Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 5| May 2010| Page m561
https://doi.org/10.1107/S1600536810012833

Tetra­aqua­bis­(1,10-phenanthroline)bis­­[μ2-1H-pyrazole-3,5-di­carboxyl­ato(3−)]tricopper(II) dihydrate

Zhi-Gang Li,a Shao-Ai Li,a De-Quan Liu,a Long Hea and Jing-Wei Xub*

aShenzhen Environmental Monitoring Center, Shenzhen 518008, People's Republic of China, and bState Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
*Correspondence e-mail: jwxu@ciac.jl.cn

(Received 18 January 2010; accepted 6 April 2010; online 24 April 2010)

The title compound, [Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2O, is a trinuclear copper(II) complex in which two centrosymmetrically related pyrazole-3,5-dicarboxyl­ate(3−) and 1,10-phenanthroline ligands bind three CuII atoms, with one CuII atom located on a center of symmetry. In each complex, there are four coordinated water mol­ecules and two solvent water mol­ecules, which participate in extensive hydrogen-bond patterns. These inter­actions, as well as π–π inter­actions between neighbouring 1,10-phenanthroline ligands [shortest atom-to-atom distance = 3.363 (3) Å], extend the crystal structure into a three-dimensional supra­molecular network.

Related literature

For the potential applications of novel coordination architectures as new classes of materials, see: Kitagawa et al. (2004[Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334-2375.]). The potential coordination sites of 3,5-pyrazoledicarboxylate are highly accessible to metal ions, see: Li (2005[Li, X.-H. (2005). Acta Cryst. E61, m2405-m2407.]). However, divalent copper ions have rarely been coordinated with 3,5-pyrazoledicarboxylic acid at ambient temperature, see: King et al. (2003[King, P., Clerac, R., Anson, C. E., Coulon, C. & Powell, A. K. (2003). Inorg. Chem. 42, 3492-3500.]).

[Scheme 1]

Experimental

Crystal data

  • [Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2O

  • Mr = 965.28

  • Triclinic, [P \overline 1]

  • a = 7.7326 (8) Å

  • b = 9.3332 (9) Å

  • c = 12.6848 (12) Å

  • α = 100.204 (2)°

  • β = 98.376 (2)°

  • γ = 103.641 (2)°

  • V = 858.59 (15) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 1.93 mm−1

  • T = 187 K

  • 0.07 × 0.07 × 0.03 mm
Data collection

  • Bruker APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2003[Bruker (2003). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsion, USA.]) Tmin = 0.872, Tmax = 0.937

  • 4550 measured reflections

  • 3151 independent reflections

  • 2361 reflections with I > 2σ(I)

  • Rint = 0.039
Refinement

  • R[F2 > 2σ(F2)] = 0.071

  • wR(F2) = 0.155

  • S = 1.10

  • 3151 reflections

  • 274 parameters

  • 2 restraints

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

  • Δρmax = 0.87 e Å−3

  • Δρmin = −0.58 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O5—H5A⋯O2i 0.87 2.05 2.842 (7) 152
O5—H5B⋯O4ii 0.90 1.95 2.824 (7) 163
O6—H6A⋯O4i 0.88 (5) 2.26 (6) 3.104 (8) 161 (7)
O6—H6B⋯O4ii 0.89 (3) 2.16 (3) 3.042 (8) 172 (10)
O7—H7A⋯O5iii 0.85 2.24 2.977 (8) 145
O7—H7B⋯O3iv 0.87 1.97 2.829 (7) 170
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z.

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsion, 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.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012833/ez2198sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012833/ez2198Isup2.hkl

checkCIF report


Comment top

The design and synthesis of novel coordination architectures has attracted wide attention because of their intriguing network topologies and potential applications as new classes of materials (Kitagawa et al., 2004). 3,5-pyrazoledicarboxylate has several potential coordination sites: both nitrogen atoms of the pyrazole ring and the four carboxylate oxygen atoms, which are highly accessible to metal ions (Li, 2005). However, divalent copper ions have rarely been coordinated with 3,5-pyrazoledicarboxylic acid under ambient temperatures (King et al., 2003). In this study, we chose 3,5-pyrazoledicarboxylic acid and 1,10-phenanthroline as mixed ligands to obtain blue crystals of the title compound (I), which as shown in Fig. 1 is a copper(II) trimer.

The central copper atom, Cu(1), lies on a crystallographic inversion center, and has a six-coordinate octahedral geometry, in the which two oxygen atoms and two nitrogen atoms from two 3,5-pyrazoledicarboxylate ligands occupy the equatorial plane. The axial coordination sites are occupied by two water molecules. The Cu(1)—N/O bond distances span a very large range from 1.974 (5) to 2.595 (5) Å. The other two symmetry-related copper atoms, Cu(2), have pentacoordinate square-pyramidal geometry: a pyrazole nitrogen N(2) and a carboxylate oxygen O(3) from one 3,5-pyrazoledicarboxylato ligand occupy two coordination sites, two nitrogen atoms from one 1,10-phenanthroline chelate the Cu(2) atoms, while the remaining position is occupied by a water molecule. The Cu(2)—N/O bond distances range from 1.979 (6) to 2.171 (5) Å. The 3,5-pyrazoledicarboxylate ligand is nearly planar, with greatest deviation from the mean plane defined by the pyrazole ring by the carboxylate groups with values ranging from 0.0015 (1) to 0.0937 (1) Å. It can be seen that the ligand bite angles at the two different copper centers Cu(1) and Cu(2) are similar, 80.9 (3)° and 82.5 (4)°, respectively. This implies that the 3,5-pyrazoledicarboxylate ligand is a fairly rigid ligand and retains its integrity on metal chelation.

In the asymmetric unit, there is one lattice water molecule, O(7), and because each trimer contains four coordinated water molecules and carboxylate oxygen atoms, a complex network of hydrogen-bonding interactions is formed. Each 3,5-pyrazoledicarboxylato contains four hydrogen bond acceptors, while each coordinated water molecule acts as both a two hydrogen bond donor and a hydrogen bond acceptor, and the lattice water molecule is only a two hydrogen bond donor. In the crystal structure, π-π interactions also exist between neighbouring 1,10-phenanthroline ligands, with the nearest atom-to-atom distance between neighbouring 1,10-phenanthroline ligands being 3.363 (3) Å. The strong hydrogen bonding interactions as well as π-π interactions extend the crystal structure into a three-dimensional supramolecular network (Fig. 2).

Related literature top

For related literature, see: Kitagawa et al. (2004); King et al. (2003); Li (2005).

Experimental top

The title complex was prepared by the addition of Cu(BF4)2 (20 mmol), 1,10-phenanthroline (30 mmol) and 3,5-pyrazoledicarboxylic acid (30 mmol) to 40 ml water. The mixture was stirred for 1 h, a blue precipitate was obtained. A minimum amount of ammonia (14 M) was added to give a blue solution. Suitable crystals were obtained after standing at room temperature for several days (yield 42% based on Cu).

Refinement top

H atoms were placed geometrically and refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C,N)], using a riding model, with a C—H distance of 0.93 Å. The H atoms bonded to O atoms of water molecules were located in a difference Fourier map and refined with fixed individual displacement parameters Uiso(H) = 1.2Ueq(O).

Structure description top

The design and synthesis of novel coordination architectures has attracted wide attention because of their intriguing network topologies and potential applications as new classes of materials (Kitagawa et al., 2004). 3,5-pyrazoledicarboxylate has several potential coordination sites: both nitrogen atoms of the pyrazole ring and the four carboxylate oxygen atoms, which are highly accessible to metal ions (Li, 2005). However, divalent copper ions have rarely been coordinated with 3,5-pyrazoledicarboxylic acid under ambient temperatures (King et al., 2003). In this study, we chose 3,5-pyrazoledicarboxylic acid and 1,10-phenanthroline as mixed ligands to obtain blue crystals of the title compound (I), which as shown in Fig. 1 is a copper(II) trimer.

The central copper atom, Cu(1), lies on a crystallographic inversion center, and has a six-coordinate octahedral geometry, in the which two oxygen atoms and two nitrogen atoms from two 3,5-pyrazoledicarboxylate ligands occupy the equatorial plane. The axial coordination sites are occupied by two water molecules. The Cu(1)—N/O bond distances span a very large range from 1.974 (5) to 2.595 (5) Å. The other two symmetry-related copper atoms, Cu(2), have pentacoordinate square-pyramidal geometry: a pyrazole nitrogen N(2) and a carboxylate oxygen O(3) from one 3,5-pyrazoledicarboxylato ligand occupy two coordination sites, two nitrogen atoms from one 1,10-phenanthroline chelate the Cu(2) atoms, while the remaining position is occupied by a water molecule. The Cu(2)—N/O bond distances range from 1.979 (6) to 2.171 (5) Å. The 3,5-pyrazoledicarboxylate ligand is nearly planar, with greatest deviation from the mean plane defined by the pyrazole ring by the carboxylate groups with values ranging from 0.0015 (1) to 0.0937 (1) Å. It can be seen that the ligand bite angles at the two different copper centers Cu(1) and Cu(2) are similar, 80.9 (3)° and 82.5 (4)°, respectively. This implies that the 3,5-pyrazoledicarboxylate ligand is a fairly rigid ligand and retains its integrity on metal chelation.

In the asymmetric unit, there is one lattice water molecule, O(7), and because each trimer contains four coordinated water molecules and carboxylate oxygen atoms, a complex network of hydrogen-bonding interactions is formed. Each 3,5-pyrazoledicarboxylato contains four hydrogen bond acceptors, while each coordinated water molecule acts as both a two hydrogen bond donor and a hydrogen bond acceptor, and the lattice water molecule is only a two hydrogen bond donor. In the crystal structure, π-π interactions also exist between neighbouring 1,10-phenanthroline ligands, with the nearest atom-to-atom distance between neighbouring 1,10-phenanthroline ligands being 3.363 (3) Å. The strong hydrogen bonding interactions as well as π-π interactions extend the crystal structure into a three-dimensional supramolecular network (Fig. 2).

For related literature, see: Kitagawa et al. (2004); King et al. (2003); Li (2005).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids. [Symmetry code: (A) 1 - x, 1 - y, 1 - z.] For clarity the lattice water molecules have been omitted.
[Figure 2] Fig. 2. Perspective view of packing structure of (I) along the c axes, with hydrogen bonds indicated by dashed lines. For the sake of clarity, H atoms not involved in hydrogen bonds have been omitted.
Tetraaquabis(1,10-phenanthroline)bis[µ2-1H-pyrazole-3,5- dicarboxylato(3-)]tricopper(II) dihydrate top
Crystal data top
[Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2OZ = 1
Mr = 965.28F(000) = 489
Triclinic, P1Dx = 1.867 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7326 (8) ÅCell parameters from 737 reflections
b = 9.3332 (9) Åθ = 2.3–22.4°
c = 12.6848 (12) ŵ = 1.93 mm−1
α = 100.204 (2)°T = 187 K
β = 98.376 (2)°Block, blue
γ = 103.641 (2)°0.07 × 0.07 × 0.03 mm
V = 858.59 (15) Å3
Data collection top
Bruker APEX CCD area-detector
diffractometer		3151 independent reflections
Radiation source: fine-focus sealed tube2361 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
φ and ω scansθmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −8→9
Tmin = 0.872, Tmax = 0.937k = −11→9
4550 measured reflectionsl = −9→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)] = 0.071Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0597P)2 + 0.8906P]
where P = (Fo2 + 2Fc2)/3
3151 reflections(Δ/σ)max = 0.027
274 parametersΔρmax = 0.87 e Å−3
2 restraintsΔρmin = −0.58 e Å−3
Crystal data top
[Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2Oγ = 103.641 (2)°
Mr = 965.28V = 858.59 (15) Å3
Triclinic, P1Z = 1
a = 7.7326 (8) ÅMo Kα radiation
b = 9.3332 (9) ŵ = 1.93 mm−1
c = 12.6848 (12) ÅT = 187 K
α = 100.204 (2)°0.07 × 0.07 × 0.03 mm
β = 98.376 (2)°
Data collection top
Bruker APEX CCD area-detector
diffractometer		3151 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		2361 reflections with I > 2σ(I)
Tmin = 0.872, Tmax = 0.937Rint = 0.039
4550 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0712 restraints
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.87 e Å−3
3151 reflectionsΔρmin = −0.58 e Å−3
274 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
Cu10.50000.50000.50000.0217 (3)
Cu20.31791 (11)0.03642 (9)0.30349 (7)0.0197 (3)
N10.5830 (7)0.3127 (5)0.4748 (4)0.0162 (12)
N20.5312 (7)0.1718 (6)0.4112 (4)0.0185 (12)
N30.3647 (7)0.1167 (6)0.1569 (4)0.0200 (13)
N40.1358 (7)−0.1271 (6)0.1893 (5)0.0223 (13)
O10.7315 (6)0.5766 (5)0.6067 (4)0.0232 (11)
O20.9943 (6)0.5210 (5)0.6534 (4)0.0256 (12)
O30.4855 (6)−0.1054 (5)0.3024 (4)0.0190 (11)
O40.7632 (6)−0.1122 (5)0.3758 (4)0.0228 (11)
O50.3188 (6)0.4290 (5)0.6487 (4)0.0301 (12)
H5A0.21050.43770.62720.036*
H5B0.27360.32800.63050.036*
O60.1384 (8)0.1048 (7)0.3818 (5)0.0413 (15)
H6A0.025 (5)0.049 (8)0.365 (7)0.050*
H6B0.175 (11)0.116 (10)0.453 (2)0.050*
O70.3725 (8)0.5886 (6)0.1884 (5)0.0453 (16)
H7A0.44020.54250.22010.054*
H7B0.41420.67890.22990.054*
C10.8372 (9)0.4887 (7)0.6033 (5)0.0168 (14)
C20.7527 (9)0.3356 (7)0.5299 (5)0.0165 (14)
C30.8129 (8)0.2092 (7)0.5029 (5)0.0159 (14)
H30.92720.19420.52960.019*
C40.6679 (8)0.1085 (7)0.4275 (5)0.0147 (14)
C50.6392 (9)−0.0491 (7)0.3650 (5)0.0144 (14)
C60.4736 (10)0.2407 (8)0.1428 (7)0.0294 (18)
H60.54170.31540.20540.035*
C70.4934 (11)0.2670 (8)0.0375 (7)0.0342 (19)
H70.57290.35760.02990.041*
C80.3963 (10)0.1598 (9)−0.0520 (6)0.0305 (18)
H80.40870.1752−0.12280.037*
C90.2791 (10)0.0281 (8)−0.0407 (6)0.0253 (17)
C100.1717 (10)−0.0923 (9)−0.1297 (6)0.0296 (18)
H100.1831−0.0840−0.20210.036*
C110.0548 (10)−0.2173 (8)−0.1152 (6)0.0277 (18)
H11−0.0148−0.2939−0.17630.033*
C120.0373 (9)−0.2327 (8)−0.0056 (6)0.0223 (16)
C13−0.0827 (10)−0.3571 (8)0.0162 (7)0.0303 (19)
H13−0.1585−0.4353−0.04200.036*
C14−0.0892 (10)−0.3643 (8)0.1231 (6)0.0309 (18)
H14−0.1693−0.44810.13930.037*
C150.0211 (9)−0.2496 (8)0.2065 (6)0.0247 (16)
H150.0158−0.25730.27970.030*
C160.1457 (9)−0.1181 (8)0.0838 (6)0.0221 (16)
C170.2664 (9)0.0116 (8)0.0656 (6)0.0217 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0237 (7)0.0135 (6)0.0264 (8)0.0099 (5)−0.0023 (5)−0.0002 (5)
Cu20.0173 (5)0.0231 (5)0.0140 (5)0.0037 (3)0.0001 (3)−0.0038 (4)
N10.019 (3)0.007 (3)0.016 (3)−0.002 (2)−0.003 (2)−0.002 (2)
N20.019 (3)0.020 (3)0.018 (3)0.008 (2)0.002 (2)0.005 (2)
N30.025 (3)0.020 (3)0.018 (3)0.012 (2)0.004 (2)0.004 (2)
N40.019 (3)0.025 (3)0.019 (3)0.006 (2)0.002 (2)−0.003 (3)
O10.024 (3)0.016 (2)0.028 (3)0.010 (2)−0.001 (2)0.000 (2)
O20.023 (3)0.021 (3)0.029 (3)0.009 (2)−0.003 (2)−0.001 (2)
O30.019 (2)0.013 (2)0.022 (3)0.0055 (19)−0.002 (2)0.000 (2)
O40.023 (3)0.021 (2)0.023 (3)0.009 (2)0.003 (2)0.000 (2)
O50.025 (3)0.022 (3)0.042 (3)0.006 (2)0.004 (2)0.006 (2)
O60.032 (3)0.047 (4)0.040 (4)0.006 (3)0.004 (3)0.006 (3)
O70.056 (4)0.027 (3)0.040 (4)0.011 (3)−0.016 (3)−0.004 (3)
C10.020 (4)0.018 (3)0.009 (3)0.004 (3)−0.002 (3)0.003 (3)
C20.025 (4)0.010 (3)0.012 (4)0.002 (3)0.003 (3)0.001 (3)
C30.015 (3)0.017 (3)0.018 (4)0.007 (3)0.001 (3)0.006 (3)
C40.021 (3)0.015 (3)0.013 (4)0.009 (3)0.010 (3)0.005 (3)
C50.021 (4)0.012 (3)0.011 (3)0.004 (3)0.004 (3)0.003 (3)
C60.031 (4)0.023 (4)0.032 (5)0.009 (3)0.003 (3)0.001 (3)
C70.039 (5)0.023 (4)0.044 (5)0.008 (3)0.011 (4)0.013 (4)
C80.028 (4)0.046 (5)0.026 (4)0.018 (4)0.013 (3)0.015 (4)
C90.027 (4)0.034 (4)0.017 (4)0.018 (3)0.005 (3)0.001 (3)
C100.034 (4)0.049 (5)0.012 (4)0.024 (4)0.005 (3)0.004 (3)
C110.031 (4)0.025 (4)0.021 (4)0.011 (3)−0.004 (3)−0.007 (3)
C120.025 (4)0.026 (4)0.015 (4)0.016 (3)−0.002 (3)−0.005 (3)
C130.029 (4)0.016 (4)0.038 (5)0.004 (3)−0.002 (3)−0.007 (3)
C140.027 (4)0.028 (4)0.029 (5)−0.003 (3)0.000 (3)0.003 (3)
C150.023 (4)0.023 (4)0.027 (4)0.006 (3)0.005 (3)0.003 (3)
C160.018 (4)0.027 (4)0.021 (4)0.009 (3)0.003 (3)−0.002 (3)
C170.024 (4)0.025 (4)0.020 (4)0.015 (3)0.006 (3)0.003 (3)
Geometric parameters (Å, º) top
Cu1—O11.974 (5)C1—C21.499 (8)
Cu1—O1i1.974 (5)C2—C31.374 (8)
Cu1—N1i1.990 (5)C3—C41.388 (8)
Cu1—N11.990 (5)C3—H30.9500
Cu2—N21.983 (5)C4—C51.491 (8)
Cu2—O61.979 (6)C6—C71.423 (10)
Cu2—N42.005 (5)C6—H60.9500
Cu2—O32.059 (4)C7—C81.359 (10)
Cu2—N32.171 (6)C7—H70.9500
N1—C21.343 (8)C8—C91.388 (10)
N1—N21.350 (7)C8—H80.9500
N2—C41.335 (8)C9—C171.399 (9)
N3—C61.318 (9)C9—C101.436 (10)
N3—C171.368 (8)C10—C111.357 (10)
N4—C151.344 (9)C10—H100.9500
N4—C161.368 (8)C11—C121.445 (10)
O1—C11.287 (8)C11—H110.9500
O2—C11.227 (7)C12—C131.402 (10)
O3—C51.266 (7)C12—C161.415 (9)
O4—C51.242 (7)C13—C141.377 (10)
O5—H5A0.8692C13—H130.9500
O5—H5B0.8987C14—C151.378 (10)
O6—H6A0.88 (2)C14—H140.9500
O6—H6B0.88 (2)C15—H150.9500
O7—H7A0.8526C16—C171.421 (10)
O7—H7B0.8695
O1—Cu1—O1i180.000 (1)C4—C3—H3128.1
O1—Cu1—N1i97.50 (19)N2—C4—C3110.0 (5)
O1i—Cu1—N1i82.50 (19)N2—C4—C5117.1 (6)
O1—Cu1—N182.50 (19)C3—C4—C5132.9 (6)
O1i—Cu1—N197.50 (19)O4—C5—O3125.9 (6)
N1i—Cu1—N1180.000 (1)O4—C5—C4119.6 (6)
N2—Cu2—O694.4 (2)O3—C5—C4114.5 (5)
N2—Cu2—N4168.4 (2)N3—C6—C7122.6 (7)
O6—Cu2—N495.8 (2)N3—C6—H6118.7
N2—Cu2—O380.9 (2)C7—C6—H6118.7
O6—Cu2—O3142.7 (2)C8—C7—C6118.6 (7)
N4—Cu2—O387.6 (2)C8—C7—H7120.7
N2—Cu2—N3100.5 (2)C6—C7—H7120.7
O6—Cu2—N3118.2 (2)C7—C8—C9120.6 (7)
N4—Cu2—N379.4 (2)C7—C8—H8119.7
O3—Cu2—N398.95 (19)C9—C8—H8119.7
C2—N1—N2107.8 (5)C8—C9—C17117.2 (7)
C2—N1—Cu1111.5 (4)C8—C9—C10125.0 (7)
N2—N1—Cu1140.3 (4)C17—C9—C10117.9 (7)
C4—N2—N1108.1 (5)C11—C10—C9123.0 (7)
C4—N2—Cu2112.9 (4)C11—C10—H10118.5
N1—N2—Cu2139.0 (4)C9—C10—H10118.5
C6—N3—C17117.7 (6)C10—C11—C12119.3 (6)
C6—N3—Cu2131.6 (5)C10—C11—H11120.4
C17—N3—Cu2110.7 (4)C12—C11—H11120.4
C15—N4—C16118.2 (6)C13—C12—C16118.4 (7)
C15—N4—Cu2126.5 (5)C13—C12—C11122.7 (6)
C16—N4—Cu2115.0 (4)C16—C12—C11118.9 (6)
C1—O1—Cu1115.1 (4)C14—C13—C12119.1 (7)
C5—O3—Cu2114.6 (4)C14—C13—H13120.5
H5A—O5—H5B88.9C12—C13—H13120.5
Cu2—O6—H6A119 (5)C15—C14—C13119.7 (7)
Cu2—O6—H6B109 (6)C15—C14—H14120.1
H6A—O6—H6B107 (8)C13—C14—H14120.1
H7A—O7—H7B100.3N4—C15—C14123.2 (7)
O2—C1—O1125.7 (6)N4—C15—H15118.4
O2—C1—C2120.2 (6)C14—C15—H15118.4
O1—C1—C2114.1 (5)N4—C16—C12121.5 (6)
N1—C2—C3110.3 (5)N4—C16—C17118.2 (6)
N1—C2—C1115.9 (5)C12—C16—C17120.3 (7)
C3—C2—C1133.8 (6)N3—C17—C9123.3 (6)
C2—C3—C4103.9 (5)N3—C17—C16116.1 (6)
C2—C3—H3128.1C9—C17—C16120.5 (6)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O2ii0.872.052.842 (7)152
O5—H5B···O4iii0.901.952.824 (7)163
O6—H6A···O4ii0.88 (5)2.26 (6)3.104 (8)161 (7)
O6—H6B···O4iii0.89 (3)2.16 (3)3.042 (8)172 (10)
O7—H7A···O5i0.852.242.977 (8)145
O7—H7B···O3iv0.871.972.829 (7)170
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu3(C5HN2O4)2(C12H8N2)2(H2O)4]·2H2O
Mr965.28
Crystal system, space groupTriclinic, P1
Temperature (K)187
a, b, c (Å)7.7326 (8), 9.3332 (9), 12.6848 (12)
α, β, γ (°)100.204 (2), 98.376 (2), 103.641 (2)
V (Å3)858.59 (15)
Z1
Radiation typeMo Kα
µ (mm−1)1.93
Crystal size (mm)0.07 × 0.07 × 0.03
Data collection
DiffractometerBruker APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.872, 0.937
No. of measured, independent and
observed [I > 2σ(I)] reflections		4550, 3151, 2361
Rint0.039
(sin θ/λ)max (Å−1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.071, 0.155, 1.10
No. of reflections3151
No. of parameters274
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.87, −0.58

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O2i0.872.052.842 (7)152
O5—H5B···O4ii0.901.952.824 (7)163
O6—H6A···O4i0.88 (5)2.26 (6)3.104 (8)161 (7)
O6—H6B···O4ii0.89 (3)2.16 (3)3.042 (8)172 (10)
O7—H7A···O5iii0.852.242.977 (8)145
O7—H7B···O3iv0.871.972.829 (7)170
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z.
 

Acknowledgements

This work was supported by the National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Changchun, China.

References

First citationBruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2003). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsion, USA.  Google Scholar
 First citationKing, P., Clerac, R., Anson, C. E., Coulon, C. & Powell, A. K. (2003). Inorg. Chem. 42, 3492–3500.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationKitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375.  Web of Science CrossRef CAS Google Scholar
 First citationLi, X.-H. (2005). Acta Cryst. E61, m2405–m2407.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 5| May 2010| Page m561
https://doi.org/10.1107/S1600536810012833
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS