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The crystal structure of the title compound, [Cu4(C6H4O7)2(H2O)4]n, has been reported twice previously, by Mastropaolo, Powers, Potenza & Schugar [(1976). Inorg. Chem. 15, 1444–1449] and Zhang, Yang & Ma [(2006). Cryst. Growth Des. 6, 375–381]. These authors used strong reflections only for the unit-cell determination. The present structure redetermination is based on intensities measured at low temperature (120 K). The new data set (including the intensities of hkl with h = 2n + 1, omitted in earlier papers) indicates a doubled cell volume and the presence of four penta­coordinated copper cations, two tetra-ionized citrate anions and four water mol­ecules in the asymmetric unit.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039086/hg2275sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039086/hg2275Isup2.hkl
Contains datablock I

CCDC reference: 660106

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.027
  • wR factor = 0.069
  • Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT301_ALERT_3_C Main Residue Disorder ......................... 6.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 8
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C3 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C13 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The crystal structure of the title compound (I) has been previously reported by Mastropaolo et al. (1976) and Zhang et al. (2006). In the first work the complex was obtained by the urea hydrolysis technique, whereas in the second one the crystals were prepared using the hydrothermal conditions. In our studies complex (I) was synthesized using the gel method (Henisch, 1970). However, in all those works not only the preparations differ, the diffraction data sets were collected using different devices. Mastropaolo et al. (1976) collected data on an Enraf–Nonius CAD–3 diffractometer with Mo radiation using a small crystal of dimensions 0.27 x 0.09 x 0.03 mm. The unit-cell parameters were determined from angular values of 11 reflections. In the second report intensities were measured on a Bruker Smart 1000 CCD diffractometer (Mo radiation), and accurate unit-cell parameters were determined by a least-squares fit of 200 strong reflections.

We report here the refinement using the data collected on a KM4 CCD diffracometer with Mo radiation at low temperature(120 K). The unit cell parameters were determined both at room temperature and at 120 K. We found that some reflection groups with h=2n+1 have lower intensities than mean intensity determined for all data. Therefore, the space group must be P21/c with unit-cell parameters: a = 13.749 (4), b = 9.713 (4), c = 14.471 (6) Å, β = 91.56 (3)°, whereas the dimensions reported by Mastropaolo et al. (1976) (in P21/a) were a' = 14.477 (9), b' = 9.718 (6), c' = 6.890 (5) Å, β' = 91.27 (5)°, and by Zhang et al. (2006) (in P21/c) were a'' = 6.929 (1), b'' = 9.762 (1), c'' = 14.537 (2) Å, β'' = 91.377 (2)°. The structural analysis based on a unit cell having a 2a''(c') indicated the asymmetric unit to be doubled. Thus, the asymmetric unit has stoichiometry of 4:2:4, viz. 4 Cu(II)/2 tetraionized citrate anions/4 H2O (Fig. 1). Note that Cu1 as well as Cu11 cation are disordered over two positions with the major sof's being 0.955 (5) and minor 0.045 (5), without the change of coordination polyhedra.

The crystal structure is based on dimeric complex with the two subunits [Cu2(cit)(H2O)2] connected by the O7–C6–O6 group. The dinuclear Cu2O9 moieties, in which one citrate anion is tridentate chelating and second one is bridging (Table 1), create three-dimensional polymeric structure.

In all works, the mode of copper coordination is the same (Fig. 2), however some differences are observed in: (i) respective Cu–O distances within the CuO5 spheres (Table 1), (ii) the citrate C–C–C–O torsion angles (Table 1), and (iii) the hydrogen bond pattern between subunits (Table 2).

Related literature top

For related literature, see: Mastropaolo et al. (1976); Zhang et al. (2006).

For synthesis, see: Henisch (1970).

Experimental top

The title complex was prepared in a silica-gel medium using the technique described by Henisch (1970). The silica gel was prepared by adding a solution of sodium metasilicate to citric acid. The final pH of the gel was 5.4. After the setting of gel an aqueous solution of Cu(NO3)2 was carefully poured over it. The crystallization was carried out in the glass tubes in 308 K. After few days green single crystals of [Cu4(C6H4O7)2(H2O)4]n appeared in the gel column.

Refinement top

Two of four copper cations are disordered over two positions with the sof's being 0.955 (5) for Cu1 and Cu11, and 0.045 (5) for Cu1A and Cu1B. The H atoms bonded to the citrate C atoms were positioned geometrically. The C—H bonds were set to 1.00 Å. The positions of the water H atoms were found in the difference maps and next the OW—HW distances were fixed at 0.84 Å. The H atoms were included in the refinement in the riding model approximation, with Uiso(H) = 1.2 Ueq(C) and Uiso(H) = 1.5 Ueq(O).

Structure description top

The crystal structure of the title compound (I) has been previously reported by Mastropaolo et al. (1976) and Zhang et al. (2006). In the first work the complex was obtained by the urea hydrolysis technique, whereas in the second one the crystals were prepared using the hydrothermal conditions. In our studies complex (I) was synthesized using the gel method (Henisch, 1970). However, in all those works not only the preparations differ, the diffraction data sets were collected using different devices. Mastropaolo et al. (1976) collected data on an Enraf–Nonius CAD–3 diffractometer with Mo radiation using a small crystal of dimensions 0.27 x 0.09 x 0.03 mm. The unit-cell parameters were determined from angular values of 11 reflections. In the second report intensities were measured on a Bruker Smart 1000 CCD diffractometer (Mo radiation), and accurate unit-cell parameters were determined by a least-squares fit of 200 strong reflections.

We report here the refinement using the data collected on a KM4 CCD diffracometer with Mo radiation at low temperature(120 K). The unit cell parameters were determined both at room temperature and at 120 K. We found that some reflection groups with h=2n+1 have lower intensities than mean intensity determined for all data. Therefore, the space group must be P21/c with unit-cell parameters: a = 13.749 (4), b = 9.713 (4), c = 14.471 (6) Å, β = 91.56 (3)°, whereas the dimensions reported by Mastropaolo et al. (1976) (in P21/a) were a' = 14.477 (9), b' = 9.718 (6), c' = 6.890 (5) Å, β' = 91.27 (5)°, and by Zhang et al. (2006) (in P21/c) were a'' = 6.929 (1), b'' = 9.762 (1), c'' = 14.537 (2) Å, β'' = 91.377 (2)°. The structural analysis based on a unit cell having a 2a''(c') indicated the asymmetric unit to be doubled. Thus, the asymmetric unit has stoichiometry of 4:2:4, viz. 4 Cu(II)/2 tetraionized citrate anions/4 H2O (Fig. 1). Note that Cu1 as well as Cu11 cation are disordered over two positions with the major sof's being 0.955 (5) and minor 0.045 (5), without the change of coordination polyhedra.

The crystal structure is based on dimeric complex with the two subunits [Cu2(cit)(H2O)2] connected by the O7–C6–O6 group. The dinuclear Cu2O9 moieties, in which one citrate anion is tridentate chelating and second one is bridging (Table 1), create three-dimensional polymeric structure.

In all works, the mode of copper coordination is the same (Fig. 2), however some differences are observed in: (i) respective Cu–O distances within the CuO5 spheres (Table 1), (ii) the citrate C–C–C–O torsion angles (Table 1), and (iii) the hydrogen bond pattern between subunits (Table 2).

For related literature, see: Mastropaolo et al. (1976); Zhang et al. (2006).

For synthesis, see: Henisch (1970).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999); molecular graphics: SHELXTL/PC (Sheldrick, 1990) and XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The atom-numbering of (I). The Cu1 and Cu11 cations with major occupancy factor (0.954) are drawn; displacement ellipsoids are drawn at the 30% probability level. Equivalence between symmetry codes given on figure and Table 1 is as follows: A = i, B = ii, C =iii, D = iv and E = v.
[Figure 2] Fig. 2. Polyhedral representation of the crystal packing for the structure (a) determined by Zhang et al. (2006) and (b) determined in the present paper. View along the b axis.
Poly[tetraaquadi-µ6-citrato-tetracopper(II)] top
Crystal data top
[Cu4(C6H4O7)2(H2O)4]F(000) = 1392
Mr = 702.45Dx = 2.415 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12949 reflections
a = 13.749 (4) Åθ = 2.9–26.6°
b = 9.713 (4) ŵ = 4.44 mm1
c = 14.471 (6) ÅT = 120 K
β = 91.56 (3)°Block, green
V = 1931.8 (13) Å30.6 × 0.34 × 0.25 mm
Z = 4
Data collection top
Oxford Diffraction KM-4 CCD area-detector
diffractometer
3973 independent reflections
Radiation source: fine-focus sealed tube3341 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scansθmax = 26.5°, θmin = 3.0°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
h = 1717
Tmin = 0.15, Tmax = 0.33k = 1210
11784 measured reflectionsl = 1817
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.043P)2]
where P = (Fo2 + 2Fc2)/3
3973 reflections(Δ/σ)max = 0.001
316 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
[Cu4(C6H4O7)2(H2O)4]V = 1931.8 (13) Å3
Mr = 702.45Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.749 (4) ŵ = 4.44 mm1
b = 9.713 (4) ÅT = 120 K
c = 14.471 (6) Å0.6 × 0.34 × 0.25 mm
β = 91.56 (3)°
Data collection top
Oxford Diffraction KM-4 CCD area-detector
diffractometer
3973 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
3341 reflections with I > 2σ(I)
Tmin = 0.15, Tmax = 0.33Rint = 0.038
11784 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.02Δρmax = 0.55 e Å3
3973 reflectionsΔρmin = 0.57 e Å3
316 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*/UeqOcc. (<1)
Cu10.46981 (8)0.33007 (10)0.36000 (4)0.00878 (16)0.955 (5)
Cu20.34787 (2)0.26017 (3)0.16600 (2)0.00760 (10)
Cu110.06839 (8)0.12127 (10)0.15292 (3)0.0103 (2)0.955 (5)
Cu120.15173 (2)0.25321 (3)0.33927 (2)0.00756 (10)
Cu1A0.4490 (14)0.3560 (19)0.3522 (12)0.016 (4)*0.045 (5)
Cu1B0.0381 (14)0.1574 (19)0.1451 (8)0.009 (3)*0.045 (5)
O1W0.58264 (14)0.3905 (2)0.44238 (13)0.0141 (4)
H1W10.61420.45850.42350.021*
H2W10.58270.40480.49960.021*
O2W0.41608 (14)0.5611 (2)0.36561 (14)0.0168 (5)
H1W20.35820.57520.34810.025*
H2W20.43810.61010.32320.025*
O11W0.07413 (14)0.1233 (2)0.07486 (14)0.0188 (5)
H1WA0.07880.11730.01700.028*
H2WA0.12400.07860.08850.028*
O12W0.08871 (13)0.08641 (19)0.11672 (14)0.0146 (4)
H1WB0.14770.09620.13200.022*
H2WB0.05290.14670.13980.022*
O10.28209 (13)0.19504 (19)0.54941 (13)0.0117 (4)
O20.39643 (14)0.2967 (2)0.46885 (13)0.0142 (4)
O30.40390 (12)0.19572 (18)0.28274 (13)0.0090 (4)
O40.44720 (13)0.1186 (2)0.24013 (13)0.0131 (4)
O50.55877 (13)0.0951 (2)0.35529 (14)0.0165 (4)
O60.22539 (13)0.06961 (19)0.26405 (13)0.0130 (4)
O70.28046 (13)0.08570 (19)0.16685 (13)0.0101 (4)
C10.31930 (19)0.2243 (3)0.47378 (19)0.0100 (6)
C20.26865 (18)0.1671 (3)0.38848 (18)0.0091 (5)
H2A0.22010.10060.40650.011*
H2B0.23550.24110.35540.011*
C30.34105 (18)0.0973 (3)0.32411 (18)0.0079 (5)
C40.40083 (18)0.0091 (3)0.37832 (18)0.0091 (5)
H4B0.35740.07780.40290.011*
H4C0.43370.03600.43020.011*
C50.47510 (18)0.0793 (3)0.32053 (19)0.0091 (5)
C60.27838 (19)0.0288 (3)0.24731 (19)0.0088 (5)
O110.22315 (13)0.29627 (19)0.04781 (13)0.0109 (4)
O120.13140 (14)0.16551 (19)0.03933 (13)0.0136 (4)
O130.09871 (13)0.29247 (18)0.21706 (12)0.0083 (4)
O140.01121 (14)0.5506 (2)0.25088 (14)0.0162 (4)
O150.04164 (15)0.6468 (2)0.11897 (14)0.0187 (5)
O160.23375 (14)0.60134 (18)0.22896 (14)0.0150 (4)
O170.22314 (13)0.42411 (19)0.32481 (13)0.0110 (4)
C110.19406 (19)0.2596 (3)0.03031 (18)0.0082 (5)
C120.23525 (18)0.3348 (3)0.11400 (18)0.0079 (5)
H12B0.27760.40820.09410.010*
H12C0.27380.27150.15180.010*
C130.15300 (18)0.3959 (3)0.17203 (18)0.0081 (5)
C140.08611 (19)0.4857 (3)0.11149 (19)0.0100 (6)
H14B0.12560.54930.07700.012*
H14C0.05150.42740.06720.012*
C150.01295 (18)0.5668 (3)0.16499 (19)0.0096 (5)
C160.20629 (18)0.4841 (3)0.24588 (19)0.0095 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0099 (3)0.0103 (3)0.0061 (2)0.0030 (2)0.00042 (19)0.00081 (19)
Cu20.00742 (17)0.00875 (18)0.00656 (19)0.00170 (12)0.00111 (13)0.00171 (12)
Cu110.0150 (4)0.0100 (3)0.0060 (2)0.0046 (3)0.00202 (17)0.00110 (17)
Cu120.00874 (17)0.00843 (18)0.00547 (19)0.00169 (12)0.00062 (13)0.00043 (12)
O1W0.0151 (9)0.0176 (11)0.0094 (10)0.0012 (8)0.0012 (8)0.0015 (8)
O2W0.0140 (10)0.0202 (11)0.0159 (11)0.0032 (8)0.0042 (8)0.0019 (9)
O11W0.0141 (10)0.0286 (12)0.0138 (11)0.0006 (9)0.0023 (8)0.0009 (9)
O12W0.0094 (9)0.0131 (10)0.0212 (12)0.0025 (8)0.0024 (8)0.0003 (8)
O10.0109 (9)0.0124 (10)0.0117 (11)0.0008 (8)0.0001 (8)0.0010 (8)
O20.0165 (10)0.0180 (10)0.0084 (10)0.0070 (8)0.0023 (8)0.0024 (8)
O30.0084 (9)0.0095 (9)0.0090 (10)0.0020 (7)0.0009 (7)0.0022 (8)
O40.0123 (9)0.0177 (10)0.0094 (10)0.0054 (8)0.0001 (8)0.0022 (8)
O50.0118 (9)0.0199 (11)0.0175 (11)0.0071 (8)0.0056 (8)0.0083 (9)
O60.0166 (10)0.0133 (10)0.0091 (10)0.0065 (8)0.0007 (8)0.0013 (8)
O70.0124 (9)0.0119 (9)0.0058 (10)0.0024 (7)0.0026 (7)0.0023 (8)
C10.0124 (13)0.0068 (13)0.0108 (15)0.0038 (10)0.0030 (11)0.0013 (11)
C20.0075 (12)0.0103 (13)0.0096 (14)0.0008 (10)0.0011 (10)0.0007 (11)
C30.0082 (12)0.0085 (13)0.0071 (14)0.0010 (10)0.0019 (10)0.0004 (10)
C40.0095 (12)0.0115 (13)0.0062 (14)0.0004 (10)0.0012 (10)0.0004 (11)
C50.0099 (12)0.0060 (12)0.0116 (15)0.0003 (10)0.0005 (11)0.0020 (11)
C60.0100 (12)0.0073 (12)0.0091 (14)0.0020 (10)0.0002 (10)0.0001 (11)
O110.0121 (9)0.0127 (10)0.0079 (10)0.0013 (8)0.0007 (8)0.0010 (8)
O120.0203 (10)0.0136 (10)0.0071 (10)0.0064 (8)0.0023 (8)0.0011 (8)
O130.0114 (9)0.0084 (9)0.0052 (10)0.0018 (7)0.0010 (7)0.0006 (7)
O140.0216 (10)0.0187 (11)0.0083 (11)0.0100 (9)0.0022 (8)0.0017 (8)
O150.0209 (10)0.0255 (11)0.0097 (11)0.0161 (9)0.0024 (8)0.0035 (9)
O160.0221 (10)0.0102 (10)0.0128 (11)0.0081 (8)0.0032 (8)0.0005 (8)
O170.0128 (9)0.0129 (10)0.0070 (10)0.0037 (8)0.0027 (7)0.0001 (8)
C110.0099 (12)0.0083 (13)0.0063 (14)0.0044 (10)0.0012 (10)0.0012 (10)
C120.0093 (12)0.0082 (13)0.0062 (14)0.0002 (10)0.0007 (10)0.0001 (10)
C130.0090 (12)0.0081 (13)0.0073 (14)0.0006 (10)0.0029 (10)0.0004 (10)
C140.0106 (12)0.0116 (13)0.0079 (14)0.0000 (10)0.0010 (10)0.0014 (11)
C150.0101 (12)0.0079 (13)0.0110 (15)0.0004 (10)0.0023 (10)0.0015 (11)
C160.0077 (12)0.0105 (13)0.0105 (14)0.0008 (10)0.0030 (10)0.0019 (11)
Geometric parameters (Å, º) top
Cu1—O21.921 (2)O11W—H2WA0.8399
Cu1—O31.929 (2)O12W—H1WB0.8399
Cu1—O4i1.934 (2)O12W—H2WB0.8402
Cu1—O1W2.018 (2)O1—C11.253 (3)
Cu1—O2W2.365 (2)O2—C11.276 (3)
Cu1—Cu1A0.40 (2)O3—C31.431 (3)
Cu2—O71.932 (2)O4—C51.273 (3)
Cu2—O5i1.934 (2)O5—C51.252 (3)
Cu2—O31.941 (2)O6—C61.230 (3)
Cu2—O1ii1.942 (2)O7—C61.290 (3)
Cu2—O16iii2.276 (2)C1—C21.507 (4)
Cu11—Cu1B0.55 (2)C2—C31.539 (4)
Cu11—O121.927 (2)C2—H2A0.9700
Cu11—O131.944 (2)C2—H2B0.9700
Cu11—O14iv1.921 (2)C3—C41.524 (4)
Cu11—O11W2.235 (2)C3—C61.539 (4)
Cu11—O12W2.105 (2)C4—C51.501 (4)
Cu12—O171.943 (2)C4—H4B0.9700
Cu12—O15iv1.943 (2)C4—H4C0.9700
Cu12—O131.932 (2)O11—C111.261 (3)
Cu12—O11v1.944 (2)O12—C111.265 (3)
Cu12—O62.335 (2)O13—C131.420 (3)
Cu1A—O21.942 (17)O14—C151.254 (3)
Cu1A—O31.945 (17)O15—C151.258 (3)
Cu1A—O4i1.997 (17)O16—C161.226 (3)
Cu1A—O2W2.05 (2)O17—C161.298 (3)
Cu1A—O1W2.250 (19)C11—C121.511 (4)
Cu1B—O11W1.854 (17)C12—C131.545 (4)
Cu1B—O131.858 (10)C12—H12B0.9700
Cu1B—O14iv1.964 (12)C12—H12C0.9700
Cu1B—O122.025 (12)C13—C141.527 (4)
O1W—H1W10.8400C13—C161.540 (4)
O1W—H2W10.8400C14—C151.508 (4)
O2W—H1W20.8400C14—H14B0.9700
O2W—H2W20.8400C14—H14C0.9700
O11W—H1WA0.8400
O2—Cu1—O396.44 (8)H1W1—O1W—H2W1101.8
O2—Cu1—O4i172.54 (8)H1W2—O2W—H2W292.6
O3—Cu1—O4i91.02 (8)H1WA—O11W—H2WA99.1
O2—Cu1—O1W88.69 (9)H1WB—O12W—H2WB112.9
O3—Cu1—O1W151.76 (11)O1—C1—O2122.2 (3)
O4i—Cu1—O1W84.71 (9)O1—C1—C2116.2 (2)
O2—Cu1—O2W87.73 (9)O2—C1—C2121.6 (2)
O3—Cu1—O2W121.32 (9)C1—C2—C3111.5 (2)
O4i—Cu1—O2W88.40 (8)C1—C2—H2A109.3
O1W—Cu1—O2W86.53 (8)C3—C2—H2A109.3
O7—Cu2—O5i163.60 (9)C1—C2—H2B109.3
O7—Cu2—O383.72 (8)C3—C2—H2B109.3
O5i—Cu2—O397.10 (8)H2A—C2—H2B108.0
O7—Cu2—O1ii89.43 (8)O3—C3—C4110.2 (2)
O5i—Cu2—O1ii89.67 (8)O3—C3—C6108.6 (2)
O3—Cu2—O1ii173.11 (8)C4—C3—C6111.2 (2)
O7—Cu2—O16iii100.36 (8)O3—C3—C2111.5 (2)
O5i—Cu2—O16iii95.85 (8)C4—C3—C2109.6 (2)
O3—Cu2—O16iii95.96 (8)C6—C3—C2105.6 (2)
O1ii—Cu2—O16iii84.58 (8)C5—C4—C3112.8 (2)
O14iv—Cu11—O12167.41 (8)C5—C4—H4B109.0
O14iv—Cu11—O1394.50 (9)C3—C4—H4B109.0
O12—Cu11—O1396.95 (8)C5—C4—H4C109.0
O14iv—Cu11—O12W85.42 (9)C3—C4—H4C109.0
O12—Cu11—O12W86.31 (9)H4B—C4—H4C107.8
O13—Cu11—O12W155.57 (10)O5—C5—O4125.5 (3)
O14iv—Cu11—O11W81.98 (9)O5—C5—C4117.6 (2)
O12—Cu11—O11W88.58 (9)O4—C5—C4116.9 (2)
O13—Cu11—O11W114.05 (10)O6—C6—O7122.6 (2)
O12W—Cu11—O11W90.17 (8)O6—C6—C3121.1 (2)
O13—Cu12—O15iv96.43 (8)O7—C6—C3116.1 (2)
O13—Cu12—O1784.95 (8)O11—C11—O12122.0 (2)
O15iv—Cu12—O17152.67 (9)O11—C11—C12117.5 (2)
O13—Cu12—O11v170.95 (8)O12—C11—C12120.5 (2)
O15iv—Cu12—O11v89.26 (9)C11—C12—C13110.9 (2)
O17—Cu12—O11v93.24 (8)C11—C12—H12B109.5
O13—Cu12—O683.21 (7)C13—C12—H12B109.5
O15iv—Cu12—O695.17 (8)C11—C12—H12C109.5
O17—Cu12—O6112.06 (8)C13—C12—H12C109.5
O11v—Cu12—O689.28 (7)H12B—C12—H12C108.0
O2—Cu1A—O395.2 (7)O13—C13—C14110.6 (2)
O2—Cu1A—O4i155.3 (12)O13—C13—C16108.8 (2)
O3—Cu1A—O4i88.7 (7)C14—C13—C16110.4 (2)
O2—Cu1A—O2W96.7 (8)O13—C13—C12112.3 (2)
O3—Cu1A—O2W139.2 (11)C14—C13—C12110.2 (2)
O4i—Cu1A—O2W96.1 (7)C16—C13—C12104.5 (2)
O2—Cu1A—O1W81.8 (7)C15—C14—C13113.8 (2)
O3—Cu1A—O1W131.5 (11)C15—C14—H14B108.8
O4i—Cu1A—O1W77.4 (6)C13—C14—H14B108.8
O2W—Cu1A—O1W88.8 (6)C15—C14—H14C108.8
Cu11—Cu1B—O11W127.5 (14)C13—C14—H14C108.8
Cu11—Cu1B—O1390.5 (12)H14B—C14—H14C107.7
O11W—Cu1B—O13141.9 (14)O14—C15—O15125.1 (3)
O11W—Cu1B—O14iv91.5 (5)O14—C15—C14118.3 (2)
O13—Cu1B—O14iv95.9 (5)O15—C15—C14116.6 (2)
O11W—Cu1B—O1297.3 (5)O16—C16—O17123.0 (2)
O13—Cu1B—O1296.5 (5)O16—C16—C13121.4 (2)
O14iv—Cu1B—O12147.0 (13)O17—C16—C13115.5 (2)
O1—C1—C2—C3131.5 (2)O11—C11—C12—C13124.4 (2)
O2—C1—C2—C347.6 (3)O12—C11—C12—C1354.2 (3)
C1—C2—C3—O369.1 (3)C11—C12—C13—O1369.7 (3)
C1—C2—C3—C453.2 (3)C11—C12—C13—C1454.1 (3)
C1—C2—C3—C6173.1 (2)C11—C12—C13—C16172.6 (2)
O3—C3—C4—C555.5 (3)O13—C13—C14—C1564.1 (3)
C6—C3—C4—C565.0 (3)C16—C13—C14—C1556.3 (3)
C2—C3—C4—C5178.6 (2)C12—C13—C14—C15171.2 (2)
C3—C4—C5—O5135.9 (2)C13—C14—C15—O142.3 (3)
C3—C4—C5—O444.4 (3)C13—C14—C15—O15177.3 (2)
O3—C3—C6—O6172.5 (2)O13—C13—C16—O16158.0 (2)
C4—C3—C6—O651.1 (3)C14—C13—C16—O1636.5 (3)
C2—C3—C6—O667.7 (3)C12—C13—C16—O1681.9 (3)
O3—C3—C6—O711.6 (3)O13—C13—C16—O1724.7 (3)
C4—C3—C6—O7133.0 (2)C14—C13—C16—O17146.1 (2)
C2—C3—C6—O7108.2 (3)C12—C13—C16—O1795.4 (3)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y1/2, z1/2; (iii) x, y1, z; (iv) x, y1/2, z+1/2; (v) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O7i0.842.333.130 (3)159
O1W—H2W1···O2Wvi0.841.982.820 (3)180
O2W—H1W2···O17iii0.841.882.706 (3)168
O11W—H2WA···O17iv0.842.403.195 (3)157
O11W—H1WA···O12Wvii0.841.962.797 (3)175
O12W—H1WB···O70.841.882.715 (3)170
O12W—H2WB···O15iii0.842.403.152 (3)149
Symmetry codes: (i) x+1, y1/2, z+1/2; (iii) x, y1, z; (iv) x, y1/2, z+1/2; (vi) x+1, y1, z+1; (vii) x, y, z.

Experimental details

Crystal data
Chemical formula[Cu4(C6H4O7)2(H2O)4]
Mr702.45
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)13.749 (4), 9.713 (4), 14.471 (6)
β (°) 91.56 (3)
V3)1931.8 (13)
Z4
Radiation typeMo Kα
µ (mm1)4.44
Crystal size (mm)0.6 × 0.34 × 0.25
Data collection
DiffractometerOxford Diffraction KM-4 CCD area-detector
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2003)
Tmin, Tmax0.15, 0.33
No. of measured, independent and
observed [I > 2σ(I)] reflections
11784, 3973, 3341
Rint0.038
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.069, 1.02
No. of reflections3973
No. of parameters316
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.55, 0.57

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999), SHELXTL/PC (Sheldrick, 1990) and XtalDraw (Downs & Hall-Wallace, 2003), SHELXL97.

Selected torsion angles (º) top
O2—C1—C2—C347.6 (3)O12—C11—C12—C1354.2 (3)
C3—C4—C5—O444.4 (3)C13—C14—C15—O142.3 (3)
C2—C3—C6—O667.7 (3)C12—C13—C16—O1681.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O7i0.842.333.130 (3)159
O1W—H2W1···O2Wii0.841.982.820 (3)180
O2W—H1W2···O17iii0.841.882.706 (3)168
O11W—H2WA···O17iv0.842.403.195 (3)157
O11W—H1WA···O12Wv0.841.962.797 (3)175
O12W—H1WB···O70.841.882.715 (3)170
O12W—H2WB···O15iii0.842.403.152 (3)149
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y1, z+1; (iii) x, y1, z; (iv) x, y1/2, z+1/2; (v) x, y, z.
 

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