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Acta Cryst. (2009). E65, m1647    [ doi:10.1107/S1600536809048995 ]

Bis(2,2'-bipyridyl)bromidocopper(II) bromide bromoacetic acid hemihydrate

Y. Liu, J. Sun and X. Wang

Abstract top

In the title compound, [CuBr(C10H8N2)2]Br·BrCH2COOH·0.5H2O, the CuII ion is coordinated by four N atoms [Cu-N = 1.985 (6)-2.125 (7) Å] from two 2,2'-bipyridine ligand molecules and a bromide anion [Cu-Br = 2.471 (2) Å] in a distorted trigonal-bipyramidal geometry. Short centroid-centroid distances [3.762 (5) and 3.867 (5) Å] between the aromatic rings of neighbouring cations suggest the existence of [pi]-[pi] interactions. Intermolecular O-H...Br hydrogen bonds and weak C-H...O and C-H...Br interactions consolidate the crystal packing.

Comment top

Metal complexes with carboxylates are among the most investigated complexes in the field of coordination chemistry. In addition, metal-2,2'-bipyridine complexes and their derivatives have attracted much attention during recent decades because of their structural features (Hammond et al., 1999; Song et al., 2004). In this work, we present the crystal structure of the title compound (I) obtained from the bromoacetic acid and cupric acetate in the presence of co-ligand of 2,2'-bipyridine.

In (I) (Fig.1), the CuII ion exhibits a five-coordinated trigonal bipyramidal geometry with four N atoms [Cu—N 1.985 (6)–2.125 (7) Å] from two 2,2'-bipyridine ligand molecules and a Br anion [Cu—Br 2.471 (2) Å]. Two N atoms and coordinated Br anion form an equatorial plane. The two rest coordinated N atoms occupy the apical positions with the N—Cu—N angle of 175.6 (3)/%. Intermolecular O—H···Br hydrogen bonds and weak C—H···O and C—H···Br interactions (Table1) consolidate the crystal packing, which exhibits relatively short intermolecular Br···Br contacts of 3.429 (3) Å.

Related literature top

For related structures, see: Hammond et al. (1999); Song et al. (2004).

Experimental top

The reaction was carried out by the solvothermal method. Bromoacetic acid (0.138 g,1 mmol) and cupric acetate(0.199 g, 1 mmol) and 2,2'-bipyridine(0.312 g, 2 mmol) were added to the airtight vessel with 1:2 ratio of ethanol and water. The resulting blue solution was filtered, and blue block-shaped crystals were obtained after several days. Yield 81%. Elemental analysis: calcd. for C22H20Br3Cu1N4O2.5: C 38.65, H 2.95, N 8.19; found: C 38.45, H 2.79, N 8.22. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II.

Refinement top

All H atoms were geometrically positioned (C—H 0.93-0.97 Å, O—H 0.82-0.85 Å), abd refined as riding, with Uiso(H) = 1.2-1.5 Ueq(C, O).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids. H atoms omitted for clarity.
Bis(2,2'-bipyridyl)bromidocopper(II) bromide bromoacetic acid hemihydrate top
Crystal data top
[CuBr(C10H8N2)2]Br·C2H3BrO2·0.5H2OZ = 2
Mr = 683.69F(000) = 668
Triclinic, P1Dx = 1.809 Mg m−3
a = 8.580 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.125 (6) ÅCell parameters from 1942 reflections
c = 13.212 (6) Åθ = 2.5–26.3°
α = 70.295 (9)°µ = 5.67 mm−1
β = 81.427 (8)°T = 273 K
γ = 76.669 (9)°Block, blue
V = 1255.3 (11) Å30.30 × 0.27 × 0.26 mm
Data collection top
Bruker SMART APEX
diffractometer		4384 independent reflections
Radiation source: fine-focus sealed tube2689 reflections with I > 2σ(I)
graphiteRint = 0.113
phi and ω scansθmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −8→10
Tmin = 0.281, Tmax = 0.320k = −11→14
6360 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.093P)2]
where P = (Fo2 + 2Fc2)/3
4384 reflections(Δ/σ)max < 0.001
299 parametersΔρmax = 1.20 e Å−3
3 restraintsΔρmin = −1.10 e Å−3
Crystal data top
[CuBr(C10H8N2)2]Br·C2H3BrO2·0.5H2Oγ = 76.669 (9)°
Mr = 683.69V = 1255.3 (11) Å3
Triclinic, P1Z = 2
a = 8.580 (4) ÅMo Kα radiation
b = 12.125 (6) ŵ = 5.67 mm−1
c = 13.212 (6) ÅT = 273 K
α = 70.295 (9)°0.30 × 0.27 × 0.26 mm
β = 81.427 (8)°
Data collection top
Bruker SMART APEX
diffractometer		4384 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2689 reflections with I > 2σ(I)
Tmin = 0.281, Tmax = 0.320Rint = 0.113
6360 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.183Δρmax = 1.20 e Å−3
S = 1.00Δρmin = −1.10 e Å−3
4384 reflectionsAbsolute structure: ?
299 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
Cu10.29541 (12)0.96050 (9)0.26233 (8)0.0355 (3)
N10.2936 (8)1.0281 (6)0.3915 (5)0.0343 (17)
N20.1969 (9)0.8397 (6)0.3826 (5)0.0396 (18)
N30.4085 (8)1.0763 (6)0.1487 (5)0.0357 (17)
N40.5077 (8)0.8468 (6)0.2359 (5)0.0335 (17)
O10.5681 (9)0.4552 (7)0.1253 (6)0.072 (2)
H10.48980.46120.16840.108*
O20.6357 (9)0.2741 (8)0.2416 (6)0.090 (3)
O30.4997 (16)0.4203 (11)0.4374 (10)0.057 (4)0.50
H3A0.43390.46670.39200.068*0.50
H3B0.56320.37110.40990.068*0.50
Br10.96870 (13)0.40992 (10)0.14479 (8)0.0541 (3)
Br20.05033 (11)1.02044 (9)0.16420 (7)0.0468 (3)
Br30.23105 (12)0.51574 (10)0.24364 (9)0.0574 (3)
C10.6651 (12)0.3530 (9)0.1639 (8)0.050 (3)
C20.8186 (12)0.3421 (10)0.0945 (8)0.054 (3)
H2A0.80020.38550.01950.064*
H2B0.86240.25890.10100.064*
C30.3481 (11)1.1248 (8)0.3882 (8)0.046 (2)
H30.39081.17060.32280.055*
C40.3426 (13)1.1581 (10)0.4791 (10)0.063 (3)
H40.38451.22350.47620.075*
C50.2718 (12)1.0902 (10)0.5760 (8)0.053 (3)
H50.25991.11270.63790.063*
C60.2192 (11)0.9878 (9)0.5783 (7)0.044 (2)
H60.17760.93880.64230.053*
C70.2305 (9)0.9621 (8)0.4850 (7)0.032 (2)
C80.1752 (10)0.8567 (8)0.4793 (6)0.037 (2)
C90.1025 (11)0.7787 (8)0.5660 (7)0.044 (2)
H90.08850.78950.63340.053*
C100.0516 (13)0.6868 (10)0.5531 (8)0.060 (3)
H100.00250.63450.61090.072*
C110.0743 (13)0.6724 (10)0.4521 (8)0.060 (3)
H110.04040.61020.44080.072*
C120.1468 (13)0.7503 (9)0.3701 (8)0.056 (3)
H120.16180.74040.30220.067*
C130.3448 (12)1.1931 (8)0.1070 (8)0.051 (3)
H130.24371.22310.13430.061*
C140.4260 (13)1.2703 (9)0.0240 (8)0.053 (3)
H140.37921.3504−0.00470.063*
C150.5761 (12)1.2258 (9)−0.0145 (7)0.046 (2)
H150.63281.2757−0.06950.055*
C160.6409 (11)1.1099 (9)0.0276 (7)0.047 (2)
H160.74291.07990.00140.056*
C170.5572 (10)1.0337 (8)0.1101 (6)0.034 (2)
C180.6133 (10)0.9048 (8)0.1607 (6)0.035 (2)
C190.7675 (11)0.8444 (9)0.1358 (8)0.049 (3)
H190.83770.88520.08370.059*
C200.8125 (13)0.7270 (10)0.1879 (9)0.060 (3)
H200.91510.68650.17350.072*
C210.7010 (13)0.6653 (9)0.2656 (9)0.059 (3)
H210.72870.58390.30150.071*
C220.5528 (12)0.7292 (9)0.2856 (8)0.053 (3)
H220.47990.68930.33590.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0381 (6)0.0378 (6)0.0242 (6)−0.0070 (5)0.0117 (4)−0.0077 (5)
N10.033 (4)0.043 (4)0.028 (4)−0.007 (3)0.008 (3)−0.016 (4)
N20.047 (5)0.040 (4)0.028 (4)−0.016 (4)0.013 (3)−0.007 (3)
N30.033 (4)0.036 (4)0.027 (4)−0.004 (3)0.009 (3)−0.002 (3)
N40.037 (4)0.033 (4)0.024 (4)0.000 (3)0.000 (3)−0.007 (3)
O10.059 (5)0.053 (5)0.069 (5)0.006 (4)0.012 (4)0.007 (4)
O20.065 (6)0.085 (6)0.065 (5)−0.006 (5)0.008 (4)0.034 (5)
O30.080 (10)0.041 (8)0.048 (8)−0.015 (7)−0.047 (8)0.007 (6)
Br10.0528 (7)0.0612 (7)0.0445 (6)−0.0112 (5)0.0059 (5)−0.0156 (5)
Br20.0376 (6)0.0617 (7)0.0353 (5)−0.0075 (5)0.0033 (4)−0.0117 (5)
Br30.0428 (6)0.0652 (7)0.0613 (7)−0.0074 (5)0.0032 (5)−0.0212 (6)
C10.049 (6)0.050 (6)0.046 (6)−0.007 (5)−0.007 (5)−0.008 (5)
C20.049 (6)0.060 (7)0.044 (6)−0.002 (5)0.005 (5)−0.014 (5)
C30.052 (6)0.042 (6)0.042 (6)−0.010 (5)0.006 (5)−0.014 (5)
C40.063 (8)0.064 (7)0.083 (9)−0.008 (6)−0.024 (6)−0.046 (7)
C50.057 (7)0.069 (7)0.036 (6)0.004 (6)−0.012 (5)−0.028 (6)
C60.044 (6)0.055 (6)0.023 (5)0.008 (5)−0.002 (4)−0.013 (5)
C70.021 (4)0.039 (5)0.029 (5)0.008 (4)−0.006 (3)−0.011 (4)
C80.031 (5)0.046 (6)0.021 (5)−0.003 (4)0.008 (4)0.000 (4)
C90.042 (6)0.050 (6)0.025 (5)−0.008 (5)0.004 (4)0.003 (4)
C100.064 (7)0.071 (8)0.037 (6)−0.033 (6)0.012 (5)0.000 (5)
C110.077 (8)0.060 (7)0.043 (6)−0.033 (6)0.014 (5)−0.012 (5)
C120.077 (8)0.053 (7)0.037 (6)−0.031 (6)0.009 (5)−0.009 (5)
C130.045 (6)0.043 (6)0.051 (6)−0.002 (5)0.005 (5)−0.007 (5)
C140.065 (7)0.035 (5)0.048 (6)−0.012 (5)−0.012 (5)0.004 (5)
C150.062 (7)0.048 (6)0.028 (5)−0.021 (5)0.001 (4)−0.006 (5)
C160.045 (6)0.062 (7)0.034 (5)−0.023 (5)0.014 (4)−0.016 (5)
C170.039 (5)0.043 (5)0.020 (4)−0.012 (4)−0.002 (4)−0.010 (4)
C180.039 (5)0.047 (6)0.022 (4)−0.007 (4)−0.003 (4)−0.014 (4)
C190.030 (5)0.062 (7)0.059 (7)−0.004 (5)0.006 (4)−0.031 (6)
C200.051 (7)0.061 (8)0.068 (7)0.010 (6)−0.006 (6)−0.033 (6)
C210.067 (8)0.043 (6)0.060 (7)0.012 (5)−0.022 (6)−0.014 (6)
C220.044 (6)0.060 (7)0.041 (6)0.003 (5)−0.003 (5)−0.007 (5)
Geometric parameters (Å, °) top
Cu1—N31.985 (6)C6—C71.355 (12)
Cu1—N21.997 (7)C6—H60.9300
Cu1—N42.078 (7)C7—C81.489 (13)
Cu1—N12.125 (7)C8—C91.388 (11)
Cu1—Br22.471 (2)C9—C101.355 (14)
N1—C71.340 (10)C9—H90.9300
N1—C31.344 (11)C10—C111.382 (14)
N2—C121.321 (12)C10—H100.9300
N2—C81.341 (11)C11—C121.354 (13)
N3—C131.347 (11)C11—H110.9300
N3—C171.354 (10)C12—H120.9300
N4—C221.343 (12)C13—C141.395 (13)
N4—C181.362 (10)C13—H130.9300
O1—C11.309 (12)C14—C151.370 (14)
O1—H10.8200C14—H140.9300
O2—C11.185 (11)C15—C161.341 (14)
O3—H3A0.8500C15—H150.9300
O3—H3B0.8500C16—C171.397 (12)
Br1—C21.972 (11)C16—H160.9300
C1—C21.496 (13)C17—C181.472 (12)
C2—H2A0.9700C18—C191.408 (12)
C2—H2B0.9700C19—C201.347 (14)
C3—C41.381 (13)C19—H190.9300
C3—H30.9300C20—C211.431 (15)
C4—C51.406 (15)C20—H200.9300
C4—H40.9300C21—C221.368 (14)
C5—C61.406 (14)C21—H210.9300
C5—H50.9300C22—H220.9300
N3—Cu1—N2175.6 (3)C6—C7—C8122.2 (8)
N3—Cu1—N480.1 (3)N2—C8—C9119.5 (9)
N2—Cu1—N497.1 (3)N2—C8—C7116.3 (7)
N3—Cu1—N198.2 (3)C9—C8—C7124.2 (8)
N2—Cu1—N179.9 (3)C10—C9—C8120.4 (9)
N4—Cu1—N1114.5 (3)C10—C9—H9119.8
N3—Cu1—Br293.4 (2)C8—C9—H9119.8
N2—Cu1—Br291.0 (2)C9—C10—C11118.7 (10)
N4—Cu1—Br2127.57 (19)C9—C10—H10120.7
N1—Cu1—Br2117.90 (19)C11—C10—H10120.7
C7—N1—C3119.6 (8)C12—C11—C10118.8 (10)
C7—N1—Cu1112.7 (5)C12—C11—H11120.6
C3—N1—Cu1127.7 (6)C10—C11—H11120.6
C12—N2—C8120.0 (8)N2—C12—C11122.6 (10)
C12—N2—Cu1123.8 (6)N2—C12—H12118.7
C8—N2—Cu1116.2 (6)C11—C12—H12118.7
C13—N3—C17118.7 (7)N3—C13—C14121.9 (9)
C13—N3—Cu1123.9 (6)N3—C13—H13119.0
C17—N3—Cu1117.4 (5)C14—C13—H13119.0
C22—N4—C18118.6 (8)C15—C14—C13118.7 (9)
C22—N4—Cu1128.6 (6)C15—C14—H14120.7
C18—N4—Cu1112.8 (6)C13—C14—H14120.7
C1—O1—H1109.5C16—C15—C14119.7 (9)
H3A—O3—H3B109.7C16—C15—H15120.2
O2—C1—O1125.6 (10)C14—C15—H15120.2
O2—C1—C2122.2 (10)C15—C16—C17120.8 (9)
O1—C1—C2112.1 (9)C15—C16—H16119.6
C1—C2—Br1106.9 (7)C17—C16—H16119.6
C1—C2—H2A110.3N3—C17—C16120.2 (8)
Br1—C2—H2A110.3N3—C17—C18113.9 (7)
C1—C2—H2B110.3C16—C17—C18126.0 (8)
Br1—C2—H2B110.3N4—C18—C19121.4 (8)
H2A—C2—H2B108.6N4—C18—C17115.8 (7)
N1—C3—C4122.0 (9)C19—C18—C17122.7 (8)
N1—C3—H3119.0C20—C19—C18119.4 (10)
C4—C3—H3119.0C20—C19—H19120.3
C3—C4—C5117.9 (10)C18—C19—H19120.3
C3—C4—H4121.0C19—C20—C21119.3 (10)
C5—C4—H4121.0C19—C20—H20120.3
C4—C5—C6119.1 (9)C21—C20—H20120.3
C4—C5—H5120.5C22—C21—C20118.3 (10)
C6—C5—H5120.5C22—C21—H21120.9
C7—C6—C5118.5 (9)C20—C21—H21120.9
C7—C6—H6120.8N4—C22—C21123.0 (10)
C5—C6—H6120.8N4—C22—H22118.5
N1—C7—C6122.8 (8)C21—C22—H22118.5
N1—C7—C8114.9 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Br30.822.343.129 (7)163
O3—H3A···Br30.852.643.426 (11)154
C14—H14···O1i0.932.463.254 (12)144
C16—H16···Br2i0.933.013.835 (9)149
C3—H3···O2ii0.932.603.374 (12)141
C4—H4···O3ii0.932.653.578 (16)172
C10—H10···Br1iii0.933.133.751 (10)126
C2—H2B···Br2iv0.972.883.815 (11)163
C13—H13···Br1v0.932.893.750 (10)154
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) x+1, y−1, z; (v) x−1, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Br30.822.343.129 (7)163
O3—H3A···Br30.852.643.426 (11)154
C14—H14···O1i0.932.463.254 (12)144
C3—H3···O2ii0.932.603.374 (12)141
C2—H2B···Br2iii0.972.883.815 (11)163
C13—H13···Br1iv0.932.893.750 (10)154
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) x+1, y−1, z; (iv) x−1, y+1, z.
Acknowledgements top

The authors thank the Postgraduate Foundation of Taishan University for financial support (grant No. Y07–2-15).

references
References top

Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Song, J. L., Mao, J. G., Zeng, H. Y. & Dong, Z. C. (2004). Eur. J. Inorg. Chem. pp. 538–543.