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Acta Cryst. (2007). E63, m2200    [ doi:10.1107/S1600536807035040 ]

catena-Poly[[([mu]-4,4'-bipyridine-[kappa]2N:N')bis[aqua(dimethylformamide-[kappa]O)copper(II)]]-di-[mu]-terephthalato-[kappa]4O1:O4]

J.-Y. Xu, B.-L. Chen and S. W. Ng

Abstract top

The title coordination polymer, [Cu2(C8H4O4)2(C10H8N2)(C3H7NO)2(H2O)2]n, adopts a ladder structure in which terephthalate functions as the rails and bipyridine, lying on inversion centres, as the rungs. The Cu atom is also coordinated by water and dimethylformamide molecules in a square-pyramidal environment. Hydrogen bonds link the ladders into a three-dimensional network.

Comment top

The hydrothermal reaction of copper(II) nitrate, terephthalic acid and 4,4'-bipyridine furnishes the expected copper terephthalate adduct with 4,4'-bipyridine as a 1/1 cocrystal with terephthalic acid. The compound adopts a layer structure and the terephthalic acid behaves as a guest molecule in the porous host (Baeg & Lee, 2003). With the addition of DMF in the hydrothermal synthesis, the dimensionality of the product is lowered to a ladder structure in the present study. The compound is formally (C10H8N2)(C8H4O4)2(C3H7NO)2(H2O)2Cu2; the terephthalate represents the rails of the ladder and the N-heterocycle the rungs. The copper atom is also coordinated by water and DMF in a square-pyramidal geometry. Although the ladder appears to have voids (Fig. 2), these are actually occupied by the DMF ligands of adjacent ladders, and there are no empty spaces in the crystal structure.

Related literature top

For the crystal structure of a copper terephthalate-4,4'-bipyridine cocrystal with terephthalic acid, see Baeg & Lee (2003).

Experimental top

Copper(II) nitrate 2.5-hydrate (0.025 g, 0.11 mmol), terephthalic acid (0.018 g, 0.11 mmol) and 4,4'-bipyridine (0.009 g, 0.06 mmol) in DMF/ethanol/water (3 ml/3 ml/2 ml) were heated at 348 K for several days. Small, dark blue crystals were collected from the cooled solution in 70% yield.

Refinement top

Carbon-bound hydrogen atoms were placed at calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2–1.5 times Ueq(C). The water H atoms were located in a difference Fourier map and were refined with a distance restraint of O—H = 0.84 (1) Å; the displacement parameters were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. A portion of the ladder structure; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. [Translational code (i): x, 1 + y, z.]
[Figure 2] Fig. 2. Space-filling plot depicting the square grid formed from the bipyridine and terephthalate linkages that make up the ladder structure.
catena-Poly[[(µ-4,4'-bipyridine-κ2N:N')bis[aqua(dimethylformamide-\kO)copper(II)]]-di-µ-terephthalato-κ4O1:O4] top
Crystal data top
[Cu2(C8H4O4)2(C10H8N2)(C3H7NO)2(H2O)2]F(000) = 816
Mr = 793.71Dx = 1.599 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4717 reflections
a = 10.8424 (2) Åθ = 2.4–27.3°
b = 14.3465 (3) ŵ = 1.36 mm−1
c = 11.1929 (2) ÅT = 173 K
β = 108.741 (1)°Prism, blue
V = 1648.75 (5) Å30.15 × 0.03 × 0.02 mm
Z = 2
Data collection top
Bruker X8 APEXII
diffractometer		4415 independent reflections
Radiation source: fine-focus sealed tube3131 reflections with I > 2σ(I)
graphiteRint = 0.043
φ and ω scansθmax = 29.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→14
Tmin = 0.813, Tmax = 0.973k = −19→19
21007 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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0434P)2 + 0.0236P]
where P = (Fo2 + 2Fc2)/3
4415 reflections(Δ/σ)max = 0.001
236 parametersΔρmax = 0.47 e Å−3
2 restraintsΔρmin = −0.45 e Å−3
Crystal data top
[Cu2(C8H4O4)2(C10H8N2)(C3H7NO)2(H2O)2]V = 1648.75 (5) Å3
Mr = 793.71Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.8424 (2) ŵ = 1.36 mm−1
b = 14.3465 (3) ÅT = 173 K
c = 11.1929 (2) Å0.15 × 0.03 × 0.02 mm
β = 108.741 (1)°
Data collection top
Bruker X8 APEXII
diffractometer		3131 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.043
Tmin = 0.813, Tmax = 0.973θmax = 29.4°
21007 measured reflectionsStandard reflections: 0
4415 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086Δρmax = 0.47 e Å−3
S = 1.04Δρmin = −0.45 e Å−3
4415 reflectionsAbsolute structure: ?
236 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.53837 (2)0.371184 (17)0.64815 (2)0.01513 (8)
O10.35686 (13)0.37764 (9)0.64009 (13)0.0196 (3)
O20.27817 (13)0.40992 (10)0.43389 (12)0.0198 (3)
O3−0.35170 (13)0.37559 (10)0.45053 (13)0.0222 (3)
O4−0.27850 (13)0.36803 (9)0.66048 (13)0.0192 (3)
O50.59539 (14)0.34997 (10)0.86385 (13)0.0250 (3)
O1w0.55072 (14)0.50852 (10)0.65718 (13)0.0183 (3)
H1w10.6064 (19)0.5313 (18)0.629 (2)0.050 (9)*
H1w20.4812 (15)0.5389 (15)0.625 (2)0.037 (7)*
N10.52007 (16)0.23600 (12)0.59914 (15)0.0169 (4)
N20.5139 (2)0.37178 (13)1.02550 (16)0.0292 (4)
C10.6080 (2)0.17317 (15)0.66171 (18)0.0218 (5)
H10.67700.19310.73360.026*
C20.6031 (2)0.08068 (15)0.62679 (18)0.0227 (5)
H20.66760.03840.67470.027*
C30.50411 (19)0.04921 (14)0.52162 (17)0.0165 (4)
C40.4123 (2)0.11503 (14)0.45831 (19)0.0232 (5)
H40.34160.09720.38660.028*
C50.4237 (2)0.20588 (15)0.49936 (19)0.0239 (5)
H50.35960.24940.45430.029*
C60.26399 (19)0.39180 (13)0.53743 (18)0.0164 (4)
C70.12944 (18)0.38330 (13)0.54406 (18)0.0158 (4)
C80.02418 (19)0.39287 (14)0.43468 (18)0.0188 (4)
H80.03870.40340.35650.023*
C9−0.10098 (19)0.38726 (14)0.43854 (18)0.0196 (4)
H9−0.17220.39320.36280.024*
C10−0.12433 (19)0.37297 (13)0.55176 (18)0.0164 (4)
C11−0.0189 (2)0.36227 (15)0.66153 (19)0.0238 (5)
H11−0.03350.35170.73970.029*
C120.1059 (2)0.36693 (15)0.65759 (19)0.0231 (5)
H120.17710.35890.73300.028*
C13−0.26200 (19)0.37214 (13)0.55229 (19)0.0173 (4)
C140.5048 (2)0.35112 (15)0.90772 (19)0.0236 (5)
H140.42080.33580.85200.028*
C150.4001 (3)0.37555 (17)1.0660 (2)0.0390 (6)
H15A0.32440.35220.99840.058*
H15B0.38440.44011.08560.058*
H15C0.41450.33681.14140.058*
C160.6383 (3)0.3923 (2)1.1183 (2)0.0481 (7)
H16A0.70720.38671.07960.072*
H16B0.65480.34831.18870.072*
H16C0.63730.45601.14970.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.00697 (13)0.02238 (14)0.01633 (13)−0.00036 (10)0.00415 (9)−0.00054 (10)
O10.0070 (7)0.0310 (8)0.0204 (7)−0.0001 (6)0.0038 (6)−0.0001 (6)
O20.0123 (7)0.0279 (8)0.0207 (7)−0.0020 (6)0.0076 (6)0.0006 (6)
O30.0092 (7)0.0330 (9)0.0233 (7)0.0020 (6)0.0037 (6)0.0009 (6)
O40.0108 (7)0.0275 (8)0.0207 (7)−0.0001 (6)0.0070 (6)0.0002 (6)
O50.0178 (8)0.0371 (9)0.0197 (7)−0.0011 (7)0.0054 (6)0.0013 (6)
O1w0.0109 (8)0.0234 (8)0.0219 (7)−0.0002 (6)0.0069 (6)0.0013 (6)
N10.0108 (8)0.0241 (9)0.0161 (8)0.0004 (7)0.0046 (6)0.0004 (7)
N20.0340 (12)0.0355 (11)0.0175 (9)0.0008 (9)0.0075 (8)−0.0031 (8)
C10.0176 (11)0.0270 (12)0.0175 (10)−0.0003 (9)0.0008 (8)0.0003 (9)
C20.0187 (11)0.0243 (12)0.0200 (10)0.0020 (9)−0.0008 (9)0.0021 (9)
C30.0125 (10)0.0247 (11)0.0140 (9)0.0000 (8)0.0063 (8)0.0028 (8)
C40.0154 (10)0.0266 (12)0.0217 (10)0.0023 (9)−0.0024 (9)−0.0030 (9)
C50.0158 (11)0.0256 (12)0.0249 (11)0.0040 (9)−0.0010 (9)−0.0013 (9)
C60.0122 (10)0.0158 (10)0.0224 (10)−0.0008 (8)0.0073 (8)−0.0017 (8)
C70.0097 (9)0.0183 (10)0.0206 (10)0.0008 (8)0.0066 (8)0.0010 (8)
C80.0147 (10)0.0259 (11)0.0174 (9)−0.0005 (9)0.0075 (8)−0.0012 (8)
C90.0096 (9)0.0283 (12)0.0192 (10)0.0012 (8)0.0023 (8)−0.0022 (8)
C100.0089 (9)0.0180 (10)0.0238 (10)−0.0001 (8)0.0075 (8)−0.0007 (8)
C110.0140 (11)0.0383 (13)0.0212 (10)0.0021 (9)0.0088 (8)0.0067 (9)
C120.0109 (10)0.0372 (13)0.0199 (10)0.0016 (9)0.0031 (8)0.0043 (9)
C130.0105 (9)0.0169 (10)0.0259 (10)−0.0001 (8)0.0077 (8)−0.0005 (8)
C140.0251 (12)0.0275 (12)0.0159 (10)−0.0003 (9)0.0036 (9)0.0012 (8)
C150.0495 (17)0.0443 (16)0.0333 (13)0.0032 (13)0.0275 (12)−0.0036 (11)
C160.0508 (18)0.0621 (19)0.0228 (12)−0.0050 (14)−0.0001 (12)−0.0094 (12)
Geometric parameters (Å, °) top
Cu1—O11.943 (1)C3—C3iii1.486 (4)
Cu1—O4i1.946 (1)C4—C51.374 (3)
Cu1—O52.312 (1)C4—H40.950
Cu1—O1w1.975 (2)C5—H50.950
Cu1—N12.008 (2)C6—C71.489 (3)
O1—C61.277 (2)C7—C81.387 (3)
O2—C61.245 (2)C7—C121.394 (3)
O3—C131.238 (2)C8—C91.374 (3)
O4—C131.281 (2)C8—H80.950
O4—Cu1ii1.9462 (14)C9—C101.385 (3)
O5—C141.231 (3)C9—H90.950
O1w—H1w10.83 (1)C10—C111.392 (3)
O1w—H1w20.84 (1)C10—C131.495 (3)
N1—C51.333 (3)C11—C121.369 (3)
N1—C11.335 (3)C11—H110.950
N2—C141.324 (3)C12—H120.950
N2—C161.444 (3)C14—H140.950
N2—C151.445 (3)C15—H15A0.980
C1—C21.379 (3)C15—H15B0.980
C1—H10.950C15—H15C0.980
C2—C31.389 (3)C16—H16A0.980
C2—H20.950C16—H16B0.980
C3—C41.390 (3)C16—H16C0.980
O1—Cu1—O4i178.07 (6)O2—C6—C7118.66 (17)
O1—Cu1—O1w90.33 (6)O1—C6—C7116.35 (17)
O4i—Cu1—O1w88.21 (6)C8—C7—C12118.79 (18)
O1—Cu1—N191.36 (6)C8—C7—C6119.31 (17)
O4i—Cu1—N190.34 (6)C12—C7—C6121.90 (17)
O1w—Cu1—N1167.58 (6)C9—C8—C7120.50 (18)
O1—Cu1—O588.96 (6)C9—C8—H8119.8
O4i—Cu1—O589.91 (5)C7—C8—H8119.8
O1w—Cu1—O594.98 (5)C8—C9—C10120.69 (18)
N1—Cu1—O597.35 (6)C8—C9—H9119.7
C6—O1—Cu1122.90 (13)C10—C9—H9119.7
C13—O4—Cu1ii112.40 (12)C9—C10—C11118.94 (18)
C14—O5—Cu1115.77 (13)C9—C10—C13118.77 (17)
Cu1—O1w—H1w1114.6 (19)C11—C10—C13122.27 (18)
Cu1—O1w—H1w2117.2 (17)C12—C11—C10120.41 (19)
H1w1—O1w—H1w2107 (3)C12—C11—H11119.8
C5—N1—C1117.13 (18)C10—C11—H11119.8
C5—N1—Cu1121.62 (14)C11—C12—C7120.65 (19)
C1—N1—Cu1121.18 (14)C11—C12—H12119.7
C14—N2—C16121.0 (2)C7—C12—H12119.7
C14—N2—C15121.5 (2)O3—C13—O4124.35 (18)
C16—N2—C15117.4 (2)O3—C13—C10119.09 (18)
N1—C1—C2123.03 (18)O4—C13—C10116.56 (17)
N1—C1—H1118.5O5—C14—N2125.9 (2)
C2—C1—H1118.5O5—C14—H14117.0
C1—C2—C3120.10 (19)N2—C14—H14117.0
C1—C2—H2120.0N2—C15—H15A109.5
C3—C2—H2120.0N2—C15—H15B109.5
C2—C3—C4116.30 (19)H15A—C15—H15B109.5
C2—C3—C3iii122.3 (2)N2—C15—H15C109.5
C4—C3—C3iii121.4 (2)H15A—C15—H15C109.5
C5—C4—C3120.08 (18)H15B—C15—H15C109.5
C5—C4—H4120.0N2—C16—H16A109.5
C3—C4—H4120.0N2—C16—H16B109.5
N1—C5—C4123.35 (19)H16A—C16—H16B109.5
N1—C5—H5118.3N2—C16—H16C109.5
C4—C5—H5118.3H16A—C16—H16C109.5
O2—C6—O1124.98 (18)H16B—C16—H16C109.5
O1w—Cu1—O1—C683.52 (14)Cu1—O1—C6—O2−5.7 (3)
N1—Cu1—O1—C6−84.17 (15)Cu1—O1—C6—C7172.75 (12)
O5—Cu1—O1—C6178.50 (14)O2—C6—C7—C82.0 (3)
O1—Cu1—O5—C14−1.64 (15)O1—C6—C7—C8−176.58 (17)
O4i—Cu1—O5—C14176.79 (15)O2—C6—C7—C12−177.32 (19)
O1w—Cu1—O5—C1488.60 (15)O1—C6—C7—C124.1 (3)
N1—Cu1—O5—C14−92.88 (15)C12—C7—C8—C90.7 (3)
O1—Cu1—N1—C550.14 (17)C6—C7—C8—C9−178.65 (18)
O4i—Cu1—N1—C5−130.78 (17)C7—C8—C9—C100.7 (3)
O1w—Cu1—N1—C5−47.6 (4)C8—C9—C10—C11−1.4 (3)
O5—Cu1—N1—C5139.27 (16)C8—C9—C10—C13176.95 (18)
O1—Cu1—N1—C1−133.23 (16)C9—C10—C11—C120.8 (3)
O4i—Cu1—N1—C145.85 (16)C13—C10—C11—C12−177.54 (19)
O1w—Cu1—N1—C1129.0 (3)C10—C11—C12—C70.6 (3)
O5—Cu1—N1—C1−44.10 (16)C8—C7—C12—C11−1.3 (3)
C5—N1—C1—C20.6 (3)C6—C7—C12—C11177.98 (19)
Cu1—N1—C1—C2−176.20 (16)Cu1ii—O4—C13—O3−1.6 (2)
N1—C1—C2—C30.5 (3)Cu1ii—O4—C13—C10178.28 (12)
C1—C2—C3—C4−1.3 (3)C9—C10—C13—O36.6 (3)
C1—C2—C3—C3iii178.7 (2)C11—C10—C13—O3−175.09 (19)
C2—C3—C4—C51.1 (3)C9—C10—C13—O4−173.25 (17)
C3iii—C3—C4—C5−178.9 (2)C11—C10—C13—O45.1 (3)
C1—N1—C5—C4−0.8 (3)Cu1—O5—C14—N2−155.75 (18)
Cu1—N1—C5—C4175.95 (16)C16—N2—C14—O5−2.5 (3)
C3—C4—C5—N10.0 (3)C15—N2—C14—O5176.9 (2)
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O2iv0.83 (1)1.83 (1)2.658 (2)175 (3)
O1w—H1w2···O3v0.84 (1)1.85 (1)2.684 (2)168 (3)
Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.943 (1)Cu1—O1w1.975 (2)
Cu1—O4i1.946 (1)Cu1—N12.008 (2)
Cu1—O52.312 (1)
Symmetry codes: (i) x+1, y, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O2ii0.83 (1)1.83 (1)2.658 (2)175 (3)
O1w—H1w2···O3iii0.84 (1)1.85 (1)2.684 (2)168 (3)
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.
Acknowledgements top

We thank the China Pharmaceutical University, the University of Texas – Pan American, the Welch Foundation (grant No. BG-0017) and the University of Malaya (F0263/2007B) for supporting this study.

references
References top

Baeg, J. Y. & Lee, S. W. (2003). Inorg. Chem. Commun. 6, 313–316.

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2004). APEX2 (Version 1.2) and SAINT (Version 7.06A). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.