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The asymmetric unit of the title compound, {[Cu(CO3)(C14H14N4)1.5]·0.5C14H14N4·5H2O}n, contains one CuII cation in a slightly distorted square-pyramidal coordination environment, one CO32− anion, one full and two half 1,4-bis­(imidazol-1-ylmeth­yl)benzene (bix) ligands, one half-mol­ecule of which is uncoordinated, and five uncoordinated water mol­ecules. One of the coordinated bix ligands and the uncoordinated bix mol­ecule are situated about centers of symmetry, located at the centers of the benzene rings. The coordinated bix ligands link the copper(II) ions into a [Cu(bix)1.5]n mol­ecular ladder. These mol­ecular ladders do not form inter­penetrated ladders but are arranged in an ABAB parallel terrace, i.e. with the ladders arranged one above another, with sequence A translated with respect to B by 8 Å. To best of our knowledge, this arrangement has not been observed in any of the mol­ecular ladder frameworks synthesized to date. The coordination environment of the CuII atom is completed by two O atoms of the CO32− anion. The framework is further strengthened by extensive O—H...O and O—H...N hydrogen bonds involving the water mol­ecules, the O atoms of the CO32− anion and the N atoms of the bix ligands. This study describes the first example of a mol­ecular ladder coordination polymer based on bix and therefore demonstrates further the usefulness of bix as a versatile multidentate ligand for constructing coordination polymers with inter­esting architectures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108028722/hj3087sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028722/hj3087Isup2.hkl
Contains datablock I

CCDC reference: 707202

Comment top

Owing to their fascinating properties and potential applications to gas storage, molecular sieves, size- or shape-selective catalysis, and ion exchange (Noro et al., 2000; Eddaoudi et al., 2002) in functional materials, the construction of organic–inorganic open framework complexes with variable cavities or channels has attracted considerable interest in the past decade (Tong et al., 1999; Wu et al., 2006; Zhang et al., 2006). These studies have shown that the careful selection of appropriate multidentate bridging ligands is helpful not only to tailor effectively the polymer architectures but also to realize various applications. The use of long bidentate nitrogen ligand spacers has afforded very interesting structural motifs, such as double helices (Carlucci et al., 1997), multiple sheets (Hennigar et al., 1997), interpenetrated ladders (Fujita et al., 1998) and other noteworthy species. Many of the architectures reported to date, however, are based on rigid, linear, linker, bidentate nitrogen ligands, with efforts only recently being focused on the use of ligands showing conformational flexibility (Carlucci et al., 2000). In addition, the design of coordination polymers from flexible ligands is highly influenced by factors such as the nature of coordination of the metal ion, the length and flexibility of the organic ligand, the metal–ligand ratio, and the possible influences of the counter-anion and solvent. Recently, we have begun to work on the architectures of polymeric structures containing flexible ligands. We describe here the synthesis and structure of a new metal–organic molecular ladder, (I), formed from bix ligands and copper sulfate.

The X-ray diffraction analysis reveals the title complex is a unique `parallel terrace' molecular ladder structure with molecular formula {[Cu(CO3)(C14H14N4)1.5].0.5C14H14N4.5H2O}n. Each Cu center in the title complex is five-coordinated, with one N atom from a bix ligand located in the apical position, and two bix N atoms and two O atoms from the CO32- anion located in the basal plane, as shown in Fig. 1. The τ value for the coordination environment of the Cu atom is 0.36, showing that the Cu atom is in a slightly distorted square-pyramidal arrangement (τ ranges between 0 and 1 for square-pyramidal and trigonal–bipyramidal structures, respectively (Addision & Rao, 1984 ). The Cu—N distances range from 1.963 (5) to 2.123 (5) Å, and the Cu—O distances are 1.966 (3) and 1.993 (3) Å. The bix ligands link the copper(II) ions into a [Cu(bix)1.5]n ladder. The bix ligands adopt two different conformations (A and B) in the ladder: the sides of the ladder adopt conformation A, with a dihedral angle of the two imidazol rings of 46°; the rungs of the ladder adopt conformation B, where the dihedral angle of the two imidazol rings is 0°, as the two imidazol ring are almost [or exactly if angle is 0°?] parallel to each other. The CO32- ligands not only act as a µ2-bridge through two O atoms to complete the coordination geometry of CuII but also act to balance the charge in the structure.

Generally, molecular ladders occur in a T-shaped unit, formed by quasi-octahedrally or octahedrally coordinated metal centers and rod-like ligands, and exhibit the phenomenon of interpenetration (Fujita et al., 1995; Blake et al.,1997). Large cavities between the rungs of the ladders encourage the inclusion of discrete symmetry-related ladders. Interpenetration was found to be perpendicular to the orientation of the original ladder to generate a three-dimensional polycatenated structure (Hennigar et al., 1997). Another interpenetrating example of a molecular ladder was decribed by Blake et al. (1997). The packing of polymer (I) is very interesting. As shown in Fig. 2, the molecular ladders do not form an interpenetrated structure. Each ladder has two ladders above it, so as to fill the spaces between the rungs of the ladder, and the ladders are arranged in an ABAB parallel terrace sequence as A is translated with respect to B by ca 8 Å . To the authors' knowledge, this fascinating (one-dimensional-to-one-dimensional) parallel terrace array shows a type of arrangement of molecular ladder that has not been observed in any of the molecular ladder frameworks synthesized to date. The structure is further stabilized by extensive O—H···N hydrogen bonds involving the water molecules, the carbonate O atoms and the N atoms of the bix ligands, as shown in Fig. 3. When O—H···O hydrogen bonds between the uncoordinated water molecules and the CO32- ligands, and O—H···N hydrogen bonds between the uncoordinated water molecules and the bix ligands, are omitted, one-dimensional water chains emerge. As shown in Fig. 4, the one-dimensional water chain is built up from four- and six-membered rings arranged alternately. The one-dimensional water chain stucture constitutes a potential form of water that is poorly understood (Liu & Xu, 2005). Many fundamental biological processes appear to depend on the unique properties of water chains. However, the nature for acquiring the structural constraints in stabilizing one-dimensional chains is not fully understood (Cheruzel et al., 2003). The one-dimensional water chains reported here represent a rare example.

Finally, it is worth mentioning that the CO32- anion may be formed by an in situ oxidation reaction from the bix ligand or originate from atmospheric carbon dioxide, as there were no carbon complexes except the bix ligands and carbon dioxide in the starting reaction mixture. The bond lengths C29—O1 [1.289 (5) Å], C29—O2 [1.276 (5) Å] and C29—O3 [1.241 (5) Å], and the O—C—O angles O1—C29—O2 [113.3 (4)°], O2—C29—O3 [122.3 (4)°] and O1—C29—O3[124.4 (4)°] for the CO32- anion are comparable to those reported in the complex [Co(C3H10N2)2(CO3)]Cl.H2O (Zhu & Chen, 1999). When using CuCO3 instead of CuSO4, the title compound could not be obtained, indicating that SO4 may play an important role in the formation of the title compound, although it did not appear in the molecular formula of the final compound.

Related literature top

For related literature, see: Blake et al. (1997); Carlucci et al. (1997, 2000); Cheruzel et al. (2003); Eddaoudi, Kim, Rosi, Vodak, Wachter, Keeffe, Yaghi & Science (2002); Fujita et al. (1995, 1998); Hennigar et al. (1997); Liu, Xu & CrystEngComm (2005); Noro, Kitagawa, Kondo, Seki, Angew & Chem (2000); Tong et al. (1999); Wu et al. (2006); Zhang et al. (2006); Zhu, Chen & Acta Cryst (1999).

Experimental top

A mixture of CuSO4.5H2O (0.50 mmol, 0.14 g), bix (1.00 mmol, 0.24 g) and water (15 ml) was stirred vigorously while the pH value was adjusted to 6 by the addition of 10% NaOH. The mixture was then heated at 433 K for 3 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. After cooling to room temperature at 50 K h-1, blue prismatic crystals were isolated, which were washed with ethanol and dried in air (yield 42%, based on Cu). Elemental analyses found: C 50.45, H 5.72, N 16.21%; calculated: C 50.47, H 5.55, N16.23%. IR (KBr, cm-1): 3415 (m), 3102 (m), 1645 (m), 1566 (s), 1521 (w), 1442 (m), 1386 (m), 1300 (m), 1245 (m), 1090 (m), 1024 (m), 952 (w), 878 (w), 848 (w), 742 (w), 718 (w), 659 (m), 622 (w), 517 (w), 466 (w).

Refinement top

C-bound H atoms were positioned geometrically and treated using a riding model, fixing the C—H bond lengths at 0.97 and 0.93 Å for CH2 and aromatic CH groups, respectively [Uiso(H) = 1.2Ueq(C)]. Water H atoms were located from difference maps and refined with O—H distance restraints of 0.86 (5) Å [Uiso(H) = 1.2Ueq(O)].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994) and XPREP in SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The local coordination around the CuII ion in (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x - 1, y - 1, z; (viii) -x - 1, -y, -z + 1.]
[Figure 2] Fig. 2. Parallel terrace arrangement of the molecular ladder in (I). H atoms, uncoordinated bix ligands and water molecules have been omitted for clarity.
[Figure 3] Fig. 3. The crystal packing of (I). Hydrogen bonds are shown as dashed lines; uncoordinated bix ligands and H atoms have been omitted for clarity.
[Figure 4] Fig. 4. The one-dimensional water chains in (I). Dashed lines represent hydrogen bonds.
Poly[(carbonato-κ2O,O')bis[µ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ2N:N']copper(II) 1,4-bis(imidazol-1-ylmethyl)benzene hemisolvate pentahydrate] top
Crystal data top
[Cu(CO3)(C14H14N4)1.5]·0.5C14H14N4·5H2OZ = 2
Mr = 690.22F(000) = 722
Triclinic, P1Dx = 1.432 Mg m3
a = 12.2286 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.4976 (7) ÅCell parameters from 3621 reflections
c = 12.951 Åθ = 2.1–27.5°
α = 103.759 (15)°µ = 0.74 mm1
β = 98.726 (12)°T = 293 K
γ = 118.767 (9)°Prism, blue
V = 1600.8 (3) Å30.20 × 0.15 × 0.05 mm
Data collection top
Bruker P4
diffractometer
7352 independent reflections
Radiation source: fine-focus sealed tube5723 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1515
Tmin = 0.875, Tmax = 0.963k = 1611
12466 measured reflectionsl = 1516
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0584P)2 + 0.5166P]
where P = (Fo2 + 2Fc2)/3
7352 reflections(Δ/σ)max = 0.019
49 parametersΔρmax = 0.52 e Å3
7 restraintsΔρmin = 0.60 e Å3
Crystal data top
[Cu(CO3)(C14H14N4)1.5]·0.5C14H14N4·5H2Oγ = 118.767 (9)°
Mr = 690.22V = 1600.8 (3) Å3
Triclinic, P1Z = 2
a = 12.2286 (2) ÅMo Kα radiation
b = 12.4976 (7) ŵ = 0.74 mm1
c = 12.951 ÅT = 293 K
α = 103.759 (15)°0.20 × 0.15 × 0.05 mm
β = 98.726 (12)°
Data collection top
Bruker P4
diffractometer
7352 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
5723 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 0.963Rint = 0.019
12466 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0477 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.52 e Å3
7352 reflectionsΔρmin = 0.60 e Å3
49 parameters
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*/Ueq
Cu10.11200 (8)0.28708 (6)0.48515 (6)0.0453 (3)
N10.3282 (5)0.0384 (5)0.9232 (4)0.0725 (12)
N20.4264 (4)0.2533 (4)0.8619 (3)0.0557 (9)
N30.0714 (5)0.1632 (4)0.6140 (4)0.0424 (11)
N40.2303 (3)0.0233 (3)0.7483 (3)0.0415 (7)
N50.8359 (3)0.5612 (3)0.5314 (3)0.0428 (7)
N60.8253 (3)0.4506 (3)0.6415 (3)0.0463 (8)
N70.2950 (3)0.1077 (3)0.6222 (3)0.0433 (7)
N80.2250 (3)0.2319 (3)0.5537 (3)0.0430 (7)
O10.0943 (4)0.3591 (3)0.3383 (3)0.0674 (9)
O1W1.1623 (9)0.5795 (8)1.1702 (8)0.117 (3)
H1WA1.129 (13)0.616 (11)1.196 (10)0.140*
H1WB1.131 (12)0.506 (7)1.223 (8)0.140*
O20.0688 (4)0.1707 (3)0.3986 (3)0.0675 (9)
O2W0.9612 (6)0.6079 (5)0.9426 (4)0.1035 (15)
H2WA0.974 (7)0.667 (5)0.886 (5)0.124*
H2WB0.903 (6)0.536 (4)0.947 (6)0.124*
O30.0379 (4)0.2304 (4)0.2367 (3)0.0807 (11)
O3W0.0683 (4)0.1886 (4)0.8758 (4)0.0832 (11)
H3WA0.006 (5)0.200 (6)0.888 (6)0.100*
H3WB0.040 (6)0.120 (5)0.861 (6)0.100*
O4W0.0247 (6)0.0662 (5)0.1206 (4)0.0935 (13)
H4WA0.011 (7)0.097 (7)0.168 (4)0.112*
H4WB0.032 (7)0.111 (6)0.058 (3)0.112*
O5W1.1286 (5)0.7671 (4)1.0416 (4)0.0802 (11)
H5WA1.071 (5)0.714 (5)1.021 (5)0.096*
H5WB1.205 (4)0.838 (4)1.014 (6)0.096*
C10.3116 (5)0.1361 (5)0.9027 (4)0.0637 (12)
H1A0.22970.12600.91480.076*
C20.4582 (7)0.0946 (6)0.8938 (5)0.0736 (15)
H2A0.50000.04890.89840.088*
C30.5204 (5)0.2246 (6)0.8569 (4)0.0693 (14)
H3A0.61080.28410.83250.083*
C40.4431 (7)0.3818 (6)0.8307 (5)0.0818 (17)
H4A0.36350.37320.81810.098*
H4B0.51420.43940.76090.098*
C50.4728 (5)0.4436 (4)0.9190 (4)0.0592 (12)
C60.5981 (5)0.5073 (5)0.9264 (4)0.0653 (13)
H6A0.66560.51270.87660.078*
C70.3750 (5)0.4369 (5)0.9931 (5)0.0648 (13)
H7A0.28990.39430.98930.078*
C80.1314 (4)0.0337 (4)0.6538 (3)0.0423 (8)
H8A0.10650.01190.61910.051*
C90.1411 (4)0.1866 (4)0.6916 (4)0.0480 (9)
H9A0.12290.26910.68730.058*
C100.2382 (4)0.0732 (4)0.7735 (4)0.0521 (10)
H10A0.29810.06310.83460.063*
C110.3150 (4)0.1639 (4)0.8132 (4)0.0528 (10)
H11A0.33050.17750.89230.063*
H11B0.27000.20630.79490.063*
C120.4446 (4)0.2264 (4)0.7913 (3)0.0440 (9)
C130.4592 (4)0.2732 (4)0.7052 (3)0.0487 (9)
H13A0.38710.26480.65910.058*
C140.5783 (4)0.3324 (4)0.6859 (4)0.0492 (10)
H14A0.58580.36360.62730.059*
C150.6872 (4)0.3459 (4)0.7531 (3)0.0439 (9)
C160.6727 (4)0.2975 (4)0.8392 (3)0.0489 (10)
H16A0.74430.30450.88460.059*
C170.5533 (4)0.2391 (4)0.8581 (3)0.0495 (10)
H17A0.54530.20760.91660.059*
C180.8222 (4)0.4160 (5)0.7411 (4)0.0611 (13)
H18A0.87910.49520.80650.073*
H18B0.85730.36080.73930.073*
C190.8401 (4)0.5607 (4)0.6332 (3)0.0442 (9)
H19A0.85190.62870.69210.053*
C200.8095 (5)0.3755 (4)0.5380 (4)0.0642 (13)
H20A0.79670.29280.51790.077*
C210.8160 (5)0.4440 (4)0.4707 (4)0.0555 (11)
H21A0.80830.41620.39520.067*
C220.2002 (4)0.1122 (4)0.5867 (3)0.0421 (8)
H22A0.12580.03990.58540.051*
C230.3431 (4)0.3077 (4)0.5691 (4)0.0498 (10)
H23A0.38590.39730.55330.060*
C240.3877 (4)0.2322 (4)0.6108 (4)0.0504 (10)
H24A0.46570.25930.62820.061*
C250.3009 (5)0.0088 (4)0.6623 (4)0.0535 (11)
H25A0.21590.08620.67620.064*
H25B0.32070.01450.73250.064*
C260.4039 (4)0.0048 (4)0.5786 (3)0.0409 (8)
C270.5209 (4)0.0204 (4)0.5969 (3)0.0483 (10)
H27A0.53630.03420.66210.058*
C280.3843 (4)0.0252 (4)0.4814 (4)0.0476 (9)
H28A0.30590.04260.46790.057*
C290.0661 (4)0.2529 (4)0.3205 (3)0.0499 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0706 (5)0.0298 (4)0.0429 (4)0.0280 (4)0.0248 (3)0.0182 (3)
N10.094 (3)0.070 (3)0.068 (3)0.052 (3)0.025 (2)0.032 (2)
N20.093 (3)0.068 (2)0.068 (2)0.049 (2)0.0243 (18)0.0350 (18)
N30.044 (3)0.033 (2)0.050 (3)0.020 (2)0.017 (2)0.016 (2)
N40.0395 (17)0.0359 (17)0.0440 (17)0.0157 (14)0.0184 (14)0.0130 (13)
N50.057 (2)0.0290 (15)0.0456 (17)0.0223 (15)0.0216 (15)0.0170 (13)
N60.0435 (18)0.0423 (18)0.057 (2)0.0194 (15)0.0187 (15)0.0310 (16)
N70.0500 (19)0.0460 (18)0.0457 (18)0.0334 (16)0.0147 (15)0.0185 (14)
N80.0471 (18)0.0393 (17)0.0491 (18)0.0269 (15)0.0146 (14)0.0182 (14)
O10.086 (4)0.043 (2)0.038 (3)0.028 (3)0.042 (3)0.024 (2)
O1W0.109 (4)0.082 (3)0.127 (5)0.057 (3)0.017 (3)0.012 (3)
O20.088 (4)0.043 (2)0.039 (3)0.026 (3)0.041 (3)0.026 (2)
O2W0.137 (4)0.082 (3)0.097 (4)0.057 (3)0.055 (3)0.036 (3)
O30.128 (3)0.065 (2)0.054 (2)0.045 (2)0.044 (2)0.0370 (17)
O3W0.090 (3)0.083 (3)0.099 (3)0.056 (3)0.039 (2)0.040 (2)
O4W0.150 (4)0.092 (3)0.084 (3)0.081 (3)0.061 (3)0.052 (3)
O5W0.097 (3)0.076 (3)0.089 (3)0.051 (2)0.048 (2)0.043 (2)
C10.066 (3)0.078 (4)0.059 (3)0.045 (3)0.020 (2)0.029 (3)
C20.106 (5)0.091 (4)0.073 (3)0.076 (4)0.043 (3)0.047 (3)
C30.067 (3)0.092 (4)0.063 (3)0.047 (3)0.026 (2)0.038 (3)
C40.069 (5)0.088 (3)0.060 (3)0.051 (4)0.027 (3)0.037 (3)
C50.083 (3)0.044 (2)0.051 (2)0.036 (2)0.023 (2)0.0126 (19)
C60.076 (3)0.055 (3)0.060 (3)0.039 (3)0.009 (2)0.014 (2)
C70.069 (3)0.050 (3)0.073 (3)0.032 (2)0.026 (3)0.016 (2)
C80.044 (2)0.0319 (18)0.050 (2)0.0183 (16)0.0173 (17)0.0177 (16)
C90.049 (2)0.041 (2)0.065 (3)0.0273 (19)0.024 (2)0.0270 (19)
C100.046 (2)0.055 (3)0.058 (3)0.025 (2)0.0143 (19)0.028 (2)
C110.051 (2)0.038 (2)0.051 (2)0.0141 (18)0.0206 (19)0.0041 (17)
C120.043 (2)0.0319 (19)0.039 (2)0.0123 (16)0.0095 (16)0.0050 (15)
C130.040 (2)0.046 (2)0.047 (2)0.0165 (18)0.0040 (17)0.0159 (18)
C140.044 (2)0.050 (2)0.046 (2)0.0176 (19)0.0077 (17)0.0279 (18)
C150.040 (2)0.039 (2)0.045 (2)0.0136 (16)0.0079 (16)0.0223 (16)
C160.046 (2)0.049 (2)0.047 (2)0.0196 (19)0.0075 (17)0.0276 (18)
C170.057 (2)0.045 (2)0.040 (2)0.0195 (19)0.0161 (18)0.0210 (17)
C180.044 (2)0.063 (3)0.040 (3)0.023 (2)0.016 (2)0.021 (3)
C190.052 (2)0.0351 (19)0.044 (2)0.0204 (17)0.0200 (17)0.0169 (16)
C200.093 (4)0.039 (2)0.075 (3)0.040 (2)0.035 (3)0.028 (2)
C210.084 (3)0.033 (2)0.054 (2)0.032 (2)0.029 (2)0.0178 (18)
C220.043 (2)0.038 (2)0.050 (2)0.0243 (17)0.0148 (17)0.0190 (17)
C230.047 (2)0.043 (2)0.062 (3)0.0242 (19)0.0141 (19)0.0258 (19)
C240.048 (2)0.057 (3)0.059 (3)0.032 (2)0.0224 (19)0.031 (2)
C250.066 (3)0.055 (3)0.049 (2)0.044 (2)0.014 (2)0.0121 (19)
C260.049 (2)0.0372 (19)0.045 (2)0.0291 (17)0.0181 (16)0.0127 (16)
C270.064 (3)0.056 (2)0.049 (2)0.042 (2)0.033 (2)0.0275 (19)
C280.048 (2)0.054 (2)0.061 (2)0.035 (2)0.0307 (19)0.028 (2)
C290.067 (3)0.039 (2)0.041 (2)0.025 (2)0.0167 (19)0.0196 (17)
Geometric parameters (Å, º) top
Cu1—N5i1.963 (3)C4—H4A0.9700
Cu1—O21.966 (3)C4—H4B0.9700
Cu1—O11.993 (3)C5—C71.369 (7)
Cu1—N82.041 (3)C5—C61.378 (7)
Cu1—N32.123 (5)C6—C7iii1.383 (8)
Cu1—C292.369 (4)C6—H6A0.9300
N1—C11.304 (7)C7—C6iii1.383 (8)
N1—C21.334 (7)C7—H7A0.9300
N2—C11.350 (7)C8—H8A0.9300
N2—C31.357 (6)C9—C101.352 (6)
N2—C41.461 (6)C9—H9A0.9300
N3—C81.324 (5)C10—H10A0.9300
N3—C91.394 (7)C11—C121.501 (6)
N4—C81.332 (5)C11—H11A0.9700
N4—C101.364 (5)C11—H11B0.9700
N4—C111.466 (5)C12—C131.374 (6)
N5—C191.314 (5)C12—C171.387 (6)
N5—C211.369 (5)C13—C141.376 (6)
N5—Cu1ii1.963 (3)C13—H13A0.9300
N6—C191.333 (5)C14—C151.387 (5)
N6—C201.365 (6)C14—H14A0.9300
N6—C181.454 (5)C15—C161.385 (5)
N7—C221.331 (5)C15—C181.506 (6)
N7—C241.367 (6)C16—C171.376 (6)
N7—C251.465 (5)C16—H16A0.9300
N8—C221.317 (5)C17—H17A0.9300
N8—C231.373 (5)C18—H18A0.9700
O1—C291.289 (5)C18—H18B0.9700
O1W—H1WA0.83 (16)C19—H19A0.9300
O1W—H1WB0.86 (5)C20—C211.345 (6)
O2—C291.276 (5)C20—H20A0.9300
O2W—H2WA0.83 (10)C21—H21A0.9300
O2W—H2WB0.82 (5)C22—H22A0.9300
O3—C291.241 (5)C23—C241.349 (6)
O3W—H3WA0.84 (10)C23—H23A0.9300
O3W—H3WB0.85 (9)C24—H24A0.9300
O4W—H4WA0.84 (10)C25—C261.505 (6)
O4W—H4WB0.83 (4)C25—H25A0.9700
O5W—H5WA0.84 (5)C25—H25B0.9700
O5W—H5WB0.86 (5)C26—C281.376 (6)
C1—H1A0.9300C26—C271.381 (5)
C2—C31.334 (8)C27—C28iv1.386 (6)
C2—H2A0.9300C27—H27A0.9300
C3—H3A0.9300C28—C27iv1.386 (6)
C4—C51.521 (7)C28—H28A0.9300
N5i—Cu1—O2163.80 (13)N3—C9—H9A124.8
N5i—Cu1—O198.53 (13)C9—C10—N4105.9 (4)
O2—Cu1—O165.57 (13)C9—C10—H10A127.1
N5i—Cu1—N896.19 (13)N4—C10—H10A127.1
O2—Cu1—N895.13 (14)N4—C11—C12112.7 (3)
O1—Cu1—N8141.92 (15)N4—C11—H11A109.0
N5i—Cu1—N394.9 (2)C12—C11—H11A109.0
O2—Cu1—N394.3 (2)N4—C11—H11B109.0
O1—Cu1—N3112.5 (2)C12—C11—H11B109.0
N8—Cu1—N3100.90 (19)H11A—C11—H11B107.8
N5i—Cu1—C29131.49 (14)C13—C12—C17118.2 (4)
O2—Cu1—C2932.60 (13)C13—C12—C11121.1 (4)
O1—Cu1—C2932.98 (13)C17—C12—C11120.7 (4)
N8—Cu1—C29121.67 (14)C12—C13—C14121.3 (4)
N3—Cu1—C29105.22 (14)C12—C13—H13A119.4
C1—N1—C2104.6 (5)C14—C13—H13A119.4
C1—N2—C3104.9 (4)C13—C14—C15120.6 (4)
C1—N2—C4126.7 (5)C13—C14—H14A119.7
C3—N2—C4128.4 (5)C15—C14—H14A119.7
C8—N3—C9103.1 (4)C16—C15—C14118.4 (4)
C8—N3—Cu1122.7 (4)C16—C15—C18118.0 (3)
C9—N3—Cu1132.3 (3)C14—C15—C18123.5 (4)
C8—N4—C10107.5 (3)C17—C16—C15120.5 (4)
C8—N4—C11126.2 (4)C17—C16—H16A119.7
C10—N4—C11126.3 (4)C15—C16—H16A119.7
C19—N5—C21105.9 (3)C16—C17—C12121.0 (4)
C19—N5—Cu1ii126.4 (3)C16—C17—H17A119.5
C21—N5—Cu1ii126.3 (3)C12—C17—H17A119.5
C19—N6—C20106.7 (4)N6—C18—C15114.0 (3)
C19—N6—C18126.2 (4)N6—C18—H18A108.7
C20—N6—C18127.0 (4)C15—C18—H18A108.7
C22—N7—C24107.5 (3)N6—C18—H18B108.7
C22—N7—C25126.1 (4)C15—C18—H18B108.7
C24—N7—C25126.4 (4)H18A—C18—H18B107.6
C22—N8—C23105.4 (3)N5—C19—N6111.5 (3)
C22—N8—Cu1125.2 (3)N5—C19—H19A124.3
C23—N8—Cu1129.3 (3)N6—C19—H19A124.3
C29—O1—Cu189.7 (2)C21—C20—N6107.0 (4)
H1WA—O1W—H1WB106 (7)C21—C20—H20A126.5
C29—O2—Cu191.3 (2)N6—C20—H20A126.5
H2WA—O2W—H2WB112 (5)C20—C21—N5108.9 (4)
H3WA—O3W—H3WB107 (4)C20—C21—H21A125.5
H4WA—O4W—H4WB110 (5)N5—C21—H21A125.5
H5WA—O5W—H5WB140 (7)N8—C22—N7111.5 (4)
N1—C1—N2112.6 (5)N8—C22—H22A124.3
N1—C1—H1A123.7N7—C22—H22A124.3
N2—C1—H1A123.7C24—C23—N8109.6 (4)
C3—C2—N1111.3 (5)C24—C23—H23A125.2
C3—C2—H2A124.4N8—C23—H23A125.2
N1—C2—H2A124.4C23—C24—N7106.0 (4)
C2—C3—N2106.7 (5)C23—C24—H24A127.0
C2—C3—H3A126.7N7—C24—H24A127.0
N2—C3—H3A126.7N7—C25—C26111.4 (3)
N2—C4—C5113.1 (4)N7—C25—H25A109.3
N2—C4—H4A109.0C26—C25—H25A109.3
C5—C4—H4A109.0N7—C25—H25B109.3
N2—C4—H4B109.0C26—C25—H25B109.3
C5—C4—H4B109.0H25A—C25—H25B108.0
H4A—C4—H4B107.8C28—C26—C27118.3 (4)
C7—C5—C6118.5 (5)C28—C26—C25120.8 (4)
C7—C5—C4120.5 (5)C27—C26—C25120.9 (4)
C6—C5—C4121.0 (5)C26—C27—C28iv120.4 (4)
C5—C6—C7iii121.0 (5)C26—C27—H27A119.8
C5—C6—H6A119.5C28iv—C27—H27A119.8
C7iii—C6—H6A119.5C26—C28—C27iv121.3 (4)
C5—C7—C6iii120.5 (5)C26—C28—H28A119.3
C5—C7—H7A119.7C27iv—C28—H28A119.3
C6iii—C7—H7A119.7O3—C29—O2122.3 (4)
N4—C8—N3112.9 (4)O3—C29—O1124.4 (4)
N4—C8—H8A123.8O2—C29—O1113.3 (4)
N3—C8—H8A123.8O3—C29—Cu1177.6 (4)
C10—C9—N3110.4 (4)O2—C29—Cu156.1 (2)
C10—C9—H9A124.8O1—C29—Cu157.3 (2)
Symmetry codes: (i) x1, y1, z; (ii) x+1, y+1, z; (iii) x1, y1, z+2; (iv) x1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O5W0.83 (16)2.40 (11)2.780 (10)108 (10)
O1W—H1WB···O1v0.86 (5)1.87 (5)2.722 (8)170 (13)
O2W—H2WA···O3vi0.83 (10)1.88 (6)2.687 (9)163 (10)
O2W—H2WB···O1Wvii0.82 (5)2.29 (9)2.964 (14)140 (10)
O3W—H3WA···O5Wiii0.84 (10)2.02 (5)2.834 (9)163 (10)
O3W—H3WB···O4Wviii0.85 (9)2.00 (5)2.803 (9)160 (10)
O4W—H4WA···O30.84 (10)2.00 (6)2.779 (8)156 (10)
O4W—H4WB···O3Wix0.83 (4)2.21 (5)3.012 (10)162 (9)
O5W—H5WA···O2W0.84 (5)1.99 (5)2.808 (10)166 (10)
O5W—H5WB···N1i0.86 (5)2.09 (6)2.868 (10)151 (9)
Symmetry codes: (i) x1, y1, z; (iii) x1, y1, z+2; (v) x1, y, z+1; (vi) x1, y1, z+1; (vii) x2, y1, z+2; (viii) x, y, z+1; (ix) x, y, z1.

Experimental details

Crystal data
Chemical formula[Cu(CO3)(C14H14N4)1.5]·0.5C14H14N4·5H2O
Mr690.22
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)12.2286 (2), 12.4976 (7), 12.951
α, β, γ (°)103.759 (15), 98.726 (12), 118.767 (9)
V3)1600.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.74
Crystal size (mm)0.20 × 0.15 × 0.05
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.875, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
12466, 7352, 5723
Rint0.019
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.120, 1.02
No. of reflections7352
No. of parameters49
No. of restraints7
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.60

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994) and XPREP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Cu1—N5i1.963 (3)Cu1—N82.041 (3)
Cu1—O21.966 (3)Cu1—N32.123 (5)
Cu1—O11.993 (3)
N5i—Cu1—O2163.80 (13)O1—Cu1—N8141.92 (15)
N5i—Cu1—O198.53 (13)N5i—Cu1—N394.9 (2)
O2—Cu1—O165.57 (13)O2—Cu1—N394.3 (2)
N5i—Cu1—N896.19 (13)O1—Cu1—N3112.5 (2)
O2—Cu1—N895.13 (14)N8—Cu1—N3100.90 (19)
Symmetry code: (i) x1, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O5W0.83 (16)2.40 (11)2.780 (10)108 (10)
O1W—H1WB···O1ii0.86 (5)1.87 (5)2.722 (8)170 (13)
O2W—H2WA···O3iii0.83 (10)1.88 (6)2.687 (9)163 (10)
O2W—H2WB···O1Wiv0.82 (5)2.29 (9)2.964 (14)140 (10)
O3W—H3WA···O5Wv0.84 (10)2.02 (5)2.834 (9)163 (10)
O3W—H3WB···O4Wvi0.85 (9)2.00 (5)2.803 (9)160 (10)
O4W—H4WA···O30.84 (10)2.00 (6)2.779 (8)156 (10)
O4W—H4WB···O3Wvii0.83 (4)2.21 (5)3.012 (10)162 (9)
O5W—H5WA···O2W0.84 (5)1.99 (5)2.808 (10)166 (10)
O5W—H5WB···N1i0.86 (5)2.09 (6)2.868 (10)151 (9)
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z+1; (iii) x1, y1, z+1; (iv) x2, y1, z+2; (v) x1, y1, z+2; (vi) x, y, z+1; (vii) x, y, z1.
 

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