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In the title compound, [Cu(C6H5N2O)Cl(C6H6N2O)], the Cu atom is coordinated by one neutral and one deprotonated pyridine-2-carboxaldehyde oxime (pco) ligand, resulting in the formation of two five-membered CuN2C2 rings. Together with the additional coordinating chloride anion, the coordination polyhedron of copper is best described as a distorted square-pyramid, the distortion parameter being 0.288. The two organic ligands are linked by an intramolecular O—H...O hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808014748/im2064sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536808014748/im2064Isup2.hkl
Contains datablock I

CCDC reference: 690861

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.030
  • wR factor = 0.110
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 -- Cl1 .. 6.24 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT432_ALERT_2_C Short Inter X...Y Contact C12 .. C12 .. 3.11 Ang. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.27 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.271 Tmax scaled 0.755 Tmin scaled 0.620 HYDTR01_ALERT_1_G Extra text has been found in the _refine_ls_hydrogen_treatment fi Explanatory text should be in the _publ_section_refinement field. Hydrogen treatment given as constrained Hydrogen treatment identified as constr PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL022_ALERT_1_A There is a mismatched ~ on line 103 2006). The title compound is a new copper complex from the reaction of CuCl~2 If you require a ~ then it should be escaped with a \, i.e. \~ Otherwise there must be a matching closing ~, e.g. C~2~H~4~ PUBL022_ALERT_1_A There is a mismatched ~ on line 104 ~with pyridine-2-carboxaldehyde oxime (pco). The compound consists of two If you require a ~ then it should be escaped with a \, i.e. \~ Otherwise there must be a matching closing ~, e.g. C~2~H~4~
2 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Comment top

Pyridine-2-carbaldehyde oxime ligands usually bind to metals in a bidentate fashion, either chelating one metal center or bridging two metals. Their complexes find application in diverse areas such as functional supramolecular design, magnetic materials and catalysis (Korpi et al., 2005; Pearse et al., 1989; Afrati et al., 2005; Stamatatos et al., 2006). The title compound is a new copper complex from the reaction of CuCl2 with pyridine-2-carbaldehyde oxime (pco). The compound consists of two N,N-chelating ligands and one chloride anion. The two pco ligands are coordinated to copper to form two five-membered CuC2N2 rings. The copper atom adopts a distorted 4 + 1 square-pyramidal coordination mode with the distortion parameter being 0.288 (Addison et al., 1984) and the angles around copper ion ranging from 79.07 (1)° for N3—Cu1—N4 to 168.37 (1)° for N2—Cu1—N3. From the viewpoint of charge balance, it is presumed there exists one deprotonated and one protonated oxime ligand with a strong intramolecular hydrogen bond between the OH group and the negatively charged oxygen of the other ligand (O1···O2 = 2.488 Å) which would also give an explanation for the rather unusal cis-arrangement of the ligands (Scheme 1, Figure 1. ).

Related literature top

For related literature, see: Addison et al. (1984); Afrati et al. (2005); Korpi et al. (2005); Pearse et al. (1989); Stamatatos et al. (2006).

Experimental top

A methanolic solution (15 ml) containing pco (0.1 mmol, 0.012 g) was added to an methanolic solution (10 ml) containing CuCl2 × 2 H2O (0.1 mmol, 0.017 g). After stirring for 2 h, the solution was filtered. Dark green needle-like crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the resulting filtrate in air for several days (yield 65.6% based on the ligand).

Refinement top

H atoms were placed geometrically and allowed to ride during refinement with C—H = 0.93–0.96 Å and O—H = 0.82 Å with Uiso(H) = 1.2 or 1.5Ueq(C or O).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
Chlorido(pyridine-2-carbaldehyde oximato-κ2N,N')(pyridine-2- carbaldehyde oxime-κ2N,N')copper(II) top
Crystal data top
[Cu(C6H5N2O)Cl(C6H6N2O)]F(000) = 1384
Mr = 342.24Dx = 1.730 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2343 reflections
a = 16.686 (2) Åθ = 2.4–26.6°
b = 12.064 (2) ŵ = 1.87 mm1
c = 13.805 (1) ÅT = 293 K
β = 109.02 (1)°Block, dark green
V = 2627.3 (5) Å30.22 × 0.18 × 0.15 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
2318 independent reflections
Radiation source: fine-focus sealed tube1788 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SHELXTL; Sheldrick, 2008)
h = 1419
Tmin = 0.488, Tmax = 0.594k = 1413
6487 measured reflectionsl = 1616
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.065P)2 + 1.2P]
where P = (Fo2 + 2Fc2)/3
2318 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
[Cu(C6H5N2O)Cl(C6H6N2O)]V = 2627.3 (5) Å3
Mr = 342.24Z = 8
Monoclinic, C2/cMo Kα radiation
a = 16.686 (2) ŵ = 1.87 mm1
b = 12.064 (2) ÅT = 293 K
c = 13.805 (1) Å0.22 × 0.18 × 0.15 mm
β = 109.02 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2318 independent reflections
Absorption correction: multi-scan
(SHELXTL; Sheldrick, 2008)
1788 reflections with I > 2σ(I)
Tmin = 0.488, Tmax = 0.594Rint = 0.034
6487 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.01Δρmax = 0.40 e Å3
2318 reflectionsΔρmin = 0.39 e Å3
181 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
Cu10.45583 (2)0.75857 (3)0.08754 (3)0.03490 (18)
Cl10.39133 (6)0.74459 (6)0.09737 (7)0.0452 (3)
N20.39301 (17)0.8985 (2)0.1014 (2)0.0365 (6)
N30.53622 (18)0.6345 (2)0.0978 (2)0.0432 (7)
N40.39418 (17)0.6311 (2)0.1352 (2)0.0386 (7)
O20.60997 (16)0.6484 (2)0.0801 (2)0.0594 (7)
C10.3107 (2)0.9115 (3)0.0892 (3)0.0445 (9)
H1A0.27610.84910.07640.053*
N10.54953 (17)0.8713 (2)0.1156 (2)0.0431 (7)
C110.4316 (2)0.5328 (3)0.1314 (3)0.0427 (9)
C50.4419 (2)0.9892 (3)0.1166 (3)0.0433 (8)
O10.63020 (15)0.8491 (3)0.1224 (2)0.0666 (8)
H1B0.63460.78340.11000.100*
C20.2750 (3)1.0126 (4)0.0946 (3)0.0585 (11)
H2A0.21771.01870.08660.070*
C90.3236 (3)0.4362 (4)0.1762 (3)0.0647 (12)
H9A0.30020.37070.19030.078*
C70.3232 (2)0.6295 (3)0.1599 (3)0.0457 (9)
H7A0.29730.69680.16380.055*
C120.5115 (2)0.5390 (3)0.1109 (3)0.0463 (9)
H12A0.54260.47600.10760.056*
C60.5299 (2)0.9703 (3)0.1257 (3)0.0483 (9)
H6A0.56921.02760.13810.058*
C100.3975 (3)0.4349 (3)0.1509 (3)0.0579 (11)
H10A0.42390.36800.14710.069*
C80.2865 (3)0.5352 (4)0.1798 (3)0.0593 (11)
H8A0.23650.53880.19570.071*
C40.4094 (3)1.0927 (3)0.1215 (3)0.0636 (12)
H4A0.44401.15500.13130.076*
C30.3253 (3)1.1034 (3)0.1118 (4)0.0718 (13)
H3A0.30291.17290.11710.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0277 (3)0.0340 (3)0.0441 (3)0.00547 (15)0.0132 (2)0.00158 (17)
Cl10.0482 (6)0.0432 (5)0.0407 (5)0.0035 (4)0.0094 (4)0.0023 (4)
N20.0355 (16)0.0317 (15)0.0418 (16)0.0041 (12)0.0118 (13)0.0026 (12)
N30.0398 (17)0.0480 (19)0.0432 (17)0.0156 (14)0.0152 (14)0.0003 (14)
N40.0385 (16)0.0366 (16)0.0392 (16)0.0031 (12)0.0107 (13)0.0023 (12)
O20.0440 (16)0.0712 (19)0.0731 (19)0.0207 (14)0.0327 (14)0.0047 (15)
C10.040 (2)0.044 (2)0.049 (2)0.0096 (16)0.0142 (17)0.0009 (16)
N10.0286 (16)0.0516 (19)0.0505 (18)0.0040 (13)0.0147 (14)0.0005 (14)
C110.052 (2)0.0372 (19)0.032 (2)0.0057 (16)0.0044 (17)0.0001 (15)
C50.052 (2)0.038 (2)0.040 (2)0.0022 (16)0.0157 (18)0.0024 (16)
O10.0326 (15)0.077 (2)0.092 (2)0.0025 (13)0.0241 (15)0.0042 (17)
C20.051 (2)0.066 (3)0.059 (3)0.029 (2)0.019 (2)0.002 (2)
C90.069 (3)0.058 (3)0.058 (3)0.024 (2)0.009 (2)0.009 (2)
C70.041 (2)0.051 (2)0.047 (2)0.0006 (17)0.0166 (17)0.0022 (17)
C120.052 (2)0.044 (2)0.040 (2)0.0195 (18)0.0113 (18)0.0006 (17)
C60.045 (2)0.045 (2)0.056 (2)0.0115 (17)0.0177 (18)0.0050 (18)
C100.071 (3)0.036 (2)0.053 (2)0.0020 (19)0.002 (2)0.0001 (18)
C80.052 (3)0.067 (3)0.057 (3)0.014 (2)0.016 (2)0.006 (2)
C40.080 (3)0.031 (2)0.079 (3)0.0027 (19)0.025 (3)0.0044 (19)
C30.088 (4)0.044 (3)0.084 (3)0.033 (2)0.029 (3)0.004 (2)
Geometric parameters (Å, º) top
Cu1—N31.984 (3)C5—C41.371 (5)
Cu1—N12.012 (3)C5—C61.451 (5)
Cu1—N22.029 (3)O1—H1B0.8200
Cu1—N42.072 (3)C2—C31.352 (6)
Cu1—Cl12.4316 (10)C2—H2A0.9300
N2—C11.338 (4)C9—C81.354 (6)
N2—C51.340 (4)C9—C101.385 (6)
N3—C121.256 (5)C9—H9A0.9300
N3—O21.341 (3)C7—C81.361 (5)
N4—C71.335 (4)C7—H7A0.9300
N4—C111.350 (4)C12—H12A0.9300
C1—C21.370 (5)C6—H6A0.9300
C1—H1A0.9300C10—H10A0.9300
N1—C61.258 (4)C8—H8A0.9300
N1—O11.345 (3)C4—C31.371 (6)
C11—C101.375 (5)C4—H4A0.9300
C11—C121.453 (5)C3—H3A0.9300
N3—Cu1—N191.79 (14)C4—C5—C6123.0 (4)
N3—Cu1—N2168.29 (12)N1—O1—H1B109.5
N1—Cu1—N279.19 (11)C3—C2—C1118.4 (4)
N3—Cu1—N479.15 (12)C3—C2—H2A120.8
N1—Cu1—N4151.07 (12)C1—C2—H2A120.8
N2—Cu1—N4105.21 (11)C8—C9—C10118.3 (4)
N3—Cu1—Cl194.60 (9)C8—C9—H9A120.9
N1—Cu1—Cl1107.40 (9)C10—C9—H9A120.9
N2—Cu1—Cl195.22 (8)N4—C7—C8124.0 (4)
N4—Cu1—Cl1100.71 (8)N4—C7—H7A118.0
C1—N2—C5118.1 (3)C8—C7—H7A118.0
C1—N2—Cu1128.8 (2)N3—C12—C11116.1 (3)
C5—N2—Cu1112.8 (2)N3—C12—H12A121.9
C12—N3—O2120.3 (3)C11—C12—H12A121.9
C12—N3—Cu1117.1 (2)N1—C6—C5115.7 (3)
O2—N3—Cu1122.1 (2)N1—C6—H6A122.2
C7—N4—C11117.2 (3)C5—C6—H6A122.2
C7—N4—Cu1131.7 (2)C11—C10—C9119.9 (4)
C11—N4—Cu1110.9 (2)C11—C10—H10A120.0
N2—C1—C2122.9 (4)C9—C10—H10A120.0
N2—C1—H1A118.5C9—C8—C7119.2 (4)
C2—C1—H1A118.5C9—C8—H8A120.4
C6—N1—O1118.2 (3)C7—C8—H8A120.4
C6—N1—Cu1116.6 (2)C5—C4—C3119.3 (4)
O1—N1—Cu1125.2 (2)C5—C4—H4A120.4
N4—C11—C10121.4 (4)C3—C4—H4A120.4
N4—C11—C12115.3 (3)C2—C3—C4119.8 (4)
C10—C11—C12123.2 (3)C2—C3—H3A120.1
N2—C5—C4121.4 (4)C4—C3—H3A120.1
N2—C5—C6115.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.821.702.488 (5)162

Experimental details

Crystal data
Chemical formula[Cu(C6H5N2O)Cl(C6H6N2O)]
Mr342.24
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)16.686 (2), 12.064 (2), 13.805 (1)
β (°) 109.02 (1)
V3)2627.3 (5)
Z8
Radiation typeMo Kα
µ (mm1)1.87
Crystal size (mm)0.22 × 0.18 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SHELXTL; Sheldrick, 2008)
Tmin, Tmax0.488, 0.594
No. of measured, independent and
observed [I > 2σ(I)] reflections
6487, 2318, 1788
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.110, 1.01
No. of reflections2318
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.39

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.821.702.488 (5)161.5
 

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