The crystal structure of the title compound, [Cu
2(C
2H
3O
2)
4(C
5H
6N
2)
2], previously reported by Antsyshkina, Porai-Koshits, Ostrikova, Garnovskii, Sadimenko & Osipov [
Koord.
Khim. (1987),
13, 836–842] has been redetermined from new intensity data, with appreciably improved precision and successful location of all H atoms. The dinuclear copper unit has crystallographic inversion symmetry with a Cu
Cu distance of 2.6771 (4) Å. The crystal packing is characterized by C—H
O hydrogen bonds.
Supporting information
CCDC reference: 239056
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.025
- wR factor = 0.067
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2 ... ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.17 Ratio
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 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
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXTL (Sheldrick, 2003); molecular graphics: SHELXTL; software used to prepare material for publication: PLATON (Spek, 1990).
tetrakis(µ-acetato-
κ2O:
O')bis[(2-aminopyridine-
κN)copper(II)]
top
Crystal data top
[Cu2(C2H3O2)4(C5H6N2)2] | F(000) = 564 |
Mr = 551.51 | Dx = 1.690 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8156 reflections |
a = 7.4498 (3) Å | θ = 2.8–27.5° |
b = 19.6500 (7) Å | µ = 2.02 mm−1 |
c = 8.1251 (4) Å | T = 293 K |
β = 114.316 (4)° | Prism, green |
V = 1083.91 (9) Å3 | 0.36 × 0.30 × 0.12 mm |
Z = 2 | |
Data collection top
Kuma KM4CCD diffractometer | 2483 independent reflections |
Radiation source: CX-Mo12x0.4-S Seifert Mo tube | 2143 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: numerical (XRED; Stoe & Cie, 1999) | h = −9→8 |
Tmin = 0.500, Tmax = 0.782 | k = −25→25 |
12569 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0394P)2] where P = (Fo2 + 2Fc2)/3 |
2483 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
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 on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR
and all goodnesses of fit S are based on F2,
conventional R-factors R are based on F, with F
set to zero for negative F2. The observed criterion of F2 >
σ(F2) is used only for calculating -R-factor-obs
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 | 0.09277 (3) | 0.055741 (10) | −0.01936 (3) | 0.02434 (8) | |
O1 | −0.17565 (19) | 0.08086 (7) | −0.19745 (18) | 0.0350 (3) | |
O2 | 0.32930 (19) | 0.01245 (7) | 0.16681 (18) | 0.0376 (3) | |
O3 | 0.0287 (2) | 0.09418 (7) | 0.17539 (18) | 0.0368 (3) | |
O4 | 0.1263 (2) | −0.00086 (7) | −0.20597 (18) | 0.0344 (3) | |
C1 | −0.3274 (3) | 0.04499 (9) | −0.2351 (2) | 0.0283 (4) | |
C2 | −0.5191 (3) | 0.07209 (11) | −0.3742 (3) | 0.0405 (5) | |
H21 | −0.5270 | 0.0627 | −0.4929 | 0.076 (9)* | |
H22 | −0.5253 | 0.1203 | −0.3589 | 0.079 (9)* | |
H23 | −0.6270 | 0.0505 | −0.3594 | 0.073 (9)* | |
C3 | −0.0617 (3) | 0.06014 (9) | 0.2492 (2) | 0.0282 (4) | |
C4 | −0.0937 (3) | 0.09335 (12) | 0.4027 (3) | 0.0433 (5) | |
H41 | −0.2276 | 0.0865 | 0.3863 | 0.097 (11)* | |
H42 | −0.0676 | 0.1412 | 0.4042 | 0.086 (10)* | |
H43 | −0.0064 | 0.0734 | 0.5151 | 0.086 (10)* | |
C5 | 0.4497 (3) | 0.13722 (10) | 0.0010 (3) | 0.0336 (4) | |
H5 | 0.5032 | 0.0956 | 0.0526 | 0.033 (5)* | |
C6 | 0.5743 (3) | 0.18548 (11) | −0.0123 (3) | 0.0400 (5) | |
H6 | 0.7087 | 0.1772 | 0.0293 | 0.054 (7)* | |
C7 | 0.4939 (3) | 0.24751 (11) | −0.0901 (3) | 0.0451 (5) | |
H7 | 0.5747 | 0.2815 | −0.1020 | 0.066 (8)* | |
C8 | 0.2965 (4) | 0.25852 (11) | −0.1491 (3) | 0.0466 (5) | |
H8 | 0.2417 | 0.3000 | −0.2003 | 0.077 (9)* | |
C9 | 0.1773 (3) | 0.20625 (10) | −0.1311 (3) | 0.0352 (4) | |
N1 | 0.2529 (2) | 0.14591 (7) | −0.0562 (2) | 0.0276 (3) | |
N2 | −0.0201 (3) | 0.21568 (12) | −0.1860 (4) | 0.0632 (7) | |
H1 | −0.106 (4) | 0.1785 (17) | −0.207 (4) | 0.079 (9)* | |
H2 | −0.066 (4) | 0.2479 (16) | −0.248 (4) | 0.071 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.02393 (13) | 0.02409 (13) | 0.02417 (12) | −0.00019 (8) | 0.00907 (9) | 0.00071 (8) |
O1 | 0.0264 (7) | 0.0332 (7) | 0.0392 (7) | 0.0019 (6) | 0.0072 (6) | 0.0059 (6) |
O2 | 0.0288 (7) | 0.0385 (8) | 0.0364 (7) | −0.0007 (6) | 0.0042 (6) | 0.0093 (6) |
O3 | 0.0482 (8) | 0.0323 (7) | 0.0373 (7) | −0.0068 (6) | 0.0250 (6) | −0.0075 (6) |
O4 | 0.0433 (8) | 0.0318 (7) | 0.0351 (7) | −0.0014 (6) | 0.0232 (6) | −0.0029 (6) |
C1 | 0.0271 (9) | 0.0325 (10) | 0.0236 (8) | 0.0054 (7) | 0.0086 (7) | −0.0020 (7) |
C2 | 0.0308 (11) | 0.0433 (12) | 0.0361 (11) | 0.0082 (9) | 0.0024 (9) | 0.0045 (9) |
C3 | 0.0294 (9) | 0.0312 (10) | 0.0224 (8) | 0.0090 (7) | 0.0091 (7) | 0.0021 (7) |
C4 | 0.0588 (14) | 0.0442 (13) | 0.0328 (10) | 0.0101 (11) | 0.0249 (10) | −0.0019 (9) |
C5 | 0.0332 (10) | 0.0288 (10) | 0.0397 (10) | −0.0001 (8) | 0.0158 (9) | 0.0013 (8) |
C6 | 0.0354 (11) | 0.0374 (11) | 0.0506 (12) | −0.0052 (8) | 0.0212 (10) | −0.0037 (9) |
C7 | 0.0555 (14) | 0.0332 (11) | 0.0547 (13) | −0.0123 (10) | 0.0308 (12) | −0.0016 (10) |
C8 | 0.0592 (14) | 0.0268 (10) | 0.0517 (13) | −0.0004 (10) | 0.0208 (11) | 0.0104 (9) |
C9 | 0.0376 (10) | 0.0270 (10) | 0.0370 (10) | 0.0024 (8) | 0.0115 (8) | 0.0035 (8) |
N1 | 0.0287 (8) | 0.0246 (7) | 0.0293 (7) | 0.0008 (6) | 0.0118 (6) | 0.0015 (6) |
N2 | 0.0401 (11) | 0.0349 (11) | 0.0975 (18) | 0.0092 (9) | 0.0110 (11) | 0.0185 (12) |
Geometric parameters (Å, º) top
Cu—O1 | 1.9883 (13) | C4—H41 | 0.96 |
Cu—O2 | 1.9803 (13) | C4—H42 | 0.96 |
Cu—O3 | 1.9811 (13) | C4—H43 | 0.96 |
Cu—O4 | 1.9773 (13) | C5—N1 | 1.355 (2) |
Cu—N1 | 2.2239 (15) | C5—C6 | 1.362 (3) |
Cu—Cui | 2.6771 (4) | C5—H5 | 0.93 |
O1—C1 | 1.259 (2) | C6—C7 | 1.390 (3) |
O2—C1i | 1.260 (2) | C6—H6 | 0.93 |
O3—C3 | 1.262 (2) | C7—C8 | 1.363 (3) |
O4—C3i | 1.254 (2) | C7—H7 | 0.93 |
C1—O2i | 1.260 (2) | C8—C9 | 1.404 (3) |
C1—C2 | 1.507 (3) | C8—H8 | 0.93 |
C2—H21 | 0.96 | C9—N1 | 1.346 (2) |
C2—H22 | 0.96 | C9—N2 | 1.362 (3) |
C2—H23 | 0.96 | N2—H1 | 0.94 (3) |
C3—O4i | 1.254 (2) | N2—H2 | 0.79 (3) |
C3—C4 | 1.511 (2) | | |
| | | |
O1—Cu—O2 | 167.03 (6) | O4i—C3—C4 | 117.37 (17) |
O1—Cu—O3 | 89.18 (6) | O3—C3—C4 | 117.38 (17) |
O1—Cu—O4 | 89.32 (6) | C3—C4—H41 | 109.5 |
O2—Cu—O3 | 89.14 (6) | C3—C4—H42 | 109.5 |
O2—Cu—O4 | 89.46 (6) | H41—C4—H42 | 109.5 |
O3—Cu—O4 | 167.15 (5) | C3—C4—H43 | 109.5 |
N1—Cu—O1 | 97.97 (6) | H41—C4—H43 | 109.5 |
N1—Cu—O2 | 95.00 (5) | H42—C4—H43 | 109.5 |
N1—Cu—O3 | 97.05 (5) | N1—C5—C6 | 124.18 (19) |
N1—Cu—O4 | 95.80 (5) | N1—C5—H5 | 117.9 |
O1—Cu—Cui | 82.84 (4) | C6—C5—H5 | 117.9 |
O2—Cu—Cui | 84.19 (4) | C5—C6—C7 | 117.82 (19) |
O3—Cu—Cui | 84.96 (4) | C5—C6—H6 | 121.1 |
O4—Cu—Cui | 82.19 (4) | C7—C6—H6 | 121.1 |
N1—Cu—Cui | 177.83 (4) | C8—C7—C6 | 119.95 (19) |
C1—O1—Cu | 124.85 (12) | C8—C7—H7 | 120.0 |
C1i—O2—Cu | 123.59 (12) | C6—C7—H7 | 120.0 |
C3—O3—Cu | 121.92 (12) | C7—C8—C9 | 119.0 (2) |
C3i—O4—Cu | 125.63 (12) | C7—C8—H8 | 120.5 |
O1—C1—O2i | 124.49 (17) | C9—C8—H8 | 120.5 |
O1—C1—C2 | 117.60 (17) | N1—C9—N2 | 117.49 (19) |
O2i—C1—C2 | 117.90 (17) | N1—C9—C8 | 121.81 (18) |
C1—C2—H21 | 109.5 | N2—C9—C8 | 120.7 (2) |
C1—C2—H22 | 109.5 | C9—N1—C5 | 117.27 (16) |
H21—C2—H22 | 109.5 | C9—N1—Cu | 127.98 (12) |
C1—C2—H23 | 109.5 | C5—N1—Cu | 114.73 (12) |
H21—C2—H23 | 109.5 | C9—N2—H1 | 121.2 (18) |
H22—C2—H23 | 109.5 | C9—N2—H2 | 116 (2) |
O4i—C3—O3 | 125.25 (16) | H1—N2—H2 | 115 (3) |
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—H1···O1 | 0.94 (3) | 2.00 (3) | 2.878 (3) | 155 (3) |
C5—H5···O2 | 0.93 | 2.49 | 3.103 (3) | 124 |
C8—H8···O3ii | 0.93 | 2.56 | 3.471 (3) | 167 |
C4—H43···O4iii | 0.96 | 2.53 | 3.454 (3) | 162 |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) x, y, z+1. |