Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039086/hg2275sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039086/hg2275Isup2.hkl |
CCDC reference: 660106
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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.
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).
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).
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.
[Cu4(C6H4O7)2(H2O)4] | F(000) = 1392 |
Mr = 702.45 | Dx = 2.415 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 12949 reflections |
a = 13.749 (4) Å | θ = 2.9–26.6° |
b = 9.713 (4) Å | µ = 4.44 mm−1 |
c = 14.471 (6) Å | T = 120 K |
β = 91.56 (3)° | Block, green |
V = 1931.8 (13) Å3 | 0.6 × 0.34 × 0.25 mm |
Z = 4 |
Oxford Diffraction KM-4 CCD area-detector diffractometer | 3973 independent reflections |
Radiation source: fine-focus sealed tube | 3341 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 26.5°, θmin = 3.0° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | h = −17→17 |
Tmin = 0.15, Tmax = 0.33 | k = −12→10 |
11784 measured reflections | l = −18→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-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 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Cu4(C6H4O7)2(H2O)4] | V = 1931.8 (13) Å3 |
Mr = 702.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.749 (4) Å | µ = 4.44 mm−1 |
b = 9.713 (4) Å | T = 120 K |
c = 14.471 (6) Å | 0.6 × 0.34 × 0.25 mm |
β = 91.56 (3)° |
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 = 0.33 | Rint = 0.038 |
11784 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.55 e Å−3 |
3973 reflections | Δρmin = −0.57 e Å−3 |
316 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.46981 (8) | −0.33007 (10) | 0.36000 (4) | 0.00878 (16) | 0.955 (5) |
Cu2 | 0.34787 (2) | −0.26017 (3) | 0.16600 (2) | 0.00760 (10) | |
Cu11 | 0.06839 (8) | 0.12127 (10) | 0.15292 (3) | 0.0103 (2) | 0.955 (5) |
Cu12 | 0.15173 (2) | 0.25321 (3) | 0.33927 (2) | 0.00756 (10) | |
Cu1A | 0.4490 (14) | −0.3560 (19) | 0.3522 (12) | 0.016 (4)* | 0.045 (5) |
Cu1B | 0.0381 (14) | 0.1574 (19) | 0.1451 (8) | 0.009 (3)* | 0.045 (5) |
O1W | 0.58264 (14) | −0.3905 (2) | 0.44238 (13) | 0.0141 (4) | |
H1W1 | 0.6142 | −0.4585 | 0.4235 | 0.021* | |
H2W1 | 0.5827 | −0.4048 | 0.4996 | 0.021* | |
O2W | 0.41608 (14) | −0.5611 (2) | 0.36561 (14) | 0.0168 (5) | |
H1W2 | 0.3582 | −0.5752 | 0.3481 | 0.025* | |
H2W2 | 0.4381 | −0.6101 | 0.3232 | 0.025* | |
O11W | −0.07413 (14) | 0.1233 (2) | 0.07486 (14) | 0.0188 (5) | |
H1WA | −0.0788 | 0.1173 | 0.0170 | 0.028* | |
H2WA | −0.1240 | 0.0786 | 0.0885 | 0.028* | |
O12W | 0.08871 (13) | −0.08641 (19) | 0.11672 (14) | 0.0146 (4) | |
H1WB | 0.1477 | −0.0962 | 0.1320 | 0.022* | |
H2WB | 0.0529 | −0.1467 | 0.1398 | 0.022* | |
O1 | 0.28209 (13) | −0.19504 (19) | 0.54941 (13) | 0.0117 (4) | |
O2 | 0.39643 (14) | −0.2967 (2) | 0.46885 (13) | 0.0142 (4) | |
O3 | 0.40390 (12) | −0.19572 (18) | 0.28274 (13) | 0.0090 (4) | |
O4 | 0.44720 (13) | 0.1186 (2) | 0.24013 (13) | 0.0131 (4) | |
O5 | 0.55877 (13) | 0.0951 (2) | 0.35529 (14) | 0.0165 (4) | |
O6 | 0.22539 (13) | 0.06961 (19) | 0.26405 (13) | 0.0130 (4) | |
O7 | 0.28046 (13) | −0.08570 (19) | 0.16685 (13) | 0.0101 (4) | |
C1 | 0.31930 (19) | −0.2243 (3) | 0.47378 (19) | 0.0100 (6) | |
C2 | 0.26865 (18) | −0.1671 (3) | 0.38848 (18) | 0.0091 (5) | |
H2A | 0.2201 | −0.1006 | 0.4065 | 0.011* | |
H2B | 0.2355 | −0.2411 | 0.3554 | 0.011* | |
C3 | 0.34105 (18) | −0.0973 (3) | 0.32411 (18) | 0.0079 (5) | |
C4 | 0.40083 (18) | 0.0091 (3) | 0.37832 (18) | 0.0091 (5) | |
H4B | 0.3574 | 0.0778 | 0.4029 | 0.011* | |
H4C | 0.4337 | −0.0360 | 0.4302 | 0.011* | |
C5 | 0.47510 (18) | 0.0793 (3) | 0.32053 (19) | 0.0091 (5) | |
C6 | 0.27838 (19) | −0.0288 (3) | 0.24731 (19) | 0.0088 (5) | |
O11 | 0.22315 (13) | 0.29627 (19) | −0.04781 (13) | 0.0109 (4) | |
O12 | 0.13140 (14) | 0.16551 (19) | 0.03933 (13) | 0.0136 (4) | |
O13 | 0.09871 (13) | 0.29247 (18) | 0.21706 (12) | 0.0083 (4) | |
O14 | 0.01121 (14) | 0.5506 (2) | 0.25088 (14) | 0.0162 (4) | |
O15 | −0.04164 (15) | 0.6468 (2) | 0.11897 (14) | 0.0187 (5) | |
O16 | 0.23375 (14) | 0.60134 (18) | 0.22896 (14) | 0.0150 (4) | |
O17 | 0.22314 (13) | 0.42411 (19) | 0.32481 (13) | 0.0110 (4) | |
C11 | 0.19406 (19) | 0.2596 (3) | 0.03031 (18) | 0.0082 (5) | |
C12 | 0.23525 (18) | 0.3348 (3) | 0.11400 (18) | 0.0079 (5) | |
H12B | 0.2776 | 0.4082 | 0.0941 | 0.010* | |
H12C | 0.2738 | 0.2715 | 0.1518 | 0.010* | |
C13 | 0.15300 (18) | 0.3959 (3) | 0.17203 (18) | 0.0081 (5) | |
C14 | 0.08611 (19) | 0.4857 (3) | 0.11149 (19) | 0.0100 (6) | |
H14B | 0.1256 | 0.5493 | 0.0770 | 0.012* | |
H14C | 0.0515 | 0.4274 | 0.0672 | 0.012* | |
C15 | 0.01295 (18) | 0.5668 (3) | 0.16499 (19) | 0.0096 (5) | |
C16 | 0.20629 (18) | 0.4841 (3) | 0.24588 (19) | 0.0095 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0099 (3) | 0.0103 (3) | 0.0061 (2) | 0.0030 (2) | 0.00042 (19) | 0.00081 (19) |
Cu2 | 0.00742 (17) | 0.00875 (18) | 0.00656 (19) | 0.00170 (12) | −0.00111 (13) | −0.00171 (12) |
Cu11 | 0.0150 (4) | 0.0100 (3) | 0.0060 (2) | −0.0046 (3) | 0.00202 (17) | −0.00110 (17) |
Cu12 | 0.00874 (17) | 0.00843 (18) | 0.00547 (19) | −0.00169 (12) | −0.00062 (13) | 0.00043 (12) |
O1W | 0.0151 (9) | 0.0176 (11) | 0.0094 (10) | 0.0012 (8) | −0.0012 (8) | 0.0015 (8) |
O2W | 0.0140 (10) | 0.0202 (11) | 0.0159 (11) | −0.0032 (8) | −0.0042 (8) | −0.0019 (9) |
O11W | 0.0141 (10) | 0.0286 (12) | 0.0138 (11) | 0.0006 (9) | −0.0023 (8) | 0.0009 (9) |
O12W | 0.0094 (9) | 0.0131 (10) | 0.0212 (12) | −0.0025 (8) | −0.0024 (8) | 0.0003 (8) |
O1 | 0.0109 (9) | 0.0124 (10) | 0.0117 (11) | 0.0008 (8) | −0.0001 (8) | 0.0010 (8) |
O2 | 0.0165 (10) | 0.0180 (10) | 0.0084 (10) | 0.0070 (8) | 0.0023 (8) | 0.0024 (8) |
O3 | 0.0084 (9) | 0.0095 (9) | 0.0090 (10) | 0.0020 (7) | −0.0009 (7) | −0.0022 (8) |
O4 | 0.0123 (9) | 0.0177 (10) | 0.0094 (10) | −0.0054 (8) | −0.0001 (8) | 0.0022 (8) |
O5 | 0.0118 (9) | 0.0199 (11) | 0.0175 (11) | −0.0071 (8) | −0.0056 (8) | 0.0083 (9) |
O6 | 0.0166 (10) | 0.0133 (10) | 0.0091 (10) | 0.0065 (8) | −0.0007 (8) | −0.0013 (8) |
O7 | 0.0124 (9) | 0.0119 (9) | 0.0058 (10) | 0.0024 (7) | −0.0026 (7) | −0.0023 (8) |
C1 | 0.0124 (13) | 0.0068 (13) | 0.0108 (15) | −0.0038 (10) | 0.0030 (11) | 0.0013 (11) |
C2 | 0.0075 (12) | 0.0103 (13) | 0.0096 (14) | −0.0008 (10) | 0.0011 (10) | −0.0007 (11) |
C3 | 0.0082 (12) | 0.0085 (13) | 0.0071 (14) | 0.0010 (10) | 0.0019 (10) | 0.0004 (10) |
C4 | 0.0095 (12) | 0.0115 (13) | 0.0062 (14) | −0.0004 (10) | 0.0012 (10) | −0.0004 (11) |
C5 | 0.0099 (12) | 0.0060 (12) | 0.0116 (15) | 0.0003 (10) | 0.0005 (11) | −0.0020 (11) |
C6 | 0.0100 (12) | 0.0073 (12) | 0.0091 (14) | −0.0020 (10) | 0.0002 (10) | 0.0001 (11) |
O11 | 0.0121 (9) | 0.0127 (10) | 0.0079 (10) | −0.0013 (8) | 0.0007 (8) | 0.0010 (8) |
O12 | 0.0203 (10) | 0.0136 (10) | 0.0071 (10) | −0.0064 (8) | 0.0023 (8) | −0.0011 (8) |
O13 | 0.0114 (9) | 0.0084 (9) | 0.0052 (10) | −0.0018 (7) | 0.0010 (7) | 0.0006 (7) |
O14 | 0.0216 (10) | 0.0187 (11) | 0.0083 (11) | 0.0100 (9) | 0.0022 (8) | 0.0017 (8) |
O15 | 0.0209 (10) | 0.0255 (11) | 0.0097 (11) | 0.0161 (9) | 0.0024 (8) | 0.0035 (9) |
O16 | 0.0221 (10) | 0.0102 (10) | 0.0128 (11) | −0.0081 (8) | 0.0032 (8) | −0.0005 (8) |
O17 | 0.0128 (9) | 0.0129 (10) | 0.0070 (10) | −0.0037 (8) | −0.0027 (7) | 0.0001 (8) |
C11 | 0.0099 (12) | 0.0083 (13) | 0.0063 (14) | 0.0044 (10) | 0.0012 (10) | 0.0012 (10) |
C12 | 0.0093 (12) | 0.0082 (13) | 0.0062 (14) | −0.0002 (10) | −0.0007 (10) | 0.0001 (10) |
C13 | 0.0090 (12) | 0.0081 (13) | 0.0073 (14) | 0.0006 (10) | 0.0029 (10) | 0.0004 (10) |
C14 | 0.0106 (12) | 0.0116 (13) | 0.0079 (14) | 0.0000 (10) | 0.0010 (10) | 0.0014 (11) |
C15 | 0.0101 (12) | 0.0079 (13) | 0.0110 (15) | −0.0004 (10) | 0.0023 (10) | 0.0015 (11) |
C16 | 0.0077 (12) | 0.0105 (13) | 0.0105 (14) | −0.0008 (10) | 0.0030 (10) | −0.0019 (11) |
Cu1—O2 | 1.921 (2) | O11W—H2WA | 0.8399 |
Cu1—O3 | 1.929 (2) | O12W—H1WB | 0.8399 |
Cu1—O4i | 1.934 (2) | O12W—H2WB | 0.8402 |
Cu1—O1W | 2.018 (2) | O1—C1 | 1.253 (3) |
Cu1—O2W | 2.365 (2) | O2—C1 | 1.276 (3) |
Cu1—Cu1A | 0.40 (2) | O3—C3 | 1.431 (3) |
Cu2—O7 | 1.932 (2) | O4—C5 | 1.273 (3) |
Cu2—O5i | 1.934 (2) | O5—C5 | 1.252 (3) |
Cu2—O3 | 1.941 (2) | O6—C6 | 1.230 (3) |
Cu2—O1ii | 1.942 (2) | O7—C6 | 1.290 (3) |
Cu2—O16iii | 2.276 (2) | C1—C2 | 1.507 (4) |
Cu11—Cu1B | 0.55 (2) | C2—C3 | 1.539 (4) |
Cu11—O12 | 1.927 (2) | C2—H2A | 0.9700 |
Cu11—O13 | 1.944 (2) | C2—H2B | 0.9700 |
Cu11—O14iv | 1.921 (2) | C3—C4 | 1.524 (4) |
Cu11—O11W | 2.235 (2) | C3—C6 | 1.539 (4) |
Cu11—O12W | 2.105 (2) | C4—C5 | 1.501 (4) |
Cu12—O17 | 1.943 (2) | C4—H4B | 0.9700 |
Cu12—O15iv | 1.943 (2) | C4—H4C | 0.9700 |
Cu12—O13 | 1.932 (2) | O11—C11 | 1.261 (3) |
Cu12—O11v | 1.944 (2) | O12—C11 | 1.265 (3) |
Cu12—O6 | 2.335 (2) | O13—C13 | 1.420 (3) |
Cu1A—O2 | 1.942 (17) | O14—C15 | 1.254 (3) |
Cu1A—O3 | 1.945 (17) | O15—C15 | 1.258 (3) |
Cu1A—O4i | 1.997 (17) | O16—C16 | 1.226 (3) |
Cu1A—O2W | 2.05 (2) | O17—C16 | 1.298 (3) |
Cu1A—O1W | 2.250 (19) | C11—C12 | 1.511 (4) |
Cu1B—O11W | 1.854 (17) | C12—C13 | 1.545 (4) |
Cu1B—O13 | 1.858 (10) | C12—H12B | 0.9700 |
Cu1B—O14iv | 1.964 (12) | C12—H12C | 0.9700 |
Cu1B—O12 | 2.025 (12) | C13—C14 | 1.527 (4) |
O1W—H1W1 | 0.8400 | C13—C16 | 1.540 (4) |
O1W—H2W1 | 0.8400 | C14—C15 | 1.508 (4) |
O2W—H1W2 | 0.8400 | C14—H14B | 0.9700 |
O2W—H2W2 | 0.8400 | C14—H14C | 0.9700 |
O11W—H1WA | 0.8400 | ||
O2—Cu1—O3 | 96.44 (8) | H1W1—O1W—H2W1 | 101.8 |
O2—Cu1—O4i | 172.54 (8) | H1W2—O2W—H2W2 | 92.6 |
O3—Cu1—O4i | 91.02 (8) | H1WA—O11W—H2WA | 99.1 |
O2—Cu1—O1W | 88.69 (9) | H1WB—O12W—H2WB | 112.9 |
O3—Cu1—O1W | 151.76 (11) | O1—C1—O2 | 122.2 (3) |
O4i—Cu1—O1W | 84.71 (9) | O1—C1—C2 | 116.2 (2) |
O2—Cu1—O2W | 87.73 (9) | O2—C1—C2 | 121.6 (2) |
O3—Cu1—O2W | 121.32 (9) | C1—C2—C3 | 111.5 (2) |
O4i—Cu1—O2W | 88.40 (8) | C1—C2—H2A | 109.3 |
O1W—Cu1—O2W | 86.53 (8) | C3—C2—H2A | 109.3 |
O7—Cu2—O5i | 163.60 (9) | C1—C2—H2B | 109.3 |
O7—Cu2—O3 | 83.72 (8) | C3—C2—H2B | 109.3 |
O5i—Cu2—O3 | 97.10 (8) | H2A—C2—H2B | 108.0 |
O7—Cu2—O1ii | 89.43 (8) | O3—C3—C4 | 110.2 (2) |
O5i—Cu2—O1ii | 89.67 (8) | O3—C3—C6 | 108.6 (2) |
O3—Cu2—O1ii | 173.11 (8) | C4—C3—C6 | 111.2 (2) |
O7—Cu2—O16iii | 100.36 (8) | O3—C3—C2 | 111.5 (2) |
O5i—Cu2—O16iii | 95.85 (8) | C4—C3—C2 | 109.6 (2) |
O3—Cu2—O16iii | 95.96 (8) | C6—C3—C2 | 105.6 (2) |
O1ii—Cu2—O16iii | 84.58 (8) | C5—C4—C3 | 112.8 (2) |
O14iv—Cu11—O12 | 167.41 (8) | C5—C4—H4B | 109.0 |
O14iv—Cu11—O13 | 94.50 (9) | C3—C4—H4B | 109.0 |
O12—Cu11—O13 | 96.95 (8) | C5—C4—H4C | 109.0 |
O14iv—Cu11—O12W | 85.42 (9) | C3—C4—H4C | 109.0 |
O12—Cu11—O12W | 86.31 (9) | H4B—C4—H4C | 107.8 |
O13—Cu11—O12W | 155.57 (10) | O5—C5—O4 | 125.5 (3) |
O14iv—Cu11—O11W | 81.98 (9) | O5—C5—C4 | 117.6 (2) |
O12—Cu11—O11W | 88.58 (9) | O4—C5—C4 | 116.9 (2) |
O13—Cu11—O11W | 114.05 (10) | O6—C6—O7 | 122.6 (2) |
O12W—Cu11—O11W | 90.17 (8) | O6—C6—C3 | 121.1 (2) |
O13—Cu12—O15iv | 96.43 (8) | O7—C6—C3 | 116.1 (2) |
O13—Cu12—O17 | 84.95 (8) | O11—C11—O12 | 122.0 (2) |
O15iv—Cu12—O17 | 152.67 (9) | O11—C11—C12 | 117.5 (2) |
O13—Cu12—O11v | 170.95 (8) | O12—C11—C12 | 120.5 (2) |
O15iv—Cu12—O11v | 89.26 (9) | C11—C12—C13 | 110.9 (2) |
O17—Cu12—O11v | 93.24 (8) | C11—C12—H12B | 109.5 |
O13—Cu12—O6 | 83.21 (7) | C13—C12—H12B | 109.5 |
O15iv—Cu12—O6 | 95.17 (8) | C11—C12—H12C | 109.5 |
O17—Cu12—O6 | 112.06 (8) | C13—C12—H12C | 109.5 |
O11v—Cu12—O6 | 89.28 (7) | H12B—C12—H12C | 108.0 |
O2—Cu1A—O3 | 95.2 (7) | O13—C13—C14 | 110.6 (2) |
O2—Cu1A—O4i | 155.3 (12) | O13—C13—C16 | 108.8 (2) |
O3—Cu1A—O4i | 88.7 (7) | C14—C13—C16 | 110.4 (2) |
O2—Cu1A—O2W | 96.7 (8) | O13—C13—C12 | 112.3 (2) |
O3—Cu1A—O2W | 139.2 (11) | C14—C13—C12 | 110.2 (2) |
O4i—Cu1A—O2W | 96.1 (7) | C16—C13—C12 | 104.5 (2) |
O2—Cu1A—O1W | 81.8 (7) | C15—C14—C13 | 113.8 (2) |
O3—Cu1A—O1W | 131.5 (11) | C15—C14—H14B | 108.8 |
O4i—Cu1A—O1W | 77.4 (6) | C13—C14—H14B | 108.8 |
O2W—Cu1A—O1W | 88.8 (6) | C15—C14—H14C | 108.8 |
Cu11—Cu1B—O11W | 127.5 (14) | C13—C14—H14C | 108.8 |
Cu11—Cu1B—O13 | 90.5 (12) | H14B—C14—H14C | 107.7 |
O11W—Cu1B—O13 | 141.9 (14) | O14—C15—O15 | 125.1 (3) |
O11W—Cu1B—O14iv | 91.5 (5) | O14—C15—C14 | 118.3 (2) |
O13—Cu1B—O14iv | 95.9 (5) | O15—C15—C14 | 116.6 (2) |
O11W—Cu1B—O12 | 97.3 (5) | O16—C16—O17 | 123.0 (2) |
O13—Cu1B—O12 | 96.5 (5) | O16—C16—C13 | 121.4 (2) |
O14iv—Cu1B—O12 | 147.0 (13) | O17—C16—C13 | 115.5 (2) |
O1—C1—C2—C3 | 131.5 (2) | O11—C11—C12—C13 | 124.4 (2) |
O2—C1—C2—C3 | −47.6 (3) | O12—C11—C12—C13 | −54.2 (3) |
C1—C2—C3—O3 | 69.1 (3) | C11—C12—C13—O13 | 69.7 (3) |
C1—C2—C3—C4 | −53.2 (3) | C11—C12—C13—C14 | −54.1 (3) |
C1—C2—C3—C6 | −173.1 (2) | C11—C12—C13—C16 | −172.6 (2) |
O3—C3—C4—C5 | 55.5 (3) | O13—C13—C14—C15 | 64.1 (3) |
C6—C3—C4—C5 | −65.0 (3) | C16—C13—C14—C15 | −56.3 (3) |
C2—C3—C4—C5 | 178.6 (2) | C12—C13—C14—C15 | −171.2 (2) |
C3—C4—C5—O5 | −135.9 (2) | C13—C14—C15—O14 | −2.3 (3) |
C3—C4—C5—O4 | 44.4 (3) | C13—C14—C15—O15 | 177.3 (2) |
O3—C3—C6—O6 | −172.5 (2) | O13—C13—C16—O16 | −158.0 (2) |
C4—C3—C6—O6 | −51.1 (3) | C14—C13—C16—O16 | −36.5 (3) |
C2—C3—C6—O6 | 67.7 (3) | C12—C13—C16—O16 | 81.9 (3) |
O3—C3—C6—O7 | 11.6 (3) | O13—C13—C16—O17 | 24.7 (3) |
C4—C3—C6—O7 | 133.0 (2) | C14—C13—C16—O17 | 146.1 (2) |
C2—C3—C6—O7 | −108.2 (3) | C12—C13—C16—O17 | −95.4 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y−1/2, z−1/2; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O7i | 0.84 | 2.33 | 3.130 (3) | 159 |
O1W—H2W1···O2Wvi | 0.84 | 1.98 | 2.820 (3) | 180 |
O2W—H1W2···O17iii | 0.84 | 1.88 | 2.706 (3) | 168 |
O11W—H2WA···O17iv | 0.84 | 2.40 | 3.195 (3) | 157 |
O11W—H1WA···O12Wvii | 0.84 | 1.96 | 2.797 (3) | 175 |
O12W—H1WB···O7 | 0.84 | 1.88 | 2.715 (3) | 170 |
O12W—H2WB···O15iii | 0.84 | 2.40 | 3.152 (3) | 149 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1/2; (vi) −x+1, −y−1, −z+1; (vii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C6H4O7)2(H2O)4] |
Mr | 702.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.749 (4), 9.713 (4), 14.471 (6) |
β (°) | 91.56 (3) |
V (Å3) | 1931.8 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.44 |
Crystal size (mm) | 0.6 × 0.34 × 0.25 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4 CCD area-detector |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2003) |
Tmin, Tmax | 0.15, 0.33 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11784, 3973, 3341 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.069, 1.02 |
No. of reflections | 3973 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
O2—C1—C2—C3 | −47.6 (3) | O12—C11—C12—C13 | −54.2 (3) |
C3—C4—C5—O4 | 44.4 (3) | C13—C14—C15—O14 | −2.3 (3) |
C2—C3—C6—O6 | 67.7 (3) | C12—C13—C16—O16 | 81.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O7i | 0.84 | 2.33 | 3.130 (3) | 159 |
O1W—H2W1···O2Wii | 0.84 | 1.98 | 2.820 (3) | 180 |
O2W—H1W2···O17iii | 0.84 | 1.88 | 2.706 (3) | 168 |
O11W—H2WA···O17iv | 0.84 | 2.40 | 3.195 (3) | 157 |
O11W—H1WA···O12Wv | 0.84 | 1.96 | 2.797 (3) | 175 |
O12W—H1WB···O7 | 0.84 | 1.88 | 2.715 (3) | 170 |
O12W—H2WB···O15iii | 0.84 | 2.40 | 3.152 (3) | 149 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y−1, −z+1; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1/2; (v) −x, −y, −z. |
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).