(2-Carb­oxy­acetato-κ2O1,O1′)(rac-5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N,N′,N′′,N′′′)nickel(II) perchlorate acetonitrile solvate

Ou, G.-C.; Ng, S.W.

doi:10.1107/S1600536810042637

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1468

https://doi.org/10.1107/S1600536810042637

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(2-Carboxyacetato-κ²O¹,O^1′)(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N,N′,N′′,N′′′)nickel(II) perchlorate acetonitrile solvate

Guang-Chuan Ou ^a and Seik Weng Ng ^b ^*

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 18 October 2010; accepted 20 October 2010; online 30 October 2010)

In the crystal structure of the title salt, [Ni(C₃H₃O₄)(C₁₆H₃₆N₄)]ClO₄·CH₃CN, the macrocycle folds around the Ni^II atom, which is also chelated by the carboxylate monoanion. The geometry is a distorted NiN₄O₂ octahedron. The formula units are connected by N—H⋯O hydrogen bonds into centrosymmetric dimers. Further N—H⋯O and O—H⋯O hydrogen bonds link the complex molecules and the perchlorate ions.

Related literature

For three related structures, see: Jiang et al. (2005 ); Ou, Zhang & Yuan (2009 ); Ou, Zhou & Ng (2009 ).

Experimental

Crystal data

[Ni(C₃H₃O₄)(C₁₆H₃₆N₄)]ClO₄·C₂H₃N
M_r = 586.76
Triclinic, $[P \overline 1]$
a = 9.5236 (4) Å
b = 10.1766 (4) Å
c = 15.3372 (6) Å
α = 92.899 (1)°
β = 107.388 (1)°
γ = 106.516 (1)°
V = 1344.99 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 173 K
0.45 × 0.40 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.695, T_max = 0.845
11181 measured reflections
5701 independent reflections
4946 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.090
S = 1.03
5701 reflections
330 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3o⋯O1ⁱ	0.83 (1)	1.84 (1)	2.669 (2)	173 (3)
N1—H1⋯O4ⁱ	0.88	2.19	3.038 (2)	161
N2—H2⋯O5	0.88	2.21	3.052 (2)	160
N3—H3⋯O6ⁱⁱ	0.88	2.44	3.291 (2)	163
N4—H4⋯O7	0.88	2.24	3.080 (2)	161
Symmetry codes: (i) -x+1, -y, -z; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810042637/bt5383sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042637/bt5383Isup2.hkl

checkCIF report

Comment top

We have reported adducts of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane with nickel carboxylates; in the synthesis, the perchlorate counterion reactant is sometimes incorporated into the crystal structure, so that the macrocycle-chelated entity is formally a mono-cation. When a dicarboxylic acid is used, only one carboxylic acid –CO₂H end is deprotonated, as noted in the butenoate (Jiang et al., 2005), phthalate (Ou, Zhang & Yuan, 2009) and malate (Ou, Zhou & Ng, 2009) salts. In Ni(C₁₆H₃₆N₄)(C₃H₃O₄)^+.ClO₄^-.CH₃CN (Scheme I), the macrocycle folds around the nickel(II) atom, which is also chelated by the carboxylate monoanion. The geometry is an NiN₄O₂ octahedron (Fig. 1). Adjacent cations and anions are linked by N–H···O hydrogen bonds to form a centrosymmetric dimer (Table 1). The acetonitrile molecule does not engage in any interaction.

Related literature top

For three related structures, see: Jiang et al. (2005); Ou, Zhang & Yuan (2009); Ou, Zhou & Ng (2009).

Experimental top

Malonic acid (0.208 g, 2 mmol) and sodium hydroxide (0.08 g, 2 mmol) were dissolved in water (10 ml). To the solution was added [Ni(rac-L)](ClO₄)₂ (0.108 g, 2 mmol) dissolved in acetonitrile (10 ml) (rac-L = 5,5,7,12,12,14-hexamethyl-1,4,8,11tetraazacyclotetradecane). The solution was left to stand at room temperature; blue crystals formed after several days.

Structure description top

For three related structures, see: Jiang et al. (2005); Ou, Zhang & Yuan (2009); Ou, Zhou & Ng (2009).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [Ni(C₁₆H₃₆N₄)(C₃H₃O₄)]^+.ClO₄^-.CH₃CN at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius.

(2-Carboxyacetato-κ²O¹,O^1')(rac-5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane- κ⁴N,N',N'',N''')nickel(II) perchlorate acetonitrile solvate top

Crystal data top

[Ni(C₃H₃O₄)(C₁₆H₃₆N₄)]ClO₄·C₂H₃N	Z = 2
M_r = 586.76	F(000) = 624
Triclinic, P1	D_x = 1.449 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5236 (4) Å	Cell parameters from 7463 reflections
b = 10.1766 (4) Å	θ = 2.3–27.0°
c = 15.3372 (6) Å	µ = 0.87 mm⁻¹
α = 92.899 (1)°	T = 173 K
β = 107.388 (1)°	Block, blue
γ = 106.516 (1)°	0.45 × 0.40 × 0.20 mm
V = 1344.99 (9) Å³

Data collection top

Bruker SMART APEX diffractometer	5701 independent reflections
Radiation source: fine-focus sealed tube	4946 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 27.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.695, T_max = 0.845	k = −12→12
11181 measured reflections	l = −19→19

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0459P)² + 0.9446P] where P = (F_o² + 2F_c²)/3
5701 reflections	(Δ/σ)_max = 0.001
330 parameters	Δρ_max = 0.55 e Å⁻³
1 restraint	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Ni(C₃H₃O₄)(C₁₆H₃₆N₄)]ClO₄·C₂H₃N	γ = 106.516 (1)°
M_r = 586.76	V = 1344.99 (9) Å³
Triclinic, P1	Z = 2
a = 9.5236 (4) Å	Mo Kα radiation
b = 10.1766 (4) Å	µ = 0.87 mm⁻¹
c = 15.3372 (6) Å	T = 173 K
α = 92.899 (1)°	0.45 × 0.40 × 0.20 mm
β = 107.388 (1)°

Data collection top

Bruker SMART APEX diffractometer	5701 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4946 reflections with I > 2σ(I)
T_min = 0.695, T_max = 0.845	R_int = 0.019
11181 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.55 e Å⁻³
5701 reflections	Δρ_min = −0.54 e Å⁻³
330 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.44427 (3)	0.26403 (2)	0.226567 (15)	0.01746 (8)
Cl1	0.11013 (6)	0.48419 (5)	0.33697 (4)	0.02939 (12)
O1	0.53455 (15)	0.20193 (14)	0.11561 (9)	0.0226 (3)
O2	0.63737 (15)	0.19233 (14)	0.26257 (9)	0.0232 (3)
O3	0.60045 (17)	−0.08012 (15)	0.05987 (10)	0.0296 (3)
H3O	0.565 (3)	−0.119 (3)	0.0053 (9)	0.048 (8)*
O4	0.75796 (18)	0.07704 (17)	0.00664 (10)	0.0366 (4)
O5	0.0676 (2)	0.4372 (3)	0.24039 (14)	0.0642 (6)
O6	−0.0232 (2)	0.4920 (2)	0.35800 (12)	0.0452 (4)
O7	0.1767 (2)	0.3921 (2)	0.39064 (17)	0.0605 (6)
O9	0.2239 (2)	0.6171 (2)	0.35917 (14)	0.0593 (5)
N1	0.26807 (18)	0.07075 (16)	0.17735 (11)	0.0211 (3)
H1	0.2850	0.0349	0.1295	0.025*
N2	0.27765 (18)	0.34713 (17)	0.15032 (11)	0.0225 (3)
H2	0.2373	0.3773	0.1888	0.027*
N3	0.60664 (18)	0.46469 (16)	0.27909 (11)	0.0211 (3)
H3	0.6984	0.4527	0.2954	0.025*
N4	0.41760 (19)	0.26668 (16)	0.35641 (11)	0.0212 (3)
H4	0.3344	0.2903	0.3533	0.025*
N5	0.9236 (3)	0.0264 (3)	0.37545 (18)	0.0560 (6)
C1	0.1245 (2)	0.1067 (2)	0.13879 (15)	0.0292 (4)
H1A	0.0876	0.1312	0.1894	0.035*
H1B	0.0427	0.0260	0.0967	0.035*
C2	0.1553 (2)	0.2276 (2)	0.08669 (14)	0.0282 (4)
H2A	0.1890	0.2023	0.0349	0.034*
H2B	0.0593	0.2523	0.0609	0.034*
C3	0.3327 (2)	0.4644 (2)	0.10165 (13)	0.0255 (4)
H3A	0.3813	0.4323	0.0588	0.031*
C4	0.1996 (3)	0.5125 (3)	0.04463 (16)	0.0371 (5)
H4A	0.1210	0.4342	0.0002	0.056*
H4B	0.2396	0.5861	0.0113	0.056*
H4C	0.1532	0.5480	0.0858	0.056*
C5	0.4547 (2)	0.5866 (2)	0.17060 (14)	0.0276 (4)
H5A	0.4677	0.6684	0.1380	0.033*
H5B	0.4118	0.6060	0.2194	0.033*
C6	0.6159 (2)	0.5764 (2)	0.21848 (13)	0.0249 (4)
C7	0.6890 (2)	0.5397 (2)	0.14827 (14)	0.0291 (4)
H7A	0.6248	0.4492	0.1117	0.044*
H7B	0.7931	0.5362	0.1809	0.044*
H7C	0.6959	0.6104	0.1072	0.044*
C8	0.7192 (3)	0.7183 (2)	0.27434 (16)	0.0346 (5)
H8A	0.8235	0.7139	0.3057	0.052*
H8B	0.6752	0.7435	0.3204	0.052*
H8C	0.7251	0.7880	0.2327	0.052*
C9	0.5823 (2)	0.5038 (2)	0.36648 (13)	0.0269 (4)
H9A	0.4917	0.5381	0.3531	0.032*
H9B	0.6745	0.5791	0.4063	0.032*
C10	0.5551 (2)	0.3792 (2)	0.41571 (13)	0.0268 (4)
H10A	0.6472	0.3470	0.4308	0.032*
H10B	0.5389	0.4049	0.4742	0.032*
C11	0.4025 (2)	0.1328 (2)	0.39390 (13)	0.0256 (4)
H11	0.4951	0.1043	0.3949	0.031*
C12	0.3970 (3)	0.1463 (2)	0.49289 (15)	0.0367 (5)
H12A	0.4898	0.2191	0.5325	0.055*
H12B	0.3933	0.0580	0.5164	0.055*
H12C	0.3044	0.1703	0.4930	0.055*
C13	0.2577 (2)	0.0191 (2)	0.33284 (14)	0.0287 (4)
H13A	0.2388	−0.0589	0.3684	0.034*
H13B	0.1692	0.0557	0.3227	0.034*
C14	0.2539 (2)	−0.0404 (2)	0.23828 (14)	0.0260 (4)
C15	0.3865 (3)	−0.0994 (2)	0.24651 (15)	0.0309 (5)
H15A	0.4856	−0.0254	0.2739	0.046*
H15B	0.3793	−0.1385	0.1850	0.046*
H15C	0.3801	−0.1722	0.2859	0.046*
C16	0.1011 (3)	−0.1599 (2)	0.19501 (17)	0.0394 (5)
H16A	0.0967	−0.1994	0.1343	0.059*
H16B	0.0134	−0.1246	0.1880	0.059*
H16C	0.0961	−0.2318	0.2352	0.059*
C17	0.6356 (2)	0.17427 (19)	0.18083 (13)	0.0213 (4)
C18	0.7602 (2)	0.1236 (2)	0.16206 (14)	0.0287 (4)
H18A	0.8514	0.2045	0.1679	0.034*
H18B	0.7930	0.0660	0.2094	0.034*
C19	0.7075 (2)	0.0401 (2)	0.06769 (14)	0.0249 (4)
C20	0.9213 (3)	0.1114 (3)	0.42492 (17)	0.0367 (5)
C21	0.9193 (3)	0.2199 (3)	0.48808 (19)	0.0461 (6)
H21A	0.9908	0.2222	0.5497	0.069*
H21B	0.8143	0.2020	0.4909	0.069*
H21C	0.9517	0.3092	0.4666	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01746 (13)	0.02064 (13)	0.01497 (12)	0.00797 (9)	0.00478 (9)	0.00037 (8)
Cl1	0.0266 (2)	0.0302 (3)	0.0345 (3)	0.0106 (2)	0.0132 (2)	0.0033 (2)
O1	0.0187 (6)	0.0258 (7)	0.0217 (7)	0.0075 (5)	0.0045 (5)	−0.0003 (5)
O2	0.0232 (7)	0.0264 (7)	0.0210 (7)	0.0109 (6)	0.0063 (5)	−0.0014 (5)
O3	0.0314 (8)	0.0322 (8)	0.0216 (7)	0.0082 (6)	0.0062 (6)	−0.0020 (6)
O4	0.0302 (8)	0.0473 (10)	0.0276 (8)	0.0037 (7)	0.0127 (7)	−0.0075 (7)
O5	0.0548 (12)	0.0906 (16)	0.0429 (11)	0.0162 (11)	0.0208 (9)	−0.0196 (11)
O6	0.0388 (9)	0.0625 (12)	0.0471 (10)	0.0282 (9)	0.0211 (8)	0.0056 (9)
O7	0.0582 (12)	0.0579 (12)	0.0934 (17)	0.0388 (11)	0.0410 (12)	0.0382 (12)
O9	0.0513 (12)	0.0460 (11)	0.0582 (13)	−0.0053 (9)	0.0046 (10)	0.0128 (9)
N1	0.0205 (8)	0.0244 (8)	0.0190 (8)	0.0070 (6)	0.0080 (6)	0.0001 (6)
N2	0.0221 (8)	0.0279 (8)	0.0188 (8)	0.0119 (7)	0.0050 (6)	0.0020 (6)
N3	0.0211 (8)	0.0238 (8)	0.0187 (8)	0.0086 (6)	0.0058 (6)	0.0014 (6)
N4	0.0241 (8)	0.0230 (8)	0.0185 (8)	0.0105 (6)	0.0072 (6)	0.0023 (6)
N5	0.0522 (14)	0.0499 (14)	0.0606 (16)	0.0148 (11)	0.0148 (12)	−0.0084 (12)
C1	0.0182 (9)	0.0338 (11)	0.0307 (11)	0.0060 (8)	0.0035 (8)	0.0011 (8)
C2	0.0202 (9)	0.0354 (11)	0.0242 (10)	0.0103 (8)	−0.0006 (8)	0.0013 (8)
C3	0.0288 (10)	0.0318 (11)	0.0214 (9)	0.0168 (9)	0.0089 (8)	0.0067 (8)
C4	0.0373 (12)	0.0470 (14)	0.0342 (12)	0.0252 (11)	0.0091 (10)	0.0163 (10)
C5	0.0356 (11)	0.0248 (10)	0.0271 (10)	0.0153 (9)	0.0109 (9)	0.0069 (8)
C6	0.0284 (10)	0.0222 (9)	0.0225 (10)	0.0062 (8)	0.0077 (8)	0.0034 (7)
C7	0.0290 (11)	0.0325 (11)	0.0272 (10)	0.0082 (9)	0.0126 (9)	0.0056 (8)
C8	0.0382 (12)	0.0247 (11)	0.0345 (12)	0.0025 (9)	0.0100 (10)	0.0014 (9)
C9	0.0343 (11)	0.0245 (10)	0.0195 (9)	0.0086 (8)	0.0067 (8)	−0.0026 (7)
C10	0.0331 (11)	0.0273 (10)	0.0168 (9)	0.0088 (8)	0.0050 (8)	−0.0014 (7)
C11	0.0316 (11)	0.0273 (10)	0.0200 (9)	0.0117 (8)	0.0089 (8)	0.0048 (8)
C12	0.0539 (15)	0.0362 (12)	0.0211 (10)	0.0121 (11)	0.0156 (10)	0.0071 (9)
C13	0.0329 (11)	0.0284 (10)	0.0270 (10)	0.0061 (9)	0.0163 (9)	0.0054 (8)
C14	0.0302 (11)	0.0230 (10)	0.0253 (10)	0.0064 (8)	0.0117 (8)	0.0030 (8)
C15	0.0423 (12)	0.0248 (10)	0.0320 (11)	0.0157 (9)	0.0163 (10)	0.0050 (8)
C16	0.0404 (13)	0.0302 (12)	0.0393 (13)	−0.0012 (10)	0.0132 (10)	0.0019 (9)
C17	0.0181 (9)	0.0201 (9)	0.0240 (9)	0.0043 (7)	0.0071 (7)	−0.0030 (7)
C18	0.0190 (9)	0.0415 (12)	0.0236 (10)	0.0121 (9)	0.0037 (8)	−0.0086 (8)
C19	0.0179 (9)	0.0330 (11)	0.0243 (10)	0.0129 (8)	0.0044 (8)	−0.0040 (8)
C20	0.0310 (12)	0.0379 (13)	0.0383 (13)	0.0099 (10)	0.0080 (10)	0.0062 (10)
C21	0.0508 (15)	0.0462 (15)	0.0453 (15)	0.0162 (12)	0.0213 (12)	0.0014 (11)

Geometric parameters (Å, º) top

Ni1—N4	2.0813 (16)	C5—H5A	0.9900
Ni1—N2	2.0868 (16)	C5—H5B	0.9900
Ni1—O2	2.1014 (13)	C6—C7	1.529 (3)
Ni1—N1	2.1144 (16)	C6—C8	1.533 (3)
Ni1—N3	2.1223 (16)	C7—H7A	0.9800
Ni1—O1	2.2603 (13)	C7—H7B	0.9800
Ni1—C17	2.5082 (18)	C7—H7C	0.9800
Cl1—O6	1.4222 (16)	C8—H8A	0.9800
Cl1—O9	1.4213 (19)	C8—H8B	0.9800
Cl1—O5	1.4306 (19)	C8—H8C	0.9800
Cl1—O7	1.4359 (19)	C9—C10	1.507 (3)
O1—C17	1.270 (2)	C9—H9A	0.9900
O2—C17	1.252 (2)	C9—H9B	0.9900
O3—C19	1.324 (3)	C10—H10A	0.9900
O3—H3o	0.83 (1)	C10—H10B	0.9900
O4—C19	1.204 (3)	C11—C13	1.526 (3)
N1—C1	1.475 (2)	C11—C12	1.535 (3)
N1—C14	1.505 (2)	C11—H11	1.0000
N1—H1	0.8800	C12—H12A	0.9800
N2—C2	1.478 (3)	C12—H12B	0.9800
N2—C3	1.491 (3)	C12—H12C	0.9800
N2—H2	0.8800	C13—C14	1.529 (3)
N3—C9	1.481 (2)	C13—H13A	0.9900
N3—C6	1.504 (2)	C13—H13B	0.9900
N3—H3	0.8800	C14—C15	1.521 (3)
N4—C10	1.478 (2)	C14—C16	1.540 (3)
N4—C11	1.491 (2)	C15—H15A	0.9800
N4—H4	0.8800	C15—H15B	0.9800
N5—C20	1.131 (3)	C15—H15C	0.9800
C1—C2	1.508 (3)	C16—H16A	0.9800
C1—H1A	0.9900	C16—H16B	0.9800
C1—H1B	0.9900	C16—H16C	0.9800
C2—H2A	0.9900	C17—C18	1.515 (3)
C2—H2B	0.9900	C18—C19	1.506 (3)
C3—C4	1.531 (3)	C18—H18A	0.9900
C3—C5	1.525 (3)	C18—H18B	0.9900
C3—H3A	1.0000	C20—C21	1.439 (3)
C4—H4A	0.9800	C21—H21A	0.9800
C4—H4B	0.9800	C21—H21B	0.9800
C4—H4C	0.9800	C21—H21C	0.9800
C5—C6	1.527 (3)

N4—Ni1—N2	104.09 (6)	C5—C6—C7	111.33 (16)
N4—Ni1—O2	95.69 (6)	N3—C6—C8	111.54 (16)
N2—Ni1—O2	159.77 (6)	C5—C6—C8	108.18 (17)
N4—Ni1—N1	91.55 (6)	C7—C6—C8	108.01 (17)
N2—Ni1—N1	85.19 (6)	C6—C7—H7A	109.5
O2—Ni1—N1	98.65 (6)	C6—C7—H7B	109.5
N4—Ni1—N3	85.63 (6)	H7A—C7—H7B	109.5
N2—Ni1—N3	91.43 (6)	C6—C7—H7C	109.5
O2—Ni1—N3	85.80 (6)	H7A—C7—H7C	109.5
N1—Ni1—N3	174.96 (6)	H7B—C7—H7C	109.5
N4—Ni1—O1	154.65 (6)	C6—C8—H8A	109.5
N2—Ni1—O1	100.65 (6)	C6—C8—H8B	109.5
O2—Ni1—O1	60.22 (5)	H8A—C8—H8B	109.5
N1—Ni1—O1	85.06 (5)	C6—C8—H8C	109.5
N3—Ni1—O1	99.27 (5)	H8A—C8—H8C	109.5
N4—Ni1—C17	125.20 (6)	H8B—C8—H8C	109.5
N2—Ni1—C17	130.70 (6)	N3—C9—C10	109.34 (16)
O2—Ni1—C17	29.89 (6)	N3—C9—H9A	109.8
N1—Ni1—C17	92.09 (6)	C10—C9—H9A	109.8
N3—Ni1—C17	92.95 (6)	N3—C9—H9B	109.8
O1—Ni1—C17	30.33 (6)	C10—C9—H9B	109.8
O6—Cl1—O9	110.07 (13)	H9A—C9—H9B	108.3
O6—Cl1—O5	109.36 (12)	N4—C10—C9	109.92 (16)
O9—Cl1—O5	108.85 (13)	N4—C10—H10A	109.7
O6—Cl1—O7	110.15 (12)	C9—C10—H10A	109.7
O9—Cl1—O7	107.90 (13)	N4—C10—H10B	109.7
O5—Cl1—O7	110.50 (14)	C9—C10—H10B	109.7
C17—O1—Ni1	85.69 (11)	H10A—C10—H10B	108.2
C17—O2—Ni1	93.34 (11)	N4—C11—C13	111.13 (16)
C19—O3—H3O	110 (2)	N4—C11—C12	111.90 (16)
C1—N1—C14	113.93 (15)	C13—C11—C12	109.05 (17)
C1—N1—Ni1	104.51 (12)	N4—C11—H11	108.2
C14—N1—Ni1	120.56 (12)	C13—C11—H11	108.2
C1—N1—H1	105.6	C12—C11—H11	108.2
C14—N1—H1	105.6	C11—C12—H12A	109.5
Ni1—N1—H1	105.6	C11—C12—H12B	109.5
C2—N2—C3	112.71 (15)	H12A—C12—H12B	109.5
C2—N2—Ni1	104.89 (12)	C11—C12—H12C	109.5
C3—N2—Ni1	116.63 (12)	H12A—C12—H12C	109.5
C2—N2—H2	107.4	H12B—C12—H12C	109.5
C3—N2—H2	107.4	C14—C13—C11	119.18 (17)
Ni1—N2—H2	107.4	C14—C13—H13A	107.5
C9—N3—C6	114.03 (15)	C11—C13—H13A	107.5
C9—N3—Ni1	104.30 (11)	C14—C13—H13B	107.5
C6—N3—Ni1	120.41 (12)	C11—C13—H13B	107.5
C9—N3—H3	105.7	H13A—C13—H13B	107.0
C6—N3—H3	105.7	N1—C14—C15	107.74 (16)
Ni1—N3—H3	105.7	N1—C14—C13	110.42 (16)
C10—N4—C11	112.07 (15)	C15—C14—C13	111.55 (17)
C10—N4—Ni1	104.22 (12)	N1—C14—C16	111.13 (17)
C11—N4—Ni1	115.03 (11)	C15—C14—C16	107.64 (18)
C10—N4—H4	108.4	C13—C14—C16	108.34 (17)
C11—N4—H4	108.4	C14—C15—H15A	109.5
Ni1—N4—H4	108.4	C14—C15—H15B	109.5
N1—C1—C2	109.58 (16)	H15A—C15—H15B	109.5
N1—C1—H1A	109.8	C14—C15—H15C	109.5
C2—C1—H1A	109.8	H15A—C15—H15C	109.5
N1—C1—H1B	109.8	H15B—C15—H15C	109.5
C2—C1—H1B	109.8	C14—C16—H16A	109.5
H1A—C1—H1B	108.2	C14—C16—H16B	109.5
N2—C2—C1	109.16 (16)	H16A—C16—H16B	109.5
N2—C2—H2A	109.8	C14—C16—H16C	109.5
C1—C2—H2A	109.8	H16A—C16—H16C	109.5
N2—C2—H2B	109.8	H16B—C16—H16C	109.5
C1—C2—H2B	109.8	O2—C17—O1	120.74 (17)
H2A—C2—H2B	108.3	O2—C17—C18	118.42 (17)
N2—C3—C4	112.02 (17)	O1—C17—C18	120.80 (17)
N2—C3—C5	110.60 (16)	O2—C17—Ni1	56.76 (9)
C4—C3—C5	109.25 (17)	O1—C17—Ni1	63.98 (10)
N2—C3—H3A	108.3	C18—C17—Ni1	174.93 (14)
C4—C3—H3A	108.3	C19—C18—C17	113.04 (16)
C5—C3—H3A	108.3	C19—C18—H18A	109.0
C3—C4—H4A	109.5	C17—C18—H18A	109.0
C3—C4—H4B	109.5	C19—C18—H18B	109.0
H4A—C4—H4B	109.5	C17—C18—H18B	109.0
C3—C4—H4C	109.5	H18A—C18—H18B	107.8
H4A—C4—H4C	109.5	O4—C19—O3	123.73 (18)
H4B—C4—H4C	109.5	O4—C19—C18	124.16 (19)
C6—C5—C3	119.38 (16)	O3—C19—C18	112.10 (18)
C6—C5—H5A	107.5	N5—C20—C21	179.6 (3)
C3—C5—H5A	107.5	C20—C21—H21A	109.5
C6—C5—H5B	107.5	C20—C21—H21B	109.5
C3—C5—H5B	107.5	H21A—C21—H21B	109.5
H5A—C5—H5B	107.0	C20—C21—H21C	109.5
N3—C6—C5	110.32 (16)	H21A—C21—H21C	109.5
N3—C6—C7	107.46 (16)	H21B—C21—H21C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···O1ⁱ	0.83 (1)	1.84 (1)	2.669 (2)	173 (3)
N1—H1···O4ⁱ	0.88	2.19	3.038 (2)	161
N2—H2···O5	0.88	2.21	3.052 (2)	160
N3—H3···O6ⁱⁱ	0.88	2.44	3.291 (2)	163
N4—H4···O7	0.88	2.24	3.080 (2)	161

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

Experimental details

Crystal data
Chemical formula	[Ni(C₃H₃O₄)(C₁₆H₃₆N₄)]ClO₄·C₂H₃N
M_r	586.76
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.5236 (4), 10.1766 (4), 15.3372 (6)
α, β, γ (°)	92.899 (1), 107.388 (1), 106.516 (1)
V (Å³)	1344.99 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.45 × 0.40 × 0.20

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.695, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	11181, 5701, 4946
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.090, 1.03
No. of reflections	5701
No. of parameters	330
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.54

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···O1ⁱ	0.83 (1)	1.84 (1)	2.669 (2)	173 (3)
N1—H1···O4ⁱ	0.88	2.19	3.038 (2)	161
N2—H2···O5	0.88	2.21	3.052 (2)	160
N3—H3···O6ⁱⁱ	0.88	2.44	3.291 (2)	163
N4—H4···O7	0.88	2.24	3.080 (2)	161

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

Acknowledgements

We thank the Key Subject Construction Project of Hunan Province (2006–180), the Scientific Research Fund of Hunan Provincial Education Department (10B039), the Scientific Research Fund of Hunan Provincial Education Department (10 C0730) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, L., Feng, X.-L. & Lu, T.-B. (2005). Cryst. Growth Des. 5, 1469–1475. Web of Science CSD CrossRef CAS Google Scholar
Ou, G.-C., Zhang, M. & Yuan, X.-Y. (2009). Acta Cryst. E65, m726. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ou, G.-C., Zhou, Q. & Ng, S. W. (2009). Acta Cryst. E65, m728. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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