metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

catena-Poly[[[di­bromidocadmium]-μ2-1,1′-(butane-1,4-di­yl)bis­­(pyridinium-4-carboxyl­ate)] monohydrate]

aThe Institute of Higher Education, Changchun Normal University, Changchun 130032, People's Republic of China, and bCollege of Chemistry, Changchun Normal University, Changchun 130032, People's Republic of China
*Correspondence e-mail: rzchen2011@yahoo.cn

(Received 26 April 2011; accepted 3 May 2011; online 7 May 2011)

In the title compound, {[CdBr2(C16H16N2O4)]·H2O}n, the CdII ion is six-coordinated by a Br2O4 donor set, with four O atoms from two bridging 1,1′-(butane-1,4-di­yl)bis­(pyridinium-4-carboxyl­ate) ligands. The ligands link the CdII ions into a zigzag chain extending along [0[\overline{1}]1]. O—H⋯O and O—H⋯Br hydrogen bonds involving the uncoordinated water mol­ecules connect the chains.

Related literature

For the design and synthesis of coordination polymers, see: Li et al. (2005[Li, S.-L., Ji, W.-Z., Hou, J.-F. & Tian, D.-K. (2005). Chin. J. Inorg. Chem. 1, 30-34.]). For a related structure, see: Ma et al. (2000[Ma, J.-F., Liu, J.-F., Xing, Y., Jia, H.-Q. & Lin, Y.-H. (2000). J. Chem. Soc. Dalton Trans. pp. 2403-2407.]).

[Scheme 1]

Experimental

Crystal data
  • [CdBr2(C16H16N2O4)]·H2O

  • Mr = 590.53

  • Triclinic, [P \overline 1]

  • a = 7.6529 (5) Å

  • b = 9.3969 (6) Å

  • c = 14.0198 (9) Å

  • α = 74.410 (1)°

  • β = 87.060 (2)°

  • γ = 71.581 (1)°

  • V = 920.75 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 5.56 mm−1

  • T = 296 K

  • 0.20 × 0.17 × 0.16 mm

Data collection
  • Bruker APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.34, Tmax = 0.41

  • 5114 measured reflections

  • 3600 independent reflections

  • 3238 reflections with I > 2σ(I)

  • Rint = 0.013

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.118

  • S = 1.08

  • 3600 reflections

  • 241 parameters

  • 4 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 1.45 e Å−3

  • Δρmin = −2.11 e Å−3

Table 1
Selected bond lengths (Å)

Cd1—O1 2.476 (4)
Cd1—O2 2.345 (4)
Cd1—O3i 2.409 (4)
Cd1—O4i 2.435 (4)
Cd1—Br1 2.5728 (8)
Cd1—Br2 2.6162 (8)
Symmetry code: (i) x, y+1, z-1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1A⋯O2ii 0.84 (7) 2.10 (7) 2.934 (6) 174 (5)
O1W—H1B⋯Br2iii 0.83 (5) 2.65 (6) 3.467 (4) 169 (6)
Symmetry codes: (ii) x, y-1, z; (iii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The design and synthesis of coordination polymers are of great interest for their intriguing architectures and potential applications (Li et al., 2005). In this paper, the structure of the title compound is described.

As shown in Fig. 1, the CdII ion is six-coordinated by two Br- anions and four O atoms from two butane-1,4-diylbis(pyridinium-1-yl-4-carboxylate (L) ligands (Table 1). The two carboxylate groups of the L ligand display a bidentate chelating mode. The bond distances and angles are normal (Ma et al., 2000). As illustrated in Fig. 2, each L ligand bridges two CdII ions, resulting in a one-dimensional zigzag chain, with a Cd···Cd separation of 14.630 (1) Å. O—H···O and O—H···Br hydrogen bonds (Table 2) involving the uncoordinated water molecules connect the chains.

Related literature top

For the design and synthesis of coordination polymers, see: Li et al. (2005). For a related structure, see: Ma et al. (2000).

Experimental top

The ligand L was synthesized according to literature (Li et al., 2005). A mixture of Cd(NO3)2.4H2O (0.015 g), L (0.023 g), NaOH (0.004 g) and water (10 ml) was heated at 80°C for 25 min. After the mixture had been cooled to room temperature, colorless crystals of the title compound were obtained (yield: 43%).

Refinement top

H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.97 (CH2) Å and with Uiso(H)= 1.2Ueq(C). Water H atoms were located in a difference Fourier map and refined with a restraint of O—H = 0.84 (1) Å and with Uiso(H) = 1.5Ueq(O). The highest residual electron density was found at 0.33 Å from Cd1 atom and the deepest hole at 0.37 Å from Br2 atom.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) x, 1+y, -1+z.]
[Figure 2] Fig. 2. View of the zigzag chain.
catena-Poly[[[dibromidocadmium]-µ-1,1'-(butane-1,4- diyl)bis(pyridinium-4-carboxylate)] monohydrate] top
Crystal data top
[CdBr2(C16H16N2O4)]·H2OZ = 2
Mr = 590.53F(000) = 572
Triclinic, P1Dx = 2.130 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6529 (5) ÅCell parameters from 3238 reflections
b = 9.3969 (6) Åθ = 1.5–26.2°
c = 14.0198 (9) ŵ = 5.56 mm1
α = 74.410 (1)°T = 296 K
β = 87.060 (2)°Block, colorless
γ = 71.581 (1)°0.20 × 0.17 × 0.16 mm
V = 920.75 (10) Å3
Data collection top
Bruker APEX CCD
diffractometer
3600 independent reflections
Radiation source: fine-focus sealed tube3238 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
ϕ and ω scansθmax = 26.2°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.34, Tmax = 0.41k = 711
5114 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0524P)2 + 9.2463P]
where P = (Fo2 + 2Fc2)/3
3600 reflections(Δ/σ)max = 0.001
241 parametersΔρmax = 1.45 e Å3
4 restraintsΔρmin = 2.11 e Å3
Crystal data top
[CdBr2(C16H16N2O4)]·H2Oγ = 71.581 (1)°
Mr = 590.53V = 920.75 (10) Å3
Triclinic, P1Z = 2
a = 7.6529 (5) ÅMo Kα radiation
b = 9.3969 (6) ŵ = 5.56 mm1
c = 14.0198 (9) ÅT = 296 K
α = 74.410 (1)°0.20 × 0.17 × 0.16 mm
β = 87.060 (2)°
Data collection top
Bruker APEX CCD
diffractometer
3600 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3238 reflections with I > 2σ(I)
Tmin = 0.34, Tmax = 0.41Rint = 0.013
5114 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0424 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 1.45 e Å3
3600 reflectionsΔρmin = 2.11 e Å3
241 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.47375 (5)1.16457 (5)0.24196 (3)0.01263 (13)
C10.7499 (8)0.9542 (7)0.3709 (4)0.0134 (11)
C21.1656 (8)0.6169 (7)0.4914 (4)0.0131 (11)
H41.25210.53170.47640.016*
C31.0287 (8)0.7160 (7)0.4228 (4)0.0149 (11)
H31.02440.69950.36060.018*
C40.8966 (8)0.8412 (7)0.4467 (4)0.0130 (11)
C50.9054 (8)0.8616 (7)0.5403 (4)0.0142 (11)
H60.81640.94240.55850.017*
C61.0467 (8)0.7616 (6)0.6065 (4)0.0129 (11)
H51.05370.77600.66910.015*
C71.3272 (8)0.5417 (7)0.6535 (4)0.0136 (11)
H7A1.36900.60450.68610.016*
H7B1.42980.48940.61870.016*
C81.2649 (8)0.4214 (7)0.7305 (4)0.0144 (11)
H8A1.25210.34300.70080.017*
H8B1.14570.47110.75390.017*
C91.4043 (8)0.3444 (7)0.8174 (4)0.0135 (11)
H9A1.52760.31920.79230.016*
H9B1.39450.41730.85650.016*
C101.3755 (8)0.1972 (7)0.8834 (4)0.0135 (11)
H10A1.38590.12430.84420.016*
H10B1.47230.14950.93490.016*
C111.1690 (8)0.2881 (7)1.0082 (4)0.0157 (12)
H111.25930.32461.02540.019*
C121.0140 (8)0.2988 (7)1.0617 (4)0.0154 (11)
H120.99880.34161.11530.019*
C130.8779 (8)0.2448 (6)1.0353 (4)0.0127 (11)
C140.9010 (8)0.1903 (7)0.9516 (4)0.0138 (11)
H140.80860.16040.92990.017*
C151.0608 (8)0.1803 (7)0.9003 (4)0.0144 (11)
H151.07710.14220.84460.017*
C160.7200 (8)0.2339 (7)1.1034 (4)0.0146 (11)
N11.1736 (7)0.6442 (6)0.5809 (3)0.0123 (9)
N21.1936 (6)0.2255 (5)0.9307 (3)0.0103 (9)
O10.7496 (6)0.9313 (5)0.2877 (3)0.0158 (8)
O20.6345 (6)1.0670 (5)0.3958 (3)0.0169 (9)
O30.6036 (6)0.1791 (5)1.0807 (3)0.0171 (9)
O40.7215 (6)0.2727 (5)1.1822 (3)0.0181 (9)
Br10.24542 (9)1.43346 (8)0.24021 (6)0.0306 (2)
Br20.26563 (10)0.98804 (8)0.25061 (5)0.02913 (19)
O1W0.4919 (7)0.2586 (5)0.5341 (3)0.0234 (10)
H1A0.529 (11)0.199 (8)0.497 (5)0.035*
H1B0.539 (11)0.207 (9)0.590 (3)0.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0110 (2)0.0143 (2)0.0108 (2)0.00276 (16)0.00083 (14)0.00187 (15)
C10.015 (3)0.014 (3)0.013 (3)0.008 (2)0.001 (2)0.002 (2)
C20.015 (3)0.014 (3)0.012 (3)0.006 (2)0.001 (2)0.004 (2)
C30.019 (3)0.016 (3)0.011 (3)0.007 (2)0.001 (2)0.005 (2)
C40.013 (3)0.014 (3)0.014 (3)0.007 (2)0.001 (2)0.003 (2)
C50.015 (3)0.014 (3)0.014 (3)0.004 (2)0.004 (2)0.005 (2)
C60.017 (3)0.011 (3)0.010 (3)0.004 (2)0.003 (2)0.003 (2)
C70.012 (3)0.017 (3)0.011 (3)0.005 (2)0.002 (2)0.000 (2)
C80.011 (3)0.014 (3)0.016 (3)0.006 (2)0.001 (2)0.001 (2)
C90.013 (3)0.015 (3)0.011 (3)0.005 (2)0.001 (2)0.000 (2)
C100.011 (3)0.015 (3)0.012 (3)0.002 (2)0.003 (2)0.003 (2)
C110.016 (3)0.020 (3)0.013 (3)0.009 (2)0.000 (2)0.004 (2)
C120.017 (3)0.017 (3)0.013 (3)0.004 (2)0.001 (2)0.005 (2)
C130.014 (3)0.009 (3)0.012 (3)0.002 (2)0.000 (2)0.001 (2)
C140.016 (3)0.013 (3)0.011 (3)0.005 (2)0.003 (2)0.001 (2)
C150.015 (3)0.014 (3)0.014 (3)0.005 (2)0.000 (2)0.003 (2)
C160.015 (3)0.012 (3)0.014 (3)0.002 (2)0.001 (2)0.002 (2)
N10.015 (2)0.012 (2)0.010 (2)0.0066 (19)0.0010 (18)0.0004 (18)
N20.012 (2)0.010 (2)0.008 (2)0.0035 (18)0.0005 (17)0.0000 (17)
O10.017 (2)0.017 (2)0.012 (2)0.0024 (17)0.0020 (16)0.0040 (16)
O20.020 (2)0.017 (2)0.012 (2)0.0018 (17)0.0011 (16)0.0040 (16)
O30.014 (2)0.026 (2)0.012 (2)0.0086 (18)0.0017 (15)0.0031 (17)
O40.017 (2)0.025 (2)0.015 (2)0.0080 (18)0.0052 (16)0.0081 (18)
Br10.0196 (3)0.0228 (4)0.0477 (5)0.0041 (3)0.0005 (3)0.0095 (3)
Br20.0287 (4)0.0294 (4)0.0303 (4)0.0093 (3)0.0054 (3)0.0102 (3)
O1W0.030 (3)0.018 (2)0.020 (2)0.005 (2)0.0032 (19)0.0052 (18)
Geometric parameters (Å, º) top
Cd1—O12.476 (4)C8—H8A0.9700
Cd1—O22.345 (4)C8—H8B0.9700
Cd1—O3i2.409 (4)C9—C101.518 (8)
Cd1—O4i2.435 (4)C9—H9A0.9700
Cd1—Br12.5728 (8)C9—H9B0.9700
Cd1—Br22.6162 (8)C10—N21.487 (7)
C1—O11.241 (7)C10—H10A0.9700
C1—O21.266 (7)C10—H10B0.9700
C1—C41.510 (8)C11—N21.347 (7)
C2—N11.354 (7)C11—C121.361 (8)
C2—C31.377 (8)C11—H110.9300
C2—H40.9300C12—C131.398 (8)
C3—C41.394 (8)C12—H120.9300
C3—H30.9300C13—C141.385 (8)
C4—C51.383 (8)C13—C161.513 (8)
C5—C61.380 (8)C14—C151.376 (8)
C5—H60.9300C14—H140.9300
C6—N11.338 (7)C15—N21.345 (7)
C6—H50.9300C15—H150.9300
C7—N11.491 (7)C16—O31.252 (7)
C7—C81.517 (8)C16—O41.254 (7)
C7—H7A0.9700O1W—H1A0.84 (7)
C7—H7B0.9700O1W—H1B0.83 (5)
C8—C91.522 (8)
O2—Cd1—O3i127.10 (14)C8—C7—H7B109.5
O2—Cd1—O4i86.07 (15)H7A—C7—H7B108.1
O3i—Cd1—O4i54.49 (14)C7—C8—C9110.3 (5)
O2—Cd1—O154.51 (14)C7—C8—H8A109.6
O3i—Cd1—O181.38 (14)C9—C8—H8A109.6
O4i—Cd1—O178.10 (14)C7—C8—H8B109.6
O2—Cd1—Br1106.91 (10)C9—C8—H8B109.6
O3i—Cd1—Br1108.36 (11)H8A—C8—H8B108.1
O4i—Cd1—Br192.51 (10)C10—C9—C8112.4 (5)
O1—Cd1—Br1159.25 (10)C10—C9—H9A109.1
O2—Cd1—Br2104.34 (11)C8—C9—H9A109.1
O3i—Cd1—Br2103.49 (10)C10—C9—H9B109.1
O4i—Cd1—Br2156.16 (10)C8—C9—H9B109.1
O1—Cd1—Br290.43 (10)H9A—C9—H9B107.8
Br1—Cd1—Br2104.48 (3)N2—C10—C9113.1 (5)
O2—Cd1—C16i106.48 (16)N2—C10—H10A108.9
O3i—Cd1—C16i27.25 (16)C9—C10—H10A108.9
O4i—Cd1—C16i27.32 (16)N2—C10—H10B108.9
O1—Cd1—C16i76.82 (15)C9—C10—H10B108.9
Br1—Cd1—C16i103.21 (12)H10A—C10—H10B107.8
Br2—Cd1—C16i129.79 (12)N2—C11—C12121.1 (5)
O2—Cd1—C127.52 (16)N2—C11—H11119.5
O3i—Cd1—C1104.69 (16)C12—C11—H11119.5
O4i—Cd1—C181.35 (16)C11—C12—C13119.4 (5)
O1—Cd1—C126.99 (15)C11—C12—H12120.3
Br1—Cd1—C1133.92 (12)C13—C12—H12120.3
Br2—Cd1—C197.91 (12)C14—C13—C12118.4 (5)
C16i—Cd1—C191.88 (17)C14—C13—C16122.0 (5)
O1—C1—O2123.8 (5)C12—C13—C16119.3 (5)
O1—C1—C4118.2 (5)C15—C14—C13120.0 (5)
O2—C1—C4118.0 (5)C15—C14—H14120.0
O1—C1—Cd164.9 (3)C13—C14—H14120.0
O2—C1—Cd158.9 (3)N2—C15—C14120.1 (5)
C4—C1—Cd1176.8 (4)N2—C15—H15120.0
N1—C2—C3119.7 (5)C14—C15—H15120.0
N1—C2—H4120.2O3—C16—O4124.4 (6)
C3—C2—H4120.2O3—C16—C13118.5 (5)
C2—C3—C4119.9 (5)O4—C16—C13116.9 (5)
C2—C3—H3120.1O3—C16—Cd1ii61.8 (3)
C4—C3—H3120.1O4—C16—Cd1ii63.0 (3)
C5—C4—C3118.7 (5)C13—C16—Cd1ii170.2 (4)
C5—C4—C1120.9 (5)C6—N1—C2121.7 (5)
C3—C4—C1120.4 (5)C6—N1—C7118.6 (5)
C6—C5—C4119.7 (5)C2—N1—C7119.8 (5)
C6—C5—H6120.1C15—N2—C11120.8 (5)
C4—C5—H6120.1C15—N2—C10120.3 (5)
N1—C6—C5120.3 (5)C11—N2—C10118.7 (5)
N1—C6—H5119.9C1—O1—Cd188.1 (3)
C5—C6—H5119.9C1—O2—Cd193.6 (3)
N1—C7—C8110.8 (4)C16—O3—Cd1ii90.9 (3)
N1—C7—H7A109.5C16—O4—Cd1ii89.7 (4)
C8—C7—H7A109.5H1A—O1W—H1B105 (8)
N1—C7—H7B109.5
Symmetry codes: (i) x, y+1, z1; (ii) x, y1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O2iii0.84 (7)2.10 (7)2.934 (6)174 (5)
O1W—H1B···Br2iv0.83 (5)2.65 (6)3.467 (4)169 (6)
Symmetry codes: (iii) x, y1, z; (iv) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[CdBr2(C16H16N2O4)]·H2O
Mr590.53
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.6529 (5), 9.3969 (6), 14.0198 (9)
α, β, γ (°)74.410 (1), 87.060 (2), 71.581 (1)
V3)920.75 (10)
Z2
Radiation typeMo Kα
µ (mm1)5.56
Crystal size (mm)0.20 × 0.17 × 0.16
Data collection
DiffractometerBruker APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.34, 0.41
No. of measured, independent and
observed [I > 2σ(I)] reflections
5114, 3600, 3238
Rint0.013
(sin θ/λ)max1)0.620
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.118, 1.08
No. of reflections3600
No. of parameters241
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.45, 2.11

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Cd1—O12.476 (4)Cd1—O4i2.435 (4)
Cd1—O22.345 (4)Cd1—Br12.5728 (8)
Cd1—O3i2.409 (4)Cd1—Br22.6162 (8)
Symmetry code: (i) x, y+1, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O2ii0.84 (7)2.10 (7)2.934 (6)174 (5)
O1W—H1B···Br2iii0.83 (5)2.65 (6)3.467 (4)169 (6)
Symmetry codes: (ii) x, y1, z; (iii) x+1, y+1, z+1.
 

Acknowledgements

We thank Changchun Normal University for support.

References

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
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