In the crystal structure of the title centrosymmetric binuclear copper(II) complex, [Cu
2(C
6H
12N
4O
2)(C
3H
4N
2)
2](ClO
4)
2 or [Cu
2(oxen)(Him)
2](ClO
4)
2 [oxen =
N,N′-bis(2-aminoethyl)ethanediamide(2−) and Him = imidazole], two Cu
II atoms are bridged by the oxen group. The Cu
Cu distance is 5.219 (2) Å and the Cu atoms have distorted square-planar coordination geometry. Molecules are connected by intermolecular N—H
O hydrogen bonds.
Supporting information
CCDC reference: 252769
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.029
- wR factor = 0.077
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors for O3
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for Cl
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[
N,
N'-ethylenediamide-bis(2-aminoethyl)]bis(imidazole)
dicopper(II) diperchlorate
top
Crystal data top
[Cu2C12H20N8O2]·2ClO4 | F(000) = 640 |
Mr = 634.34 | Dx = 1.866 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.7884 (15) Å | θ = 13.6–18.9° |
b = 13.765 (3) Å | µ = 2.19 mm−1 |
c = 10.2773 (12) Å | T = 293 K |
β = 114.741 (12)° | Block, blue |
V = 1129.1 (4) Å3 | 0.60 × 0.50 × 0.50 mm |
Z = 2 | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 2058 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 26.0°, θmin = 3.0° |
ω/2θ scans | h = 0→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = 0→16 |
Tmin = 0.291, Tmax = 0.335 | l = −12→11 |
2294 measured reflections | 3 standard reflections every 300 reflections |
2154 independent reflections | intensity decay: 1.0% |
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)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0425P)2 + 0.9241P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2154 reflections | Δρmax = 0.77 e Å−3 |
155 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.060 (4) |
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 | |
Cu | 0.23315 (3) | 0.10063 (2) | 0.19970 (3) | 0.02772 (15) | |
Cl | 0.07268 (7) | 0.35787 (4) | 0.24939 (6) | 0.03650 (19) | |
O | −0.1626 (2) | −0.07167 (13) | 0.00895 (17) | 0.0306 (4) | |
O1 | 0.0969 (3) | 0.43705 (19) | 0.1715 (3) | 0.0680 (7) | |
O2 | −0.0675 (3) | 0.3811 (2) | 0.2798 (3) | 0.0739 (7) | |
O3 | 0.0330 (3) | 0.27124 (16) | 0.1643 (2) | 0.0579 (6) | |
O4 | 0.2184 (3) | 0.34287 (16) | 0.3802 (2) | 0.0559 (6) | |
N1 | 0.0387 (2) | 0.02667 (14) | 0.1743 (2) | 0.0280 (4) | |
N2 | 0.2527 (3) | 0.11431 (16) | 0.4018 (2) | 0.0333 (5) | |
H2A | 0.3309 | 0.0731 | 0.4603 | 0.040* | |
H2D | 0.2838 | 0.1753 | 0.4335 | 0.040* | |
N3 | 0.4364 (3) | 0.16672 (16) | 0.2182 (2) | 0.0346 (5) | |
N4 | 0.6528 (3) | 0.2618 (2) | 0.2876 (3) | 0.0511 (6) | |
H4A | 0.7240 | 0.3059 | 0.3342 | 0.061* | |
C1 | −0.0379 (3) | −0.01392 (15) | 0.0517 (2) | 0.0243 (4) | |
C2 | 0.0047 (3) | 0.0108 (2) | 0.2990 (3) | 0.0370 (6) | |
H2B | 0.0492 | −0.0515 | 0.3424 | 0.044* | |
H2C | −0.1151 | 0.0113 | 0.2720 | 0.044* | |
C3 | 0.0885 (4) | 0.0921 (2) | 0.4026 (3) | 0.0458 (7) | |
H3A | 0.0181 | 0.1495 | 0.3754 | 0.055* | |
H3B | 0.1041 | 0.0732 | 0.4983 | 0.055* | |
C4 | 0.5204 (4) | 0.2354 (2) | 0.3091 (3) | 0.0454 (7) | |
H4B | 0.4907 | 0.2617 | 0.3786 | 0.054* | |
C5 | 0.6567 (3) | 0.2067 (2) | 0.1787 (3) | 0.0487 (7) | |
H5A | 0.7367 | 0.2089 | 0.1417 | 0.058* | |
C6 | 0.5214 (3) | 0.1485 (2) | 0.1357 (3) | 0.0422 (6) | |
H6A | 0.4906 | 0.1033 | 0.0619 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0252 (2) | 0.0322 (2) | 0.0236 (2) | −0.00950 (10) | 0.00814 (13) | −0.00460 (10) |
Cl | 0.0312 (3) | 0.0332 (3) | 0.0369 (3) | −0.0074 (2) | 0.0061 (2) | 0.0049 (2) |
O | 0.0291 (8) | 0.0363 (9) | 0.0246 (8) | −0.0126 (7) | 0.0094 (7) | −0.0021 (7) |
O1 | 0.0644 (15) | 0.0603 (14) | 0.0607 (14) | −0.0244 (12) | 0.0079 (12) | 0.0242 (12) |
O2 | 0.0516 (14) | 0.0915 (19) | 0.0845 (19) | −0.0082 (13) | 0.0344 (14) | −0.0105 (16) |
O3 | 0.0655 (14) | 0.0429 (12) | 0.0462 (12) | −0.0018 (10) | 0.0046 (10) | −0.0045 (9) |
O4 | 0.0489 (12) | 0.0552 (13) | 0.0410 (11) | −0.0049 (10) | −0.0034 (9) | 0.0054 (10) |
N1 | 0.0274 (9) | 0.0332 (10) | 0.0220 (9) | −0.0069 (8) | 0.0089 (8) | −0.0012 (8) |
N2 | 0.0352 (11) | 0.0344 (11) | 0.0257 (10) | −0.0053 (8) | 0.0082 (8) | −0.0056 (8) |
N3 | 0.0299 (10) | 0.0370 (11) | 0.0345 (11) | −0.0111 (8) | 0.0111 (8) | −0.0066 (9) |
N4 | 0.0402 (13) | 0.0508 (14) | 0.0541 (15) | −0.0235 (11) | 0.0116 (11) | −0.0065 (12) |
C1 | 0.0228 (10) | 0.0240 (10) | 0.0226 (10) | −0.0017 (8) | 0.0061 (8) | 0.0022 (8) |
C2 | 0.0401 (13) | 0.0446 (14) | 0.0280 (12) | −0.0128 (11) | 0.0160 (10) | −0.0022 (10) |
C3 | 0.0541 (17) | 0.0536 (17) | 0.0356 (14) | −0.0119 (13) | 0.0246 (13) | −0.0081 (12) |
C4 | 0.0423 (14) | 0.0464 (16) | 0.0459 (15) | −0.0183 (12) | 0.0170 (12) | −0.0142 (13) |
C5 | 0.0340 (14) | 0.0619 (18) | 0.0530 (17) | −0.0102 (13) | 0.0211 (12) | 0.0075 (14) |
C6 | 0.0384 (14) | 0.0487 (16) | 0.0420 (14) | −0.0087 (12) | 0.0192 (12) | −0.0071 (12) |
Geometric parameters (Å, º) top
Cu—N1 | 1.9107 (19) | N3—C4 | 1.317 (3) |
Cu—N3 | 1.942 (2) | N3—C6 | 1.367 (3) |
Cu—Oi | 2.0071 (16) | N4—C4 | 1.322 (4) |
Cu—N2 | 2.020 (2) | N4—C5 | 1.364 (4) |
Cl—O1 | 1.420 (2) | N4—H4A | 0.8600 |
Cl—O2 | 1.428 (3) | C1—C1i | 1.521 (4) |
Cl—O4 | 1.431 (2) | C2—C3 | 1.508 (4) |
Cl—O3 | 1.433 (2) | C2—H2B | 0.9700 |
O—C1 | 1.274 (3) | C2—H2C | 0.9700 |
O—Cui | 2.0071 (16) | C3—H3A | 0.9700 |
N1—C1 | 1.281 (3) | C3—H3B | 0.9700 |
N1—C2 | 1.450 (3) | C4—H4B | 0.9300 |
N2—C3 | 1.478 (4) | C5—C6 | 1.346 (4) |
N2—H2A | 0.9000 | C5—H5A | 0.9300 |
N2—H2D | 0.9000 | C6—H6A | 0.9300 |
| | | |
N1—Cu—N3 | 175.16 (9) | C4—N4—H4A | 126.0 |
N1—Cu—Oi | 83.63 (7) | C5—N4—H4A | 126.0 |
N3—Cu—Oi | 93.33 (8) | O—C1—N1 | 129.3 (2) |
N1—Cu—N2 | 82.91 (8) | O—C1—C1i | 118.7 (2) |
N3—Cu—N2 | 100.18 (9) | N1—C1—C1i | 111.9 (2) |
Oi—Cu—N2 | 166.48 (8) | N1—C2—C3 | 106.9 (2) |
O1—Cl—O2 | 107.34 (19) | N1—C2—H2B | 110.3 |
O1—Cl—O4 | 110.71 (14) | C3—C2—H2B | 110.3 |
O2—Cl—O4 | 109.96 (17) | N1—C2—H2C | 110.3 |
O1—Cl—O3 | 110.53 (16) | C3—C2—H2C | 110.3 |
O2—Cl—O3 | 107.95 (16) | H2B—C2—H2C | 108.6 |
O4—Cl—O3 | 110.26 (13) | N2—C3—C2 | 109.9 (2) |
C1—O—Cui | 109.23 (13) | N2—C3—H3A | 109.7 |
C1—N1—C2 | 125.82 (19) | C2—C3—H3A | 109.7 |
C1—N1—Cu | 116.02 (15) | N2—C3—H3B | 109.7 |
C2—N1—Cu | 117.60 (15) | C2—C3—H3B | 109.7 |
C3—N2—Cu | 108.85 (16) | H3A—C3—H3B | 108.2 |
C3—N2—H2A | 109.9 | N3—C4—N4 | 110.5 (3) |
Cu—N2—H2A | 109.9 | N3—C4—H4B | 124.8 |
C3—N2—H2D | 109.9 | N4—C4—H4B | 124.8 |
Cu—N2—H2D | 109.9 | C6—C5—N4 | 106.2 (2) |
H2A—N2—H2D | 108.3 | C6—C5—H5A | 126.9 |
C4—N3—C6 | 106.4 (2) | N4—C5—H5A | 126.9 |
C4—N3—Cu | 128.73 (19) | C5—C6—N3 | 108.9 (3) |
C6—N3—Cu | 124.90 (18) | C5—C6—H6A | 125.5 |
C4—N4—C5 | 108.1 (2) | N3—C6—H6A | 125.5 |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···O4 | 0.90 | 2.39 | 3.159 (3) | 144 |
N2—H2A···O1ii | 0.90 | 2.44 | 3.212 (3) | 144 |
Symmetry code: (ii) x+1/2, −y+1/2, z+1/2. |