(Acetato-κO)(aqua-κO)(2-{bis­[(3,5-dimethyl-1H-pyrazol-1-yl-κN2)methyl]amino-κN}ethanol-κO)nickel(II) perchlorate monohydrate

Zhou, J.; Shu, M.

doi:10.1107/S1600536812007970

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m399

doi:10.1107/S1600536812007970

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(Acetato-κO)(aqua-κO)(2-{bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]amino-κN}ethanol-κO)nickel(II) perchlorate monohydrate

Jia Zhou ^a and Mouhai Shu ^a ^*

^aState Key Laboratory of Metal Matrix Composites, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, People's Republic of China
^*Correspondence e-mail: mhshu@sjtu.edu.cn

(Received 16 February 2012; accepted 22 February 2012; online 10 March 2012)

In the structure of the title complex, [Ni(CH₃CO₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O, the Ni^II centre has a distorted octahedral environment defined by one O and three N atoms derived from the tetradentate ligand, and two O atoms, one from a water molecule and the other from an acetate anion. The molecules are connected into a three-dimensional architecture by O—H⋯O hydrogen bonds. The perchlorate anion is disordered over two positions; the major component has a site-occupancy factor of 0.525 (19).

Related literature

For the preparation of the tripodal ligand, see: Malachowski et al. (1992 ). For background to hydrolytic enzymes, see: Koike et al. (1995 ); Lipscomb & Sträter (1996 ). For related structures, see: Shin et al. (2011 ); Sundaravel et al. (2011 ); Xia et al. (2001 ).

Experimental

Crystal data

[Ni(C₂H₃O₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O
M_r = 530.61
Monoclinic, P 2₁ /c
a = 9.6055 (11) Å
b = 9.9889 (11) Å
c = 24.258 (3) Å
β = 90.284 (2)°
V = 2327.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 293 K
0.43 × 0.37 × 0.21 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2003 ) T_min = 0.732, T_max = 1.000
13249 measured reflections
5057 independent reflections
2284 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.142
S = 0.82
5057 reflections
310 parameters
26 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H26⋯O3ⁱ	0.86 (1)	1.80 (1)	2.631 (10)	163 (1)
O4—H27⋯O5ⁱⁱ	0.86 (1)	2.03 (1)	2.882 (10)	171 (1)
O4—H28⋯O3	0.86 (1)	1.87 (1)	2.684 (10)	158 (5)
O5—H29⋯O11′	0.86 (1)	1.84 (1)	2.695 (10)	174 (1)
O5—H29⋯O11	0.86 (1)	2.09 (1)	2.940 (10)	168 (1)
O5—H30⋯O12′ⁱⁱⁱ	0.86 (1)	2.59 (1)	3.162 (10)	125 (1)
Symmetry codes: (i) $[-x-1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z; (iii) -x, -y+2, -z+2.

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 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007970/tk5060sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007970/tk5060Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007970/tk5060Isup3.mol

checkCIF report

Comment top

Zn^II-bound alkoxides, resulting from the deprotonation of the Zn^II-coordinated alcoholic hydroxides in Zn^II-containing enzymes (Lipscomb & Sträter, 1996), usually act as nucleophiles to attack the substrates (e.g. phosphates, CO₂, and carboxy esters). Polyamines with a pendant ethoxyl group can mimic the chemical surroundings of Zn^II in the active site of the Zn^II-containing enzymes (Koike et al., 1995). This encouraged us to investigate the coordination chemistry of transition metal ions with a new ligand containing a N₃O donor set. In this work, N,N-bis(3,5-dimethyl-pyrazol-1-yl-methylene)aminoethanol (Malachowski et al., 1992) was reacted with nickel acetate in the presence of sodium perchlorate to yield the title complex as blue crystals in 68% yield. Related structures have been reported previously (Shin et al., 2011; Sundaravel et al., 2011; Xia et al., 2001).

In the structure, the Ni^II cation has a six-coordinated geometry consisting of three N atoms and an O atom from the organic ligand, and two O atoms from a water molecule and an acetate (Fig. 1). The Ni—N_pyrazolyl bond distances are 2.071 (4) and 2.044 (4) Å, which are shorter than the Ni—N_amino bond length (2.124 (3) Å). The Ni—O_acetate bond distance is 1.999 (3) Å, which is about 0.1 Å shorter than those of Ni—O_alcohol (2.097 (3) Å) and Ni—O_water (2.126 (4) Å). The cis bond angles are deviate from 90° by about 10°, and the trans bond angles deviate from 180° by about 20°. Therefore, the coordination geometry of the Ni^II centre is a distorted octahedron. In the crystal, there are O—H···O hydrogen bonds. The unit contents are illustrated in Fig. 2.

Related literature top

For the preparation of the tripodal ligand, see: Malachowski et al. (1992). For background to hydrolytic enzymes, see: Koike et al. (1995); Lipscomb & Sträter (1996). For related structures, see: Shin et al. (2011); Sundaravel et al. (2011); Xia et al. (2001).

Experimental top

A solution of Ni(OAc)₂.4H₂O(0.2 mmol) in 2 ml H₂O was added dropwise to a solution of N,N-bis(3,5-dimethyl-pyrazol-1-yl-methylene-)aminoethanol (0.2 mmol) in 10 ml of methanol. The blue solution was stirred for 30 min and a drop of saturated NaClO₄ solution was added to the mixture. The clear solution in a test tube was left undisturbed. Blue crystals were obtained after a week.

Structure description top

For the preparation of the tripodal ligand, see: Malachowski et al. (1992). For background to hydrolytic enzymes, see: Koike et al. (1995); Lipscomb & Sträter (1996). For related structures, see: Shin et al. (2011); Sundaravel et al. (2011); Xia et al. (2001).

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) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title complex with atom labels and 30% probability displacement ellipsoids for non-H atoms. H atoms bound to the C atoms were omitted for clarity.
	Fig. 2. The packing of the complex, viewed approximately down the a axis, showing the O—H···O hydrogen bonds (dashed lines).

(Acetato-κO)(aqua-κO)(2-{bis[(3,5-dimethyl-1H- pyrazol-1-yl-κN²)methyl]amino-κN}ethanol-κO)nickel(II) perchlorate monohydrate top

Crystal data top

[Ni(C₂H₃O₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O	F(000) = 1112
M_r = 530.61	D_x = 1.514 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1110 reflections
a = 9.6055 (11) Å	θ = 5.3°
b = 9.9889 (11) Å	µ = 1.00 mm⁻¹
c = 24.258 (3) Å	T = 293 K
β = 90.284 (2)°	Block, blue
V = 2327.5 (5) Å³	0.43 × 0.37 × 0.21 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	5057 independent reflections
Radiation source: fine-focus sealed tube	2284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
φ and ω scans	θ_max = 27.0°, θ_min = 1.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2003)	h = −12→12
T_min = 0.732, T_max = 1.000	k = −9→12
13249 measured reflections	l = −30→24

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 0.82	w = 1/[σ²(F_o²) + (0.0493P)²] where P = (F_o² + 2F_c²)/3
5057 reflections	(Δ/σ)_max = 0.001
310 parameters	Δρ_max = 0.66 e Å⁻³
26 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Ni(C₂H₃O₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O	V = 2327.5 (5) Å³
M_r = 530.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6055 (11) Å	µ = 1.00 mm⁻¹
b = 9.9889 (11) Å	T = 293 K
c = 24.258 (3) Å	0.43 × 0.37 × 0.21 mm
β = 90.284 (2)°

Data collection top

Bruker APEX CCD diffractometer	5057 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2003)	2284 reflections with I > 2σ(I)
T_min = 0.732, T_max = 1.000	R_int = 0.082
13249 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	26 restraints
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 0.82	Δρ_max = 0.66 e Å⁻³
5057 reflections	Δρ_min = −0.50 e Å⁻³
310 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	Occ. (<1)
Ni	−0.44003 (7)	1.26474 (6)	0.84018 (3)	0.0315 (2)
Cl	−0.00311 (17)	0.76885 (16)	0.95183 (7)	0.0575 (4)	0.525 (19)
Cl'	−0.00311 (17)	0.76885 (16)	0.95183 (7)	0.0575 (4)	0.475 (19)
N1	−0.2854 (4)	1.2368 (4)	0.90201 (15)	0.0328 (10)
N2	−0.2798 (4)	1.1888 (4)	0.79269 (17)	0.0342 (10)
N3	−0.1741 (4)	1.1411 (4)	0.82475 (17)	0.0355 (10)
N4	−0.5531 (5)	1.3175 (4)	0.90797 (17)	0.0374 (11)
N5	−0.4845 (5)	1.2870 (4)	0.95579 (18)	0.0436 (12)
O1	−0.3473 (4)	1.4547 (3)	0.83710 (15)	0.0383 (9)
H26	−0.357 (6)	1.491 (5)	0.8051 (10)	0.07 (2)*
O2	−0.5772 (3)	1.3140 (3)	0.78136 (14)	0.0383 (9)
O3	−0.6299 (4)	1.1117 (3)	0.74957 (14)	0.0437 (9)
O4	−0.5166 (4)	1.0662 (4)	0.84915 (19)	0.0434 (9)
H27	−0.572 (4)	1.067 (5)	0.8766 (14)	0.050 (19)*
H28	−0.565 (5)	1.062 (6)	0.8195 (14)	0.08 (2)*
O5	0.2962 (5)	1.0394 (6)	0.9409 (2)	0.0831 (15)
H29	0.240 (5)	0.972 (4)	0.938 (2)	0.09 (3)*
H30	0.276 (6)	1.100 (4)	0.965 (2)	0.08 (3)*
O11	0.1400 (8)	0.7866 (11)	0.9351 (5)	0.088 (3)	0.525 (19)
O11'	0.1098 (13)	0.8400 (14)	0.9279 (5)	0.106 (3)	0.475 (19)
O12	−0.0120 (12)	0.7935 (11)	1.0102 (3)	0.088 (3)	0.525 (19)
O12'	−0.0278 (16)	0.8426 (13)	1.0018 (4)	0.106 (3)	0.475 (19)
O13	−0.1096 (9)	0.8469 (13)	0.9288 (5)	0.088 (3)	0.525 (19)
O13'	−0.1122 (10)	0.7788 (18)	0.9127 (5)	0.106 (3)	0.475 (19)
O14	−0.0262 (12)	0.6290 (7)	0.9444 (5)	0.088 (3)	0.525 (19)
O14'	0.0112 (16)	0.6299 (8)	0.9658 (6)	0.106 (3)	0.475 (19)
C1	−0.1981 (6)	1.1237 (5)	0.8832 (2)	0.0438 (14)
H1A	−0.1102	1.1230	0.9030	0.053*
H1B	−0.2452	1.0394	0.8899	0.053*
C2	−0.0605 (6)	1.1114 (5)	0.7946 (2)	0.0459 (15)
C3	−0.0943 (6)	1.1418 (5)	0.7411 (2)	0.0482 (16)
H3A	−0.0374	1.1314	0.7105	0.058*
C4	−0.2312 (6)	1.1917 (5)	0.7410 (2)	0.0409 (14)
C5	−0.3171 (6)	1.2402 (5)	0.6948 (2)	0.0535 (16)
H5A	−0.4067	1.2672	0.7083	0.080*
H5B	−0.3287	1.1698	0.6683	0.080*
H5C	−0.2721	1.3152	0.6778	0.080*
C6	0.0674 (6)	1.0516 (6)	0.8194 (3)	0.072 (2)
H6A	0.0559	1.0437	0.8585	0.107*
H6B	0.1458	1.1081	0.8118	0.107*
H6C	0.0829	0.9646	0.8038	0.107*
C7	−0.3614 (6)	1.2020 (5)	0.9529 (2)	0.0475 (15)
H7A	−0.3885	1.1084	0.9522	0.057*
H7B	−0.3024	1.2166	0.9850	0.057*
C8	−0.5593 (7)	1.3211 (6)	1.0010 (2)	0.0497 (16)
C9	−0.6788 (7)	1.3771 (5)	0.9807 (2)	0.0536 (17)
H9A	−0.7517	1.4113	1.0014	0.064*
C10	−0.6722 (6)	1.3739 (5)	0.9235 (2)	0.0442 (15)
C11	−0.7764 (6)	1.4210 (5)	0.8818 (3)	0.0629 (18)
H11B	−0.7416	1.4047	0.8454	0.094*
H11C	−0.7923	1.5152	0.8866	0.094*
H11D	−0.8623	1.3734	0.8867	0.094*
C12	−0.5118 (7)	1.2947 (6)	1.0577 (2)	0.078 (2)
H12A	−0.4213	1.2540	1.0569	0.117*
H12B	−0.5761	1.2354	1.0755	0.117*
H12C	−0.5070	1.3774	1.0778	0.117*
C13	−0.2072 (6)	1.3644 (5)	0.9084 (2)	0.0425 (14)
H13A	−0.1120	1.3446	0.9191	0.051*
H13B	−0.2490	1.4167	0.9377	0.051*
C14	−0.2067 (6)	1.4462 (5)	0.8560 (2)	0.0424 (14)
H14A	−0.1700	1.5350	0.8632	0.051*
H14B	−0.1491	1.4035	0.8284	0.051*
C15	−0.6364 (5)	1.2371 (5)	0.7480 (2)	0.0351 (12)
C16	−0.7201 (6)	1.3043 (5)	0.7039 (2)	0.0552 (16)
H16A	−0.7145	1.3996	0.7084	0.083*
H16B	−0.8155	1.2763	0.7064	0.083*
H16C	−0.6840	1.2800	0.6684	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0311 (4)	0.0329 (4)	0.0304 (4)	0.0005 (3)	−0.0002 (3)	−0.0012 (3)
Cl	0.0533 (10)	0.0626 (11)	0.0566 (10)	−0.0156 (8)	−0.0060 (8)	0.0043 (9)
Cl'	0.0533 (10)	0.0626 (11)	0.0566 (10)	−0.0156 (8)	−0.0060 (8)	0.0043 (9)
N1	0.037 (3)	0.032 (2)	0.029 (2)	−0.003 (2)	−0.0011 (19)	0.0008 (19)
N2	0.031 (3)	0.039 (2)	0.032 (3)	0.0024 (19)	0.000 (2)	−0.0026 (19)
N3	0.029 (3)	0.041 (3)	0.036 (3)	0.005 (2)	−0.002 (2)	0.001 (2)
N4	0.039 (3)	0.039 (2)	0.034 (3)	−0.001 (2)	0.003 (2)	0.000 (2)
N5	0.051 (3)	0.044 (3)	0.036 (3)	−0.008 (2)	0.012 (2)	−0.003 (2)
O1	0.037 (2)	0.036 (2)	0.042 (2)	−0.0039 (16)	−0.0077 (19)	0.0048 (18)
O2	0.039 (2)	0.036 (2)	0.040 (2)	0.0020 (16)	−0.0108 (18)	−0.0072 (17)
O3	0.052 (3)	0.034 (2)	0.045 (2)	−0.0001 (17)	−0.0064 (19)	−0.0017 (17)
O4	0.042 (3)	0.044 (2)	0.045 (3)	−0.0032 (18)	−0.003 (2)	0.001 (2)
O5	0.084 (4)	0.073 (4)	0.092 (4)	−0.034 (3)	0.006 (3)	0.006 (3)
O11	0.086 (5)	0.067 (4)	0.109 (5)	0.005 (3)	−0.015 (3)	0.000 (3)
O11'	0.118 (7)	0.093 (6)	0.106 (6)	−0.028 (4)	−0.013 (4)	0.003 (4)
O12	0.086 (5)	0.067 (4)	0.109 (5)	0.005 (3)	−0.015 (3)	0.000 (3)
O12'	0.118 (7)	0.093 (6)	0.106 (6)	−0.028 (4)	−0.013 (4)	0.003 (4)
O13	0.086 (5)	0.067 (4)	0.109 (5)	0.005 (3)	−0.015 (3)	0.000 (3)
O13'	0.118 (7)	0.093 (6)	0.106 (6)	−0.028 (4)	−0.013 (4)	0.003 (4)
O14	0.086 (5)	0.067 (4)	0.109 (5)	0.005 (3)	−0.015 (3)	0.000 (3)
O14'	0.118 (7)	0.093 (6)	0.106 (6)	−0.028 (4)	−0.013 (4)	0.003 (4)
C1	0.047 (4)	0.042 (3)	0.043 (4)	0.008 (3)	−0.008 (3)	0.001 (3)
C2	0.036 (4)	0.046 (3)	0.056 (4)	0.000 (3)	0.009 (3)	−0.004 (3)
C3	0.036 (4)	0.052 (4)	0.056 (4)	0.001 (3)	0.019 (3)	−0.006 (3)
C4	0.046 (4)	0.037 (3)	0.040 (4)	−0.004 (3)	0.008 (3)	−0.005 (3)
C5	0.054 (4)	0.078 (4)	0.029 (3)	0.002 (3)	0.007 (3)	0.003 (3)
C6	0.039 (4)	0.081 (5)	0.095 (6)	0.014 (3)	0.005 (4)	0.011 (4)
C7	0.059 (4)	0.052 (4)	0.031 (3)	−0.001 (3)	−0.004 (3)	0.006 (3)
C8	0.059 (5)	0.053 (4)	0.037 (4)	−0.017 (3)	0.018 (3)	−0.009 (3)
C9	0.051 (4)	0.054 (4)	0.055 (4)	−0.012 (3)	0.027 (4)	−0.020 (3)
C10	0.044 (4)	0.030 (3)	0.058 (4)	−0.011 (3)	0.018 (3)	−0.011 (3)
C11	0.039 (4)	0.057 (4)	0.092 (5)	0.008 (3)	0.009 (4)	−0.014 (4)
C12	0.103 (6)	0.096 (5)	0.036 (4)	−0.014 (4)	0.020 (4)	−0.008 (3)
C13	0.046 (4)	0.042 (3)	0.040 (3)	−0.007 (3)	−0.004 (3)	−0.006 (3)
C14	0.044 (4)	0.041 (3)	0.042 (4)	−0.007 (3)	−0.010 (3)	0.003 (3)
C15	0.028 (3)	0.045 (3)	0.033 (3)	0.001 (3)	0.002 (2)	0.002 (3)
C16	0.051 (4)	0.055 (4)	0.059 (4)	0.000 (3)	−0.021 (3)	0.002 (3)

Geometric parameters (Å, º) top

Ni—O2	1.999 (3)	C2—C6	1.490 (7)
Ni—N4	2.044 (4)	C3—C4	1.406 (7)
Ni—N2	2.071 (4)	C3—H3A	0.9300
Ni—O1	2.097 (3)	C4—C5	1.471 (7)
Ni—N1	2.124 (4)	C5—H5A	0.9600
Ni—O4	2.126 (4)	C5—H5B	0.9600
Cl—O13	1.401 (7)	C5—H5C	0.9600
Cl—O14	1.426 (7)	C6—H6A	0.9600
Cl—O12	1.439 (7)	C6—H6B	0.9600
Cl—O11	1.446 (7)	C6—H6C	0.9600
N1—C7	1.480 (6)	C7—H7A	0.9700
N1—C1	1.481 (6)	C7—H7B	0.9700
N1—C13	1.487 (6)	C8—C9	1.368 (8)
N2—C4	1.339 (6)	C8—C12	1.471 (8)
N2—N3	1.362 (5)	C9—C10	1.389 (7)
N3—C2	1.349 (6)	C9—H9A	0.9300
N3—C1	1.447 (6)	C10—C11	1.495 (7)
N4—C10	1.332 (6)	C11—H11B	0.9600
N4—N5	1.366 (5)	C11—H11C	0.9600
N5—C8	1.358 (6)	C11—H11D	0.9600
N5—C7	1.458 (6)	C12—H12A	0.9600
O1—C14	1.427 (6)	C12—H12B	0.9600
O1—H26	0.863 (10)	C12—H12C	0.9600
O2—C15	1.251 (6)	C13—C14	1.512 (6)
O3—C15	1.255 (5)	C13—H13A	0.9700
O4—H27	0.858 (10)	C13—H13B	0.9700
O4—H28	0.856 (10)	C14—H14A	0.9700
O5—H29	0.861 (10)	C14—H14B	0.9700
O5—H30	0.862 (10)	C15—C16	1.494 (7)
C1—H1A	0.9700	C16—H16A	0.9600
C1—H1B	0.9700	C16—H16B	0.9600
C2—C3	1.371 (7)	C16—H16C	0.9600

O2—Ni—N4	99.19 (16)	C3—C4—C5	129.7 (5)
O2—Ni—N2	100.50 (15)	C4—C5—H5A	109.5
N4—Ni—N2	160.25 (17)	C4—C5—H5B	109.5
O2—Ni—O1	91.73 (14)	H5A—C5—H5B	109.5
N4—Ni—O1	91.29 (15)	C4—C5—H5C	109.5
N2—Ni—O1	89.70 (15)	H5A—C5—H5C	109.5
O2—Ni—N1	172.99 (14)	H5B—C5—H5C	109.5
N4—Ni—N1	80.69 (16)	C2—C6—H6A	109.5
N2—Ni—N1	79.96 (16)	C2—C6—H6B	109.5
O1—Ni—N1	81.27 (14)	H6A—C6—H6B	109.5
O2—Ni—O4	94.35 (15)	C2—C6—H6C	109.5
N4—Ni—O4	88.45 (16)	H6A—C6—H6C	109.5
N2—Ni—O4	88.49 (16)	H6B—C6—H6C	109.5
O1—Ni—O4	173.88 (16)	N5—C7—N1	107.8 (4)
N1—Ni—O4	92.65 (16)	N5—C7—H7A	110.1
O13—Cl—O14	112.4 (5)	N1—C7—H7A	110.1
O13—Cl—O12	104.5 (6)	N5—C7—H7B	110.1
O14—Cl—O12	106.4 (5)	N1—C7—H7B	110.1
O13—Cl—O11	120.9 (6)	H7A—C7—H7B	108.5
O14—Cl—O11	103.4 (6)	N5—C8—C9	104.9 (5)
O12—Cl—O11	108.4 (7)	N5—C8—C12	123.3 (6)
C7—N1—C1	111.1 (4)	C9—C8—C12	131.9 (6)
C7—N1—C13	111.4 (4)	C8—C9—C10	108.0 (5)
C1—N1—C13	113.6 (4)	C8—C9—H9A	126.0
C7—N1—Ni	105.9 (3)	C10—C9—H9A	126.0
C1—N1—Ni	106.1 (3)	N4—C10—C9	109.6 (6)
C13—N1—Ni	108.2 (3)	N4—C10—C11	121.0 (5)
C4—N2—N3	106.2 (4)	C9—C10—C11	129.4 (5)
C4—N2—Ni	140.9 (4)	C10—C11—H11B	109.5
N3—N2—Ni	111.4 (3)	C10—C11—H11C	109.5
C2—N3—N2	111.7 (4)	H11B—C11—H11C	109.5
C2—N3—C1	129.6 (5)	C10—C11—H11D	109.5
N2—N3—C1	118.6 (4)	H11B—C11—H11D	109.5
C10—N4—N5	105.4 (4)	H11C—C11—H11D	109.5
C10—N4—Ni	142.9 (4)	C8—C12—H12A	109.5
N5—N4—Ni	111.7 (3)	C8—C12—H12B	109.5
C8—N5—N4	112.1 (5)	H12A—C12—H12B	109.5
C8—N5—C7	128.1 (5)	C8—C12—H12C	109.5
N4—N5—C7	118.5 (4)	H12A—C12—H12C	109.5
C14—O1—Ni	109.7 (3)	H12B—C12—H12C	109.5
C14—O1—H26	114 (4)	N1—C13—C14	112.3 (4)
Ni—O1—H26	112 (4)	N1—C13—H13A	109.2
C15—O2—Ni	127.3 (3)	C14—C13—H13A	109.2
Ni—O4—H27	107 (3)	N1—C13—H13B	109.2
Ni—O4—H28	99 (4)	C14—C13—H13B	109.2
H27—O4—H28	108 (5)	H13A—C13—H13B	107.9
H29—O5—H30	117 (3)	O1—C14—C13	107.2 (4)
N3—C1—N1	107.7 (4)	O1—C14—H14A	110.3
N3—C1—H1A	110.2	C13—C14—H14A	110.3
N1—C1—H1A	110.2	O1—C14—H14B	110.3
N3—C1—H1B	110.2	C13—C14—H14B	110.3
N1—C1—H1B	110.2	H14A—C14—H14B	108.5
H1A—C1—H1B	108.5	O2—C15—O3	124.8 (5)
N3—C2—C3	106.0 (5)	O2—C15—C16	115.4 (5)
N3—C2—C6	122.5 (5)	O3—C15—C16	119.8 (5)
C3—C2—C6	131.5 (5)	C15—C16—H16A	109.5
C2—C3—C4	107.3 (5)	C15—C16—H16B	109.5
C2—C3—H3A	126.4	H16A—C16—H16B	109.5
C4—C3—H3A	126.4	C15—C16—H16C	109.5
N2—C4—C3	108.8 (5)	H16A—C16—H16C	109.5
N2—C4—C5	121.5 (5)	H16B—C16—H16C	109.5

O2—Ni—N1—C7	118.3 (11)	O4—Ni—O1—C14	18.1 (16)
N4—Ni—N1—C7	28.7 (3)	N4—Ni—O2—C15	−115.7 (4)
N2—Ni—N1—C7	−147.3 (3)	N2—Ni—O2—C15	62.7 (4)
O1—Ni—N1—C7	121.4 (3)	O1—Ni—O2—C15	152.7 (4)
O4—Ni—N1—C7	−59.3 (3)	N1—Ni—O2—C15	155.8 (11)
O2—Ni—N1—C1	−123.5 (11)	O4—Ni—O2—C15	−26.6 (4)
N4—Ni—N1—C1	146.9 (3)	C2—N3—C1—N1	145.0 (5)
N2—Ni—N1—C1	−29.1 (3)	N2—N3—C1—N1	−38.1 (6)
O1—Ni—N1—C1	−120.4 (3)	C7—N1—C1—N3	157.0 (4)
O4—Ni—N1—C1	58.9 (3)	C13—N1—C1—N3	−76.5 (5)
O2—Ni—N1—C13	−1.3 (13)	Ni—N1—C1—N3	42.3 (4)
N4—Ni—N1—C13	−90.9 (3)	N2—N3—C2—C3	0.3 (6)
N2—Ni—N1—C13	93.1 (3)	C1—N3—C2—C3	177.3 (5)
O1—Ni—N1—C13	1.9 (3)	N2—N3—C2—C6	−177.1 (5)
O4—Ni—N1—C13	−178.9 (3)	C1—N3—C2—C6	−0.1 (8)
O2—Ni—N2—C4	20.1 (6)	N3—C2—C3—C4	0.6 (6)
N4—Ni—N2—C4	−164.6 (5)	C6—C2—C3—C4	177.7 (6)
O1—Ni—N2—C4	−71.6 (5)	N3—N2—C4—C3	1.4 (5)
N1—Ni—N2—C4	−152.8 (6)	Ni—N2—C4—C3	165.0 (4)
O4—Ni—N2—C4	114.2 (5)	N3—N2—C4—C5	−179.1 (4)
O2—Ni—N2—N3	−176.8 (3)	Ni—N2—C4—C5	−15.5 (8)
N4—Ni—N2—N3	−1.5 (6)	C2—C3—C4—N2	−1.3 (6)
O1—Ni—N2—N3	91.5 (3)	C2—C3—C4—C5	179.3 (5)
N1—Ni—N2—N3	10.3 (3)	C8—N5—C7—N1	−157.5 (5)
O4—Ni—N2—N3	−82.7 (3)	N4—N5—C7—N1	36.8 (6)
C4—N2—N3—C2	−1.1 (5)	C1—N1—C7—N5	−155.8 (4)
Ni—N2—N3—C2	−170.1 (3)	C13—N1—C7—N5	76.5 (5)
C4—N2—N3—C1	−178.5 (4)	Ni—N1—C7—N5	−41.0 (4)
Ni—N2—N3—C1	12.5 (5)	N4—N5—C8—C9	−0.9 (6)
O2—Ni—N4—C10	−4.3 (6)	C7—N5—C8—C9	−167.4 (5)
N2—Ni—N4—C10	−179.7 (5)	N4—N5—C8—C12	177.7 (5)
O1—Ni—N4—C10	87.6 (6)	C7—N5—C8—C12	11.2 (8)
N1—Ni—N4—C10	168.6 (6)	N5—C8—C9—C10	0.4 (6)
O4—Ni—N4—C10	−98.5 (6)	C12—C8—C9—C10	−178.0 (6)
O2—Ni—N4—N5	176.8 (3)	N5—N4—C10—C9	−0.7 (5)
N2—Ni—N4—N5	1.4 (6)	Ni—N4—C10—C9	−179.7 (4)
O1—Ni—N4—N5	−91.3 (3)	N5—N4—C10—C11	−179.9 (4)
N1—Ni—N4—N5	−10.3 (3)	Ni—N4—C10—C11	1.2 (8)
O4—Ni—N4—N5	82.6 (3)	C8—C9—C10—N4	0.2 (6)
C10—N4—N5—C8	1.0 (5)	C8—C9—C10—C11	179.2 (5)
Ni—N4—N5—C8	−179.6 (3)	C7—N1—C13—C14	−143.8 (4)
C10—N4—N5—C7	169.0 (4)	C1—N1—C13—C14	89.8 (5)
Ni—N4—N5—C7	−11.7 (5)	Ni—N1—C13—C14	−27.7 (5)
O2—Ni—O1—C14	−155.1 (3)	Ni—O1—C14—C13	−46.3 (4)
N4—Ni—O1—C14	105.7 (3)	N1—C13—C14—O1	49.7 (5)
N2—Ni—O1—C14	−54.6 (3)	Ni—O2—C15—O3	7.7 (7)
N1—Ni—O1—C14	25.3 (3)	Ni—O2—C15—C16	−172.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H26···O3ⁱ	0.86 (1)	1.80 (1)	2.631 (10)	163 (1)
O4—H27···O5ⁱⁱ	0.86 (1)	2.03 (1)	2.882 (10)	171 (1)
O4—H28···O3	0.86 (1)	1.87 (1)	2.684 (10)	158 (5)
O5—H29···O11′	0.86 (1)	1.84 (1)	2.695 (10)	174 (1)
O5—H29···O11	0.86 (1)	2.09 (1)	2.940 (10)	168 (1)
O5—H30···O12′ⁱⁱⁱ	0.86 (1)	2.59 (1)	3.162 (10)	125 (1)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₂H₃O₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O
M_r	530.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.6055 (11), 9.9889 (11), 24.258 (3)
β (°)	90.284 (2)
V (Å³)	2327.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.43 × 0.37 × 0.21

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Empirical (using intensity measurements) (SADABS; Sheldrick, 2003)
T_min, T_max	0.732, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13249, 5057, 2284
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.142, 0.82
No. of reflections	5057
No. of parameters	310
No. of restraints	26
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.50

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H26···O3ⁱ	0.863 (10)	1.795 (10)	2.631 (10)	163 (1)
O4—H27···O5ⁱⁱ	0.858 (10)	2.031 (10)	2.882 (10)	171 (1)
O4—H28···O3	0.856 (10)	1.872 (10)	2.684 (10)	158 (5)
O5—H29···O11'	0.861 (10)	1.837 (10)	2.695 (10)	174 (1)
O5—H29···O11	0.861 (10)	2.092 (10)	2.940 (10)	168 (1)
O5—H30···O12'ⁱⁱⁱ	0.862 (10)	2.585 (10)	3.162 (10)	125 (1)

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

Acknowledgements

The authors thank Professor D.-J. Xu, Zhejiang University, China, for his helpful suggestions.

References

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