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ISSN: 2056-9890

Chlorido­tetra­kis(pyridine-4-carb­alde­hyde-κN)copper(II) chloride

aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004, People's Republic of China, and bKey Laboratory of New Processing Technology for Nonferrous Metals & Materials, Ministry of Education, Guilin University of Technology, Guilin, Guangxi 541004, People's Republic of China
*Correspondence e-mail: mengxiujin@163.com

(Received 17 August 2009; accepted 13 October 2009; online 17 October 2009)

In the mol­ecular structure of the title compound, [CuCl(C6H5NO)4]Cl, the CuII atom is coordinated by four N atoms of four pyridine-4-carboxaldehyde ligands and one chloride anion in a slightly distorted square-pyramidal coordination geometry. There is also a non-coordinating Cl anion in the crystal structure. The CuII atom and both Cl atoms are situated on fourfold rotation axes. A weak C—H⋯Cl inter­action is also present.

Related literature

For other compounds with pyridine-4-carbaldehyde ligands, see: Rivera & Sheldrick (1977[Rivera, A. V. & Sheldrick, G. M. (1977). Acta Cryst. B33, 154-155.]); Choi & Wong (1999[Choi, Y.-Y. & Wong, W.-T. (1999). J. Organomet. Chem. 573, 189-201.]); Briand et al. (2007[Briand, G. G., Smith, A. D., Schatte, G., Rossini, A. J. & Schurko, R. W. (2007). Inorg. Chem. 46, 8625-8637.]); Sie et al. (2008[Sie, W.-S., Lee, G.-H., Tsai, K. Y.-D., Chang, I.-J. & Shiu, K. B. (2008). J. Mol. Struct. 890, 198-202.]).

[Scheme 1]

Experimental

Crystal data
  • [CuCl(C6H5NO)4]Cl

  • Mr = 562.88

  • Tetragonal, P 4/n

  • a = 10.5035 (3) Å

  • c = 11.3751 (6) Å

  • V = 1254.94 (8) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.12 mm−1

  • T = 296 K

  • 0.38 × 0.21 × 0.18 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.675, Tmax = 0.825

  • 9150 measured reflections

  • 1126 independent reflections

  • 1083 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.114

  • S = 1.03

  • 1126 reflections

  • 82 parameters

  • 13 restraints

  • H-atom parameters constrained

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C5—H5⋯Cl2 0.93 2.84 3.732 (2) 160

Data collection: SMART (Bruker, 2004[Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Only one structurally characterized coordination compound with pyridine-4- carboxaldehyde acting as the ligand has been reported up to now. In that article, pyridine-4-carboxaldehyde and CoBr2 form [CoBr2(C5H4N-CHO)4] (Rivera et al. 1977). This compound is highly related to the title compound. In addition, three crystal structures with pyridine-4-carboxaldehyde acting as independent components were reported (Choi et al. 1999; Briand et al. 2007; Sie et al. 2008).

In the cation of the title compound [CuCl(OCHC5H4N)4]Cl, the CuII centre is coordinated to four N atoms from four pyridine-4-carboxaldehyde ligands and one chloro ligand. Cu exhibits a slightly distorted square-pyramidal coordination geometry. Another non-coordinating chloride anion is observed in the crystal structure. The [CuCl(C5H4N-CHO)4]+ ion has a perfect C4 symmetry with the direction of the C4 axis being collinear with the Cu1—Cl1 direction. Cu1, Cl1 and Cl2 are all situated on the same crystallographic 4-fold rotoinversion axis. In the cation therefore all Cu—N bond lengths and angles are equivalent.

Several donor CH functions and the chloride acceptor groups participate in the observed hydrogen bonding pattern forming a two-dimensional network in the ab plane (Fig. 2)

Related literature top

For other compounds with pyridine-4-carbaldehyde ligands, see: Rivera et al. (1977); Choi et al. (1999); Briand et al. (2007); Sie et al. (2008).

Experimental top

For the preparation of the title compound, a solution of CuCl2 × 2 H2O (0.08524 g, 0.5 mmol) in H2O(5 ml) was slowly added over a period of 2 h to a solution of L-Cysteic acid (0.094 g, 0.5 mmol), KOH (0.056 g, 1 mmol), pyridine-4-carboxaldehyde (0.06 ml, 0.6 mmol) and NaBH4 (0.03028 g, 0.8 mmol) in methanol (20 ml) resulting in a blue solution that was stirred for another 4 h at 298 K. Then, the solution was left to evaporate slowly at room temperature. After ten days, blue block crystals of the title compoound were obtained with a yield of 70%.

Refinement top

H atom bonded to C atom were positioned geometrically with the C—H distance of 0.9303 Å, and treated as riding atoms, with Uiso(H) = 1.2Ueq(C).

Structure description top

Only one structurally characterized coordination compound with pyridine-4- carboxaldehyde acting as the ligand has been reported up to now. In that article, pyridine-4-carboxaldehyde and CoBr2 form [CoBr2(C5H4N-CHO)4] (Rivera et al. 1977). This compound is highly related to the title compound. In addition, three crystal structures with pyridine-4-carboxaldehyde acting as independent components were reported (Choi et al. 1999; Briand et al. 2007; Sie et al. 2008).

In the cation of the title compound [CuCl(OCHC5H4N)4]Cl, the CuII centre is coordinated to four N atoms from four pyridine-4-carboxaldehyde ligands and one chloro ligand. Cu exhibits a slightly distorted square-pyramidal coordination geometry. Another non-coordinating chloride anion is observed in the crystal structure. The [CuCl(C5H4N-CHO)4]+ ion has a perfect C4 symmetry with the direction of the C4 axis being collinear with the Cu1—Cl1 direction. Cu1, Cl1 and Cl2 are all situated on the same crystallographic 4-fold rotoinversion axis. In the cation therefore all Cu—N bond lengths and angles are equivalent.

Several donor CH functions and the chloride acceptor groups participate in the observed hydrogen bonding pattern forming a two-dimensional network in the ab plane (Fig. 2)

For other compounds with pyridine-4-carbaldehyde ligands, see: Rivera et al. (1977); Choi et al. (1999); Briand et al. (2007); Sie et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Ellipsoid plot (30% probability) of the title compound showing the numbering scheme. Dashed lines indicate hydrogen bonds. Symmetry code: 1# -x + 1/2, y + 1/2, z.
[Figure 2] Fig. 2. 2-D network, as viewed down the c axis. Dashed lines indicate hydrogen bonds.
Chloridotetrakis(pyridine-4-carbaldehyde-κN)copper(II) chloride top
Crystal data top
[CuCl(C6H5NO)4]ClDx = 1.490 Mg m3
Mr = 562.88Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/nCell parameters from 1162 reflections
Hall symbol: -P 4aθ = 2.6–25.1°
a = 10.5035 (3) ŵ = 1.12 mm1
c = 11.3751 (6) ÅT = 296 K
V = 1254.94 (8) Å3Block, blue
Z = 20.38 × 0.21 × 0.18 mm
F(000) = 574
Data collection top
Bruker SMART CCD area-detector
diffractometer
1126 independent reflections
Radiation source: fine-focus sealed tube1083 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
phi and ω scansθmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.675, Tmax = 0.825k = 1212
9150 measured reflectionsl = 1213
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.091P)2 + 0.4771P]
where P = (Fo2 + 2Fc2)/3
1126 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 0.56 e Å3
13 restraintsΔρmin = 0.48 e Å3
Crystal data top
[CuCl(C6H5NO)4]ClZ = 2
Mr = 562.88Mo Kα radiation
Tetragonal, P4/nµ = 1.12 mm1
a = 10.5035 (3) ÅT = 296 K
c = 11.3751 (6) Å0.38 × 0.21 × 0.18 mm
V = 1254.94 (8) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
1126 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1083 reflections with I > 2σ(I)
Tmin = 0.675, Tmax = 0.825Rint = 0.017
9150 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03313 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.03Δρmax = 0.56 e Å3
1126 reflectionsΔρmin = 0.48 e Å3
82 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*/Ueq
Cu10.75000.75000.81702 (4)0.0289 (3)
Cl10.75000.75001.03833 (9)0.0373 (3)
C10.8616 (2)0.5010 (2)0.8824 (2)0.0376 (5)
H10.86310.53720.95700.045*
C20.9093 (3)0.3791 (2)0.8675 (2)0.0418 (6)
H20.94040.33420.93190.050*
C30.9109 (2)0.3241 (2)0.7569 (2)0.0342 (5)
C40.8612 (3)0.3938 (2)0.6653 (2)0.0411 (6)
H40.86010.36030.58960.049*
C50.8132 (3)0.5140 (3)0.6867 (2)0.0422 (6)
H50.77900.55930.62400.051*
C60.9662 (3)0.1930 (2)0.7405 (3)0.0466 (6)
H60.99390.14280.80270.056*
N10.81319 (18)0.56845 (17)0.79272 (17)0.0320 (4)
O10.9721 (2)0.1535 (2)0.6224 (2)0.0598 (6)
Cl20.75000.75000.44844 (12)0.0562 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0261 (3)0.0261 (3)0.0344 (4)0.0000.0000.000
Cl10.0410 (4)0.0410 (4)0.0299 (5)0.0000.0000.000
C10.0418 (13)0.0357 (12)0.0354 (11)0.0033 (10)0.0029 (10)0.0013 (9)
C20.0487 (15)0.0378 (13)0.0390 (13)0.0075 (11)0.0068 (10)0.0066 (10)
C30.0288 (11)0.0306 (11)0.0434 (12)0.0011 (8)0.0001 (9)0.0016 (9)
C40.0485 (15)0.0372 (13)0.0377 (11)0.0062 (11)0.0016 (10)0.0031 (10)
C50.0527 (16)0.0355 (13)0.0385 (13)0.0079 (11)0.0074 (10)0.0039 (9)
C60.0514 (15)0.0348 (13)0.0536 (15)0.0105 (11)0.0040 (12)0.0009 (11)
N10.0314 (10)0.0282 (9)0.0364 (9)0.0000 (7)0.0003 (8)0.0025 (8)
O10.0654 (14)0.0500 (12)0.0642 (13)0.0141 (10)0.0063 (10)0.0171 (10)
Cl20.0619 (6)0.0619 (6)0.0448 (7)0.0000.0000.000
Geometric parameters (Å, º) top
Cu1—N1i2.0380 (19)C2—H20.9300
Cu1—N12.0380 (19)C3—C41.377 (3)
Cu1—N1ii2.0380 (19)C3—C61.506 (3)
Cu1—N1iii2.0380 (19)C4—C51.381 (4)
Cu1—Cl12.5175 (11)C4—H40.9300
C1—N11.342 (3)C5—N11.335 (3)
C1—C21.385 (4)C5—H50.9300
C1—H10.9300C6—O11.407 (4)
C2—C31.384 (4)C6—H60.9300
N1i—Cu1—N188.946 (16)C4—C3—C2117.5 (2)
N1i—Cu1—N1ii164.41 (11)C4—C3—C6122.6 (2)
N1—Cu1—N1ii88.946 (16)C2—C3—C6119.9 (2)
N1i—Cu1—N1iii88.946 (15)C3—C4—C5119.4 (2)
N1—Cu1—N1iii164.41 (11)C3—C4—H4120.3
N1ii—Cu1—N1iii88.946 (16)C5—C4—H4120.3
N1i—Cu1—Cl197.79 (6)N1—C5—C4123.4 (2)
N1—Cu1—Cl197.79 (6)N1—C5—H5118.3
N1ii—Cu1—Cl197.79 (6)C4—C5—H5118.3
N1iii—Cu1—Cl197.79 (6)O1—C6—C3113.9 (2)
N1—C1—C2122.2 (2)O1—C6—H6123.0
N1—C1—H1118.9C3—C6—H6123.0
C2—C1—H1118.9C5—N1—C1117.4 (2)
C3—C2—C1120.1 (2)C5—N1—Cu1121.56 (16)
C3—C2—H2120.0C1—N1—Cu1120.97 (16)
C1—C2—H2120.0
Symmetry codes: (i) y, x+3/2, z; (ii) y+3/2, x, z; (iii) x+3/2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl20.932.843.732 (2)160

Experimental details

Crystal data
Chemical formula[CuCl(C6H5NO)4]Cl
Mr562.88
Crystal system, space groupTetragonal, P4/n
Temperature (K)296
a, c (Å)10.5035 (3), 11.3751 (6)
V3)1254.94 (8)
Z2
Radiation typeMo Kα
µ (mm1)1.12
Crystal size (mm)0.38 × 0.21 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.675, 0.825
No. of measured, independent and
observed [I > 2σ(I)] reflections
9150, 1126, 1083
Rint0.017
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.114, 1.03
No. of reflections1126
No. of parameters82
No. of restraints13
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.48

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl20.932.8443.732 (2)160.1
 

Acknowledgements

This work was funded by the Guangxi Science Foundation of the Guangxi Zhuang Autonomous Region of the People's Republic of China (grant No. 0731053).

References

First citationBriand, G. G., Smith, A. D., Schatte, G., Rossini, A. J. & Schurko, R. W. (2007). Inorg. Chem. 46, 8625–8637.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationBruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChoi, Y.-Y. & Wong, W.-T. (1999). J. Organomet. Chem. 573, 189–201.  Web of Science CSD CrossRef CAS Google Scholar
First citationRivera, A. V. & Sheldrick, G. M. (1977). Acta Cryst. B33, 154–155.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSie, W.-S., Lee, G.-H., Tsai, K. Y.-D., Chang, I.-J. & Shiu, K. B. (2008). J. Mol. Struct. 890, 198–202.  Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2056-9890
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