Hexa-μ-acetato-1:2κ4O,O′;1:2κ2O:O;2:3κ4O,O′;2:3κ2O:O-bis­(4,4′-dimethyl-2,2′-bi­pyridine)-1κ2N,N′;3κ2N,N′-2-calcium-1,3-dizinc

Pramanik, A.; Fronczek, F.R.; Venkatraman, R.; Hossain, M.A.

doi:10.1107/S1600536813030122

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages m643-m644

doi:10.1107/S1600536813030122

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Hexa-μ-acetato-1:2κ⁴O,O′;1:2κ²O:O;2:3κ⁴O,O′;2:3κ²O:O-bis(4,4′-dimethyl-2,2′-bipyridine)-1κ²N,N′;3κ²N,N′-2-calcium-1,3-dizinc

Avijit Pramanik,^a Frank R. Fronczek,^b Ramaiyer Venkatraman ^a and Md. Alamgir Hossain ^a ^*

^aDepartment of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: alamgir.hossain@jsums.edu

(Received 16 October 2013; accepted 3 November 2013; online 9 November 2013)

In the centrosymmetric trinuclear Zn^II⋯Ca^II⋯Zn^II title complex, [CaZn₂(CH₃COO)₆(C₁₂H₁₂N₂)₂], the Ca^II ion lies on an inversion centre and is octahedrally coordinated by six acetate O atoms. The Zn^II ion is coordinated by two N atoms from a bidentate dimethylbipyridine ligand and three O atoms from acetate ligands bridging to the Ca^II ion, leading to a distorted square-pyramidal coordination sphere. The Zn⋯Ca distance is 3.4668 (5) Å.

CCDC reference: 969906

Related literature

For a review of the coordination chemistry of metal carboxylates, see: Rao et al. (2004 ). For applications of metal complexes in anion binding, see: Saeed et al. (2010 ); Mendy et al. (2010 ). For multimetallic complexes involving azide, cyanide, isocyanate, isothiocyanate, hydroxide, oxide and carboxylate anions, see: Herold & Lippard (1997 ). For coordination modes of carboxylate ions acting as bidentate ligands in metalloenzymes, see: Voegtli et al. (2000 ). For details of the synthesis, see: Hossain et al. (2010 ).

Experimental

Crystal data

[CaZn₂(C₂H₃O₂)₆(C₁₂H₁₂N₂)₂]
M_r = 893.56
Triclinic, $[P \overline 1]$
a = 8.3356 (10) Å
b = 8.841 (1) Å
c = 13.696 (2) Å
α = 74.103 (7)°
β = 83.263 (6)°
γ = 83.560 (7)°
V = 960.6 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 100 K
0.34 × 0.32 × 0.27 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.639, T_max = 0.699
16096 measured reflections
8962 independent reflections
7497 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.086
S = 1.05
8962 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 969906

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813030122/fj2647sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030122/fj2647Isup2.hkl

checkCIF report

Comment top

Multimetallic coordination complexes have many practical applications in a number of areas including molecular magnetism, crystal engineering, catalysis, gas storage, ion exchange, nonlinear optics, and biomimetic materials (Rao et al., 2004). In general, multimetallic complexes invoves azido, cyano, isocyanate, isothiocyanate, hydroxo, oxo and carboxylate ions (Herold & Lippard, 1997). Multimetallic complexation is also important in many biological systems; for example, in metalloenzymes where carboxylate ions serve as bidentate ligands showing three different coordination modes: syn-syn, syn-anti and anti-anti (Voegtli et al., 2000). However, as compared to traditional mononuclear metal complexes, the chemistry of multimetallic complexes with well established structures is much under developed. In our continuing interests in dinuclear metal complexes (Saeed et al., 2010; Mendy, et al., 2010) for anion binding, we attempted to obtain zinc complex of mixed ligands with 4,4'dimethyl-2,2'-bipyridine and hexa N-substituted (p-cyano benzamido) para xylyl based octa-aza cryptand. However, single-crystal structure analysis reveals the formation of the title compound. The source of calcium could be a contaminant from the reagents used for this reaction. Herein, we present a structural characterization of 4,4'-dimethyl-2,2'-bipyridine coordinated heterotrinuclear Zn^II—Ca^II—Zn^II hexa-carboxylate complex.

The heteronuclear complex is crystallized in triclinic P-1 space group, with one calcium ion, two zinc ions, six acetate and two 4,4'-dimethyl-2,2'-bipyridine groups. As can be seen in Figure 1, one calcium ion is located at the center surrounded by two zinc ions and six acetate ions. Two zinc ions from opposite sides are linearly coordinated with the central calcium ion forming trinuclear Zn^II–Ca^II–Zn^II backbone, while six acetate ions are coordinated with six Ca–O bonds. In addition, each zinc is hexacoordinated with two N atoms from one bipyridine and four O atoms from four six acetates, forming a centrosymmetric complex. In the complex, four acetates serve as bidentate ligands to coordinate with both calcium and zinc ions, while each of other two serves as a monodentate ligand for a single zinc ion. Both Ca^II and Zn^II ions are connected by two pairs of carboxylate ligands in syn±syn, and syn±anti bridging modes (Voegtli et al., 2000). Another pair of carboxylates is coordinated with one Ca^II ion and two Zn^II via (O,O') bridges. The distorted square pyramidal geometry around the Zn^II ion is completed by the coordination of N atoms of 4,4'-dimethyl-2,2'-bipyridine.

Related literature top

For a review of the coordination chemistry of metal carboxylates, see: Rao et al.(2004). For applications of metal complexes in anion binding, see Saeed et al. (2010); Mendy et al. (2010). In general, multimetallic complexes invoves azido,

cyano, isocyanate, isothiocyanate, hydroxo, oxo and carboxylate ions, see: Herold & Lippard (1997). For coordination modes of carboxylate ions acting as bidentate ligands in metalloenzymes, see: Voegtli et al. (2000). For details of the synthesis, see: Hossain et al. (2010);

Experimental top

4,4'-dimethyl-2,2'-bipyridine (0.5 g, 2.71 mmol) and zinc acetate (0.9 g, 4.1 mmol) of was added to hexa N-substituted (p-cyano benzamido) para xylyl based octa-aza cryptand (0.15 g) in 20 mL of ethanol-water (1:1, v/v) mixture at room temperature (Hossain et al., 2010). The mixture was further diluted with 10 mL DMSO solvent with constant stirring. Only a few crystals were grown after a week, which was characterized by single-crystal diffraction method. Further analysis was not possible because of the small quantity of the product.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP drawings of the crystal structure and atomic numbering scheme of trinuclear Zn^II—Ca^II—Zn^II complex. Ellipsoids are set at the 50% probability level.

Hexa-µ-acetato-1:2κ⁴O,O';1:2κ²O:O;2:3κ⁴O,O';2:3κ²O:O-bis(4,4'-dimethyl-2,2'-bipyridine)-1κ²N,N';3κ²N,N'-2-calcium-1,3-dizinc top

Crystal data top

[CaZn₂(C₂H₃O₂)₆(C₁₂H₁₂N₂)₂]	Z = 1
M_r = 893.56	F(000) = 462
Triclinic, P1	D_x = 1.545 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3356 (10) Å	Cell parameters from 7990 reflections
b = 8.841 (1) Å	θ = 2.5–36.7°
c = 13.696 (2) Å	µ = 1.45 mm⁻¹
α = 74.103 (7)°	T = 100 K
β = 83.263 (6)°	Parallelepiped, colorless
γ = 83.560 (7)°	0.34 × 0.32 × 0.27 mm
V = 960.6 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	8962 independent reflections
Radiation source: fine-focus sealed tube	7497 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and ϕ scans	θ_max = 36.7°, θ_min = 3.0°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −13→13
T_min = 0.639, T_max = 0.699	k = −14→14
16096 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0386P)² + 0.3887P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
8962 reflections	Δρ_max = 0.65 e Å⁻³
256 parameters	Δρ_min = −0.78 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (13)

Crystal data top

[CaZn₂(C₂H₃O₂)₆(C₁₂H₁₂N₂)₂]	γ = 83.560 (7)°
M_r = 893.56	V = 960.6 (2) Å³
Triclinic, P1	Z = 1
a = 8.3356 (10) Å	Mo Kα radiation
b = 8.841 (1) Å	µ = 1.45 mm⁻¹
c = 13.696 (2) Å	T = 100 K
α = 74.103 (7)°	0.34 × 0.32 × 0.27 mm
β = 83.263 (6)°

Data collection top

Nonius KappaCCD diffractometer	8962 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	7497 reflections with I > 2σ(I)
T_min = 0.639, T_max = 0.699	R_int = 0.025
16096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	Δρ_max = 0.65 e Å⁻³
8962 reflections	Δρ_min = −0.78 e Å⁻³
256 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
Zn1	0.645512 (17)	0.565205 (16)	0.245482 (10)	0.01344 (4)
Ca1	0.5000	0.5000	0.5000	0.01472 (6)
O1	0.42917 (11)	0.57148 (11)	0.33397 (7)	0.01780 (16)
O2	0.36225 (13)	0.71366 (13)	0.18192 (8)	0.02391 (19)
O3	0.83825 (11)	0.42210 (11)	0.30301 (7)	0.01864 (16)
O4	0.69345 (13)	0.32456 (12)	0.45013 (8)	0.02265 (18)
O5	0.71692 (12)	0.76819 (11)	0.26269 (7)	0.01935 (17)
O6	0.68069 (13)	0.68704 (12)	0.43296 (7)	0.02151 (18)
N1	0.73039 (13)	0.60239 (13)	0.09209 (8)	0.01657 (18)
N2	0.56062 (13)	0.37004 (12)	0.20333 (8)	0.01583 (17)
C1	0.81557 (16)	0.72407 (16)	0.04117 (10)	0.0197 (2)
H1	0.8270	0.8035	0.0740	0.024*
C2	0.88835 (16)	0.73989 (19)	−0.05764 (10)	0.0240 (3)
C3	0.87138 (17)	0.62079 (19)	−0.10347 (10)	0.0252 (3)
H3	0.9215	0.6255	−0.1701	0.030*
C4	0.78117 (17)	0.49493 (18)	−0.05182 (10)	0.0222 (2)
H4	0.7676	0.4143	−0.0832	0.027*
C5	0.71088 (15)	0.48875 (15)	0.04678 (9)	0.0172 (2)
C6	0.61311 (15)	0.35900 (15)	0.10892 (9)	0.0169 (2)
C7	0.57756 (16)	0.23203 (17)	0.07454 (11)	0.0218 (2)
H7	0.6131	0.2261	0.0071	0.026*
C8	0.48959 (17)	0.11521 (16)	0.14069 (12)	0.0232 (3)
H8	0.4667	0.0273	0.1189	0.028*
C9	0.43442 (15)	0.12613 (15)	0.23931 (11)	0.0196 (2)
C10	0.47342 (15)	0.25801 (14)	0.26603 (10)	0.0176 (2)
H10	0.4362	0.2690	0.3322	0.021*
C11	0.9812 (2)	0.8811 (2)	−0.11066 (13)	0.0346 (4)
H11A	1.0352	0.8670	−0.1755	0.052*
H11B	1.0625	0.8915	−0.0673	0.052*
H11C	0.9061	0.9765	−0.1237	0.052*
C12	0.34091 (18)	0.00266 (16)	0.31539 (13)	0.0256 (3)
H12A	0.3132	0.0348	0.3787	0.038*
H12B	0.4074	−0.0983	0.3295	0.038*
H12C	0.2413	−0.0090	0.2876	0.038*
C13	0.32312 (15)	0.64702 (15)	0.27164 (10)	0.0181 (2)
C14	0.14820 (17)	0.6467 (2)	0.31439 (13)	0.0278 (3)
H14A	0.0848	0.7359	0.2725	0.042*
H14B	0.1400	0.6562	0.3845	0.042*
H14C	0.1060	0.5478	0.3141	0.042*
C15	0.82225 (15)	0.33229 (14)	0.39256 (10)	0.0172 (2)
C16	0.97115 (18)	0.22946 (17)	0.43100 (12)	0.0258 (3)
H16A	1.0392	0.2906	0.4569	0.039*
H16B	1.0326	0.1928	0.3751	0.039*
H16C	0.9382	0.1383	0.4860	0.039*
C17	0.71988 (15)	0.78611 (14)	0.35138 (10)	0.0168 (2)
C18	0.77759 (17)	0.93922 (15)	0.35734 (11)	0.0211 (2)
H18A	0.7256	0.9663	0.4190	0.032*
H18B	0.7491	1.0235	0.2972	0.032*
H18C	0.8955	0.9271	0.3597	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01502 (6)	0.01454 (7)	0.01144 (6)	−0.00042 (4)	−0.00181 (4)	−0.00464 (4)
Ca1	0.01700 (14)	0.01496 (13)	0.01184 (13)	−0.00157 (10)	−0.00028 (10)	−0.00328 (10)
O1	0.0157 (4)	0.0207 (4)	0.0197 (4)	0.0005 (3)	−0.0035 (3)	−0.0098 (3)
O2	0.0267 (5)	0.0276 (5)	0.0201 (4)	−0.0007 (4)	−0.0052 (4)	−0.0103 (4)
O3	0.0182 (4)	0.0205 (4)	0.0170 (4)	0.0008 (3)	−0.0045 (3)	−0.0043 (3)
O4	0.0236 (4)	0.0183 (4)	0.0232 (5)	−0.0002 (3)	0.0002 (4)	−0.0024 (3)
O5	0.0234 (4)	0.0193 (4)	0.0172 (4)	−0.0026 (3)	−0.0031 (3)	−0.0072 (3)
O6	0.0267 (5)	0.0201 (4)	0.0180 (4)	−0.0057 (3)	−0.0054 (3)	−0.0026 (3)
N1	0.0152 (4)	0.0210 (5)	0.0138 (4)	0.0009 (3)	−0.0031 (3)	−0.0053 (3)
N2	0.0169 (4)	0.0158 (4)	0.0168 (4)	0.0015 (3)	−0.0045 (3)	−0.0076 (3)
C1	0.0180 (5)	0.0246 (6)	0.0152 (5)	−0.0017 (4)	−0.0014 (4)	−0.0032 (4)
C2	0.0177 (5)	0.0345 (7)	0.0161 (5)	0.0009 (5)	−0.0013 (4)	−0.0017 (5)
C3	0.0210 (6)	0.0391 (8)	0.0132 (5)	0.0048 (5)	−0.0015 (4)	−0.0058 (5)
C4	0.0209 (5)	0.0320 (7)	0.0149 (5)	0.0056 (5)	−0.0042 (4)	−0.0104 (5)
C5	0.0159 (5)	0.0235 (5)	0.0137 (5)	0.0044 (4)	−0.0050 (4)	−0.0080 (4)
C6	0.0154 (5)	0.0209 (5)	0.0166 (5)	0.0041 (4)	−0.0061 (4)	−0.0091 (4)
C7	0.0212 (6)	0.0259 (6)	0.0234 (6)	0.0042 (5)	−0.0075 (5)	−0.0152 (5)
C8	0.0211 (6)	0.0225 (6)	0.0322 (7)	0.0032 (4)	−0.0095 (5)	−0.0166 (5)
C9	0.0166 (5)	0.0166 (5)	0.0281 (6)	0.0024 (4)	−0.0072 (4)	−0.0097 (4)
C10	0.0171 (5)	0.0166 (5)	0.0211 (5)	0.0007 (4)	−0.0039 (4)	−0.0081 (4)
C11	0.0299 (7)	0.0446 (9)	0.0227 (7)	−0.0096 (7)	0.0040 (6)	0.0022 (6)
C12	0.0218 (6)	0.0177 (5)	0.0392 (8)	−0.0020 (4)	−0.0039 (5)	−0.0102 (5)
C13	0.0159 (5)	0.0188 (5)	0.0241 (6)	−0.0008 (4)	−0.0039 (4)	−0.0129 (4)
C14	0.0143 (5)	0.0355 (7)	0.0371 (8)	−0.0019 (5)	−0.0008 (5)	−0.0160 (6)
C15	0.0204 (5)	0.0133 (5)	0.0189 (5)	0.0013 (4)	−0.0063 (4)	−0.0053 (4)
C16	0.0263 (6)	0.0225 (6)	0.0279 (7)	0.0090 (5)	−0.0108 (5)	−0.0066 (5)
C17	0.0168 (5)	0.0155 (5)	0.0195 (5)	0.0000 (4)	−0.0049 (4)	−0.0063 (4)
C18	0.0259 (6)	0.0165 (5)	0.0234 (6)	−0.0039 (4)	−0.0062 (5)	−0.0067 (4)

Geometric parameters (Å, º) top

Zn1—O3	2.0243 (10)	C4—C5	1.3968 (18)
Zn1—O5	2.0334 (10)	C4—H4	0.9500
Zn1—O1	2.0556 (10)	C5—C6	1.4887 (19)
Zn1—N1	2.0851 (11)	C6—C7	1.4023 (18)
Zn1—N2	2.1741 (10)	C7—C8	1.388 (2)
Zn1—Ca1	3.4668 (5)	C7—H7	0.9500
Ca1—O4ⁱ	2.2876 (10)	C8—C9	1.400 (2)
Ca1—O4	2.2876 (10)	C8—H8	0.9500
Ca1—O6ⁱ	2.2910 (10)	C9—C10	1.3949 (17)
Ca1—O6	2.2910 (10)	C9—C12	1.504 (2)
Ca1—O1	2.3158 (10)	C10—H10	0.9500
Ca1—O1ⁱ	2.3158 (10)	C11—H11A	0.9800
Ca1—Zn1ⁱ	3.4668 (5)	C11—H11B	0.9800
O1—C13	1.2994 (16)	C11—H11C	0.9800
O2—C13	1.2313 (17)	C12—H12A	0.9800
O3—C15	1.2666 (15)	C12—H12B	0.9800
O4—C15	1.2520 (17)	C12—H12C	0.9800
O5—C17	1.2706 (15)	C13—C14	1.5061 (19)
O6—C17	1.2509 (16)	C14—H14A	0.9800
N1—C1	1.3386 (17)	C14—H14B	0.9800
N1—C5	1.3502 (16)	C14—H14C	0.9800
N2—C10	1.3401 (17)	C15—C16	1.5106 (18)
N2—C6	1.3415 (16)	C16—H16A	0.9800
C1—C2	1.3935 (19)	C16—H16B	0.9800
C1—H1	0.9500	C16—H16C	0.9800
C2—C3	1.393 (2)	C17—C18	1.5121 (17)
C2—C11	1.507 (2)	C18—H18A	0.9800
C3—C4	1.391 (2)	C18—H18B	0.9800
C3—H3	0.9500	C18—H18C	0.9800

O3—Zn1—O5	96.76 (4)	N2—C6—C5	114.92 (10)
O3—Zn1—O1	120.20 (4)	C7—C6—C5	124.11 (11)
O5—Zn1—O1	95.68 (4)	C8—C7—C6	118.89 (12)
O3—Zn1—N1	96.90 (4)	C8—C7—H7	120.6
O5—Zn1—N1	96.21 (4)	C6—C7—H7	120.6
O1—Zn1—N1	139.18 (4)	C7—C8—C9	120.39 (12)
O3—Zn1—N2	89.55 (4)	C7—C8—H8	119.8
O5—Zn1—N2	171.01 (4)	C9—C8—H8	119.8
O1—Zn1—N2	86.60 (4)	C10—C9—C8	116.57 (13)
N1—Zn1—N2	76.62 (4)	C10—C9—C12	120.25 (13)
O4ⁱ—Ca1—O4	180.0	C8—C9—C12	123.17 (12)
O4ⁱ—Ca1—O6ⁱ	86.56 (4)	N2—C10—C9	123.49 (12)
O4—Ca1—O6ⁱ	93.44 (4)	N2—C10—H10	118.3
O4ⁱ—Ca1—O6	93.44 (4)	C9—C10—H10	118.3
O4—Ca1—O6	86.56 (4)	C2—C11—H11A	109.5
O6ⁱ—Ca1—O6	180.0	C2—C11—H11B	109.5
O4ⁱ—Ca1—O1	93.28 (4)	H11A—C11—H11B	109.5
O4—Ca1—O1	86.72 (4)	C2—C11—H11C	109.5
O6ⁱ—Ca1—O1	97.73 (3)	H11A—C11—H11C	109.5
O6—Ca1—O1	82.27 (3)	H11B—C11—H11C	109.5
O4ⁱ—Ca1—O1ⁱ	86.72 (4)	C9—C12—H12A	109.5
O4—Ca1—O1ⁱ	93.28 (4)	C9—C12—H12B	109.5
O6ⁱ—Ca1—O1ⁱ	82.27 (3)	H12A—C12—H12B	109.5
O6—Ca1—O1ⁱ	97.73 (3)	C9—C12—H12C	109.5
O1—Ca1—O1ⁱ	179.999 (17)	H12A—C12—H12C	109.5
C13—O1—Zn1	105.63 (8)	H12B—C12—H12C	109.5
C13—O1—Ca1	146.51 (8)	O2—C13—O1	122.19 (12)
Zn1—O1—Ca1	104.79 (4)	O2—C13—C14	121.36 (13)
C15—O3—Zn1	119.31 (8)	O1—C13—C14	116.44 (12)
C15—O4—Ca1	136.47 (8)	C13—C14—H14A	109.5
C17—O5—Zn1	120.05 (8)	C13—C14—H14B	109.5
C17—O6—Ca1	140.65 (8)	H14A—C14—H14B	109.5
C1—N1—C5	119.60 (11)	C13—C14—H14C	109.5
C1—N1—Zn1	122.94 (9)	H14A—C14—H14C	109.5
C5—N1—Zn1	117.12 (9)	H14B—C14—H14C	109.5
C10—N2—C6	119.69 (11)	O4—C15—O3	124.57 (12)
C10—N2—Zn1	125.10 (8)	O4—C15—C16	118.87 (12)
C6—N2—Zn1	115.00 (9)	O3—C15—C16	116.56 (12)
N1—C1—C2	123.20 (13)	C15—C16—H16A	109.5
N1—C1—H1	118.4	C15—C16—H16B	109.5
C2—C1—H1	118.4	H16A—C16—H16B	109.5
C3—C2—C1	117.19 (13)	C15—C16—H16C	109.5
C3—C2—C11	122.54 (13)	H16A—C16—H16C	109.5
C1—C2—C11	120.27 (14)	H16B—C16—H16C	109.5
C4—C3—C2	120.09 (12)	O6—C17—O5	125.19 (11)
C4—C3—H3	120.0	O6—C17—C18	118.20 (11)
C2—C3—H3	120.0	O5—C17—C18	116.61 (11)
C3—C4—C5	119.08 (13)	C17—C18—H18A	109.5
C3—C4—H4	120.5	C17—C18—H18B	109.5
C5—C4—H4	120.5	H18A—C18—H18B	109.5
N1—C5—C4	120.82 (13)	C17—C18—H18C	109.5
N1—C5—C6	115.76 (10)	H18A—C18—H18C	109.5
C4—C5—C6	123.42 (12)	H18B—C18—H18C	109.5
N2—C6—C7	120.96 (12)

O3—Zn1—O1—C13	−167.59 (7)	O1—Zn1—N2—C6	148.38 (9)
O5—Zn1—O1—C13	91.19 (8)	N1—Zn1—N2—C6	5.87 (8)
N1—Zn1—O1—C13	−15.15 (11)	C5—N1—C1—C2	−0.71 (19)
N2—Zn1—O1—C13	−80.09 (8)	Zn1—N1—C1—C2	172.43 (10)
Ca1—Zn1—O1—C13	165.81 (10)	N1—C1—C2—C3	−0.8 (2)
O3—Zn1—O1—Ca1	26.60 (5)	N1—C1—C2—C11	179.41 (13)
O5—Zn1—O1—Ca1	−74.63 (4)	C1—C2—C3—C4	1.7 (2)
N1—Zn1—O1—Ca1	179.04 (5)	C11—C2—C3—C4	−178.52 (14)
N2—Zn1—O1—Ca1	114.10 (4)	C2—C3—C4—C5	−1.1 (2)
O4ⁱ—Ca1—O1—C13	−12.60 (15)	C1—N1—C5—C4	1.28 (18)
O4—Ca1—O1—C13	167.40 (15)	Zn1—N1—C5—C4	−172.25 (9)
O6ⁱ—Ca1—O1—C13	74.37 (15)	C1—N1—C5—C6	−179.45 (11)
O6—Ca1—O1—C13	−105.63 (15)	Zn1—N1—C5—C6	7.02 (13)
O4ⁱ—Ca1—O1—Zn1	142.08 (4)	C3—C4—C5—N1	−0.37 (19)
O4—Ca1—O1—Zn1	−37.92 (4)	C3—C4—C5—C6	−179.58 (11)
O6ⁱ—Ca1—O1—Zn1	−130.95 (4)	C10—N2—C6—C7	0.24 (17)
O6—Ca1—O1—Zn1	49.05 (4)	Zn1—N2—C6—C7	175.22 (9)
O5—Zn1—O3—C15	103.30 (9)	C10—N2—C6—C5	−179.08 (10)
O1—Zn1—O3—C15	2.69 (10)	Zn1—N2—C6—C5	−4.10 (13)
N1—Zn1—O3—C15	−159.58 (9)	N1—C5—C6—N2	−1.71 (15)
N2—Zn1—O3—C15	−83.12 (9)	C4—C5—C6—N2	177.54 (11)
O6ⁱ—Ca1—O4—C15	165.69 (13)	N1—C5—C6—C7	178.99 (11)
O6—Ca1—O4—C15	−14.31 (13)	C4—C5—C6—C7	−1.76 (19)
O1—Ca1—O4—C15	68.13 (13)	N2—C6—C7—C8	−1.36 (18)
O1ⁱ—Ca1—O4—C15	−111.87 (13)	C5—C6—C7—C8	177.90 (12)
O3—Zn1—O5—C17	−68.30 (10)	C6—C7—C8—C9	1.38 (19)
O1—Zn1—O5—C17	53.08 (10)	C7—C8—C9—C10	−0.33 (19)
N1—Zn1—O5—C17	−166.04 (10)	C7—C8—C9—C12	−178.98 (12)
O4ⁱ—Ca1—O6—C17	−89.17 (14)	C6—N2—C10—C9	0.90 (18)
O4—Ca1—O6—C17	90.83 (14)	Zn1—N2—C10—C9	−173.54 (9)
O1—Ca1—O6—C17	3.67 (14)	C8—C9—C10—N2	−0.85 (18)
O1ⁱ—Ca1—O6—C17	−176.33 (14)	C12—C9—C10—N2	177.85 (12)
O3—Zn1—N1—C1	−92.32 (10)	Zn1—O1—C13—O2	−8.12 (14)
O5—Zn1—N1—C1	5.29 (10)	Ca1—O1—C13—O2	146.45 (12)
O1—Zn1—N1—C1	111.43 (10)	Zn1—O1—C13—C14	170.85 (9)
N2—Zn1—N1—C1	179.79 (11)	Ca1—O1—C13—C14	−34.6 (2)
O3—Zn1—N1—C5	80.97 (9)	Ca1—O4—C15—O3	−47.00 (19)
O5—Zn1—N1—C5	178.58 (9)	Ca1—O4—C15—C16	132.51 (12)
O1—Zn1—N1—C5	−75.27 (11)	Zn1—O3—C15—O4	−0.07 (17)
N2—Zn1—N1—C5	−6.91 (8)	Zn1—O3—C15—C16	−179.59 (9)
O3—Zn1—N2—C10	83.33 (10)	Ca1—O6—C17—O5	−35.1 (2)
O1—Zn1—N2—C10	−36.95 (10)	Ca1—O6—C17—C18	145.71 (11)
N1—Zn1—N2—C10	−179.46 (10)	Zn1—O5—C17—O6	−0.38 (18)
O3—Zn1—N2—C6	−91.33 (9)	Zn1—O5—C17—C18	178.85 (8)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[CaZn₂(C₂H₃O₂)₆(C₁₂H₁₂N₂)₂]
M_r	893.56
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.3356 (10), 8.841 (1), 13.696 (2)
α, β, γ (°)	74.103 (7), 83.263 (6), 83.560 (7)
V (Å³)	960.6 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.34 × 0.32 × 0.27

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.639, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	16096, 8962, 7497
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.841

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.086, 1.05
No. of reflections	8962
No. of parameters	256
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.78

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Acknowledgements

The National Science Foundation is acknowledged for a CAREER award (CHE-1056927) to MAH. The NMR core facility at Jackson State University is supported by the National Institutes of Health (G12RR013459). Purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

References

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