Bis[4-hydr­oxy-N′-(4-meth­oxy-2-oxido­benzyl­idene-κO ²)benzohydrazidato-κ² O,N′]cadmium(II) dimethyl sulfoxide disolvate

Abstract

The metal atom in the title compound, [Cd(C₁₅H₁₃N₂O₄)₂]·2C₂H₆OS, is twice O,N,O′-chelated by two symmetry-related Schiff base ligands to define a trans-N₂O₄ octa­hedral geometry. Each anion occupies meridional sites of the octa­hedron; the metal atom lies on a special position of site symmetry 2. The dimethyl sulfoxide mol­ecule is a hydrogen-bond acceptor to the –NH– unit, and O—H⋯O hydrogen bonds link mol­ecules into a supra­molecular chain.

Related literature

For the monohydrated Schiff base ligand, see: Mohd Lair et al. (2009 ▶).

Experimental

Crystal data

• [Cd(C₁₅H₁₃N₂O₄)₂]·2C₂H₆OS

• M _r = 839.20

• Monoclinic,

• a = 23.891 (2) Å

• b = 10.439 (1) Å

• c = 19.874 (1) Å

• β = 132.137 (4)°

• V = 3675.3 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.77 mm⁻¹

• T = 118 K

• 0.12 × 0.06 × 0.03 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.507, T _max = 0.745 (expected range = 0.665–0.977)

• 10208 measured reflections

• 3243 independent reflections

• 2147 reflections with I > 2σ(I)

• R _int = 0.103

Refinement

• R[F ² > 2σ(F ²)] = 0.059

• wR(F ²) = 0.153

• S = 1.02

• 3243 reflections

• 211 parameters

• H-atom parameters constrained

• Δρ_max = 1.31 e Å⁻³

• Δρ_min = −0.90 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1i	0.84	1.79	2.603 (6)	163
N2—H2⋯O5	0.88	1.93	2.766 (6)	159

Symmetry code: (i) .

supplementary crystallographic information

Experimental

4-Hydroxy-N'-(2-hydroxy-4-methoxybenzylidene)benzohydrazide monohydrate (0.30 g, 1 mmol) and cadmium diacetate (0.14 g, 0.5 mmol) were heated in ethanol (50 ml) for 4 h. The solvent was removed and the product was recrystallized from DMSO to give prismatic crystals.

Refinement

Owing to the small number of observed reflections, the aromatic rings were refined as rigid hexagons with sides of 1.39 Å in order to reduce the number of refined parameters. Hydrogen atoms were placed at calculated positions (C–H 0.95–0.98, N–H 0.88, O–H 0.84 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times U_eq(C,N,O). The final difference Fourier map had a large peak/deep hole in the vicinity of the Cd atom.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of Cd(C15H13N2O4)2.2DMSO at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

[Cd(C15H13N2O4)2]·2C2H6OS	F(000) = 1720
Mr = 839.20	Dx = 1.517 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 638 reflections
a = 23.891 (2) Å	θ = 2.2–18.8°
b = 10.439 (1) Å	µ = 0.77 mm−1
c = 19.874 (1) Å	T = 118 K
β = 132.137 (4)°	Prism, yellow
V = 3675.3 (4) Å3	0.12 × 0.06 × 0.03 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	3243 independent reflections
Radiation source: fine-focus sealed tube	2147 reflections with I > 2σ(I)
graphite	Rint = 0.103
ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −28→28
Tmin = 0.507, Tmax = 0.745	k = −12→12
10208 measured reflections	l = −23→23

Refinement

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0692P)2 + 0.0136P] where P = (Fo2 + 2Fc2)/3
3243 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 1.31 e Å−3
0 restraints	Δρmin = −0.90 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.32500 (7)	0.7500	0.0253 (2)
S1	0.18289 (10)	0.48574 (18)	0.67220 (12)	0.0335 (5)
O1	0.4272 (2)	0.1893 (4)	0.6323 (3)	0.0276 (10)
O2	0.2426 (3)	−0.1133 (5)	0.4273 (3)	0.0373 (12)
O3	0.5137 (2)	0.4972 (4)	0.8391 (3)	0.0264 (10)
O4	0.4911 (2)	0.8669 (4)	1.0697 (3)	0.0304 (11)
H4	0.4624	0.8507	1.0791	0.046*
N1	0.3944 (3)	0.3437 (5)	0.7273 (3)	0.0227 (12)
N2	0.3971 (3)	0.4373 (5)	0.7788 (4)	0.0262 (13)
H2	0.3589	0.4493	0.7755	0.031*
O5	0.2603 (2)	0.4283 (5)	0.7353 (4)	0.0432 (13)
C1	0.35890 (17)	0.1366 (4)	0.5922 (3)	0.0261 (16)
C2	0.3336 (2)	0.0367 (4)	0.5313 (3)	0.0291 (16)
H2A	0.3643	0.0060	0.5204	0.035*
C3	0.2633 (2)	−0.0181 (4)	0.4865 (3)	0.0295 (16)
C4	0.21840 (18)	0.0268 (4)	0.5025 (3)	0.0339 (17)
H4A	0.1704	−0.0107	0.4719	0.041*
C5	0.2437 (2)	0.1267 (4)	0.5634 (3)	0.0326 (17)
H5	0.2130	0.1574	0.5743	0.039*
C6	0.3140 (2)	0.1815 (4)	0.6082 (3)	0.0286 (15)
C7	0.1732 (4)	−0.1797 (8)	0.3856 (5)	0.0438 (19)
H7A	0.1662	−0.2488	0.3471	0.066*
H7B	0.1309	−0.1196	0.3484	0.066*
H7C	0.1754	−0.2159	0.4328	0.066*
C8	0.3314 (4)	0.2851 (6)	0.6694 (5)	0.0269 (16)
H8	0.2915	0.3119	0.6658	0.032*
C9	0.4604 (4)	0.5100 (6)	0.8344 (4)	0.0269 (15)
C10	0.4616 (2)	0.6071 (4)	0.8911 (2)	0.0236 (15)
C11	0.5075 (2)	0.7141 (4)	0.9198 (3)	0.0289 (16)
H11	0.5330	0.7276	0.8990	0.035*
C12	0.5159 (2)	0.8012 (3)	0.9790 (3)	0.0314 (17)
H12	0.5472	0.8743	0.9986	0.038*
C13	0.4785 (2)	0.7813 (4)	1.0094 (3)	0.0282 (16)
C14	0.4326 (2)	0.6744 (4)	0.9807 (3)	0.0241 (14)
H14	0.4071	0.6609	1.0015	0.029*
C15	0.4242 (2)	0.5873 (3)	0.9215 (3)	0.0244 (15)
H15	0.3929	0.5142	0.9019	0.029*
C16	0.1442 (4)	0.4487 (8)	0.7214 (5)	0.0372 (18)
H16A	0.1335	0.3567	0.7154	0.056*
H16B	0.0974	0.4970	0.6902	0.056*
H16C	0.1805	0.4720	0.7858	0.056*
C17	0.1980 (4)	0.6515 (7)	0.6951 (5)	0.0424 (19)
H17A	0.2175	0.6882	0.6690	0.064*
H17B	0.2346	0.6653	0.7609	0.064*
H17C	0.1502	0.6932	0.6682	0.064*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cd1	0.0238 (4)	0.0338 (4)	0.0243 (4)	0.000	0.0186 (3)	0.000
S1	0.0368 (10)	0.0355 (11)	0.0337 (11)	−0.0019 (8)	0.0259 (9)	−0.0040 (9)
O1	0.025 (2)	0.037 (3)	0.027 (3)	0.000 (2)	0.019 (2)	0.000 (2)
O2	0.041 (3)	0.041 (3)	0.032 (3)	−0.010 (2)	0.026 (3)	−0.012 (2)
O3	0.025 (2)	0.035 (3)	0.029 (3)	−0.001 (2)	0.022 (2)	−0.003 (2)
O4	0.034 (3)	0.038 (3)	0.032 (3)	−0.007 (2)	0.028 (2)	−0.010 (2)
N1	0.024 (3)	0.026 (3)	0.020 (3)	−0.001 (2)	0.016 (2)	0.000 (2)
N2	0.030 (3)	0.033 (3)	0.025 (3)	0.000 (3)	0.022 (3)	−0.005 (3)
O5	0.035 (3)	0.042 (3)	0.061 (4)	0.004 (2)	0.036 (3)	0.002 (3)
C1	0.025 (3)	0.031 (4)	0.020 (4)	0.006 (3)	0.014 (3)	0.007 (3)
C2	0.034 (4)	0.033 (4)	0.027 (4)	0.007 (3)	0.024 (3)	0.002 (3)
C3	0.037 (4)	0.025 (4)	0.032 (4)	−0.003 (3)	0.025 (4)	0.000 (3)
C4	0.024 (3)	0.045 (5)	0.021 (4)	−0.012 (3)	0.010 (3)	−0.006 (3)
C5	0.030 (4)	0.044 (5)	0.026 (4)	0.005 (3)	0.019 (3)	0.003 (3)
C6	0.027 (3)	0.035 (4)	0.026 (4)	0.007 (3)	0.018 (3)	0.010 (4)
C7	0.047 (4)	0.044 (5)	0.035 (4)	−0.004 (4)	0.025 (4)	−0.002 (4)
C8	0.027 (4)	0.024 (4)	0.035 (4)	0.003 (3)	0.024 (3)	0.005 (3)
C9	0.027 (4)	0.027 (4)	0.022 (4)	0.007 (3)	0.015 (3)	0.006 (3)
C10	0.021 (3)	0.029 (4)	0.020 (4)	−0.002 (3)	0.014 (3)	0.000 (3)
C11	0.035 (4)	0.034 (4)	0.029 (4)	−0.001 (3)	0.026 (3)	−0.002 (3)
C12	0.033 (4)	0.036 (5)	0.035 (4)	−0.006 (3)	0.027 (3)	0.001 (3)
C13	0.035 (4)	0.033 (4)	0.022 (4)	0.005 (3)	0.021 (3)	0.002 (3)
C14	0.025 (3)	0.029 (4)	0.021 (3)	0.004 (3)	0.017 (3)	0.003 (3)
C15	0.026 (3)	0.026 (4)	0.020 (4)	−0.002 (3)	0.015 (3)	0.001 (3)
C16	0.031 (4)	0.051 (5)	0.037 (5)	−0.004 (3)	0.025 (4)	−0.006 (4)
C17	0.050 (4)	0.039 (5)	0.047 (5)	0.004 (4)	0.035 (4)	−0.001 (4)

Geometric parameters (Å, °)

Cd1—O1	2.246 (4)	C4—H4A	0.9500
Cd1—O1i	2.246 (4)	C5—C6	1.3900
Cd1—N1i	2.254 (5)	C5—H5	0.9500
Cd1—N1	2.254 (5)	C6—C8	1.464 (7)
Cd1—O3	2.386 (4)	C7—H7A	0.9800
Cd1—O3i	2.386 (4)	C7—H7B	0.9800
S1—O5	1.497 (5)	C7—H7C	0.9800
S1—C17	1.764 (7)	C8—H8	0.9500
S1—C16	1.782 (6)	C9—C10	1.500 (7)
O1—C1	1.362 (5)	C10—C11	1.3900
O2—C3	1.355 (5)	C10—C15	1.3900
O2—C7	1.439 (8)	C11—C12	1.3900
O3—C9	1.221 (7)	C11—H11	0.9500
O4—C13	1.356 (5)	C12—C13	1.3900
O4—H4	0.8400	C12—H12	0.9500
N1—C8	1.280 (8)	C13—C14	1.3900
N1—N2	1.385 (7)	C14—C15	1.3900
N2—C9	1.356 (8)	C14—H14	0.9500
N2—H2	0.8800	C15—H15	0.9500
C1—C2	1.3900	C16—H16A	0.9800
C1—C6	1.3900	C16—H16B	0.9800
C2—C3	1.3900	C16—H16C	0.9800
C2—H2A	0.9500	C17—H17A	0.9800
C3—C4	1.3900	C17—H17B	0.9800
C4—C5	1.3900	C17—H17C	0.9800
O1—Cd1—O1i	101.8 (2)	C5—C6—C8	112.7 (3)
O1—Cd1—N1i	104.12 (16)	C1—C6—C8	127.3 (3)
O1i—Cd1—N1i	82.26 (16)	O2—C7—H7A	109.5
O1—Cd1—N1	82.26 (16)	O2—C7—H7B	109.5
O1i—Cd1—N1	104.12 (16)	H7A—C7—H7B	109.5
N1i—Cd1—N1	170.1 (3)	O2—C7—H7C	109.5
O1—Cd1—O3	150.75 (14)	H7A—C7—H7C	109.5
O1i—Cd1—O3	94.45 (15)	H7B—C7—H7C	109.5
N1i—Cd1—O3	102.05 (16)	N1—C8—C6	127.4 (5)
N1—Cd1—O3	70.17 (16)	N1—C8—H8	116.3
O1—Cd1—O3i	94.45 (15)	C6—C8—H8	116.3
O1i—Cd1—O3i	150.75 (14)	O3—C9—N2	122.3 (6)
N1i—Cd1—O3i	70.17 (16)	O3—C9—C10	121.5 (6)
N1—Cd1—O3i	102.05 (16)	N2—C9—C10	116.1 (5)
O3—Cd1—O3i	82.3 (2)	C11—C10—C15	120.0
O5—S1—C17	104.7 (3)	C11—C10—C9	117.7 (3)
O5—S1—C16	104.9 (3)	C15—C10—C9	122.0 (4)
C17—S1—C16	99.3 (4)	C12—C11—C10	120.0
C1—O1—Cd1	130.6 (3)	C12—C11—H11	120.0
C3—O2—C7	117.6 (5)	C10—C11—H11	120.0
C9—O3—Cd1	114.2 (4)	C11—C12—C13	120.0
C13—O4—H4	109.5	C11—C12—H12	120.0
C8—N1—N2	116.5 (5)	C13—C12—H12	120.0
C8—N1—Cd1	128.4 (4)	O4—C13—C14	122.6 (3)
N2—N1—Cd1	114.9 (3)	O4—C13—C12	117.3 (3)
C9—N2—N1	118.2 (5)	C14—C13—C12	120.0
C9—N2—H2	120.9	C13—C14—C15	120.0
N1—N2—H2	120.9	C13—C14—H14	120.0
O1—C1—C2	117.6 (3)	C15—C14—H14	120.0
O1—C1—C6	122.4 (3)	C14—C15—C10	120.0
C2—C1—C6	120.0	C14—C15—H15	120.0
C1—C2—C3	120.0	C10—C15—H15	120.0
C1—C2—H2A	120.0	S1—C16—H16A	109.5
C3—C2—H2A	120.0	S1—C16—H16B	109.5
O2—C3—C2	116.1 (3)	H16A—C16—H16B	109.5
O2—C3—C4	123.9 (3)	S1—C16—H16C	109.5
C2—C3—C4	120.0	H16A—C16—H16C	109.5
C5—C4—C3	120.0	H16B—C16—H16C	109.5
C5—C4—H4A	120.0	S1—C17—H17A	109.5
C3—C4—H4A	120.0	S1—C17—H17B	109.5
C4—C5—C6	120.0	H17A—C17—H17B	109.5
C4—C5—H5	120.0	S1—C17—H17C	109.5
C6—C5—H5	120.0	H17A—C17—H17C	109.5
C5—C6—C1	120.0	H17B—C17—H17C	109.5
O1i—Cd1—O1—C1	90.7 (4)	C3—C4—C5—C6	0.0
N1i—Cd1—O1—C1	175.5 (4)	C4—C5—C6—C1	0.0
N1—Cd1—O1—C1	−12.2 (4)	C4—C5—C6—C8	180.0 (4)
O3—Cd1—O1—C1	−31.7 (6)	O1—C1—C6—C5	178.1 (4)
O3i—Cd1—O1—C1	−113.8 (4)	C2—C1—C6—C5	0.0
O1—Cd1—O3—C9	24.1 (6)	O1—C1—C6—C8	−1.8 (6)
O1i—Cd1—O3—C9	−99.9 (4)	C2—C1—C6—C8	−179.9 (5)
N1i—Cd1—O3—C9	177.1 (4)	N2—N1—C8—C6	−178.8 (5)
N1—Cd1—O3—C9	3.5 (4)	Cd1—N1—C8—C6	6.1 (9)
O3i—Cd1—O3—C9	109.4 (5)	C5—C6—C8—N1	171.3 (6)
O1—Cd1—N1—C8	2.3 (5)	C1—C6—C8—N1	−8.8 (9)
O1i—Cd1—N1—C8	−97.9 (5)	Cd1—O3—C9—N2	−3.9 (8)
O3—Cd1—N1—C8	172.4 (6)	Cd1—O3—C9—C10	175.5 (4)
O3i—Cd1—N1—C8	95.3 (5)	N1—N2—C9—O3	1.4 (9)
O1—Cd1—N1—N2	−172.8 (4)	N1—N2—C9—C10	−178.1 (5)
O1i—Cd1—N1—N2	86.9 (4)	O3—C9—C10—C11	25.7 (7)
O3—Cd1—N1—N2	−2.8 (4)	N2—C9—C10—C11	−154.8 (4)
O3i—Cd1—N1—N2	−79.9 (4)	O3—C9—C10—C15	−148.5 (5)
C8—N1—N2—C9	−173.7 (6)	N2—C9—C10—C15	31.0 (7)
Cd1—N1—N2—C9	2.1 (7)	C15—C10—C11—C12	0.0
Cd1—O1—C1—C2	−168.0 (3)	C9—C10—C11—C12	−174.3 (4)
Cd1—O1—C1—C6	13.8 (6)	C10—C11—C12—C13	0.0
O1—C1—C2—C3	−178.2 (4)	C11—C12—C13—O4	177.6 (4)
C6—C1—C2—C3	0.0	C11—C12—C13—C14	0.0
C7—O2—C3—C2	174.7 (5)	O4—C13—C14—C15	−177.4 (4)
C7—O2—C3—C4	−6.5 (7)	C12—C13—C14—C15	0.0
C1—C2—C3—O2	178.9 (5)	C13—C14—C15—C10	0.0
C1—C2—C3—C4	0.0	C11—C10—C15—C14	0.0
O2—C3—C4—C5	−178.8 (5)	C9—C10—C15—C14	174.1 (4)
C2—C3—C4—C5	0.0

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1ii	0.84	1.79	2.603 (6)	163
N2—H2···O5	0.88	1.93	2.766 (6)	159

Symmetry codes: (ii) x, −y+1, z+1/2.