Dichlorido[2,2′-(oxydimethyl­ene)dipyridine]copper(II)

In the title complex, [CuCl₂(C₁₂H₁₂N₂O)], the Cu^II ion is coordinated in a distorted trigonal-bipyramidal environment. In the crystal structure, there is a weak π–π stacking inter­action between symmetry-related pyridine rings, with a centroid-to-centroid distance of 3.8134 (17) Å. In addition, there is relatively close contact between the pyridine ring π-system and a symmetry-related Cu^II ion (Cu...centroid distance of 3.868 Å).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.024
• wR factor = 0.066
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  Cl1     ..      12.38 su

Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92

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      0.918
            Tmax scaled      0.497 Tmin scaled      0.414

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

   0 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
   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

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S1. Comment

2,2'-[oxydi(methylene)]dipyridine is an useful tridentate terminal ligand and the Cd^II complex with it as ligand has already been published (Li, 2007). Herein the crystal structure of the title complex, (I), is reported.

The molecular structure of (I) is shown in Fig. 1. The atom Cu1 is coordinated in a distorted trigonal-bipyramidal environment (Table 1). In the crystal structure, there is a weak π-π stacking interaction between symmetry related pyridyl rings, with the relevant distances being Cg1···Cg1ⁱ = 3.8134 (17) Å and a perpendicular distance of 3.556 Å [symmetry code (i) -x, 2 - y, -z; Cg1 is the centroid of the N1/C2—C6 ring]. In addition, there is close contact between a π-ring system and symmetry related Cu atom, with the relative distances being: Cg2···Cu1ⁱⁱ = 3.868 Å, Cg2_perp···Cu1ⁱⁱ = 3.635 Å [symmetry code: (ii) -x, 1 - y, -z; Cg2 is the centroid of the N2/C8—C12 ring; Cg2_perp···Cu1ⁱⁱ is the perpendicular distance from Cu1ⁱⁱ to N2/C8—C12 ring]. The title compound is isostructural with the Cadmium analog (Li, 2007) although the Cd analog was solved and refined in the non-standard P2₁/n setting of space group P2₁/c.

Related literature

For the isostructural Cd and Cu analogs of the title compound, see: Li (2007, 2008).

S2. Experimental

6 ml me thanol solution of 2,2'-[oxydi(methylene)]dipyridine (0.0418 g, 0.209 mmol) was added into 8 ml H₂O solution containing CuCl₂.2H₂O (0.0362 g, 0.212 mmol), and the mixed soulution was stirred for a few minutes. The green single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

S3. Refinement

All H atoms were placed in calculated positions and refined as riding, C—H = 0.93–0.97 Å, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. View of complex (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level

Dichlorido[2,2'-(oxydimethylene)dipyridine]copper(II)

Crystal data

[CuCl2(C12H12N2O)]	F(000) = 676
Mr = 334.68	Dx = 1.693 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4907 reflections
a = 8.1599 (10) Å	θ = 2.3–28.3°
b = 12.5534 (15) Å	µ = 2.06 mm^−1
c = 15.3846 (14) Å	T = 298 K
β = 123.574 (9)°	Block, green
V = 1313.0 (3) Å^3	0.46 × 0.40 × 0.34 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2323 independent reflections
Radiation source: fine-focus sealed tube	2152 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ϕ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.451, Tmax = 0.541	k = −11→14
5381 measured reflections	l = −18→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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 0.5176P] where P = (Fo^2 + 2Fc^2)/3
2323 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.27 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
C1	−0.0360 (3)	0.76246 (18)	−0.10853 (17)	0.0407 (5)
H1A	−0.1499	0.7554	−0.1795	0.049*
H1B	0.0687	0.7967	−0.1103	0.049*
C2	−0.0341 (4)	0.8555 (2)	0.1167 (2)	0.0481 (6)
H2	0.0297	0.8372	0.1868	0.058*
C3	−0.1666 (4)	0.9378 (2)	0.0794 (2)	0.0576 (7)
H3	−0.1909	0.9750	0.1235	0.069*
C4	−0.2628 (4)	0.9644 (2)	−0.0242 (2)	0.0604 (7)
H4	−0.3532	1.0200	−0.0516	0.072*
C5	−0.2232 (4)	0.9072 (2)	−0.0868 (2)	0.0507 (6)
H5	−0.2882	0.9231	−0.1574	0.061*
C6	−0.0864 (3)	0.82611 (17)	−0.04415 (17)	0.0357 (5)
C7	0.1210 (3)	0.59462 (18)	−0.09417 (16)	0.0369 (5)
H7A	0.2093	0.6368	−0.1039	0.044*
H7B	0.0243	0.5614	−0.1601	0.044*
C8	0.2343 (3)	0.51119 (17)	−0.01249 (15)	0.0320 (4)
C9	0.3812 (3)	0.46002 (18)	0.15917 (17)	0.0368 (5)
H9	0.4090	0.4735	0.2255	0.044*
C10	0.4063 (3)	0.34591 (18)	0.0442 (2)	0.0427 (5)
H10	0.4507	0.2836	0.0311	0.051*
C11	0.2964 (3)	0.41864 (18)	−0.03445 (18)	0.0405 (5)
H11	0.2645	0.4055	−0.1016	0.049*
C12	0.4491 (3)	0.36715 (19)	0.14218 (19)	0.0420 (5)
H12	0.5231	0.3193	0.1965	0.050*
Cl1	0.46540 (8)	0.76638 (5)	0.12142 (4)	0.04202 (15)
Cl2	0.20944 (9)	0.63873 (5)	0.25169 (4)	0.04202 (15)
Cu1	0.18810 (4)	0.673873 (19)	0.102078 (18)	0.03121 (10)
N1	0.0076 (3)	0.80023 (14)	0.05709 (14)	0.0359 (4)
N2	0.2764 (2)	0.53190 (13)	0.08332 (13)	0.0310 (4)
O1	0.0261 (2)	0.66050 (11)	−0.05971 (11)	0.0324 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0432 (12)	0.0411 (13)	0.0352 (11)	0.0067 (10)	0.0201 (10)	0.0108 (10)
C2	0.0580 (15)	0.0417 (13)	0.0490 (14)	0.0070 (12)	0.0323 (12)	−0.0021 (11)
C3	0.0632 (17)	0.0426 (14)	0.0748 (19)	0.0087 (13)	0.0430 (16)	−0.0074 (13)
C4	0.0536 (15)	0.0377 (14)	0.086 (2)	0.0142 (12)	0.0366 (15)	0.0069 (14)
C5	0.0452 (13)	0.0427 (14)	0.0552 (15)	0.0097 (11)	0.0221 (12)	0.0123 (12)
C6	0.0320 (11)	0.0316 (11)	0.0395 (12)	0.0005 (8)	0.0173 (10)	0.0059 (9)
C7	0.0425 (12)	0.0396 (12)	0.0326 (11)	−0.0007 (10)	0.0232 (10)	−0.0024 (9)
C8	0.0300 (10)	0.0321 (11)	0.0352 (10)	−0.0050 (8)	0.0189 (9)	−0.0044 (9)
C9	0.0341 (11)	0.0374 (12)	0.0345 (11)	0.0015 (9)	0.0162 (9)	0.0023 (9)
C10	0.0391 (12)	0.0308 (11)	0.0646 (16)	0.0000 (9)	0.0327 (12)	−0.0045 (11)
C11	0.0420 (12)	0.0394 (13)	0.0470 (13)	−0.0066 (10)	0.0290 (11)	−0.0112 (10)
C12	0.0355 (11)	0.0354 (12)	0.0523 (14)	0.0047 (10)	0.0225 (11)	0.0072 (10)
Cl1	0.0417 (3)	0.0411 (3)	0.0482 (3)	−0.0068 (2)	0.0279 (3)	−0.0045 (2)
Cl2	0.0550 (3)	0.0420 (3)	0.0353 (3)	−0.0009 (3)	0.0289 (3)	0.0015 (2)
Cu1	0.03650 (16)	0.02880 (16)	0.02902 (15)	0.00285 (10)	0.01855 (12)	0.00079 (9)
N1	0.0363 (10)	0.0307 (9)	0.0402 (10)	0.0028 (8)	0.0209 (8)	0.0014 (8)
N2	0.0314 (8)	0.0288 (9)	0.0325 (9)	−0.0017 (7)	0.0175 (7)	−0.0023 (7)
O1	0.0341 (8)	0.0336 (8)	0.0286 (7)	0.0023 (6)	0.0168 (6)	0.0025 (6)

Geometric parameters (Å, º)

C1—O1	1.428 (3)	C7—H7B	0.9700
C1—C6	1.496 (3)	C8—N2	1.341 (3)
C1—H1A	0.9700	C8—C11	1.382 (3)
C1—H1B	0.9700	C9—N2	1.343 (3)
C2—N1	1.336 (3)	C9—C12	1.376 (3)
C2—C3	1.372 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—C12	1.372 (4)
C3—C4	1.373 (4)	C10—C11	1.379 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.375 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.379 (3)	Cl1—Cu1	2.4109 (6)
C5—H5	0.9300	Cl2—Cu1	2.2538 (6)
C6—N1	1.341 (3)	Cu1—N2	2.0021 (17)
C7—O1	1.421 (3)	Cu1—N1	2.0092 (18)
C7—C8	1.499 (3)	Cu1—O1	2.0813 (14)
C7—H7A	0.9700
O1—C1—C6	106.14 (17)	N2—C9—H9	118.9
O1—C1—H1A	110.5	C12—C9—H9	118.9
C6—C1—H1A	110.5	C12—C10—C11	118.8 (2)
O1—C1—H1B	110.5	C12—C10—H10	120.6
C6—C1—H1B	110.5	C11—C10—H10	120.6
H1A—C1—H1B	108.7	C10—C11—C8	119.4 (2)
N1—C2—C3	123.0 (2)	C10—C11—H11	120.3
N1—C2—H2	118.5	C8—C11—H11	120.3
C3—C2—H2	118.5	C10—C12—C9	119.3 (2)
C2—C3—C4	118.8 (3)	C10—C12—H12	120.4
C2—C3—H3	120.6	C9—C12—H12	120.4
C4—C3—H3	120.6	N2—Cu1—N1	155.06 (7)
C3—C4—C5	118.8 (2)	N2—Cu1—O1	78.29 (6)
C3—C4—H4	120.6	N1—Cu1—O1	77.99 (7)
C5—C4—H4	120.6	N2—Cu1—Cl2	98.17 (5)
C4—C5—C6	119.6 (2)	N1—Cu1—Cl2	97.71 (6)
C4—C5—H5	120.2	O1—Cu1—Cl2	147.65 (4)
C6—C5—H5	120.2	N2—Cu1—Cl1	93.36 (5)
N1—C6—C5	121.6 (2)	N1—Cu1—Cl1	96.97 (6)
N1—C6—C1	116.70 (18)	O1—Cu1—Cl1	96.81 (4)
C5—C6—C1	121.7 (2)	Cl2—Cu1—Cl1	115.53 (2)
O1—C7—C8	107.73 (16)	C2—N1—C6	118.2 (2)
O1—C7—H7A	110.2	C2—N1—Cu1	126.14 (16)
C8—C7—H7A	110.2	C6—N1—Cu1	115.53 (15)
O1—C7—H7B	110.2	C8—N2—C9	118.52 (18)
C8—C7—H7B	110.2	C8—N2—Cu1	115.92 (14)
H7A—C7—H7B	108.5	C9—N2—Cu1	125.45 (14)
N2—C8—C11	121.7 (2)	C7—O1—C1	115.70 (16)
N2—C8—C7	116.77 (18)	C7—O1—Cu1	112.11 (12)
C11—C8—C7	121.47 (19)	C1—O1—Cu1	111.27 (12)
N2—C9—C12	122.3 (2)
N1—C2—C3—C4	0.7 (4)	Cl1—Cu1—N1—C6	81.62 (15)
C2—C3—C4—C5	0.2 (4)	C11—C8—N2—C9	−0.2 (3)
C3—C4—C5—C6	−1.0 (4)	C7—C8—N2—C9	−178.63 (18)
C4—C5—C6—N1	1.0 (4)	C11—C8—N2—Cu1	176.38 (15)
C4—C5—C6—C1	−179.2 (2)	C7—C8—N2—Cu1	−2.1 (2)
O1—C1—C6—N1	27.4 (3)	C12—C9—N2—C8	1.0 (3)
O1—C1—C6—C5	−152.4 (2)	C12—C9—N2—Cu1	−175.19 (16)
O1—C7—C8—N2	−20.0 (2)	N1—Cu1—N2—C8	33.8 (2)
O1—C7—C8—C11	161.56 (18)	O1—Cu1—N2—C8	15.52 (14)
C12—C10—C11—C8	0.7 (3)	Cl2—Cu1—N2—C8	162.86 (13)
N2—C8—C11—C10	−0.7 (3)	Cl1—Cu1—N2—C8	−80.74 (14)
C7—C8—C11—C10	177.7 (2)	N1—Cu1—N2—C9	−149.93 (18)
C11—C10—C12—C9	0.1 (3)	O1—Cu1—N2—C9	−168.19 (18)
N2—C9—C12—C10	−1.0 (3)	Cl2—Cu1—N2—C9	−20.85 (17)
C3—C2—N1—C6	−0.7 (4)	Cl1—Cu1—N2—C9	95.55 (17)
C3—C2—N1—Cu1	−176.6 (2)	C8—C7—O1—C1	160.80 (17)
C5—C6—N1—C2	−0.1 (3)	C8—C7—O1—Cu1	31.76 (19)
C1—C6—N1—C2	−180.0 (2)	C6—C1—O1—C7	−166.95 (17)
C5—C6—N1—Cu1	176.21 (18)	C6—C1—O1—Cu1	−37.49 (19)
C1—C6—N1—Cu1	−3.6 (2)	N2—Cu1—O1—C7	−26.88 (13)
N2—Cu1—N1—C2	143.8 (2)	N1—Cu1—O1—C7	160.88 (14)
O1—Cu1—N1—C2	162.1 (2)	Cl2—Cu1—O1—C7	−113.67 (13)
Cl2—Cu1—N1—C2	14.7 (2)	Cl1—Cu1—O1—C7	65.17 (13)
Cl1—Cu1—N1—C2	−102.4 (2)	N2—Cu1—O1—C1	−158.20 (14)
N2—Cu1—N1—C6	−32.2 (3)	N1—Cu1—O1—C1	29.56 (14)
O1—Cu1—N1—C6	−13.90 (15)	Cl2—Cu1—O1—C1	115.01 (13)
Cl2—Cu1—N1—C6	−161.33 (15)	Cl1—Cu1—O1—C1	−66.16 (13)