metal-organic compounds
catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethanolato-κ4N,O:O,N′)dicopper(II)(Cu—Cu)]-di-μ-bromido]
aDepartment of Chemistry, Youngstown State University, Youngstown, OH 44555, USA, and bDepartment of Chemistry and Biochemistry, Central Connecticut State University, New Britain, CT 06050, USA
*Correspondence e-mail: westcottb@ccsu.edu
The title complex, [Cu2Br3(C11H9N2O2)]n, was one of three isolated by slow evaporation of an acetonitrile reaction mixture of CuBr2 with di-2-pyridyl ketone (1:1 molar ratio). The title complex contains a 2:1 metal-to-ligand ratio of copper(II) with the hydrated form of the ligand, di-2-pyridylmethanediol. The two copper centers are bridged by a bromide ion and the alkoxy O atom, and the Cu—Cu distance is 2.9801 (5) Å. The dimeric units are further linked by bromide ions, leading to a two-dimensional extended bridged structure. O—H⋯O hydrogen bonds are present in the crystal structure.
Related literature
Apart from the title complex, two others were isolated from the reaction mixture and structurally characterized. One was identical to that of Parker et al. (2000), the other is reported in the following paper by Westcott et al. (2008). For other related structures, see: Wang et al. (1986); Mariezcurrena et al. (1999).
Experimental
Crystal data
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Refinement
|
Data collection: SMART (Bruker, 2002); cell SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808024197/fj2131sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808024197/fj2131Isup2.hkl
Di-2-pyridyl ketone (dpk) was purchased from Aldrich and used as received. Copper(II) bromide hexahydrate was dried in an oven at 110 C for 48 h before use. DPK (1 mmol) and copper(II) bromide (1 mmol) were combined in 40 ml of acetonitirle and stirred for 30 minutes. The resulting green crystals were isolated after 4 days by slow evaporation of the solution.
For structure solution,
were used to locate the initial structural model that consisted of all non-hydrogen atoms. All ligand-based H atoms were added during the stage at idealized positions (C—H 0.95 Å; O—H 0.84 Å). All H atoms were refined with isotropic displacement parameter set equal to 1.5 times the isotropic equivalent value for the attached atom. All non-hydrogen atoms were refined anisotropically.Data collection: SMART (Bruker, 2002); cell
SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. ORTEP-3 (Farrugia, 1997) representation of the asymmetric unit. Ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Packing diagram showing the extended structure. |
[Cu2Br3(C11H9N2O2)] | Z = 2 |
Mr = 568.01 | F(000) = 536 |
Triclinic, P1 | Dx = 2.626 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7708 (7) Å | Cell parameters from 6753 reflections |
b = 9.6018 (8) Å | θ = 2.4–30.6° |
c = 10.1839 (8) Å | µ = 11.30 mm−1 |
α = 73.706 (1)° | T = 100 K |
β = 70.852 (1)° | Hexagon, green |
γ = 63.928 (1)° | 0.39 × 0.19 × 0.08 mm |
V = 718.28 (10) Å3 |
Bruker SMART APEX CCD diffractometer | 3537 independent reflections |
Radiation source: fine-focus sealed tube | 3305 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −11→11 |
Tmin = 0.122, Tmax = 0.424 | k = −12→12 |
7397 measured reflections | l = −13→13 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0301P)2 + 0.561P] where P = (Fo2 + 2Fc2)/3 |
3537 reflections | (Δ/σ)max = 0.002 |
182 parameters | Δρmax = 1.02 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Cu2Br3(C11H9N2O2)] | γ = 63.928 (1)° |
Mr = 568.01 | V = 718.28 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7708 (7) Å | Mo Kα radiation |
b = 9.6018 (8) Å | µ = 11.30 mm−1 |
c = 10.1839 (8) Å | T = 100 K |
α = 73.706 (1)° | 0.39 × 0.19 × 0.08 mm |
β = 70.852 (1)° |
Bruker SMART APEX CCD diffractometer | 3537 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 3305 reflections with I > 2σ(I) |
Tmin = 0.122, Tmax = 0.424 | Rint = 0.021 |
7397 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.02 e Å−3 |
3537 reflections | Δρmin = −0.61 e Å−3 |
182 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 | ||
Br2 | 0.12154 (3) | 1.22298 (3) | 0.70734 (3) | 0.01693 (7) | |
Br3 | −0.23030 (3) | 1.19011 (3) | 1.00202 (3) | 0.01823 (7) | |
Br1 | 0.57965 (3) | 0.99477 (3) | 0.65263 (3) | 0.01507 (7) | |
Cu1 | 0.32811 (4) | 0.96542 (3) | 0.64120 (3) | 0.01335 (8) | |
Cu2 | −0.03366 (4) | 1.04405 (4) | 0.82256 (3) | 0.01406 (8) | |
O2 | 0.1101 (2) | 0.9459 (2) | 0.65750 (18) | 0.0130 (3) | |
O1 | 0.1005 (2) | 0.7855 (2) | 0.53023 (19) | 0.0181 (4) | |
H1 | 0.0027 | 0.8513 | 0.5168 | 0.027* | |
N1 | 0.4203 (3) | 0.7340 (2) | 0.6562 (2) | 0.0142 (4) | |
C6 | 0.1192 (3) | 0.7966 (3) | 0.6588 (3) | 0.0136 (5) | |
N2 | −0.1178 (3) | 0.8719 (3) | 0.8672 (2) | 0.0148 (4) | |
C7 | −0.0283 (3) | 0.7649 (3) | 0.7798 (3) | 0.0146 (5) | |
C5 | 0.3027 (3) | 0.6743 (3) | 0.6683 (2) | 0.0132 (5) | |
C4 | 0.3512 (3) | 0.5141 (3) | 0.6783 (3) | 0.0165 (5) | |
H4 | 0.2670 | 0.4726 | 0.6880 | 0.020* | |
C3 | 0.5248 (3) | 0.4151 (3) | 0.6739 (3) | 0.0181 (5) | |
H3 | 0.5603 | 0.3051 | 0.6801 | 0.022* | |
C11 | −0.2540 (3) | 0.8573 (3) | 0.9709 (3) | 0.0194 (5) | |
H11 | −0.3182 | 0.9345 | 1.0310 | 0.023* | |
C1 | 0.5880 (3) | 0.6375 (3) | 0.6519 (3) | 0.0181 (5) | |
H1A | 0.6702 | 0.6812 | 0.6426 | 0.022* | |
C10 | −0.3034 (4) | 0.7321 (4) | 0.9924 (3) | 0.0231 (6) | |
H10 | −0.3998 | 0.7232 | 1.0667 | 0.028* | |
C9 | −0.2103 (4) | 0.6209 (3) | 0.9042 (3) | 0.0250 (6) | |
H9 | −0.2400 | 0.5328 | 0.9187 | 0.030* | |
C2 | 0.6449 (3) | 0.4767 (3) | 0.6606 (3) | 0.0185 (5) | |
H2 | 0.7641 | 0.4106 | 0.6575 | 0.022* | |
C8 | −0.0737 (4) | 0.6390 (3) | 0.7948 (3) | 0.0213 (5) | |
H8 | −0.0116 | 0.5661 | 0.7305 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br2 | 0.01628 (12) | 0.01244 (12) | 0.02349 (13) | −0.00619 (10) | −0.00358 (10) | −0.00520 (10) |
Br3 | 0.01571 (12) | 0.01965 (14) | 0.01898 (13) | −0.00469 (10) | −0.00213 (9) | −0.00841 (10) |
Br1 | 0.01576 (12) | 0.01633 (13) | 0.01651 (12) | −0.00878 (10) | −0.00493 (9) | −0.00191 (9) |
Cu1 | 0.01234 (14) | 0.01089 (15) | 0.01833 (16) | −0.00526 (12) | −0.00342 (11) | −0.00347 (12) |
Cu2 | 0.01375 (15) | 0.01408 (15) | 0.01601 (15) | −0.00656 (12) | −0.00140 (11) | −0.00535 (12) |
O2 | 0.0129 (8) | 0.0090 (8) | 0.0178 (8) | −0.0051 (6) | −0.0021 (6) | −0.0038 (6) |
O1 | 0.0200 (9) | 0.0172 (9) | 0.0191 (9) | −0.0040 (7) | −0.0094 (7) | −0.0055 (7) |
N1 | 0.0152 (10) | 0.0135 (10) | 0.0149 (10) | −0.0050 (8) | −0.0044 (8) | −0.0034 (8) |
C6 | 0.0159 (11) | 0.0111 (11) | 0.0162 (11) | −0.0057 (9) | −0.0054 (9) | −0.0028 (9) |
N2 | 0.0146 (10) | 0.0163 (10) | 0.0153 (10) | −0.0068 (8) | −0.0055 (8) | −0.0014 (8) |
C7 | 0.0130 (11) | 0.0138 (12) | 0.0191 (12) | −0.0063 (9) | −0.0062 (9) | −0.0010 (9) |
C5 | 0.0155 (11) | 0.0130 (12) | 0.0110 (10) | −0.0056 (9) | −0.0027 (9) | −0.0023 (9) |
C4 | 0.0181 (12) | 0.0144 (12) | 0.0177 (12) | −0.0074 (10) | −0.0028 (9) | −0.0033 (9) |
C3 | 0.0222 (13) | 0.0105 (11) | 0.0174 (12) | −0.0041 (10) | −0.0036 (10) | −0.0010 (9) |
C11 | 0.0174 (12) | 0.0253 (14) | 0.0162 (12) | −0.0098 (11) | −0.0051 (10) | −0.0005 (10) |
C1 | 0.0168 (12) | 0.0207 (13) | 0.0186 (12) | −0.0064 (10) | −0.0045 (9) | −0.0065 (10) |
C10 | 0.0208 (13) | 0.0283 (15) | 0.0228 (13) | −0.0165 (12) | −0.0082 (10) | 0.0074 (11) |
C9 | 0.0230 (14) | 0.0217 (14) | 0.0346 (16) | −0.0151 (12) | −0.0106 (12) | 0.0044 (12) |
C2 | 0.0170 (12) | 0.0158 (12) | 0.0205 (13) | −0.0021 (10) | −0.0057 (10) | −0.0051 (10) |
C8 | 0.0191 (12) | 0.0146 (12) | 0.0329 (15) | −0.0085 (10) | −0.0083 (11) | −0.0021 (11) |
Br2—Cu1 | 2.4592 (4) | N2—C11 | 1.341 (3) |
Br2—Cu2 | 2.4613 (4) | N2—C7 | 1.346 (3) |
Br3—Cu2 | 2.3507 (4) | C7—C8 | 1.386 (4) |
Br1—Cu1 | 2.3862 (4) | C5—C4 | 1.387 (3) |
Br1—Cu1i | 2.7923 (4) | C4—C3 | 1.389 (4) |
Cu1—O2 | 1.9513 (17) | C4—H4 | 0.9500 |
Cu1—N1 | 1.981 (2) | C3—C2 | 1.374 (4) |
Cu1—Br1i | 2.7923 (4) | C3—H3 | 0.9500 |
Cu1—Cu2 | 2.9801 (5) | C11—C10 | 1.389 (4) |
Cu2—O2 | 1.9386 (17) | C11—H11 | 0.9500 |
Cu2—N2 | 1.979 (2) | C1—C2 | 1.384 (4) |
O2—C6 | 1.396 (3) | C1—H1A | 0.9500 |
O1—C6 | 1.410 (3) | C10—C9 | 1.380 (4) |
O1—H1 | 0.8400 | C10—H10 | 0.9500 |
N1—C1 | 1.344 (3) | C9—C8 | 1.381 (4) |
N1—C5 | 1.344 (3) | C9—H9 | 0.9500 |
C6—C5 | 1.535 (3) | C2—H2 | 0.9500 |
C6—C7 | 1.542 (3) | C8—H8 | 0.9500 |
Cu1—Br2—Cu2 | 74.551 (13) | O2—C6—C7 | 108.55 (19) |
Cu1—Br1—Cu1i | 87.045 (12) | O1—C6—C7 | 109.37 (19) |
O2—Cu1—N1 | 82.07 (8) | C5—C6—C7 | 113.9 (2) |
O2—Cu1—Br1 | 172.49 (5) | C11—N2—C7 | 119.6 (2) |
N1—Cu1—Br1 | 99.71 (6) | C11—N2—Cu2 | 126.15 (19) |
O2—Cu1—Br2 | 81.11 (5) | C7—N2—Cu2 | 114.21 (17) |
N1—Cu1—Br2 | 155.54 (6) | N2—C7—C8 | 121.3 (2) |
Br1—Cu1—Br2 | 94.848 (14) | N2—C7—C6 | 115.8 (2) |
O2—Cu1—Br1i | 94.28 (5) | C8—C7—C6 | 122.8 (2) |
N1—Cu1—Br1i | 91.84 (6) | N1—C5—C4 | 121.0 (2) |
Br1—Cu1—Br1i | 92.955 (12) | N1—C5—C6 | 115.0 (2) |
Br2—Cu1—Br1i | 107.004 (14) | C4—C5—C6 | 123.9 (2) |
O2—Cu1—Cu2 | 39.84 (5) | C5—C4—C3 | 119.0 (2) |
N1—Cu1—Cu2 | 103.54 (6) | C5—C4—H4 | 120.5 |
Br1—Cu1—Cu2 | 132.975 (15) | C3—C4—H4 | 120.5 |
Br2—Cu1—Cu2 | 52.757 (10) | C2—C3—C4 | 119.8 (2) |
Br1i—Cu1—Cu2 | 126.084 (13) | C2—C3—H3 | 120.1 |
O2—Cu2—N2 | 82.40 (8) | C4—C3—H3 | 120.1 |
O2—Cu2—Br3 | 172.22 (6) | N2—C11—C10 | 121.6 (3) |
N2—Cu2—Br3 | 99.71 (6) | N2—C11—H11 | 119.2 |
O2—Cu2—Br2 | 81.30 (5) | C10—C11—H11 | 119.2 |
N2—Cu2—Br2 | 163.70 (6) | N1—C1—C2 | 122.2 (2) |
Br3—Cu2—Br2 | 96.420 (15) | N1—C1—H1A | 118.9 |
O2—Cu2—Cu1 | 40.15 (5) | C2—C1—H1A | 118.9 |
N2—Cu2—Cu1 | 113.10 (6) | C9—C10—C11 | 119.0 (3) |
Br3—Cu2—Cu1 | 142.336 (15) | C9—C10—H10 | 120.5 |
Br2—Cu2—Cu1 | 52.692 (10) | C11—C10—H10 | 120.5 |
C6—O2—Cu2 | 117.17 (15) | C10—C9—C8 | 119.3 (3) |
C6—O2—Cu1 | 117.19 (14) | C10—C9—H9 | 120.3 |
Cu2—O2—Cu1 | 100.01 (8) | C8—C9—H9 | 120.3 |
C6—O1—H1 | 109.5 | C3—C2—C1 | 118.3 (2) |
C1—N1—C5 | 119.6 (2) | C3—C2—H2 | 120.8 |
C1—N1—Cu1 | 124.95 (18) | C1—C2—H2 | 120.8 |
C5—N1—Cu1 | 115.39 (17) | C9—C8—C7 | 119.2 (3) |
O2—C6—O1 | 111.3 (2) | C9—C8—H8 | 120.4 |
O2—C6—C5 | 109.75 (19) | C7—C8—H8 | 120.4 |
O1—C6—C5 | 104.04 (19) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.84 | 2.33 | 3.014 (2) | 139 |
Symmetry code: (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Br3(C11H9N2O2)] |
Mr | 568.01 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.7708 (7), 9.6018 (8), 10.1839 (8) |
α, β, γ (°) | 73.706 (1), 70.852 (1), 63.928 (1) |
V (Å3) | 718.28 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.30 |
Crystal size (mm) | 0.39 × 0.19 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.122, 0.424 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7397, 3537, 3305 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.061, 1.09 |
No. of reflections | 3537 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.02, −0.61 |
Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.84 | 2.33 | 3.014 (2) | 139 |
Symmetry code: (i) −x, −y+2, −z+1. |
Acknowledgements
The authors thank Dr Guy Crundwell (CCSU) for helpful discussions. BLW acknowledges funding from the National Science Foundation (NSF
0420322). MZ and ADH acknowledge funding from the National Science Foundation (NSF #0087210) and the Ohio Board of Regents (CAP-491).References
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The structure of the title compound, is shown below. The complex was one of three Cu-dpkoh complexes isolated from the 1:1 molar mixture of copper(II)bromide and di-2-pyridyl ketone. The title complex was the second isolated from solution. One other complex had been reported previously by Parker, et al., another unique complex is described elsewhere: Westcott, et al.(2008).
The complex contains two copper centers that are 2.9801 (5) Å apart and are bridged by the hydrated form of the ligand di-2-pyridylketone. Each copper center is also coordinated to the ligand through one unique nitrogen atom and a by a µ-hydroxyl bridge. Additionally, each Cu center coordinates one bromide ion. The bromide ion then acts as a bridging ligand to the next di-copper unit, leading to a polymeric structure as shown in Figure 2.