Crystal structure of (4-(4-chlorophenyl)-5-ethyl-1,3-dioxane-5-carboxylato-κ2O,O′)-(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate, C29H52Cl2N4NiO9

Fang Liu; Guo-Kai Jia; Guang-Chuan Ou

doi:10.1515/ncrs-2018-0095

Open Access Published by De Gruyter (O) August 8, 2018

Crystal structure of (4-(4-chlorophenyl)-5-ethyl-1,3-dioxane-5-carboxylato-κ²O,O′)-(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate, C₂₉H₅₂Cl₂N₄NiO₉

Fang Liu , Guo-Kai Jia and Guang-Chuan Ou

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2018-0095

Abstract

C₂₉H₅₂Cl₂N₄NiO₉, monoclinic, P2₁/n (no. 14), a =10.8347(19) Å, b = 14.502(3) Å, c = 21.731(4) Å, β = 93.344(2)°, V = 3408.6(10) Å³, Z = 4, R_gt(F) = 0.0360, wR_ref(F²) = 0.1009, T = 296(2) K.

CCDC no.: 1569959

The crystal structure is shown in the figure. Hydrogen atoms are omitted for clarity. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Prism, blue
Size:	0.45 × 0.42 × 0.30 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.78 mm⁻¹
Diffractometer, scan mode:	Bruker SMART, φ and ω-scans
θ_max, completeness:	27.5°, >97% (up to 25.2°, >99%)
N(hkl)_measured, N(hkl)_unique, R_int:	37399, 7623, 0.019
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 6625
N(param)_refined:	419
Programs:	Bruker programs [1], SHELX [2], [3]

Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²).

Atom	x	y	z	U_iso*/U_eq
Ni1	0.26359(2)	0.52040(2)	0.16501(2)	0.02486(8)
Cl1	0.82771(6)	0.82560(4)	0.19051(3)	0.05458(16)
Cl2	−0.34104(7)	0.02911(5)	0.00498(4)	0.0705(2)
N1	0.09651(14)	0.51940(11)	0.10828(7)	0.0305(3)
H1C	0.1159	0.4846	0.0714	0.037*
N2	0.27869(14)	0.65691(10)	0.13539(7)	0.0295(3)
H2C	0.2389	0.6962	0.1651	0.035*
N3	0.42254(14)	0.53193(11)	0.22709(7)	0.0294(3)
H3A	0.4565	0.4695	0.2313	0.035*
N4	0.16406(13)	0.53492(10)	0.24460(7)	0.0265(3)
H4D	0.1503	0.6012	0.2499	0.032*
O1	0.29848(12)	0.36685(9)	0.16072(6)	0.0344(3)
O1W	0.34802(17)	0.24713(12)	0.25914(8)	0.0539(4)
H1WB	0.322(2)	0.2800(17)	0.2283(9)	0.065*
H1WA	0.4210(13)	0.2635(19)	0.2701(11)	0.065*
O2	0.34195(13)	0.46143(9)	0.08699(6)	0.0351(3)
O3	0.21761(13)	0.18276(10)	0.08573(6)	0.0397(3)
O4	0.17587(14)	0.28523(10)	0.00549(6)	0.0389(3)
O5	0.7527(2)	0.8441(2)	0.23994(11)	0.0928(7)
O6	0.9437(2)	0.8692(2)	0.19691(14)	0.1018(9)
O7	0.7664(3)	0.8636(4)	0.13739(14)	0.1602(18)
O8	0.8442(4)	0.7349(2)	0.1815(3)	0.203(3)
C1	0.07826(19)	0.61579(15)	0.08696(10)	0.0403(5)
H1A	0.0360	0.6506	0.1175	0.048*
H1B	0.0274	0.6165	0.0487	0.048*
C2	0.2013(2)	0.65943(15)	0.07704(9)	0.0397(5)
H2A	0.2422	0.6263	0.0452	0.048*
H2B	0.1895	0.7228	0.0636	0.048*
C3	0.40550(18)	0.69357(13)	0.12869(9)	0.0335(4)
H3	0.4454	0.6557	0.0982	0.040*
C4	0.4040(2)	0.79333(16)	0.10613(12)	0.0501(6)
H4A	0.3595	0.7969	0.0667	0.075*
H4B	0.4873	0.8142	0.1024	0.075*
H4C	0.3642	0.8316	0.1351	0.075*
C5	0.48196(19)	0.68724(14)	0.18932(9)	0.0362(4)
H5A	0.4328	0.7123	0.2213	0.043*
H5B	0.5532	0.7272	0.1865	0.043*
C6	0.52901(17)	0.59238(14)	0.21085(9)	0.0341(4)
C7	0.59570(19)	0.54337(16)	0.16040(11)	0.0437(5)
H7A	0.6347	0.4886	0.1769	0.066*
H7B	0.6573	0.5836	0.1451	0.066*
H7C	0.5372	0.5271	0.1273	0.066*
C8	0.62207(19)	0.60658(18)	0.26621(11)	0.0472(5)
H8A	0.5863	0.6459	0.2959	0.071*
H8B	0.6959	0.6346	0.2525	0.071*
H8C	0.6422	0.5480	0.2848	0.071*
C9	0.37464(17)	0.55461(15)	0.28784(9)	0.0351(4)
H9A	0.3634	0.6208	0.2911	0.042*
H9B	0.4340	0.5354	0.3205	0.042*
C10	0.25306(17)	0.50647(15)	0.29512(9)	0.0340(4)
H10A	0.2648	0.4402	0.2940	0.041*
H10B	0.2213	0.5225	0.3345	0.041*
C11	0.04105(17)	0.48930(13)	0.24930(9)	0.0316(4)
H11	0.0537	0.4224	0.2503	0.038*
C12	−0.0210(2)	0.51756(18)	0.30777(10)	0.0472(5)
H12A	0.0344	0.5062	0.3431	0.071*
H12B	−0.0952	0.4823	0.3112	0.071*
H12C	−0.0411	0.5820	0.3058	0.071*
C13	−0.04677(17)	0.51258(14)	0.19390(9)	0.0336(4)
H13A	−0.0513	0.5792	0.1907	0.040*
H13B	−0.1285	0.4910	0.2029	0.040*
C14	−0.01813(17)	0.47499(14)	0.13036(9)	0.0343(4)
C15	−0.1293(2)	0.4952(2)	0.08481(11)	0.0511(6)
H15A	−0.1509	0.5592	0.0872	0.077*
H15B	−0.1985	0.4581	0.0952	0.077*
H15C	−0.1078	0.4808	0.0437	0.077*
C16	0.0032(2)	0.37139(16)	0.13215(12)	0.0488(5)
H16A	0.0133	0.3492	0.0911	0.073*
H16B	−0.0667	0.3416	0.1488	0.073*
H16C	0.0763	0.3580	0.1577	0.073*
C17	0.33519(16)	0.38038(13)	0.10742(8)	0.0295(4)
C18	0.37371(18)	0.30143(13)	0.06555(9)	0.0333(4)
C19	0.5133(2)	0.31096(17)	0.05644(12)	0.0490(5)
H19A	0.5352	0.2690	0.0241	0.059*
H19B	0.5295	0.3732	0.0426	0.059*
C20	0.5958(2)	0.2913(2)	0.11373(15)	0.0651(7)
H20A	0.5715	0.3297	0.1469	0.098*
H20B	0.6802	0.3042	0.1055	0.098*
H20C	0.5880	0.2277	0.1250	0.098*
C21	0.34589(19)	0.20577(14)	0.09103(10)	0.0377(4)
H21A	0.3917	0.1601	0.0691	0.045*
H21B	0.3745	0.2033	0.1341	0.045*
C22	0.3028(2)	0.31099(16)	0.00260(9)	0.0407(5)
H22A	0.3076	0.3744	−0.0113	0.049*
H22B	0.3413	0.2722	−0.0272	0.049*
C23	0.1700(2)	0.19155(14)	0.02419(9)	0.0377(4)
H23	0.2203	0.1543	−0.0024	0.045*
C24	0.0396(2)	0.15631(14)	0.01918(9)	0.0379(4)
C25	−0.0079(2)	0.11880(17)	−0.03608(11)	0.0491(5)
H25	0.0396	0.1195	−0.0704	0.059*
C26	−0.1247(2)	0.08056(18)	−0.04062(12)	0.0551(6)
H26	−0.1558	0.0556	−0.0778	0.066*
C27	−0.1944(2)	0.07955(15)	0.00986(12)	0.0462(5)
C28	−0.1507(2)	0.11636(17)	0.06520(12)	0.0497(5)
H28	−0.1990	0.1158	0.0992	0.060*
C29	−0.0330(2)	0.15441(16)	0.06931(10)	0.0445(5)
H29	−0.0025	0.1792	0.1066	0.053*

Source of material

An acetonitrile solution (20 mL) of [NiL](ClO₄)₂ (0.270 g, 0.5 mmol) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) was added to a solution of 4-(4-chlorophenyl)-5-ethyl-1,3-dioxane-5-carboxylic acid (0.270 g, 1.0 mmol) and NaOH (0.04 g, 1.0 mmol) in the minimum amount of water. After a few days, blue crystals were separated in ∼32% yield. Anal. Calcd. for C₂₉H₅₂Cl₂N₄NiO₉: C, 47.69; H, 7.17; N, 7.67%. Found: C, 47.25; H, 7.51; N, 7.89%. IR data (cm⁻¹, KBr): 3456(m), 3209(s), 2962(m), 1545(s), 1450(s), 1090(s).

Experimental details

All the hydrogen atoms of the ligands were placed in calculated positions with fixed isotropic thermal parameters and included in the final stage of refinement. The U_iso (H) values of methyl groups were set to 1.5U_eq(C) and the U_iso values of all other hydrogen atoms were set to 1.2U_eq(C, N).

Discussion

Ketal compounds are subjects of great interest because they are usually used as a protection of carbonyl or synthetic intermediates [4], and have been widely applied in fragrance and flavors as well as a new type of spices.

X-ray crystal structural analysis reveals that the title compound contains one complex cation [Ni(C₁₆H₃₆N₄)(C₁₃H₁₄O₄Cl)]⁺, one anion [ClO₄]⁻, and one water molecule. Each Ni(II) ion lies on a general position of the monoclinic space group and is coordinated by four macrocyclic nitrogen atoms of L in a folded conformation and two carboxylate oxygen atoms of the anionic 4-(chlorophenyl)-5-ethyl-1,3-dioxane-5-carboxylato ligand. The Ni-N bond lengths [2.090(6)–2.131(6) Å] are slightly shorter than the Ni-O bond lengths [2.120(4) and 2.261(4) Å]. Neighbouring cations and anions are discrete, connected to each other through hydrogen bonds between the carboxylate oxygen atom of 4-(chlorophenyl)-5-ethyl-1,3-dioxane-5-carboxylato ligand and water and nitrogen atom of adjacent cation, forming a one-dimensional chain.

Acknowledgements

This work was financially Supported by the NSFC (51772091), the Scientific Research Fund of Hunan Education Department (17A081) and the Science and Technology Innovative plan of Hunan (2017).

References

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Received: 2018-05-22

Accepted: 2018-07-26

Published Online: 2018-08-08

Published in Print: 2018-11-27

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.