Acta Cryst.(2003). E59, m803±m805 DOI: 10.1107/S1600536803017434 Sieron [Cu(CHO2)2(C6H12N2)(H2O)]
m803
metal-organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
catena
-Poly[[aqua(diformato-j
O
)copper(II)]-l-1,4-diazabicyclo[2.2.2]octane-j
2N
:
N
000]
Lesøaw SieronÂ
Institute of General and Ecological Chemistry, Technical University of èoÂdzÂ, Z.wirki 36, 90-924 èoÂdzÂ, Poland
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.023
wRfactor = 0.062
Data-to-parameter ratio = 10.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, [Cu(CHO2)2(C6H12N2)(H2O)]n, forms a polymeric chain, [Cu(HCOO)2(dabco)(H2O)]1(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 OwaterÐH Ocarboxyhydrogen 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 ismm, and the formate anions lie on the mirror planes1 4,
y, zand3 4,y, z.
Comment
So far, CuII±dabco coordination compounds has not been
intensively investigated. Only one mononuclear structure (Karanet al., 1999), two dinuclear structures (Durley et al., 1980; Mavericket al., 1986) and one polymeric structure (Rao et al., 1983) of CuIIcompounds containing the dabco ligand
have been reported. The present paper reports the ®rst example of the coordination of the dabco ligand in a basal position of a square-pyramidal CuIIpolyhedron. The structure
of the title complex, (I), is polymeric, with
[Cu(HCOO)2(dabco)(H2O)]1chains running along theaaxis.
In Fig. 1, the labelled atoms indicate the independent frag-ment of the chain.
The chain consists of pentacoordinated CuII ions in a
distorted square-pyramidal (SQP) geometry, with two CuÐN bonds of 2.093 (2) AÊ and two CuÐO(formate) bonds of 1.962 (2) AÊ in the basal plane. The apical position is occupied by the water molecule [CuÐOH2= 2.238 (2) AÊ]. The Cu atom
is displaced from the basal plane by 0.124 (1) AÊ towards atom O1. The point symmetry of the CuIIpolyhedron and the dabco
ligand ismm, and the formate anions lie on the mirror planes1 4,
y, zand3 4,y, z.
The observed SQP coordination is distinctly deformed in the direction of trigonal-bipyramidal (TBP) coordination, with
metal-organic papers
m804
Sieron [Cu(CHO2)2(C6H12N2)(H2O)] Acta Cryst.(2003). E59, m803±m805 the trigonality parameter = 0.24 [is de®ned by Addisonetal. (1984)]; for the 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
being 3.287 (3) AÊ. 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 thecaxis, are shown in Fig. 2. This strong hydrogen bond does not cause a delocalization of thebond in the carboxyl group as the C2ÐO2 and C2ÐO3 bonds are distinctly different [1.257 (3) and 1.214 (4) AÊ, respectively].
The intrachain Cu Cu distance of 6.808 (1) AÊ is longer than the shortest interchain Cu Cu distance of 6.422 (2) AÊ along thecaxis. Other short interchain Cu Cu distances of 7.246 (2) and 8.157 (2) AÊ are between the two CuII ions
related by the 21 screw axis, and with no spacer between
them.
Experimental
The title complex was prepared by dissolving cupric formate [Cu(HCOO)22H2O, 2 mmol] in 50 ml of water with dabco (C6H12N2, 2 mmol). After heating to boiling, a few drops of formic acid were added to clear the solution. The solution was ®ltered and allowed to cool. After several days, turquoise crystals were obtained.
Crystal data
[Cu(CHO2)2(C6H12N2)(H2O)]
Mr= 283.77
Orthorhombic,Pmmn a= 6.8084 (13) AÊ b= 12.071 (2) AÊ c= 6.4224 (15) AÊ V= 527.80 (19) AÊ3
Z= 2
Dx= 1.786 Mg mÿ3
MoKradiation Cell parameters from 38
re¯ections
= 5±18 = 2.08 mmÿ1
T= 293 K Prism, turquoise 0.300.200.20 mm
Data collection
SiemensP3 diffractometer
!±2scans
Absorption correction: scan (Northet al., 1968) Tmin= 0.557,Tmax= 0.661
719 measured re¯ections 719 independent re¯ections 710 re¯ections withI> 2(I)
max= 28.0
h= 0!8 k= 0!15 l= 0!8
3 standard re¯ections every 100 re¯ections intensity decay: none
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.023
wR(F2) = 0.062
S= 1.23 719 re¯ections 66 parameters
All H-atom parameters re®ned
w= 1/[2(F
o2) + (0.0345P)2
+ 0.21P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.39 e AÊÿ3 min=ÿ0.49 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
CuÐO1 2.238 (2)
CuÐO2 1.962 (2)
CuÐN1 2.093 (2)
O2ÐC2 1.257 (3)
O3ÐC2 1.214 (4)
O1ÐCuÐO2 98.42 (6)
O1ÐCuÐN1 88.90 (5)
O2ÐCuÐN1 90.16 (1)
O2ÐCuÐO2i 163.16 (11)
N1ÐCuÐN1i 177.81 (9)
Symmetry code: (i)1
2ÿx;12ÿy;z.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O1ÐH1 O3ii 0.94 (4) 1.77 (4) 2.699 (3) 170 (4)
Symmetry code: (ii)1
2ÿx;12ÿy;1z.
All H atoms were located from a difference synthesis and re®ned isotropically. The CÐH distances range from 0.92 (3) to 1.00 (4) AÊ and the OÐH distance re®ned to 0.94 (4) AÊ.
Data collection: P3 (Siemens, 1993); cell re®nement: P3; data reduction:XDISKin SHELXTL/PC(Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:XPinSHELXTL/PC; software used to prepare material for publication:PLATON(Spek, 1990).
Figure 2
Perspective view of the crystal packing in the unit cell, showing the linkage of the polymeric chains by hydrogen bonding as dashed lines.
Figure 1
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans.pp. 1349±1356.
Durley, R. C. E., Hughes, D. L. & Truter, M. R. (1980).Acta Cryst.B36, 2991± 2997.
Karan, N. K., Sen, S., Saha, M. K., Mitra, S. & Tiekink, E. R. T. (1999).Z. Kristallogr. New Cryst. Struct.214, 203±204.
Maverick, A. W., Buckingham, S. C., Yao, Q., Bradbury, J. R. & Stanley, G. G. (1986).J. Am. Chem. Soc.108, 7430±7431.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.
Rao, V. M., Sathyanarayana, D. N. & Manohar, H. (1983).J. Chem. Soc. Dalton Trans.pp. 2167±2173.
Sheldrick, G. M. (1990). SHELXTL/PC. Siemens Analytical X-ray Instru-ments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Siemens (1993).P3. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990).Acta Cryst.A46, C-34.
supporting information
sup-1
Acta Cryst. (2003). E59, m803–m805supporting information
Acta Cryst. (2003). E59, m803–m805 [doi:10.1107/S1600536803017434]
catena
-Poly[[aqua(diformato-
κ
O
)copper(II)]-
µ
-1,4-diazabicyclo[2.2.2]octane-κ
2N
:
N
′
]
Les
ł
aw Siero
ń
S1. Comment
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.
S2. Experimental
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.
S3. Refinement
supporting information
[image:5.610.128.485.73.267.2]sup-2
Acta Cryst. (2003). E59, m803–m805Figure 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
[image:5.610.127.483.324.605.2]supporting information
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Acta Cryst. (2003). E59, m803–m805catena-Poly[[aqua(diformato-κO)copper(II)]-µ-1,4-diazabicyclo[2.2.2]octane- κ2N:N′]
Crystal data
[Cu(CHO2)2(C6H12N2)(H2O)] Mr = 283.77
Orthorhombic, Pmmn
Hall symbol: -P 2ab 2a
a = 6.8084 (13) Å
b = 12.071 (2) Å
c = 6.4224 (15) Å
V = 527.80 (19) Å3 Z = 2
F(000) = 294
Dx = 1.786 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 38 reflections
θ = 5–18°
µ = 2.08 mm−1 T = 293 K Prism, turquoise 0.30 × 0.20 × 0.20 mm
Data collection
Siemens P3 diffractometer
Radiation source: FK60-10 Siemens Mo tube Graphite monochromator
ω–2θ scans
Absorption correction: psi scan (North et al., 1968)
Tmin = 0.557, Tmax = 0.661
719 measured reflections
719 independent reflections 710 reflections with I > 2σ(I)
Rint = 0.000
θmax = 28.0°, θmin = 3.2° h = 0→8
k = 0→15
l = 0→8
3 standard reflections every 100 reflections intensity decay: none
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.023 wR(F2) = 0.062 S = 1.23 719 reflections 66 parameters 0 restraints 0 constraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: structure-invariant direct methods
Hydrogen site location: difference Fourier map All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.0345P)2 + 0.21P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.39 e Å−3
Δρmin = −0.49 e Å−3
Special details
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)
x y z Uiso*/Ueq
supporting information
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Acta Cryst. (2003). E59, m803–m805N1 0.5573 (3) 0.25 0.3413 (3) 0.0197 (4) C2 0.25 0.03800 (19) 0.1200 (4) 0.0315 (7) C3 0.6379 (3) 0.25 0.1269 (4) 0.0299 (7) C4 0.6384 (2) 0.15119 (16) 0.4490 (3) 0.0360 (5) H1 0.25 0.316 (3) 0.761 (8) 0.074 (13)* H2 0.25 −0.041 (3) 0.139 (5) 0.039 (9)* H3 0.588 (4) 0.313 (2) 0.068 (5) 0.054 (7)* H4A 0.585 (5) 0.089 (3) 0.385 (5) 0.083 (11)* H4B 0.580 (5) 0.154 (3) 0.591 (6) 0.079 (10)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cu 0.0165 (2) 0.0164 (2) 0.0212 (2) 0 0 0 O1 0.0450 (15) 0.0361 (14) 0.0211 (11) 0 0 0
O2 0.0275 (8) 0.0212 (7) 0.0382 (8) 0 0 −0.0071 (7) O3 0.109 (2) 0.0426 (12) 0.0373 (10) 0 0 0.0064 (10) N1 0.0180 (7) 0.0182 (8) 0.0229 (8) 0 −0.0003 (6) 0
C2 0.0381 (13) 0.0194 (10) 0.0370 (11) 0 0 −0.0021 (9) C3 0.0217 (11) 0.0467 (14) 0.0212 (9) 0 −0.0009 (8) 0
C4 0.0206 (8) 0.0337 (9) 0.0537 (10) −0.0016 (7) −0.0027 (7) 0.0226 (8)
Geometric parameters (Å, º)
Cu—O1 2.238 (2) N1—C4 1.485 (2)
Cu—O2 1.962 (2) C3—C3i 1.526 (4)
Cu—N1 2.093 (2) C4—C4ii 1.520 (3)
O2—C2 1.257 (3) C2—H2 0.97 (3)
O3—C2 1.214 (4) C3—H3 0.92 (3)
O1—H1 0.94 (4) C4—H4A 0.93 (4)
N1—C3 1.482 (3) C4—H4B 1.00 (4)
O1—Cu—O2 98.42 (6) N1—C3—C3i 111.7 (2)
O1—Cu—N1 88.90 (5) N1—C4—C4ii 111.82 (15)
O2—Cu—N1 90.16 (1) O2—C2—H2 112.2 (19) O2—Cu—O2iii 163.16 (11) O3—C2—H2 118.6 (19)
N1—Cu—N1iii 177.81 (9) N1—C3—H3 104 (2)
Cu—O2—C2 127.92 (16) C3i—C3—H3 111.8 (17)
H1—O1—H1iii 116 (4) H3—C3—H3iv 112 (3)
Cu—O1—H1 122 (3) N1—C4—H4A 107 (2)
Cu—N1—C3 110.63 (14) N1—C4—H4B 105 (2) Cu—N1—C4 112.37 (10) H4A—C4—H4B 106 (3) C4—N1—C4iv 106.85 (16) C4ii—C4—H4A 113 (2)
C3—N1—C4 107.16 (12) C4ii—C4—H4B 114 (2)
O2—C2—O3 129.2 (2)
supporting information
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Acta Cryst. (2003). E59, m803–m805O1—Cu—N1—C4 60.28 (12) Cu—N1—C4—C4ii 178.97 (12)
O2—Cu—N1—C3 81.58 (6) C3—N1—C4—C4ii 57.25 (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)
D—H···A D—H H···A D···A D—H···A
O1—H1···O3v 0.94 (4) 1.77 (4) 2.699 (3) 170 (4)
