Crystal structure of bis­(acetato-κO)bis­(pyridine-2-carboxamide oxime-κ2N,N′)cadmium ethanol disolvate

Liu, J.

doi:10.1107/S1600536814017978

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages 142-144

doi:10.1107/S1600536814017978

Open

access

Crystal structure of bis(acetato-κO)bis(pyridine-2-carboxamide oxime-κ²N,N′)cadmium ethanol disolvate

Jiyong Liu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: shawnLau.zj@hotmail.com

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 8 July 2014; accepted 5 August 2014; online 23 August 2014)

In the title compound, [Cd(CH₃COO)₂(C₆H₇N₃O)₂]·2C₂H₅OH, the Cd^II atom, which lies on a twofold rotation axis, is coordinated by two monodentate acetate groups and two N,N′-chelating pyridine-2-carboxamide oxime ligands, leading to a distorted octahedral coordination sphere. The mononuclear complex molecules are assembled into chains along the c-axis direction via N—H⋯O hydrogen-bonding interactions. These chains are further assembled by O—H⋯O hydrogen bonds involving the ethanol solvent molecules into a three-dimensional supramolecular structure.

Keywords: crystal structure; Cd^II complex; acetate; pyridine-2-carboxamide oxime; N—H⋯O hydrogen bonding.

CCDC reference: 1017896

1. Chemical context

The monoanions of simple of 2-pyridyl oximes, (py)C(R)NOH (R = a non-coordinating group, e.g. H, Me, Ph etc.), are remarkable sources of homo- and heterometallic complexes with novel structures and interesting physical properties (Miyasaka et al., 2003 ; Stamatatos et al., 2007 ). A logical extension of such studies is the investigation of the coordination chemistry of analogous organic molecules in which the non-donor R group is replaced by a donor group such as pyridine, cyano etc. (Alcazar et al., 2013 ; Escuer et al., 2011 ). When R is an amino group, the resulting ligand is pyridine-2-amidoxime, (py)C(NH₂)NOH, which belongs to the class of amidoximes. The presence of the amine functionality is expected to alter the coordination behaviour of this ligand in comparison with that of the (py)C(R)NOH (R = a non-coordinating group) ligands. The characteristics that differentiate the amino group are its coordination capability, potential for deprotonation, different electronic properties and hydrogen-bonding effects.

The present work reports the first use of (py)C(NH₂)NOH in Cd^II coordination chemistry and describes the synthesis and structure of the mononuclear title compound.

2. Structural commentary

The title complex consists of isolated [Cd(O₂CMe)₂{(py)C(NH₂)NOH}₂] complex molecules and ethanol solvent molecules. The central Cd^II atom is located on a twofold rotation axis (Wyckoff site 4e). The Cd^II atom is coordinated by two monodentate MeCO₂⁻ groups and two N,N′-chelating (py)C(NH₂)NOH ligands (Fig. 1 and Table 1). The (py)C(NH₂)NOH donor atoms are the N atoms of the neutral oxime and the 2-pyridyl groups. The amino N atom of each ligand remains uncoordinating, albeit participating in an extensive intermolecular hydrogen-bonding network. Each of the two coordinating (py)C(NH₂)NOH molecules results in the formation of a five-membered chelate ring including a Cd^II atom, in which the chelate angle N1—Cd1—N1 [86.7 (2)°] is noteably larger than comparable angles found in [Cd(HCO₂)₂(pya)₂] (pya = pyridine-2-aldoxime; Croitor et al., 2013 ).

Table 1
Selected bond lengths (Å)

Cd1—O2	2.288 (3)	Cd1—N3	2.315 (3)
Cd1—N1	2.413 (4)

Figure 1
The title compound with displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ .]

3. Supramolecular features

Table 2 shows the hydrogen-bonding interactions. There are two strong symmetry-related intramolecular hydrogen bonds between the unbound oxime (–O1—H1) group and uncoordinating acetate atom O3. Uncoordinating amino atom N2 acts as a donor for two hydrogen bonds; in one of these, the acceptor is coordinating atom O2 from the acetate group, which leads to the formation of chains running along the c-axis direction (Fig. 2). These chains are further linked into a three-dimensional network by hydrogen bonds involving the ethanol solvent molecule (O4), acting as a donor for the uncoordinating carboxylate O atom (O3) and as an acceptor for the remaining amino H atom H2B (Table 2 and Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.85 (1)	1.86 (4)	2.600 (5)	145 (6)
N2—H2A⋯O2ⁱⁱ	0.85 (1)	2.20 (2)	3.040 (5)	169 (5)
N2—H2B⋯O4	0.85 (1)	2.45 (4)	3.113 (6)	136 (5)
O4—H4A⋯O3ⁱⁱⁱ	0.85 (1)	2.09 (3)	2.903 (5)	161 (8)
Symmetry codes: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The hydrogen-bonded chain along the c axis. Dashed lines represent hydrogen bonds and H atoms bonded to C atoms have been omitted for clarity.

Figure 3
The crystal structure projected along the c axis. Dashed lines represent hydrogen bonds and H atoms bonded to C atoms have been omitted for clarity.

4. Synthesis and crystallization

A stoichiometric amount of (py)C(NH₂)NOH and Cd(OAc)₂·3H₂O in a 2:1 ratio was dissolved in 20 ml ethanol and 10 ml DMF, and the solution left to evaporate slowly to afford colourless block-like crystals after three weeks at room temperature.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms bonded to C atoms were placed in geometrically calculated position and were refined using a riding model, with C—H = 0.93 (aromatic) or 0.96 Å (methyl) and U_iso(H) = 1.2U_eq(C_aromatic) and 1.5U_eq(C_methyl). The N- and O-bound H atoms were located in a difference map and the coordinates were refined with N—H = 0.86 (1) Å and U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	[Cd(C₂H₃O₂)₂(C₆H₇N₃O)₂]·2C₂H₆O
M_r	596.92
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	15.894 (3), 10.9654 (17), 15.0212 (16)
β (°)	91.746 (12)
V (Å³)	2616.7 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.89
Crystal size (mm)	0.28 × 0.26 × 0.2

Data collection
Diffractometer	Agilent Xcalibur, Atlas, Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5661, 2400, 2017
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 1.05
No. of reflections	2400
No. of parameters	173
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.48
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1017896

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814017978/bg2533sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814017978/bg2533Isup2.hkl

checkCIF report

Chemical context top

The monoanions of simple of 2-pyridyl oximes, (py)C(R)NOH (R = a non-coordinating group, e.g. H, Me, Ph etc.), are remarkable sources of homo- and heterometallic complexes with novel structures and interesting physical properties (Miyasaka et al., 2003; Stamatatos et al., 2007). A logical extension of such studies is the investigation of the coordination chemistry of analogous organic molecules in which the non-donor R group is replaced by a donor group (e.g. pyridine, cyano etc.; Alcazar et al., 2013; Escuer et al., 2011). When R is an amino group, the resulting ligand is pyridine-2-amidoxime (systematic name: N-hydroxy-pyridine-2-carboxamidine), (py)C(NH₂)NOH, which belongs to the class of amidoximes. The presence of the amine functionality is expected to alter the coordination behaviour of this ligand in comparison with that of the (py)C(R)NOH (R = a non-coordinating group) ligands. Characteristics that differentiate the amino group are its coordination capability, potential for deprotonation, different electronic properties and hydrogen-bonding effects. In the present work, we report the first use of (py)C(NH₂)NOH in Cd^II coordination chemistry by describing the synthesis and structure of the mononuclear titlecompound.

Structural commentary top

The title complex consists of isolated [Cd(O₂CMe)₂{(py)C(NH₂)NOH}₂] complex molecules and ethanol solvent molecules. It crystallizes in the monoclinic space group C2/c and the central Cd^II atom is located on a twofold axis (Wyckoff site 4e). The Cd^II atom is coordinated by two monodentate MeCO^2- groups and two N,N'-chelating (η²)(py)C(NH₂)NOH ligands (Fig. 1 and Table 1). The (py)C(NH₂)NOH donor atoms are the N atoms of the neutral oxime and the 2-pyridyl groups. The amino N atom of each ligand remains uncoordinated albeit participating in an extensive intermolecular hydrogen-bonding network. Each of the two coordinating (py)C(NH₂)NOH molecules results in the formation of a five-membered chelate ring including a Cd^II atom, in which the chelate angle N1—Cd1—N1 [86.7 (2)°] is noteably larger than comparable angles found in [Cd(HCO₂)₂(pya)₂] (pya = pyridine-2-aldoxime; Croitor et al., 2013) and Cd—N distances of 2.413 (4) and 2.315 (3) Å.

Supramolecular features top

Table 2 shows the hydrogen-bonding interactions. There are two very strong symmetry-related intramolecular hydrogen bonds between the unbound oxime (–O1—H1) group and uncoordinating acetate atom O3. Uncoordinating amino atom N2 acts as a donor for two hydrogen bonds; in one of these, the acceptor is coordinating atom O2 from the acetate group, which leads to the formation of chains running along the c-axis direction (Fig. 2). These chains are further linked by hydrogen bonds involving the ethanol solvent molecule (O4), acting as a donor for the uncoordinating carboxylate O atom (O3) and as an acceptor for the remaining amino H atom H2B (Table 2 and Fig. 3).

Synthesis and crystallization top

A stoichiometric amount in the ratio of 2:1 of (py)C(NH₂)NOH and Cd(OAc)₂·3H₂O were dissolved in 20 ml ethanol and 10 ml DMF, and the solution left to evaporate slowly to afford colourless block-like crystals after three weeks at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms bonded to C atoms were placed in geometrically calculated position and were refined using a riding model, with C—H = 0.93 or 0.96 Å and U_iso(H) = 1.2U_eq(C). The N- and O-bound H atoms were located in a difference map and the coordinates were refined with N—H = 0.86 (1) Å and U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O).

Related literature top

For related literature, see: Alcazar et al. (2013); Escuer et al. (2011); Miyasaka et al. (2003); Stamatatos et al. (2007).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The title compound with displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x+1, y, -z+3/2.]
	Fig. 2. The hydrogen-bonded chain along the c axis. Dashed lines represent hydrogen bonds and H atoms bonded to C atoms have been omitted for clarity.
	Fig. 3. The crystal structure projected along the c axis. Dashed lines represent hydrogen bonds and H atoms bonded to C atoms have been omitted for clarity.

Bis(acetato-κO)bis(pyridine-2-carboxamide oxime-κ²N,N')cadmium ethanol disolvate top

Crystal data top

[Cd(C₂H₃O₂)₂(C₆H₇N₃O)₂]·2C₂H₆O	F(000) = 1224
M_r = 596.92	D_x = 1.515 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.894 (3) Å	Cell parameters from 1816 reflections
b = 10.9654 (17) Å	θ = 2.9–29.6°
c = 15.0212 (16) Å	µ = 0.89 mm⁻¹
β = 91.746 (12)°	T = 294 K
V = 2616.7 (7) Å³	Block, colourless
Z = 4	0.28 × 0.26 × 0.2 mm

Data collection top

Agilent Xcalibur, Atlas, Gemini ultra diffractometer	2400 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2017 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 10.3592 pixels mm^-1	θ_max = 25.4°, θ_min = 3.5°
ω scans	h = −19→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→11
T_min = 0.910, T_max = 1.000	l = −18→16
5661 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0689P)²] where P = (F_o² + 2F_c²)/3
2400 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.85 e Å⁻³
4 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cd(C₂H₃O₂)₂(C₆H₇N₃O)₂]·2C₂H₆O	V = 2616.7 (7) Å³
M_r = 596.92	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.894 (3) Å	µ = 0.89 mm⁻¹
b = 10.9654 (17) Å	T = 294 K
c = 15.0212 (16) Å	0.28 × 0.26 × 0.2 mm
β = 91.746 (12)°

Data collection top

Agilent Xcalibur, Atlas, Gemini ultra diffractometer	2400 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2017 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.050
5661 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	4 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.85 e Å⁻³
2400 reflections	Δρ_min = −0.48 e Å⁻³
173 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	0.5000	0.55546 (4)	0.7500	0.0336 (2)
O1	0.3289 (2)	0.5799 (3)	0.6185 (2)	0.0456 (9)
H1	0.323 (4)	0.623 (5)	0.664 (2)	0.068*
O2	0.5829 (2)	0.6898 (3)	0.67588 (19)	0.0448 (8)
O3	0.6590 (3)	0.7760 (3)	0.7846 (2)	0.0627 (11)
N1	0.5479 (2)	0.3954 (4)	0.6536 (2)	0.0349 (9)
N2	0.3668 (3)	0.4189 (4)	0.5009 (3)	0.0411 (10)
H2A	0.384 (3)	0.381 (4)	0.456 (2)	0.049*
H2B	0.333 (3)	0.478 (3)	0.493 (4)	0.049*
N3	0.4048 (2)	0.5170 (4)	0.6337 (2)	0.0348 (9)
C1	0.6196 (3)	0.3347 (5)	0.6661 (3)	0.0510 (13)
H1A	0.6528	0.3520	0.7166	0.061*
C2	0.6469 (4)	0.2478 (5)	0.6083 (4)	0.0574 (14)
H2	0.6969	0.2059	0.6200	0.069*
C3	0.5988 (3)	0.2237 (5)	0.5326 (4)	0.0548 (14)
H3	0.6165	0.1666	0.4914	0.066*
C4	0.5238 (3)	0.2855 (4)	0.5189 (3)	0.0421 (12)
H4	0.4900	0.2698	0.4686	0.051*
C5	0.4994 (3)	0.3717 (4)	0.5812 (3)	0.0304 (10)
C6	0.4200 (3)	0.4393 (4)	0.5716 (3)	0.0307 (10)
C7	0.6314 (3)	0.7709 (5)	0.7064 (3)	0.0423 (12)
C8	0.6594 (5)	0.8661 (6)	0.6421 (4)	0.077 (2)
H8A	0.6782	0.8273	0.5890	0.115*
H8B	0.7047	0.9125	0.6688	0.115*
H8C	0.6132	0.9194	0.6273	0.115*
O4	0.2093 (3)	0.5194 (5)	0.3968 (3)	0.0762 (13)
H4A	0.207 (6)	0.583 (5)	0.364 (5)	0.114*
C9	0.1674 (7)	0.4180 (8)	0.3623 (6)	0.105 (3)
H9A	0.1766	0.3505	0.4032	0.126*
H9B	0.1927	0.3961	0.3066	0.126*
C10	0.0799 (7)	0.4315 (9)	0.3466 (8)	0.146 (5)
H10A	0.0541	0.4565	0.4006	0.219*
H10B	0.0563	0.3551	0.3271	0.219*
H10C	0.0698	0.4922	0.3014	0.219*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0343 (3)	0.0403 (3)	0.0260 (3)	0.000	−0.00478 (18)	0.000
O1	0.0355 (19)	0.053 (2)	0.047 (2)	0.0123 (16)	−0.0101 (15)	−0.0073 (16)
O2	0.054 (2)	0.046 (2)	0.0348 (17)	−0.0145 (18)	−0.0026 (14)	−0.0009 (15)
O3	0.089 (3)	0.042 (2)	0.055 (2)	−0.020 (2)	−0.027 (2)	0.0086 (17)
N1	0.036 (2)	0.034 (2)	0.0340 (19)	0.0011 (18)	−0.0032 (16)	−0.0007 (16)
N2	0.043 (2)	0.045 (3)	0.034 (2)	0.005 (2)	−0.0100 (18)	−0.0086 (18)
N3	0.031 (2)	0.040 (2)	0.033 (2)	0.0060 (18)	−0.0039 (15)	−0.0039 (17)
C1	0.039 (3)	0.065 (4)	0.049 (3)	0.013 (3)	−0.012 (2)	−0.008 (3)
C2	0.048 (3)	0.051 (3)	0.073 (4)	0.019 (3)	−0.004 (3)	−0.002 (3)
C3	0.058 (3)	0.048 (3)	0.059 (3)	0.008 (3)	0.008 (3)	−0.009 (3)
C4	0.046 (3)	0.041 (3)	0.039 (2)	0.004 (2)	−0.001 (2)	−0.010 (2)
C5	0.035 (2)	0.028 (2)	0.028 (2)	−0.003 (2)	0.0008 (18)	0.0048 (17)
C6	0.031 (2)	0.035 (2)	0.026 (2)	−0.003 (2)	0.0000 (17)	0.0072 (18)
C7	0.043 (3)	0.046 (3)	0.038 (3)	−0.001 (2)	−0.001 (2)	−0.006 (2)
C8	0.097 (5)	0.075 (5)	0.057 (4)	−0.045 (4)	−0.008 (3)	0.020 (3)
O4	0.081 (3)	0.068 (3)	0.079 (3)	−0.001 (3)	−0.021 (2)	0.015 (2)
C9	0.148 (9)	0.080 (6)	0.086 (6)	−0.003 (6)	−0.029 (6)	0.001 (4)
C10	0.139 (10)	0.150 (11)	0.147 (9)	−0.070 (8)	−0.041 (8)	0.044 (7)

Geometric parameters (Å, º) top

Cd1—O2	2.288 (3)	C2—C3	1.376 (8)
Cd1—O2ⁱ	2.288 (3)	C3—H3	0.9300
Cd1—N1	2.413 (4)	C3—C4	1.381 (7)
Cd1—N1ⁱ	2.413 (4)	C4—H4	0.9300
Cd1—N3ⁱ	2.315 (3)	C4—C5	1.394 (6)
Cd1—N3	2.315 (3)	C5—C6	1.468 (6)
O1—H1	0.846 (10)	C7—C8	1.498 (7)
O1—N3	1.404 (5)	C8—H8A	0.9600
O2—C7	1.254 (6)	C8—H8B	0.9600
O3—C7	1.244 (5)	C8—H8C	0.9600
N1—C1	1.328 (6)	O4—H4A	0.851 (10)
N1—C5	1.339 (5)	O4—C9	1.388 (10)
N2—H2A	0.851 (10)	C9—H9A	0.9700
N2—H2B	0.847 (10)	C9—H9B	0.9700
N2—C6	1.355 (6)	C9—C10	1.412 (14)
N3—C6	1.291 (6)	C10—H10A	0.9600
C1—H1A	0.9300	C10—H10B	0.9600
C1—C2	1.368 (7)	C10—H10C	0.9600
C2—H2	0.9300

O2—Cd1—O2ⁱ	99.86 (18)	C2—C3—C4	118.9 (5)
O2—Cd1—N1	88.81 (13)	C4—C3—H3	120.5
O2ⁱ—Cd1—N1	163.16 (12)	C3—C4—H4	120.4
O2—Cd1—N1ⁱ	163.16 (12)	C3—C4—C5	119.3 (4)
O2ⁱ—Cd1—N1ⁱ	88.81 (13)	C5—C4—H4	120.4
O2—Cd1—N3ⁱ	96.42 (12)	N1—C5—C4	120.8 (4)
O2—Cd1—N3	97.07 (12)	N1—C5—C6	117.0 (4)
O2ⁱ—Cd1—N3	96.42 (12)	C4—C5—C6	122.2 (4)
O2ⁱ—Cd1—N3ⁱ	97.07 (12)	N2—C6—C5	120.5 (4)
N1ⁱ—Cd1—N1	86.69 (19)	N3—C6—N2	123.3 (4)
N3—Cd1—N1	68.01 (13)	N3—C6—C5	116.1 (4)
N3—Cd1—N1ⁱ	96.27 (13)	O2—C7—C8	116.7 (4)
N3ⁱ—Cd1—N1ⁱ	68.01 (13)	O3—C7—O2	124.9 (5)
N3ⁱ—Cd1—N1	96.27 (13)	O3—C7—C8	118.3 (5)
N3ⁱ—Cd1—N3	159.0 (2)	C7—C8—H8A	109.5
N3—O1—H1	106 (4)	C7—C8—H8B	109.5
C7—O2—Cd1	129.4 (3)	C7—C8—H8C	109.5
C1—N1—Cd1	124.4 (3)	H8A—C8—H8B	109.5
C1—N1—C5	119.2 (4)	H8A—C8—H8C	109.5
C5—N1—Cd1	116.4 (3)	H8B—C8—H8C	109.5
H2A—N2—H2B	119 (5)	C9—O4—H4A	116 (6)
C6—N2—H2A	120 (4)	O4—C9—H9A	108.3
C6—N2—H2B	111 (4)	O4—C9—H9B	108.3
O1—N3—Cd1	124.9 (3)	O4—C9—C10	115.9 (9)
C6—N3—Cd1	122.3 (3)	H9A—C9—H9B	107.4
C6—N3—O1	112.6 (3)	C10—C9—H9A	108.3
N1—C1—H1A	118.5	C10—C9—H9B	108.3
N1—C1—C2	123.1 (4)	C9—C10—H10A	109.5
C2—C1—H1A	118.5	C9—C10—H10B	109.5
C1—C2—H2	120.7	C9—C10—H10C	109.5
C1—C2—C3	118.7 (5)	H10A—C10—H10B	109.5
C3—C2—H2	120.7	H10A—C10—H10C	109.5
C2—C3—H3	120.5	H10B—C10—H10C	109.5

Cd1—O2—C7—O3	17.9 (8)	N1—Cd1—N3—O1	−178.6 (4)
Cd1—O2—C7—C8	−164.0 (4)	N1—Cd1—N3—C6	−3.7 (3)
Cd1—N1—C1—C2	−177.2 (4)	N1ⁱ—Cd1—N3—C6	−87.6 (4)
Cd1—N1—C5—C4	176.5 (3)	N1—C1—C2—C3	1.3 (9)
Cd1—N1—C5—C6	−4.1 (5)	N1—C5—C6—N2	−178.9 (4)
Cd1—N3—C6—N2	−177.2 (3)	N1—C5—C6—N3	0.9 (6)
Cd1—N3—C6—C5	3.0 (5)	N3—Cd1—O2—C7	157.2 (4)
O1—N3—C6—N2	−1.7 (6)	N3ⁱ—Cd1—O2—C7	−38.9 (4)
O1—N3—C6—C5	178.5 (3)	N3ⁱ—Cd1—N1—C1	−13.3 (4)
O2ⁱ—Cd1—O2—C7	59.4 (4)	N3—Cd1—N1—C1	−178.9 (4)
O2ⁱ—Cd1—N1—C1	−155.5 (4)	N3ⁱ—Cd1—N1—C5	169.5 (3)
O2—Cd1—N1—C1	83.0 (4)	N3—Cd1—N1—C5	3.9 (3)
O2—Cd1—N1—C5	−94.2 (3)	N3ⁱ—Cd1—N3—O1	137.7 (3)
O2ⁱ—Cd1—N1—C5	27.3 (6)	N3ⁱ—Cd1—N3—C6	−47.4 (3)
O2ⁱ—Cd1—N3—O1	8.1 (4)	C1—N1—C5—C4	−0.8 (7)
O2—Cd1—N3—O1	−92.8 (3)	C1—N1—C5—C6	178.6 (4)
O2ⁱ—Cd1—N3—C6	−177.1 (4)	C1—C2—C3—C4	−1.7 (9)
O2—Cd1—N3—C6	82.1 (4)	C2—C3—C4—C5	0.9 (8)
N1—Cd1—O2—C7	−135.1 (4)	C3—C4—C5—N1	0.4 (7)
N1ⁱ—Cd1—O2—C7	−60.6 (6)	C3—C4—C5—C6	−179.0 (4)
N1ⁱ—Cd1—N1—C1	−80.8 (4)	C4—C5—C6—N2	0.5 (6)
N1ⁱ—Cd1—N1—C5	102.1 (3)	C4—C5—C6—N3	−179.7 (4)
N1ⁱ—Cd1—N3—O1	97.6 (3)	C5—N1—C1—C2	−0.1 (8)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.85 (1)	1.86 (4)	2.600 (5)	145 (6)
N2—H2A···O2ⁱⁱ	0.85 (1)	2.20 (2)	3.040 (5)	169 (5)
N2—H2B···O4	0.85 (1)	2.45 (4)	3.113 (6)	136 (5)
O4—H4A···O3ⁱⁱⁱ	0.85 (1)	2.09 (3)	2.903 (5)	161 (8)

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

Selected bond lengths (Å) top

Cd1—O2	2.288 (3)	Cd1—N3	2.315 (3)
Cd1—N1	2.413 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.846 (10)	1.86 (4)	2.600 (5)	145 (6)
N2—H2A···O2ⁱⁱ	0.851 (10)	2.200 (15)	3.040 (5)	169 (5)
N2—H2B···O4	0.847 (10)	2.45 (4)	3.113 (6)	136 (5)
O4—H4A···O3ⁱⁱⁱ	0.851 (10)	2.09 (3)	2.903 (5)	161 (8)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₂H₃O₂)₂(C₆H₇N₃O)₂]·2C₂H₆O
M_r	596.92
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	15.894 (3), 10.9654 (17), 15.0212 (16)
β (°)	91.746 (12)
V (Å³)	2616.7 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.28 × 0.26 × 0.2

Data collection
Diffractometer	Agilent Xcalibur, Atlas, Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5661, 2400, 2017
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 1.05
No. of reflections	2400
No. of parameters	173
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.48

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Olex2 (Dolomanov et al., 2009).

Acknowledgements

This project was supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Science and Technology Department of Zhejiang Province (grant No. 2006 C21105) and the Education Department of Zhejiang Province.

References

Agilent (2011). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Google Scholar
Alcazar, A., Cordero, B., Esteban, J., Tangoulis, V., Font-Bardia, M., Calvet, T. & Escuer, A. (2013). Dalton Trans. 42, 12334–12345. Web of Science CSD CrossRef CAS PubMed Google Scholar
Croitor, L., Coropceanu, E. B., Siminel, A. V., Masunov, A. E. & Fonari, M. S. (2013). Polyhedron, 60, 140–150. Web of Science CSD CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Escuer, A., Vlahopoulou, G., Perlepes, S. P. & Mautner, F. A. (2011). Inorg. Chem. 50, 2468–2478. Web of Science CSD CrossRef CAS PubMed Google Scholar
Miyasaka, H., Nezu, T., Iwahori, F., Furukawa, S., Sugimoto, K., Cleŕac, R., Sugiura, K. & Yamashita, M. (2003). Inorg. Chem. 42, 4504–4503. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stamatatos, T. C., Foguet-Albiol, D., Lee, S. C., Raptopoulou, C. P., Terzis, A., Wernsdorfer, W., Hill, S. O., Perlepes, S. P. & Christou, G. (2007). J.Am.Chem.Soc. 129, 9484–9499. Web of Science CSD CrossRef CAS 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 70| Part 9| September 2014| Pages 142-144

doi:10.1107/S1600536814017978

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

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)