(2-Amino­benzoato-κ2O,O′)(rac-5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate

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

doi:10.1107/S1600536810037116

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages m1295-m1296

doi:10.1107/S1600536810037116

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(2-Aminobenzoato-κ²O,O′)(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate

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 15 September 2010; accepted 16 September 2010; online 25 September 2010)

In the title salt, [Ni(C₇H₆NO₂)(C₁₆H₃₆N₄)]ClO₄·H₂O, the Ni^II cation is O,O′-chelated by the benzoate anion and N,N′,N′′,N′′′-chelated by the macrocycle ligand, confering a distorted octahedral geometry on the metal atom. The complex cations, perchlorate anions and uncoordinated water molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network. The perchlorate ion is disordered over two positions in a 0.554 (8):0.446 (8) ratio.

Related literature

For two related structures, see: Ou et al. (2008a ,b ).

Experimental

Crystal data

[Ni(C₇H₆NO₂)(C₁₆H₃₆N₄)]ClO₄·H₂O
M_r = 596.79
Monoclinic, C c
a = 9.6452 (5) Å
b = 21.5350 (11) Å
c = 13.5083 (7) Å
β = 90.784 (1)°
V = 2805.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 110 K
0.45 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.818, T_max = 1.000
6638 measured reflections
3832 independent reflections
3667 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.064
S = 1.08
3832 reflections
410 parameters
142 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 874 Friedel pairs
Flack parameter: −0.012 (9)

Table 1
Selected bond lengths (Å)

Ni1—N1	2.124 (2)
Ni1—N2	2.084 (2)
Ni1—N3	2.138 (2)
Ni1—N4	2.087 (2)
Ni1—O1	2.1659 (17)
Ni1—O2	2.1280 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1wⁱ	0.86 (2)	2.15 (2)	2.995 (3)	166 (2)
N2—H2⋯O5′ⁱⁱ	0.86 (2)	2.35 (2)	3.125 (11)	150 (3)
N3—H3⋯O1	0.86 (2)	2.49 (3)	2.885 (3)	109 (2)
N4—H4⋯O6′ⁱⁱ	0.86 (3)	2.40 (2)	3.195 (6)	155 (3)
N5—H51⋯O2	0.85 (3)	2.13 (3)	2.751 (3)	129 (2)
N5—H52⋯O4′ⁱ	0.85 (1)	2.32 (1)	3.155 (6)	168 (3)
O1w—H11⋯O1	0.84 (2)	1.96 (2)	2.795 (2)	172 (3)
O1w—H12⋯O3	0.83 (2)	2.26 (2)	3.077 (9)	167 (3)
O1w—H12⋯O3′	0.83 (2)	2.09 (2)	2.890 (9)	160 (3)
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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: 10.1107/S1600536810037116/xu5028sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037116/xu5028Isup2.hkl

checkCIF report

Comment top

Previous studies on (5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel benzoate perchlorate salts have documented a chelating mode for the carboxylate ion. The perchlorate counterion is not directly involved in coordination but forms hydrogen bonds with the amino portions of the macrocycle (Ou et al., 2008a, 2008b). The title substituted benzoate has an additional amino unit that also engages in hydrogen bonding. In the salt, [Ni(C₁₆H₃₆N₄)(C₇H₆NO₂)][ClO₄]^.H₂O (Scheme I, Fig. 1), the metal atom is O,O'-chelated by the carboxylate anion and N,N',N'',N'''-chelated by the macrocycle to confer an octahedral geometry to the metal center. The cation, anion and lattice water molecules are linked by N–H···O and O–H···O hydrogen bonds into a three-dimensional network.

Related literature top

For two related structures, see: Ou et al. (2008a,b).

Experimental top

Anthranilic acid (0.27 g, 2 mmol) and sodium hydroxide (0.08 g, 2 mmol) were dissolved in water (15 ml). To this solution was added (rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel diperchlorate (0.11 g, 2 mmol) dissolved in acetonitrile (10 ml). The solution was set aside for the growth of violet crystals after a few days.

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)(C₇H₆NO₂)][ClO₄]^.H₂O at the 50% probability level; hydrogen atoms are shown as spheres of arbitrary radius. The disorder in the perchlorate is not shown.

(2-Aminobenzoato-κ²O,O')(rac- 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane- κ⁴N,N',N'',N''')nickel(II) perchlorate monohydrate top

Crystal data top

[Ni(C₇H₆NO₂)(C₁₆H₃₆N₄)]ClO₄·H₂O	F(000) = 1272
M_r = 596.79	D_x = 1.413 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5267 reflections
a = 9.6452 (5) Å	θ = 2.3–27.0°
b = 21.5350 (11) Å	µ = 0.84 mm⁻¹
c = 13.5083 (7) Å	T = 110 K
β = 90.784 (1)°	Prism, violet
V = 2805.5 (3) Å³	0.45 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3832 independent reflections
Radiation source: fine-focus sealed tube	3667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.818, T_max = 1.000	k = −26→26
6638 measured reflections	l = −8→17

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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0373P)² + 0.1275P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3832 reflections	Δρ_max = 0.25 e Å⁻³
410 parameters	Δρ_min = −0.21 e Å⁻³
142 restraints	Absolute structure: Flack (1983), 874 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.012 (9)

Crystal data top

[Ni(C₇H₆NO₂)(C₁₆H₃₆N₄)]ClO₄·H₂O	V = 2805.5 (3) Å³
M_r = 596.79	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 9.6452 (5) Å	µ = 0.84 mm⁻¹
b = 21.5350 (11) Å	T = 110 K
c = 13.5083 (7) Å	0.45 × 0.20 × 0.10 mm
β = 90.784 (1)°

Data collection top

Bruker SMART APEX diffractometer	3832 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3667 reflections with I > 2σ(I)
T_min = 0.818, T_max = 1.000	R_int = 0.016
6638 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	Δρ_max = 0.25 e Å⁻³
S = 1.08	Δρ_min = −0.21 e Å⁻³
3832 reflections	Absolute structure: Flack (1983), 874 Friedel pairs
410 parameters	Absolute structure parameter: −0.012 (9)
142 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.50011 (3)	0.399116 (12)	0.49992 (3)	0.01859 (8)
O1	0.58175 (16)	0.44546 (8)	0.37089 (12)	0.0219 (4)
O2	0.66792 (16)	0.46225 (7)	0.51979 (12)	0.0201 (3)
Cl1	0.6956 (5)	0.2675 (2)	0.1539 (3)	0.0295 (7)	0.554 (8)
O3	0.5575 (5)	0.2886 (4)	0.1347 (6)	0.0444 (19)	0.554 (8)
O4	0.7620 (5)	0.3111 (2)	0.2197 (4)	0.0581 (17)	0.554 (8)
O5	0.6945 (9)	0.2080 (2)	0.2001 (5)	0.0439 (19)	0.554 (8)
O6	0.7708 (7)	0.2650 (3)	0.0641 (4)	0.070 (2)	0.554 (8)
Cl1'	0.6956 (6)	0.2641 (3)	0.1262 (4)	0.0311 (10)	0.446 (8)
O3'	0.5794 (8)	0.2974 (4)	0.1623 (6)	0.042 (2)	0.446 (8)
O4'	0.8213 (6)	0.2957 (3)	0.1496 (6)	0.060 (3)	0.446 (8)
O5'	0.6992 (12)	0.2028 (3)	0.1656 (9)	0.057 (3)	0.446 (8)
O6'	0.6838 (8)	0.2577 (3)	0.0218 (4)	0.058 (2)	0.446 (8)
O1W	0.5173 (2)	0.42855 (9)	0.17034 (14)	0.0296 (4)
H11	0.545 (3)	0.4343 (13)	0.2291 (11)	0.044*
H12	0.537 (4)	0.3925 (8)	0.153 (2)	0.044*
N1	0.3714 (2)	0.46844 (10)	0.56243 (16)	0.0190 (4)
H1	0.423 (2)	0.4982 (10)	0.585 (2)	0.023*
N2	0.4909 (2)	0.35763 (9)	0.63905 (16)	0.0211 (4)
H2	0.428 (2)	0.3296 (10)	0.636 (2)	0.025*
N3	0.6127 (2)	0.32080 (10)	0.44631 (17)	0.0243 (4)
H3	0.652 (3)	0.3351 (13)	0.3944 (14)	0.029*
N4	0.3296 (2)	0.36063 (10)	0.42555 (16)	0.0242 (4)
H4	0.280 (3)	0.3380 (12)	0.4632 (19)	0.029*
N5	0.7978 (2)	0.57537 (11)	0.53966 (18)	0.0289 (5)
H51	0.739 (3)	0.5514 (12)	0.567 (2)	0.035*
H52	0.814 (3)	0.6115 (8)	0.563 (2)	0.035*
C1	0.3207 (3)	0.44029 (12)	0.65532 (18)	0.0245 (5)
H1A	0.2438	0.4112	0.6402	0.029*
H1B	0.2852	0.4732	0.6995	0.029*
C2	0.4374 (3)	0.40601 (11)	0.70620 (19)	0.0253 (5)
H2A	0.5126	0.4354	0.7241	0.030*
H2B	0.4037	0.3866	0.7678	0.030*
C3	0.6234 (3)	0.33020 (13)	0.6779 (2)	0.0282 (6)
H3a	0.6968	0.3629	0.6751	0.034*
C4	0.6109 (3)	0.30893 (15)	0.7856 (2)	0.0378 (7)
H4A	0.5814	0.3440	0.8265	0.057*
H4B	0.7011	0.2937	0.8096	0.057*
H4C	0.5423	0.2755	0.7895	0.057*
C5	0.6684 (3)	0.27612 (12)	0.6133 (2)	0.0293 (6)
H5A	0.5883	0.2477	0.6059	0.035*
H5B	0.7418	0.2532	0.6499	0.035*
C6	0.7230 (3)	0.28992 (12)	0.5088 (2)	0.0298 (6)
C7	0.8464 (3)	0.33447 (13)	0.5146 (2)	0.0353 (7)
H7A	0.8832	0.3409	0.4481	0.053*
H7B	0.9188	0.3167	0.5575	0.053*
H7C	0.8162	0.3743	0.5418	0.053*
C8	0.7727 (3)	0.22831 (14)	0.4626 (3)	0.0393 (7)
H8A	0.7921	0.2348	0.3923	0.059*
H8B	0.7003	0.1967	0.4692	0.059*
H8C	0.8573	0.2143	0.4969	0.059*
C9	0.5037 (3)	0.27846 (12)	0.4086 (2)	0.0297 (6)
H9A	0.4632	0.2551	0.4643	0.036*
H9B	0.5444	0.2483	0.3620	0.036*
C10	0.3920 (3)	0.31573 (13)	0.3564 (2)	0.0288 (6)
H10A	0.4324	0.3383	0.2998	0.035*
H10B	0.3194	0.2874	0.3304	0.035*
C11	0.2384 (3)	0.40671 (11)	0.37461 (19)	0.0241 (5)
H11A	0.2979	0.4328	0.3310	0.029*
C12	0.1271 (3)	0.37581 (15)	0.3090 (2)	0.0335 (6)
H12A	0.1719	0.3517	0.2568	0.050*
H12B	0.0680	0.4078	0.2788	0.050*
H12C	0.0704	0.3481	0.3494	0.050*
C13	0.1684 (2)	0.45014 (12)	0.44934 (19)	0.0238 (5)
H13A	0.1253	0.4240	0.5007	0.029*
H13B	0.0923	0.4722	0.4142	0.029*
C14	0.2594 (2)	0.49930 (12)	0.50235 (18)	0.0217 (5)
C15	0.3297 (3)	0.54169 (12)	0.42814 (19)	0.0237 (5)
H15A	0.3819	0.5740	0.4637	0.036*
H15B	0.2592	0.5611	0.3853	0.036*
H15C	0.3932	0.5173	0.3876	0.036*
C16	0.1671 (3)	0.54025 (13)	0.5675 (2)	0.0259 (6)
H16A	0.2256	0.5678	0.6079	0.039*
H16B	0.1117	0.5138	0.6109	0.039*
H16C	0.1053	0.5652	0.5253	0.039*
C17	0.6690 (2)	0.47306 (11)	0.42754 (19)	0.0186 (5)
C18	0.7701 (2)	0.51743 (11)	0.38477 (18)	0.0198 (5)
C19	0.8068 (2)	0.51078 (12)	0.28554 (19)	0.0234 (5)
H19	0.7678	0.4777	0.2479	0.028*
C20	0.8984 (3)	0.55104 (13)	0.2407 (2)	0.0292 (6)
H20	0.9247	0.5450	0.1739	0.035*
C21	0.9514 (3)	0.60087 (12)	0.2959 (2)	0.0301 (6)
H21	1.0125	0.6296	0.2657	0.036*
C22	0.9161 (3)	0.60871 (12)	0.3934 (2)	0.0276 (6)
H22	0.9532	0.6430	0.4292	0.033*
C23	0.8259 (2)	0.56699 (12)	0.4417 (2)	0.0219 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01972 (13)	0.01555 (14)	0.02064 (13)	−0.00292 (12)	0.00605 (9)	−0.00109 (13)
O1	0.0225 (8)	0.0217 (9)	0.0217 (8)	−0.0068 (7)	0.0050 (7)	−0.0017 (7)
O2	0.0227 (8)	0.0171 (9)	0.0207 (8)	−0.0015 (6)	0.0043 (7)	−0.0002 (7)
Cl1	0.0273 (9)	0.0245 (10)	0.0371 (17)	0.0031 (6)	0.0107 (11)	0.0046 (11)
O3	0.036 (2)	0.035 (3)	0.062 (4)	0.005 (2)	−0.007 (2)	−0.016 (3)
O4	0.053 (3)	0.045 (3)	0.075 (4)	−0.004 (2)	−0.017 (3)	−0.008 (2)
O5	0.055 (3)	0.015 (2)	0.062 (4)	0.000 (2)	0.014 (3)	0.010 (2)
O6	0.071 (4)	0.077 (4)	0.065 (4)	0.031 (3)	0.052 (4)	0.012 (3)
Cl1'	0.0308 (12)	0.0213 (12)	0.041 (3)	0.0025 (8)	0.0045 (16)	0.0042 (15)
O3'	0.048 (4)	0.033 (4)	0.047 (4)	0.016 (3)	0.024 (3)	0.001 (3)
O4'	0.055 (3)	0.038 (3)	0.087 (6)	−0.014 (3)	−0.021 (3)	0.020 (3)
O5'	0.051 (4)	0.027 (4)	0.094 (7)	0.008 (3)	0.017 (5)	0.010 (4)
O6'	0.055 (4)	0.079 (4)	0.041 (3)	0.016 (3)	0.009 (3)	−0.017 (3)
O1W	0.0405 (11)	0.0243 (10)	0.0239 (9)	0.0039 (8)	−0.0026 (8)	0.0000 (7)
N1	0.0222 (10)	0.0145 (10)	0.0205 (10)	−0.0003 (8)	0.0027 (8)	0.0008 (8)
N2	0.0208 (10)	0.0180 (10)	0.0248 (10)	0.0008 (8)	0.0057 (8)	0.0009 (8)
N3	0.0254 (10)	0.0186 (11)	0.0291 (11)	−0.0042 (8)	0.0107 (9)	−0.0014 (9)
N4	0.0258 (10)	0.0228 (11)	0.0242 (10)	−0.0061 (8)	0.0086 (8)	−0.0022 (9)
N5	0.0337 (12)	0.0215 (11)	0.0315 (12)	−0.0095 (9)	0.0063 (9)	−0.0075 (9)
C1	0.0287 (12)	0.0262 (13)	0.0187 (11)	0.0058 (10)	0.0078 (10)	0.0013 (10)
C2	0.0314 (13)	0.0246 (13)	0.0202 (11)	0.0062 (10)	0.0056 (10)	0.0018 (10)
C3	0.0250 (12)	0.0240 (14)	0.0356 (15)	0.0034 (10)	0.0030 (11)	0.0032 (11)
C4	0.0416 (16)	0.0366 (16)	0.0353 (15)	0.0169 (13)	0.0014 (13)	0.0070 (13)
C5	0.0295 (13)	0.0180 (12)	0.0406 (15)	0.0043 (10)	0.0081 (11)	0.0038 (11)
C6	0.0245 (13)	0.0232 (14)	0.0420 (16)	0.0016 (10)	0.0122 (11)	−0.0024 (12)
C7	0.0229 (13)	0.0326 (16)	0.0507 (17)	0.0009 (11)	0.0090 (12)	−0.0002 (13)
C8	0.0370 (16)	0.0235 (15)	0.058 (2)	0.0074 (12)	0.0127 (15)	−0.0063 (14)
C9	0.0347 (13)	0.0181 (13)	0.0368 (14)	−0.0057 (10)	0.0146 (11)	−0.0073 (11)
C10	0.0315 (14)	0.0250 (14)	0.0301 (14)	−0.0081 (10)	0.0079 (11)	−0.0125 (11)
C11	0.0247 (12)	0.0247 (13)	0.0232 (12)	−0.0063 (9)	0.0049 (10)	−0.0010 (10)
C12	0.0295 (13)	0.0429 (17)	0.0282 (13)	−0.0081 (12)	0.0010 (11)	−0.0065 (12)
C13	0.0193 (11)	0.0276 (13)	0.0245 (12)	−0.0013 (9)	0.0031 (10)	0.0017 (10)
C14	0.0229 (11)	0.0224 (12)	0.0200 (11)	0.0015 (9)	0.0040 (9)	0.0031 (10)
C15	0.0278 (12)	0.0222 (12)	0.0212 (11)	0.0021 (9)	0.0048 (10)	0.0034 (10)
C16	0.0263 (13)	0.0259 (15)	0.0256 (13)	0.0059 (10)	0.0062 (10)	0.0040 (11)
C17	0.0197 (11)	0.0140 (11)	0.0222 (12)	0.0024 (9)	0.0045 (9)	−0.0008 (9)
C18	0.0190 (11)	0.0170 (12)	0.0236 (12)	0.0000 (8)	0.0017 (9)	0.0014 (9)
C19	0.0210 (12)	0.0238 (13)	0.0255 (12)	−0.0011 (9)	0.0037 (10)	0.0014 (10)
C20	0.0253 (12)	0.0355 (15)	0.0269 (13)	0.0006 (10)	0.0083 (10)	0.0080 (11)
C21	0.0210 (12)	0.0288 (14)	0.0405 (15)	−0.0034 (9)	0.0045 (11)	0.0131 (12)
C22	0.0249 (12)	0.0199 (13)	0.0378 (15)	−0.0048 (9)	−0.0005 (11)	0.0034 (11)
C23	0.0194 (11)	0.0193 (12)	0.0269 (12)	0.0015 (9)	0.0022 (10)	0.0017 (10)

Geometric parameters (Å, º) top

Ni1—N1	2.124 (2)	C5—C6	1.541 (4)
Ni1—N2	2.084 (2)	C5—H5A	0.9900
Ni1—N3	2.138 (2)	C5—H5B	0.9900
Ni1—N4	2.087 (2)	C6—C7	1.530 (4)
Ni1—O1	2.1659 (17)	C6—C8	1.546 (4)
Ni1—O2	2.1280 (16)	C7—H7A	0.9800
O1—C17	1.276 (3)	C7—H7B	0.9800
O2—C17	1.268 (3)	C7—H7C	0.9800
Cl1—O6	1.423 (4)	C8—H8A	0.9800
Cl1—O5	1.425 (5)	C8—H8B	0.9800
Cl1—O3	1.427 (5)	C8—H8C	0.9800
Cl1—O4	1.437 (5)	C9—C10	1.510 (4)
Cl1'—O6'	1.421 (5)	C9—H9A	0.9900
Cl1'—O5'	1.423 (6)	C9—H9B	0.9900
Cl1'—O3'	1.422 (5)	C10—H10A	0.9900
Cl1'—O4'	1.422 (6)	C10—H10B	0.9900
O1W—H11	0.843 (10)	C11—C12	1.534 (4)
O1W—H12	0.833 (10)	C11—C13	1.539 (3)
N1—C1	1.482 (3)	C11—H11A	1.0000
N1—C14	1.498 (3)	C12—H12A	0.9800
N1—H1	0.861 (10)	C12—H12B	0.9800
N2—C2	1.479 (3)	C12—H12C	0.9800
N2—C3	1.496 (3)	C13—C14	1.545 (3)
N2—H2	0.858 (10)	C13—H13A	0.9900
N3—C9	1.477 (3)	C13—H13B	0.9900
N3—C6	1.504 (4)	C14—C15	1.522 (3)
N3—H3	0.860 (10)	C14—C16	1.538 (3)
N4—C10	1.478 (3)	C15—H15A	0.9800
N4—C11	1.489 (3)	C15—H15B	0.9800
N4—H4	0.86 (3)	C15—H15C	0.9800
N5—C23	1.366 (3)	C16—H16A	0.9800
N5—H51	0.86 (3)	C16—H16B	0.9800
N5—H52	0.854 (10)	C16—H16C	0.9800
C1—C2	1.504 (3)	C17—C18	1.487 (3)
C1—H1A	0.9900	C18—C19	1.399 (3)
C1—H1B	0.9900	C18—C23	1.418 (3)
C2—H2A	0.9900	C19—C20	1.383 (3)
C2—H2B	0.9900	C19—H19	0.9500
C3—C5	1.522 (4)	C20—C21	1.400 (4)
C3—C4	1.532 (4)	C20—H20	0.9500
C3—H3a	1.0000	C21—C22	1.375 (4)
C4—H4A	0.9800	C21—H21	0.9500
C4—H4B	0.9800	C22—C23	1.416 (4)
C4—H4C	0.9800	C22—H22	0.9500

N2—Ni1—N4	102.76 (8)	N3—C6—C7	107.2 (2)
N2—Ni1—N1	84.86 (8)	N3—C6—C5	110.60 (19)
N4—Ni1—N1	90.54 (8)	C7—C6—C5	110.5 (2)
N2—Ni1—O2	101.64 (7)	N3—C6—C8	111.9 (2)
N4—Ni1—O2	155.16 (8)	C7—C6—C8	108.2 (2)
N1—Ni1—O2	87.05 (7)	C5—C6—C8	108.4 (2)
N2—Ni1—N3	89.73 (8)	C6—C7—H7A	109.5
N4—Ni1—N3	85.66 (8)	C6—C7—H7B	109.5
N1—Ni1—N3	172.56 (8)	H7A—C7—H7B	109.5
O2—Ni1—N3	99.07 (7)	C6—C7—H7C	109.5
N2—Ni1—O1	160.67 (7)	H7A—C7—H7C	109.5
N4—Ni1—O1	95.07 (7)	H7B—C7—H7C	109.5
N1—Ni1—O1	102.53 (7)	C6—C8—H8A	109.5
O2—Ni1—O1	61.50 (6)	C6—C8—H8B	109.5
N3—Ni1—O1	84.20 (7)	H8A—C8—H8B	109.5
C17—O1—Ni1	88.63 (14)	C6—C8—H8C	109.5
C17—O2—Ni1	90.56 (14)	H8A—C8—H8C	109.5
O6—Cl1—O5	110.2 (4)	H8B—C8—H8C	109.5
O6—Cl1—O3	110.1 (4)	N3—C9—C10	109.4 (2)
O5—Cl1—O3	110.7 (4)	N3—C9—H9A	109.8
O6—Cl1—O4	108.9 (4)	C10—C9—H9A	109.8
O5—Cl1—O4	108.8 (4)	N3—C9—H9B	109.8
O3—Cl1—O4	108.1 (4)	C10—C9—H9B	109.8
O6'—Cl1'—O5'	106.4 (7)	H9A—C9—H9B	108.2
O6'—Cl1'—O3'	109.6 (5)	N4—C10—C9	110.3 (2)
O5'—Cl1'—O3'	110.8 (5)	N4—C10—H10A	109.6
O6'—Cl1'—O4'	108.9 (5)	C9—C10—H10A	109.6
O5'—Cl1'—O4'	110.2 (5)	N4—C10—H10B	109.6
O3'—Cl1'—O4'	110.8 (5)	C9—C10—H10B	109.6
H11—O1W—H12	109.4 (17)	H10A—C10—H10B	108.1
C1—N1—C14	113.35 (19)	N4—C11—C12	112.5 (2)
C1—N1—Ni1	104.50 (15)	N4—C11—C13	111.3 (2)
C14—N1—Ni1	121.17 (16)	C12—C11—C13	109.5 (2)
C1—N1—H1	101.7 (19)	N4—C11—H11A	107.8
C14—N1—H1	105.3 (19)	C12—C11—H11A	107.8
Ni1—N1—H1	109.1 (18)	C13—C11—H11A	107.8
C2—N2—C3	111.5 (2)	C11—C12—H12A	109.5
C2—N2—Ni1	105.70 (15)	C11—C12—H12B	109.5
C3—N2—Ni1	116.01 (15)	H12A—C12—H12B	109.5
C2—N2—H2	106 (2)	C11—C12—H12C	109.5
C3—N2—H2	110 (2)	H12A—C12—H12C	109.5
Ni1—N2—H2	107 (2)	H12B—C12—H12C	109.5
C9—N3—C6	114.5 (2)	C11—C13—C14	117.97 (19)
C9—N3—Ni1	103.96 (15)	C11—C13—H13A	107.8
C6—N3—Ni1	121.14 (16)	C14—C13—H13A	107.8
C9—N3—H3	105 (2)	C11—C13—H13B	107.8
C6—N3—H3	107 (2)	C14—C13—H13B	107.8
Ni1—N3—H3	103 (2)	H13A—C13—H13B	107.2
C10—N4—C11	112.8 (2)	N1—C14—C15	107.37 (19)
C10—N4—Ni1	103.81 (15)	N1—C14—C16	111.3 (2)
C11—N4—Ni1	114.50 (15)	C15—C14—C16	107.4 (2)
C10—N4—H4	104 (2)	N1—C14—C13	110.4 (2)
C11—N4—H4	109 (2)	C15—C14—C13	111.2 (2)
Ni1—N4—H4	113 (2)	C16—C14—C13	109.19 (19)
C23—N5—H51	119 (2)	C14—C15—H15A	109.5
C23—N5—H52	116 (2)	C14—C15—H15B	109.5
H51—N5—H52	121 (3)	H15A—C15—H15B	109.5
N1—C1—C2	109.5 (2)	C14—C15—H15C	109.5
N1—C1—H1A	109.8	H15A—C15—H15C	109.5
C2—C1—H1A	109.8	H15B—C15—H15C	109.5
N1—C1—H1B	109.8	C14—C16—H16A	109.5
C2—C1—H1B	109.8	C14—C16—H16B	109.5
H1A—C1—H1B	108.2	H16A—C16—H16B	109.5
N2—C2—C1	109.3 (2)	C14—C16—H16C	109.5
N2—C2—H2A	109.8	H16A—C16—H16C	109.5
C1—C2—H2A	109.8	H16B—C16—H16C	109.5
N2—C2—H2B	109.8	O2—C17—O1	119.3 (2)
C1—C2—H2B	109.8	O2—C17—C18	120.9 (2)
H2A—C2—H2B	108.3	O1—C17—C18	119.8 (2)
N2—C3—C5	110.5 (2)	C19—C18—C23	119.9 (2)
N2—C3—C4	111.9 (2)	C19—C18—C17	118.9 (2)
C5—C3—C4	110.0 (2)	C23—C18—C17	121.3 (2)
N2—C3—H3a	108.1	C20—C19—C18	121.8 (2)
C5—C3—H3a	108.1	C20—C19—H19	119.1
C4—C3—H3a	108.1	C18—C19—H19	119.1
C3—C4—H4A	109.5	C19—C20—C21	118.6 (2)
C3—C4—H4B	109.5	C19—C20—H20	120.7
H4A—C4—H4B	109.5	C21—C20—H20	120.7
C3—C4—H4C	109.5	C22—C21—C20	120.7 (2)
H4A—C4—H4C	109.5	C22—C21—H21	119.6
H4B—C4—H4C	109.5	C20—C21—H21	119.6
C3—C5—C6	118.7 (2)	C21—C22—C23	121.7 (3)
C3—C5—H5A	107.6	C21—C22—H22	119.1
C6—C5—H5A	107.6	C23—C22—H22	119.1
C3—C5—H5B	107.6	N5—C23—C18	123.1 (2)
C6—C5—H5B	107.6	N5—C23—C22	119.6 (2)
H5A—C5—H5B	107.1	C18—C23—C22	117.3 (2)

N2—Ni1—O1—C17	−31.3 (3)	C2—N2—C3—C4	51.2 (3)
N4—Ni1—O1—C17	171.28 (14)	Ni1—N2—C3—C4	172.23 (19)
N1—Ni1—O1—C17	79.59 (14)	N2—C3—C5—C6	71.2 (3)
O2—Ni1—O1—C17	0.00 (13)	C4—C3—C5—C6	−164.7 (2)
N3—Ni1—O1—C17	−103.62 (14)	C9—N3—C6—C7	163.1 (2)
N2—Ni1—O2—C17	169.89 (14)	Ni1—N3—C6—C7	−71.0 (2)
N4—Ni1—O2—C17	−21.1 (2)	C9—N3—C6—C5	−76.4 (3)
N1—Ni1—O2—C17	−105.97 (14)	Ni1—N3—C6—C5	49.4 (3)
N3—Ni1—O2—C17	78.28 (15)	C9—N3—C6—C8	44.6 (3)
O1—Ni1—O2—C17	0.00 (13)	Ni1—N3—C6—C8	170.46 (18)
N2—Ni1—N1—C1	−14.19 (16)	C3—C5—C6—N3	−61.6 (3)
N4—Ni1—N1—C1	88.57 (16)	C3—C5—C6—C7	56.8 (3)
O2—Ni1—N1—C1	−116.17 (16)	C3—C5—C6—C8	175.3 (2)
O1—Ni1—N1—C1	−176.11 (15)	C6—N3—C9—C10	174.1 (2)
N2—Ni1—N1—C14	−143.61 (18)	Ni1—N3—C9—C10	39.7 (2)
N4—Ni1—N1—C14	−40.84 (18)	C11—N4—C10—C9	169.1 (2)
O2—Ni1—N1—C14	114.42 (17)	Ni1—N4—C10—C9	44.6 (2)
O1—Ni1—N1—C14	54.48 (18)	N3—C9—C10—N4	−59.9 (3)
N4—Ni1—N2—C2	−104.54 (16)	C10—N4—C11—C12	53.3 (3)
N1—Ni1—N2—C2	−15.15 (16)	Ni1—N4—C11—C12	171.73 (16)
O2—Ni1—N2—C2	70.77 (16)	C10—N4—C11—C13	176.57 (19)
N3—Ni1—N2—C2	169.98 (16)	Ni1—N4—C11—C13	−65.0 (2)
O1—Ni1—N2—C2	98.6 (2)	N4—C11—C13—C14	71.8 (3)
N4—Ni1—N2—C3	131.31 (17)	C12—C11—C13—C14	−163.2 (2)
N1—Ni1—N2—C3	−139.30 (18)	C1—N1—C14—C15	163.3 (2)
O2—Ni1—N2—C3	−53.38 (18)	Ni1—N1—C14—C15	−71.2 (2)
N3—Ni1—N2—C3	45.83 (18)	C1—N1—C14—C16	46.1 (3)
O1—Ni1—N2—C3	−25.6 (3)	Ni1—N1—C14—C16	171.49 (16)
N2—Ni1—N3—C9	90.51 (16)	C1—N1—C14—C13	−75.4 (2)
N4—Ni1—N3—C9	−12.31 (16)	Ni1—N1—C14—C13	50.1 (2)
O2—Ni1—N3—C9	−167.74 (16)	C11—C13—C14—N1	−61.3 (3)
O1—Ni1—N3—C9	−107.87 (16)	C11—C13—C14—C15	57.7 (3)
N2—Ni1—N3—C6	−40.04 (18)	C11—C13—C14—C16	176.0 (2)
N4—Ni1—N3—C6	−142.86 (18)	Ni1—O2—C17—O1	0.0 (2)
O2—Ni1—N3—C6	61.70 (18)	Ni1—O2—C17—C18	179.87 (19)
O1—Ni1—N3—C6	121.58 (18)	Ni1—O1—C17—O2	0.0 (2)
N2—Ni1—N4—C10	−105.88 (17)	Ni1—O1—C17—C18	−179.88 (19)
N1—Ni1—N4—C10	169.26 (17)	O2—C17—C18—C19	155.0 (2)
O2—Ni1—N4—C10	85.1 (2)	O1—C17—C18—C19	−25.2 (3)
N3—Ni1—N4—C10	−17.14 (17)	O2—C17—C18—C23	−26.9 (3)
O1—Ni1—N4—C10	66.63 (17)	O1—C17—C18—C23	152.9 (2)
N2—Ni1—N4—C11	130.71 (15)	C23—C18—C19—C20	0.8 (4)
N1—Ni1—N4—C11	45.86 (16)	C17—C18—C19—C20	178.9 (2)
O2—Ni1—N4—C11	−38.3 (3)	C18—C19—C20—C21	−2.2 (4)
N3—Ni1—N4—C11	−140.55 (16)	C19—C20—C21—C22	1.7 (4)
O1—Ni1—N4—C11	−56.77 (16)	C20—C21—C22—C23	0.3 (4)
C14—N1—C1—C2	175.3 (2)	C19—C18—C23—N5	−178.1 (2)
Ni1—N1—C1—C2	41.4 (2)	C17—C18—C23—N5	3.8 (4)
C3—N2—C2—C1	169.3 (2)	C19—C18—C23—C22	1.1 (3)
Ni1—N2—C2—C1	42.4 (2)	C17—C18—C23—C22	−176.9 (2)
N1—C1—C2—N2	−58.6 (3)	C21—C22—C23—N5	177.6 (2)
C2—N2—C3—C5	174.1 (2)	C21—C22—C23—C18	−1.7 (4)
Ni1—N2—C3—C5	−64.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1wⁱ	0.86 (2)	2.15 (2)	2.995 (3)	166 (2)
N2—H2···O5ⁱⁱ	0.86 (2)	2.56 (2)	3.304 (8)	147 (2)
N2—H2···O5′ⁱⁱ	0.86 (2)	2.35 (2)	3.125 (11)	150 (3)
N3—H3···O1	0.86 (2)	2.49 (3)	2.885 (3)	109 (2)
N4—H4···O6ⁱⁱ	0.86 (3)	2.61 (2)	3.343 (6)	145 (3)
N4—H4···O6′ⁱⁱ	0.86 (3)	2.40 (2)	3.195 (6)	155 (3)
N5—H51···O2	0.85 (3)	2.13 (3)	2.751 (3)	129 (2)
N5—H52···O4′ⁱ	0.85 (1)	2.32 (1)	3.155 (6)	168 (3)
O1w—H11···O1	0.84 (2)	1.96 (2)	2.795 (2)	172 (3)
O1w—H12···O3	0.83 (2)	2.26 (2)	3.077 (9)	167 (3)
O1w—H12···O3′	0.83 (2)	2.09 (2)	2.890 (9)	160 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₆NO₂)(C₁₆H₃₆N₄)]ClO₄·H₂O
M_r	596.79
Crystal system, space group	Monoclinic, Cc
Temperature (K)	110
a, b, c (Å)	9.6452 (5), 21.5350 (11), 13.5083 (7)
β (°)	90.784 (1)
V (Å³)	2805.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.45 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.818, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6638, 3832, 3667
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.064, 1.08
No. of reflections	3832
No. of parameters	410
No. of restraints	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21
Absolute structure	Flack (1983), 874 Friedel pairs
Absolute structure parameter	−0.012 (9)

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

Selected bond lengths (Å) top

Ni1—N1	2.124 (2)	Ni1—N4	2.087 (2)
Ni1—N2	2.084 (2)	Ni1—O1	2.1659 (17)
Ni1—N3	2.138 (2)	Ni1—O2	2.1280 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1wⁱ	0.86 (2)	2.15 (2)	2.995 (3)	166 (2)
N2—H2···O5'ⁱⁱ	0.86 (2)	2.35 (2)	3.125 (11)	150 (3)
N3—H3···O1	0.86 (2)	2.49 (3)	2.885 (3)	109 (2)
N4—H4···O6'ⁱⁱ	0.86 (3)	2.399 (17)	3.195 (6)	155 (3)
N5—H51···O2	0.85 (3)	2.13 (3)	2.751 (3)	129 (2)
N5—H52···O4'ⁱ	0.85 (1)	2.316 (14)	3.155 (6)	168 (3)
O1w—H11···O1	0.843 (17)	1.958 (16)	2.795 (2)	172 (3)
O1w—H12···O3	0.83 (2)	2.26 (2)	3.077 (9)	167 (3)
O1w—H12···O3'	0.83 (2)	2.094 (18)	2.890 (9)	160 (3)

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

Acknowledgements

We thank the Key Subject Construction Project of Hunan Province (No. 2006–180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023, 05 C736), the NSF of Hunan Province (09 J J3028) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
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