Dichlorido{2,2′-[oxydi(methyl­ene)]dipyridine-κ³N,N,N′}cadmium(II)

In the title complex, [CdCl₂(C₁₂H₁₂N₂O)], the Cd^II ion is coordinated by two Cl atoms [Cd—Cl = 2.4402 (9) and 2.4422 (8) Å], and by one O [Cd—O = 2.396 (2) Å] and two N atoms [Cd—N = 2.303 (2) and 2.305 (2) Å] from a tridentate 2,2′-[oxydi(methyl­ene)]dipyridine ligand in a distorted trigonal–bipyramidal geometry. In the ligand, the two pyridyl rings make a dihedral angle of 16.85 (15)°. Weak inter­molecular C—H...Cl hydrogen bonds link the mol­ecules into two-dimensional layers parallel to the plane formed by the a+c and b vectors.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.028
• wR factor = 0.074
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level B
SYMMS02_ALERT_1_B  All angles should not be 90 for a monoclinic cell
  Cell       8.1397   12.5970   13.8230
  Angles    90.0000   90.0000   90.0000

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1         (2)       2.13

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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

Complexes containing Cd(II) are very common and useful, and play a pivotal role in the area of optics. In most known structures, Cd^II ions assume octahedral coordination geometry, whereas five-coordinated Cd(II) complexes are very limited (Sawitzki et al. 1974; Reger et al., 2002; Zhang et al. 2007). Herewith we report the crystal structure of of the title compound, (I)- a new five-coordinated Cd(II) complex.

In (I) (Fig. 1), Cd1 has a distorted trigonal bipyramidal CdN₂OCl₂ coordination geometry. In a tridentate 2,2'-[oxydi(methylene)]dipyridine ligand, two pyridyl rings make a dihedral angle of 16.85 (15)°. In two neighbouring complexes related by inversion centre, there is a weak π-π interaction proved by short distance C3···C9ⁱ of 3.453 (5) Å [symmetry code: -x, -y, -z]. The weak intermolecular C—H···Cl hydrogen bonds (Table 1, Fig. 2) link the molecules into two-dimensional layers parallel to the plane formed by a+c and b vectors.

Related literature

For crystal structures of related five-coordinated Cd^II complexes, see: Sawitzki & Schnering (1974); Reger et al. (2002); Zhang & Shi (2007).

S2. Experimental

5 ml me thanol solution of 2,2'-[oxydi(methylene)]dipyridine (0.0327 g, 0.163 mmol) was added into 8 ml H₂O solution containing CdCl₂.2.5H₂O (0.0402 g, 0.176 mmol), and the mixture was stirred for a few minutes. The red single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

S3. Refinement

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

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I), showing the atom numbering scheme and displacement ellipsoids drawn at the 30% probability level
	Fig. 2. A portion of the crystal packing of (I) showing the intermolecular hydrogen bonds as dashed lines.

Dichlorido{2,2'-[oxydi(methylene)]dipyridine-κ³N,N,N'}cadmium(II)

Crystal data

[CdCl2(C12H12N2O)]	F(000) = 752
Mr = 383.54	Dx = 1.797 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5221 reflections
a = 8.1397 (15) Å	θ = 2.2–28.2°
b = 12.597 (2) Å	µ = 1.91 mm^−1
c = 13.823 (3) Å	T = 298 K
β = 90.00 (1)°	Block, red
V = 1417.3 (4) Å^3	0.35 × 0.30 × 0.26 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2504 independent reflections
Radiation source: fine-focus sealed tube	2259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.555, Tmax = 0.637	k = −12→14
6908 measured reflections	l = −13→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 0.0413P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2504 reflections	Δρmax = 0.51 e Å^−3
164 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0071 (6)

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
Cd1	0.11080 (2)	0.310375 (16)	0.121183 (14)	0.04107 (13)
O1	0.1024 (3)	0.32605 (17)	−0.05150 (16)	0.0573 (6)
N1	−0.0571 (3)	0.18529 (17)	0.0506 (2)	0.0463 (6)
N2	0.2095 (3)	0.47121 (19)	0.06695 (17)	0.0412 (5)
C3	−0.0493 (3)	0.1670 (2)	−0.0436 (2)	0.0454 (7)
C9	0.3299 (4)	0.6388 (3)	0.1051 (3)	0.0549 (8)
H9	0.3558	0.6898	0.1514	0.066*
C7	−0.1646 (4)	0.1293 (3)	0.1042 (3)	0.0597 (8)
H7	−0.1710	0.1429	0.1702	0.072*
C10	0.3719 (4)	0.6525 (3)	0.0100 (3)	0.0566 (8)
H10	0.4281	0.7132	−0.0092	0.068*
C8	0.2480 (4)	0.5471 (2)	0.1301 (2)	0.0497 (7)
H8	0.2181	0.5377	0.1944	0.060*
C2	0.0691 (4)	0.2318 (3)	−0.1024 (2)	0.0535 (7)
H2A	0.1699	0.1922	−0.1126	0.064*
H2B	0.0217	0.2482	−0.1650	0.064*
C4	−0.1469 (4)	0.0920 (3)	−0.0877 (3)	0.0662 (9)
H4	−0.1410	0.0808	−0.1541	0.079*
C5	−0.2547 (4)	0.0334 (3)	−0.0304 (4)	0.0787 (12)
H5	−0.3196	−0.0193	−0.0581	0.094*
C1	0.2060 (4)	0.3997 (2)	−0.0970 (2)	0.0487 (7)
H1A	0.1509	0.4302	−0.1527	0.058*
H1B	0.3052	0.3647	−0.1191	0.058*
C6	−0.2647 (4)	0.0532 (3)	0.0654 (3)	0.0705 (10)
H6	−0.3381	0.0159	0.1041	0.085*
C11	0.3312 (3)	0.5770 (3)	−0.0566 (3)	0.0530 (8)
H11	0.3581	0.5863	−0.1214	0.064*
Cl2	0.36235 (10)	0.21466 (7)	0.16135 (6)	0.0580 (2)
Cl1	−0.05175 (10)	0.36258 (7)	0.26186 (6)	0.0595 (2)
C12	0.2489 (3)	0.4856 (2)	−0.0264 (2)	0.0419 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.05013 (17)	0.04633 (18)	0.02674 (16)	−0.00318 (8)	0.00138 (10)	0.00116 (8)
O1	0.0820 (15)	0.0613 (13)	0.0286 (12)	−0.0183 (11)	0.0046 (11)	−0.0049 (10)
N1	0.0484 (13)	0.0449 (14)	0.0457 (17)	0.0009 (10)	−0.0018 (12)	−0.0020 (11)
N2	0.0461 (12)	0.0429 (13)	0.0347 (13)	0.0004 (10)	0.0025 (10)	0.0026 (11)
C3	0.0420 (14)	0.0469 (16)	0.0473 (19)	0.0082 (12)	−0.0065 (13)	−0.0114 (14)
C9	0.0514 (16)	0.0481 (18)	0.065 (2)	0.0002 (14)	−0.0015 (16)	−0.0024 (16)
C7	0.0607 (18)	0.060 (2)	0.058 (2)	−0.0040 (16)	0.0061 (16)	0.0084 (17)
C10	0.0455 (16)	0.0470 (17)	0.077 (3)	−0.0017 (13)	0.0035 (16)	0.0100 (18)
C8	0.0565 (16)	0.0504 (17)	0.0423 (17)	−0.0007 (14)	0.0017 (14)	−0.0038 (14)
C2	0.0589 (17)	0.0634 (19)	0.0381 (17)	0.0016 (15)	−0.0001 (14)	−0.0158 (16)
C4	0.0671 (19)	0.061 (2)	0.070 (2)	0.0027 (17)	−0.0153 (18)	−0.0223 (19)
C5	0.062 (2)	0.056 (2)	0.118 (4)	−0.0077 (17)	−0.017 (2)	−0.018 (2)
C1	0.0489 (15)	0.0631 (19)	0.0341 (16)	−0.0001 (13)	0.0057 (13)	0.0041 (14)
C6	0.063 (2)	0.052 (2)	0.097 (3)	−0.0113 (16)	0.001 (2)	0.009 (2)
C11	0.0474 (15)	0.0584 (19)	0.0532 (19)	0.0019 (14)	0.0077 (14)	0.0204 (16)
Cl2	0.0549 (4)	0.0674 (5)	0.0516 (5)	0.0075 (4)	−0.0007 (4)	0.0050 (4)
Cl1	0.0673 (5)	0.0726 (6)	0.0387 (4)	0.0084 (4)	0.0136 (4)	−0.0028 (4)
C12	0.0354 (13)	0.0514 (16)	0.0388 (16)	0.0056 (11)	0.0015 (11)	0.0072 (13)

Geometric parameters (Å, º)

Cd1—N1	2.303 (2)	C7—H7	0.9300
Cd1—N2	2.305 (2)	C10—C11	1.365 (5)
Cd1—O1	2.396 (2)	C10—H10	0.9300
Cd1—Cl2	2.4402 (9)	C8—H8	0.9300
Cd1—Cl1	2.4422 (8)	C2—H2A	0.9700
O1—C1	1.403 (3)	C2—H2B	0.9700
O1—C2	1.407 (4)	C4—C5	1.394 (6)
N1—C3	1.325 (4)	C4—H4	0.9300
N1—C7	1.345 (4)	C5—C6	1.349 (6)
N2—C8	1.332 (4)	C5—H5	0.9300
N2—C12	1.342 (4)	C1—C12	1.498 (4)
C3—C4	1.376 (4)	C1—H1A	0.9700
C3—C2	1.502 (5)	C1—H1B	0.9700
C9—C10	1.370 (5)	C6—H6	0.9300
C9—C8	1.378 (4)	C11—C12	1.396 (4)
C9—H9	0.9300	C11—H11	0.9300
C7—C6	1.368 (5)
N1—Cd1—N2	132.11 (9)	N2—C8—C9	123.5 (3)
N1—Cd1—O1	67.52 (8)	N2—C8—H8	118.3
N2—Cd1—O1	67.26 (8)	C9—C8—H8	118.3
N1—Cd1—Cl2	104.85 (6)	O1—C2—C3	108.1 (2)
N2—Cd1—Cl2	102.47 (6)	O1—C2—H2A	110.1
O1—Cd1—Cl2	106.94 (6)	C3—C2—H2A	110.1
N1—Cd1—Cl1	101.53 (7)	O1—C2—H2B	110.1
N2—Cd1—Cl1	102.19 (6)	C3—C2—H2B	110.1
O1—Cd1—Cl1	139.08 (6)	H2A—C2—H2B	108.4
Cl2—Cd1—Cl1	113.98 (3)	C3—C4—C5	118.4 (4)
C1—O1—C2	116.7 (2)	C3—C4—H4	120.8
C1—O1—Cd1	118.96 (17)	C5—C4—H4	120.8
C2—O1—Cd1	115.74 (18)	C6—C5—C4	119.8 (3)
C3—N1—C7	118.8 (3)	C6—C5—H5	120.1
C3—N1—Cd1	120.5 (2)	C4—C5—H5	120.1
C7—N1—Cd1	120.8 (2)	O1—C1—C12	109.0 (2)
C8—N2—C12	118.5 (2)	O1—C1—H1A	109.9
C8—N2—Cd1	120.00 (19)	C12—C1—H1A	109.9
C12—N2—Cd1	120.97 (19)	O1—C1—H1B	109.9
N1—C3—C4	121.8 (3)	C12—C1—H1B	109.9
N1—C3—C2	118.0 (3)	H1A—C1—H1B	108.3
C4—C3—C2	120.2 (3)	C5—C6—C7	118.6 (4)
C10—C9—C8	117.8 (3)	C5—C6—H6	120.7
C10—C9—H9	121.1	C7—C6—H6	120.7
C8—C9—H9	121.1	C10—C11—C12	119.4 (3)
N1—C7—C6	122.6 (4)	C10—C11—H11	120.3
N1—C7—H7	118.7	C12—C11—H11	120.3
C6—C7—H7	118.7	N2—C12—C11	120.9 (3)
C11—C10—C9	119.9 (3)	N2—C12—C1	118.3 (2)
C11—C10—H10	120.0	C11—C12—C1	120.8 (3)
C9—C10—H10	120.0
N1—Cd1—O1—C1	−174.5 (2)	Cd1—N1—C3—C2	−1.2 (3)
N2—Cd1—O1—C1	21.70 (19)	C3—N1—C7—C6	0.9 (5)
Cl2—Cd1—O1—C1	−75.0 (2)	Cd1—N1—C7—C6	−179.0 (3)
Cl1—Cd1—O1—C1	104.0 (2)	C8—C9—C10—C11	0.6 (4)
N1—Cd1—O1—C2	−27.6 (2)	C12—N2—C8—C9	−1.6 (4)
N2—Cd1—O1—C2	168.6 (2)	Cd1—N2—C8—C9	170.0 (2)
Cl2—Cd1—O1—C2	71.9 (2)	C10—C9—C8—N2	0.7 (5)
Cl1—Cd1—O1—C2	−109.1 (2)	C1—O1—C2—C3	−177.3 (2)
N2—Cd1—N1—C3	35.0 (3)	Cd1—O1—C2—C3	35.0 (3)
O1—Cd1—N1—C3	14.7 (2)	N1—C3—C2—O1	−22.5 (4)
Cl2—Cd1—N1—C3	−87.8 (2)	C4—C3—C2—O1	156.9 (3)
Cl1—Cd1—N1—C3	153.3 (2)	N1—C3—C4—C5	−0.8 (5)
N2—Cd1—N1—C7	−145.2 (2)	C2—C3—C4—C5	179.7 (3)
O1—Cd1—N1—C7	−165.4 (2)	C3—C4—C5—C6	1.9 (5)
Cl2—Cd1—N1—C7	92.1 (2)	C2—O1—C1—C12	−170.9 (3)
Cl1—Cd1—N1—C7	−26.8 (2)	Cd1—O1—C1—C12	−24.3 (3)
N1—Cd1—N2—C8	153.2 (2)	C4—C5—C6—C7	−1.6 (6)
O1—Cd1—N2—C8	173.5 (2)	N1—C7—C6—C5	0.2 (5)
Cl2—Cd1—N2—C8	−83.2 (2)	C9—C10—C11—C12	−0.9 (4)
Cl1—Cd1—N2—C8	35.1 (2)	C8—N2—C12—C11	1.2 (4)
N1—Cd1—N2—C12	−35.5 (2)	Cd1—N2—C12—C11	−170.33 (19)
O1—Cd1—N2—C12	−15.17 (18)	C8—N2—C12—C1	179.7 (3)
Cl2—Cd1—N2—C12	88.18 (19)	Cd1—N2—C12—C1	8.2 (3)
Cl1—Cd1—N2—C12	−153.55 (18)	C10—C11—C12—N2	0.0 (4)
C7—N1—C3—C4	−0.6 (4)	C10—C11—C12—C1	−178.5 (3)
Cd1—N1—C3—C4	179.3 (2)	O1—C1—C12—N2	10.7 (3)
C7—N1—C3—C2	178.9 (3)	O1—C1—C12—C11	−170.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···Cl2^i	0.97	2.77	3.735 (3)	175
C6—H6···Cl1^ii	0.93	2.82	3.701 (4)	158

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