trans-Bis(diethanolamine-N,O)bis(saccharinato-N)cadmium(II)

The structure of the title complex consists of isolated [Cd(C₇H₄NO₃S)₂(C₄H₁₁NO₂)₂] units. The Cd²⁺ cation lies on an inversion centre and is octahedrally coordinated by two N,O-bidentate diethanol­amine (dea) and two N-bonded saccharinate (sac) ligands [saccharin is 1,2-benziso­thia­zol-3(2H)-one 1,1-dioxide]. The dea ligands constitute the equatorial plane of the octahedron, forming two five-membered chelate rings around the Cd^II ion, while the sac ligands are localized at the axial positions. The Cd-N_sac, Cd-N_dea and Cd-O_dea bond distances are 2.3879 (12), 2.3544 (14) and 2.3702 (13) Å, respectively. The H atoms of the free and coordinated hydroxyl groups of the dea ligands are involved in hydrogen bonding with the carbonyl and sulfonyl O atoms of the neighbouring sac ions, while the amine H atom forms a hydrogen bond with the free hydroxyl O atom. The individual mol­ecules are held together by strong hydrogen bonds, forming an infinite three-dimensional network.

S1. Comment

This work is part of our extensive research into the synthesis and spectral, thermal and structural characterization of mixed ligand complexes of the saccharinate ion (sac), chemically known as o-sulphobenzimide, with other bidentate N– and O-donor ligands such as ethanolamine (Yilmaz, Andac et al., 2001; Andac et al., 2001), monoethanolethylenediamine (Yilmaz, Karadag & Thoene, 2001) and diethanolamine (Yilmaz, Topcu et al., 2001). In order to extend this investigation to the IIB metal complexes, we report here the structural characterization of the title complex, [Cd(dea)₂(sac)₂], (I), of cadmium(II) saccharinate with diethanolamine (dea). \sch

A molecular view of (I) is shown in Fig. 1. The structure is built up of individual molecules, each containing a Cd²⁺ cation, two sac anions and two neutral dea molecules. The Cd^II ion sits on the centre of symmetry and the coordination around the Cd^II ion is a distorted CdN₄O₂ octahedron, with two N-bonded sac and two bidentate dea ligands. Both dea and sac ligands occupy the trans positions of the octahedron.

The dea ligands are chelated to the Cd^II ion symmetrically through one hydroxyl O atom and the amine N atoms, forming two five-membered rings, and one ethanol group of the dea ligand remains uncomplexed. The two dea ligands constitute the equatorial plane of the octahedron, while the sac ligands are localized at the axial positions. The Cd—N_dea and Cd—O_dea bond distances are 2.3544 (14) and 2.3702 (13) Å, respectively. The Cd—N_sac bond distance of 2.3879 (12) Å is noticeably longer than those found in [Cd(sac)₂(H₂O)₄]·2H₂O (2.323 Å; Haider et al., 1984), [Cd₂(sac)₂(im)₄] [im is?; 2.323 (5) and 2.367 (5) Å; Jianmin et al., 1997] and [Cd(sac)₂(bipy)₂] [bipy is 2,2'-bipyridine?; 2.320 (4) Å; Johns et al., 2001], and also somewhat shorter than the values reported for [Cd(sac)₂(NH₃)₄] [2.423 (8) Å; Pascual, 1995] and [Cd(sac)₂(HydEt-en)₂] [HydEt-en is?; 2.412 (4) and 2.525 (5) Å; Yilmaz, Karadag & Thoene, 2001]. The large differences in the reported Cd—N_sac bond distances seem to be a consequence of the presence of sterically hindered groups in the coligands, although NH₃ does not obey the rule. The interatomic distances within both sac and dea ligands are similar to the corresponding values found in the free Hsac molecule (Okaya, 1969) and [Cu(SCN)₂(dea)₂] (Yilmaz et al., 2000), respectively.

A packing diagram with the hydrogen-bonding scheme is shown in Fig. 2. Both sac ions are essentially planar, with an r.m.s. deviation of 0.02 Å. The sac ions of adjacent molecules are almost perpendicular to each other and the dihedral angles between the corresponding planes with symmetry code 1 - x, y - 1/2, 3/2 - z are 86.44 (3)°. The individual molecules are linked by intermolecular hydrogen bonds, forming infinite three-dimensional zigzag chains.

The H atom of the free hydroxyl group (O2) of the dea ligand forms a relatively strong intramolecular hydrogen bond with the sulfonyl O atom (O5) of the sac ligand [O2···O5 2.785 (2) Å; symmetry code: -x, 1 - y, 1 - z], while the H atoms of the coordinated hydroxyl (O1) and amine (N1) groups of the dea ligand are involved in intermolecular hydrogen bonding with the carbonyl O atom [O1···O3 2.818 (2) Å; symmetry code: x - 1, y, z] and the free hydroxyl O atom [N1···O2 3.205 (2) Å; symmetry code: -x, -y, 1 - z] of the neighbouring molecules, respectively. Furthermore, some weak interactions between the phenyl H atoms on C7 and C10 and the hydroxyl and sulfonyl O atoms (O1, O4 and O5) also occur (Table 2).

The sum of the van der Waals radii of H and O (1.20 + 1.52 = 2.72 Å; ref?) is comperatively longer than the distances found for the C7—H7···O5 (2.53 Å) and C10—H10···O4 (2.58 Å) interactions, with C—H···O angles of 133 and 169°, respectively, and somewhat shorther than the distance found for C7—H7···O1 (2.84 Å), with a C—H···O angle of 144°. Therefore, the C10—H10···O4 interaction, with a nearly linear angle, may be considered as a weak hydrogen bond, while the C7—H7···O5 and C7—H7···O1 interactions, with highly deviated angles, are classical van der Waals contacts (Steiner, 1997; Steiner & Desiraju, 1998). Additionally, the phenyl H atom on C9 interacts with the ring centroid, Cg, of the phenyl ring of the sac anion, forming an non-conventional hydrogen bond of the C—H···π type (Madhavi et al., 1997). The hydrogen bonds maintain the crystal structure by forming an infinite three-dimensional lattice.

S2. Experimental

To synthesize (I), previously prepared [Cd(sac)₂(H₂O)₄]·2H₂O (1.17 g, 2.0 mmol) was dissolved in 40 ml of a methanol-2-propanol mixture (1:1) at 333 K with stirring. Next, dea (0.21 g, 4.0 mmol) was added dropwise at 333 K and the solution was cooled to room temperature. The resulting solution was left at room temperature until evaporation resulted in the formation of colourless crystals of (I) suitable for X-ray diffraction analysis.

S3. Refinement

H atoms on O and N atoms were found in difference maps and were positionally refined with geometric restraints (O—H = 0.82 and N—H = 0.89 Å) and with U_iso(H) = 1.2U_eq(N,O). The remaining H atoms were placed in calculated positions and refined with a riding model with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I) with 50% displacement ellipsoids and the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii [symmetry code: (i) -x, 1 - y, 1 - z].
	Fig. 2. A packing diagram for (I) showing the hydrogen-bonding scheme.

trans-Bis(diethanolamine-N,O)bis(saccharinato-N)cadmium(II)

Crystal data

[Cd(C7H4NO3S)2(C4H11NO2)2]	F(000) = 700
Mr = 687.02	Dx = 1.686 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8444 (3) Å	Cell parameters from 6160 reflections
b = 8.4654 (3) Å	θ = 2.6–30.0°
c = 20.4378 (8) Å	µ = 1.02 mm^−1
β = 94.188 (1)°	T = 298 K
V = 1353.57 (9) Å^3	Chunk, colourless
Z = 2	0.36 × 0.25 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	3933 independent reflections
Radiation source: fine-focus sealed tube	3314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→11
Tmin = 0.687, Tmax = 0.832	k = −9→11
11324 measured reflections	l = −28→28

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)] = 0.025	Hydrogen site location: mixed
wR(F^2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 0.0284P] where P = (Fo^2 + 2Fc^2)/3
3933 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 0.30 e Å^−3
3 restraints	Δρmin = −0.30 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
Cd1	0.0000	0.5000	0.5000	0.03099 (6)
S1	0.07767 (5)	0.73297 (5)	0.646860 (18)	0.03080 (9)
N1	0.03475 (18)	0.26011 (17)	0.55773 (7)	0.0342 (3)
H1N	−0.013 (2)	0.1861 (19)	0.5324 (8)	0.041*
N2	0.15601 (16)	0.62705 (17)	0.58990 (6)	0.0321 (3)
O1	−0.23214 (16)	0.49010 (15)	0.56790 (7)	0.0406 (3)
H1O	−0.3284 (16)	0.509 (3)	0.5541 (12)	0.049*
O2	0.2219 (2)	0.01848 (17)	0.48977 (9)	0.0549 (4)
H2O	0.170 (3)	0.054 (3)	0.4574 (9)	0.066*
O3	0.41817 (16)	0.56976 (19)	0.55431 (7)	0.0477 (3)
O4	0.01425 (18)	0.63702 (18)	0.69724 (7)	0.0532 (4)
O5	−0.04006 (15)	0.84862 (17)	0.61873 (7)	0.0480 (3)
C1	−0.0693 (2)	0.2762 (2)	0.61508 (9)	0.0435 (4)
H1A	−0.0136	0.3493	0.6463	0.052*
H1B	−0.0772	0.1745	0.6365	0.052*
C2	−0.2457 (2)	0.3351 (2)	0.59482 (10)	0.0462 (4)
H2A	−0.3009	0.2648	0.5623	0.055*
H2B	−0.3140	0.3382	0.6325	0.055*
C3	0.2080 (2)	0.2039 (2)	0.57927 (10)	0.0443 (4)
H3A	0.1989	0.1189	0.6107	0.053*
H3B	0.2711	0.2895	0.6014	0.053*
C4	0.3059 (2)	0.1460 (2)	0.52353 (11)	0.0486 (5)
H4A	0.3198	0.2320	0.4931	0.058*
H4B	0.4188	0.1122	0.5405	0.058*
C5	0.32855 (19)	0.6444 (2)	0.59042 (7)	0.0304 (3)
C6	0.39780 (18)	0.76307 (19)	0.63938 (7)	0.0282 (3)
C7	0.5659 (2)	0.8104 (2)	0.65214 (9)	0.0407 (4)
H7	0.6528	0.7686	0.6288	0.049*
C8	0.5999 (3)	0.9215 (3)	0.70064 (11)	0.0574 (6)
H8	0.7117	0.9558	0.7100	0.069*
C9	0.4720 (3)	0.9826 (3)	0.73540 (12)	0.0624 (6)
H9	0.4993	1.0579	0.7676	0.075*
C10	0.3020 (2)	0.9350 (3)	0.72385 (9)	0.0457 (4)
H10	0.2153	0.9757	0.7476	0.055*
C11	0.27071 (19)	0.82439 (19)	0.67529 (7)	0.0285 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03396 (9)	0.02423 (9)	0.03435 (8)	−0.00209 (6)	−0.00034 (6)	−0.00108 (6)
S1	0.02309 (16)	0.0330 (2)	0.03682 (18)	−0.00274 (14)	0.00598 (13)	−0.00514 (16)
N1	0.0381 (7)	0.0239 (7)	0.0401 (7)	−0.0014 (6)	−0.0005 (6)	−0.0010 (5)
N2	0.0257 (6)	0.0343 (7)	0.0362 (6)	−0.0032 (5)	0.0028 (5)	−0.0101 (5)
O1	0.0290 (6)	0.0366 (7)	0.0561 (7)	−0.0012 (5)	0.0014 (5)	−0.0036 (6)
O2	0.0619 (10)	0.0340 (8)	0.0680 (10)	−0.0001 (6)	−0.0007 (8)	−0.0052 (7)
O3	0.0316 (6)	0.0602 (9)	0.0519 (7)	0.0018 (6)	0.0077 (5)	−0.0243 (7)
O4	0.0550 (8)	0.0554 (9)	0.0520 (7)	−0.0175 (7)	0.0227 (6)	−0.0005 (7)
O5	0.0285 (6)	0.0489 (8)	0.0655 (8)	0.0089 (5)	−0.0033 (6)	−0.0083 (7)
C1	0.0554 (11)	0.0349 (10)	0.0408 (8)	−0.0016 (8)	0.0085 (8)	0.0051 (7)
C2	0.0436 (10)	0.0435 (11)	0.0533 (10)	−0.0080 (8)	0.0151 (8)	−0.0012 (8)
C3	0.0467 (10)	0.0311 (9)	0.0533 (10)	0.0044 (8)	−0.0084 (8)	0.0016 (8)
C4	0.0373 (9)	0.0343 (10)	0.0737 (13)	0.0007 (8)	0.0005 (9)	−0.0007 (9)
C5	0.0258 (7)	0.0336 (8)	0.0316 (7)	−0.0006 (6)	0.0016 (5)	−0.0031 (6)
C6	0.0255 (7)	0.0305 (8)	0.0285 (6)	−0.0024 (6)	0.0006 (5)	0.0000 (6)
C7	0.0261 (8)	0.0524 (11)	0.0433 (8)	−0.0078 (7)	0.0015 (6)	−0.0046 (8)
C8	0.0383 (10)	0.0709 (16)	0.0617 (12)	−0.0199 (10)	−0.0059 (9)	−0.0163 (11)
C9	0.0591 (13)	0.0635 (16)	0.0629 (13)	−0.0157 (11)	−0.0065 (11)	−0.0317 (11)
C10	0.0450 (10)	0.0480 (11)	0.0438 (9)	0.0015 (9)	0.0013 (7)	−0.0183 (9)
C11	0.0274 (7)	0.0280 (8)	0.0301 (6)	−0.0013 (6)	0.0010 (5)	−0.0018 (6)

Geometric parameters (Å, º)

Cd1—N1	2.3544 (14)	C1—H1A	0.9700
Cd1—N1^i	2.3544 (14)	C1—H1B	0.9700
Cd1—N2^i	2.3879 (12)	C2—H2A	0.9700
Cd1—N2	2.3879 (12)	C2—H2B	0.9700
Cd1—O1^i	2.3702 (13)	C3—C4	1.502 (3)
Cd1—O1	2.3702 (13)	C3—H3A	0.9700
S1—O4	1.4291 (13)	C3—H3B	0.9700
S1—O5	1.4368 (13)	C4—H4A	0.9700
S1—N2	1.6252 (13)	C4—H4B	0.9700
S1—C11	1.7610 (16)	C5—C6	1.492 (2)
N1—C3	1.477 (2)	C6—C11	1.382 (2)
N1—C1	1.483 (2)	C6—C7	1.384 (2)
N1—H1N	0.879 (9)	C7—C8	1.379 (3)
N2—C5	1.3606 (19)	C7—H7	0.9300
O1—C2	1.430 (2)	C8—C9	1.372 (3)
O1—H1O	0.803 (9)	C8—H8	0.9300
O2—C4	1.417 (2)	C9—C10	1.397 (3)
O2—H2O	0.808 (10)	C9—H9	0.9300
O3—C5	1.2303 (19)	C10—C11	1.374 (2)
C1—C2	1.500 (3)	C10—H10	0.9300
N1—Cd1—N1^i	180.00 (6)	O1—C2—C1	108.54 (15)
N1—Cd1—O1^i	104.96 (5)	O1—C2—H2A	110.0
N1^i—Cd1—O1^i	75.04 (5)	C1—C2—H2A	110.0
N1—Cd1—O1	75.04 (5)	O1—C2—H2B	110.0
N1^i—Cd1—O1	104.96 (5)	C1—C2—H2B	110.0
O1^i—Cd1—O1	180.0	H2A—C2—H2B	108.4
N1—Cd1—N2^i	91.78 (5)	N1—C3—C4	112.92 (15)
N1^i—Cd1—N2^i	88.22 (5)	N1—C3—H3A	109.0
O1^i—Cd1—N2^i	86.44 (4)	C4—C3—H3A	109.0
O1—Cd1—N2^i	93.56 (4)	N1—C3—H3B	109.0
N1—Cd1—N2	88.22 (5)	C4—C3—H3B	109.0
N1^i—Cd1—N2	91.78 (5)	H3A—C3—H3B	107.8
O1^i—Cd1—N2	93.56 (4)	O2—C4—C3	111.90 (17)
O1—Cd1—N2	86.44 (4)	O2—C4—H4A	109.2
N2^i—Cd1—N2	180.0	C3—C4—H4A	109.2
O4—S1—O5	115.35 (9)	O2—C4—H4B	109.2
O4—S1—N2	111.86 (8)	C3—C4—H4B	109.2
O5—S1—N2	110.79 (8)	H4A—C4—H4B	107.9
O4—S1—C11	110.38 (8)	O3—C5—N2	123.48 (15)
O5—S1—C11	110.16 (8)	O3—C5—C6	123.50 (14)
N2—S1—C11	96.76 (7)	N2—C5—C6	113.02 (13)
C3—N1—C1	109.99 (14)	C11—C6—C7	120.37 (15)
C3—N1—Cd1	119.84 (11)	C11—C6—C5	111.57 (13)
C1—N1—Cd1	105.45 (11)	C7—C6—C5	128.03 (14)
C3—N1—H1N	106.9 (13)	C8—C7—C6	117.68 (17)
C1—N1—H1N	107.2 (13)	C8—C7—H7	121.2
Cd1—N1—H1N	106.9 (14)	C6—C7—H7	121.2
C5—N2—S1	111.28 (10)	C9—C8—C7	121.26 (17)
C5—N2—Cd1	120.54 (9)	C9—C8—H8	119.4
S1—N2—Cd1	126.89 (7)	C7—C8—H8	119.4
C2—O1—Cd1	109.86 (10)	C8—C9—C10	121.94 (18)
C2—O1—H1O	102.9 (16)	C8—C9—H9	119.0
Cd1—O1—H1O	122.1 (18)	C10—C9—H9	119.0
C4—O2—H2O	108 (2)	C11—C10—C9	115.90 (18)
N1—C1—C2	111.25 (15)	C11—C10—H10	122.1
N1—C1—H1A	109.4	C9—C10—H10	122.1
C2—C1—H1A	109.4	C10—C11—C6	122.84 (15)
N1—C1—H1B	109.4	C10—C11—S1	129.93 (13)
C2—C1—H1B	109.4	C6—C11—S1	107.23 (11)
H1A—C1—H1B	108.0
O1^i—Cd1—N1—C3	36.65 (13)	N1—C1—C2—O1	−63.4 (2)
O1—Cd1—N1—C3	−143.35 (13)	C1—N1—C3—C4	165.49 (16)
N2^i—Cd1—N1—C3	123.44 (12)	Cd1—N1—C3—C4	−72.13 (18)
N2—Cd1—N1—C3	−56.56 (12)	N1—C3—C4—O2	−59.8 (2)
O1^i—Cd1—N1—C1	161.22 (11)	S1—N2—C5—O3	175.93 (15)
O1—Cd1—N1—C1	−18.78 (11)	Cd1—N2—C5—O3	−16.2 (2)
N2^i—Cd1—N1—C1	−111.98 (11)	S1—N2—C5—C6	−4.00 (17)
N2—Cd1—N1—C1	68.02 (11)	Cd1—N2—C5—C6	163.90 (10)
O4—S1—N2—C5	−111.64 (13)	O3—C5—C6—C11	−177.45 (16)
O5—S1—N2—C5	118.14 (12)	N2—C5—C6—C11	2.47 (19)
C11—S1—N2—C5	3.54 (13)	O3—C5—C6—C7	0.8 (3)
O4—S1—N2—Cd1	81.41 (11)	N2—C5—C6—C7	−179.24 (16)
O5—S1—N2—Cd1	−48.82 (12)	C11—C6—C7—C8	−1.1 (3)
C11—S1—N2—Cd1	−163.41 (9)	C5—C6—C7—C8	−179.24 (19)
N1—Cd1—N2—C5	91.74 (13)	C6—C7—C8—C9	0.4 (3)
N1^i—Cd1—N2—C5	−88.26 (13)	C7—C8—C9—C10	0.4 (4)
O1^i—Cd1—N2—C5	−13.14 (13)	C8—C9—C10—C11	−0.5 (4)
O1—Cd1—N2—C5	166.86 (13)	C9—C10—C11—C6	−0.2 (3)
N1—Cd1—N2—S1	−102.39 (10)	C9—C10—C11—S1	179.01 (17)
N1^i—Cd1—N2—S1	77.61 (10)	C7—C6—C11—C10	1.0 (3)
O1^i—Cd1—N2—S1	152.73 (10)	C5—C6—C11—C10	179.48 (17)
O1—Cd1—N2—S1	−27.27 (10)	C7—C6—C11—S1	−178.35 (13)
N1—Cd1—O1—C2	−12.37 (11)	C5—C6—C11—S1	0.09 (16)
N1^i—Cd1—O1—C2	167.63 (11)	O4—S1—C11—C10	−65.0 (2)
N2^i—Cd1—O1—C2	78.53 (12)	O5—S1—C11—C10	63.51 (19)
N2—Cd1—O1—C2	−101.47 (12)	N2—S1—C11—C10	178.62 (18)
C3—N1—C1—C2	179.31 (16)	O4—S1—C11—C6	114.32 (12)
Cd1—N1—C1—C2	48.77 (17)	O5—S1—C11—C6	−117.15 (12)
Cd1—O1—C2—C1	41.56 (17)	N2—S1—C11—C6	−2.04 (12)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^ii	0.88 (1)	2.40 (1)	3.205 (2)	152 (17)
O1—H1O···O3^iii	0.80 (1)	2.05 (1)	2.819 (2)	159 (2)
O2—H2O···O5^i	0.81 (1)	1.98 (1)	2.785 (2)	177 (3)
C7—H7···O5^iv	0.93	2.53	3.231 (2)	133
C7—H7···O1^iv	0.93	2.84	3.637 (2)	144
C10—H10···O4^v	0.93	2.58	3.502 (2)	169
C9—H9···Cg1^vi	0.93	2.85	3.707 (2)	153

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