was left to stand at room temperture and blue blocks of (I) were obtained after several days.
All H-atoms bound to carbon were refined using a riding model [C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C)]. The amino H atom was located in a difference map and it sposition was freely refined with Uiso(H) = 1.2 Ueq(N).
Copper(II) complexes with various organic ligands have been a subject of intense study because of their important biological properties (Solomon et al., 1996). Here, we report the synthesis and structure of the new title complex, Cu(dmp)Cl, (I), where dmp is 2,4-dibromo-6((pyridine-2-ylmethylamino)methy)phenol.
Selected bond lengths are listed in Table 1. The CuII atom is four-coordinated by one pyridine N atom, one amine N atom and one phenolate O atom from the ligand and one chloride ion in a distorted square-planar arangement (Fig. 1). The metal to ligand-atom distances in (I) are similar to the ones found in bis[2,4-dibromo-6((pyridnine-2-ylmethylamino)methy) phenolato]bis[nitratocopper(II)] (Ma et al., 2007).
An N—H···O hydrogen bond (Table 2) helps to stabilize the packing in (I).
For background, see: Solomon et al. (1996); Ma et al. (2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). |
[Cu(C13H11Br2N2O)Cl] | F(000) = 908 |
Mr = 470.05 | Dx = 2.056 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8947 reflections |
a = 13.447 (4) Å | θ = 2.0–28.2° |
b = 16.628 (5) Å | µ = 6.87 mm−1 |
c = 6.881 (2) Å | T = 305 K |
β = 99.179 (4)° | Block, blue |
V = 1518.8 (8) Å3 | 0.32 × 0.26 × 0.20 mm |
Z = 4 |
Bruker APEX CCD diffractometer | 3459 independent reflections |
Radiation source: fine-focus sealed tube | 2044 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ω scans | θmax = 28.2°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→11 |
Tmin = 0.133, Tmax = 0.251 | k = −21→20 |
8786 measured reflections | l = −9→8 |
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)] = 0.051 | Hydrogen site location: difmap and geom |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0706P)2] where P = (Fo2 + 2Fc2)/3 |
3459 reflections | (Δ/σ)max < 0.001 |
184 parameters | Δρmax = 1.04 e Å−3 |
1 restraint | Δρmin = −0.83 e Å−3 |
[Cu(C13H11Br2N2O)Cl] | V = 1518.8 (8) Å3 |
Mr = 470.05 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.447 (4) Å | µ = 6.87 mm−1 |
b = 16.628 (5) Å | T = 305 K |
c = 6.881 (2) Å | 0.32 × 0.26 × 0.20 mm |
β = 99.179 (4)° |
Bruker APEX CCD diffractometer | 3459 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2044 reflections with I > 2σ(I) |
Tmin = 0.133, Tmax = 0.251 | Rint = 0.073 |
8786 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 1.04 e Å−3 |
3459 reflections | Δρmin = −0.83 e Å−3 |
184 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 | −0.0249 (5) | 0.1997 (4) | 0.2698 (10) | 0.0567 (18) | |
H1 | −0.0348 | 0.2549 | 0.2769 | 0.068* | |
C2 | −0.1045 (5) | 0.1518 (5) | 0.1881 (12) | 0.071 (2) | |
H2 | −0.1667 | 0.1746 | 0.1402 | 0.085* | |
C3 | −0.0908 (5) | 0.0702 (4) | 0.1784 (10) | 0.064 (2) | |
H3 | −0.1436 | 0.0370 | 0.1239 | 0.077* | |
C4 | 0.0020 (5) | 0.0386 (4) | 0.2504 (10) | 0.0555 (17) | |
H4 | 0.0131 | −0.0165 | 0.2453 | 0.067* | |
C5 | 0.0794 (4) | 0.0900 (3) | 0.3312 (9) | 0.0433 (14) | |
C6 | 0.1807 (4) | 0.0582 (3) | 0.4151 (10) | 0.0517 (16) | |
H6A | 0.1775 | 0.0324 | 0.5405 | 0.062* | |
H6B | 0.2010 | 0.0180 | 0.3269 | 0.062* | |
C7 | 0.3373 (4) | 0.1065 (3) | 0.6124 (9) | 0.0423 (14) | |
H7A | 0.3642 | 0.0530 | 0.5977 | 0.051* | |
H7B | 0.3093 | 0.1074 | 0.7338 | 0.051* | |
C8 | 0.4210 (4) | 0.1665 (3) | 0.6255 (8) | 0.0376 (13) | |
C9 | 0.5188 (4) | 0.1412 (3) | 0.6364 (8) | 0.0388 (13) | |
H9 | 0.5326 | 0.0864 | 0.6338 | 0.047* | |
C10 | 0.5971 (4) | 0.1957 (4) | 0.6513 (9) | 0.0442 (14) | |
C11 | 0.5778 (4) | 0.2781 (4) | 0.6515 (9) | 0.0460 (15) | |
H11 | 0.6303 | 0.3150 | 0.6598 | 0.055* | |
C12 | 0.4791 (4) | 0.3039 (3) | 0.6390 (8) | 0.0381 (13) | |
C13 | 0.3969 (4) | 0.2501 (3) | 0.6281 (8) | 0.0358 (13) | |
N1 | 0.0656 (3) | 0.1695 (3) | 0.3389 (7) | 0.0453 (12) | |
N2 | 0.2557 (3) | 0.1231 (3) | 0.4435 (7) | 0.0372 (11) | |
O1 | 0.3038 (3) | 0.2762 (2) | 0.6237 (6) | 0.0431 (10) | |
Cu1 | 0.19000 (5) | 0.23063 (4) | 0.45485 (11) | 0.0392 (2) | |
Br1 | 0.45266 (5) | 0.41577 (3) | 0.63413 (9) | 0.0508 (2) | |
Br2 | 0.73138 (5) | 0.15965 (5) | 0.66154 (15) | 0.0798 (3) | |
Cl1 | 0.12562 (12) | 0.35288 (9) | 0.3686 (3) | 0.0528 (4) | |
H2N | 0.291 (4) | 0.133 (4) | 0.337 (8) | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.045 (4) | 0.049 (4) | 0.073 (5) | 0.002 (3) | −0.002 (3) | −0.009 (3) |
C2 | 0.043 (4) | 0.069 (6) | 0.093 (6) | 0.002 (3) | −0.009 (4) | 0.003 (4) |
C3 | 0.061 (4) | 0.055 (5) | 0.072 (5) | −0.019 (3) | −0.003 (4) | 0.002 (4) |
C4 | 0.053 (4) | 0.045 (4) | 0.066 (5) | −0.012 (3) | 0.002 (3) | −0.005 (3) |
C5 | 0.056 (4) | 0.032 (3) | 0.041 (4) | −0.005 (3) | 0.005 (3) | −0.004 (3) |
C6 | 0.054 (4) | 0.024 (3) | 0.075 (5) | −0.008 (3) | 0.004 (3) | −0.005 (3) |
C7 | 0.050 (3) | 0.027 (3) | 0.050 (4) | 0.003 (2) | 0.007 (3) | 0.002 (3) |
C8 | 0.055 (3) | 0.022 (3) | 0.034 (3) | 0.002 (2) | 0.000 (3) | −0.001 (2) |
C9 | 0.041 (3) | 0.033 (3) | 0.038 (3) | 0.004 (2) | −0.007 (2) | −0.001 (2) |
C10 | 0.046 (3) | 0.039 (4) | 0.046 (4) | 0.008 (3) | 0.000 (3) | −0.001 (3) |
C11 | 0.050 (4) | 0.042 (4) | 0.045 (4) | −0.010 (3) | 0.003 (3) | −0.005 (3) |
C12 | 0.049 (3) | 0.024 (3) | 0.039 (3) | 0.001 (2) | 0.002 (3) | 0.001 (2) |
C13 | 0.045 (3) | 0.029 (3) | 0.032 (3) | 0.002 (2) | 0.004 (2) | −0.004 (2) |
N1 | 0.046 (3) | 0.039 (3) | 0.050 (3) | −0.003 (2) | 0.006 (2) | −0.006 (2) |
N2 | 0.038 (3) | 0.023 (2) | 0.049 (3) | −0.0042 (19) | 0.002 (2) | 0.002 (2) |
O1 | 0.045 (2) | 0.028 (2) | 0.053 (3) | 0.0031 (16) | −0.0033 (18) | −0.0094 (18) |
Cu1 | 0.0457 (4) | 0.0235 (4) | 0.0461 (5) | 0.0024 (3) | 0.0001 (3) | −0.0024 (3) |
Br1 | 0.0744 (5) | 0.0233 (3) | 0.0519 (4) | −0.0046 (3) | 0.0015 (3) | −0.0005 (3) |
Br2 | 0.0459 (4) | 0.0605 (5) | 0.1286 (8) | 0.0074 (3) | 0.0000 (4) | −0.0052 (5) |
Cl1 | 0.0572 (9) | 0.0307 (8) | 0.0698 (11) | 0.0100 (6) | 0.0079 (8) | 0.0083 (7) |
C1—N1 | 1.331 (7) | C7—H7B | 0.9700 |
C1—C2 | 1.379 (9) | C8—C9 | 1.372 (7) |
C1—H1 | 0.9300 | C8—C13 | 1.428 (7) |
C2—C3 | 1.372 (9) | C9—C10 | 1.380 (8) |
C2—H2 | 0.9300 | C9—H9 | 0.9300 |
C3—C4 | 1.373 (9) | C10—C11 | 1.395 (8) |
C3—H3 | 0.9300 | C10—Br2 | 1.893 (6) |
C4—C5 | 1.392 (8) | C11—C12 | 1.385 (8) |
C4—H4 | 0.9300 | C11—H11 | 0.9300 |
C5—N1 | 1.338 (7) | C12—C13 | 1.414 (8) |
C5—C6 | 1.490 (8) | C12—Br1 | 1.893 (5) |
C6—N2 | 1.469 (7) | C13—O1 | 1.321 (6) |
C6—H6A | 0.9700 | N2—H2N | 0.94 (4) |
C6—H6B | 0.9700 | Cu1—O1 | 1.923 (4) |
C7—N2 | 1.492 (7) | Cu1—N2 | 2.001 (4) |
C7—C8 | 1.496 (7) | Cu1—N1 | 2.011 (5) |
C7—H7A | 0.9700 | Cu1—Cl1 | 2.2517 (16) |
N1—C1—C2 | 122.3 (6) | C8—C9—H9 | 119.5 |
N1—C1—H1 | 118.9 | C10—C9—H9 | 119.5 |
C2—C1—H1 | 118.9 | C9—C10—C11 | 120.4 (5) |
C3—C2—C1 | 119.3 (6) | C9—C10—Br2 | 120.5 (4) |
C3—C2—H2 | 120.4 | C11—C10—Br2 | 119.1 (4) |
C1—C2—H2 | 120.4 | C12—C11—C10 | 118.8 (5) |
C2—C3—C4 | 118.9 (6) | C12—C11—H11 | 120.6 |
C2—C3—H3 | 120.6 | C10—C11—H11 | 120.6 |
C4—C3—H3 | 120.6 | C11—C12—C13 | 122.7 (5) |
C3—C4—C5 | 119.2 (6) | C11—C12—Br1 | 118.8 (4) |
C3—C4—H4 | 120.4 | C13—C12—Br1 | 118.6 (4) |
C5—C4—H4 | 120.4 | O1—C13—C12 | 121.5 (5) |
N1—C5—C4 | 121.6 (6) | O1—C13—C8 | 122.4 (5) |
N1—C5—C6 | 117.4 (5) | C12—C13—C8 | 116.1 (5) |
C4—C5—C6 | 121.0 (6) | C1—N1—C5 | 118.9 (5) |
N2—C6—C5 | 110.9 (5) | C1—N1—Cu1 | 127.4 (4) |
N2—C6—H6A | 109.5 | C5—N1—Cu1 | 113.8 (4) |
C5—C6—H6A | 109.5 | C6—N2—C7 | 111.8 (4) |
N2—C6—H6B | 109.5 | C6—N2—Cu1 | 111.3 (4) |
C5—C6—H6B | 109.5 | C7—N2—Cu1 | 114.2 (3) |
H6A—C6—H6B | 108.1 | C6—N2—H2N | 116 (4) |
N2—C7—C8 | 112.1 (5) | C7—N2—H2N | 104 (4) |
N2—C7—H7A | 109.2 | Cu1—N2—H2N | 99 (4) |
C8—C7—H7A | 109.2 | C13—O1—Cu1 | 123.0 (3) |
N2—C7—H7B | 109.2 | O1—Cu1—N2 | 93.56 (16) |
C8—C7—H7B | 109.2 | O1—Cu1—N1 | 166.0 (2) |
H7A—C7—H7B | 107.9 | N2—Cu1—N1 | 82.99 (19) |
C9—C8—C13 | 121.0 (5) | O1—Cu1—Cl1 | 92.22 (12) |
C9—C8—C7 | 120.2 (5) | N2—Cu1—Cl1 | 161.76 (15) |
C13—C8—C7 | 118.8 (5) | N1—Cu1—Cl1 | 95.21 (15) |
C8—C9—C10 | 121.1 (5) | ||
N1—C1—C2—C3 | 0.5 (12) | C2—C1—N1—Cu1 | 178.1 (6) |
C1—C2—C3—C4 | 0.0 (12) | C4—C5—N1—C1 | 0.9 (10) |
C2—C3—C4—C5 | 0.1 (11) | C6—C5—N1—C1 | −178.3 (6) |
C3—C4—C5—N1 | −0.5 (10) | C4—C5—N1—Cu1 | −178.2 (5) |
C3—C4—C5—C6 | 178.6 (6) | C6—C5—N1—Cu1 | 2.6 (7) |
N1—C5—C6—N2 | −15.6 (8) | C5—C6—N2—C7 | 149.8 (5) |
C4—C5—C6—N2 | 165.2 (6) | C5—C6—N2—Cu1 | 20.7 (7) |
N2—C7—C8—C9 | −127.8 (6) | C8—C7—N2—C6 | 172.3 (5) |
N2—C7—C8—C13 | 52.8 (7) | C8—C7—N2—Cu1 | −60.2 (5) |
C13—C8—C9—C10 | 0.3 (9) | C12—C13—O1—Cu1 | 138.6 (4) |
C7—C8—C9—C10 | −179.1 (5) | C8—C13—O1—Cu1 | −42.4 (7) |
C8—C9—C10—C11 | −1.3 (9) | C13—O1—Cu1—N2 | 26.5 (4) |
C8—C9—C10—Br2 | −178.9 (4) | C13—O1—Cu1—N1 | 101.6 (8) |
C9—C10—C11—C12 | 0.8 (9) | C13—O1—Cu1—Cl1 | −136.2 (4) |
Br2—C10—C11—C12 | 178.4 (4) | C6—N2—Cu1—O1 | 150.7 (4) |
C10—C11—C12—C13 | 0.7 (9) | C7—N2—Cu1—O1 | 22.9 (4) |
C10—C11—C12—Br1 | −178.8 (4) | C6—N2—Cu1—N1 | −15.7 (4) |
C11—C12—C13—O1 | 177.4 (5) | C7—N2—Cu1—N1 | −143.5 (4) |
Br1—C12—C13—O1 | −3.1 (7) | C6—N2—Cu1—Cl1 | −101.1 (5) |
C11—C12—C13—C8 | −1.6 (8) | C7—N2—Cu1—Cl1 | 131.1 (4) |
Br1—C12—C13—C8 | 177.9 (4) | C1—N1—Cu1—O1 | 112.1 (8) |
C9—C8—C13—O1 | −177.9 (5) | C5—N1—Cu1—O1 | −68.8 (9) |
C7—C8—C13—O1 | 1.5 (8) | C1—N1—Cu1—N2 | −171.6 (6) |
C9—C8—C13—C12 | 1.1 (8) | C5—N1—Cu1—N2 | 7.5 (4) |
C7—C8—C13—C12 | −179.5 (5) | C1—N1—Cu1—Cl1 | −9.8 (6) |
C2—C1—N1—C5 | −0.9 (10) | C5—N1—Cu1—Cl1 | 169.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.94 (4) | 2.14 (5) | 2.918 (6) | 139 (5) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C13H11Br2N2O)Cl] |
Mr | 470.05 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 305 |
a, b, c (Å) | 13.447 (4), 16.628 (5), 6.881 (2) |
β (°) | 99.179 (4) |
V (Å3) | 1518.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.87 |
Crystal size (mm) | 0.32 × 0.26 × 0.20 |
Data collection | |
Diffractometer | Bruker APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.133, 0.251 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8786, 3459, 2044 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.664 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.137, 0.94 |
No. of reflections | 3459 |
No. of parameters | 184 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.04, −0.83 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.94 (4) | 2.14 (5) | 2.918 (6) | 139 (5) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Copper(II) complexes with various organic ligands have been a subject of intense study because of their important biological properties (Solomon et al., 1996). Here, we report the synthesis and structure of the new title complex, Cu(dmp)Cl, (I), where dmp is 2,4-dibromo-6((pyridine-2-ylmethylamino)methy)phenol.
Selected bond lengths are listed in Table 1. The CuII atom is four-coordinated by one pyridine N atom, one amine N atom and one phenolate O atom from the ligand and one chloride ion in a distorted square-planar arangement (Fig. 1). The metal to ligand-atom distances in (I) are similar to the ones found in bis[2,4-dibromo-6((pyridnine-2-ylmethylamino)methy) phenolato]bis[nitratocopper(II)] (Ma et al., 2007).
An N—H···O hydrogen bond (Table 2) helps to stabilize the packing in (I).