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

Meng, X.-J.; Zhang, S.-H.; Yang, G.-G.; Huang, X.-R.; Jiang, Y.-M.

doi:10.1107/S1600536809041816

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1380

https://doi.org/10.1107/S1600536809041816

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

Xiu-Jin Meng,^a Shu-Hua Zhang,^b Ge-Ge Yang,^a Xue-Ren Huang ^a and Yi-Min Jiang ^a,^b ^*

^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 Cu^II 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 Cu^II 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 ); Choi & Wong (1999 ); Briand et al. (2007 ); Sie et al. (2008 ).

Experimental

Crystal data

[CuCl(C₆H₅NO)₄]Cl
M_r = 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 ) T_min = 0.675, T_max = 0.825
9150 measured reflections
1126 independent reflections
1083 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041816/im2137sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041816/im2137Isup2.hkl

checkCIF report

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 Cu^II 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%.

Structure description top

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

	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.
	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]Cl	D_x = 1.490 Mg m⁻³
M_r = 562.88	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 1162 reflections
Hall symbol: -P 4a	θ = 2.6–25.1°
a = 10.5035 (3) Å	µ = 1.12 mm⁻¹
c = 11.3751 (6) Å	T = 296 K
V = 1254.94 (8) Å³	Block, blue
Z = 2	0.38 × 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 tube	1083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
phi and ω scans	θ_max = 25.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.675, T_max = 0.825	k = −12→12
9150 measured reflections	l = −12→13

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.091P)² + 0.4771P] where P = (F_o² + 2F_c²)/3
1126 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.56 e Å⁻³
13 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[CuCl(C₆H₅NO)4]Cl	Z = 2
M_r = 562.88	Mo Kα radiation
Tetragonal, P4/n	µ = 1.12 mm⁻¹
a = 10.5035 (3) Å	T = 296 K
c = 11.3751 (6) Å	0.38 × 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)
T_min = 0.675, T_max = 0.825	R_int = 0.017
9150 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	13 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.03	Δρ_max = 0.56 e Å⁻³
1126 reflections	Δρ_min = −0.48 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cu1	0.7500	0.7500	0.81702 (4)	0.0289 (3)
Cl1	0.7500	0.7500	1.03833 (9)	0.0373 (3)
C1	0.8616 (2)	0.5010 (2)	0.8824 (2)	0.0376 (5)
H1	0.8631	0.5372	0.9570	0.045*
C2	0.9093 (3)	0.3791 (2)	0.8675 (2)	0.0418 (6)
H2	0.9404	0.3342	0.9319	0.050*
C3	0.9109 (2)	0.3241 (2)	0.7569 (2)	0.0342 (5)
C4	0.8612 (3)	0.3938 (2)	0.6653 (2)	0.0411 (6)
H4	0.8601	0.3603	0.5896	0.049*
C5	0.8132 (3)	0.5140 (3)	0.6867 (2)	0.0422 (6)
H5	0.7790	0.5593	0.6240	0.051*
C6	0.9662 (3)	0.1930 (2)	0.7405 (3)	0.0466 (6)
H6	0.9939	0.1428	0.8027	0.056*
N1	0.81319 (18)	0.56845 (17)	0.79272 (17)	0.0320 (4)
O1	0.9721 (2)	0.1535 (2)	0.6224 (2)	0.0598 (6)
Cl2	0.7500	0.7500	0.44844 (12)	0.0562 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0261 (3)	0.0261 (3)	0.0344 (4)	0.000	0.000	0.000
Cl1	0.0410 (4)	0.0410 (4)	0.0299 (5)	0.000	0.000	0.000
C1	0.0418 (13)	0.0357 (12)	0.0354 (11)	0.0033 (10)	−0.0029 (10)	−0.0013 (9)
C2	0.0487 (15)	0.0378 (13)	0.0390 (13)	0.0075 (11)	−0.0068 (10)	0.0066 (10)
C3	0.0288 (11)	0.0306 (11)	0.0434 (12)	−0.0011 (8)	0.0001 (9)	0.0016 (9)
C4	0.0485 (15)	0.0372 (13)	0.0377 (11)	0.0062 (11)	−0.0016 (10)	−0.0031 (10)
C5	0.0527 (16)	0.0355 (13)	0.0385 (13)	0.0079 (11)	−0.0074 (10)	0.0039 (9)
C6	0.0514 (15)	0.0348 (13)	0.0536 (15)	0.0105 (11)	−0.0040 (12)	−0.0009 (11)
N1	0.0314 (10)	0.0282 (9)	0.0364 (9)	0.0000 (7)	−0.0003 (8)	0.0025 (8)
O1	0.0654 (14)	0.0500 (12)	0.0642 (13)	0.0141 (10)	−0.0063 (10)	−0.0171 (10)
Cl2	0.0619 (6)	0.0619 (6)	0.0448 (7)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Cu1—N1ⁱ	2.0380 (19)	C2—H2	0.9300
Cu1—N1	2.0380 (19)	C3—C4	1.377 (3)
Cu1—N1ⁱⁱ	2.0380 (19)	C3—C6	1.506 (3)
Cu1—N1ⁱⁱⁱ	2.0380 (19)	C4—C5	1.381 (4)
Cu1—Cl1	2.5175 (11)	C4—H4	0.9300
C1—N1	1.342 (3)	C5—N1	1.335 (3)
C1—C2	1.385 (4)	C5—H5	0.9300
C1—H1	0.9300	C6—O1	1.407 (4)
C2—C3	1.384 (4)	C6—H6	0.9300

N1ⁱ—Cu1—N1	88.946 (16)	C4—C3—C2	117.5 (2)
N1ⁱ—Cu1—N1ⁱⁱ	164.41 (11)	C4—C3—C6	122.6 (2)
N1—Cu1—N1ⁱⁱ	88.946 (16)	C2—C3—C6	119.9 (2)
N1ⁱ—Cu1—N1ⁱⁱⁱ	88.946 (15)	C3—C4—C5	119.4 (2)
N1—Cu1—N1ⁱⁱⁱ	164.41 (11)	C3—C4—H4	120.3
N1ⁱⁱ—Cu1—N1ⁱⁱⁱ	88.946 (16)	C5—C4—H4	120.3
N1ⁱ—Cu1—Cl1	97.79 (6)	N1—C5—C4	123.4 (2)
N1—Cu1—Cl1	97.79 (6)	N1—C5—H5	118.3
N1ⁱⁱ—Cu1—Cl1	97.79 (6)	C4—C5—H5	118.3
N1ⁱⁱⁱ—Cu1—Cl1	97.79 (6)	O1—C6—C3	113.9 (2)
N1—C1—C2	122.2 (2)	O1—C6—H6	123.0
N1—C1—H1	118.9	C3—C6—H6	123.0
C2—C1—H1	118.9	C5—N1—C1	117.4 (2)
C3—C2—C1	120.1 (2)	C5—N1—Cu1	121.56 (16)
C3—C2—H2	120.0	C1—N1—Cu1	120.97 (16)
C1—C2—H2	120.0

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

Experimental details

Crystal data
Chemical formula	[CuCl(C₆H₅NO)4]Cl
M_r	562.88
Crystal system, space group	Tetragonal, P4/n
Temperature (K)	296
a, c (Å)	10.5035 (3), 11.3751 (6)
V (Å³)	1254.94 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.38 × 0.21 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.675, 0.825
No. of measured, independent and observed [I > 2σ(I)] reflections	9150, 1126, 1083
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.114, 1.03
No. of reflections	1126
No. of parameters	82
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl2	0.93	2.844	3.732 (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

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