Retracted: Dichlorido(1,10-phenanthroline)copper(II)

In the title compound, [CuCl₂(C₁₂H₈N₂)], the Cu^II atom adopts a distorted tetra­hedral coordination formed by two N atoms from one 1,10-phenanthroline ligand and two Cl atoms. In the crystal structure, mol­ecules form inter­molecular C—H...Cl contacts and π–π stacking inter­actions [centroid-to-centroid distances = 3.803 and 3.671 Å]. The shortest inter­molecular Cu...Cl contacts are 4.306 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.091
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   Cl2     ..       5.91 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  CL2     ..       2.88 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.01

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   1 ALERT type 5 Informative message, check

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S1. Comment

As shown in Fig. 1, the title compound is a monomeric complex in which the Cu^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from one 1,10-phenanthroline ligand and two Cl atoms. In the crystal structure, molecules form intermolecular C—H···Cl contacts and π-π stacking interactions (Fig. 2). The dihedral angle and centroid-to-centroid distance between rings [C4–C8, C12] and [C1–C5, N1]ⁱ (symmetry code: (i) 1 - x, 1 - y, 1 - z) are 1.4° and 3.803 Å, respectively. Between rings [C4–C8, C12] and [C8–C12, N2]ⁱⁱ (symmetry code: (ii) 2 - x, 1 - y, 1 - z), the corresponding measurements are 3.0° and 3.671 Å.

Related literature

For related dimeric and polymeric structures, [(C₁₂H₈N₂)CuCl₂]₂ and [(C₁₂H₈N₂)Cu₂Cl₂]_n, see: Viossat et al. (1998); Wang et al. (2002).

S2. Experimental

A mixture of 1,10-phenanthroline (0.161 g, 0.001 mol) and CuCl₂ (0.135 g, 0.001 mol) was added to methanol (20 ml), and the mixture was heated at 365 K for 5 h under reflux with stirring. The resulting solution was then filtered and single crystals suitable for X-ray diffraction analysis formed after a week by slow evaporation of the solvent.

S3. Refinement

All H atoms were located at calculated positions and refined as riding on their parent C atoms with the C—H = 0.93 Å and U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. The molecular structure, showing displacement ellipsoids at 50% probability for non-H atoms.
	Fig. 2. Packing diagram viewed along the b axis.

Dichlorido(1,10-phenanthroline)copper(II)

Crystal data

[CuCl2(C12H8N2)]	F(000) = 628
Mr = 314.65	Dx = 1.743 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3375 reflections
a = 8.000 (5) Å	θ = 1.0–28.3°
b = 15.669 (8) Å	µ = 2.24 mm^−1
c = 11.348 (5) Å	T = 293 K
β = 122.53 (3)°	Block, blue
V = 1199.3 (12) Å^3	0.26 × 0.07 × 0.06 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	1510 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 25.5°, θmin = 2.5°
phi and ω scans	h = −9→9
7416 measured reflections	k = −18→18
2220 independent reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0486P)^2] where P = (Fo^2 + 2Fc^2)/3
2220 reflections	(Δ/σ)max = 0.001
162 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.73800 (6)	0.22097 (2)	0.95569 (4)	0.04570 (17)
Cl1	0.57194 (15)	0.31386 (6)	0.99943 (11)	0.0681 (3)
Cl2	0.92896 (14)	0.27755 (5)	0.89018 (11)	0.0621 (3)
N1	0.5460 (4)	0.12799 (16)	0.8272 (3)	0.0438 (7)
N2	0.8850 (4)	0.11559 (17)	1.0788 (3)	0.0456 (7)
C1	0.3787 (5)	0.1347 (2)	0.7024 (4)	0.0508 (9)
H1	0.3393	0.1885	0.6621	0.055 (10)*
C2	0.2612 (5)	0.0655 (2)	0.6306 (4)	0.0591 (10)
H2	0.1457	0.0728	0.5432	0.074 (12)*
C3	0.3154 (5)	−0.0135 (2)	0.6880 (4)	0.0550 (10)
H3	0.2374	−0.0606	0.6402	0.060 (10)*
C4	0.4892 (5)	−0.0243 (2)	0.8191 (4)	0.0452 (8)
C5	0.6006 (5)	0.04917 (19)	0.8855 (3)	0.0398 (7)
C6	0.5560 (5)	−0.1041 (2)	0.8883 (4)	0.0539 (9)
H6	0.4798	−0.1528	0.8468	0.066 (11)*
C7	0.7274 (5)	−0.1107 (2)	1.0122 (4)	0.0564 (10)
H7	0.7685	−0.1639	1.0547	0.069 (12)*
C8	0.8498 (5)	−0.0375 (2)	1.0818 (4)	0.0481 (8)
C9	1.0331 (5)	−0.0415 (3)	1.2071 (4)	0.0587 (10)
H9	1.0841	−0.0936	1.2513	0.057 (10)*
C10	1.1382 (6)	0.0321 (3)	1.2647 (4)	0.0596 (10)
H10	1.2618	0.0301	1.3477	0.065 (11)*
C11	1.0576 (5)	0.1093 (2)	1.1984 (3)	0.0542 (9)
H11	1.1290	0.1590	1.2401	0.047 (9)*
C12	0.7828 (5)	0.0422 (2)	1.0188 (3)	0.0420 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0442 (3)	0.0321 (2)	0.0536 (3)	−0.00146 (18)	0.0216 (2)	−0.00104 (19)
Cl1	0.0739 (7)	0.0533 (6)	0.0802 (7)	0.0106 (5)	0.0436 (6)	−0.0022 (5)
Cl2	0.0557 (6)	0.0442 (5)	0.0879 (7)	0.0035 (4)	0.0397 (5)	0.0093 (5)
N1	0.0454 (16)	0.0361 (15)	0.0458 (16)	−0.0035 (13)	0.0219 (14)	0.0025 (13)
N2	0.0447 (16)	0.0437 (16)	0.0436 (16)	0.0004 (13)	0.0206 (14)	−0.0038 (13)
C1	0.050 (2)	0.045 (2)	0.053 (2)	0.0025 (17)	0.0241 (18)	0.0037 (17)
C2	0.050 (2)	0.061 (3)	0.051 (2)	−0.0022 (19)	0.0165 (19)	−0.0053 (19)
C3	0.046 (2)	0.048 (2)	0.062 (3)	−0.0079 (17)	0.023 (2)	−0.0093 (19)
C4	0.046 (2)	0.0351 (18)	0.063 (2)	−0.0001 (15)	0.0349 (18)	−0.0065 (16)
C5	0.0423 (18)	0.0372 (18)	0.0472 (19)	0.0015 (15)	0.0289 (16)	0.0014 (15)
C6	0.054 (2)	0.0359 (19)	0.077 (3)	0.0008 (17)	0.039 (2)	−0.0028 (18)
C7	0.062 (3)	0.039 (2)	0.079 (3)	0.0106 (18)	0.045 (2)	0.0073 (19)
C8	0.053 (2)	0.044 (2)	0.057 (2)	0.0087 (17)	0.0355 (18)	0.0054 (17)
C9	0.057 (2)	0.061 (3)	0.060 (2)	0.019 (2)	0.033 (2)	0.018 (2)
C10	0.051 (2)	0.077 (3)	0.044 (2)	0.019 (2)	0.0209 (19)	0.010 (2)
C11	0.045 (2)	0.063 (2)	0.046 (2)	−0.0009 (19)	0.0181 (18)	−0.0077 (19)
C12	0.0442 (19)	0.0400 (19)	0.0479 (19)	0.0046 (15)	0.0289 (16)	0.0022 (16)

Geometric parameters (Å, º)

Cu1—N1	2.049 (3)	C4—C5	1.402 (4)
Cu1—N2	2.072 (3)	C4—C6	1.419 (5)
Cu1—Cl1	2.1998 (13)	C5—C12	1.433 (5)
Cu1—Cl2	2.2122 (14)	C6—C7	1.340 (5)
N1—C1	1.330 (4)	C6—H6	0.930
N1—C5	1.357 (4)	C7—C8	1.437 (5)
N2—C11	1.320 (4)	C7—H7	0.930
N2—C12	1.362 (4)	C8—C9	1.391 (5)
C1—C2	1.379 (5)	C8—C12	1.396 (5)
C1—H1	0.930	C9—C10	1.368 (6)
C2—C3	1.357 (5)	C9—H9	0.930
C2—H2	0.930	C10—C11	1.387 (5)
C3—C4	1.397 (5)	C10—H10	0.930
C3—H3	0.930	C11—H11	0.930
N1—Cu1—N2	81.35 (11)	N1—C5—C4	122.7 (3)
N1—Cu1—Cl1	108.56 (9)	N1—C5—C12	117.5 (3)
N2—Cu1—Cl1	124.60 (8)	C4—C5—C12	119.8 (3)
N1—Cu1—Cl2	115.78 (9)	C7—C6—C4	121.1 (3)
N2—Cu1—Cl2	107.56 (9)	C7—C6—H6	119.4
Cl1—Cu1—Cl2	114.87 (5)	C4—C6—H6	119.5
C1—N1—C5	117.8 (3)	C6—C7—C8	121.7 (3)
C1—N1—Cu1	129.9 (2)	C6—C7—H7	119.4
C5—N1—Cu1	112.3 (2)	C8—C7—H7	118.9
C11—N2—C12	117.8 (3)	C9—C8—C12	117.8 (3)
C11—N2—Cu1	130.8 (2)	C9—C8—C7	123.9 (3)
C12—N2—Cu1	111.4 (2)	C12—C8—C7	118.2 (3)
N1—C1—C2	122.9 (3)	C10—C9—C8	119.4 (4)
N1—C1—H1	118.4	C10—C9—H9	120.2
C2—C1—H1	118.7	C8—C9—H9	120.4
C3—C2—C1	119.6 (4)	C9—C10—C11	119.3 (4)
C3—C2—H2	120.2	C9—C10—H10	120.1
C1—C2—H2	120.3	C11—C10—H10	120.6
C2—C3—C4	120.0 (3)	N2—C11—C10	123.1 (4)
C2—C3—H3	120.2	N2—C11—H11	118.5
C4—C3—H3	119.8	C10—C11—H11	118.3
C3—C4—C5	117.0 (3)	N2—C12—C8	122.6 (3)
C3—C4—C6	124.0 (3)	N2—C12—C5	117.4 (3)
C5—C4—C6	119.0 (3)	C8—C12—C5	120.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl2^i	0.93	2.88	3.572 (3)	132
C3—H3···Cl2^ii	0.93	2.80	3.669 (3)	157
C7—H7···Cl2^iii	0.93	2.79	3.513 (3)	135

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, −y, −z+2.