metal-organic compounds
Tetra-μ-acetato-κ8O:O′-bis{[2-methylsulfanyl-4-(pyridin-4-yl-κN)pyrimidine]copper(II)}(Cu—Cu)
aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: zhuhaibin@seu.edu.cn
The binuclear title compound, [Cu2(CH3CO2)4(C10H9N3S)2], comprises a Cu2(CH3CO2)4 paddle-wheel core axially bound by two 2-methylsulfanyl-4-(pyridin-4-yl)pyrimidine ligands. The complex molecule has an inversion center lying at the mid-point of the Cu—Cu bond.
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536811029837/hy2450sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811029837/hy2450Isup2.hkl
A mixture of Cu(CH3CO2)2 (0.1 mmol), L (0.1 mmol) in ethanol (15 ml) was stirred for 20 min at room temperature. After filtration, the mother liquid was allowed to stand for one week to give blue crystals suitable for X-ray diffraction analysis.
H atoms bound to C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl) Å and Uiso(H) = 1.2(1.5 for methyl)Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell
SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (A) 1-x, -y, 1-z.] |
[Cu2(C2H3O2)4(C10H9N3S)2] | F(000) = 788 |
Mr = 769.82 | Dx = 1.548 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2827 reflections |
a = 15.192 (2) Å | θ = 2.3–25.5° |
b = 13.003 (2) Å | µ = 1.47 mm−1 |
c = 8.6108 (13) Å | T = 298 K |
β = 103.781 (2)° | Block, blue |
V = 1652.0 (4) Å3 | 0.41 × 0.25 × 0.18 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 2827 independent reflections |
Radiation source: fine-focus sealed tube | 2354 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→18 |
Tmin = 0.650, Tmax = 0.768 | k = −15→15 |
9568 measured reflections | l = −10→10 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0614P)2 + 0.3763P] where P = (Fo2 + 2Fc2)/3 |
2827 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu2(C2H3O2)4(C10H9N3S)2] | V = 1652.0 (4) Å3 |
Mr = 769.82 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.192 (2) Å | µ = 1.47 mm−1 |
b = 13.003 (2) Å | T = 298 K |
c = 8.6108 (13) Å | 0.41 × 0.25 × 0.18 mm |
β = 103.781 (2)° |
Bruker APEXII CCD diffractometer | 2827 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2354 reflections with I > 2σ(I) |
Tmin = 0.650, Tmax = 0.768 | Rint = 0.024 |
9568 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.38 e Å−3 |
2827 reflections | Δρmin = −0.32 e Å−3 |
208 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.42790 (2) | 0.03013 (2) | 0.39231 (4) | 0.03313 (14) | |
O2 | 0.39177 (14) | −0.11545 (15) | 0.3826 (3) | 0.0474 (5) | |
O4 | 0.50560 (15) | −0.00064 (17) | 0.2452 (2) | 0.0462 (5) | |
N1 | 0.31254 (16) | 0.08776 (18) | 0.2112 (3) | 0.0380 (5) | |
O1 | 0.62838 (15) | −0.05037 (17) | 0.4261 (3) | 0.0522 (6) | |
O3 | 0.51441 (14) | −0.16651 (15) | 0.5641 (3) | 0.0518 (6) | |
C14 | 0.5845 (2) | −0.03341 (19) | 0.2841 (4) | 0.0396 (7) | |
C8 | 0.2390 (2) | 0.0311 (2) | 0.1478 (4) | 0.0440 (7) | |
H8 | 0.2376 | −0.0368 | 0.1810 | 0.053* | |
C6 | 0.16582 (19) | 0.1693 (2) | −0.0149 (3) | 0.0377 (6) | |
C10 | 0.2425 (2) | 0.2277 (2) | 0.0483 (3) | 0.0427 (7) | |
H10 | 0.2459 | 0.2956 | 0.0164 | 0.051* | |
C9 | 0.3132 (2) | 0.1843 (2) | 0.1582 (3) | 0.0410 (7) | |
H9 | 0.3644 | 0.2243 | 0.1980 | 0.049* | |
C12 | 0.4403 (2) | −0.1827 (2) | 0.4653 (4) | 0.0412 (7) | |
C7 | 0.1662 (2) | 0.0681 (2) | 0.0368 (4) | 0.0477 (7) | |
H7 | 0.1169 | 0.0256 | −0.0042 | 0.057* | |
N2 | 0.02885 (17) | 0.1470 (2) | −0.2225 (3) | 0.0491 (6) | |
C5 | 0.08668 (19) | 0.2131 (2) | −0.1331 (3) | 0.0417 (7) | |
C4 | 0.0726 (2) | 0.3178 (3) | −0.1478 (4) | 0.0573 (9) | |
H4 | 0.1123 | 0.3640 | −0.0846 | 0.069* | |
S1 | −0.11441 (7) | 0.09520 (9) | −0.43675 (14) | 0.0806 (3) | |
N3 | −0.0610 (2) | 0.2871 (3) | −0.3527 (4) | 0.0620 (8) | |
C13 | 0.6315 (3) | −0.0562 (3) | 0.1536 (4) | 0.0579 (9) | |
H13A | 0.5910 | −0.0426 | 0.0517 | 0.087* | |
H13B | 0.6494 | −0.1271 | 0.1590 | 0.087* | |
H13C | 0.6842 | −0.0133 | 0.1664 | 0.087* | |
C2 | −0.0421 (2) | 0.1878 (3) | −0.3268 (4) | 0.0514 (8) | |
C11 | 0.4090 (2) | −0.2928 (2) | 0.4448 (5) | 0.0609 (9) | |
H11A | 0.4514 | −0.3358 | 0.5166 | 0.091* | |
H11B | 0.4050 | −0.3141 | 0.3366 | 0.091* | |
H11C | 0.3504 | −0.2986 | 0.4681 | 0.091* | |
C3 | −0.0023 (3) | 0.3513 (3) | −0.2593 (5) | 0.0657 (10) | |
H3 | −0.0127 | 0.4216 | −0.2707 | 0.079* | |
C1 | −0.2020 (2) | 0.1704 (4) | −0.5637 (5) | 0.0900 (14) | |
H1A | −0.2452 | 0.1254 | −0.6301 | 0.135* | |
H1B | −0.1757 | 0.2145 | −0.6298 | 0.135* | |
H1C | −0.2319 | 0.2114 | −0.4990 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0360 (2) | 0.0322 (2) | 0.0284 (2) | 0.00451 (13) | 0.00199 (15) | −0.00098 (13) |
O2 | 0.0452 (12) | 0.0375 (11) | 0.0524 (13) | −0.0012 (9) | −0.0028 (10) | 0.0009 (9) |
O4 | 0.0511 (13) | 0.0567 (12) | 0.0316 (11) | 0.0104 (10) | 0.0111 (10) | 0.0027 (9) |
N1 | 0.0412 (14) | 0.0382 (13) | 0.0322 (13) | 0.0043 (10) | 0.0039 (11) | 0.0004 (10) |
O1 | 0.0528 (13) | 0.0680 (15) | 0.0362 (12) | 0.0198 (11) | 0.0116 (11) | 0.0003 (10) |
O3 | 0.0536 (14) | 0.0350 (10) | 0.0552 (13) | −0.0022 (10) | −0.0099 (11) | −0.0011 (9) |
C14 | 0.0538 (19) | 0.0307 (14) | 0.0372 (17) | 0.0042 (13) | 0.0166 (15) | 0.0001 (12) |
C8 | 0.0453 (18) | 0.0382 (15) | 0.0444 (18) | 0.0003 (13) | 0.0024 (15) | 0.0087 (13) |
C6 | 0.0379 (16) | 0.0397 (15) | 0.0339 (15) | 0.0062 (12) | 0.0057 (13) | 0.0037 (12) |
C10 | 0.0484 (18) | 0.0342 (14) | 0.0410 (17) | 0.0016 (13) | 0.0019 (14) | 0.0030 (12) |
C9 | 0.0419 (16) | 0.0369 (15) | 0.0393 (16) | 0.0005 (12) | 0.0001 (13) | −0.0026 (12) |
C12 | 0.0482 (18) | 0.0357 (15) | 0.0396 (17) | −0.0016 (13) | 0.0103 (14) | −0.0075 (13) |
C7 | 0.0403 (17) | 0.0469 (17) | 0.0503 (19) | −0.0071 (14) | −0.0002 (15) | 0.0053 (14) |
N2 | 0.0401 (15) | 0.0544 (15) | 0.0480 (16) | 0.0030 (12) | 0.0009 (13) | 0.0101 (12) |
C5 | 0.0365 (16) | 0.0485 (16) | 0.0384 (17) | 0.0052 (13) | 0.0056 (14) | 0.0069 (13) |
C4 | 0.053 (2) | 0.0488 (18) | 0.062 (2) | 0.0087 (16) | −0.0018 (17) | 0.0036 (16) |
S1 | 0.0607 (6) | 0.0805 (7) | 0.0812 (8) | −0.0150 (5) | −0.0214 (5) | 0.0158 (6) |
N3 | 0.0477 (17) | 0.0690 (19) | 0.0622 (19) | 0.0113 (14) | −0.0007 (15) | 0.0157 (15) |
C13 | 0.077 (3) | 0.057 (2) | 0.047 (2) | 0.0175 (18) | 0.0314 (19) | 0.0038 (16) |
C2 | 0.0376 (17) | 0.067 (2) | 0.0468 (19) | 0.0017 (15) | 0.0045 (15) | 0.0123 (16) |
C11 | 0.063 (2) | 0.0362 (16) | 0.076 (2) | −0.0064 (15) | 0.0006 (19) | −0.0080 (16) |
C3 | 0.062 (2) | 0.052 (2) | 0.076 (3) | 0.0151 (18) | 0.001 (2) | 0.0134 (19) |
C1 | 0.045 (2) | 0.126 (4) | 0.082 (3) | −0.004 (2) | −0.020 (2) | 0.018 (3) |
Cu1—O1i | 1.970 (2) | C12—C11 | 1.505 (4) |
Cu1—O2 | 1.967 (2) | C7—H7 | 0.9300 |
Cu1—O3i | 1.974 (2) | N2—C2 | 1.338 (4) |
Cu1—O4 | 1.967 (2) | N2—C5 | 1.335 (4) |
Cu1—N1 | 2.183 (2) | C5—C4 | 1.379 (4) |
Cu1—Cu1i | 2.6299 (7) | C4—C3 | 1.373 (5) |
O2—C12 | 1.251 (4) | C4—H4 | 0.9300 |
O4—C14 | 1.241 (4) | S1—C2 | 1.748 (4) |
N1—C9 | 1.337 (4) | S1—C1 | 1.796 (4) |
N1—C8 | 1.341 (4) | N3—C2 | 1.330 (5) |
O1—C14 | 1.265 (4) | N3—C3 | 1.341 (5) |
O3—C12 | 1.257 (4) | C13—H13A | 0.9600 |
C14—C13 | 1.498 (4) | C13—H13B | 0.9600 |
C8—C7 | 1.366 (4) | C13—H13C | 0.9600 |
C8—H8 | 0.9300 | C11—H11A | 0.9600 |
C6—C10 | 1.388 (4) | C11—H11B | 0.9600 |
C6—C7 | 1.389 (4) | C11—H11C | 0.9600 |
C6—C5 | 1.491 (4) | C3—H3 | 0.9300 |
C10—C9 | 1.372 (4) | C1—H1A | 0.9600 |
C10—H10 | 0.9300 | C1—H1B | 0.9600 |
C9—H9 | 0.9300 | C1—H1C | 0.9600 |
O4—Cu1—O2 | 88.92 (9) | O2—C12—C11 | 118.1 (3) |
O4—Cu1—O1i | 168.10 (9) | O3—C12—C11 | 116.5 (3) |
O2—Cu1—O1i | 89.58 (9) | C8—C7—C6 | 119.9 (3) |
O4—Cu1—O3i | 89.87 (9) | C8—C7—H7 | 120.0 |
O2—Cu1—O3i | 168.30 (8) | C6—C7—H7 | 120.0 |
O1i—Cu1—O3i | 89.20 (10) | C2—N2—C5 | 116.5 (3) |
O4—Cu1—N1 | 96.46 (9) | N2—C5—C4 | 121.1 (3) |
O2—Cu1—N1 | 97.57 (9) | N2—C5—C6 | 117.4 (3) |
O1i—Cu1—N1 | 95.44 (9) | C4—C5—C6 | 121.5 (3) |
O3i—Cu1—N1 | 94.13 (9) | C3—C4—C5 | 117.5 (3) |
O4—Cu1—Cu1i | 82.34 (7) | C3—C4—H4 | 121.3 |
O2—Cu1—Cu1i | 85.43 (6) | C5—C4—H4 | 121.3 |
O1i—Cu1—Cu1i | 85.77 (7) | C2—S1—C1 | 103.5 (2) |
O3i—Cu1—Cu1i | 82.88 (6) | C2—N3—C3 | 114.7 (3) |
N1—Cu1—Cu1i | 176.77 (7) | C14—C13—H13A | 109.5 |
C12—O2—Cu1 | 121.89 (19) | C14—C13—H13B | 109.5 |
C14—O4—Cu1 | 125.8 (2) | H13A—C13—H13B | 109.5 |
C9—N1—C8 | 116.8 (2) | C14—C13—H13C | 109.5 |
C9—N1—Cu1 | 119.7 (2) | H13A—C13—H13C | 109.5 |
C8—N1—Cu1 | 123.46 (19) | H13B—C13—H13C | 109.5 |
C14—O1—Cu1 | 65.15 (17) | N3—C2—N2 | 127.2 (3) |
C12—O3—Cu1 | 66.66 (15) | N3—C2—S1 | 119.7 (3) |
O4—C14—O1 | 125.0 (3) | N2—C2—S1 | 113.1 (3) |
O4—C14—C13 | 117.9 (3) | C12—C11—H11A | 109.5 |
O1—C14—C13 | 117.1 (3) | C12—C11—H11B | 109.5 |
N1—C8—C7 | 123.3 (3) | H11A—C11—H11B | 109.5 |
N1—C8—H8 | 118.4 | C12—C11—H11C | 109.5 |
C7—C8—H8 | 118.4 | H11A—C11—H11C | 109.5 |
C10—C6—C7 | 117.0 (3) | H11B—C11—H11C | 109.5 |
C10—C6—C5 | 121.6 (3) | N3—C3—C4 | 123.0 (3) |
C7—C6—C5 | 121.4 (3) | N3—C3—H3 | 118.5 |
C9—C10—C6 | 119.5 (3) | C4—C3—H3 | 118.5 |
C9—C10—H10 | 120.3 | S1—C1—H1A | 109.5 |
C6—C10—H10 | 120.3 | S1—C1—H1B | 109.5 |
N1—C9—C10 | 123.5 (3) | H1A—C1—H1B | 109.5 |
N1—C9—H9 | 118.2 | S1—C1—H1C | 109.5 |
C10—C9—H9 | 118.2 | H1A—C1—H1C | 109.5 |
O2—C12—O3 | 125.4 (3) | H1B—C1—H1C | 109.5 |
O4—Cu1—O2—C12 | 81.3 (2) | Cu1—O4—C14—C13 | 177.6 (2) |
O1i—Cu1—O2—C12 | −86.9 (2) | C9—N1—C8—C7 | −1.4 (4) |
O3i—Cu1—O2—C12 | −2.9 (6) | Cu1—N1—C8—C7 | 178.6 (2) |
N1—Cu1—O2—C12 | 177.7 (2) | C7—C6—C10—C9 | −0.9 (4) |
Cu1i—Cu1—O2—C12 | −1.1 (2) | C5—C6—C10—C9 | 179.2 (3) |
O2—Cu1—O4—C14 | −85.3 (2) | C8—N1—C9—C10 | 2.1 (4) |
O1i—Cu1—O4—C14 | −2.5 (6) | Cu1—N1—C9—C10 | −178.0 (2) |
O3i—Cu1—O4—C14 | 83.0 (2) | C6—C10—C9—N1 | −0.9 (4) |
N1—Cu1—O4—C14 | 177.2 (2) | Cu1—O2—C12—C11 | −177.5 (2) |
Cu1i—Cu1—O4—C14 | 0.2 (2) | N1—C8—C7—C6 | −0.4 (5) |
O4—Cu1—N1—C9 | −80.7 (2) | C10—C6—C7—C8 | 1.5 (4) |
O2—Cu1—N1—C9 | −170.5 (2) | C5—C6—C7—C8 | −178.6 (3) |
O1i—Cu1—N1—C9 | 99.2 (2) | C2—N2—C5—C4 | 0.6 (4) |
O3i—Cu1—N1—C9 | 9.6 (2) | C2—N2—C5—C6 | 179.4 (3) |
O4—Cu1—N1—C8 | 99.3 (2) | C10—C6—C5—N2 | 160.4 (3) |
O2—Cu1—N1—C8 | 9.5 (2) | C7—C6—C5—N2 | −19.5 (4) |
O1i—Cu1—N1—C8 | −80.8 (2) | C10—C6—C5—C4 | −20.7 (4) |
O3i—Cu1—N1—C8 | −170.4 (2) | C7—C6—C5—C4 | 159.4 (3) |
O4—Cu1—O1i—C14i | 4.2 (6) | N2—C5—C4—C3 | −0.9 (5) |
O2—Cu1—O1i—C14i | 86.9 (2) | C6—C5—C4—C3 | −179.7 (3) |
O3i—Cu1—O1i—C14i | −81.4 (2) | C3—N3—C2—N2 | −1.7 (5) |
N1—Cu1—O1i—C14i | −175.5 (2) | C3—N3—C2—S1 | 178.5 (3) |
Cu1i—Cu1—O1i—C14i | 1.5 (2) | C5—N2—C2—N3 | 0.8 (5) |
O4—Cu1—O3i—C12i | −82.5 (2) | C5—N2—C2—S1 | −179.4 (2) |
O2—Cu1—O3i—C12i | 1.5 (6) | C1—S1—C2—N3 | −0.4 (3) |
O1i—Cu1—O3i—C12i | 85.6 (2) | C1—S1—C2—N2 | 179.7 (2) |
N1—Cu1—O3i—C12i | −179.0 (2) | C2—N3—C3—C4 | 1.2 (5) |
Cu1i—Cu1—O3i—C12i | −0.2 (2) | C5—C4—C3—N3 | 0.0 (6) |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H3O2)4(C10H9N3S)2] |
Mr | 769.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 15.192 (2), 13.003 (2), 8.6108 (13) |
β (°) | 103.781 (2) |
V (Å3) | 1652.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.41 × 0.25 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.650, 0.768 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9568, 2827, 2354 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.097, 1.04 |
No. of reflections | 2827 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.32 |
Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cu1—O1i | 1.970 (2) | Cu1—O4 | 1.967 (2) |
Cu1—O2 | 1.967 (2) | Cu1—N1 | 2.183 (2) |
Cu1—O3i | 1.974 (2) | Cu1—Cu1i | 2.6299 (7) |
Symmetry code: (i) −x+1, −y, −z+1. |
Acknowledgements
The authors acknowledge the Research Program for Excellent Young Teachers of Southeast University (grant No. 3207041202).
References
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, L., Xu, G. & Zhu, H.-B. (2009). Acta Cryst. E65, m476. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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In our previous work, we have reported a mononuclear Cu(II) complex with 4-(pyridin-4-yl)pyrimidine-2-sulfonate ligand (Li et al., 2009). Herein, we report a binuclear Cu(II) coordination compound with 2-(methylthio)-4-(pyridin-4-yl)pyrimidine (L) ligand. The title compound lies on an inversion center with a Cu—Cu separation of 2.6299 (7) Å (Fig. 1). The L ligand acts as a terminal ligand via its pyridine N atom, with a Cu—N distance of 2.183 (2) Å (Table 1).