Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805025626/ci6617sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805025626/ci6617Isup2.hkl |
CCDC reference: 287505
The ligand 2-[tris(hydroxymethyl)methyliminomethyl]phenol was prepared according to the literature procedure of Asgedom et al. (1996). Cuprous chloride (0.105 g, 0.5 mmol) was added to a solution of the ligand (0.111 g, 0.5 mmol) in water (10 ml). After stirring for a short time, the solution turned dark green. The filtrate was left for 2 d at room temperature and green needle-shaped crystals were obtained in about 62% yield.
H atoms were placed in idealized positions [N—H = 0.82 Å, C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C)] and were included in the refinement in the riding-model approximation.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Fig. 1. An ORTEPII plot (Johnson, 1976) of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. |
[Cu(C11H14NO4)Cl] | Dx = 1.750 Mg m−3 |
Mr = 323.22 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P421c | Cell parameters from 1879 reflections |
Hall symbol: P -4 2n | θ = 2.4–23.3° |
a = 16.7345 (6) Å | µ = 2.00 mm−1 |
c = 8.7634 (6) Å | T = 293 K |
V = 2454.1 (2) Å3 | Needle, green |
Z = 8 | 0.21 × 0.09 × 0.07 mm |
F(000) = 1320 |
Bruker APEX area-dectector diffractometer | 2918 independent reflections |
Radiation source: fine-focus sealed tube | 2661 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 27.9°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −21→21 |
Tmin = 0.679, Tmax = 0.873 | k = −21→21 |
20984 measured reflections | l = −11→11 |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0354P)2 + 1.812P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2918 reflections | Δρmax = 0.36 e Å−3 |
165 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1265 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.007 (15) |
[Cu(C11H14NO4)Cl] | Z = 8 |
Mr = 323.22 | Mo Kα radiation |
Tetragonal, P421c | µ = 2.00 mm−1 |
a = 16.7345 (6) Å | T = 293 K |
c = 8.7634 (6) Å | 0.21 × 0.09 × 0.07 mm |
V = 2454.1 (2) Å3 |
Bruker APEX area-dectector diffractometer | 2918 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2661 reflections with I > 2σ(I) |
Tmin = 0.679, Tmax = 0.873 | Rint = 0.049 |
20984 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 0.36 e Å−3 |
S = 1.01 | Δρmin = −0.21 e Å−3 |
2918 reflections | Absolute structure: Flack (1983), 1265 Friedel pairs |
165 parameters | Absolute structure parameter: 0.007 (15) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.18286 (2) | 0.741879 (19) | 0.09321 (5) | 0.02794 (11) | |
Cl1 | 0.28495 (5) | 0.76534 (5) | −0.06532 (11) | 0.0405 (2) | |
N1 | 0.09148 (14) | 0.73905 (15) | 0.2314 (3) | 0.0234 (5) | |
O1 | 0.21555 (13) | 0.63628 (13) | 0.1344 (3) | 0.0335 (5) | |
O2 | 0.13204 (14) | 0.84338 (13) | 0.0301 (3) | 0.0351 (5) | |
H2A | 0.1380 | 0.8636 | −0.0544 | 0.053* | |
O3 | −0.08821 (14) | 0.86992 (15) | 0.2373 (2) | 0.0337 (5) | |
H3 | −0.1088 | 0.8869 | 0.3158 | 0.051* | |
O4 | 0.07400 (15) | 0.84538 (14) | 0.5015 (3) | 0.0337 (5) | |
H4 | 0.1005 | 0.8046 | 0.5127 | 0.051* | |
C1 | 0.1834 (2) | 0.58627 (18) | 0.2323 (3) | 0.0289 (6) | |
C2 | 0.2141 (2) | 0.5080 (2) | 0.2414 (4) | 0.0376 (8) | |
H2 | 0.2556 | 0.4931 | 0.1770 | 0.045* | |
C3 | 0.1843 (2) | 0.4534 (2) | 0.3426 (4) | 0.0439 (9) | |
H3A | 0.2054 | 0.4020 | 0.3446 | 0.053* | |
C4 | 0.1232 (2) | 0.4736 (2) | 0.4422 (4) | 0.0421 (9) | |
H4A | 0.1051 | 0.4370 | 0.5140 | 0.051* | |
C5 | 0.0901 (2) | 0.54798 (19) | 0.4334 (4) | 0.0354 (7) | |
H5 | 0.0483 | 0.5611 | 0.4987 | 0.043* | |
C6 | 0.11758 (19) | 0.60572 (18) | 0.3277 (4) | 0.0278 (6) | |
C7 | 0.07552 (17) | 0.68002 (18) | 0.3202 (3) | 0.0249 (6) | |
H7 | 0.0324 | 0.6862 | 0.3860 | 0.030* | |
C8 | 0.04322 (17) | 0.81324 (18) | 0.2348 (3) | 0.0234 (6) | |
C9 | 0.05021 (18) | 0.84912 (19) | 0.0741 (4) | 0.0298 (7) | |
H9A | 0.0167 | 0.8198 | 0.0031 | 0.036* | |
H9B | 0.0333 | 0.9046 | 0.0747 | 0.036* | |
C10 | −0.04503 (17) | 0.79829 (18) | 0.2701 (3) | 0.0273 (6) | |
H10A | −0.0651 | 0.7547 | 0.2080 | 0.033* | |
H10B | −0.0515 | 0.7840 | 0.3766 | 0.033* | |
C11 | 0.0808 (2) | 0.87221 (18) | 0.3487 (4) | 0.0295 (7) | |
H11A | 0.1368 | 0.8793 | 0.3239 | 0.035* | |
H11B | 0.0547 | 0.9237 | 0.3390 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02737 (19) | 0.02232 (17) | 0.03414 (19) | 0.00267 (14) | 0.00942 (16) | 0.00233 (16) |
Cl1 | 0.0386 (4) | 0.0303 (4) | 0.0527 (5) | 0.0000 (3) | 0.0219 (4) | 0.0010 (4) |
N1 | 0.0232 (12) | 0.0231 (12) | 0.0239 (12) | −0.0004 (10) | 0.0004 (9) | −0.0011 (10) |
O1 | 0.0352 (11) | 0.0274 (10) | 0.0378 (13) | 0.0095 (10) | 0.0115 (10) | 0.0053 (9) |
O2 | 0.0352 (12) | 0.0351 (12) | 0.0350 (12) | 0.0087 (10) | 0.0143 (10) | 0.0136 (10) |
O3 | 0.0281 (11) | 0.0502 (14) | 0.0228 (11) | 0.0163 (11) | 0.0025 (9) | 0.0021 (10) |
O4 | 0.0450 (14) | 0.0304 (12) | 0.0258 (12) | 0.0083 (10) | −0.0084 (10) | −0.0055 (9) |
C1 | 0.0315 (16) | 0.0292 (15) | 0.0261 (15) | 0.0050 (13) | −0.0033 (13) | −0.0009 (12) |
C2 | 0.0416 (19) | 0.0308 (16) | 0.0404 (19) | 0.0082 (15) | 0.0033 (16) | 0.0012 (15) |
C3 | 0.050 (2) | 0.0251 (16) | 0.056 (2) | 0.0072 (16) | −0.0002 (19) | 0.0070 (15) |
C4 | 0.044 (2) | 0.0311 (17) | 0.051 (2) | −0.0064 (15) | 0.0007 (17) | 0.0187 (16) |
C5 | 0.0349 (16) | 0.0338 (16) | 0.0376 (19) | −0.0021 (14) | 0.0031 (15) | 0.0046 (14) |
C6 | 0.0310 (17) | 0.0234 (15) | 0.0291 (16) | −0.0039 (12) | −0.0021 (13) | 0.0024 (13) |
C7 | 0.0228 (14) | 0.0268 (15) | 0.0251 (14) | −0.0017 (12) | 0.0024 (11) | −0.0033 (13) |
C8 | 0.0231 (13) | 0.0272 (14) | 0.0197 (13) | 0.0033 (13) | 0.0002 (11) | −0.0003 (12) |
C9 | 0.0282 (14) | 0.0331 (15) | 0.0282 (16) | 0.0081 (12) | 0.0063 (13) | 0.0062 (14) |
C10 | 0.0235 (14) | 0.0352 (17) | 0.0232 (14) | 0.0031 (13) | −0.0003 (11) | 0.0002 (13) |
C11 | 0.0331 (16) | 0.0210 (14) | 0.0344 (17) | 0.0042 (13) | −0.0034 (13) | −0.0021 (13) |
Cu1—O1 | 1.885 (2) | C3—C4 | 1.386 (5) |
Cu1—N1 | 1.951 (2) | C3—H3A | 0.93 |
Cu1—O2 | 1.979 (2) | C4—C5 | 1.365 (5) |
Cu1—Cl1 | 2.2366 (8) | C4—H4A | 0.93 |
N1—C7 | 1.286 (4) | C5—C6 | 1.415 (4) |
N1—C8 | 1.481 (4) | C5—H5 | 0.93 |
O1—C1 | 1.313 (4) | C6—C7 | 1.430 (4) |
O2—C9 | 1.426 (3) | C7—H7 | 0.93 |
O2—H2A | 0.82 | C8—C11 | 1.538 (4) |
O3—C10 | 1.429 (4) | C8—C10 | 1.529 (4) |
O3—H3 | 0.82 | C8—C9 | 1.535 (4) |
O4—C11 | 1.417 (4) | C9—H9A | 0.97 |
O4—H4 | 0.82 | C9—H9B | 0.97 |
C1—C2 | 1.408 (4) | C10—H10A | 0.97 |
C1—C6 | 1.421 (4) | C10—H10B | 0.97 |
C2—C3 | 1.367 (5) | C11—H11A | 0.97 |
C2—H2 | 0.93 | C11—H11B | 0.97 |
O1—Cu1—N1 | 94.92 (10) | C5—C6—C1 | 118.7 (3) |
O1—Cu1—O2 | 169.50 (10) | C5—C6—C7 | 117.6 (3) |
N1—Cu1—O2 | 81.81 (10) | C1—C6—C7 | 123.6 (3) |
O1—Cu1—Cl1 | 93.56 (7) | N1—C7—C6 | 126.4 (3) |
N1—Cu1—Cl1 | 171.25 (8) | N1—C7—H7 | 116.8 |
O2—Cu1—Cl1 | 90.22 (7) | C6—C7—H7 | 116.8 |
C7—N1—C8 | 121.2 (2) | N1—C8—C11 | 109.1 (2) |
C7—N1—Cu1 | 123.9 (2) | N1—C8—C10 | 113.2 (2) |
C8—N1—Cu1 | 114.80 (18) | C11—C8—C10 | 111.6 (2) |
C1—O1—Cu1 | 127.2 (2) | N1—C8—C9 | 105.5 (2) |
C9—O2—Cu1 | 113.26 (17) | C11—C8—C9 | 108.3 (3) |
C9—O2—H2A | 109.5 | C10—C8—C9 | 108.9 (2) |
Cu1—O2—H2A | 123.7 | O2—C9—C8 | 107.2 (2) |
C10—O3—H3 | 109.5 | O2—C9—H9A | 110.3 |
C11—O4—H4 | 109.5 | C8—C9—H9A | 110.3 |
O1—C1—C2 | 118.7 (3) | O2—C9—H9B | 110.3 |
O1—C1—C6 | 123.7 (3) | C8—C9—H9B | 110.3 |
C2—C1—C6 | 117.5 (3) | H9A—C9—H9B | 108.5 |
C3—C2—C1 | 121.7 (3) | O3—C10—C8 | 108.1 (2) |
C3—C2—H2 | 119.1 | O3—C10—H10A | 110.1 |
C1—C2—H2 | 119.1 | C8—C10—H10A | 110.1 |
C2—C3—C4 | 120.9 (3) | O3—C10—H10B | 110.1 |
C2—C3—H3A | 119.5 | C8—C10—H10B | 110.1 |
C4—C3—H3A | 119.5 | H10A—C10—H10B | 108.4 |
C5—C4—C3 | 119.1 (3) | O4—C11—C8 | 112.2 (2) |
C5—C4—H4A | 120.5 | O4—C11—H11A | 109.2 |
C3—C4—H4A | 120.5 | C8—C11—H11A | 109.2 |
C4—C5—C6 | 121.9 (3) | O4—C11—H11B | 109.2 |
C4—C5—H5 | 119.1 | C8—C11—H11B | 109.2 |
C6—C5—H5 | 119.1 | H11A—C11—H11B | 107.9 |
O1—Cu1—N1—C7 | 5.2 (2) | C2—C1—C6—C7 | −173.8 (3) |
O2—Cu1—N1—C7 | 175.2 (2) | C8—N1—C7—C6 | −179.9 (3) |
O1—Cu1—N1—C8 | −178.54 (19) | Cu1—N1—C7—C6 | −3.9 (4) |
O2—Cu1—N1—C8 | −8.59 (19) | C5—C6—C7—N1 | −179.7 (3) |
N1—Cu1—O1—C1 | −2.7 (3) | C1—C6—C7—N1 | −1.6 (5) |
O2—Cu1—O1—C1 | −74.0 (6) | C7—N1—C8—C11 | 91.1 (3) |
Cl1—Cu1—O1—C1 | 175.1 (3) | Cu1—N1—C8—C11 | −85.3 (2) |
O1—Cu1—O2—C9 | 54.0 (6) | C7—N1—C8—C10 | −33.9 (4) |
N1—Cu1—O2—C9 | −18.4 (2) | Cu1—N1—C8—C10 | 149.79 (18) |
Cl1—Cu1—O2—C9 | 165.2 (2) | C7—N1—C8—C9 | −152.8 (3) |
Cu1—O1—C1—C2 | 176.9 (2) | Cu1—N1—C8—C9 | 30.9 (3) |
Cu1—O1—C1—C6 | −1.4 (4) | Cu1—O2—C9—C8 | 39.6 (3) |
O1—C1—C2—C3 | 178.9 (3) | N1—C8—C9—O2 | −43.8 (3) |
C6—C1—C2—C3 | −2.8 (5) | C11—C8—C9—O2 | 72.9 (3) |
C1—C2—C3—C4 | −1.0 (6) | C10—C8—C9—O2 | −165.6 (2) |
C2—C3—C4—C5 | 3.1 (6) | N1—C8—C10—O3 | −167.3 (2) |
C3—C4—C5—C6 | −1.4 (6) | C11—C8—C10—O3 | 69.1 (3) |
C4—C5—C6—C1 | −2.4 (5) | C9—C8—C10—O3 | −50.3 (3) |
C4—C5—C6—C7 | 175.9 (3) | N1—C8—C11—O4 | −68.1 (3) |
O1—C1—C6—C5 | −177.4 (3) | C10—C8—C11—O4 | 57.7 (3) |
C2—C1—C6—C5 | 4.4 (5) | C9—C8—C11—O4 | 177.5 (2) |
O1—C1—C6—C7 | 4.5 (5) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C11H14NO4)Cl] |
Mr | 323.22 |
Crystal system, space group | Tetragonal, P421c |
Temperature (K) | 293 |
a, c (Å) | 16.7345 (6), 8.7634 (6) |
V (Å3) | 2454.1 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.00 |
Crystal size (mm) | 0.21 × 0.09 × 0.07 |
Data collection | |
Diffractometer | Bruker APEX area-dectector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.679, 0.873 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20984, 2918, 2661 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.077, 1.01 |
No. of reflections | 2918 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.21 |
Absolute structure | Flack (1983), 1265 Friedel pairs |
Absolute structure parameter | 0.007 (15) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Cu1—O1 | 1.885 (2) | Cu1—O2 | 1.979 (2) |
Cu1—N1 | 1.951 (2) | Cu1—Cl1 | 2.2366 (8) |
O1—Cu1—N1 | 94.92 (10) | O1—Cu1—Cl1 | 93.56 (7) |
O1—Cu1—O2 | 169.50 (10) | N1—Cu1—Cl1 | 171.25 (8) |
N1—Cu1—O2 | 81.81 (10) | O2—Cu1—Cl1 | 90.22 (7) |
The chemistry of transition metal ion complexes of hydroxy (aryl and alkyl OH) rich molecules containing imine/amine groups is important in biomimetic chemistry (Cornman et al., 1992). Many complexes of this kind have been reported (Asgedom & Rao, 1996; Dey, Rao, Saarenketo & Rissanen, 2002; Dey, Rao, Saarenketo, Rissanen & Kolehmainen, 2002). We report here a new copper(II) complex, (I), with a tridentate Schiff base ligand.
In compound (I), the CuII center is four-coordinated in a square-planar configuration by one N and two O atoms of the Schiff base ligand and one Cl atom. The Cu—O bond lengths are 1.885 (2) and 1.979 (2) Å; the shorter distance between copper and the phenoxy O atom indicates that the electronegativity of atom O1 is stronger than that of the other O atoms of the ligand.