Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042328/hg2288sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042328/hg2288Isup2.hkl |
CCDC reference: 663549
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.012 Å
- R factor = 0.061
- wR factor = 0.182
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu (2) 2.12 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A solution of 4-vinylpyridine (1.05 g, 10 mmol) in alcohol (10 ml) was added to Cu(OAc)2.H2O (2.00 g, 10 mmol) in alcohol (40 ml). The solution was stirred during 2 h and a precipitate was formed. The blue precipitate was filtered off, washed with alcohol and dried in vacuo over CaCO3. Blue crystals were obtained from recrystallization in alcohol after a few days.
H atoms were positioned geometrically (C—H = 0.93 Å or 0.96 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 or 1.5 times Ueq(C).
The title compound,(I), (Fig. 1), consists of centrosymmetric dinuclear units, in which four acetate groups bridge the two copper atoms and a 4-vinylpyridine neutral ligand occupies the axis position of each copper atom, coordinated to them through the pyridine nitrogen atom. Each copper atom has a distorted square-planar pyramidal coordination, with four oxygen atoms in a plane. The distances for Cu—O1, O2, O3 and O4 are 1.979 (4), 1.969 (4), 1.971 (4) and 1.977 (5) Å, respectively. The fifth coordination position is occupied by the pyridine nitrogen, N, of a ligand molecule at 2.178 (5) Å. All these values agree well with those observed in [Cu2(υ-OOCCH3)4(PhNHpy)2] (PhNHpy is 2-anilinopyridine) (Seco et al., 2002). The copper atom rises from the basal plane to the apical N atom by 0.217 (1) Å. The Cu···Cu separation is 2.6405 (14) Å. Weak intramolecular C—H···O interactions contribute to the crystal packing stability.
For related literature, see: Seco et al. (2002).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.
C22H26Cu2N2O8 | F(000) = 588 |
Mr = 573.53 | Dx = 1.520 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3329 reflections |
a = 10.696 (2) Å | θ = 2.5–25.1° |
b = 12.830 (3) Å | µ = 1.74 mm−1 |
c = 9.4820 (19) Å | T = 293 K |
β = 105.65 (3)° | Block, blue |
V = 1253.0 (5) Å3 | 0.30 × 0.20 × 0.10 mm |
Z = 2 |
Bruker SMART 1K CCD area-detector diffractometer | 2358 independent reflections |
Radiation source: fine-focus sealed tube | 1830 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
thin–slice ω scans | θmax = 26.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→12 |
Tmin = 0.623, Tmax = 0.845 | k = 0→15 |
2455 measured reflections | l = 0→11 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.1P)2 + 3P] where P = (Fo2 + 2Fc2)/3 |
2358 reflections | (Δ/σ)max = 0.002 |
144 parameters | Δρmax = 1.47 e Å−3 |
1 restraint | Δρmin = −1.13 e Å−3 |
C22H26Cu2N2O8 | V = 1253.0 (5) Å3 |
Mr = 573.53 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.696 (2) Å | µ = 1.74 mm−1 |
b = 12.830 (3) Å | T = 293 K |
c = 9.4820 (19) Å | 0.30 × 0.20 × 0.10 mm |
β = 105.65 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 2358 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1830 reflections with I > 2σ(I) |
Tmin = 0.623, Tmax = 0.845 | Rint = 0.013 |
2455 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 1 restraint |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.47 e Å−3 |
2358 reflections | Δρmin = −1.13 e Å−3 |
144 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 | 0.40251 (7) | 0.02266 (5) | 0.05538 (7) | 0.0441 (3) | |
O1 | 0.3606 (5) | −0.1277 (3) | 0.0336 (5) | 0.0612 (11) | |
O2 | 0.4745 (5) | 0.1639 (3) | 0.0554 (5) | 0.0630 (12) | |
O3 | 0.3013 (5) | 0.0430 (4) | −0.1496 (5) | 0.0641 (12) | |
O4 | 0.5344 (5) | −0.0066 (4) | 0.2417 (5) | 0.0663 (12) | |
N | 0.2542 (5) | 0.0760 (4) | 0.1573 (5) | 0.0508 (11) | |
C1 | −0.0518 (10) | 0.2562 (8) | 0.4014 (10) | 0.101 | |
H1A | 0.0269 | 0.2911 | 0.4345 | 0.121* | |
H1B | −0.1233 | 0.2774 | 0.4321 | 0.121* | |
C2 | −0.0617 (10) | 0.1780 (8) | 0.3125 (10) | 0.100 | |
H2A | −0.1386 | 0.1412 | 0.2771 | 0.120* | |
C3 | 0.0585 (7) | 0.1517 (7) | 0.2715 (8) | 0.074 (2) | |
C4 | 0.1672 (8) | 0.2085 (5) | 0.2806 (8) | 0.0677 (19) | |
H4A | 0.1774 | 0.2736 | 0.3251 | 0.081* | |
C5 | 0.2638 (6) | 0.1679 (5) | 0.2221 (7) | 0.0562 (15) | |
H5A | 0.3382 | 0.2073 | 0.2293 | 0.067* | |
C6 | 0.1465 (7) | 0.0221 (6) | 0.1532 (8) | 0.0691 (19) | |
H6A | 0.1387 | −0.0437 | 0.1106 | 0.083* | |
C7 | 0.0486 (8) | 0.0551 (8) | 0.2057 (9) | 0.083 (2) | |
H7A | −0.0243 | 0.0136 | 0.1978 | 0.099* | |
C8 | 0.6099 (8) | 0.3033 (6) | 0.0297 (10) | 0.082 (2) | |
H8A | 0.5859 | 0.3336 | 0.1111 | 0.123* | |
H8B | 0.5659 | 0.3391 | −0.0587 | 0.123* | |
H8C | 0.7020 | 0.3093 | 0.0448 | 0.123* | |
C9 | 0.5718 (6) | 0.1895 (5) | 0.0165 (7) | 0.0501 (14) | |
C10 | 0.7308 (8) | −0.0547 (7) | 0.4061 (7) | 0.080 (2) | |
H10A | 0.8105 | −0.0162 | 0.4246 | 0.121* | |
H10B | 0.7496 | −0.1279 | 0.4161 | 0.121* | |
H10C | 0.6842 | −0.0343 | 0.4752 | 0.121* | |
C11 | 0.6490 (7) | −0.0322 (4) | 0.2527 (7) | 0.0563 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0535 (4) | 0.0386 (4) | 0.0448 (4) | 0.0010 (3) | 0.0212 (3) | 0.0026 (3) |
O1 | 0.076 (3) | 0.044 (2) | 0.074 (3) | −0.012 (2) | 0.038 (2) | 0.001 (2) |
O2 | 0.073 (3) | 0.042 (2) | 0.085 (3) | −0.007 (2) | 0.041 (3) | 0.000 (2) |
O3 | 0.066 (3) | 0.073 (3) | 0.051 (2) | 0.012 (2) | 0.011 (2) | 0.004 (2) |
O4 | 0.085 (3) | 0.069 (3) | 0.045 (2) | 0.011 (3) | 0.017 (2) | 0.004 (2) |
N | 0.054 (3) | 0.052 (3) | 0.049 (3) | 0.000 (2) | 0.019 (2) | −0.001 (2) |
C1 | 0.101 | 0.101 | 0.101 | 0.000 | 0.027 | 0.000 |
C2 | 0.100 | 0.100 | 0.100 | 0.000 | 0.027 | 0.000 |
C3 | 0.067 (4) | 0.107 (7) | 0.058 (4) | 0.029 (4) | 0.034 (3) | 0.028 (4) |
C4 | 0.099 (5) | 0.048 (4) | 0.068 (4) | 0.020 (4) | 0.043 (4) | 0.010 (3) |
C5 | 0.061 (4) | 0.053 (4) | 0.063 (4) | 0.000 (3) | 0.030 (3) | 0.008 (3) |
C6 | 0.064 (4) | 0.074 (5) | 0.077 (5) | −0.020 (4) | 0.033 (4) | −0.018 (4) |
C7 | 0.066 (4) | 0.103 (7) | 0.091 (6) | −0.009 (4) | 0.043 (4) | −0.003 (5) |
C8 | 0.089 (5) | 0.047 (4) | 0.120 (7) | −0.016 (4) | 0.047 (5) | 0.002 (4) |
C9 | 0.061 (4) | 0.039 (3) | 0.056 (3) | −0.004 (3) | 0.024 (3) | 0.007 (3) |
C10 | 0.104 (6) | 0.073 (5) | 0.051 (4) | 0.021 (4) | −0.002 (4) | −0.001 (3) |
C11 | 0.083 (5) | 0.034 (3) | 0.046 (3) | 0.006 (3) | 0.006 (3) | −0.001 (2) |
Cu—O2 | 1.969 (4) | C3—C7 | 1.379 (12) |
Cu—O3 | 1.971 (4) | C4—C5 | 1.399 (9) |
Cu—O4 | 1.977 (5) | C4—H4A | 0.9300 |
Cu—O1 | 1.979 (4) | C5—H5A | 0.9300 |
Cu—N | 2.178 (5) | C6—C7 | 1.343 (10) |
Cu—Cui | 2.6405 (14) | C6—H6A | 0.9300 |
O1—C9i | 1.251 (7) | C7—H7A | 0.9300 |
O2—C9 | 1.238 (7) | C8—C9 | 1.511 (9) |
O3—C11i | 1.240 (8) | C8—H8A | 0.9600 |
O4—C11 | 1.246 (9) | C8—H8B | 0.9600 |
N—C5 | 1.320 (8) | C8—H8C | 0.9600 |
N—C6 | 1.335 (8) | C9—O1i | 1.251 (7) |
C1—C2 | 1.296 (8) | C10—C11 | 1.509 (8) |
C1—H1A | 0.9300 | C10—H10A | 0.9600 |
C1—H1B | 0.9300 | C10—H10B | 0.9600 |
C2—C3 | 1.479 (12) | C10—H10C | 0.9600 |
C2—H2A | 0.9300 | C11—O3i | 1.240 (8) |
C3—C4 | 1.355 (11) | ||
O2—Cu—O3 | 89.4 (2) | C3—C4—C5 | 119.2 (7) |
O2—Cu—O4 | 89.4 (2) | C3—C4—H4A | 120.4 |
O3—Cu—O4 | 167.5 (2) | C5—C4—H4A | 120.4 |
O2—Cu—O1 | 167.15 (17) | N—C5—C4 | 122.9 (6) |
O3—Cu—O1 | 88.7 (2) | N—C5—H5A | 118.5 |
O4—Cu—O1 | 89.7 (2) | C4—C5—H5A | 118.5 |
O2—Cu—N | 92.43 (19) | N—C6—C7 | 125.4 (8) |
O3—Cu—N | 97.14 (19) | N—C6—H6A | 117.3 |
O4—Cu—N | 95.30 (19) | C7—C6—H6A | 117.3 |
O1—Cu—N | 100.41 (19) | C6—C7—C3 | 118.6 (8) |
O2—Cu—Cui | 81.48 (13) | C6—C7—H7A | 120.7 |
O3—Cu—Cui | 85.37 (14) | C3—C7—H7A | 120.7 |
O4—Cu—Cui | 82.19 (15) | C9—C8—H8A | 109.5 |
O1—Cu—Cui | 85.69 (13) | C9—C8—H8B | 109.5 |
N—Cu—Cui | 173.42 (15) | H8A—C8—H8B | 109.5 |
C9i—O1—Cu | 121.3 (4) | C9—C8—H8C | 109.5 |
C9—O2—Cu | 127.2 (4) | H8A—C8—H8C | 109.5 |
C11i—O3—Cu | 121.6 (4) | H8B—C8—H8C | 109.5 |
C11—O4—Cu | 125.0 (4) | O2—C9—O1i | 124.3 (6) |
C5—N—C6 | 115.7 (6) | O2—C9—C8 | 117.5 (6) |
C5—N—Cu | 120.8 (4) | O1i—C9—C8 | 118.2 (6) |
C6—N—Cu | 123.4 (5) | C11—C10—H10A | 109.5 |
C2—C1—H1A | 120.0 | C11—C10—H10B | 109.5 |
C2—C1—H1B | 120.0 | H10A—C10—H10B | 109.5 |
H1A—C1—H1B | 120.0 | C11—C10—H10C | 109.5 |
C1—C2—C3 | 115.1 (10) | H10A—C10—H10C | 109.5 |
C1—C2—H2A | 122.5 | H10B—C10—H10C | 109.5 |
C3—C2—H2A | 122.5 | O3i—C11—O4 | 125.8 (6) |
C4—C3—C7 | 118.1 (7) | O3i—C11—C10 | 118.6 (7) |
C4—C3—C2 | 130.7 (9) | O4—C11—C10 | 115.6 (6) |
C7—C3—C2 | 111.0 (8) | ||
O2—Cu—O1—C9i | 4.5 (12) | O4—Cu—N—C5 | 73.6 (5) |
O3—Cu—O1—C9i | 86.0 (5) | O1—Cu—N—C5 | 164.3 (5) |
O4—Cu—O1—C9i | −81.6 (5) | O2—Cu—N—C6 | 160.8 (6) |
N—Cu—O1—C9i | −177.0 (5) | O3—Cu—N—C6 | 71.1 (6) |
Cui—Cu—O1—C9i | 0.6 (5) | O4—Cu—N—C6 | −109.6 (6) |
O3—Cu—O2—C9 | −87.1 (6) | O1—Cu—N—C6 | −18.9 (6) |
O4—Cu—O2—C9 | 80.5 (6) | C1—C2—C3—C4 | −18.3 (14) |
O1—Cu—O2—C9 | −5.7 (12) | C1—C2—C3—C7 | 166.1 (9) |
N—Cu—O2—C9 | 175.8 (5) | C7—C3—C4—C5 | 0.6 (11) |
Cui—Cu—O2—C9 | −1.7 (5) | C2—C3—C4—C5 | −174.6 (7) |
O2—Cu—O3—C11i | 80.3 (5) | C6—N—C5—C4 | −1.4 (9) |
O4—Cu—O3—C11i | −4.3 (13) | Cu—N—C5—C4 | 175.7 (5) |
O1—Cu—O3—C11i | −87.0 (5) | C3—C4—C5—N | 0.2 (10) |
N—Cu—O3—C11i | 172.7 (5) | C5—N—C6—C7 | 1.8 (12) |
Cui—Cu—O3—C11i | −1.2 (5) | Cu—N—C6—C7 | −175.2 (7) |
O2—Cu—O4—C11 | −81.0 (5) | N—C6—C7—C3 | −1.0 (14) |
O3—Cu—O4—C11 | 3.6 (13) | C4—C3—C7—C6 | −0.3 (12) |
O1—Cu—O4—C11 | 86.1 (5) | C2—C3—C7—C6 | 175.8 (8) |
N—Cu—O4—C11 | −173.4 (5) | Cu—O2—C9—O1i | 1.8 (10) |
Cui—Cu—O4—C11 | 0.4 (5) | Cu—O2—C9—C8 | −178.7 (5) |
O2—Cu—N—C5 | −16.0 (5) | Cu—O4—C11—O3i | 0.4 (10) |
O3—Cu—N—C5 | −105.7 (5) | Cu—O4—C11—C10 | −177.7 (5) |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C22H26Cu2N2O8 |
Mr | 573.53 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.696 (2), 12.830 (3), 9.4820 (19) |
β (°) | 105.65 (3) |
V (Å3) | 1253.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.623, 0.845 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2455, 2358, 1830 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.182, 1.01 |
No. of reflections | 2358 |
No. of parameters | 144 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.47, −1.13 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001) and local programs.
Cu—O2 | 1.969 (4) | Cu—O1 | 1.979 (4) |
Cu—O3 | 1.971 (4) | Cu—N | 2.178 (5) |
Cu—O4 | 1.977 (5) | Cu—Cui | 2.6405 (14) |
O2—Cu—O3 | 89.4 (2) | O1—Cu—N | 100.41 (19) |
O3—Cu—O4 | 167.5 (2) | O2—Cu—Cui | 81.48 (13) |
O3—Cu—O1 | 88.7 (2) | O3—Cu—Cui | 85.37 (14) |
O4—Cu—O1 | 89.7 (2) | O4—Cu—Cui | 82.19 (15) |
O2—Cu—N | 92.43 (19) | O1—Cu—Cui | 85.69 (13) |
O3—Cu—N | 97.14 (19) | N—Cu—Cui | 173.42 (15) |
O4—Cu—N | 95.30 (19) |
Symmetry code: (i) −x+1, −y, −z. |
The title compound,(I), (Fig. 1), consists of centrosymmetric dinuclear units, in which four acetate groups bridge the two copper atoms and a 4-vinylpyridine neutral ligand occupies the axis position of each copper atom, coordinated to them through the pyridine nitrogen atom. Each copper atom has a distorted square-planar pyramidal coordination, with four oxygen atoms in a plane. The distances for Cu—O1, O2, O3 and O4 are 1.979 (4), 1.969 (4), 1.971 (4) and 1.977 (5) Å, respectively. The fifth coordination position is occupied by the pyridine nitrogen, N, of a ligand molecule at 2.178 (5) Å. All these values agree well with those observed in [Cu2(υ-OOCCH3)4(PhNHpy)2] (PhNHpy is 2-anilinopyridine) (Seco et al., 2002). The copper atom rises from the basal plane to the apical N atom by 0.217 (1) Å. The Cu···Cu separation is 2.6405 (14) Å. Weak intramolecular C—H···O interactions contribute to the crystal packing stability.