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The crystal structure of the title compound, [Cu(ClO
4)
2(C
4H
12N
2)
2], (I), is reported at 100, 250 and 400 K. The Cu
II cation in this complex is coordinated in a distorted octahedral mode characteristic of Jahn-Teller systems. The coordination of the perchlorate ligands
via longer, and presumably weaker, axial Cu-O distances varies significantly as a function of temperature. One of the Cu-O distances increases between 100 and 250 K, and one of the Cu-O-Cl angles expands between 250 and 400 K. At all temperatures, the complex forms a two-dimensional N-H
O hydrogen-bond network in the (001) plane.
Supporting information
CCDC references: 908121; 908122; 908123
Compound (I) was prepared according to the procedure of Akitsu & Einaga (2004)
by adding N,N'-dimethylethylenediamine (0.176 g, 2.00 mmol)
dropwise to a methanol solution (20 ml) of Cu(ClO4)2.6H2O (0.375 g, 1.01 mmol) at room temperature (yield 87.7%). Violet plates suitable for
single-crystal X-ray diffraction were obtained after 2 d by diffusion between
solutions of both reactants in methanol at room temperature. Elemental
analysis, calculated (%): C 21.90, H 5.51, N 12.77; found: C 21.95, H 5.63, N
12.73.
H atoms attached to N atoms in (Ia) and (Ib) were refined
isotropically, with Uiso(H) = 1.2Ueq(N) and with N—H
restrained to similarity. H atoms attached to N atoms in (Ic) and all
other H atoms were introduced in their idealized positions and treated as
riding, with methyl C—H = 0.98 Å for (Ia), 0.97 Å for (Ib)
and 0.96 Å for (Ic), and with Uiso(H) = 1.5Ueq(C);
methylene C—H = 0.99 Å for (Ia), 0.98 Å for (Ib) and 0.97 Å for (Ic), and with Uiso(H) = 1.2Ueq(C); N—H =
0.91 Å for (Ic) and Uiso(H) = 1.2Ueq(N).
Data set (Ic) was collected at 400 K. At this temperature, the
displacement parameters indicate the pronounced mobility of all ligands in the
complex. Obvious disorder was encountered in one of the perchlorate anions and
in an ethylendiamine ligand. Split positions were refined for the atoms of the
chelating ligand associated with N1 and N2 and for those of the perchlorate
ligand associated with Cl1. Site occupancies for the alternative orientations
were refined, and the sum of these occupancies was constrained to unity. All
atom sites with fractional occupancies were assigned isotropic displacement
parameters. These displacement parameters, and the distances and angles in the
alternative conformations, were restrained to similarity, resulting in a total
of 69 restraints. In (Ic), the occurrence of intensities with
I(obs) >> I(calc) indicated nonmerohedral twinning (180°
rotation about a*); PLATON (Spek, 2009) was used to generate an
expanded set of intensity data in which a small fraction (225 out of 3479
reflections) was assigned as overlapped with contributions from a second
smaller domain with a volume fraction of 0.348 (10).
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(Ia) bis(
N,
N'-dimethylethylenediamine-
κ2N,
N')bis(perchlorato-
κO)copper(II)
top
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | F(000) = 908 |
Mr = 438.75 | Dx = 1.717 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 1517 reflections |
a = 8.5395 (17) Å | θ = 2.8–20.6° |
b = 13.543 (3) Å | µ = 1.65 mm−1 |
c = 14.743 (4) Å | T = 100 K |
β = 95.358 (3)° | Plate, violet |
V = 1697.6 (6) Å3 | 0.19 × 0.11 × 0.03 mm |
Z = 4 | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer | 3488 independent reflections |
Radiation source: Incoatec microsource | 3137 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.055 |
ω scans | θmax = 26.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.745, Tmax = 0.952 | k = −16→16 |
9912 measured reflections | l = −18→18 |
Refinement top
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0217P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
3488 reflections | Δρmax = 0.45 e Å−3 |
224 parameters | Δρmin = −0.38 e Å−3 |
8 restraints | Absolute structure: Flack (1983), with 1739 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.004 (14) |
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | V = 1697.6 (6) Å3 |
Mr = 438.75 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 8.5395 (17) Å | µ = 1.65 mm−1 |
b = 13.543 (3) Å | T = 100 K |
c = 14.743 (4) Å | 0.19 × 0.11 × 0.03 mm |
β = 95.358 (3)° | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer | 3488 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 3137 reflections with I > 2σ(I) |
Tmin = 0.745, Tmax = 0.952 | Rint = 0.055 |
9912 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | Δρmax = 0.45 e Å−3 |
S = 0.99 | Δρmin = −0.38 e Å−3 |
3488 reflections | Absolute structure: Flack (1983), with 1739 Friedel pairs |
224 parameters | Absolute structure parameter: 0.004 (14) |
8 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.72281 (5) | 0.13390 (3) | 0.08201 (4) | 0.01293 (12) | |
Cl1 | 0.71786 (11) | −0.11944 (7) | 0.01687 (7) | 0.0163 (2) | |
Cl2 | 0.73233 (11) | 0.39566 (7) | 0.19654 (7) | 0.0161 (2) | |
O1 | 0.7488 (4) | −0.0189 (2) | −0.0068 (2) | 0.0277 (7) | |
O2 | 0.7117 (3) | −0.1792 (2) | −0.06348 (19) | 0.0235 (7) | |
O3 | 0.8394 (4) | −0.1541 (3) | 0.0827 (2) | 0.0362 (9) | |
O4 | 0.5694 (4) | −0.1229 (2) | 0.0561 (2) | 0.0236 (8) | |
O8 | 0.7107 (4) | 0.4664 (2) | 0.1238 (2) | 0.0290 (7) | |
O5 | 0.7179 (4) | 0.2978 (2) | 0.1591 (2) | 0.0257 (7) | |
O6 | 0.6155 (4) | 0.4109 (2) | 0.2582 (2) | 0.0300 (8) | |
O7 | 0.8861 (3) | 0.4056 (2) | 0.2433 (2) | 0.0286 (8) | |
C1 | 0.7319 (5) | 0.2764 (3) | −0.0591 (3) | 0.0213 (10) | |
H1A | 0.7767 | 0.2999 | −0.1147 | 0.026* | |
H1B | 0.7080 | 0.3345 | −0.0220 | 0.026* | |
C2 | 0.5847 (5) | 0.2180 (3) | −0.0842 (3) | 0.0189 (9) | |
H2A | 0.5023 | 0.2614 | −0.1144 | 0.023* | |
H2B | 0.6062 | 0.1645 | −0.1271 | 0.023* | |
C3 | 0.9388 (6) | 0.1502 (3) | −0.0664 (3) | 0.0230 (11) | |
H3A | 0.9956 | 0.1942 | −0.1046 | 0.035* | |
H3B | 0.8673 | 0.1080 | −0.1052 | 0.035* | |
H3C | 1.0141 | 0.1088 | −0.0293 | 0.035* | |
C4 | 0.4021 (5) | 0.1034 (3) | −0.0222 (3) | 0.0201 (10) | |
H4A | 0.4445 | 0.0450 | −0.0507 | 0.030* | |
H4B | 0.3206 | 0.1337 | −0.0646 | 0.030* | |
H4C | 0.3562 | 0.0837 | 0.0335 | 0.030* | |
C5 | 0.7079 (4) | 0.0179 (3) | 0.2421 (3) | 0.0152 (9) | |
H5A | 0.7348 | −0.0477 | 0.2182 | 0.018* | |
H5B | 0.6604 | 0.0081 | 0.3002 | 0.018* | |
C6 | 0.8537 (5) | 0.0804 (3) | 0.2577 (3) | 0.0180 (9) | |
H6A | 0.8281 | 0.1444 | 0.2853 | 0.022* | |
H6B | 0.9334 | 0.0464 | 0.2997 | 0.022* | |
C7 | 0.4940 (6) | 0.1369 (3) | 0.2221 (3) | 0.0193 (11) | |
H7A | 0.5595 | 0.1828 | 0.2605 | 0.029* | |
H7B | 0.4277 | 0.0988 | 0.2602 | 0.029* | |
H7C | 0.4272 | 0.1741 | 0.1765 | 0.029* | |
C8 | 1.0500 (5) | 0.1650 (3) | 0.1790 (3) | 0.0203 (10) | |
H8A | 1.1229 | 0.1445 | 0.2309 | 0.030* | |
H8B | 1.0125 | 0.2321 | 0.1894 | 0.030* | |
H8C | 1.1043 | 0.1639 | 0.1233 | 0.030* | |
N1 | 0.8464 (4) | 0.2101 (3) | −0.0056 (2) | 0.0157 (8) | |
H1 | 0.903 (4) | 0.253 (2) | 0.020 (3) | 0.019* | |
N2 | 0.5298 (4) | 0.1753 (3) | 0.0005 (2) | 0.0164 (8) | |
H2 | 0.494 (5) | 0.222 (2) | 0.026 (3) | 0.020* | |
N3 | 0.5959 (4) | 0.0690 (3) | 0.1758 (2) | 0.0139 (7) | |
H3 | 0.541 (4) | 0.026 (2) | 0.152 (3) | 0.017* | |
N4 | 0.9153 (4) | 0.0968 (3) | 0.1690 (3) | 0.0158 (7) | |
H4 | 0.950 (5) | 0.044 (2) | 0.152 (3) | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0105 (2) | 0.0124 (2) | 0.0161 (2) | 0.0002 (2) | 0.00230 (17) | 0.0009 (2) |
Cl1 | 0.0161 (5) | 0.0128 (5) | 0.0203 (5) | −0.0000 (4) | 0.0027 (4) | −0.0020 (4) |
Cl2 | 0.0172 (5) | 0.0119 (5) | 0.0198 (5) | −0.0001 (4) | 0.0047 (4) | −0.0010 (4) |
O1 | 0.0347 (19) | 0.0159 (16) | 0.0346 (19) | −0.0072 (14) | 0.0145 (15) | −0.0021 (14) |
O2 | 0.0324 (18) | 0.0182 (16) | 0.0203 (16) | −0.0012 (14) | 0.0049 (14) | −0.0067 (13) |
O3 | 0.029 (2) | 0.048 (2) | 0.029 (2) | 0.0213 (17) | −0.0099 (16) | −0.0048 (17) |
O4 | 0.0210 (17) | 0.0189 (17) | 0.033 (2) | −0.0066 (13) | 0.0117 (15) | −0.0049 (14) |
O8 | 0.038 (2) | 0.0176 (17) | 0.0326 (18) | 0.0041 (14) | 0.0075 (15) | 0.0097 (14) |
O5 | 0.0308 (18) | 0.0119 (16) | 0.0346 (19) | −0.0006 (13) | 0.0039 (15) | −0.0082 (13) |
O6 | 0.0287 (18) | 0.034 (2) | 0.0297 (18) | 0.0105 (15) | 0.0178 (15) | 0.0001 (15) |
O7 | 0.0179 (17) | 0.0353 (19) | 0.0314 (18) | −0.0059 (14) | −0.0032 (14) | −0.0030 (15) |
C1 | 0.027 (3) | 0.017 (2) | 0.020 (2) | 0.0044 (19) | 0.0030 (19) | 0.0054 (18) |
C2 | 0.016 (2) | 0.024 (2) | 0.016 (2) | −0.0033 (18) | −0.0004 (17) | 0.0035 (18) |
C3 | 0.023 (3) | 0.021 (3) | 0.026 (3) | −0.005 (2) | 0.009 (2) | −0.004 (2) |
C4 | 0.016 (2) | 0.015 (2) | 0.028 (3) | −0.0009 (19) | −0.0023 (19) | 0.003 (2) |
C5 | 0.017 (2) | 0.011 (2) | 0.018 (2) | −0.0001 (16) | 0.0007 (17) | 0.0036 (16) |
C6 | 0.016 (2) | 0.023 (2) | 0.015 (2) | −0.0011 (18) | 0.0034 (17) | 0.0036 (18) |
C7 | 0.019 (2) | 0.021 (3) | 0.018 (2) | −0.0004 (19) | 0.0056 (19) | −0.0029 (19) |
C8 | 0.011 (2) | 0.023 (2) | 0.027 (3) | −0.000 (2) | 0.0013 (18) | −0.004 (2) |
N1 | 0.0118 (18) | 0.0153 (19) | 0.020 (2) | −0.0026 (14) | 0.0031 (14) | −0.0012 (15) |
N2 | 0.0150 (19) | 0.017 (2) | 0.018 (2) | 0.0013 (16) | 0.0044 (15) | −0.0011 (16) |
N3 | 0.0143 (18) | 0.0128 (19) | 0.0143 (18) | −0.0040 (14) | −0.0004 (14) | −0.0021 (14) |
N4 | 0.0121 (18) | 0.0122 (19) | 0.023 (2) | −0.0004 (15) | 0.0005 (14) | −0.0016 (16) |
Geometric parameters (Å, º) top
Cu1—N2 | 2.026 (4) | C4—N2 | 1.477 (5) |
Cu1—N1 | 2.026 (3) | C4—H4A | 0.9800 |
Cu1—N3 | 2.035 (3) | C4—H4B | 0.9800 |
Cu1—N4 | 2.051 (4) | C4—H4C | 0.9800 |
Cl1—O2 | 1.432 (3) | C5—N3 | 1.475 (5) |
Cl1—O3 | 1.432 (3) | C5—C6 | 1.506 (5) |
Cl1—O1 | 1.436 (3) | C5—H5A | 0.9900 |
Cl1—O4 | 1.442 (3) | C5—H5B | 0.9900 |
Cl2—O6 | 1.426 (3) | C6—N4 | 1.471 (5) |
Cl2—O7 | 1.431 (3) | C6—H6A | 0.9900 |
Cl2—O5 | 1.436 (3) | C6—H6B | 0.9900 |
Cl2—O8 | 1.437 (3) | C7—N3 | 1.477 (5) |
C1—N1 | 1.497 (5) | C7—H7A | 0.9800 |
C1—C2 | 1.502 (5) | C7—H7B | 0.9800 |
C1—H1A | 0.9900 | C7—H7C | 0.9800 |
C1—H1B | 0.9900 | C8—N4 | 1.472 (5) |
C2—N2 | 1.491 (5) | C8—H8A | 0.9800 |
C2—H2A | 0.9900 | C8—H8B | 0.9800 |
C2—H2B | 0.9900 | C8—H8C | 0.9800 |
C3—N1 | 1.488 (5) | N1—H1 | 0.82 (2) |
C3—H3A | 0.9800 | N2—H2 | 0.82 (2) |
C3—H3B | 0.9800 | N3—H3 | 0.81 (2) |
C3—H3C | 0.9800 | N4—H4 | 0.82 (2) |
| | | |
N2—Cu1—N1 | 85.67 (14) | N3—C5—H5B | 110.0 |
N2—Cu1—N3 | 93.84 (14) | C6—C5—H5B | 110.0 |
N1—Cu1—N3 | 174.90 (15) | H5A—C5—H5B | 108.4 |
N2—Cu1—N4 | 177.27 (15) | N4—C6—C5 | 107.9 (3) |
N1—Cu1—N4 | 95.09 (14) | N4—C6—H6A | 110.1 |
N3—Cu1—N4 | 85.17 (14) | C5—C6—H6A | 110.1 |
O2—Cl1—O3 | 110.1 (2) | N4—C6—H6B | 110.1 |
O2—Cl1—O1 | 109.16 (19) | C5—C6—H6B | 110.1 |
O3—Cl1—O1 | 109.7 (2) | H6A—C6—H6B | 108.4 |
O2—Cl1—O4 | 110.33 (18) | N3—C7—H7A | 109.5 |
O3—Cl1—O4 | 109.0 (2) | N3—C7—H7B | 109.5 |
O1—Cl1—O4 | 108.48 (18) | H7A—C7—H7B | 109.5 |
O6—Cl2—O7 | 110.1 (2) | N3—C7—H7C | 109.5 |
O6—Cl2—O5 | 109.8 (2) | H7A—C7—H7C | 109.5 |
O7—Cl2—O5 | 108.29 (19) | H7B—C7—H7C | 109.5 |
O6—Cl2—O8 | 109.30 (19) | N4—C8—H8A | 109.5 |
O7—Cl2—O8 | 110.19 (19) | N4—C8—H8B | 109.5 |
O5—Cl2—O8 | 109.13 (19) | H8A—C8—H8B | 109.5 |
N1—C1—C2 | 107.8 (3) | N4—C8—H8C | 109.5 |
N1—C1—H1A | 110.1 | H8A—C8—H8C | 109.5 |
C2—C1—H1A | 110.1 | H8B—C8—H8C | 109.5 |
N1—C1—H1B | 110.1 | C3—N1—C1 | 111.6 (3) |
C2—C1—H1B | 110.2 | C3—N1—Cu1 | 116.3 (3) |
H1A—C1—H1B | 108.5 | C1—N1—Cu1 | 106.7 (2) |
N2—C2—C1 | 108.6 (3) | C3—N1—H1 | 110 (3) |
N2—C2—H2A | 110.0 | C1—N1—H1 | 98 (3) |
C1—C2—H2A | 110.0 | Cu1—N1—H1 | 113 (3) |
N2—C2—H2B | 110.0 | C4—N2—C2 | 110.4 (3) |
C1—C2—H2B | 110.0 | C4—N2—Cu1 | 119.7 (3) |
H2A—C2—H2B | 108.4 | C2—N2—Cu1 | 107.6 (2) |
N1—C3—H3A | 109.5 | C4—N2—H2 | 108 (3) |
N1—C3—H3B | 109.5 | C2—N2—H2 | 105 (3) |
H3A—C3—H3B | 109.5 | Cu1—N2—H2 | 105 (3) |
N1—C3—H3C | 109.5 | C5—N3—C7 | 111.0 (3) |
H3A—C3—H3C | 109.5 | C5—N3—Cu1 | 107.4 (2) |
H3B—C3—H3C | 109.5 | C7—N3—Cu1 | 114.8 (3) |
N2—C4—H4A | 109.5 | C5—N3—H3 | 106 (3) |
N2—C4—H4B | 109.5 | C7—N3—H3 | 108 (3) |
H4A—C4—H4B | 109.5 | Cu1—N3—H3 | 109 (3) |
N2—C4—H4C | 109.5 | C8—N4—C6 | 110.3 (3) |
H4A—C4—H4C | 109.5 | C8—N4—Cu1 | 118.8 (3) |
H4B—C4—H4C | 109.5 | C6—N4—Cu1 | 105.1 (3) |
N3—C5—C6 | 108.3 (3) | C8—N4—H4 | 106 (3) |
N3—C5—H5A | 110.0 | C6—N4—H4 | 108 (3) |
C6—C5—H5A | 110.0 | Cu1—N4—H4 | 108 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.82 (3) | 2.23 (3) | 3.041 (5) | 167 (4) |
N2—H2···O3ii | 0.81 (3) | 2.34 (4) | 3.133 (5) | 168 (4) |
N3—H3···O4 | 0.81 (3) | 2.49 (3) | 3.138 (5) | 139 (3) |
N3—H3···O7iii | 0.81 (3) | 2.56 (3) | 3.071 (5) | 123 (4) |
N4—H4···O8iv | 0.82 (3) | 2.53 (4) | 3.200 (5) | 139 (3) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z. |
(Ib) bis(
N,
N'-dimethylethylenediamine-
κ2N,
N')bis(perchlorato-
κO)copper(II)]
top
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | F(000) = 908 |
Mr = 438.75 | Dx = 1.667 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 1054 reflections |
a = 8.5966 (14) Å | θ = 2.7–17.4° |
b = 13.655 (2) Å | µ = 1.60 mm−1 |
c = 14.966 (3) Å | T = 250 K |
β = 95.533 (4)° | Plate, violet |
V = 1748.5 (5) Å3 | 0.19 × 0.11 × 0.03 mm |
Z = 4 | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area detector diffractometer | 3607 independent reflections |
Radiation source: Incoatec microsource | 2853 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.064 |
ω scans | θmax = 26.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.751, Tmax = 0.954 | k = −17→17 |
10331 measured reflections | l = −18→18 |
Refinement top
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)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0375P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
3607 reflections | Δρmax = 0.42 e Å−3 |
224 parameters | Δρmin = −0.29 e Å−3 |
8 restraints | Absolute structure: Flack (1983), with 1793 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.011 (19) |
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | V = 1748.5 (5) Å3 |
Mr = 438.75 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 8.5966 (14) Å | µ = 1.60 mm−1 |
b = 13.655 (2) Å | T = 250 K |
c = 14.966 (3) Å | 0.19 × 0.11 × 0.03 mm |
β = 95.533 (4)° | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area detector diffractometer | 3607 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2853 reflections with I > 2σ(I) |
Tmin = 0.751, Tmax = 0.954 | Rint = 0.064 |
10331 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.103 | Δρmax = 0.42 e Å−3 |
S = 0.99 | Δρmin = −0.29 e Å−3 |
3607 reflections | Absolute structure: Flack (1983), with 1793 Friedel pairs |
224 parameters | Absolute structure parameter: 0.011 (19) |
8 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.72412 (6) | 0.13488 (4) | 0.08342 (5) | 0.02801 (16) | |
Cl1 | 0.71462 (16) | −0.12157 (10) | 0.01464 (10) | 0.0394 (4) | |
Cl2 | 0.73034 (16) | 0.39598 (10) | 0.19336 (10) | 0.0377 (3) | |
O1 | 0.7487 (7) | −0.0230 (3) | −0.0005 (4) | 0.0762 (16) | |
O2 | 0.7076 (7) | −0.1750 (4) | −0.0647 (3) | 0.0814 (17) | |
O3 | 0.8227 (8) | −0.1630 (6) | 0.0791 (4) | 0.108 (2) | |
O4 | 0.5666 (6) | −0.1229 (3) | 0.0540 (4) | 0.0718 (17) | |
O8 | 0.7133 (7) | 0.4660 (4) | 0.1243 (3) | 0.0737 (15) | |
O5 | 0.7223 (6) | 0.3009 (3) | 0.1558 (4) | 0.0640 (14) | |
O6 | 0.6136 (7) | 0.4085 (4) | 0.2523 (4) | 0.0785 (17) | |
O7 | 0.8808 (6) | 0.4068 (4) | 0.2406 (4) | 0.0801 (17) | |
C1 | 0.7362 (8) | 0.2708 (5) | −0.0596 (5) | 0.0545 (18) | |
H1A | 0.7807 | 0.2914 | −0.1145 | 0.065* | |
H1B | 0.7145 | 0.3295 | −0.0252 | 0.065* | |
C2 | 0.5885 (7) | 0.2145 (5) | −0.0829 (4) | 0.0541 (18) | |
H2A | 0.5088 | 0.2574 | −0.1135 | 0.065* | |
H2B | 0.6078 | 0.1603 | −0.1234 | 0.065* | |
C3 | 0.9426 (10) | 0.1445 (5) | −0.0605 (6) | 0.058 (2) | |
H3A | 1.0032 | 0.1861 | −0.0967 | 0.087* | |
H3B | 0.8735 | 0.1034 | −0.0995 | 0.087* | |
H3C | 1.0126 | 0.1036 | −0.0219 | 0.087* | |
C4 | 0.4081 (7) | 0.1037 (5) | −0.0205 (5) | 0.0504 (18) | |
H4A | 0.4501 | 0.0470 | −0.0490 | 0.076* | |
H4B | 0.3256 | 0.1327 | −0.0608 | 0.076* | |
H4C | 0.3661 | 0.0837 | 0.0346 | 0.076* | |
C5 | 0.7070 (6) | 0.0194 (4) | 0.2408 (4) | 0.0346 (13) | |
H5A | 0.7318 | −0.0452 | 0.2174 | 0.042* | |
H5B | 0.6597 | 0.0102 | 0.2972 | 0.042* | |
C6 | 0.8533 (7) | 0.0797 (4) | 0.2568 (4) | 0.0388 (14) | |
H6A | 0.8304 | 0.1416 | 0.2860 | 0.047* | |
H6B | 0.9319 | 0.0442 | 0.2961 | 0.047* | |
C7 | 0.4982 (8) | 0.1395 (5) | 0.2210 (5) | 0.0431 (18) | |
H7A | 0.5639 | 0.1860 | 0.2560 | 0.065* | |
H7B | 0.4367 | 0.1027 | 0.2605 | 0.065* | |
H7C | 0.4289 | 0.1743 | 0.1769 | 0.065* | |
C8 | 1.0489 (7) | 0.1642 (5) | 0.1813 (4) | 0.0424 (15) | |
H8A | 1.1208 | 0.1414 | 0.2308 | 0.064* | |
H8B | 1.0151 | 0.2302 | 0.1936 | 0.064* | |
H8C | 1.1009 | 0.1641 | 0.1265 | 0.064* | |
N1 | 0.8491 (5) | 0.2061 (3) | −0.0050 (3) | 0.0348 (11) | |
H1 | 0.904 (6) | 0.248 (3) | 0.022 (4) | 0.042* | |
N2 | 0.5331 (5) | 0.1759 (4) | 0.0003 (3) | 0.0343 (11) | |
H2 | 0.491 (6) | 0.224 (3) | 0.022 (4) | 0.041* | |
N3 | 0.5967 (5) | 0.0717 (4) | 0.1749 (3) | 0.0308 (10) | |
H3 | 0.549 (6) | 0.027 (3) | 0.147 (3) | 0.037* | |
N4 | 0.9126 (5) | 0.0991 (3) | 0.1704 (4) | 0.0331 (11) | |
H4 | 0.937 (7) | 0.045 (3) | 0.152 (4) | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0227 (3) | 0.0272 (3) | 0.0343 (3) | 0.0004 (3) | 0.0042 (2) | 0.0023 (3) |
Cl1 | 0.0433 (8) | 0.0280 (8) | 0.0473 (9) | −0.0005 (6) | 0.0060 (7) | −0.0045 (6) |
Cl2 | 0.0411 (8) | 0.0272 (7) | 0.0462 (9) | −0.0004 (6) | 0.0118 (6) | −0.0021 (7) |
O1 | 0.087 (4) | 0.032 (3) | 0.116 (4) | −0.016 (3) | 0.040 (3) | −0.012 (3) |
O2 | 0.121 (5) | 0.064 (3) | 0.061 (3) | −0.014 (3) | 0.017 (3) | −0.023 (3) |
O3 | 0.105 (5) | 0.130 (5) | 0.083 (5) | 0.070 (4) | −0.023 (4) | 0.001 (4) |
O4 | 0.056 (3) | 0.060 (3) | 0.105 (5) | −0.020 (2) | 0.034 (3) | −0.007 (3) |
O8 | 0.096 (4) | 0.050 (3) | 0.077 (4) | 0.011 (3) | 0.017 (3) | 0.025 (2) |
O5 | 0.076 (3) | 0.029 (3) | 0.089 (4) | −0.003 (2) | 0.021 (3) | −0.024 (2) |
O6 | 0.085 (4) | 0.079 (4) | 0.080 (4) | 0.017 (3) | 0.052 (3) | −0.002 (3) |
O7 | 0.053 (3) | 0.093 (4) | 0.091 (4) | −0.016 (3) | −0.012 (3) | −0.010 (3) |
C1 | 0.062 (5) | 0.049 (4) | 0.053 (4) | −0.002 (3) | 0.009 (4) | 0.016 (3) |
C2 | 0.047 (4) | 0.072 (5) | 0.042 (4) | −0.006 (3) | −0.001 (3) | 0.017 (3) |
C3 | 0.061 (5) | 0.054 (5) | 0.065 (6) | −0.026 (3) | 0.031 (4) | −0.017 (4) |
C4 | 0.032 (4) | 0.053 (4) | 0.063 (5) | 0.003 (3) | −0.012 (3) | −0.001 (4) |
C5 | 0.036 (3) | 0.032 (3) | 0.036 (3) | −0.001 (2) | 0.003 (2) | 0.008 (2) |
C6 | 0.036 (3) | 0.041 (3) | 0.039 (3) | 0.007 (3) | −0.001 (3) | 0.002 (3) |
C7 | 0.033 (4) | 0.054 (5) | 0.045 (4) | 0.002 (3) | 0.017 (3) | 0.003 (3) |
C8 | 0.023 (3) | 0.048 (4) | 0.056 (4) | −0.005 (3) | 0.001 (3) | 0.003 (3) |
N1 | 0.035 (3) | 0.031 (3) | 0.039 (3) | −0.007 (2) | 0.003 (2) | −0.000 (2) |
N2 | 0.024 (3) | 0.037 (3) | 0.041 (3) | 0.007 (2) | 0.003 (2) | 0.004 (2) |
N3 | 0.027 (2) | 0.033 (3) | 0.032 (3) | −0.003 (2) | 0.003 (2) | 0.001 (2) |
N4 | 0.029 (3) | 0.024 (3) | 0.046 (3) | 0.002 (2) | 0.002 (2) | −0.005 (2) |
Geometric parameters (Å, º) top
Cu1—N3 | 2.026 (5) | C4—N2 | 1.469 (8) |
Cu1—N1 | 2.030 (5) | C4—H4A | 0.9700 |
Cu1—N4 | 2.037 (5) | C4—H4B | 0.9700 |
Cu1—N2 | 2.040 (5) | C4—H4C | 0.9700 |
Cl1—O2 | 1.390 (5) | C5—N3 | 1.485 (7) |
Cl1—O3 | 1.393 (6) | C5—C6 | 1.504 (8) |
Cl1—O1 | 1.401 (5) | C5—H5A | 0.9800 |
Cl1—O4 | 1.453 (5) | C5—H5B | 0.9800 |
Cl2—O8 | 1.405 (5) | C6—N4 | 1.459 (8) |
Cl2—O6 | 1.409 (5) | C6—H6A | 0.9800 |
Cl2—O5 | 1.414 (4) | C6—H6B | 0.9800 |
Cl2—O7 | 1.420 (5) | C7—N3 | 1.471 (7) |
C1—N1 | 1.496 (8) | C7—H7A | 0.9700 |
C1—C2 | 1.498 (8) | C7—H7B | 0.9700 |
C1—H1A | 0.9800 | C7—H7C | 0.9700 |
C1—H1B | 0.9800 | C8—N4 | 1.468 (7) |
C2—N2 | 1.474 (7) | C8—H8A | 0.9700 |
C2—H2A | 0.9800 | C8—H8B | 0.9700 |
C2—H2B | 0.9800 | C8—H8C | 0.9700 |
C3—N1 | 1.474 (8) | N1—H1 | 0.82 (3) |
C3—H3A | 0.9700 | N2—H2 | 0.83 (3) |
C3—H3B | 0.9700 | N3—H3 | 0.82 (3) |
C3—H3C | 0.9700 | N4—H4 | 0.82 (3) |
| | | |
N3—Cu1—N1 | 176.6 (2) | N3—C5—H5B | 110.1 |
N3—Cu1—N4 | 85.12 (19) | C6—C5—H5B | 110.1 |
N1—Cu1—N4 | 95.33 (19) | H5A—C5—H5B | 108.4 |
N3—Cu1—N2 | 94.16 (18) | N4—C6—C5 | 108.4 (5) |
N1—Cu1—N2 | 85.2 (2) | N4—C6—H6A | 110.0 |
N4—Cu1—N2 | 177.3 (2) | C5—C6—H6A | 110.0 |
O2—Cl1—O3 | 110.5 (4) | N4—C6—H6B | 110.0 |
O2—Cl1—O1 | 111.0 (4) | C5—C6—H6B | 110.0 |
O3—Cl1—O1 | 111.5 (4) | H6A—C6—H6B | 108.4 |
O2—Cl1—O4 | 111.9 (3) | N3—C7—H7A | 109.5 |
O3—Cl1—O4 | 105.4 (4) | N3—C7—H7B | 109.5 |
O1—Cl1—O4 | 106.4 (3) | H7A—C7—H7B | 109.5 |
O8—Cl2—O6 | 110.3 (3) | N3—C7—H7C | 109.5 |
O8—Cl2—O5 | 109.5 (3) | H7A—C7—H7C | 109.5 |
O6—Cl2—O5 | 110.5 (3) | H7B—C7—H7C | 109.5 |
O8—Cl2—O7 | 108.7 (4) | N4—C8—H8A | 109.5 |
O6—Cl2—O7 | 110.2 (4) | N4—C8—H8B | 109.5 |
O5—Cl2—O7 | 107.5 (3) | H8A—C8—H8B | 109.5 |
N1—C1—C2 | 108.3 (5) | N4—C8—H8C | 109.5 |
N1—C1—H1A | 110.0 | H8A—C8—H8C | 109.5 |
C2—C1—H1A | 110.0 | H8B—C8—H8C | 109.5 |
N1—C1—H1B | 110.0 | C3—N1—C1 | 112.9 (6) |
C2—C1—H1B | 110.0 | C3—N1—Cu1 | 116.5 (4) |
H1A—C1—H1B | 108.4 | C1—N1—Cu1 | 106.4 (4) |
N2—C2—C1 | 108.8 (5) | C3—N1—H1 | 110 (4) |
N2—C2—H2A | 109.9 | C1—N1—H1 | 100 (4) |
C1—C2—H2A | 109.9 | Cu1—N1—H1 | 110 (4) |
N2—C2—H2B | 109.9 | C4—N2—C2 | 110.5 (5) |
C1—C2—H2B | 109.9 | C4—N2—Cu1 | 118.3 (4) |
H2A—C2—H2B | 108.3 | C2—N2—Cu1 | 107.9 (3) |
N1—C3—H3A | 109.5 | C4—N2—H2 | 106 (4) |
N1—C3—H3B | 109.5 | C2—N2—H2 | 104 (4) |
H3A—C3—H3B | 109.5 | Cu1—N2—H2 | 109 (4) |
N1—C3—H3C | 109.5 | C7—N3—C5 | 110.5 (5) |
H3A—C3—H3C | 109.5 | C7—N3—Cu1 | 115.0 (4) |
H3B—C3—H3C | 109.5 | C5—N3—Cu1 | 107.6 (3) |
N2—C4—H4A | 109.5 | C7—N3—H3 | 115 (4) |
N2—C4—H4B | 109.5 | C5—N3—H3 | 103 (4) |
H4A—C4—H4B | 109.5 | Cu1—N3—H3 | 105 (4) |
N2—C4—H4C | 109.5 | C6—N4—C8 | 110.8 (5) |
H4A—C4—H4C | 109.5 | C6—N4—Cu1 | 106.6 (3) |
H4B—C4—H4C | 109.5 | C8—N4—Cu1 | 120.2 (4) |
N3—C5—C6 | 108.2 (4) | C6—N4—H4 | 105 (4) |
N3—C5—H5A | 110.1 | C8—N4—H4 | 111 (4) |
C6—C5—H5A | 110.1 | Cu1—N4—H4 | 102 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.82 (5) | 2.27 (5) | 3.068 (6) | 163 (5) |
N2—H2···O3ii | 0.83 (5) | 2.33 (5) | 3.149 (9) | 167 (5) |
N3—H3···O4 | 0.83 (4) | 2.49 (4) | 3.211 (7) | 147 (5) |
N3—H3···O7iii | 0.83 (4) | 2.67 (5) | 3.136 (7) | 117 (4) |
N4—H4···O8iv | 0.82 (5) | 2.68 (6) | 3.287 (7) | 132 (5) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z. |
(Ic) bis(
N,
N'-dimethylethylenediamine-
κ2N,
N')bis(perchlorato-
κO)copper(II)]
top
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | F(000) = 908 |
Mr = 438.75 | Dx = 1.582 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 1270 reflections |
a = 8.731 (3) Å | θ = 2.7–26.4° |
b = 13.824 (5) Å | µ = 1.52 mm−1 |
c = 15.314 (6) Å | T = 400 K |
β = 94.866 (9)° | Plate, violet |
V = 1841.7 (12) Å3 | 0.32 × 0.10 × 0.04 mm |
Z = 4 | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer | 3479 independent reflections |
Radiation source: Incoatec microsource | 2156 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.088 |
ω scans | θmax = 26.6°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.643, Tmax = 0.942 | k = −17→17 |
9966 measured reflections | l = −19→19 |
Refinement top
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)] = 0.075 | H-atom parameters constrained |
wR(F2) = 0.207 | w = 1/[σ2(Fo2) + (0.103P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3479 reflections | Δρmax = 0.86 e Å−3 |
210 parameters | Δρmin = −0.37 e Å−3 |
69 restraints | Absolute structure: Flack (1983), with 1702 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (4) |
Crystal data top
[Cu(ClO4)2(C4H12N2)2] | V = 1841.7 (12) Å3 |
Mr = 438.75 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 8.731 (3) Å | µ = 1.52 mm−1 |
b = 13.824 (5) Å | T = 400 K |
c = 15.314 (6) Å | 0.32 × 0.10 × 0.04 mm |
β = 94.866 (9)° | |
Data collection top
Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer | 3479 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2156 reflections with I > 2σ(I) |
Tmin = 0.643, Tmax = 0.942 | Rint = 0.088 |
9966 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.075 | H-atom parameters constrained |
wR(F2) = 0.207 | Δρmax = 0.86 e Å−3 |
S = 1.01 | Δρmin = −0.37 e Å−3 |
3479 reflections | Absolute structure: Flack (1983), with 1702 Friedel pairs |
210 parameters | Absolute structure parameter: 0.03 (4) |
69 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.27856 (15) | 0.86485 (7) | 0.91397 (10) | 0.0537 (3) | |
Cl2 | 0.2710 (4) | 0.6054 (2) | 0.8137 (2) | 0.0847 (9) | |
Cl1 | 0.2880 (4) | 1.12682 (17) | 0.9907 (2) | 0.0804 (9) | |
O1 | 0.2748 (18) | 1.0309 (6) | 0.9767 (10) | 0.156 (5) | |
O2 | 0.169 (2) | 1.1507 (15) | 1.0420 (15) | 0.160 (11)* | 0.53 (2) |
O3 | 0.281 (3) | 1.1825 (13) | 0.9207 (11) | 0.151 (9)* | 0.53 (2) |
O4 | 0.420 (2) | 1.1425 (14) | 1.0435 (15) | 0.153 (11)* | 0.53 (2) |
O2A | 0.300 (3) | 1.1788 (18) | 1.0646 (12) | 0.130 (10)* | 0.47 (2) |
O3A | 0.170 (3) | 1.153 (2) | 0.9316 (15) | 0.140 (11)* | 0.47 (2) |
O4A | 0.425 (2) | 1.1311 (19) | 0.9494 (16) | 0.142 (12)* | 0.47 (2) |
O8 | 0.281 (2) | 0.5330 (9) | 0.8722 (10) | 0.185 (7) | |
O5 | 0.2761 (17) | 0.6960 (7) | 0.8475 (10) | 0.151 (5) | |
O6 | 0.392 (3) | 0.5926 (14) | 0.7598 (16) | 0.263 (13) | |
O7 | 0.129 (2) | 0.5913 (14) | 0.7690 (16) | 0.223 (9) | |
C1 | 0.248 (3) | 0.796 (3) | 1.0876 (14) | 0.116 (14)* | 0.33 (2) |
H1A | 0.1986 | 0.7584 | 1.1306 | 0.139* | 0.33 (2) |
H1B | 0.2773 | 0.8587 | 1.1124 | 0.139* | 0.33 (2) |
C2 | 0.387 (3) | 0.743 (2) | 1.0557 (18) | 0.088 (12)* | 0.33 (2) |
H2A | 0.3555 | 0.6857 | 1.0216 | 0.106* | 0.33 (2) |
H2B | 0.4589 | 0.7232 | 1.1045 | 0.106* | 0.33 (2) |
N1 | 0.1450 (12) | 0.8066 (7) | 1.0024 (7) | 0.076 (3) | 0.33 (2) |
H1 | 0.1039 | 0.7489 | 0.9838 | 0.091* | 0.33 (2) |
N2 | 0.4592 (13) | 0.8200 (8) | 0.9979 (6) | 0.084 (3) | 0.33 (2) |
H2 | 0.5231 | 0.7872 | 0.9644 | 0.101* | 0.33 (2) |
C3 | 0.017 (4) | 0.883 (2) | 1.021 (3) | 0.058 (9)* | 0.33 (2) |
H3A | −0.0135 | 0.8732 | 1.0793 | 0.087* | 0.33 (2) |
H3B | −0.0707 | 0.8739 | 0.9794 | 0.087* | 0.33 (2) |
H3C | 0.0566 | 0.9469 | 1.0158 | 0.087* | 0.33 (2) |
C4 | 0.559 (5) | 0.890 (3) | 1.050 (3) | 0.090 (15)* | 0.33 (2) |
H4A | 0.5201 | 0.8989 | 1.1068 | 0.135* | 0.33 (2) |
H4B | 0.5578 | 0.9514 | 1.0205 | 0.135* | 0.33 (2) |
H4C | 0.6619 | 0.8661 | 1.0579 | 0.135* | 0.33 (2) |
C1A | 0.250 (2) | 0.7376 (14) | 1.0584 (12) | 0.094 (7)* | 0.67 (2) |
H1A1 | 0.2775 | 0.6818 | 1.0247 | 0.113* | 0.67 (2) |
H1A2 | 0.2008 | 0.7157 | 1.1095 | 0.113* | 0.67 (2) |
C2A | 0.391 (2) | 0.8010 (16) | 1.0848 (10) | 0.092 (6)* | 0.67 (2) |
H2A1 | 0.3608 | 0.8610 | 1.1115 | 0.110* | 0.67 (2) |
H2A2 | 0.4634 | 0.7672 | 1.1255 | 0.110* | 0.67 (2) |
N1A | 0.1450 (12) | 0.8066 (7) | 1.0024 (7) | 0.076 (3) | 0.67 (2) |
H1A3 | 0.0752 | 0.7685 | 0.9711 | 0.091* | 0.67 (2) |
N2A | 0.4592 (13) | 0.8200 (8) | 0.9979 (6) | 0.084 (3) | 0.67 (2) |
H2A3 | 0.4974 | 0.7638 | 0.9777 | 0.101* | 0.67 (2) |
C3A | 0.052 (4) | 0.8726 (17) | 1.059 (2) | 0.104 (9)* | 0.67 (2) |
H3A1 | −0.0330 | 0.8369 | 1.0787 | 0.157* | 0.67 (2) |
H3A2 | 0.0129 | 0.9268 | 1.0242 | 0.157* | 0.67 (2) |
H3A3 | 0.1162 | 0.8955 | 1.1081 | 0.157* | 0.67 (2) |
C4A | 0.589 (3) | 0.8930 (14) | 1.0138 (17) | 0.078 (6)* | 0.67 (2) |
H4A1 | 0.5469 | 0.9563 | 1.0210 | 0.117* | 0.67 (2) |
H4A2 | 0.6504 | 0.8932 | 0.9646 | 0.117* | 0.67 (2) |
H4A3 | 0.6524 | 0.8755 | 1.0657 | 0.117* | 0.67 (2) |
C5 | 0.303 (2) | 0.9723 (11) | 0.7604 (9) | 0.104 (5) | |
H5A | 0.2863 | 1.0367 | 0.7829 | 0.125* | |
H5B | 0.3500 | 0.9793 | 0.7057 | 0.125* | |
C6 | 0.1591 (19) | 0.9267 (14) | 0.7433 (10) | 0.112 (5) | |
H6A | 0.1706 | 0.8674 | 0.7107 | 0.135* | |
H6B | 0.0887 | 0.9689 | 0.7088 | 0.135* | |
C7 | 0.515 (2) | 0.8524 (11) | 0.7847 (12) | 0.102 (6) | |
H7A | 0.4648 | 0.8244 | 0.7326 | 0.153* | |
H7B | 0.5441 | 0.8021 | 0.8261 | 0.153* | |
H7C | 0.6052 | 0.8867 | 0.7703 | 0.153* | |
C8 | −0.0309 (18) | 0.8395 (10) | 0.8104 (11) | 0.097 (5) | |
H8A | −0.1147 | 0.8735 | 0.7795 | 0.145* | |
H8B | −0.0628 | 0.8153 | 0.8648 | 0.145* | |
H8C | −0.0006 | 0.7864 | 0.7754 | 0.145* | |
N3 | 0.4095 (10) | 0.9199 (7) | 0.8234 (6) | 0.070 (2) | |
H3 | 0.4699 | 0.9659 | 0.8515 | 0.084* | |
N4 | 0.0988 (11) | 0.9052 (8) | 0.8281 (6) | 0.072 (2) | |
H4 | 0.0609 | 0.9615 | 0.8484 | 0.086* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0537 (6) | 0.0472 (5) | 0.0606 (6) | 0.0022 (6) | 0.0065 (4) | 0.0047 (6) |
Cl2 | 0.093 (2) | 0.0521 (14) | 0.109 (2) | −0.0032 (14) | 0.0073 (19) | −0.0086 (15) |
Cl1 | 0.108 (2) | 0.0455 (13) | 0.088 (2) | −0.0017 (15) | 0.0090 (17) | −0.0036 (14) |
O1 | 0.198 (13) | 0.064 (6) | 0.207 (13) | −0.028 (8) | 0.030 (12) | −0.036 (7) |
O8 | 0.281 (19) | 0.075 (7) | 0.204 (15) | 0.014 (9) | 0.052 (15) | 0.042 (7) |
O5 | 0.165 (11) | 0.058 (5) | 0.233 (15) | −0.010 (6) | 0.037 (11) | −0.058 (7) |
O6 | 0.35 (3) | 0.168 (14) | 0.30 (3) | 0.079 (17) | 0.23 (2) | 0.021 (16) |
O7 | 0.182 (17) | 0.180 (15) | 0.29 (2) | −0.059 (13) | −0.057 (16) | −0.023 (16) |
N1 | 0.076 (6) | 0.072 (6) | 0.081 (6) | −0.023 (5) | 0.009 (5) | 0.012 (5) |
N2 | 0.093 (8) | 0.083 (7) | 0.076 (7) | 0.030 (6) | 0.006 (6) | 0.008 (6) |
N1A | 0.076 (6) | 0.072 (6) | 0.081 (6) | −0.023 (5) | 0.009 (5) | 0.012 (5) |
N2A | 0.093 (8) | 0.083 (7) | 0.076 (7) | 0.030 (6) | 0.006 (6) | 0.008 (6) |
C5 | 0.136 (13) | 0.102 (10) | 0.073 (8) | −0.021 (9) | −0.005 (8) | 0.045 (7) |
C6 | 0.108 (12) | 0.152 (15) | 0.077 (9) | 0.021 (11) | 0.006 (8) | 0.032 (10) |
C7 | 0.105 (13) | 0.114 (12) | 0.095 (12) | 0.008 (9) | 0.045 (10) | 0.004 (8) |
C8 | 0.070 (9) | 0.092 (9) | 0.122 (12) | 0.020 (8) | −0.032 (8) | −0.012 (8) |
N3 | 0.071 (6) | 0.066 (5) | 0.074 (6) | −0.022 (5) | 0.012 (5) | −0.010 (5) |
N4 | 0.073 (7) | 0.072 (6) | 0.070 (6) | 0.017 (5) | 0.000 (5) | 0.004 (5) |
Geometric parameters (Å, º) top
Cu1—N3 | 2.020 (9) | C4—H4B | 0.9600 |
Cu1—N1 | 2.028 (9) | C4—H4C | 0.9600 |
Cu1—N4 | 2.038 (9) | C1A—C2A | 1.54 (2) |
Cu1—N2 | 2.045 (10) | C1A—H1A1 | 0.9700 |
Cl2—O8 | 1.340 (13) | C1A—H1A2 | 0.9700 |
Cl2—O5 | 1.354 (9) | C2A—H2A1 | 0.9700 |
Cl2—O7 | 1.376 (18) | C2A—H2A2 | 0.9700 |
Cl2—O6 | 1.407 (16) | C3A—H3A1 | 0.9600 |
Cl1—O3 | 1.316 (14) | C3A—H3A2 | 0.9600 |
Cl1—O2A | 1.337 (14) | C3A—H3A3 | 0.9600 |
Cl1—O1 | 1.346 (8) | C4A—H4A1 | 0.9600 |
Cl1—O3A | 1.360 (15) | C4A—H4A2 | 0.9600 |
Cl1—O4 | 1.368 (14) | C4A—H4A3 | 0.9600 |
Cl1—O2 | 1.396 (14) | C5—C6 | 1.41 (2) |
Cl1—O4A | 1.400 (15) | C5—N3 | 1.474 (16) |
C1—N1 | 1.53 (2) | C5—H5A | 0.9700 |
C1—C2 | 1.54 (3) | C5—H5B | 0.9700 |
C1—H1A | 0.9700 | C6—N4 | 1.472 (17) |
C1—H1B | 0.9700 | C6—H6A | 0.9700 |
C2—N2 | 1.56 (2) | C6—H6B | 0.9700 |
C2—H2A | 0.9700 | C7—N3 | 1.471 (18) |
C2—H2B | 0.9700 | C7—H7A | 0.9600 |
N1—C3 | 1.58 (3) | C7—H7B | 0.9600 |
N1—H1 | 0.9100 | C7—H7C | 0.9600 |
N2—C4 | 1.49 (2) | C8—N4 | 1.459 (18) |
N2—H2 | 0.9100 | C8—H8A | 0.9600 |
C3—H3A | 0.9600 | C8—H8B | 0.9600 |
C3—H3B | 0.9600 | C8—H8C | 0.9600 |
C3—H3C | 0.9600 | N3—H3 | 0.9100 |
C4—H4A | 0.9600 | N4—H4 | 0.9100 |
| | | |
N3—Cu1—N1 | 178.4 (4) | C2—N2—Cu1 | 103.8 (11) |
N3—Cu1—N4 | 84.5 (4) | C4—N2—H2 | 105.9 |
N1—Cu1—N4 | 94.9 (4) | C2—N2—H2 | 105.9 |
N3—Cu1—N2 | 95.4 (4) | Cu1—N2—H2 | 105.9 |
N1—Cu1—N2 | 85.2 (4) | C2A—C1A—H1A1 | 111.2 |
N4—Cu1—N2 | 178.1 (5) | C2A—C1A—H1A2 | 111.2 |
O8—Cl2—O5 | 115.9 (10) | H1A1—C1A—H1A2 | 109.2 |
O8—Cl2—O7 | 103.2 (13) | C1A—C2A—H2A1 | 111.1 |
O5—Cl2—O7 | 108.7 (11) | C1A—C2A—H2A2 | 111.1 |
O8—Cl2—O6 | 106.9 (12) | H2A1—C2A—H2A2 | 109.0 |
O5—Cl2—O6 | 109.8 (12) | H3A1—C3A—H3A2 | 109.5 |
O7—Cl2—O6 | 112.2 (17) | H3A1—C3A—H3A3 | 109.5 |
O3—Cl1—O2A | 111.7 (15) | H3A2—C3A—H3A3 | 109.5 |
O3—Cl1—O1 | 116.6 (10) | H4A1—C4A—H4A2 | 109.5 |
O2A—Cl1—O1 | 131.5 (14) | H4A1—C4A—H4A3 | 109.5 |
O3—Cl1—O3A | 47.1 (16) | H4A2—C4A—H4A3 | 109.5 |
O2A—Cl1—O3A | 114.8 (12) | C6—C5—N3 | 113.9 (11) |
O1—Cl1—O3A | 96.1 (14) | C6—C5—H5A | 108.8 |
O3—Cl1—O4 | 111.7 (11) | N3—C5—H5A | 108.8 |
O2A—Cl1—O4 | 54.2 (12) | C6—C5—H5B | 108.8 |
O1—Cl1—O4 | 107.8 (9) | N3—C5—H5B | 108.8 |
O3A—Cl1—O4 | 154.5 (14) | H5A—C5—H5B | 107.7 |
O3—Cl1—O2 | 109.4 (10) | C5—C6—N4 | 107.8 (12) |
O2A—Cl1—O2 | 53.4 (13) | C5—C6—H6A | 110.1 |
O1—Cl1—O2 | 105.3 (9) | N4—C6—H6A | 110.1 |
O3A—Cl1—O2 | 75.8 (15) | C5—C6—H6B | 110.1 |
O4—Cl1—O2 | 105.1 (10) | N4—C6—H6B | 110.1 |
O3—Cl1—O4A | 66.0 (16) | H6A—C6—H6B | 108.5 |
O2A—Cl1—O4A | 110.7 (11) | N3—C7—H7A | 109.5 |
O1—Cl1—O4A | 92.0 (12) | N3—C7—H7B | 109.5 |
O3A—Cl1—O4A | 108.3 (11) | H7A—C7—H7B | 109.5 |
O4—Cl1—O4A | 63.4 (14) | N3—C7—H7C | 109.5 |
O2—Cl1—O4A | 161.9 (13) | H7A—C7—H7C | 109.5 |
N1—C1—C2 | 101.5 (15) | H7B—C7—H7C | 109.5 |
N1—C1—H1A | 111.5 | N4—C8—H8A | 109.5 |
C2—C1—H1A | 111.5 | N4—C8—H8B | 109.5 |
N1—C1—H1B | 111.5 | H8A—C8—H8B | 109.5 |
C2—C1—H1B | 111.5 | N4—C8—H8C | 109.5 |
H1A—C1—H1B | 109.3 | H8A—C8—H8C | 109.5 |
C1—C2—N2 | 102.5 (15) | H8B—C8—H8C | 109.5 |
C1—C2—H2A | 111.3 | C7—N3—C5 | 115.6 (13) |
N2—C2—H2A | 111.3 | C7—N3—Cu1 | 116.6 (9) |
C1—C2—H2B | 111.3 | C5—N3—Cu1 | 105.7 (8) |
N2—C2—H2B | 111.3 | C7—N3—H3 | 106.0 |
H2A—C2—H2B | 109.2 | C5—N3—H3 | 106.0 |
C1—N1—C3 | 107 (2) | Cu1—N3—H3 | 106.0 |
C1—N1—Cu1 | 106.1 (12) | C8—N4—C6 | 107.0 (12) |
C3—N1—Cu1 | 108.3 (15) | C8—N4—Cu1 | 119.5 (9) |
C1—N1—H1 | 111.9 | C6—N4—Cu1 | 108.1 (8) |
C3—N1—H1 | 111.9 | C8—N4—H4 | 107.2 |
Cu1—N1—H1 | 111.9 | C6—N4—H4 | 107.2 |
C4—N2—C2 | 113 (2) | Cu1—N4—H4 | 107.2 |
C4—N2—Cu1 | 122 (2) | | |
Experimental details
| (Ia) | (Ib) | (Ic) |
Crystal data |
Chemical formula | [Cu(ClO4)2(C4H12N2)2] | [Cu(ClO4)2(C4H12N2)2] | [Cu(ClO4)2(C4H12N2)2] |
Mr | 438.75 | 438.75 | 438.75 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, Cc | Monoclinic, Cc |
Temperature (K) | 100 | 250 | 400 |
a, b, c (Å) | 8.5395 (17), 13.543 (3), 14.743 (4) | 8.5966 (14), 13.655 (2), 14.966 (3) | 8.731 (3), 13.824 (5), 15.314 (6) |
β (°) | 95.358 (3) | 95.533 (4) | 94.866 (9) |
V (Å3) | 1697.6 (6) | 1748.5 (5) | 1841.7 (12) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.65 | 1.60 | 1.52 |
Crystal size (mm) | 0.19 × 0.11 × 0.03 | 0.19 × 0.11 × 0.03 | 0.32 × 0.10 × 0.04 |
|
Data collection |
Diffractometer | Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer | Bruker D8 goniometer with a SMART APEX CCD area detector diffractometer | Bruker D8 goniometer with a SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.745, 0.952 | 0.751, 0.954 | 0.643, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9912, 3488, 3137 | 10331, 3607, 2853 | 9966, 3479, 2156 |
Rint | 0.055 | 0.064 | 0.088 |
(sin θ/λ)max (Å−1) | 0.627 | 0.628 | 0.629 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.075, 0.99 | 0.047, 0.103, 0.99 | 0.075, 0.207, 1.01 |
No. of reflections | 3488 | 3607 | 3479 |
No. of parameters | 224 | 224 | 210 |
No. of restraints | 8 | 8 | 69 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.38 | 0.42, −0.29 | 0.86, −0.37 |
Absolute structure | Flack (1983), with 1739 Friedel pairs | Flack (1983), with 1793 Friedel pairs | Flack (1983), with 1702 Friedel pairs |
Absolute structure parameter | 0.004 (14) | 0.011 (19) | 0.03 (4) |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.82 (3) | 2.23 (3) | 3.041 (5) | 167 (4) |
N2—H2···O3ii | 0.81 (3) | 2.34 (4) | 3.133 (5) | 168 (4) |
N3—H3···O4 | 0.81 (3) | 2.49 (3) | 3.138 (5) | 139 (3) |
N3—H3···O7iii | 0.81 (3) | 2.56 (3) | 3.071 (5) | 123 (4) |
N4—H4···O8iv | 0.82 (3) | 2.53 (4) | 3.200 (5) | 139 (3) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z. |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.82 (5) | 2.27 (5) | 3.068 (6) | 163 (5) |
N2—H2···O3ii | 0.83 (5) | 2.33 (5) | 3.149 (9) | 167 (5) |
N3—H3···O4 | 0.83 (4) | 2.49 (4) | 3.211 (7) | 147 (5) |
N3—H3···O7iii | 0.83 (4) | 2.67 (5) | 3.136 (7) | 117 (4) |
N4—H4···O8iv | 0.82 (5) | 2.68 (6) | 3.287 (7) | 132 (5) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z. |
Selected geometric parameters (Å, °) top | (Ia) | (Ib) | (Ic) |
Cu1—N1 | 2.026 (3) | 2.031 (4) | 2.027 (11) |
Cu1—N2 | 2.026 (4) | 2.041 (5) | 2.045 (11) |
Cu1—N3 | 2.035 (3) | 2.027 (5) | 2.020 (9) |
Cu1—N4 | 2.051 (4) | 2.038 (5) | 2.038 (10) |
Cu1—O1 | 2.470 (3) | 2.514 (5) | 2.490 (10) |
Cu1—O5 | 2.496 (3) | 2.513 (5) | 2.546 (11) |
| | | |
| (Ia) | (Ib) | (Ic) |
N1—Cu1—N2 | 85.66 (14) | 85.21 (18) | 85.2 (4) |
N2—Cu1—N3 | 93.85 (13) | 94.19 (18) | 95.4 (4) |
N1—Cu1—N3 | 174.88 (15) | 176.57 (19) | 178.4 (4) |
N2—Cu1—N4 | 177.28 (16) | 177.3 (2) | 178.1 (4) |
N1—Cu1—N4 | 95.09 (15) | 95.34 (19) | 94.9 (4) |
O1—Cu1—O5 | 173.07 (10) | 173.27 (18) | 178.6 (5) |
Comparison of perchlorate coordination (Å, °) topComplex | Cl1···Cl2 | Cu1—O1—Cl1 | Cu1—O5—Cl2 |
(Ia) | 7.459 (2) | 129.63 (18) | 172.3 (2) |
(Ib) | 7.553 (2) | 135.6 (4) | 176.0 (3) |
(Ic) | 7.698 (5) | 164.9 (10) | 178.2 (9) |
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The perchlorate group (ClO4-) represents a rather weakly coordinating anion (Pascal & Favier, 1998). A search of the Cambridge Structural Database (CSD; Version 5.33 of November 2011, including updates until May 2012; Allen, 2002) resulted in 10249 error-free entries without disorder which contain both one or more perchlorate anions and at least one metal atom; 1205 entries (11.8%) showed at least one perchlorate bonded to the metal. In an attempt to identify suitable cations for the coordination of weak ligands (Şerb et al., 2007; Schnitzler et al., 2010), we envisaged CuII as a good candidate. This cation is notoriously Jahn–Teller distorted (Atkins et al., 2009) and we presumed that the more distant vertices in the coordination polyhedron might be more readily accessible to weakly coordinating groups. A CSD search confirmed this simple idea: 581 entries, corresponding to a higher fraction of 18.1%, featured a coordinated perchlorate, out of a total of 3213 error-free and undisordered entries with at least one CuII and one perchlorate in the structure. 204 structures showed (almost exclusively trans) geometries with two coordinated perchlorate groups.
In this contribution, we report the influence of temperature on the crystal structure of a compound in that category. For the title compound, (I), lattice parameters and space group at ambient temperature, but no atomic coordinates, had previously been determined by Näsänen et al. (1966) (CSD refcode ZZZHVW) based on Weissenberg photographs. Complex (I) features four N-donor atoms in the equatorial plane of an elongated pseudo-octahedron (see scheme) and shows two longer and presumably weaker bonds between the CuII centre and the symmetrically independent perchlorate anions. In the present work, intensity data were collected at 100, 250 and 400 K, denoted data sets (Ia), (Ib) and (Ic), respectively, and the resulting displacement ellipsoid plots are provided in Figs. 1–3.
The intramolecular distances and angles at 100 K are unexceptional. Packing in this solid is dominated by classical intermolecular N—H···O hydrogen bonding, with N···O > 3 Å; a two-dimensional network in the ab plane is formed. The hydrogen-bond geometry has been compiled in Tables 1 [for (Ia)] and 2 [for (Ib)].
The main focus of this contribution is the effect of temperature on perchlorate coordination. In this context, two observations merit discussion. Firstly, comparison of the structures at 100 and 250 K, i.e. (Ia) and (Ib), shows only one significant difference, namely an increase in the Cu1—O1 distance (Table 3). In view of the more elevated standard uncertainties in (Ic), the results obtained at the highest temperature should not be overinterpreted. Secondly, the weak perchlorate coordination is also reflected in the Cl1···Cl2 distances at different temperatures (Table 4); (Ia) and (Ib) consistently show two different Cu—O—Cl angles, whereas both angles are large in the case of (Ic), resulting in a significantly longer Cl1···Cl2 separation. Both these observations lead to the conclusion that the increase in temperature is sufficient to trigger a significant change in the coordination of the weak perchlorate ligand.