Bis(2,2′-bipyridyl-κ2N,N′)bis­(2-hydroxy­benzoato)-κO1;κ2O1,O1′-cadmium(II) methanol solvate

Benrabah, R.; Viossat, B.; Tomas, A.; Lemoine, P.

doi:10.1107/S1600536809054610

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m156-m157

https://doi.org/10.1107/S1600536809054610

Open

access

Bis(2,2′-bipyridyl-κ²N,N′)bis(2-hydroxybenzoato)-κO¹;κ²O¹,O^1′-cadmium(II) methanol solvate

Rymel Benrabah,^a Bernard Viossat,^a Alain Tomas ^a and Pascale Lemoine ^a ^*

^aLaboratoire de Cristallographie et RMN Biologiques, UMR 8015 CNRS, Faculté des Sciences Pharmaceutiques et Biologiques de Paris Descartes, 4, avenue de l'Observatoire 75270 Paris Cedex 06, France
^*Correspondence e-mail: pascale.lemoine@parisdescartes.fr

(Received 17 November 2009; accepted 18 December 2009; online 16 January 2010)

The title compound, [Cd(C₇H₅O₃)₂(C₁₀H₈N₂)₂]·CH₃OH, contains one monomeric seven-coordinate cadmium complex and one methanol solvate molecule. The Cd^II atom is coordinated to two 2,2′-bipyridyl ligands via the N atoms and to two salicylate anions (Hsal⁻) via the carboxylate O atoms, which act as monodentate ligand for the one and bidentate ligand for the second. The Cd^II atom exhibits a {6 + 1} environment, approximately described as a distorted capped octahedron with the apical positions occupied by one of the two N atoms belonging to one bipyridyl ligand and one of the two carboxylate O atoms from the monodentate Hsal⁻ ligand. Two intramolecular six-membered hydrogen-bonded rings are present, generated from interactions between the carboxylate and hydroxy groups of the salicylate ligands. There is one intermolecular hydrogen-bonding interaction involving the methanol solvent molecule and the carboxylate group from the monodentate Hsal⁻ ligand. The crystal packing is governed by π–π stacking interactions [centroid–centroid distance = 3.783 (4) Å] which occur between bipyridyl ligands, by C—H⋯O and C—H⋯π interactions and by numerous van der Waals contacts.

Related literature

For related structures, see: Lemoine et al. (2004 ); Mazurier et al. (2000 ); Tomas et al. (2006 ); Turner et al. (1982 ). For the anti-inflammatory properties of zinc complexes, see: Sorensen (2002 and references therein).

Experimental

Crystal data

[Cd(C₇H₅O₃)₂(C₁₀H₈N₂)₂]·CH₄O
M_r = 731.03
Triclinic, $[P \overline 1]$
a = 9.115 (4) Å
b = 12.189 (2) Å
c = 14.883 (2) Å
α = 97.64 (1)°
β = 92.30 (3)°
γ = 101.00 (3)°
V = 1605.1 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 293 K
0.40 × 0.18 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
9433 measured reflections
9117 independent reflections
4943 reflections with I > 2σ(I)
R_int = 0.040
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.138
S = 0.97
9117 reflections
423 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.82	1.82	2.545 (7)	147
O13—H13⋯O11	0.82	1.78	2.505 (4)	147
O61—H61⋯O12	0.82	1.98	2.802 (6)	177
C23—H23⋯O61ⁱ	0.93	2.57	3.429 (8)	154
C43—H43⋯O12ⁱⁱ	0.93	2.43	3.356 (6)	172
C45—H45⋯O13ⁱⁱⁱ	0.93	2.47	3.370 (6)	163
C15—H15⋯Cg1^iv	0.93	2.81	3.620 (6)	147
C47—H47⋯Cg2^v	0.93	2.79	3.589 (6)	145
C62—H62A⋯Cg1^vi	0.96	2.94	3.858 (8)	160
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z; (iv) -x, -y+1, -z+2; (v) -x+1, -y+1, -z+2; (vi) x+1, y+1, z. Cg1 and Cg2 are the centroids of the C2–C7 and C12–C17 rings, respectively.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809054610/dn2517sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809054610/dn2517Isup2.hkl

checkCIF report

Comment top

Recently we described the crystal structure of bis(3,5-diisopropylsalicylato)(2,9-dimethyl-1,10-phenanthroline)cadmium(II) complex (Tomas et al., 2006) as an extension of an ongoing crystal structure investigation of non-steroidal anti-inflammatory drug zinc carboxylate complexes. Zinc is an essential metalloelement required by all cells for activation of a large number of Zn-dependent enzymes (Sorenson, 2002 and references therein). Various zinc carboxylates exhibit favorable anti-inflammatory, analgesic and antipyretic properties. In previous work, we have synthesized and structurally characterized two ternary complexes of Zn(II) with 3,5-diisopropylsalicylate and 1,10-phenanthroline or 2,9-dimethyl-1,10-phenanthroline (Lemoine et al., 2004). Anticonvulsant and rotorod toxicity activities of these complexes were determined to examine structure-anticonvulsant and structure-hypnotic activities of these Zn(II) non- steroidal antiinflammatory agent complexes. Since zinc and cadmium belong to the same group 12 of the periodic system of elements, following this work, we report in this paper the synthesis and the structure of the bis(2,2'-bipyridyl- κ²N,N')(salicylato-κ²O,O')(salicylato-κO)cadmium(II) methanol solvate.

The title compound contains one monomeric seven- coordinate cadmium complex and one methanol solvate molecule. Cd^II is coordinate-covalently bonded to two 2,2'-bipyridyl bidendate ligands via N21 and N30 or N41 and N50 atoms and to two salicylate (Hsal^-) anionic ligands, one of which is monodentate via O11 atom and the other is bidentate via O1 and O2 atoms (Fig. 1). Therefore, the cadmium atom exhibits a {6 + 1} environment, approximately described as a distorted capped octahedron. According to this description, the Cd atom lies 0.127 (2) Å out of the basal plane [O1, N30, N41, N50] with the apical positions occupied by N21 and O11. The O2 atom caps the triangular face formed by O1, N21 and N50. This very irregular geometry is imposed by the small bite angles of one salicylate [O1—Cd—O2, 50.7 (2)°] and the two bipyridyl [N21—Cd—N30, 69.0 (1) °; N41—Cd—N50, 69.3 (1) °] bidentate ligands, mainly due to the rigidity of these chelate molecules. The Cd—N bond lengths are very similar [average 2.367 (4) Å] and comparable with distances found in other bipyridine containing Cd complexes (Turner et al., 1982). The distances between Cd and the oxygen atoms are the following: d(Cd—O1) = 2.391 (5) Å and d(Cd—O2) = 2.685 (5) Å for the first salicylate ligand and d(Cd—O11) = 2.305 (3) Å for the second ligand. The longer Cd—O2 distance is comparable to that described in the bis(salicylato)(2,2'-bipyridyl) (dimethylformamide)cadmium(II) (Mazurier et al., 2000) in a (6 + 1) environment (2.667 Å). The bond lengths and angles of the complexed salicylate ligands and 2,2'-bipyridyl are normal. The chelation of Cd^II by the Hsal^- ligand leads to planar ring, P1 (O1/C1/O2/Cd) with the maximum deviation of 0.026 (4) Å for C1 atom. The phenyl mean planes P2 [C2—C7] and P3 [C12—C17] [maximum deviation of 0.003 (4) Å for C7] in the salicylate ligands make a dihedral 70.5 (2) °. The bipyridyl ligands are essentially planar (maximum deviation of 0.067 (5) Å for C48) and the Cd^II atom is displaced from the least-squares planes P4 [N21/C22- C29/N30/C31—C32] by 0.139 (5) Å and from P5 [N41/C42- C49/N50/C51—C52] by 0.251 (5) Å. The dihedral angles between planes P4 and P5 is 82.1 (1) °.

The hydroxy H3 (or H13) atom attached to O3 (or O13) is involved in intramolecular via O1 (or O11) atom (Table 1) thus contributing to planarity of the rings [O1 C1 C2 C3 O3 H3 and O11 C11 C12 C13 O13 H13] (maximum deviation of 0.022 (2) Å for H3). There is one intermolecular hydrogen bonding interaction involving the solvate methanol molecule and the carboxylate O12 atom (Table 1).

Moreover, the packing is governed by π - π stacking interactions which occur between bipyridyl ligands [N21/C22—C25/C32 and N30/C26—C29/C31] through inversion centre at (1/2, 1/2, 1/2) with a centroid-to-centroid distance of 3.783 (4) Å, an average spacing of 3.50 Å with an offset of 22.1°. In addition, there are three C—H···O interactions (Table 1) and three C– H···Cg(π-ring) interactions (Table 1, Cg1 being the centroid of the ring C2 to C7 and Cg2 the centroid of the ring C12 to C17).

Related literature top

For related structures, see: Lemoine et al. (2004); Mazurier et al. (2000); Tomas et al. (2006); Turner et al. (1982). For the anti-inflammatory properties of zinc complexes, see: Sorensen (2002 and references therein).

Experimental top

The cadmium(II) salicylate [Cd^II(Sal)₂] was prepared by reaction of Cd(NO₃)₂.4H₂O with NaSal after neutralizing HSal by a NaOH solution. An amount of 0.387 g of Cd^II(Sal)₂ (1 mmole) and 0.313 g of 2,2'-bipyridyl (2 mmole) were dissolved in 20 ml of methanol. The solution was stirred at 60°C under reflux conditions for one hour to give the complex. Single crystals were obtained by slow evaporation of this solution at room temperature (293 K).

Structure description top

For related structures, see: Lemoine et al. (2004); Mazurier et al. (2000); Tomas et al. (2006); Turner et al. (1982). For the anti-inflammatory properties of zinc complexes, see: Sorensen (2002 and references therein).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Version 1.63.02; Farrugia, 1999).

Figures top

Fig. 1. Molecular view of the solvate methanol complex showing atomic numbering and O—H–O hydrogen bonds in dotted lines. Displacements ellipsoïds are drawn at the 30% probability level.

Bis(2,2'-bipyridyl-κ²N,N')bis(2-hydroxybenzoato)- κO¹;κ²O¹,O^1'-cadmium(II) methanol solvate top

Crystal data top

[Cd(C₇H₅O₃)₂(C₁₀H₈N₂)₂]·CH₄O	Z = 2
M_r = 731.03	F(000) = 744
Triclinic, P1	D_x = 1.513 Mg m⁻³ D_m = 1.53 (2) Mg m⁻³ D_m measured by flotation (CCl₄/CH₂Cl₂)
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.115 (4) Å	Cell parameters from 25 reflections
b = 12.189 (2) Å	θ = 1.7–8.9°
c = 14.883 (2) Å	µ = 0.74 mm⁻¹
α = 97.64 (1)°	T = 293 K
β = 92.30 (3)°	Parallelepiped, colourless
γ = 101.00 (3)°	0.40 × 0.18 × 0.13 mm
V = 1605.1 (8) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.040
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 2.1°
Graphite monochromator	h = −12→12
ω–2θ scans	k = −17→16
9433 measured reflections	l = 0→20
9117 independent reflections	3 standard reflections every 60 min
4943 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0472P)²] where P = (F_o² + 2F_c²)/3
9117 reflections	(Δ/σ)_max = 0.001
423 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

[Cd(C₇H₅O₃)₂(C₁₀H₈N₂)₂]·CH₄O	γ = 101.00 (3)°
M_r = 731.03	V = 1605.1 (8) Å³
Triclinic, P1	Z = 2
a = 9.115 (4) Å	Mo Kα radiation
b = 12.189 (2) Å	µ = 0.74 mm⁻¹
c = 14.883 (2) Å	T = 293 K
α = 97.64 (1)°	0.40 × 0.18 × 0.13 mm
β = 92.30 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.040
9433 measured reflections	3 standard reflections every 60 min
9117 independent reflections	intensity decay: none
4943 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 0.97	Δρ_max = 0.37 e Å⁻³
9117 reflections	Δρ_min = −0.85 e Å⁻³
423 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
Cd1	0.22853 (3)	0.25632 (3)	0.68934 (2)	0.04219 (10)
O1	−0.0186 (6)	0.1908 (3)	0.7336 (3)	0.1081 (18)
O2	0.1325 (5)	0.0950 (5)	0.7918 (3)	0.1118 (18)
O3	−0.2935 (6)	0.1625 (4)	0.7678 (3)	0.0960 (14)
H3	−0.2179	0.1873	0.7431	0.115*
C1	0.0072 (8)	0.1196 (5)	0.7824 (4)	0.081 (2)
C2	−0.1228 (5)	0.0620 (4)	0.8296 (3)	0.0522 (11)
C3	−0.2629 (6)	0.0880 (4)	0.8216 (3)	0.0570 (12)
C4	−0.3779 (6)	0.0353 (5)	0.8688 (4)	0.0689 (14)
H4	−0.4730	0.0519	0.8634	0.083*
C5	−0.3499 (6)	−0.0414 (5)	0.9234 (4)	0.0707 (14)
H5	−0.4266	−0.0764	0.9554	0.085*
C6	−0.2113 (7)	−0.0672 (5)	0.9316 (4)	0.0716 (14)
H6	−0.1937	−0.1193	0.9690	0.086*
C7	−0.0989 (6)	−0.0162 (4)	0.8848 (3)	0.0617 (12)
H7	−0.0046	−0.0344	0.8900	0.074*
O11	0.1346 (4)	0.4193 (2)	0.7177 (2)	0.0562 (8)
O12	0.2733 (5)	0.5535 (3)	0.6553 (2)	0.0748 (11)
O13	0.0194 (4)	0.4604 (3)	0.8654 (2)	0.0648 (9)
H13	0.0384	0.4223	0.8193	0.078*
C11	0.1982 (5)	0.5224 (3)	0.7164 (3)	0.0442 (9)
C12	0.1700 (4)	0.6045 (3)	0.7947 (3)	0.0407 (8)
C13	0.0823 (5)	0.5701 (4)	0.8645 (3)	0.0467 (10)
C14	0.0580 (6)	0.6490 (5)	0.9356 (3)	0.0645 (13)
H14	−0.0014	0.6260	0.9817	0.077*
C15	0.1213 (7)	0.7609 (5)	0.9381 (3)	0.0740 (16)
H15	0.1056	0.8132	0.9863	0.089*
C16	0.2082 (6)	0.7965 (4)	0.8697 (4)	0.0696 (14)
H16	0.2503	0.8726	0.8715	0.083*
C17	0.2322 (6)	0.7187 (4)	0.7989 (3)	0.0558 (11)
H17	0.2911	0.7428	0.7530	0.067*
N21	0.2855 (4)	0.0894 (3)	0.6089 (3)	0.0526 (9)
C22	0.3627 (6)	0.0235 (5)	0.6465 (4)	0.0751 (15)
H22	0.3981	0.0448	0.7071	0.090*
C23	0.3936 (7)	−0.0744 (5)	0.6013 (6)	0.090 (2)
H23	0.4506	−0.1174	0.6294	0.108*
C24	0.3379 (8)	−0.1058 (5)	0.5145 (6)	0.098 (2)
H24	0.3548	−0.1727	0.4824	0.118*
C27	−0.0004 (7)	0.1813 (6)	0.3642 (4)	0.0818 (17)
H27	−0.0448	0.1652	0.3053	0.098*
C28	−0.0146 (6)	0.2783 (5)	0.4192 (4)	0.0712 (15)
H28	−0.0696	0.3282	0.3991	0.085*
C29	0.0553 (6)	0.2984 (4)	0.5045 (3)	0.0605 (12)
H29	0.0483	0.3645	0.5419	0.073*
N30	0.1333 (4)	0.2278 (3)	0.5370 (2)	0.0472 (8)
C31	0.1458 (5)	0.1334 (4)	0.4834 (3)	0.0496 (10)
C26	0.0791 (6)	0.1089 (5)	0.3964 (3)	0.0727 (15)
H26	0.0884	0.0430	0.3596	0.087*
C25	0.2571 (7)	−0.0412 (4)	0.4727 (4)	0.0771 (16)
H25	0.2196	−0.0629	0.4126	0.092*
C32	0.2323 (5)	0.0582 (4)	0.5224 (3)	0.0512 (10)
N41	0.4715 (4)	0.3495 (3)	0.6612 (2)	0.0459 (8)
C42	0.5095 (5)	0.3697 (4)	0.5786 (3)	0.0547 (11)
H42	0.4367	0.3481	0.5306	0.066*
C43	0.6514 (6)	0.4210 (4)	0.5607 (4)	0.0664 (13)
H43	0.6740	0.4356	0.5025	0.080*
C44	0.7574 (6)	0.4497 (5)	0.6315 (4)	0.0779 (16)
H44	0.8550	0.4831	0.6219	0.094*
C47	0.5660 (7)	0.3693 (5)	0.9829 (4)	0.0762 (16)
H47	0.6298	0.3856	1.0353	0.091*
C48	0.4174 (7)	0.3288 (5)	0.9872 (3)	0.0740 (16)
H48	0.3772	0.3186	1.0427	0.089*
C49	0.3281 (7)	0.3034 (5)	0.9085 (3)	0.0741 (16)
H49	0.2265	0.2752	0.9118	0.089*
N50	0.3790 (4)	0.3170 (3)	0.8270 (2)	0.0545 (9)
C51	0.5237 (5)	0.3598 (4)	0.8221 (3)	0.0482 (10)
C46	0.6214 (6)	0.3861 (5)	0.8992 (3)	0.0665 (13)
H46	0.7227	0.4146	0.8949	0.080*
C45	0.7201 (5)	0.4292 (5)	0.7171 (4)	0.0704 (14)
H45	0.7922	0.4481	0.7655	0.084*
C52	0.5742 (4)	0.3801 (3)	0.7306 (3)	0.0447 (9)
O61	0.5469 (6)	0.7016 (4)	0.6474 (3)	0.1025 (14)
H61	0.4652	0.6606	0.6503	0.123*
C62	0.6266 (9)	0.7191 (6)	0.7309 (5)	0.110 (2)
H62A	0.6469	0.7982	0.7543	0.165*
H62B	0.7195	0.6937	0.7239	0.165*
H62C	0.5689	0.6777	0.7724	0.165*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.04206 (16)	0.04538 (17)	0.03578 (14)	0.00416 (11)	−0.00069 (11)	0.00118 (11)
O1	0.169 (5)	0.061 (2)	0.080 (3)	−0.021 (3)	0.061 (3)	0.007 (2)
O2	0.071 (3)	0.145 (5)	0.090 (3)	−0.034 (3)	0.022 (3)	−0.014 (3)
O3	0.140 (4)	0.085 (3)	0.078 (3)	0.044 (3)	0.019 (3)	0.031 (2)
C1	0.095 (5)	0.069 (4)	0.054 (3)	−0.033 (3)	0.029 (3)	−0.022 (3)
C2	0.061 (3)	0.045 (2)	0.039 (2)	−0.011 (2)	0.014 (2)	−0.0069 (18)
C3	0.081 (3)	0.044 (2)	0.044 (2)	0.011 (2)	0.006 (2)	−0.0001 (19)
C4	0.055 (3)	0.085 (4)	0.065 (3)	0.013 (3)	0.010 (2)	0.006 (3)
C5	0.064 (3)	0.081 (4)	0.062 (3)	−0.003 (3)	0.021 (3)	0.015 (3)
C6	0.082 (4)	0.068 (3)	0.064 (3)	0.008 (3)	0.004 (3)	0.019 (3)
C7	0.058 (3)	0.067 (3)	0.056 (3)	0.007 (2)	0.000 (2)	0.002 (2)
O11	0.0567 (19)	0.0455 (17)	0.0627 (19)	0.0080 (14)	0.0092 (15)	−0.0037 (14)
O12	0.111 (3)	0.062 (2)	0.052 (2)	0.015 (2)	0.034 (2)	0.0050 (16)
O13	0.061 (2)	0.069 (2)	0.061 (2)	0.0034 (17)	0.0169 (16)	0.0076 (17)
C11	0.052 (2)	0.043 (2)	0.037 (2)	0.0111 (18)	−0.0021 (18)	0.0018 (17)
C12	0.044 (2)	0.042 (2)	0.0356 (19)	0.0112 (17)	−0.0067 (16)	0.0019 (16)
C13	0.040 (2)	0.058 (3)	0.042 (2)	0.0124 (19)	−0.0037 (17)	0.0044 (19)
C14	0.068 (3)	0.086 (4)	0.042 (2)	0.028 (3)	0.009 (2)	−0.001 (2)
C15	0.096 (4)	0.080 (4)	0.048 (3)	0.041 (3)	−0.003 (3)	−0.016 (3)
C16	0.076 (4)	0.050 (3)	0.076 (3)	0.012 (2)	−0.006 (3)	−0.012 (2)
C17	0.066 (3)	0.048 (3)	0.053 (3)	0.013 (2)	0.004 (2)	0.004 (2)
N21	0.052 (2)	0.048 (2)	0.059 (2)	0.0140 (17)	0.0044 (18)	0.0080 (17)
C22	0.067 (3)	0.071 (4)	0.094 (4)	0.019 (3)	0.012 (3)	0.027 (3)
C23	0.073 (4)	0.065 (4)	0.148 (7)	0.029 (3)	0.028 (4)	0.041 (4)
C24	0.090 (5)	0.055 (3)	0.154 (7)	0.026 (3)	0.048 (5)	0.001 (4)
C27	0.080 (4)	0.109 (5)	0.047 (3)	0.007 (4)	−0.018 (3)	0.001 (3)
C28	0.067 (3)	0.087 (4)	0.059 (3)	0.007 (3)	−0.012 (3)	0.024 (3)
C29	0.065 (3)	0.064 (3)	0.052 (3)	0.016 (2)	−0.009 (2)	0.006 (2)
N30	0.048 (2)	0.049 (2)	0.0397 (18)	0.0045 (16)	−0.0023 (15)	−0.0026 (15)
C31	0.047 (2)	0.051 (2)	0.042 (2)	−0.0027 (19)	0.0040 (18)	−0.0054 (18)
C26	0.080 (4)	0.079 (4)	0.044 (3)	0.000 (3)	−0.008 (2)	−0.017 (2)
C25	0.083 (4)	0.055 (3)	0.086 (4)	0.011 (3)	0.022 (3)	−0.015 (3)
C32	0.045 (2)	0.045 (2)	0.059 (3)	0.0016 (18)	0.009 (2)	−0.003 (2)
N41	0.0443 (19)	0.048 (2)	0.0446 (19)	0.0089 (15)	0.0057 (15)	0.0040 (15)
C42	0.057 (3)	0.061 (3)	0.047 (2)	0.010 (2)	0.008 (2)	0.008 (2)
C43	0.070 (3)	0.065 (3)	0.068 (3)	0.015 (3)	0.021 (3)	0.018 (3)
C44	0.053 (3)	0.092 (4)	0.091 (4)	0.006 (3)	0.021 (3)	0.027 (3)
C47	0.081 (4)	0.089 (4)	0.052 (3)	0.011 (3)	−0.028 (3)	0.003 (3)
C48	0.100 (4)	0.075 (4)	0.041 (3)	0.000 (3)	−0.007 (3)	0.015 (2)
C49	0.078 (4)	0.086 (4)	0.044 (3)	−0.022 (3)	−0.001 (2)	0.013 (3)
N50	0.057 (2)	0.060 (2)	0.0382 (18)	−0.0092 (18)	−0.0053 (16)	0.0098 (17)
C51	0.046 (2)	0.045 (2)	0.051 (2)	0.0090 (18)	−0.0109 (19)	0.0029 (19)
C46	0.056 (3)	0.084 (4)	0.054 (3)	0.012 (3)	−0.013 (2)	−0.001 (3)
C45	0.041 (3)	0.086 (4)	0.079 (4)	−0.005 (2)	−0.005 (2)	0.021 (3)
C52	0.037 (2)	0.044 (2)	0.053 (2)	0.0092 (17)	0.0001 (18)	0.0048 (18)
O61	0.115 (4)	0.105 (4)	0.080 (3)	−0.002 (3)	0.014 (3)	0.020 (3)
C62	0.102 (5)	0.113 (6)	0.110 (6)	0.021 (5)	0.004 (5)	0.001 (5)

Geometric parameters (Å, º) top

Cd1—O11	2.305 (3)	C23—H23	0.9300
Cd1—N30	2.352 (3)	C24—C25	1.365 (9)
Cd1—N50	2.368 (4)	C24—H24	0.9300
Cd1—N41	2.369 (4)	C27—C26	1.365 (8)
Cd1—N21	2.377 (4)	C27—C28	1.375 (8)
Cd1—O1	2.391 (5)	C27—H27	0.9300
Cd1—O2	2.685 (5)	C28—C29	1.368 (7)
O1—C1	1.253 (8)	C28—H28	0.9300
O2—C1	1.242 (8)	C29—N30	1.340 (6)
O3—C3	1.348 (6)	C29—H29	0.9300
O3—H3	0.8200	N30—C31	1.336 (5)
C1—C2	1.507 (7)	C31—C26	1.378 (6)
C2—C3	1.377 (7)	C31—C32	1.476 (6)
C2—C7	1.380 (7)	C26—H26	0.9300
C3—C4	1.389 (7)	C25—C32	1.394 (6)
C4—C5	1.369 (7)	C25—H25	0.9300
C4—H4	0.9300	N41—C52	1.330 (5)
C5—C6	1.364 (8)	N41—C42	1.333 (5)
C5—H5	0.9300	C42—C43	1.378 (7)
C6—C7	1.360 (7)	C42—H42	0.9300
C6—H6	0.9300	C43—C44	1.363 (8)
C7—H7	0.9300	C43—H43	0.9300
O11—C11	1.283 (5)	C44—C45	1.374 (8)
O12—C11	1.217 (5)	C44—H44	0.9300
O13—C13	1.353 (5)	C47—C48	1.358 (8)
O13—H13	0.8200	C47—C46	1.388 (7)
C11—C12	1.497 (5)	C47—H47	0.9300
C12—C17	1.391 (6)	C48—C49	1.364 (7)
C12—C13	1.395 (6)	C48—H48	0.9300
C13—C14	1.387 (6)	C49—N50	1.335 (6)
C14—C15	1.371 (8)	C49—H49	0.9300
C14—H14	0.9300	N50—C51	1.332 (6)
C15—C16	1.379 (8)	C51—C46	1.387 (6)
C15—H15	0.9300	C51—C52	1.492 (6)
C16—C17	1.375 (6)	C46—H46	0.9300
C16—H16	0.9300	C45—C52	1.384 (6)
C17—H17	0.9300	C45—H45	0.9300
N21—C22	1.326 (6)	O61—C62	1.384 (8)
N21—C32	1.337 (6)	O61—H61	0.8200
C22—C23	1.374 (8)	C62—H62A	0.9600
C22—H22	0.9300	C62—H62B	0.9600
C23—C24	1.347 (10)	C62—H62C	0.9600

O11—Cd1—N30	90.83 (12)	C24—C23—C22	117.4 (6)
O11—Cd1—N50	87.64 (13)	C24—C23—H23	121.3
N30—Cd1—N50	164.41 (12)	C22—C23—H23	121.3
O11—Cd1—N41	95.01 (12)	C23—C24—C25	121.1 (6)
N30—Cd1—N41	95.40 (12)	C23—C24—H24	119.5
N50—Cd1—N41	69.31 (12)	C25—C24—H24	119.5
O11—Cd1—N21	159.80 (13)	C26—C27—C28	119.7 (5)
N30—Cd1—N21	68.98 (13)	C26—C27—H27	120.2
N50—Cd1—N21	111.80 (14)	C28—C27—H27	120.2
N41—Cd1—N21	87.26 (13)	C29—C28—C27	117.5 (5)
O11—Cd1—O1	76.61 (14)	C29—C28—H28	121.2
N30—Cd1—O1	89.34 (15)	C27—C28—H28	121.2
N50—Cd1—O1	105.36 (15)	N30—C29—C28	123.3 (5)
N41—Cd1—O1	170.46 (12)	N30—C29—H29	118.4
N21—Cd1—O1	102.18 (14)	C28—C29—H29	118.4
O11—Cd1—O2	116.15 (14)	C31—N30—C29	118.9 (4)
N30—Cd1—O2	117.82 (13)	C31—N30—Cd1	119.0 (3)
N50—Cd1—O2	76.51 (13)	C29—N30—Cd1	121.8 (3)
N41—Cd1—O2	132.29 (14)	N30—C31—C26	120.6 (5)
N21—Cd1—O2	75.45 (14)	N30—C31—C32	116.8 (4)
O1—Cd1—O2	50.73 (17)	C26—C31—C32	122.6 (4)
C1—O1—Cd1	100.0 (5)	C27—C26—C31	120.1 (5)
C1—O2—Cd1	86.3 (4)	C27—C26—H26	120.0
C3—O3—H3	109.5	C31—C26—H26	120.0
O2—C1—O1	122.8 (6)	C24—C25—C32	118.4 (6)
O2—C1—C2	120.3 (7)	C24—C25—H25	120.8
O1—C1—C2	116.9 (7)	C32—C25—H25	120.8
C3—C2—C7	119.3 (4)	N21—C32—C25	120.9 (5)
C3—C2—C1	121.9 (5)	N21—C32—C31	116.6 (4)
C7—C2—C1	118.7 (5)	C25—C32—C31	122.4 (5)
O3—C3—C2	122.0 (5)	C52—N41—C42	119.2 (4)
O3—C3—C4	118.2 (5)	C52—N41—Cd1	118.3 (3)
C2—C3—C4	119.8 (5)	C42—N41—Cd1	122.5 (3)
C5—C4—C3	119.3 (5)	N41—C42—C43	123.2 (5)
C5—C4—H4	120.3	N41—C42—H42	118.4
C3—C4—H4	120.3	C43—C42—H42	118.4
C6—C5—C4	121.0 (5)	C44—C43—C42	117.5 (5)
C6—C5—H5	119.5	C44—C43—H43	121.2
C4—C5—H5	119.5	C42—C43—H43	121.2
C7—C6—C5	119.6 (5)	C43—C44—C45	120.0 (5)
C7—C6—H6	120.2	C43—C44—H44	120.0
C5—C6—H6	120.2	C45—C44—H44	120.0
C6—C7—C2	120.9 (5)	C48—C47—C46	119.1 (5)
C6—C7—H7	119.5	C48—C47—H47	120.4
C2—C7—H7	119.5	C46—C47—H47	120.4
C11—O11—Cd1	130.0 (3)	C47—C48—C49	118.6 (5)
C13—O13—H13	109.5	C47—C48—H48	120.7
O12—C11—O11	123.5 (4)	C49—C48—H48	120.7
O12—C11—C12	121.3 (4)	N50—C49—C48	123.5 (5)
O11—C11—C12	115.2 (4)	N50—C49—H49	118.3
C17—C12—C13	118.5 (4)	C48—C49—H49	118.3
C17—C12—C11	119.7 (4)	C51—N50—C49	118.5 (4)
C13—C12—C11	121.9 (4)	C51—N50—Cd1	118.1 (3)
O13—C13—C14	118.1 (4)	C49—N50—Cd1	123.3 (3)
O13—C13—C12	121.7 (4)	N50—C51—C46	121.1 (4)
C14—C13—C12	120.1 (4)	N50—C51—C52	116.9 (4)
C15—C14—C13	120.0 (5)	C46—C51—C52	122.0 (4)
C15—C14—H14	120.0	C47—C46—C51	119.1 (5)
C13—C14—H14	120.0	C47—C46—H46	120.5
C14—C15—C16	120.7 (4)	C51—C46—H46	120.5
C14—C15—H15	119.7	C44—C45—C52	119.4 (5)
C16—C15—H15	119.7	C44—C45—H45	120.3
C17—C16—C15	119.5 (5)	C52—C45—H45	120.3
C17—C16—H16	120.3	N41—C52—C45	120.7 (4)
C15—C16—H16	120.3	N41—C52—C51	116.8 (4)
C16—C17—C12	121.2 (5)	C45—C52—C51	122.5 (4)
C16—C17—H17	119.4	C62—O61—H61	109.5
C12—C17—H17	119.4	O61—C62—H62A	109.5
C22—N21—C32	118.4 (4)	O61—C62—H62B	109.5
C22—N21—Cd1	123.3 (4)	H62A—C62—H62B	109.5
C32—N21—Cd1	118.3 (3)	O61—C62—H62C	109.5
N21—C22—C23	123.7 (6)	H62A—C62—H62C	109.5
N21—C22—H22	118.1	H62B—C62—H62C	109.5
C23—C22—H22	118.1

O2—C1—C2—C3	179.3 (5)	Cd1—O12—C11—C12	158.7 (5)
O1—C1—C2—C3	−1.5 (7)	Cd1—O11—C11—C12	−135.3 (3)
O2—C1—C2—C7	1.5 (7)	C11—C12—C13—O13	0.7 (6)
O1—C1—C2—C7	−179.4 (4)	Cd1—N30—C29—C28	−173.1 (4)
Cd1—O2—C1—C2	−177.0 (4)	Cd1—N30—C31—C32	−5.6 (5)
Cd1—O1—C1—C2	176.4 (3)	Cd1—N30—C31—C26	173.9 (4)
C1—C2—C3—O3	3.1 (7)	Cd1—N21—C22—C23	178.6 (4)
O12—C11—C12—C13	179.0 (4)	Cd1—N21—C32—C31	1.9 (5)
O11—C11—C12—C13	0.9 (6)	Cd1—N50—C51—C52	8.0 (5)
O12—C11—C12—C17	−1.0 (6)	Cd1—N21—C32—C25	−177.6 (4)
O11—C11—C12—C17	−179.1 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C12–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.82	1.82	2.545 (7)	147
O13—H13···O11	0.82	1.78	2.505 (4)	147
O61—H61···O12	0.82	1.98	2.802 (6)	177
C23—H23···O61ⁱ	0.93	2.57	3.429 (8)	154
C43—H43···O12ⁱⁱ	0.93	2.43	3.356 (6)	172
C45—H45···O13ⁱⁱⁱ	0.93	2.47	3.370 (6)	163
C15—H15···Cg1^iv	0.93	2.81	3.620 (6)	147
C47—H47···Cg2^v	0.93	2.79	3.589 (6)	145
C62—H62A···Cg1^vi	0.96	2.94	3.858 (8)	160

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x, −y+1, −z+2; (v) −x+1, −y+1, −z+2; (vi) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cd(C₇H₅O₃)₂(C₁₀H₈N₂)₂]·CH₄O
M_r	731.03
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.115 (4), 12.189 (2), 14.883 (2)
α, β, γ (°)	97.64 (1), 92.30 (3), 101.00 (3)
V (Å³)	1605.1 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.40 × 0.18 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9433, 9117, 4943
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.138, 0.97
No. of reflections	9117
No. of parameters	423
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.85

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), CAMERON (Watkin et al., 1996), WinGX (Version 1.63.02; Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C12–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.82	1.82	2.545 (7)	146.5
O13—H13···O11	0.82	1.78	2.505 (4)	147.0
O61—H61···O12	0.82	1.98	2.802 (6)	176.5
C23—H23···O61ⁱ	0.93	2.57	3.429 (8)	154.3
C43—H43···O12ⁱⁱ	0.93	2.43	3.356 (6)	172.3
C45—H45···O13ⁱⁱⁱ	0.93	2.47	3.370 (6)	163.3
C15—H15···Cg1^iv	0.93	2.81	3.620 (6)	147
C47—H47···Cg2^v	0.93	2.79	3.589 (6)	145
C62—H62A···Cg1^vi	0.96	2.94	3.858 (8)	160

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x, −y+1, −z+2; (v) −x+1, −y+1, −z+2; (vi) x+1, y+1, z.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lemoine, P., Viossat, B., Nguyen-Huy, D., Tomas, A., Morgant, G., Greenaway, F. T. & Sorenson, J. R. J. (2004). J. Inorg. Biochem. 98, 1734–1749. Web of Science CSD CrossRef PubMed CAS Google Scholar
Mazurier, A., Billy, I., Lemoine, P., Viossat, B. & Tomas, A. (2000). Z. Kristallogr. New Cryst. Struct. 215, 113–114. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sorenson, J. R. J. (2002). Curr. Med. Chem. pp. 1867–1890. Google Scholar
Tomas, A., Retailleau, P., Viossat, B., Prangé, T. & Lemoine, P. (2006). Z. Kristallogr. New Cryst. Struct. 221, 517–519. CAS Google Scholar
Turner, R. W., Rodesiler, P. F. & Amma, P. E. L. (1982). Inorg. Chim. Acta, 66, L13–L15 CSD CrossRef CAS Web of Science Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m156-m157

https://doi.org/10.1107/S1600536809054610

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)