[2-Formyl-4-methyl-6-({2-[2-(4-nitro­benzyl­amino)­ethyl­amino]­ethyl­imino}­meth­yl)phenolato]nickel(II) perchlorate

Wang, Y.; Mao, J.-W.; Song, H.-T.; Zhou, H.

doi:10.1107/S1600536812021058

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m766

doi:10.1107/S1600536812021058

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[2-Formyl-4-methyl-6-({2-[2-(4-nitrobenzylamino)ethylamino]ethylimino}methyl)phenolato]nickel(II) perchlorate

Yang Wang,^a Jia-Wei Mao,^b Hui-Ting Song ^a and Hong Zhou ^a ^*

^aKey Laboratory for Green Chemical Processes of the Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, People's Republic of China, and ^bCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, People's Republic of China
^*Correspondence e-mail: hzhouh@126.com

(Received 28 April 2012; accepted 9 May 2012; online 12 May 2012)

In the unsymmetrical title complex, [Ni(C₂₀H₂₃N₄O₄)]ClO₄, the coordination geometry for the Ni^II atom can be described as square planar. The aromatic rings in the two ligands are almost vertical, with a dihedral angle of 85.3°. In the crystal, cations and anions are linked by weak C(N)—H⋯O hydrogen bonding.

Related literature

For Schiff base complexes containing polynitrogen ligands, see: Gao et al. (2002 ); Souza et al. (2009 ); Tsubomura et al. (2000 ) and for nickel–Schiff base complexes, see: Wu et al. (2011 ); Cheng et al. (2011 ); Wang et al. (2008 ). For the synthesis, see: Zhou et al. (2009 ). For the preparation of 2,6-diformyl-4-methylphenol, see: Long & Hendrickson (1983 ); Mandal et al. (1989 ) and for the preparation of N¹-(2-aminoethyl)-N²-(4-nitrobenzyl)ethane-1,2-diamine, see: Hu et al. (2011 ); Jian et al. (2004 ).

Experimental

Crystal data

[Ni(C₂₀H₂₃N₄O₄)]ClO₄
M_r = 541.58
Triclinic, $[P \overline 1]$
a = 9.5240 (14) Å
b = 9.6423 (14) Å
c = 14.024 (2) Å
α = 97.897 (2)°
β = 109.415 (3)°
γ = 107.453 (2)°
V = 1117.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 291 K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.739, T_max = 0.786
6276 measured reflections
4314 independent reflections
3004 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.138
S = 1.10
4314 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected bond lengths (Å)

N2—Ni1	1.841 (3)
N3—Ni1	1.893 (3)
N4—Ni1	1.936 (4)
Ni1—O1	1.829 (3)

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021058/kp2412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021058/kp2412Isup2.hkl

checkCIF report

Comment top

For a long time Schiff base complexes containing polynitrogen ligands have been given considerable attention (Gao et al. 2002; Tsubomura et al. 2000; Souza et al. 2009). In this paper, we report on the synthesis and crystal structure determination of the title complex obtained by the reaction of 2,6-diformyl-4-methylphenol (L¹) and the polynitrogen ligand N¹-(2-aminoethyl)-N²-(4-nitrobenzyl)ethane-1,2-diamine (L²) in the presence of Ni(ClO₄)₂.6H₂O.

In the title complex, [NiC₂₀H₂₃N₄O₄].ClO₄, the Ni^II atom is four-coordinated by three amino N atoms from the ligand L² and one O atom from the ligand L¹, the basal bond distances around the Ni^II atom are in the range of 1.829–1.936 Å (Fig. 1, Table 1), and the Ni–O distance shorter than that of Ni–N. The four atoms are coplanar with mean plane deviation of 0.027 (4) Å.

Related literature top

For Schiff base complexes containing polynitrogen ligands, see: Gao et al. (2002); Souza et al. (2009); Tsubomura et al. (2000) and for nickel–Schiff base complexes, see: Wu et al. (2011); Cheng et al. (2011); Wang et al. (2008). For the synthesis, see: Zhou et al. (2009). For the prparation of 2,6-diformyl-4-methylphenol, see: Long & Hendrickson (1983); Mandal et al. (1989) and for the preparation of N¹-(2-aminoethyl)-N²-(4-nitrobenzyl)ethane-1,2-diamine, see: Hu et al. (2011); Jian et al. (2004).

Experimental top

All the solvents and chemicals were of analytical grade and used without further purification. 2,6-Diformyl-4-methylphenol was prepared according to the literature method (Mandal et al. 1989; Long et al. 1983). N¹-(2-aminoethyl)- N²-(4-nitrobenzyl)ethane-1,2-diamine was prepared according to the literature method (Jian et al. 2004; Hu et al. 2011). L² (0.119 g, 0.5 mmol) dissolved in 10 mL water was added dropwise to a solution of L¹ (0.082 g, 0.5 mmol) and Ni(ClO₄)₂.6H₂O (0.183g, 0.5 mmol) in anhydrous ethanol (25 mL), the mixture was stirred at ambient temperature for 8 h and filtered. The orange block crystals suitable for the X-ray measurement were obtained by evaporation of the filtrate at room temperature for three weeks.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title complex with displacement ellipsoids at the 30% probability level. H atoms are excluded for clarity.

[2-Formyl-4-methyl-6-({2-[2-(4- nitrobenzylamino)ethylamino]ethylimino}methyl)phenolato]nickel(II) perchlorate top

Crystal data top

[Ni(C₂₀H₂₃N₄O₄)]ClO₄	Z = 2
M_r = 541.58	F(000) = 560
Triclinic, P1	D_x = 1.609 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5240 (14) Å	Cell parameters from 3108 reflections
b = 9.6423 (14) Å	θ = 2.3–28.0°
c = 14.024 (2) Å	µ = 1.04 mm⁻¹
α = 97.897 (2)°	T = 291 K
β = 109.415 (3)°	Block, orange
γ = 107.453 (2)°	0.28 × 0.24 × 0.22 mm
V = 1117.7 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	4314 independent reflections
Radiation source: sealed tube	3004 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.739, T_max = 0.786	k = −9→11
6276 measured reflections	l = −17→15

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0689P)² + 0.0812P] where P = (F_o² + 2F_c²)/3
4314 reflections	(Δ/σ)_max < 0.001
308 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Ni(C₂₀H₂₃N₄O₄)]ClO₄	γ = 107.453 (2)°
M_r = 541.58	V = 1117.7 (3) Å³
Triclinic, P1	Z = 2
a = 9.5240 (14) Å	Mo Kα radiation
b = 9.6423 (14) Å	µ = 1.04 mm⁻¹
c = 14.024 (2) Å	T = 291 K
α = 97.897 (2)°	0.28 × 0.24 × 0.22 mm
β = 109.415 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4314 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3004 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.786	R_int = 0.028
6276 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.10	Δρ_max = 0.49 e Å⁻³
4314 reflections	Δρ_min = −0.44 e Å⁻³
308 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.2128 (6)	0.2151 (5)	0.6715 (3)	0.0490 (11)
H1	0.3112	0.2616	0.7281	0.059*
C2	0.1781 (4)	0.2941 (4)	0.5895 (3)	0.0349 (8)
C3	0.0262 (4)	0.2311 (4)	0.5055 (3)	0.0361 (8)
H3	−0.0489	0.1421	0.5039	0.043*
C4	−0.0125 (4)	0.3010 (4)	0.4249 (3)	0.0371 (8)
C5	0.1016 (5)	0.4324 (5)	0.4308 (3)	0.0474 (10)
H5	0.0762	0.4798	0.3776	0.057*
C6	0.2522 (5)	0.4988 (4)	0.5112 (3)	0.0370 (8)
C7	0.2919 (4)	0.4294 (4)	0.5956 (3)	0.0328 (8)
C8	0.3605 (5)	0.6361 (5)	0.5105 (3)	0.0444 (9)
H8	0.3318	0.6709	0.4510	0.053*
C9	0.5962 (5)	0.8644 (5)	0.5798 (3)	0.0418 (9)
H9A	0.5653	0.9445	0.6055	0.050*
H9B	0.5828	0.8606	0.5077	0.050*
C10	0.7678 (5)	0.8907 (5)	0.6473 (3)	0.0456 (10)
H10A	0.8073	0.8262	0.6128	0.055*
H10B	0.8365	0.9949	0.6616	0.055*
C11	0.9105 (5)	0.8406 (5)	0.8155 (3)	0.0472 (10)
H11A	0.9946	0.9394	0.8498	0.057*
H11B	0.9477	0.7792	0.7764	0.057*
C12	0.8651 (5)	0.7671 (4)	0.8951 (3)	0.0400 (9)
H12A	0.9505	0.7381	0.9362	0.048*
H12B	0.8471	0.8368	0.9422	0.048*
C13	0.6434 (4)	0.5655 (4)	0.9063 (3)	0.0353 (8)
H13A	0.5598	0.4680	0.8666	0.042*
H13B	0.7246	0.5495	0.9624	0.042*
C14	0.5743 (4)	0.6609 (4)	0.9526 (3)	0.0312 (7)
C15	0.6606 (5)	0.7570 (4)	1.0532 (3)	0.0390 (9)
H15	0.7632	0.7612	1.0912	0.047*
C16	0.5967 (5)	0.8476 (5)	1.0984 (3)	0.0509 (11)
H16	0.6567	0.9150	1.1644	0.061*
C17	0.4424 (4)	0.8333 (4)	1.0419 (3)	0.0341 (8)
C18	0.3494 (5)	0.7342 (5)	0.9422 (3)	0.0424 (9)
H18	0.2446	0.7261	0.9062	0.051*
C19	0.4163 (5)	0.6489 (5)	0.8986 (3)	0.0496 (11)
H19	0.3560	0.5825	0.8323	0.060*
C20	−0.1760 (5)	0.2319 (5)	0.3341 (3)	0.0455 (10)
H20A	−0.2257	0.3053	0.3274	0.068*
H20B	−0.2422	0.1461	0.3472	0.068*
H20C	−0.1634	0.2008	0.2704	0.068*
Cl1	0.88876 (12)	0.32607 (11)	0.79500 (8)	0.0463 (3)
N2	0.4978 (4)	0.7171 (3)	0.5876 (3)	0.0393 (7)
N3	0.7633 (3)	0.8528 (3)	0.7458 (2)	0.0307 (6)
H3A	0.7438	0.9259	0.7817	0.037*
N4	0.7161 (4)	0.6317 (4)	0.8366 (3)	0.0463 (8)
H4	0.7513	0.5615	0.8131	0.056*
N5	0.3722 (4)	0.9276 (3)	1.0862 (3)	0.0393 (7)
Ni1	0.58985 (5)	0.66844 (6)	0.70964 (4)	0.03821 (17)
O1	0.4300 (3)	0.4860 (3)	0.6787 (2)	0.0460 (7)
O2	0.1258 (3)	0.0957 (3)	0.6725 (2)	0.0457 (7)
O3	0.4487 (4)	1.0016 (4)	1.1791 (2)	0.0542 (8)
O4	0.2448 (3)	0.9331 (3)	1.0331 (2)	0.0458 (7)
O11	0.9790 (4)	0.4623 (4)	0.8000 (3)	0.0642 (10)
O12	0.8093 (4)	0.2515 (3)	0.6896 (2)	0.0553 (8)
O13	0.9309 (4)	0.2177 (3)	0.8403 (2)	0.0494 (7)
O14	0.7706 (4)	0.3386 (3)	0.8214 (3)	0.0527 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.057 (3)	0.034 (2)	0.0290 (19)	−0.0028 (19)	0.0020 (18)	0.0108 (16)
C2	0.0257 (16)	0.0219 (16)	0.0395 (19)	0.0004 (13)	0.0019 (14)	0.0016 (14)
C3	0.0340 (19)	0.0333 (18)	0.0306 (18)	0.0112 (16)	0.0044 (15)	0.0006 (15)
C4	0.0330 (18)	0.041 (2)	0.0288 (17)	0.0206 (16)	0.0001 (14)	−0.0013 (15)
C5	0.039 (2)	0.048 (2)	0.035 (2)	0.0113 (18)	−0.0043 (17)	0.0095 (17)
C6	0.0396 (19)	0.0278 (17)	0.042 (2)	0.0162 (15)	0.0107 (16)	0.0097 (15)
C7	0.0268 (16)	0.0225 (16)	0.0392 (19)	0.0095 (14)	0.0007 (14)	0.0084 (14)
C8	0.046 (2)	0.038 (2)	0.043 (2)	0.0146 (18)	0.0089 (18)	0.0186 (17)
C9	0.045 (2)	0.040 (2)	0.036 (2)	0.0135 (17)	0.0109 (17)	0.0121 (16)
C10	0.051 (2)	0.037 (2)	0.042 (2)	0.0060 (18)	0.0174 (19)	0.0155 (18)
C11	0.041 (2)	0.043 (2)	0.047 (2)	0.0061 (18)	0.0127 (18)	0.0121 (18)
C12	0.0399 (19)	0.0326 (18)	0.0293 (18)	0.0033 (16)	0.0019 (15)	0.0061 (14)
C13	0.0355 (19)	0.0280 (17)	0.042 (2)	0.0137 (15)	0.0111 (16)	0.0147 (15)
C14	0.0332 (18)	0.0202 (15)	0.0344 (18)	0.0082 (14)	0.0076 (14)	0.0083 (13)
C15	0.046 (2)	0.0255 (18)	0.0349 (19)	0.0162 (16)	0.0035 (17)	0.0025 (14)
C16	0.049 (2)	0.048 (2)	0.037 (2)	0.014 (2)	0.0058 (18)	−0.0099 (18)
C17	0.0376 (19)	0.0390 (19)	0.0334 (19)	0.0109 (16)	0.0239 (16)	0.0147 (15)
C18	0.037 (2)	0.049 (2)	0.037 (2)	0.0136 (18)	0.0078 (16)	0.0194 (17)
C19	0.039 (2)	0.042 (2)	0.038 (2)	0.0032 (18)	−0.0005 (17)	−0.0135 (17)
C20	0.040 (2)	0.046 (2)	0.035 (2)	0.0166 (19)	0.0017 (17)	−0.0023 (17)
Cl1	0.0463 (6)	0.0431 (6)	0.0465 (6)	0.0159 (4)	0.0142 (4)	0.0146 (4)
N2	0.0400 (17)	0.0305 (16)	0.0445 (18)	0.0154 (14)	0.0107 (14)	0.0117 (13)
N3	0.0364 (16)	0.0258 (14)	0.0349 (16)	0.0115 (12)	0.0196 (13)	0.0092 (12)
N4	0.0458 (19)	0.0414 (18)	0.0373 (18)	0.0090 (16)	0.0078 (15)	0.0043 (14)
N5	0.0464 (18)	0.0294 (15)	0.0393 (18)	0.0135 (14)	0.0147 (15)	0.0071 (13)
Ni1	0.0278 (3)	0.0389 (3)	0.0393 (3)	0.0069 (2)	0.0085 (2)	0.0086 (2)
O1	0.0350 (14)	0.0392 (15)	0.0425 (16)	0.0036 (12)	−0.0002 (12)	0.0087 (12)
O2	0.0385 (15)	0.0402 (15)	0.0300 (13)	−0.0050 (12)	−0.0028 (11)	0.0086 (11)
O3	0.0502 (17)	0.0526 (18)	0.0440 (17)	0.0139 (14)	0.0136 (14)	−0.0118 (14)
O4	0.0422 (15)	0.0493 (17)	0.0461 (16)	0.0191 (13)	0.0152 (13)	0.0142 (13)
O11	0.056 (2)	0.055 (2)	0.0561 (19)	−0.0056 (16)	0.0158 (16)	0.0115 (15)
O12	0.0471 (16)	0.0429 (16)	0.0541 (18)	0.0146 (13)	−0.0071 (14)	0.0198 (14)
O13	0.0488 (16)	0.0480 (17)	0.0433 (15)	0.0168 (13)	0.0077 (13)	0.0165 (13)
O14	0.0452 (16)	0.0505 (17)	0.063 (2)	0.0222 (14)	0.0182 (15)	0.0161 (15)

Geometric parameters (Å, º) top

C1—O2	1.205 (5)	C13—C14	1.478 (5)
C1—C2	1.466 (5)	C13—N4	1.483 (5)
C1—H1	0.9300	C13—H13A	0.9700
C2—C7	1.394 (5)	C13—H13B	0.9700
C2—C3	1.411 (5)	C14—C15	1.392 (5)
C3—C4	1.397 (5)	C14—C19	1.402 (5)
C3—H3	0.9300	C15—C16	1.400 (6)
C4—C5	1.370 (6)	C15—H15	0.9300
C4—C20	1.522 (5)	C16—C17	1.372 (6)
C5—C6	1.384 (5)	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.398 (5)
C6—C8	1.417 (6)	C17—N5	1.465 (5)
C6—C7	1.437 (5)	C18—C19	1.376 (6)
C7—O1	1.327 (4)	C18—H18	0.9300
C8—N2	1.305 (5)	C19—H19	0.9300
C8—H8	0.9300	C20—H20A	0.9600
C9—N2	1.489 (5)	C20—H20B	0.9600
C9—C10	1.513 (6)	C20—H20C	0.9600
C9—H9A	0.9700	Cl1—O11	1.314 (3)
C9—H9B	0.9700	Cl1—O14	1.328 (3)
C10—N3	1.487 (5)	Cl1—O12	1.383 (3)
C10—H10A	0.9700	Cl1—O13	1.386 (3)
C10—H10B	0.9700	N2—Ni1	1.841 (3)
C11—N3	1.468 (5)	N3—Ni1	1.893 (3)
C11—C12	1.513 (6)	N3—H3A	0.9100
C11—H11A	0.9700	N4—Ni1	1.936 (4)
C11—H11B	0.9700	N4—H4	0.9100
C12—N4	1.487 (5)	N5—O4	1.216 (4)
C12—H12A	0.9700	N5—O3	1.241 (4)
C12—H12B	0.9700	Ni1—O1	1.829 (3)

O2—C1—C2	126.2 (4)	C15—C14—C13	120.8 (3)
O2—C1—H1	116.9	C19—C14—C13	120.4 (3)
C2—C1—H1	116.9	C14—C15—C16	121.5 (4)
C7—C2—C3	121.0 (3)	C14—C15—H15	119.2
C7—C2—C1	120.5 (3)	C16—C15—H15	119.2
C3—C2—C1	118.4 (3)	C17—C16—C15	117.5 (4)
C4—C3—C2	120.7 (3)	C17—C16—H16	121.2
C4—C3—H3	119.6	C15—C16—H16	121.2
C2—C3—H3	119.6	C16—C17—C18	122.8 (4)
C5—C4—C3	117.6 (3)	C16—C17—N5	119.0 (3)
C5—C4—C20	121.9 (3)	C18—C17—N5	118.1 (3)
C3—C4—C20	120.5 (4)	C19—C18—C17	118.5 (4)
C4—C5—C6	124.0 (4)	C19—C18—H18	120.7
C4—C5—H5	118.0	C17—C18—H18	120.8
C6—C5—H5	118.0	C18—C19—C14	120.9 (4)
C5—C6—C8	119.4 (4)	C18—C19—H19	119.6
C5—C6—C7	118.8 (3)	C14—C19—H19	119.6
C8—C6—C7	121.7 (3)	C4—C20—H20A	109.5
O1—C7—C2	118.2 (3)	C4—C20—H20B	109.5
O1—C7—C6	124.0 (3)	H20A—C20—H20B	109.5
C2—C7—C6	117.8 (3)	C4—C20—H20C	109.5
N2—C8—C6	124.6 (4)	H20A—C20—H20C	109.5
N2—C8—H8	117.7	H20B—C20—H20C	109.5
C6—C8—H8	117.7	O11—Cl1—O14	107.3 (2)
N2—C9—C10	105.6 (3)	O11—Cl1—O12	106.0 (2)
N2—C9—H9A	110.6	O14—Cl1—O12	102.5 (2)
C10—C9—H9A	110.6	O11—Cl1—O13	129.9 (2)
N2—C9—H9B	110.6	O14—Cl1—O13	105.0 (2)
C10—C9—H9B	110.6	O12—Cl1—O13	103.12 (18)
H9A—C9—H9B	108.8	C8—N2—C9	119.4 (3)
N3—C10—C9	105.2 (3)	C8—N2—Ni1	126.6 (3)
N3—C10—H10A	110.7	C9—N2—Ni1	114.0 (2)
C9—C10—H10A	110.7	C11—N3—C10	115.1 (3)
N3—C10—H10B	110.7	C11—N3—Ni1	109.1 (2)
C9—C10—H10B	110.7	C10—N3—Ni1	108.2 (2)
H10A—C10—H10B	108.8	C11—N3—H3A	108.1
N3—C11—C12	105.3 (3)	C10—N3—H3A	108.1
N3—C11—H11A	110.7	Ni1—N3—H3A	108.1
C12—C11—H11A	110.7	C13—N4—C12	112.6 (3)
N3—C11—H11B	110.7	C13—N4—Ni1	121.8 (3)
C12—C11—H11B	110.7	C12—N4—Ni1	109.0 (3)
H11A—C11—H11B	108.8	C13—N4—H4	103.8
N4—C12—C11	107.6 (3)	C12—N4—H4	103.8
N4—C12—H12A	110.2	Ni1—N4—H4	103.8
C11—C12—H12A	110.2	O4—N5—O3	122.0 (3)
N4—C12—H12B	110.2	O4—N5—C17	120.8 (3)
C11—C12—H12B	110.2	O3—N5—C17	117.2 (3)
H12A—C12—H12B	108.5	O1—Ni1—N2	96.40 (13)
C14—C13—N4	113.3 (3)	O1—Ni1—N3	176.88 (13)
C14—C13—H13A	108.9	N2—Ni1—N3	86.25 (13)
N4—C13—H13A	108.9	O1—Ni1—N4	90.39 (14)
C14—C13—H13B	108.9	N2—Ni1—N4	171.64 (15)
N4—C13—H13B	108.9	N3—Ni1—N4	86.84 (14)
H13A—C13—H13B	107.7	C7—O1—Ni1	126.2 (2)
C15—C14—C19	118.7 (4)

O2—C1—C2—C7	−177.4 (5)	C13—C14—C19—C18	178.2 (4)
O2—C1—C2—C3	3.6 (7)	C6—C8—N2—C9	−176.1 (4)
C7—C2—C3—C4	1.6 (6)	C6—C8—N2—Ni1	4.6 (7)
C1—C2—C3—C4	−179.4 (4)	C10—C9—N2—C8	−153.0 (4)
C2—C3—C4—C5	−0.4 (6)	C10—C9—N2—Ni1	26.4 (4)
C2—C3—C4—C20	179.6 (4)	C12—C11—N3—C10	−167.1 (3)
C3—C4—C5—C6	0.5 (6)	C12—C11—N3—Ni1	−45.2 (4)
C20—C4—C5—C6	−179.4 (4)	C9—C10—N3—C11	168.3 (3)
C4—C5—C6—C8	−179.1 (4)	C9—C10—N3—Ni1	46.0 (3)
C4—C5—C6—C7	−1.8 (7)	C14—C13—N4—C12	69.5 (4)
C3—C2—C7—O1	177.3 (3)	C14—C13—N4—Ni1	−62.8 (4)
C1—C2—C7—O1	−1.7 (6)	C11—C12—N4—C13	−169.7 (3)
C3—C2—C7—C6	−2.8 (6)	C11—C12—N4—Ni1	−31.3 (4)
C1—C2—C7—C6	178.2 (4)	C16—C17—N5—O4	169.9 (4)
C5—C6—C7—O1	−177.2 (4)	C18—C17—N5—O4	−8.8 (5)
C8—C6—C7—O1	0.1 (6)	C16—C17—N5—O3	−9.5 (5)
C5—C6—C7—C2	2.9 (6)	C18—C17—N5—O3	171.8 (3)
C8—C6—C7—C2	−179.8 (4)	C8—N2—Ni1—O1	0.3 (4)
C5—C6—C8—N2	171.9 (4)	C9—N2—Ni1—O1	−179.0 (3)
C7—C6—C8—N2	−5.4 (7)	C8—N2—Ni1—N3	178.7 (4)
N2—C9—C10—N3	−45.3 (4)	C9—N2—Ni1—N3	−0.6 (3)
N3—C11—C12—N4	49.4 (4)	C11—N3—Ni1—N2	−152.1 (3)
N4—C13—C14—C15	−97.3 (4)	C10—N3—Ni1—N2	−26.2 (3)
N4—C13—C14—C19	86.9 (4)	C11—N3—Ni1—N4	23.2 (3)
C19—C14—C15—C16	−3.8 (6)	C10—N3—Ni1—N4	149.1 (3)
C13—C14—C15—C16	−179.7 (4)	C13—N4—Ni1—O1	−42.5 (3)
C14—C15—C16—C17	3.0 (6)	C12—N4—Ni1—O1	−176.3 (3)
C15—C16—C17—C18	−0.6 (6)	C13—N4—Ni1—N3	138.9 (3)
C15—C16—C17—N5	−179.3 (4)	C12—N4—Ni1—N3	5.1 (3)
C16—C17—C18—C19	−0.8 (6)	C2—C7—O1—Ni1	−174.5 (3)
N5—C17—C18—C19	177.8 (4)	C6—C7—O1—Ni1	5.7 (6)
C17—C18—C19—C14	0.0 (6)	N2—Ni1—O1—C7	−5.3 (4)
C15—C14—C19—C18	2.3 (6)	N4—Ni1—O1—C7	179.6 (3)

Experimental details

Crystal data
Chemical formula	[Ni(C₂₀H₂₃N₄O₄)]ClO₄
M_r	541.58
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.5240 (14), 9.6423 (14), 14.024 (2)
α, β, γ (°)	97.897 (2), 109.415 (3), 107.453 (2)
V (Å³)	1117.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.739, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	6276, 4314, 3004
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.138, 1.10
No. of reflections	4314
No. of parameters	308
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.44

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

N2—Ni1	1.841 (3)	N4—Ni1	1.936 (4)
N3—Ni1	1.893 (3)	Ni1—O1	1.829 (3)

Acknowledgements

The authors would like to thank the National Natural Science Foundation of China (21171135).

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