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The title compound, [Cu(CHO2)2(C6H12N2)(H2O)]n, forms a polymeric chain, [Cu(HCOO)2(dabco)(H2O)] (dabco is 1,4-di­aza­bi­cyclo­[2.2.2]­octane). Both formate ligands are O-monodentate anions and dabco acts as a bridging ligand, creating a linear polymeric arrangement interconnected by Owater—H...Ocarboxy hydrogen bonds. The deformed square-pyramidal CuII coordination comprises two N and two O atoms as the base, and a water mol­ecule in the apical position. The point symmetry of the CuII polyhedron and the dabco ligand is mm, and the formate anions lie on the mirror planes ¼, y, z and ¾, y, z.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017434/lh6095sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017434/lh6095Isup2.hkl
Contains datablock I

CCDC reference: 222826

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.023
  • wR factor = 0.062
  • Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level C CRYSC01_ALERT_1_C The word below has not been recognised as a standard identifier. turquoise CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour. PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 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 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

So far, CuII–dabco coordination has not been intensively investigated. Only one mononuclear structure (Karan et al., 1999), two dinuclear structures (Durley et al., 1980; Maverick et al., 1986) and one polymeric structure (Rao et al., 1983) of CuII compounds containing the dabco ligand have been reported. The present paper reports the first example of the coordination of the dabco ligand in an equatorial position of a square-pyramidal CuII polyhedron. The structure of the title complex, (I), is polymeric with [Cu(HCOO)2(dabco)(H2O)] chains running along the a axis. Fig. 1 shows the independent fragment of the chain.

The chain consists of pentacoordinated CuII ions in a distorted square-pyramidal (SQP) geometry, with two Cu—N bonds of 2.093 (2) Å and two Cu—O bonds of 1.962 (2) Å of the formate groups in the basal plane. The apical position is occupied by the water molecule [Cu—OH2 = 2.238 (2) Å]. The Cu atom is displaced from the basal plane by 0.124 (1) Å towards atom O1. The point symmetry of the CuII polyhedron and the dabco ligand is mm, and the formate anions lie on the mirror planes 1/4,y,z and 3/4,y,z.

The observed SQP coordination is distinctly deformed in the direction of trigonal-bipiramidal (TBP) coordination, with the trigonality parameter τ = 0.24 [τ is defined by Addison et al. (1984); for a regular SQP structure, the trigonality parameter is 0, and for TBP distortion it increases to 1].

The formate group acts as a monodentate ligand, the distance between the CuII ion and uncoordinated atom O3 is 3.287 (3) Å. Such behaviour may be caused by the participation of this atom in a strong hydrogen bond with the water molecule. These interchain interactions, running along the z axis, are shown in Fig. 2. This strong hydrogen bond does not cause a delocalization of the π bond in the carboxyl group. The C2—O2 and C2—O3 bonds are distinctly different [1.257 (3) and 1.214 (4) Å, respectively].

The intrachain Cu···Cu distance of 6.808 (1) Å is longer than the shortest interchain Cu···Cu distance of 6.422 (2) Å along the c axis. Another short interchain Cu···Cu distances of 7.246 (2) and 8.157 (2) Å are between the two CuII ions related by the screw axis 21 and with no spacer between them.

Experimental top

The title complex was prepared by dissolving cupric formate [2 mmol, Cu(HCOO)2·2H2O] in 50 ml of water with dabco (2 mmol, C6H12N2). After heating to boiling, a few drops of formic acid were added to clear the solution. The solution was filtered and allowed to cool. After several days, turquoise crystals were obtained.

Refinement top

All H atoms were located from a difference synthesis and refined isotropically.

Computing details top

Data collection: P3 (Siemens, 1993); cell refinement: P3; data reduction: XDISK in SHELXTL/PC (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: XP in SHELXTL/PC; software used to prepare material for publication: PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. A fragment of the polymeric structure of the title compound. Displacement ellipsoids for non-H atoms are drawn at the 40% probability level.
[Figure 2] Fig. 2. Perspective view of the crystal packing in the unit cell, showing the linkage of the polymeric chains by hydrogen bonding.
catena-Poly[[aqua(diformato-κO)copper(II)]-µ-1,4-diazabicyclo[2.2.2]octane- κ2N:N'] top
Crystal data top
[Cu(CHO2)2(C6H12N2)(H2O)]F(000) = 294
Mr = 283.77Dx = 1.786 Mg m3
Orthorhombic, PmmnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2aCell parameters from 38 reflections
a = 6.8084 (13) Åθ = 5–18°
b = 12.071 (2) ŵ = 2.08 mm1
c = 6.4224 (15) ÅT = 293 K
V = 527.80 (19) Å3Prism, turquoise
Z = 20.30 × 0.20 × 0.20 mm
Data collection top
Siemens P3
diffractometer
710 reflections with I > 2σ(I)
Radiation source: FK60-10 Siemens Mo tubeRint = 0.000
Graphite monochromatorθmax = 28.0°, θmin = 3.2°
ω–2θ scansh = 08
Absorption correction: psi scan
(North et al., 1968)
k = 015
Tmin = 0.557, Tmax = 0.661l = 08
719 measured reflections3 standard reflections every 100 reflections
719 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: difference Fourier map
wR(F2) = 0.062All H-atom parameters refined
S = 1.23 w = 1/[σ2(Fo2) + (0.0345P)2 + 0.21P]
where P = (Fo2 + 2Fc2)/3
719 reflections(Δ/σ)max < 0.001
66 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.49 e Å3
0 constraints
Crystal data top
[Cu(CHO2)2(C6H12N2)(H2O)]V = 527.80 (19) Å3
Mr = 283.77Z = 2
Orthorhombic, PmmnMo Kα radiation
a = 6.8084 (13) ŵ = 2.08 mm1
b = 12.071 (2) ÅT = 293 K
c = 6.4224 (15) Å0.30 × 0.20 × 0.20 mm
Data collection top
Siemens P3
diffractometer
710 reflections with I > 2σ(I)
Absorption correction: psi scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.557, Tmax = 0.6613 standard reflections every 100 reflections
719 measured reflections intensity decay: none
719 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.062All H-atom parameters refined
S = 1.23Δρmax = 0.39 e Å3
719 reflectionsΔρmin = 0.49 e Å3
66 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Cu0.250.250.33505 (5)0.0180 (1)
O10.250.250.6835 (4)0.0341 (8)
O20.250.08926 (14)0.2903 (3)0.0290 (4)
O30.250.0745 (2)0.0562 (4)0.0630 (8)
N10.5573 (3)0.250.3413 (3)0.0197 (4)
C20.250.03800 (19)0.1200 (4)0.0315 (7)
C30.6379 (3)0.250.1269 (4)0.0299 (7)
C40.6384 (2)0.15119 (16)0.4490 (3)0.0360 (5)
H10.250.316 (3)0.761 (8)0.074 (13)*
H20.250.041 (3)0.139 (5)0.039 (9)*
H30.588 (4)0.313 (2)0.068 (5)0.054 (7)*
H4A0.585 (5)0.089 (3)0.385 (5)0.083 (11)*
H4B0.580 (5)0.154 (3)0.591 (6)0.079 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0165 (2)0.0164 (2)0.0212 (2)000
O10.0450 (15)0.0361 (14)0.0211 (11)000
O20.0275 (8)0.0212 (7)0.0382 (8)000.0071 (7)
O30.109 (2)0.0426 (12)0.0373 (10)000.0064 (10)
N10.0180 (7)0.0182 (8)0.0229 (8)00.0003 (6)0
C20.0381 (13)0.0194 (10)0.0370 (11)000.0021 (9)
C30.0217 (11)0.0467 (14)0.0212 (9)00.0009 (8)0
C40.0206 (8)0.0337 (9)0.0537 (10)0.0016 (7)0.0027 (7)0.0226 (8)
Geometric parameters (Å, º) top
Cu—O12.238 (2)N1—C41.485 (2)
Cu—O21.962 (2)C3—C3i1.526 (4)
Cu—N12.093 (2)C4—C4ii1.520 (3)
O2—C21.257 (3)C2—H20.97 (3)
O3—C21.214 (4)C3—H30.92 (3)
O1—H10.94 (4)C4—H4A0.93 (4)
N1—C31.482 (3)C4—H4B1.00 (4)
O1—Cu—O298.42 (6)N1—C3—C3i111.7 (2)
O1—Cu—N188.90 (5)N1—C4—C4ii111.82 (15)
O2—Cu—N190.16 (1)O2—C2—H2112.2 (19)
O2—Cu—O2iii163.16 (11)O3—C2—H2118.6 (19)
N1—Cu—N1iii177.81 (9)N1—C3—H3104 (2)
Cu—O2—C2127.92 (16)C3i—C3—H3111.8 (17)
H1—O1—H1iii116 (4)H3—C3—H3iv112 (3)
Cu—O1—H1122 (3)N1—C4—H4A107 (2)
Cu—N1—C3110.63 (14)N1—C4—H4B105 (2)
Cu—N1—C4112.37 (10)H4A—C4—H4B106 (3)
C4—N1—C4iv106.85 (16)C4ii—C4—H4A113 (2)
C3—N1—C4107.16 (12)C4ii—C4—H4B114 (2)
O2—C2—O3129.2 (2)
N1—Cu—O2—C291.09 (5)O2—Cu—N1—C438.15 (13)
O1—Cu—N1—C460.28 (12)Cu—N1—C4—C4ii178.97 (12)
O2—Cu—N1—C381.58 (6)C3—N1—C4—C4ii57.25 (19)
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+3/2, y, z; (iii) x+1/2, y+1/2, z; (iv) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3v0.94 (4)1.77 (4)2.699 (3)170 (4)
Symmetry code: (v) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formula[Cu(CHO2)2(C6H12N2)(H2O)]
Mr283.77
Crystal system, space groupOrthorhombic, Pmmn
Temperature (K)293
a, b, c (Å)6.8084 (13), 12.071 (2), 6.4224 (15)
V3)527.80 (19)
Z2
Radiation typeMo Kα
µ (mm1)2.08
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerSiemens P3
diffractometer
Absorption correctionPsi scan
(North et al., 1968)
Tmin, Tmax0.557, 0.661
No. of measured, independent and
observed [I > 2σ(I)] reflections
719, 719, 710
Rint0.000
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.062, 1.23
No. of reflections719
No. of parameters66
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.39, 0.49

Computer programs: P3 (Siemens, 1993), P3, XDISK in SHELXTL/PC (Sheldrick, 1990), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997b), XP in SHELXTL/PC, PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Cu—O12.238 (2)O2—C21.257 (3)
Cu—O21.962 (2)O3—C21.214 (4)
Cu—N12.093 (2)
O1—Cu—O298.42 (6)O2—Cu—O2i163.16 (11)
O1—Cu—N188.90 (5)N1—Cu—N1i177.81 (9)
O2—Cu—N190.16 (1)
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3ii0.94 (4)1.77 (4)2.699 (3)170 (4)
Symmetry code: (ii) x+1/2, y+1/2, z+1.
 

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