Download citation
Download citation
link to html
The crystal structure of [Cu(C11H10N2O2)2](C2H3O2)2·4H2O reveals an extended O—H...O hydrogen-bond network between helicoidal chains of water mol­ecules and layers of [Cu(N,O,N′-dpkdiol)2]2+ complex cations and acetate anions held together by means of carboxyl­ate–diol hydrogen bonds. The cation has crystallographic inversion symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803014399/ac6048sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803014399/ac6048Isup2.hkl
Contains datablock I

CCDC reference: 217431

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.049
  • wR factor = 0.115
  • Data-to-parameter ratio = 21.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 0.84(3), Rep 0.845(10) ...... 3.00 su-Rat O10 -H10B 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.848(10) ...... 3.00 su-Rat O11 -H11A 1.555 1.555 PLAT_731 Alert C Bond Calc 0.84(3), Rep 0.842(10) ...... 3.00 su-Rat O11 -H11B 1.555 1.555 PLAT_735 Alert C D-H Calc 0.84(3), Rep 0.845(10) ...... 3.00 su-Rat O10 -H10B 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.848(10) ...... 3.00 su-Rat O11 -H11A 1.555 1.555 PLAT_735 Alert C D-H Calc 0.84(3), Rep 0.842(10) ...... 3.00 su-Rat O11 -H11B 1.555 1.555 PLAT_736 Alert C H...A Calc 1.91(3), Rep 1.906(12) ...... 2.50 su-Rat H10B -O11 1.555 2.454 PLAT_736 Alert C H...A Calc 1.92(3), Rep 1.915(14) ...... 2.14 su-Rat H11A -O1 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
8 Alert Level C = Please check

Comment top

The di-2-pyridyl-ketone ligand (dpk) has been observed to undergo hydration of the ketocarbonyl group, forming a gem-diol after initial N,N'-coordination to a transition metal (Wang et al., 1986). This gem-diol ligand (dpkdiol) can coordinate both as a N,N'-bidentate ligand (Parker et al., 2000) or as an N,O,N'-tridentate ligand, either protonated (Sommerer et al., 1993; Tangoulis et al., 1997; Yang et al., 1998; Serna et al., 1999) or deprotonated (Sommerer et al., 1990; Breeze et al., 1996; Tong et al., 1998; Hemmert et al., 1999; Woltz et al., 2002). The title complex, (I), which was obtained in the attempt to prepare a copper-dpk-Keggin complex, consists of [Cu(N,O,N'-dpkdiol)2]2+ complex cations, acetate anions and hydration water molecules.

The Cu atom lies in a distorted elongated octahedral CuN4O2 environment. The equatorial coordination positions are occupied by the N atoms of the dpkdiol ligands, while two hydroxyl groups occupy the axial ones. The two hydroxyl groups of the ligands and the acetate anions are forming two strong face-to-face carboxylate–diol hydrogen bonds, leading to trimeric entities built up of one cationic complex and two acetate anions (Fig. 1). These entities are placed in layers parallel to the (001) plane which are connected by an extented O—H···O hydrogen-bond network between the O atoms of the acetate anions and helicoidal chains of hydration water running parallel to the b axis (Fig. 2).

Experimental top

A solution containing 68 mg of CuCl2·2H2O, 25 mg of oxalic acid and 74 mg of dpk in 30 ml of water and 10 ml of methanol was added to a solution of 667 mg of K4SiW12O40 in 50 ml of water and a violet precipitate was formed. The title compound was obtained upon recrystallization of the precipitate in a 2:1 mixture of an acetate buffer and DMF. Elemental analysis(%): found (C, H, N) 46.76, 5.16, 8.42; calculated for C26CuH26N4O8·4H2O: 47.45, 5.21, 8.51. IR (cm−1): 1523, 1427, 1230, 1217, 1032.

Refinement top

The H atoms of the water molecules and hydroxyl groups of the dpkdiol ligand were located in a Fourier difference map. The positions of all remaining H atoms were calculated geometrically. Water molecule H atoms were refined with the O—H distance constrained to 0.85 (1) Å. All remaining H atoms were refined as riding, with isotropic displacement parameters fixed at 1.2 (aromatic C) or 1.5 (methyl and hydroxyl groups) times the equivalent isotropic displacement parameters of their parent atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: DIRDIF99.2 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) (50% probability displacement ellipsoids). Suffix a on atom labels represents symmetry operation (-x, −y, −z).
[Figure 2] Fig. 2. View of the crystal packing along the b axis.
(I) top
Crystal data top
[Cu(C11H10N2O2)2](C2H3O2)2·4H2OF(000) = 686
Mr = 658.11Dx = 1.408 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6500 reflections
a = 8.617 (1) Åθ = 3.5–25°
b = 7.8765 (9) ŵ = 0.77 mm1
c = 23.103 (3) ÅT = 293 K
β = 98.00 (1)°Prism, purple
V = 1552.8 (3) Å30.37 × 0.23 × 0.10 mm
Z = 2
Data collection top
Xcalibur
diffractometer
4484 independent reflections
Radiation source: fine-focus sealed tube2765 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 1024 × 1024 with blocks 2 × 2 pixels mm-1θmax = 30°, θmin = 3.5°
ω scansh = 1212
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2002)
k = 118
Tmin = 0.793, Tmax = 0.931l = 3232
12971 measured reflections
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)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115 w = 1/[σ2(Fo2) + (0.0588P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
4480 reflectionsΔρmax = 0.47 e Å3
211 parametersΔρmin = 0.34 e Å3
4 restraints
Crystal data top
[Cu(C11H10N2O2)2](C2H3O2)2·4H2OV = 1552.8 (3) Å3
Mr = 658.11Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.617 (1) ŵ = 0.77 mm1
b = 7.8765 (9) ÅT = 293 K
c = 23.103 (3) Å0.37 × 0.23 × 0.10 mm
β = 98.00 (1)°
Data collection top
Xcalibur
diffractometer
4484 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2002)
2765 reflections with I > 2σ(I)
Tmin = 0.793, Tmax = 0.931Rint = 0.044
12971 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0494 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.47 e Å3
4480 reflectionsΔρmin = 0.34 e Å3
211 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.00000.00000.00000.03418 (12)
O140.03830 (18)0.26003 (18)0.05417 (6)0.0367 (3)
H140.04350.25760.08990.055*
O150.2598 (2)0.43429 (19)0.06184 (7)0.0479 (4)
H150.26230.43410.09750.072*
N10.2177 (2)0.0169 (2)0.04184 (7)0.0342 (4)
N130.0808 (2)0.1706 (2)0.05422 (7)0.0362 (4)
C20.2932 (3)0.1636 (3)0.05549 (11)0.0448 (6)
H20.24290.26540.04450.054*
C30.4424 (3)0.1677 (3)0.08517 (13)0.0568 (7)
H30.49190.27080.09490.068*
C40.5179 (3)0.0169 (3)0.10027 (13)0.0607 (7)
H40.61980.01710.11980.073*
C50.4416 (3)0.1343 (3)0.08622 (11)0.0479 (6)
H50.49090.23720.09640.058*
C60.2907 (2)0.1307 (3)0.05680 (9)0.0339 (5)
C70.1888 (3)0.2873 (2)0.03881 (9)0.0352 (5)
C80.1650 (2)0.2981 (2)0.02719 (10)0.0356 (5)
C90.2239 (3)0.4264 (3)0.05854 (11)0.0462 (6)
H90.28250.51410.03940.055*
C100.1942 (3)0.4222 (3)0.11879 (12)0.0547 (7)
H100.23190.50800.14070.066*
C110.1092 (3)0.2917 (3)0.14599 (11)0.0563 (7)
H110.08910.28680.18660.068*
C120.0535 (3)0.1673 (3)0.11248 (10)0.0458 (6)
H120.00470.07840.13100.055*
C200.1655 (3)0.3480 (3)0.19680 (11)0.0532 (7)
C210.1604 (5)0.3642 (5)0.26154 (13)0.0883 (11)
H21A0.18040.25540.27980.132*
H21B0.05880.40370.26790.132*
H21C0.23870.44370.27810.132*
O10.0614 (2)0.2591 (2)0.16774 (8)0.0582 (5)
O20.2713 (2)0.4210 (3)0.17510 (8)0.0656 (5)
O100.5910 (3)0.3908 (3)0.21450 (10)0.0762 (6)
O110.2041 (3)0.1290 (3)0.20391 (11)0.0742 (6)
H10A0.4931 (14)0.409 (5)0.2079 (14)0.089*
H10B0.619 (4)0.473 (3)0.2368 (13)0.089*
H11A0.124 (3)0.184 (4)0.1972 (15)0.089*
H11B0.263 (3)0.210 (3)0.2101 (16)0.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0351 (2)0.03151 (19)0.0341 (2)0.00007 (17)0.00151 (13)0.00008 (16)
O140.0406 (8)0.0370 (8)0.0332 (8)0.0042 (6)0.0071 (6)0.0024 (6)
O150.0667 (12)0.0307 (7)0.0457 (10)0.0103 (8)0.0053 (8)0.0059 (7)
N10.0376 (9)0.0291 (9)0.0349 (9)0.0042 (8)0.0014 (7)0.0009 (7)
N130.0378 (10)0.0400 (9)0.0295 (9)0.0066 (8)0.0006 (7)0.0005 (7)
C20.0480 (15)0.0339 (11)0.0522 (15)0.0091 (10)0.0058 (11)0.0009 (10)
C30.0493 (16)0.0505 (15)0.0685 (18)0.0192 (13)0.0010 (13)0.0020 (13)
C40.0362 (13)0.0736 (19)0.0683 (18)0.0137 (13)0.0067 (11)0.0014 (14)
C50.0363 (13)0.0512 (13)0.0540 (15)0.0065 (11)0.0016 (11)0.0078 (12)
C60.0347 (12)0.0349 (11)0.0317 (11)0.0006 (9)0.0032 (9)0.0019 (9)
C70.0424 (12)0.0280 (10)0.0350 (11)0.0023 (9)0.0044 (9)0.0017 (8)
C80.0372 (12)0.0296 (10)0.0405 (12)0.0068 (9)0.0076 (9)0.0005 (9)
C90.0524 (15)0.0362 (11)0.0523 (15)0.0028 (11)0.0149 (11)0.0056 (11)
C100.0648 (18)0.0510 (14)0.0527 (16)0.0167 (13)0.0234 (13)0.0190 (13)
C110.0663 (18)0.0675 (17)0.0356 (13)0.0176 (15)0.0087 (12)0.0078 (12)
C120.0486 (14)0.0538 (14)0.0339 (12)0.0072 (11)0.0023 (10)0.0008 (10)
C200.0591 (18)0.0570 (15)0.0418 (14)0.0085 (13)0.0009 (13)0.0054 (12)
C210.109 (3)0.111 (3)0.0429 (17)0.022 (2)0.0045 (17)0.0133 (17)
O10.0571 (11)0.0771 (12)0.0400 (10)0.0093 (10)0.0057 (8)0.0055 (9)
O20.0598 (12)0.0834 (13)0.0515 (11)0.0163 (11)0.0007 (9)0.0118 (10)
O100.0565 (13)0.0928 (16)0.0798 (16)0.0000 (13)0.0111 (12)0.0166 (12)
O110.0554 (14)0.0713 (14)0.0963 (16)0.0008 (10)0.0124 (12)0.0062 (12)
Geometric parameters (Å, º) top
Cu1—N1i1.9918 (17)C6—C71.537 (3)
Cu1—N11.9918 (17)C7—C81.512 (3)
Cu1—N13i2.0257 (18)C8—C91.381 (3)
Cu1—N132.0257 (18)C9—C101.380 (4)
Cu1—O14i2.3990 (14)C9—H90.9300
O14—C71.408 (3)C10—C111.364 (4)
O14—H140.8200C10—H100.9300
O15—C71.381 (2)C11—C121.376 (4)
O15—H150.8200C11—H110.9300
N1—C21.342 (3)C12—H120.9300
N1—C61.344 (3)C20—O21.240 (3)
N13—C121.334 (3)C20—O11.257 (3)
N13—C81.341 (3)C20—C211.508 (4)
C2—C31.371 (3)C21—H21A0.9600
C2—H20.9300C21—H21B0.9600
C3—C41.375 (4)C21—H21C0.9600
C3—H30.9300O10—H10A0.848 (10)
C4—C51.377 (3)O10—H10B0.845 (10)
C4—H40.9300O11—H11A0.848 (10)
C5—C61.381 (3)O11—H11B0.842 (10)
C5—H50.9300
N1i—Cu1—N1180.00 (14)O15—C7—O14113.88 (17)
N1i—Cu1—N13i87.86 (7)O15—C7—C8109.37 (17)
N1—Cu1—N13i92.14 (7)O14—C7—C8105.19 (17)
N1i—Cu1—N1392.14 (7)O15—C7—C6111.29 (17)
N1—Cu1—N1387.86 (7)O14—C7—C6108.72 (16)
N13i—Cu1—N13180.00 (11)C8—C7—C6108.08 (16)
N1i—Cu1—O14i75.63 (6)N13—C8—C9121.2 (2)
N1—Cu1—O14i104.37 (6)N13—C8—C7114.58 (18)
N13i—Cu1—O14i73.86 (6)C9—C8—C7124.2 (2)
N13—Cu1—O14i106.14 (6)C10—C9—C8118.8 (2)
C7—O14—H14109.5C10—C9—H9120.6
C7—O15—H15109.5C8—C9—H9120.6
C2—N1—C6119.38 (18)C11—C10—C9119.7 (2)
C2—N1—Cu1124.37 (15)C11—C10—H10120.2
C6—N1—Cu1116.25 (13)C9—C10—H10120.2
C12—N13—C8119.5 (2)C10—C11—C12119.0 (2)
C12—N13—Cu1125.69 (16)C10—C11—H11120.5
C8—N13—Cu1114.77 (14)C12—C11—H11120.5
N1—C2—C3121.9 (2)N13—C12—C11121.8 (2)
N1—C2—H2119.1N13—C12—H12119.1
C3—C2—H2119.1C11—C12—H12119.1
C2—C3—C4118.9 (2)O2—C20—O1123.5 (2)
C2—C3—H3120.5O2—C20—C21119.1 (3)
C4—C3—H3120.5O1—C20—C21117.4 (3)
C3—C4—C5119.6 (2)C20—C21—H21A109.5
C3—C4—H4120.2C20—C21—H21B109.5
C5—C4—H4120.2H21A—C21—H21B109.5
C4—C5—C6119.0 (2)C20—C21—H21C109.5
C4—C5—H5120.5H21A—C21—H21C109.5
C6—C5—H5120.5H21B—C21—H21C109.5
N1—C6—C5121.25 (19)H10A—O10—H10B100 (3)
N1—C6—C7113.31 (18)H11A—O11—H11B100 (3)
C5—C6—C7125.43 (19)
N13i—Cu1—N1—C249.06 (18)N1—C6—C7—O15171.84 (18)
N13—Cu1—N1—C2130.94 (18)C5—C6—C7—O157.2 (3)
O14i—Cu1—N1—C224.82 (19)N1—C6—C7—O1445.6 (2)
N13i—Cu1—N1—C6130.93 (15)C5—C6—C7—O14133.4 (2)
N13—Cu1—N1—C649.07 (15)N1—C6—C7—C868.0 (2)
O14i—Cu1—N1—C6155.19 (14)C5—C6—C7—C8112.9 (2)
N1i—Cu1—N13—C1249.05 (18)C12—N13—C8—C90.1 (3)
N1—Cu1—N13—C12130.95 (18)Cu1—N13—C8—C9178.18 (16)
O14i—Cu1—N13—C1226.61 (19)C12—N13—C8—C7179.62 (19)
N1i—Cu1—N13—C8129.10 (15)Cu1—N13—C8—C72.1 (2)
N1—Cu1—N13—C850.90 (15)O15—C7—C8—N13172.77 (18)
O14i—Cu1—N13—C8155.24 (14)O14—C7—C8—N1350.1 (2)
C6—N1—C2—C31.0 (3)C6—C7—C8—N1365.9 (2)
Cu1—N1—C2—C3179.0 (2)O15—C7—C8—C97.5 (3)
N1—C2—C3—C41.4 (4)O14—C7—C8—C9130.2 (2)
C2—C3—C4—C51.1 (4)C6—C7—C8—C9113.8 (2)
C3—C4—C5—C60.4 (4)N13—C8—C9—C100.3 (3)
C2—N1—C6—C50.3 (3)C7—C8—C9—C10180.0 (2)
Cu1—N1—C6—C5179.67 (17)C8—C9—C10—C110.6 (4)
C2—N1—C6—C7179.4 (2)C9—C10—C11—C120.6 (4)
Cu1—N1—C6—C70.6 (2)C8—N13—C12—C110.1 (3)
C4—C5—C6—N10.0 (4)Cu1—N13—C12—C11177.93 (18)
C4—C5—C6—C7179.0 (2)C10—C11—C12—N130.2 (4)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O14—H14···O10.821.782.603 (2)178
O15—H15···O20.821.792.607 (3)177
O10—H10A···O20.85 (1)1.96 (1)2.788 (3)166 (3)
O10—H10B···O11ii0.85 (1)1.91 (1)2.741 (3)169 (3)
O11—H11A···O10.85 (1)1.92 (1)2.741 (3)164 (3)
O11—H11B···O10iii0.84 (1)1.91 (1)2.748 (3)173 (4)
Symmetry codes: (ii) x1/2, y+1/2, z1/2; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Cu(C11H10N2O2)2](C2H3O2)2·4H2O
Mr658.11
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)8.617 (1), 7.8765 (9), 23.103 (3)
β (°) 98.00 (1)
V3)1552.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.77
Crystal size (mm)0.37 × 0.23 × 0.10
Data collection
DiffractometerXcalibur
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2002)
Tmin, Tmax0.793, 0.931
No. of measured, independent and
observed [I > 2σ(I)] reflections
12971, 4484, 2765
Rint0.044
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.115, 0.96
No. of reflections4480
No. of parameters211
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.47, 0.34

Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2002), CrysAlis RED, DIRDIF99.2 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cu1—N1i1.9918 (17)O14—C71.408 (3)
Cu1—N13i2.0257 (18)O15—C71.381 (2)
Cu1—O14i2.3990 (14)
N1i—Cu1—N13i87.86 (7)N13—Cu1—O14i106.14 (6)
N1i—Cu1—N1392.14 (7)C2—N1—Cu1124.37 (15)
N1—Cu1—N1387.86 (7)C6—N1—Cu1116.25 (13)
N1i—Cu1—O14i75.63 (6)C12—N13—Cu1125.69 (16)
N1—Cu1—O14i104.37 (6)C8—N13—Cu1114.77 (14)
N13i—Cu1—O14i73.86 (6)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O14—H14···O10.821.782.603 (2)178
O15—H15···O20.821.792.607 (3)177
O10—H10A···O20.848 (10)1.958 (13)2.788 (3)166 (3)
O10—H10B···O11ii0.845 (10)1.906 (12)2.741 (3)169 (3)
O11—H11A···O10.848 (10)1.915 (14)2.741 (3)164 (3)
O11—H11B···O10iii0.842 (10)1.910 (11)2.748 (3)173 (4)
Symmetry codes: (ii) x1/2, y+1/2, z1/2; (iii) x+1, y, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds