Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010400349X/ob1168sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010400349X/ob1168Isup2.hkl |
CCDC reference: 237910
To a methanol solution (20 ml) of Cu(ClO4)2 (0.375 g, 1.01 mmol), N,N'-dimethylethylenediamine (0.176 g, 2.00 mmol) was added dropwise at 298 K, giving rise to blue precipitates of the precursor bis(N,N'-dimethylethylenediamine)copper(II) diperchlorate. Blue prismatic crystals of (I) suitable for X-ray analysis were grown from an acetone–methanol solution (4:1, v/v) at 298 K over a period of a few days.
Despite an epoxy coating to retain the solvent, the crystal used for analysis was seriously damaged by the X-ray radiation during the data collection. There is a positional disorder of atom C1 over two equally occupied sites. It was assumed that the ethylenediamine moiety has two possible conformations, namely N1(H1A)—C1A(H2A/H3A)—C1Ai(H2Ai/H3Ai) and N1(H1B)—C1B(H2B/H3B)—C1Bi(H2Bi/H3Bi) [symmetry code: (i) 1 − x, 1/2 − y, z]. In an approximation, positional disorder of atom C2 was not taken into account, because the ratio of its maximum/minimum principal r.m.s. displacements was fairly small (1.14) and there was no remarkable peak in the difference map. All H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom).
Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
[Cu(C4H12N2)2(C3H6O)6](ClO4)2 | F(000) = 1164.0 |
Mr = 554.92 | Dx = 1.467 Mg m−3 |
Orthorhombic, Ccca | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -C 2b 2bc | Cell parameters from 25 reflections |
a = 13.145 (5) Å | θ = 11.1–12.3° |
b = 13.333 (4) Å | µ = 1.13 mm−1 |
c = 14.332 (4) Å | T = 297 K |
V = 2511.9 (14) Å3 | Prismatic, blue |
Z = 4 | 0.30 × 0.30 × 0.30 mm |
Rigaku AFC-7R diffractometer | Rint = 0.008 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North, et al., 1968) | h = −17→0 |
Tmin = 0.712, Tmax = 0.719 | k = 0→17 |
1525 measured reflections | l = 0→18 |
1449 independent reflections | 3 standard reflections every 150 reflections |
747 reflections with I > 2σ(I) | intensity decay: 87.2% |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.055 | w = 1/[σ2(Fo2) + (0.1P)2 where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.180 | (Δ/σ)max = 0.010 |
S = 1.08 | Δρmax = 0.44 e Å−3 |
747 reflections | Δρmin = −0.46 e Å−3 |
83 parameters |
[Cu(C4H12N2)2(C3H6O)6](ClO4)2 | V = 2511.9 (14) Å3 |
Mr = 554.92 | Z = 4 |
Orthorhombic, Ccca | Mo Kα radiation |
a = 13.145 (5) Å | µ = 1.13 mm−1 |
b = 13.333 (4) Å | T = 297 K |
c = 14.332 (4) Å | 0.30 × 0.30 × 0.30 mm |
Rigaku AFC-7R diffractometer | 747 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North, et al., 1968) | Rint = 0.008 |
Tmin = 0.712, Tmax = 0.719 | 3 standard reflections every 150 reflections |
1525 measured reflections | intensity decay: 87.2% |
1449 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 83 parameters |
wR(F2) = 0.180 | H-atom parameters not refined |
S = 1.08 | Δρmax = 0.44 e Å−3 |
747 reflections | Δρmin = −0.46 e Å−3 |
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.5000 | 0.2500 | 0.2500 | 0.0362 (2) | |
Cl1 | 0.2500 | 0.5000 | 0.41131 (8) | 0.0650 (3) | |
O1 | 0.6909 (2) | 0.2500 | 0.2500 | 0.071 (1) | |
O2 | 0.2801 (3) | 0.4173 (3) | 0.4642 (3) | 0.126 (1) | |
O3 | 0.3316 (3) | 0.5270 (4) | 0.3563 (3) | 0.194 (2) | |
N1 | 0.4970 (2) | 0.3531 (2) | 0.3552 (2) | 0.0482 (7) | |
C1A | 0.5337 (5) | 0.2942 (6) | 0.4404 (5) | 0.055 (2) | 0.50 |
C1B | 0.4757 (7) | 0.2993 (7) | 0.4452 (5) | 0.082 (3) | 0.50 |
C2 | 0.5706 (3) | 0.4378 (3) | 0.3533 (3) | 0.081 (1) | |
C3 | 0.7824 (3) | 0.2500 | 0.2500 | 0.055 (1) | |
C4 | 0.8407 (3) | 0.2887 (4) | 0.3298 (3) | 0.085 (1) | |
H1A | 0.4285 | 0.3772 | 0.3663 | 0.0582* | 0.50 |
H1B | 0.4321 | 0.3864 | 0.3460 | 0.0582* | 0.50 |
H2A | 0.6018 | 0.2780 | 0.4331 | 0.1013* | 0.50 |
H2B | 0.5065 | 0.3401 | 0.4959 | 0.1013* | 0.50 |
H3A | 0.5224 | 0.3326 | 0.4950 | 0.1013* | 0.50 |
H3B | 0.4057 | 0.2964 | 0.4569 | 0.1013* | 0.50 |
H4 | 0.6373 | 0.4136 | 0.3462 | 0.1009* | |
H5 | 0.5545 | 0.4818 | 0.3022 | 0.1009* | |
H6 | 0.5658 | 0.4761 | 0.4098 | 0.1009* | |
H7 | 0.8271 | 0.2512 | 0.3846 | 0.1040* | |
H8 | 0.9134 | 0.2831 | 0.3170 | 0.1040* | |
H9 | 0.8263 | 0.3575 | 0.3405 | 0.1040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0376 (3) | 0.0406 (4) | 0.0302 (3) | 0.0000 | 0.0000 | 0.0000 |
Cl1 | 0.0669 (6) | 0.0802 (8) | 0.0480 (6) | 0.0224 (7) | 0.0000 | 0.0000 |
O1 | 0.037 (2) | 0.097 (3) | 0.078 (2) | 0.0000 | 0.0000 | −0.020 (2) |
O2 | 0.146 (3) | 0.121 (3) | 0.113 (2) | 0.022 (2) | −0.021 (2) | 0.050 (2) |
O3 | 0.183 (3) | 0.163 (3) | 0.236 (4) | 0.077 (3) | 0.139 (3) | 0.082 (3) |
N1 | 0.059 (1) | 0.045 (1) | 0.041 (1) | 0.007 (1) | 0.003 (1) | −0.002 (1) |
C1A | 0.063 (4) | 0.063 (4) | 0.039 (3) | 0.012 (3) | 0.015 (3) | −0.018 (4) |
C1B | 0.134 (7) | 0.077 (5) | 0.035 (4) | 0.055 (5) | 0.014 (4) | 0.010 (4) |
C2 | 0.084 (2) | 0.074 (2) | 0.084 (3) | −0.007 (2) | −0.009 (2) | −0.039 (2) |
C3 | 0.046 (2) | 0.049 (3) | 0.069 (3) | 0.0000 | 0.0000 | −0.009 (3) |
C4 | 0.073 (2) | 0.103 (3) | 0.080 (3) | −0.005 (2) | −0.017 (2) | −0.023 (3) |
Cu1—O1 | 2.507 (5) | C1A—C1Aii | 1.48 (2) |
Cu1—N1 | 2.041 (3) | C1A—H2A | 0.926 |
Cu1—N1i | 2.041 (3) | C1A—H3A | 0.947 |
Cu1—N1ii | 2.041 (3) | C1B—C1Bii | 1.46 (2) |
Cu1—N1iii | 2.041 (3) | C1B—H2B | 0.994 |
Cl1—O2 | 1.395 (4) | C1B—H3B | 0.936 |
Cl1—O2iv | 1.395 (4) | C2—H4 | 0.939 |
Cl1—O3 | 1.380 (4) | C2—H5 | 0.961 |
Cl1—O3iv | 1.380 (4) | C2—H6 | 0.959 |
O1—C3 | 1.203 (5) | C3—C4 | 1.471 (5) |
N1—C1A | 1.530 (8) | C3—C4i | 1.471 (5) |
N1—C1B | 1.503 (9) | C4—H7 | 0.948 |
N1—C2 | 1.488 (5) | C4—H8 | 0.975 |
N1—H1A | 0.969 | C4—H9 | 0.948 |
N1—H1B | 0.970 | ||
O1—Cu1—N1 | 91.11 (7) | N1—C1A—H3A | 109.4 |
N1—Cu1—N1i | 177.8 (1) | C1Aii—C1A—H2A | 113.2 |
N1—Cu1—N1ii | 84.7 (1) | C1Aii—C1A—H3A | 109.7 |
N1—Cu1—N1iii | 95.3 (1) | H2A—C1A—H3A | 111.8 |
N1i—Cu1—N1ii | 95.3 (1) | N1—C1B—C1Bii | 110.4 (5) |
N1i—Cu1—N1iii | 84.7 (1) | N1—C1B—H2B | 106.8 |
N1ii—Cu1—N1iii | 177.8 (1) | N1—C1B—H3B | 110.9 |
O2—Cl1—O2iv | 114.2 (3) | C1Bii—C1B—H2B | 108.3 |
O2—Cl1—O3 | 107.2 (2) | C1Bii—C1B—H3B | 113.2 |
O2—Cl1—O3iv | 109.0 (3) | H2B—C1B—H3B | 107.0 |
O2iv—Cl1—O3 | 109.0 (3) | N1—C2—H4 | 110.3 |
O2iv—Cl1—O3iv | 107.2 (2) | N1—C2—H5 | 109.5 |
O3—Cl1—O3iv | 110.3 (4) | N1—C2—H6 | 110.1 |
Cu1—N1—C1A | 103.8 (3) | H4—C2—H5 | 109.5 |
Cu1—N1—C1B | 108.4 (4) | H4—C2—H6 | 109.6 |
Cu1—N1—C2 | 119.0 (2) | H5—C2—H6 | 107.8 |
Cu1—N1—H1A | 111.2 | O1—C3—C4 | 121.4 (2) |
Cu1—N1—H1B | 103.0 | O1—C3—C4i | 121.4 (2) |
C1A—N1—C2 | 101.5 (4) | C4—C3—C4i | 117.2 (4) |
C1A—N1—H1A | 109.5 | C3—C4—H7 | 111.1 |
C1B—N1—C2 | 120.0 (4) | C3—C4—H8 | 109.6 |
C1B—N1—H1B | 99.9 | C3—C4—H9 | 111.1 |
C2—N1—H1A | 110.9 | H7—C4—H8 | 107.6 |
C2—N1—H1B | 102.8 | H7—C4—H9 | 109.8 |
N1—C1A—C1Aii | 102.7 (4) | H8—C4—H9 | 107.5 |
N1—C1A—H2A | 109.6 | ||
Cu1—N1—C1A—C1Aii | −52.3 (6) | N1—Cu1—N1ii—C2ii | 129.8 (3) |
Cu1—N1—C1B—C1Bii | 35.5 (10) | N1—Cu1—N1iii—C1Aiii | −159.7 (3) |
Cu1—N1i—C1Ai—C1Aiii | −52.3 (6) | N1—Cu1—N1iii—C1Biii | 170.1 (4) |
Cu1—N1i—C1Bi—C1Biii | 35.5 (10) | N1—C1A—C1Aii—N1ii | 70.2 (8) |
Cu1—N1ii—C1Aii—C1A | −52.3 (6) | N1—C1B—C1Bii—N1ii | −47 (1) |
Cu1—N1ii—C1Bii—C1B | 35.5 (10) | C1A—C1Aii—N1ii—C2ii | −176.3 (5) |
Cu1—N1iii—C1Aiii—C1Ai | −52.3 (6) | C1B—C1Bii—N1ii—C2ii | −106.0 (8) |
N1—Cu1—N1ii—C1Aii | 18.0 (3) | C1B—C1Bii—N1ii—C2ii | −106.0 (8) |
N1—Cu1—N1ii—C1Bii | −12.2 (4) |
Symmetry codes: (i) x, −y+1/2, −z+1/2; (ii) −x+1, −y+1/2, z; (iii) −x+1, y, −z+1/2; (iv) −x+1/2, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.97 | 2.46 | 3.362 (4) | 154 |
N1—H1B···O2 | 0.97 | 2.65 | 3.362 (4) | 130 |
N1—H1A···O3 | 0.97 | 2.37 | 3.177 (5) | 140 |
N1—H1B···O3 | 0.97 | 2.30 | 3.177 (5) | 150 |
Experimental details
Crystal data | |
Chemical formula | [Cu(C4H12N2)2(C3H6O)6](ClO4)2 |
Mr | 554.92 |
Crystal system, space group | Orthorhombic, Ccca |
Temperature (K) | 297 |
a, b, c (Å) | 13.145 (5), 13.333 (4), 14.332 (4) |
V (Å3) | 2511.9 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.30 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North, et al., 1968) |
Tmin, Tmax | 0.712, 0.719 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1525, 1449, 747 |
Rint | 0.008 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.180, 1.08 |
No. of reflections | 747 |
No. of parameters | 83 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.44, −0.46 |
Computer programs: WinAFC Diffractometer Control Software (Rigaku, 1999), WinAFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 2001), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.
Cu1—O1 | 2.507 (5) | N1—C2 | 1.488 (5) |
Cu1—N1 | 2.041 (3) | C1A—C1Ai | 1.48 (2) |
O1—C3 | 1.203 (5) | C1B—C1Bi | 1.46 (2) |
N1—C1A | 1.530 (8) | C3—C4 | 1.471 (5) |
N1—C1B | 1.503 (9) | ||
O1—Cu1—N1 | 91.11 (7) | N1—Cu1—N1i | 84.7 (1) |
N1—Cu1—N1ii | 177.8 (1) | N1—Cu1—N1iii | 95.3 (1) |
N1—C1A—C1Ai—N1i | 70.2 (8) | N1—C1B—C1Bi—N1i | −47 (1) |
Symmetry codes: (i) −x+1, −y+1/2, z; (ii) x, −y+1/2, −z+1/2; (iii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.97 | 2.46 | 3.362 (4) | 154 |
N1—H1B···O2 | 0.97 | 2.65 | 3.362 (4) | 130 |
N1—H1A···O3 | 0.97 | 2.37 | 3.177 (5) | 140 |
N1—H1B···O3 | 0.97 | 2.30 | 3.177 (5) | 150 |
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One of the most promising strategies for development of optical switching materials of metal complexes is to investigate candidates exhibiting thermal phase transition or having physical properties described by bistable potentials. Since there have been reported on intercalated hybrid materials (Choy et al., 2002), thermochromism (Narayanan & Bhadbhade, 1998) and photochromism (Takahashi et al., 2002), CuII complexes with ethylenediamine derivatives have been of interest as candidates for such functional materials.
Varied stereochemistry of the CuII complexes, for instance distortion (Simmons, 1993) and semi-coordination (Hathaway, 1984), has been the subject of the Jahn–Teller effect (Murphy & Hathaway, 2003). Strictly speaking, the pseudo-Jahn–Teller effect can be applied to the systems involving non-equivalent ligands, such as trans-[CuA4B2] in D4 h symmetry. Mixing between non-degenerated ground states and excited states through spin-orbit vibronic coupling results in stabilization of potential energy by a pseudo-Jahn–Teller effect. Elongated axial (semi-coordination) bonds under appropriate conditions may occur thermally accessible distortion, and there is also possibility for photo-controlling.
So far, the structures of semi-coordinated CuII complexes with N-substituted ethylenediamine ligands have been investigated: ethylenediamine (en) by Maxcy & Turnbull (1999), N-methylethylenediamine (N-Meen) by Akitsu & Einaga (2003), N-ethylethylenediamine (N-Eten) by Grenthe et al. (1979) and N,N-dimethylethylenediamine (N—Me2en) by Akitsu & Einaga (2004). We have determined the crystal structure of bis(acetone-κO)bis(N,N'-dimethylethylenediamine-κ2N,N')copper(II) diperchlorate, (I). This is the first structurally characterized example of the CuII complexes coordinated by acetone as axial ligands.
Complex (I) adopts an elongated octahedral trans-[CuN4O2] coordination geometry, where atom Cu1 lies on 222 site symmetry (Fig. 1 and Table 1). The axial Cu1—O1 bond length of 2.507 (5) Å is in the range of semi-coordination (2.22–2.89 Å for H2O; Hathaway, 1973) caused by a Jahn–Teller effect. As for analogous CuII complexes with axial perchlorate ligands, the corresponding Cu—O(perchlorate) bond lengths are 2.579 (4), 2.569 (2), 2.594 (3) and 2.605 (4) Å for the en, N-Meen, N-Eten and N—Me2en complexes, respectively. Interestingly, the axial Cu—O(acetone) bond is relatively shorter than the Cu—O(perchlorate) bond, regardless of the acetone ligands being neutral; however, it is considerably longer than corresponding values for dimeric CuII complexes having acetone ligands, which range from 2.1379 (5) (Agterberg et al., 1997) to 2.206 (3) Å (Castellari et al., 1999). Furthermore, in these similar complexes, the Cu—O═C(acetone) bond angles are bent (133°; Steward et al., 1996), whereas the Cu—O—C bond angles are 180° in (I). The Cu1—N1 bond length of 2.041 (3) Å for (I) is comparable to that of 2.057 (2) Å for the N-Meen complex. Indeed, the number of substituted groups on the N atom is reflected in the Cu—N bond distance for a series of these complexes: Cu—N(H2) = 2.012 (2) Å for the en, Cu—N(HMe) = 2.057 (2) Å for the N-Meen, Cu—N(HEt) = 2.031 (3) Å for the N-Eten and Cu—N(Me2) = 2.098 (2) Å for the N—Me2en complex. The T values, i.e. the Cu—N(in-plane)/Cu—O(axial) bond-length ratio (Hathaway et al., 1970) of 0.81 for (I) is comparable or slightly larger than those of the perchlorate complexes (0.76–0.81).
The N1—Cu1—N1i [symmetry code: (i) 1 − x, 1/2 − y, z] chelate angle of 84.7 (1)° is almost the same as that of the N-Meen complex [84.58 (7)°]. The perchrolate ion lies on a twofold axis and has usual geometric parameters. N—H···O hydrogen bonds are formed between the complex cation and the the perchrolate ions (Table 2). The crystal packing of (I) is illustrated in Fig. 2. The trans-O—Cu—O axial bonds lie on twofold axes parallel to the a axis. Each complex cation is linked to four perchrolate anions and each perchrolate anion is linked to two cations via hydrogen bonds. The complex cations and perchlorate anions are aligned alternately along the a axis, forming networks of two-dimensional sheets.
The crystal structures of metal complexes having two acetone ligands at axial sites, i.e. having trans-O—M—O axial bonds, have been reported for the MnIII (Zhang et al., 1990), ZnII (Bench, Beveridge et al., 2002) and CoII (Bench, Brennessel et al., 2002) complexes. Despite the trans-coordination mode, the acetone ligands are inclined in the MnIII, ZnII and CoII complexes, whereas they are coordinated in a linear fashion in (I) as a result of the symmetry of the crystal structure. The semi-coordination sites, namely the trans-coordination mode, being ready for acetone ligands may be dominated by steric restriction of the sites in the equatorial plane occupied by chelate or macrocyclic ligands.