Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102019728/fg1669sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102019728/fg1669Isup2.hkl |
CCDC reference: 187387
To a suspension of bis(ethanediamine)copper(II) perchlorate (5.0 g, 13 mmol) in methanol (100 ml) were added 2-hydroxyethylamine (2.5 ml) and triethanolamine (2.5 ml). A solution of formaldehyde (2.5 ml, 37% aqueous solution) in methanol (8 ml) was then added dropwise to the refluxing suspension over a period of 1 h. The solution was refluxed for a further 4 h and then cooled in an ice bath, and the purple-red product was collected. Purple single crystals of (I) were obtained after recrystallizing from water containing NaSCN.
The H atoms were visible in difference maps and were allowed for as riding atoms, with C—H = 0.97, N—H = 0.91 and O—H = 0.82 Å.
Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1990a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXTL-Plus.
[Cu(SCN)2(C12H30N6O2] | Z = 1 |
Mr = 470.12 | F(000) = 247 |
Triclinic, P1 | Dx = 1.502 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.118 (1) Å | Cell parameters from 30 reflections |
b = 9.328 (1) Å | θ = 2.5–15.4° |
c = 9.483 (1) Å | µ = 1.28 mm−1 |
α = 111.00 (1)° | T = 296 K |
β = 106.80 (1)° | Prism, purple |
γ = 103.85 (1)° | 0.56 × 0.56 × 0.40 mm |
V = 519.65 (15) Å3 |
Siemens P4 diffractometer | 1639 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.009 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −9→9 |
Tmin = 0.451, Tmax = 0.600 | l = −11→10 |
1903 measured reflections | 3 standard reflections every 97 reflections |
1747 independent reflections | intensity decay: 2.0% |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.5754P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1747 reflections | Δρmax = 0.73 e Å−3 |
126 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.117 (7) |
[Cu(SCN)2(C12H30N6O2] | γ = 103.85 (1)° |
Mr = 470.12 | V = 519.65 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.118 (1) Å | Mo Kα radiation |
b = 9.328 (1) Å | µ = 1.28 mm−1 |
c = 9.483 (1) Å | T = 296 K |
α = 111.00 (1)° | 0.56 × 0.56 × 0.40 mm |
β = 106.80 (1)° |
Siemens P4 diffractometer | 1639 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.009 |
Tmin = 0.451, Tmax = 0.600 | 3 standard reflections every 97 reflections |
1903 measured reflections | intensity decay: 2.0% |
1747 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.73 e Å−3 |
1747 reflections | Δρmin = −0.37 e Å−3 |
126 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 | ||
Cu | 0.0000 | 0.5000 | 0.5000 | 0.0245 (2) | |
S1 | 0.46607 (13) | 0.61456 (12) | 0.68477 (10) | 0.0493 (3) | |
O1 | 0.5732 (4) | 0.9549 (3) | 0.3151 (3) | 0.0523 (7) | |
H1 | 0.5950 | 0.9050 | 0.2345 | 0.063* | |
N1 | 0.0580 (3) | 0.7262 (3) | 0.5124 (3) | 0.0249 (5) | |
H1A | 0.2015 | 0.7820 | 0.5631 | 0.030* | |
N2 | 0.0688 (4) | 0.6450 (3) | 0.2393 (3) | 0.0299 (5) | |
N3 | 0.0622 (3) | 0.4092 (3) | 0.2989 (3) | 0.0242 (5) | |
H3 | 0.2060 | 0.4436 | 0.3358 | 0.029* | |
N4 | 0.6316 (7) | 0.7877 (7) | 1.0238 (4) | 0.1080 (18) | |
C1 | −0.0302 (5) | 0.8129 (3) | 0.6251 (4) | 0.0316 (6) | |
H1B | −0.1831 | 0.7745 | 0.5671 | 0.038* | |
H1C | 0.0313 | 0.9319 | 0.6638 | 0.038* | |
C2 | −0.0161 (5) | 0.7286 (4) | 0.3493 (4) | 0.0325 (6) | |
H2A | −0.1700 | 0.6764 | 0.2955 | 0.039* | |
H2B | 0.0241 | 0.8433 | 0.3688 | 0.039* | |
C3 | −0.0112 (4) | 0.4677 (4) | 0.1732 (3) | 0.0306 (6) | |
H3A | 0.0330 | 0.4218 | 0.0850 | 0.037* | |
H3B | −0.1652 | 0.4249 | 0.1248 | 0.037* | |
C4 | −0.0234 (5) | 0.2257 (3) | 0.2301 (3) | 0.0307 (6) | |
H4A | 0.0402 | 0.1776 | 0.1571 | 0.037* | |
H4B | −0.1762 | 0.1800 | 0.1670 | 0.037* | |
C5 | 0.2965 (4) | 0.7243 (4) | 0.2860 (4) | 0.0323 (6) | |
H5A | 0.3389 | 0.6491 | 0.2124 | 0.039* | |
H5B | 0.3753 | 0.7443 | 0.3980 | 0.039* | |
C6 | 0.3537 (5) | 0.8869 (4) | 0.2776 (4) | 0.0409 (7) | |
H6A | 0.2705 | 0.8687 | 0.1672 | 0.049* | |
H6B | 0.3198 | 0.9650 | 0.3558 | 0.049* | |
C7 | 0.5587 (6) | 0.7215 (5) | 0.8851 (5) | 0.0574 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0352 (3) | 0.0204 (3) | 0.0258 (3) | 0.0125 (2) | 0.0174 (2) | 0.01383 (19) |
S1 | 0.0350 (4) | 0.0654 (6) | 0.0408 (5) | 0.0190 (4) | 0.0159 (4) | 0.0177 (4) |
O1 | 0.0512 (14) | 0.0382 (13) | 0.0443 (13) | −0.0075 (11) | 0.0278 (11) | 0.0048 (10) |
N1 | 0.0261 (11) | 0.0226 (11) | 0.0327 (12) | 0.0104 (9) | 0.0163 (9) | 0.0157 (9) |
N2 | 0.0313 (12) | 0.0335 (13) | 0.0315 (12) | 0.0108 (10) | 0.0158 (10) | 0.0204 (10) |
N3 | 0.0228 (11) | 0.0236 (11) | 0.0255 (11) | 0.0057 (9) | 0.0109 (9) | 0.0120 (9) |
N4 | 0.064 (2) | 0.156 (5) | 0.0310 (19) | −0.010 (3) | 0.0052 (17) | 0.014 (2) |
C1 | 0.0373 (15) | 0.0225 (14) | 0.0441 (16) | 0.0146 (12) | 0.0242 (13) | 0.0167 (12) |
C2 | 0.0363 (15) | 0.0370 (16) | 0.0433 (16) | 0.0201 (13) | 0.0226 (13) | 0.0292 (13) |
C3 | 0.0291 (14) | 0.0354 (16) | 0.0254 (13) | 0.0059 (12) | 0.0111 (11) | 0.0162 (12) |
C4 | 0.0340 (14) | 0.0235 (14) | 0.0318 (14) | 0.0080 (11) | 0.0182 (12) | 0.0081 (11) |
C5 | 0.0313 (14) | 0.0352 (16) | 0.0335 (14) | 0.0097 (12) | 0.0172 (12) | 0.0180 (12) |
C6 | 0.0462 (18) | 0.0322 (16) | 0.0380 (16) | 0.0042 (14) | 0.0192 (14) | 0.0152 (13) |
C7 | 0.0389 (18) | 0.068 (2) | 0.069 (3) | 0.0193 (18) | 0.0330 (19) | 0.027 (2) |
Cu—N1 | 2.004 (2) | N4—C7 | 1.118 (5) |
Cu—N3 | 2.015 (2) | C1—C4i | 1.510 (4) |
Cu—S1 | 2.9696 (10) | C1—H1B | 0.9700 |
S1—C7 | 1.626 (4) | C1—H1C | 0.9700 |
O1—C6 | 1.418 (4) | C2—H2A | 0.9700 |
O1—H1 | 0.8200 | C2—H2B | 0.9700 |
N1—C1 | 1.484 (3) | C3—H3A | 0.9700 |
N1—C2 | 1.493 (3) | C3—H3B | 0.9700 |
N1—H1A | 0.9100 | C4—H4A | 0.9700 |
N2—C3 | 1.432 (4) | C4—H4B | 0.9700 |
N2—C2 | 1.438 (4) | C5—C6 | 1.511 (4) |
N2—C5 | 1.466 (4) | C5—H5A | 0.9700 |
N3—C4 | 1.482 (3) | C5—H5B | 0.9700 |
N3—C3 | 1.496 (3) | C6—H6A | 0.9700 |
N3—H3 | 0.9100 | C6—H6B | 0.9700 |
N1—Cu—N3i | 86.04 (9) | N2—C2—H2A | 108.8 |
N1—Cu—N3 | 93.96 (9) | N1—C2—H2A | 108.8 |
N1i—Cu—S1 | 93.44 (7) | N2—C2—H2B | 108.8 |
N1—Cu—S1 | 86.56 (7) | N1—C2—H2B | 108.8 |
N3i—Cu—S1 | 96.22 (6) | H2A—C2—H2B | 107.7 |
N3—Cu—S1 | 83.78 (6) | N2—C3—N3 | 113.8 (2) |
C7—S1—Cu | 115.95 (13) | N2—C3—H3A | 108.8 |
C6—O1—H1 | 109.5 | N3—C3—H3A | 108.8 |
C1—N1—C2 | 113.3 (2) | N2—C3—H3B | 108.8 |
C1—N1—Cu | 106.83 (16) | N3—C3—H3B | 108.8 |
C2—N1—Cu | 115.40 (17) | H3A—C3—H3B | 107.7 |
C1—N1—H1A | 106.9 | N3—C4—C1i | 107.2 (2) |
C2—N1—H1A | 106.9 | N3—C4—H4A | 110.3 |
Cu—N1—H1A | 106.9 | C1i—C4—H4A | 110.3 |
C3—N2—C2 | 115.2 (2) | N3—C4—H4B | 110.3 |
C3—N2—C5 | 114.9 (2) | C1i—C4—H4B | 110.3 |
C2—N2—C5 | 116.8 (2) | H4A—C4—H4B | 108.5 |
C4—N3—C3 | 113.5 (2) | N2—C5—C6 | 112.6 (2) |
C4—N3—Cu | 106.80 (15) | N2—C5—H5A | 109.1 |
C3—N3—Cu | 115.39 (17) | C6—C5—H5A | 109.1 |
C4—N3—H3 | 106.9 | N2—C5—H5B | 109.1 |
C3—N3—H3 | 106.9 | C6—C5—H5B | 109.1 |
Cu—N3—H3 | 106.9 | H5A—C5—H5B | 107.8 |
N1—C1—C4i | 107.7 (2) | O1—C6—C5 | 110.8 (3) |
N1—C1—H1B | 110.2 | O1—C6—H6A | 109.5 |
C4i—C1—H1B | 110.2 | C5—C6—H6A | 109.5 |
N1—C1—H1C | 110.2 | O1—C6—H6B | 109.5 |
C4i—C1—H1C | 110.2 | C5—C6—H6B | 109.5 |
H1B—C1—H1C | 108.5 | H6A—C6—H6B | 108.1 |
N2—C2—N1 | 113.7 (2) | N4—C7—S1 | 174.6 (5) |
N1i—Cu—S1—C7 | −96.96 (19) | C2—N1—C1—C4i | 169.7 (2) |
N1—Cu—S1—C7 | 83.04 (19) | Cu—N1—C1—C4i | 41.5 (2) |
N3i—Cu—S1—C7 | −2.59 (19) | C3—N2—C2—N1 | 70.2 (3) |
N3—Cu—S1—C7 | 177.41 (19) | C5—N2—C2—N1 | −69.2 (3) |
N3i—Cu—N1—C1 | −14.80 (17) | C1—N1—C2—N2 | 179.9 (2) |
N3—Cu—N1—C1 | 165.20 (17) | Cu—N1—C2—N2 | −56.5 (3) |
S1—Cu—N1—C1 | −111.29 (17) | C2—N2—C3—N3 | −69.7 (3) |
N3i—Cu—N1—C2 | −141.75 (18) | C5—N2—C3—N3 | 70.4 (3) |
N3—Cu—N1—C2 | 38.25 (18) | C4—N3—C3—N2 | 179.2 (2) |
S1—Cu—N1—C2 | 121.76 (17) | Cu—N3—C3—N2 | 55.5 (3) |
N1i—Cu—N3—C4 | 15.02 (17) | C3—N3—C4—C1i | −169.8 (2) |
N1—Cu—N3—C4 | −164.98 (17) | Cu—N3—C4—C1i | −41.5 (2) |
S1—Cu—N3—C4 | 108.92 (16) | C3—N2—C5—C6 | 153.2 (2) |
N1i—Cu—N3—C3 | 142.24 (18) | C2—N2—C5—C6 | −67.3 (3) |
N1—Cu—N3—C3 | −37.76 (18) | N2—C5—C6—O1 | −176.9 (2) |
S1—Cu—N3—C3 | −123.86 (17) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N4ii | 0.82 | 2.03 | 2.850 (5) | 175 |
N1—H1A···O1iii | 0.91 | 2.22 | 2.951 (3) | 137 |
N3—H3···S1iv | 0.91 | 2.56 | 3.381 (2) | 150 |
Symmetry codes: (ii) x, y, z−1; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(SCN)2(C12H30N6O2] |
Mr | 470.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.118 (1), 9.328 (1), 9.483 (1) |
α, β, γ (°) | 111.00 (1), 106.80 (1), 103.85 (1) |
V (Å3) | 519.65 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.28 |
Crystal size (mm) | 0.56 × 0.56 × 0.40 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.451, 0.600 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1903, 1747, 1639 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.089, 1.08 |
No. of reflections | 1747 |
No. of parameters | 126 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.37 |
Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXTL-Plus (Sheldrick, 1990a), SHELXS97 (Sheldrick, 1990b), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXTL-Plus.
Cu—N1 | 2.004 (2) | S1—C7 | 1.626 (4) |
Cu—N3 | 2.015 (2) | N4—C7 | 1.118 (5) |
Cu—S1 | 2.9696 (10) | ||
N1—Cu—N3 | 93.96 (9) | C7—S1—Cu | 115.95 (13) |
N1—Cu—S1 | 86.56 (7) | N4—C7—S1 | 174.6 (5) |
N3—Cu—S1 | 83.78 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N4i | 0.82 | 2.03 | 2.850 (5) | 175 |
N1—H1A···O1ii | 0.91 | 2.22 | 2.951 (3) | 137 |
N3—H3···S1iii | 0.91 | 2.56 | 3.381 (2) | 150 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1. |
The synthesis of azamacrocyclic polydentate ligands, and their interaction with metal ions, has attracted a great deal of attention (Hancock & Martell, 1989; Bernhardt & Lawrance, 1990). Research on such a system may provide a basis for a better knowledge of biochemical function of these compounds. For instance, studies of the NiIII complexes of pentaazacyclic ligands have shown that appropriately designed complexes may cause DNA scission under physiological conditions using only O2 at ambient pressure (Cheng et al., 1993). The trans isomer of [FeIIILCl2]+ (where L is 1,4,8,11-tetraazacyclotetradecane) was found to activate dioxygen in the presence of reducing agents (Nishida & Tanaka, 1994). Mimic studies have revealed that two MnII complexes with pentaazamacrocyclic ligands have high catalytic SOD (superoxide dismutase) activity (Salvemini et al., 1999). A series of CuII or ZnII complexes with tetraazamacrocyclic ligands involving different substituents have been synthesized, in order to study their EET (electronic energy transfer) properties (Bernhardt et al., 2002). Attempts have been made to clarify the structural correlation with the biological and chemical properties of transition metal complexes with azamacrocyclic polydentate ligands. We report here the preparation and structure of the title novel CuII complex, (I), with the macrocyclic ligand 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane. \sch
Complex (I) possesses an inverson centre at the Cu atom, and thus the N donors of the macrocycle form a perfect plane including the CuII cation. The CuII atom has an elongated octahedral coordination, as shown in Fig. 1. Four secondary N atoms of the macrocycle coordinate to the CuII atom in the equatorial plane. The axial positions are occupied by N atoms Please clarify - Scheme and Fig. 1 both show S from thiocyanate groups. The Cu—N bond distances are 2.004 (2) and 2.015 (2) Å, which are close to the values of 2.002 and 2.018 Å observed in [CuL(H2O)]n[(CuL)Fe(CN)6]2n [L is ?; Lu et al., 2000; Cambridge Structural Database (Allen & Kennard, 1993) refcode XASHOO]. The Cu—S bond distances of 2.9696 (10) Å are shorter than the sum of the van der Walls radii of Cu and S atoms (3.4 Å; Pauling, 1960) and similar to the values found in other complexes in which the S atoms adopt an axial position in a distorted octahedron around CuII (Ribas et al., 1995; Vicente et al., 1997; Ferlay et al., 1998).
The bite distances of the five- and six-membered chelate rings are 2.742 (3) and 2.938 (3) Å, repectively, and the bite angles are 86.04 (9) and 93.96 (9)°, respectively. These data are also similar to those of [CuL(H2O)]n[(CuL)Fe(CN)6]2n (Lu et al., 2000). The six-membered chelate rings adopt a chair conformation, and the alkyl chains on the bridgehead N atoms are axial. The five-membered chelate rings assume a gauche conformation. The average N—C bond distance involving the bridged tertiary atom N2 is 1.445 (4) Å, which is shorter than the normal C—N single bond distance, and the average C—N—C angles involving N2 are 115.6 (2)°.
The C—N [1.118 (6) Å] and C—S [1.626 (4) Å] distances, and N—C—S angles [174.6 (5)°], in the SCN- moiety show the normal thiocyanate structure in (I).
Hydrogen-bonding interactions play an important role in the solid-state structure of (I). O—H···N and N—H···O hydrogen bonds link the molecules into sheets, in which there are centrosymmetric hydrogen-bonded rings (Fig. 2a). The hydroxy group O1—H1 at (x,y,z) acts as a hydrogen-bond donor to the thiocyanate atom N4 at (x,y,z - 1), while O1—H1 at (x,y,z - 1) acts as a donor to atom N4 at (1 - x,2 - y,1 - z). In this way, an R44(16) ring (Bernstein et al., 1995) is generated about the inversion centre at (1/2,1,0). The N1—H1A moiety at (x,y,z) acts as a hydrogen-bond donor to the hydroxyl atom O1 at (1 - x,2 - y,1 - z) and, coupled with the inversion centre at (1/2,1,1/2), an R22(14) ring is generated. Also generated is an R22(22) ring with its centre at the inversion centre at (0,1/2,0). These sheets are then linked to generate a three-dimensional network via pairs of N—H···S hydrogen bonds (Fig. 2 b), which generates an R22(8) ring centred at (1/2,1/2,1/2), with N3—H3 acting as a donor to atom S1 at (1 - x,1 - y,1 - z).