Literature DB >> 21588877

catena-Poly[[bis-(μ-5-bromo-pyridine-3-carboxyl-ato-κO:O')dicopper(II)]-bis-(μ-5-bromo-pyridine-3-carboxyl-ato)-κO,O':N;κN:O,O'].

Paul Deburgomaster1, Jon Zubieta.   

Abstract

The title compound [Cu(2)(C(6)H(3)BrNO(2))(4)](n), forms sheets in the bc plane. The structure features the dinuclear paddle-wheel cage motif common to copper(II) carboxyl-ates. The polymeric structure is achieved through bridging between binuclear units by the pyridyl donors of two of the four carboxyl-ates of the cage. Each cage engages in axial bonding at each copper atom to a pyridyl nitro-gen donor and extends two 5-bromo-pyridine-3-carboxyl-ate groups to bridge to adjacent binuclear sites in the bc plane. Each cage is linked to four adjacent cages in the plane. The intra-dimer Cu⋯Cu distance is 2.6465 (5) Å. The remaining 5-bromo-pyridine-3-carboxyl-ate groups project into the inter-lamellar domain and inter-digitate in pairs from each neighboring layer.

Entities:  

Year:  2010        PMID： 21588877      PMCID： PMC3009202          DOI： 10.1107/S160053681004242X

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For a general review of copper(II) carboxyl­ates, see: Doedens (1976 ▶). For polynuclear copper carboxyl­ates with the [Cu2(O2CR)4] core, see: Agterberg et al. (1997 ▶); Valentine et al. (1974 ▶); Yamanaka et al. (1991 ▶). For the preparation of copper coordination polymers under hydro­thermal conditions, see: Lu (2003 ▶). For general discussion of hydro­thermal methods, see: Gopalakrishnan (1995 ▶); Zubieta (2004 ▶).

Experimental

Crystal data

[Cu2(C6H3BrNO2)4] M = 931.11 Monoclinic, a = 11.1390 (12) Å b = 11.5866 (13) Å c = 12.6325 (14) Å β = 115.432 (2)° V = 1472.4 (3) Å3 Z = 2 Mo Kα radiation μ = 6.93 mm−1 T = 90 K 0.35 × 0.30 × 0.27 mm

Data collection

Bruker n class="Gene">APEX CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.196, T max = 0.256 14281 measured reflections 3571 independent reflections 3218 reflections with I > 2σ(I) R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.021 wR(F 2) = 0.054 S = 1.05 3571 reflections 190 parameters H-atom parameters constrained Δρmax = 0.77 e Å−3 Δρmin = −0.51 e Å−3 Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004242X/rn2072sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053681004242X/rn2072Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Cu2(C6H3BrNO2)4]F(000) = 892
Mr = 931.11Dx = 2.100 Mg m−3Dm = 2.09 (2) Mg m−3Dm measured by flotation
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3266 reflections
a = 11.1390 (12) Åθ = 2.4–28.3°
b = 11.5866 (13) ŵ = 6.93 mm−1
c = 12.6325 (14) ÅT = 90 K
β = 115.432 (2)°Block, blue
V = 1472.4 (3) Å30.35 × 0.30 × 0.27 mm
Z = 2
Bruker APEX CCD area-detector diffractometer3571 independent reflections
Radiation source: fine-focus sealed tube3218 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 512 pixels mm-1θmax = 28.1°, θmin = 2.0°
φ and ω scansh = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 1998)k = −15→14
Tmin = 0.196, Tmax = 0.256l = −15→16
14281 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0258P)2 + 1.3076P] where P = (Fo2 + 2Fc2)/3
3571 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.77 e Å−3
0 restraintsΔρmin = −0.51 e Å−3
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.
xyzUiso*/Ueq
Br1−0.18056 (2)0.76143 (2)−0.11231 (2)0.02559 (7)
Br20.84249 (2)0.868086 (18)0.603257 (19)0.02064 (6)
Cu10.56886 (2)1.02600 (2)0.11208 (2)0.01009 (6)
O10.40781 (14)0.98221 (13)0.12844 (14)0.0179 (3)
O20.29176 (14)0.93567 (13)−0.06153 (13)0.0174 (3)
O31.00043 (14)1.31393 (12)0.57312 (13)0.0153 (3)
O40.88355 (15)1.36151 (12)0.38361 (13)0.0176 (3)
N10.08987 (19)0.89646 (18)0.19994 (17)0.0232 (4)
N20.70137 (17)1.05035 (15)0.29489 (15)0.0142 (3)
C1−0.0161 (2)0.8474 (2)0.1151 (2)0.0214 (5)
H1−0.08750.82330.13200.026*
C2−0.0258 (2)0.83017 (19)0.00277 (19)0.0176 (4)
C30.0770 (2)0.86282 (17)−0.0242 (2)0.0161 (4)
H30.07180.8518−0.10060.019*
C40.1886 (2)0.91256 (18)0.06474 (19)0.0146 (4)
C50.1900 (2)0.92849 (19)0.17425 (19)0.0181 (4)
H50.26570.96390.23400.022*
C60.30570 (19)0.94647 (17)0.04201 (19)0.0139 (4)
C70.7262 (2)0.96880 (18)0.37741 (18)0.0146 (4)
H70.68060.89710.35610.018*
C80.8166 (2)0.98675 (17)0.49263 (18)0.0137 (4)
C90.8847 (2)1.09039 (17)0.52675 (18)0.0138 (4)
H90.94701.10340.60560.017*
C100.85843 (19)1.17443 (17)0.44120 (18)0.0116 (4)
C110.76676 (19)1.15074 (17)0.32653 (18)0.0132 (4)
H110.75001.20830.26830.016*
C120.92049 (19)1.29269 (17)0.46889 (18)0.0124 (4)
U11U22U33U12U13U23
Br10.01981 (11)0.03107 (13)0.02547 (13)−0.01189 (9)0.00931 (10)−0.00522 (10)
Br20.03049 (12)0.01399 (11)0.01496 (11)−0.00414 (8)0.00738 (9)0.00332 (8)
Cu10.01025 (11)0.00862 (12)0.00980 (12)0.00020 (8)0.00280 (9)0.00007 (9)
O10.0152 (7)0.0211 (8)0.0180 (8)−0.0049 (6)0.0078 (6)−0.0028 (6)
O20.0140 (7)0.0229 (8)0.0163 (8)−0.0013 (6)0.0073 (6)0.0000 (6)
O30.0183 (7)0.0113 (7)0.0127 (7)−0.0035 (6)0.0033 (6)−0.0016 (6)
O40.0220 (8)0.0105 (7)0.0139 (8)−0.0030 (6)0.0015 (6)0.0012 (6)
N10.0233 (10)0.0302 (11)0.0186 (10)−0.0033 (8)0.0113 (8)0.0015 (8)
N20.0163 (8)0.0120 (8)0.0130 (9)−0.0012 (6)0.0049 (7)−0.0006 (7)
C10.0197 (10)0.0245 (11)0.0239 (12)−0.0031 (9)0.0130 (9)0.0016 (9)
C20.0142 (9)0.0171 (10)0.0201 (11)−0.0033 (8)0.0060 (8)−0.0010 (9)
C30.0176 (10)0.0140 (10)0.0184 (11)0.0002 (8)0.0092 (8)0.0003 (8)
C40.0143 (9)0.0124 (9)0.0175 (10)0.0008 (7)0.0073 (8)0.0024 (8)
C50.0169 (10)0.0190 (11)0.0170 (11)−0.0025 (8)0.0060 (8)0.0001 (8)
C60.0132 (9)0.0090 (9)0.0197 (11)0.0008 (7)0.0071 (8)0.0017 (8)
C70.0168 (10)0.0119 (9)0.0151 (10)−0.0038 (7)0.0068 (8)−0.0024 (8)
C80.0174 (9)0.0116 (9)0.0125 (10)0.0005 (7)0.0068 (8)0.0038 (8)
C90.0145 (9)0.0143 (10)0.0115 (10)−0.0005 (7)0.0045 (8)−0.0016 (8)
C100.0130 (9)0.0094 (9)0.0127 (10)0.0000 (7)0.0056 (7)−0.0011 (7)
C110.0142 (9)0.0114 (9)0.0132 (10)−0.0007 (7)0.0053 (8)0.0013 (7)
C120.0125 (9)0.0107 (9)0.0154 (10)0.0004 (7)0.0072 (8)−0.0007 (8)
Br1—C21.888 (2)C1—C21.390 (3)
Br2—C81.892 (2)C1—H10.9500
Cu1—O11.9588 (14)C2—C31.380 (3)
Cu1—O2i1.9665 (14)C3—C41.393 (3)
Cu1—O4ii1.9726 (14)C3—H30.9500
Cu1—O3iii1.9852 (14)C4—C51.389 (3)
Cu1—N22.1595 (18)C4—C61.504 (3)
Cu1—Cu1i2.6465 (5)C5—H50.9500
O1—C61.261 (3)C7—C81.384 (3)
O2—C61.255 (3)C7—H70.9500
O3—C121.257 (2)C8—C91.387 (3)
O4—C121.259 (2)C9—C101.389 (3)
N1—C11.334 (3)C9—H90.9500
N1—C51.340 (3)C10—C111.395 (3)
N2—C111.339 (3)C10—C121.507 (3)
N2—C71.345 (3)C11—H110.9500
O1—Cu1—O2i168.33 (6)C2—C3—H3121.2
O1—Cu1—O4ii89.67 (6)C4—C3—H3121.2
O2i—Cu1—O4ii89.25 (7)C5—C4—C3118.87 (19)
O1—Cu1—O3iii89.81 (6)C5—C4—C6121.06 (19)
O2i—Cu1—O3iii88.91 (6)C3—C4—C6120.06 (19)
O4ii—Cu1—O3iii168.37 (6)N1—C5—C4123.3 (2)
O1—Cu1—N299.05 (7)N1—C5—H5118.3
O2i—Cu1—N292.60 (6)C4—C5—H5118.3
O4ii—Cu1—N292.56 (6)O2—C6—O1126.63 (18)
O3iii—Cu1—N299.00 (6)O2—C6—C4116.34 (18)
O1—Cu1—Cu1i85.28 (5)O1—C6—C4117.03 (18)
O2i—Cu1—Cu1i83.08 (5)N2—C7—C8121.60 (18)
O4ii—Cu1—Cu1i80.50 (4)N2—C7—H7119.2
O3iii—Cu1—Cu1i87.88 (4)C8—C7—H7119.2
N2—Cu1—Cu1i171.84 (5)C7—C8—C9120.71 (18)
C6—O1—Cu1121.33 (13)C7—C8—Br2118.60 (15)
C6—O2—Cu1i123.66 (13)C9—C8—Br2120.67 (16)
C12—O3—Cu1iv117.81 (13)C8—C9—C10117.44 (19)
C12—O4—Cu1v127.10 (14)C8—C9—H9121.3
C1—N1—C5117.7 (2)C10—C9—H9121.3
C11—N2—C7118.33 (18)C9—C10—C11119.06 (18)
C11—N2—Cu1117.85 (14)C9—C10—C12122.30 (18)
C7—N2—Cu1123.76 (14)C11—C10—C12118.57 (17)
N1—C1—C2122.4 (2)N2—C11—C10122.86 (18)
N1—C1—H1118.8N2—C11—H11118.6
C2—C1—H1118.8C10—C11—H11118.6
C3—C2—C1120.2 (2)O3—C12—O4126.62 (18)
C3—C2—Br1120.35 (17)O3—C12—C10117.99 (18)
C1—C2—Br1119.44 (15)O4—C12—C10115.38 (18)
C2—C3—C4117.5 (2)
O2i—Cu1—O1—C65.4 (4)Cu1—O1—C6—C4178.63 (13)
O4ii—Cu1—O1—C6−79.30 (16)C5—C4—C6—O2−175.55 (19)
O3iii—Cu1—O1—C689.08 (16)C3—C4—C6—O25.4 (3)
N2—Cu1—O1—C6−171.84 (15)C5—C4—C6—O14.8 (3)
Cu1i—Cu1—O1—C61.20 (15)C3—C4—C6—O1−174.31 (19)
O1—Cu1—N2—C11−127.00 (15)C11—N2—C7—C80.1 (3)
O2i—Cu1—N2—C1153.57 (15)Cu1—N2—C7—C8177.04 (15)
O4ii—Cu1—N2—C11142.93 (15)N2—C7—C8—C90.1 (3)
O3iii—Cu1—N2—C11−35.75 (15)N2—C7—C8—Br2178.81 (15)
O1—Cu1—N2—C756.05 (17)C7—C8—C9—C100.1 (3)
O2i—Cu1—N2—C7−123.39 (16)Br2—C8—C9—C10−178.61 (14)
O4ii—Cu1—N2—C7−34.03 (16)C8—C9—C10—C11−0.4 (3)
O3iii—Cu1—N2—C7147.30 (16)C8—C9—C10—C12176.54 (18)
C5—N1—C1—C2−0.7 (3)C7—N2—C11—C10−0.5 (3)
N1—C1—C2—C30.8 (4)Cu1—N2—C11—C10−177.61 (15)
N1—C1—C2—Br1−179.34 (18)C9—C10—C11—N20.7 (3)
C1—C2—C3—C40.1 (3)C12—C10—C11—N2−176.43 (18)
Br1—C2—C3—C4−179.72 (15)Cu1iv—O3—C12—O44.0 (3)
C2—C3—C4—C5−1.1 (3)Cu1iv—O3—C12—C10−174.39 (12)
C2—C3—C4—C6178.03 (19)Cu1v—O4—C12—O3−3.7 (3)
C1—N1—C5—C4−0.3 (3)Cu1v—O4—C12—C10174.71 (12)
C3—C4—C5—N11.2 (3)C9—C10—C12—O31.3 (3)
C6—C4—C5—N1−177.9 (2)C11—C10—C12—O3178.26 (18)
Cu1i—O2—C6—O1−0.2 (3)C9—C10—C12—O4−177.28 (18)
Cu1i—O2—C6—C4−179.81 (13)C11—C10—C12—O4−0.3 (3)
Cu1—O1—C6—O2−1.0 (3)
  2 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Dinuclear Paddle-Wheel Copper(II) Carboxylates in the Catalytic Oxidation of Carboxylic Acids. Unusual Polymeric Chains Found in the Single-Crystal X-ray Structures of [Tetrakis(&mgr;-1-phenylcyclopropane-1-carboxylato-O,O')bis(ethanol-O)dicopper(II)] and catena-Poly[[bis(&mgr;-diphenylacetato-O:O')dicopper](&mgr;(3)-diphenylacetato-1-O:2-O':1'-O')(&mgr;(3)-diphenylacetato-1-O:2-O':2'-O')].

Authors:  Frank P. W. Agterberg; Hajo A. J. Provó Kluit; Willem L. Driessen; Henk Oevering; Wim Buijs; Miles T. Lakin; Anthony L. Spek; Jan Reedijk
Journal:  Inorg Chem       Date:  1997-09-24       Impact factor: 5.165
  2 in total

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