Poly[[tetra­aqua­bis[μ3-1-ethyl-6-fluoro-4-oxo-7-(piperazinium-1-yl)-1H-quinoline-3-carboxyl­ato]dinickel(II)] hydroxide nitrate]

Song, W.-D.; Wan, Y.-L.; Hong, P.-Z.; Ng, S.W.

doi:10.1107/S1600536807062885

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m70

https://doi.org/10.1107/S1600536807062885

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Poly[[tetraaquabis[μ₃-1-ethyl-6-fluoro-4-oxo-7-(piperazinium-1-yl)-1H-quinoline-3-carboxylato]dinickel(II)] hydroxide nitrate]

Wen-Dong Song,^a Yi-Ling Wan,^b Peng-Zhi Hong ^b and Seik Weng Ng ^c ^*

^aCollege of Science, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, ^bSchool of Food Science and Technology, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 14 November 2007; accepted 24 November 2007; online 6 December 2007)

In the title compound, [Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄](OH)(NO₃), the cationic [Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄]²⁺ building units are linked through Ni–O_carboxylate and Ni—N_amino bridges into a layer structure. The two independent nickel atoms lie on inversion centres: one adopts an NiO₆ octahedral geometry, the other a trans-NiN₂O₄ octahedral arrangement. The charge-balancing hydroxide and nitrate ions are of half site occupancy each. A network of O—H⋯O and N—H⋯O hydrogen bonds helps to establish the packing.

Related literature

For related structures, see Barbas et al. (2007 ); Florence et al. (2000 ). For medical background on norfloxacin, see Goldstein (1987 ).

Experimental

Crystal data

[Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄](NO₃)(OH)
M_r = 907.17
Triclinic, $[P \overline 1]$
a = 8.9633 (2) Å
b = 9.8121 (2) Å
c = 13.2119 (3) Å
α = 101.504 (2)°
β = 106.301 (2)°
γ = 113.528 (2)°
V = 956.34 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 295 (2) K
0.18 × 0.16 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.686, T_max = 0.856
11320 measured reflections
4304 independent reflections
2869 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.219
S = 1.03
4304 reflections
280 parameters
34 restraints
H-atom parameters constrained
Δρ_max = 1.65 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.022 (3)
Ni1—O1w	2.103 (4)
Ni1—N3ⁱ	2.157 (5)
Ni2—O2	1.979 (4)
Ni2—O3	2.021 (3)
Ni2—O3w	2.108 (6)
Symmetry code: (i) x, y, z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807062885/hb2663sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062885/hb2663Isup2.hkl

checkCIF report

Comment top

The drug norfloxacin has been used in the synthesis of metal complexes as it is a carboxylic acid. There are many crystal structure reports of transition metal derivatives (Cambridge Structural Database Version 5.28, Nov. 2006) but all these have the compound in the mono-deprotonated form, in which the piperazinyl group is a neutral substitutent. In the title compound (I), the substituent is protonated (Fig. 1). There are two nickel ions in the asymmetric unit of (I), both with site symmety 1. One adopts an NiO₆ geometry, the other a trans-NiN₂O₄ arrangement (Table 1). A network of O—H···O and N—H···O hydrogen bonds (Table 2) helps to establish the packing.

For related structures, see Barbas et al. (2007) and Florence et al. (2000). For medical background on norfloxacin, see Goldstein (1987).

Related literature top

For related structures, see Barbas et al. (2007); Florence et al. (2000). For medical background on norfloxacin, see Goldstein (1987).

Experimental top

Nickel nitrate (1.0 mmol), 2,2'-bipyridine (1.0 mmol), norfloxacin (1 mmol) and water (10 ml) were hydrothermally treated in a Parr bomb at K22 K for 48 h. The bomb was cooled (5 K h^-1) to room temperature to furnish blue blocks of (I).

Structure description top

For related structures, see Barbas et al. (2007) and Florence et al. (2000). For medical background on norfloxacin, see Goldstein (1987).

For related structures, see Barbas et al. (2007); Florence et al. (2000). For medical background on norfloxacin, see Goldstein (1987).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top

Fig. 1. View of a fragment of the polymeric structure of (I). Displacement ellipsoids are drawn at the 30% probability level, and hydrogen atoms as sphere of arbitrary radius. Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, y, 1 + z; (iii) 1 - x, 1 - y, -z; (iv) 2 - x, 2 - y, 1 - z.

Poly[[tetraaquabis[µ₃-1-ethyl-6-fluoro-4-oxo-7-(piperazinium-1-yl)- 1H-quinoline-3-carboxylato]dinickel(II)] hydroxide nitrate] top

Crystal data top

[Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄](NO₃)(OH)	Z = 1
M_r = 907.17	F(000) = 472
Triclinic, P1	D_x = 1.575 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9633 (2) Å	Cell parameters from 2076 reflections
b = 9.8121 (2) Å	θ = 2.6–28.0°
c = 13.2119 (3) Å	µ = 1.07 mm⁻¹
α = 101.504 (2)°	T = 295 K
β = 106.301 (2)°	Block, blue
γ = 113.528 (2)°	0.18 × 0.16 × 0.15 mm
V = 956.34 (4) Å³

Data collection top

Bruker APEXII diffractometer	4304 independent reflections
Radiation source: medium-focus sealed tube	2869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
φ and ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.686, T_max = 0.856	k = −12→12
11320 measured reflections	l = −17→17

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.219	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1076P)² + 1.3612P] where P = (F_o² + 2F_c²)/3
4304 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 1.65 e Å⁻³
34 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄](NO₃)(OH)	γ = 113.528 (2)°
M_r = 907.17	V = 956.34 (4) Å³
Triclinic, P1	Z = 1
a = 8.9633 (2) Å	Mo Kα radiation
b = 9.8121 (2) Å	µ = 1.07 mm⁻¹
c = 13.2119 (3) Å	T = 295 K
α = 101.504 (2)°	0.18 × 0.16 × 0.15 mm
β = 106.301 (2)°

Data collection top

Bruker APEXII diffractometer	4304 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2869 reflections with I > 2σ(I)
T_min = 0.686, T_max = 0.856	R_int = 0.051
11320 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	34 restraints
wR(F²) = 0.219	H-atom parameters constrained
S = 1.03	Δρ_max = 1.65 e Å⁻³
4304 reflections	Δρ_min = −0.59 e Å⁻³
280 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.5000	0.5000	0.5000	0.0328 (3)
Ni2	1.0000	1.0000	0.5000	0.0362 (3)
F1	0.8924 (5)	1.1417 (4)	0.0053 (3)	0.0597 (10)
O1	0.5117 (4)	0.6049 (4)	0.3832 (3)	0.0403 (9)
O2	0.7870 (5)	0.8001 (5)	0.4694 (3)	0.0522 (11)
O3	0.9054 (5)	0.9832 (5)	0.3374 (3)	0.0450 (10)
O1w	0.7762 (5)	0.5892 (5)	0.5746 (3)	0.0516 (10)
H1w1	0.8119	0.6231	0.6459	0.077*
H1w2	0.8280	0.6650	0.5537	0.077*
O2w	1.4635 (5)	0.9364 (5)	0.4764 (3)	0.079 (3)	0.50
H2w	1.4173	0.8742	0.4083	0.118*	0.50
O3w	1.1392 (8)	0.8776 (7)	0.4696 (5)	0.0892 (17)
H3w1	1.2209	0.9326	0.4513	0.134*
H3w2	1.0678	0.7887	0.4163	0.134*
N1	0.4068 (5)	0.6750 (5)	0.0911 (3)	0.0353 (9)
N2	0.5693 (6)	0.9176 (6)	−0.1764 (3)	0.0445 (11)
H2n	0.5624	1.0037	−0.1616	0.053*
N3	0.5140 (6)	0.7018 (5)	−0.3881 (4)	0.0399 (10)
H3n	0.4886	0.7535	−0.4294	0.048*
C1	0.6428 (6)	0.7216 (6)	0.3853 (4)	0.0355 (11)
C2	0.6166 (6)	0.7618 (6)	0.2808 (4)	0.0343 (11)
C3	0.4548 (7)	0.6655 (6)	0.1942 (4)	0.0372 (11)
H3	0.3704	0.5865	0.2075	0.045*
C4	0.7510 (6)	0.8857 (6)	0.2651 (4)	0.0330 (10)
C5	0.6994 (6)	0.8949 (6)	0.1519 (4)	0.0324 (10)
C6	0.8197 (7)	1.0130 (6)	0.1263 (4)	0.0378 (11)
H6	0.9307	1.0882	0.1824	0.045*
C7	0.7757 (7)	1.0182 (6)	0.0216 (4)	0.0400 (12)
C8	0.6112 (7)	0.9076 (6)	−0.0698 (4)	0.0367 (11)
C9	0.4899 (7)	0.7932 (6)	−0.0432 (4)	0.0360 (11)
H9	0.3790	0.7186	−0.0996	0.043*
C10	0.5301 (6)	0.7878 (6)	0.0651 (4)	0.0328 (10)
C11	0.2248 (7)	0.5575 (7)	0.0058 (5)	0.0445 (13)
H11A	0.1846	0.6056	−0.0457	0.053*
H11B	0.1444	0.5287	0.0434	0.053*
C12	0.2190 (9)	0.4110 (8)	−0.0597 (6)	0.0684 (19)
H12A	0.0997	0.3378	−0.1137	0.103*
H12B	0.2569	0.3622	−0.0091	0.103*
H12C	0.2965	0.4389	−0.0984	0.103*
C13	0.6999 (9)	0.9619 (7)	−0.2271 (5)	0.0551 (16)
H13A	0.8181	1.0297	−0.1679	0.066*
H13B	0.6758	1.0214	−0.2739	0.066*
C14	0.6927 (7)	0.8160 (7)	−0.2977 (4)	0.0481 (14)
H14A	0.7776	0.8489	−0.3319	0.058*
H14B	0.7280	0.7627	−0.2490	0.058*
C15	0.3826 (7)	0.6632 (7)	−0.3352 (4)	0.0431 (12)
H15A	0.4053	0.6045	−0.2873	0.052*
H15B	0.2638	0.5959	−0.3938	0.052*
C16	0.3921 (8)	0.8111 (8)	−0.2659 (5)	0.0489 (14)
H16A	0.3623	0.8665	−0.3147	0.059*
H16B	0.3056	0.7812	−0.2327	0.059*
O4	0.9439 (11)	0.5634 (8)	0.7796 (6)	0.0490 (19)	0.50
O5	1.0325 (17)	0.4310 (17)	0.6823 (12)	0.126 (5)	0.50
O6	0.8282 (11)	0.3095 (10)	0.7300 (8)	0.063 (2)	0.50
N4	0.9354 (9)	0.4383 (9)	0.7316 (5)	0.046 (2)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0328 (5)	0.0316 (5)	0.0269 (5)	0.0082 (4)	0.0117 (4)	0.0128 (4)
Ni2	0.0337 (5)	0.0332 (5)	0.0259 (5)	0.0042 (4)	0.0075 (4)	0.0122 (4)
F1	0.074 (2)	0.0439 (19)	0.0362 (17)	0.0039 (17)	0.0227 (16)	0.0180 (15)
O1	0.0361 (19)	0.040 (2)	0.0340 (18)	0.0079 (16)	0.0113 (15)	0.0198 (16)
O2	0.044 (2)	0.050 (2)	0.0309 (19)	−0.0013 (18)	0.0047 (16)	0.0212 (18)
O3	0.0351 (19)	0.045 (2)	0.0303 (18)	0.0017 (17)	0.0050 (15)	0.0163 (17)
O1w	0.041 (2)	0.051 (2)	0.053 (2)	0.0136 (19)	0.0144 (18)	0.024 (2)
O2w	0.069 (7)	0.093 (9)	0.067 (7)	0.037 (7)	0.024 (6)	0.024 (7)
O3w	0.084 (4)	0.093 (4)	0.094 (4)	0.050 (3)	0.034 (3)	0.028 (3)
N1	0.029 (2)	0.041 (2)	0.029 (2)	0.0115 (18)	0.0106 (16)	0.0132 (18)
N2	0.064 (3)	0.041 (3)	0.028 (2)	0.024 (2)	0.018 (2)	0.015 (2)
N3	0.046 (3)	0.035 (2)	0.034 (2)	0.013 (2)	0.0175 (19)	0.0142 (19)
C1	0.037 (3)	0.037 (3)	0.028 (2)	0.013 (2)	0.013 (2)	0.014 (2)
C2	0.035 (3)	0.035 (3)	0.027 (2)	0.012 (2)	0.0110 (19)	0.013 (2)
C3	0.037 (3)	0.040 (3)	0.037 (3)	0.015 (2)	0.019 (2)	0.020 (2)
C4	0.036 (3)	0.033 (3)	0.029 (2)	0.015 (2)	0.013 (2)	0.014 (2)
C5	0.035 (2)	0.033 (3)	0.027 (2)	0.013 (2)	0.0120 (19)	0.013 (2)
C6	0.035 (3)	0.035 (3)	0.031 (2)	0.009 (2)	0.012 (2)	0.009 (2)
C7	0.048 (3)	0.033 (3)	0.034 (3)	0.012 (2)	0.018 (2)	0.015 (2)
C8	0.048 (3)	0.039 (3)	0.031 (2)	0.025 (2)	0.017 (2)	0.017 (2)
C9	0.037 (3)	0.035 (3)	0.027 (2)	0.014 (2)	0.0076 (19)	0.010 (2)
C10	0.036 (3)	0.034 (3)	0.029 (2)	0.017 (2)	0.0125 (19)	0.012 (2)
C11	0.029 (3)	0.056 (3)	0.037 (3)	0.014 (2)	0.007 (2)	0.017 (3)
C12	0.056 (4)	0.046 (4)	0.069 (5)	0.011 (3)	0.009 (3)	0.004 (3)
C13	0.072 (4)	0.039 (3)	0.031 (3)	0.006 (3)	0.022 (3)	0.012 (2)
C14	0.045 (3)	0.044 (3)	0.033 (3)	0.002 (3)	0.019 (2)	0.007 (2)
C15	0.044 (3)	0.047 (3)	0.033 (3)	0.020 (3)	0.015 (2)	0.009 (2)
C16	0.062 (4)	0.067 (4)	0.032 (3)	0.043 (3)	0.017 (3)	0.021 (3)
O4	0.062 (5)	0.030 (4)	0.038 (4)	0.019 (3)	0.006 (3)	0.005 (3)
O5	0.126 (8)	0.116 (8)	0.138 (8)	0.022 (5)	0.098 (7)	0.060 (7)
O6	0.057 (5)	0.046 (5)	0.080 (6)	0.016 (4)	0.029 (4)	0.026 (4)
N4	0.044 (5)	0.058 (5)	0.048 (5)	0.026 (4)	0.018 (4)	0.037 (4)

Geometric parameters (Å, º) top

Ni1—O1	2.022 (3)	C1—C2	1.492 (6)
Ni1—O1ⁱ	2.022 (3)	C2—C3	1.359 (7)
Ni1—O1w	2.103 (4)	C2—C4	1.430 (6)
Ni1—O1wⁱ	2.103 (4)	C3—H3	0.9300
Ni1—N3ⁱⁱ	2.157 (5)	C4—C5	1.468 (6)
Ni1—N3ⁱⁱⁱ	2.157 (5)	C5—C6	1.408 (6)
Ni2—O2	1.979 (4)	C5—C10	1.411 (7)
Ni2—O2^iv	1.979 (4)	C6—C7	1.345 (7)
Ni2—O3^iv	2.021 (3)	C6—H6	0.9300
Ni2—O3	2.021 (3)	C7—C8	1.418 (7)
Ni2—O3w^iv	2.108 (6)	C8—C9	1.401 (7)
Ni2—O3w	2.108 (6)	C9—C10	1.390 (6)
F1—C7	1.352 (6)	C9—H9	0.9300
O1—C1	1.260 (6)	C11—C12	1.496 (10)
O2—C1	1.247 (6)	C11—H11A	0.9700
O3—C4	1.256 (6)	C11—H11B	0.9700
O1w—H1w1	0.8501	C12—H12A	0.9600
O1w—H1w2	0.8500	C12—H12B	0.9600
O2w—O2w^v	1.088 (8)	C12—H12C	0.9600
O2w—H2w	0.8500	C13—C14	1.511 (9)
O3w—H3w1	0.8501	C13—H13A	0.9700
O3w—H3w2	0.8501	C13—H13B	0.9700
N1—C3	1.343 (6)	C14—H14A	0.9700
N1—C10	1.398 (6)	C14—H14B	0.9700
N1—C11	1.486 (6)	C15—C16	1.509 (8)
N2—C8	1.387 (6)	C15—H15A	0.9700
N2—C16	1.463 (7)	C15—H15B	0.9700
N2—C13	1.469 (7)	C16—H16A	0.9700
N2—H2n	0.8600	C16—H16B	0.9700
N3—C14	1.485 (7)	O4—N4	1.225 (8)
N3—C15	1.493 (7)	O5—N4	1.241 (9)
N3—Ni1^vi	2.157 (5)	O6—N4	1.237 (8)
N3—H3n	0.8600

O1—Ni1—O1ⁱ	180.000 (1)	N1—C3—H3	117.3
O1—Ni1—O1w	94.08 (14)	C2—C3—H3	117.3
O1ⁱ—Ni1—O1w	85.92 (14)	O3—C4—C2	126.4 (4)
O1—Ni1—O1wⁱ	85.92 (14)	O3—C4—C5	118.6 (4)
O1ⁱ—Ni1—O1wⁱ	94.08 (14)	C2—C4—C5	115.0 (4)
O1w—Ni1—O1wⁱ	180.0	C6—C5—C10	117.4 (4)
O1—Ni1—N3ⁱⁱⁱ	89.36 (15)	C6—C5—C4	120.4 (4)
O1ⁱ—Ni1—N3ⁱⁱⁱ	90.64 (15)	C10—C5—C4	122.2 (4)
O1w—Ni1—N3ⁱⁱⁱ	87.36 (16)	C7—C6—C5	120.7 (5)
O1wⁱ—Ni1—N3ⁱⁱⁱ	92.64 (16)	C7—C6—H6	119.7
O1—Ni1—N3ⁱⁱ	90.64 (15)	C5—C6—H6	119.7
O1ⁱ—Ni1—N3ⁱⁱ	89.36 (15)	C6—C7—F1	117.3 (5)
O1w—Ni1—N3ⁱⁱ	92.64 (16)	C6—C7—C8	123.8 (4)
O1wⁱ—Ni1—N3ⁱⁱ	87.36 (16)	F1—C7—C8	118.8 (4)
N3ⁱⁱⁱ—Ni1—N3ⁱⁱ	180.0 (2)	N2—C8—C9	122.3 (5)
O2^iv—Ni2—O2	180.0	N2—C8—C7	122.3 (4)
O2^iv—Ni2—O3^iv	91.12 (14)	C9—C8—C7	115.3 (4)
O2—Ni2—O3^iv	88.88 (14)	C10—C9—C8	122.0 (5)
O2^iv—Ni2—O3	88.88 (14)	C10—C9—H9	119.0
O2—Ni2—O3	91.12 (14)	C8—C9—H9	119.0
O3^iv—Ni2—O3	180.000 (1)	C9—C10—N1	121.5 (4)
O2^iv—Ni2—O3w^iv	91.8 (2)	C9—C10—C5	120.7 (4)
O2—Ni2—O3w^iv	88.2 (2)	N1—C10—C5	117.8 (4)
O3^iv—Ni2—O3w^iv	92.6 (2)	N1—C11—C12	111.7 (5)
O3—Ni2—O3w^iv	87.4 (2)	N1—C11—H11A	109.3
O2^iv—Ni2—O3w	88.2 (2)	C12—C11—H11A	109.3
O2—Ni2—O3w	91.8 (2)	N1—C11—H11B	109.3
O3^iv—Ni2—O3w	87.4 (2)	C12—C11—H11B	109.3
O3—Ni2—O3w	92.6 (2)	H11A—C11—H11B	107.9
O3w^iv—Ni2—O3w	180.000 (3)	C11—C12—H12A	109.5
C1—O1—Ni1	128.4 (3)	C11—C12—H12B	109.5
C1—O2—Ni2	130.1 (3)	H12A—C12—H12B	109.5
C4—O3—Ni2	125.3 (3)	C11—C12—H12C	109.5
Ni1—O1w—H1w1	109.5	H12A—C12—H12C	109.5
Ni1—O1w—H1w2	109.5	H12B—C12—H12C	109.5
H1w1—O1w—H1w2	109.5	N2—C13—C14	110.9 (4)
O2w^v—O2w—H2w	138.4	N2—C13—H13A	109.5
Ni2—O3w—H3w1	109.5	C14—C13—H13A	109.5
Ni2—O3w—H3w2	109.4	N2—C13—H13B	109.5
H3w1—O3w—H3w2	109.5	C14—C13—H13B	109.5
C3—N1—C10	119.8 (4)	H13A—C13—H13B	108.0
C3—N1—C11	118.1 (4)	N3—C14—C13	113.3 (5)
C10—N1—C11	122.0 (4)	N3—C14—H14A	108.9
C8—N2—C16	120.9 (4)	C13—C14—H14A	108.9
C8—N2—C13	122.5 (5)	N3—C14—H14B	108.9
C16—N2—C13	109.1 (4)	C13—C14—H14B	108.9
C8—N2—H2n	99.1	H14A—C14—H14B	107.7
C16—N2—H2n	99.1	N3—C15—C16	111.8 (5)
C13—N2—H2n	99.1	N3—C15—H15A	109.2
C14—N3—C15	108.2 (4)	C16—C15—H15A	109.2
C14—N3—Ni1^vi	115.0 (4)	N3—C15—H15B	109.2
C15—N3—Ni1^vi	115.5 (3)	C16—C15—H15B	109.2
C14—N3—H3n	105.7	H15A—C15—H15B	107.9
C15—N3—H3n	105.7	N2—C16—C15	111.5 (5)
Ni1^vi—N3—H3n	105.7	N2—C16—H16A	109.3
O2—C1—O1	122.5 (4)	C15—C16—H16A	109.3
O2—C1—C2	121.2 (4)	N2—C16—H16B	109.3
O1—C1—C2	116.2 (4)	C15—C16—H16B	109.3
C3—C2—C4	119.6 (4)	H16A—C16—H16B	108.0
C3—C2—C1	115.7 (4)	O4—N4—O6	121.5 (9)
C4—C2—C1	124.6 (4)	O4—N4—O5	123.2 (10)
N1—C3—C2	125.4 (4)	O6—N4—O5	115.3 (10)

O1w—Ni1—O1—C1	−20.5 (5)	C4—C5—C6—C7	177.4 (5)
O1wⁱ—Ni1—O1—C1	159.5 (5)	C5—C6—C7—F1	175.2 (5)
N3ⁱⁱⁱ—Ni1—O1—C1	−107.8 (5)	C5—C6—C7—C8	−1.0 (9)
N3ⁱⁱ—Ni1—O1—C1	72.2 (5)	C16—N2—C8—C9	2.1 (8)
O3^iv—Ni2—O2—C1	168.0 (5)	C13—N2—C8—C9	−144.4 (5)
O3—Ni2—O2—C1	−12.0 (5)	C16—N2—C8—C7	−174.0 (5)
O3w^iv—Ni2—O2—C1	75.3 (6)	C13—N2—C8—C7	39.5 (8)
O3w—Ni2—O2—C1	−104.7 (6)	C6—C7—C8—N2	179.2 (5)
O2^iv—Ni2—O3—C4	−170.1 (5)	F1—C7—C8—N2	3.0 (8)
O2—Ni2—O3—C4	9.9 (5)	C6—C7—C8—C9	2.9 (8)
O3w^iv—Ni2—O3—C4	−78.3 (5)	F1—C7—C8—C9	−173.3 (5)
O3w—Ni2—O3—C4	101.7 (5)	N2—C8—C9—C10	−177.4 (5)
Ni2—O2—C1—O1	−172.1 (4)	C7—C8—C9—C10	−1.0 (8)
Ni2—O2—C1—C2	7.9 (8)	C8—C9—C10—N1	178.8 (5)
Ni1—O1—C1—O2	−6.5 (8)	C8—C9—C10—C5	−2.6 (8)
Ni1—O1—C1—C2	173.5 (3)	C3—N1—C10—C9	174.9 (5)
O2—C1—C2—C3	178.7 (5)	C11—N1—C10—C9	−1.6 (8)
O1—C1—C2—C3	−1.2 (7)	C3—N1—C10—C5	−3.7 (7)
O2—C1—C2—C4	2.5 (8)	C11—N1—C10—C5	179.7 (5)
O1—C1—C2—C4	−177.5 (5)	C6—C5—C10—C9	4.4 (7)
C10—N1—C3—C2	2.2 (8)	C4—C5—C10—C9	−175.7 (5)
C11—N1—C3—C2	178.9 (5)	C6—C5—C10—N1	−177.0 (5)
C4—C2—C3—N1	0.3 (9)	C4—C5—C10—N1	3.0 (7)
C1—C2—C3—N1	−176.1 (5)	C3—N1—C11—C12	−89.1 (6)
Ni2—O3—C4—C2	−4.4 (8)	C10—N1—C11—C12	87.5 (6)
Ni2—O3—C4—C5	176.5 (3)	C8—N2—C13—C14	92.7 (6)
C3—C2—C4—O3	179.8 (5)	C16—N2—C13—C14	−57.2 (6)
C1—C2—C4—O3	−4.1 (9)	C15—N3—C14—C13	−53.8 (5)
C3—C2—C4—C5	−1.0 (7)	Ni1^vi—N3—C14—C13	175.4 (3)
C1—C2—C4—C5	175.1 (5)	N2—C13—C14—N3	56.8 (6)
O3—C4—C5—C6	−1.4 (8)	C14—N3—C15—C16	54.0 (6)
C2—C4—C5—C6	179.3 (5)	Ni1^vi—N3—C15—C16	−175.4 (3)
O3—C4—C5—C10	178.6 (5)	C8—N2—C16—C15	−91.7 (6)
C2—C4—C5—C10	−0.7 (7)	C13—N2—C16—C15	58.7 (6)
C10—C5—C6—C7	−2.6 (8)	N3—C15—C16—N2	−58.6 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O4	0.85	2.16	2.820 (8)	135
O1w—H1w2···O2	0.85	1.97	2.700 (5)	143
O2w—H2w···O6^vii	0.85	2.17	2.90 (1)	145
O3w—H3w1···O2w	0.85	2.09	2.699 (7)	128
O3w—H3w2···O5^vii	0.85	1.96	2.77 (2)	161
N3—H3n···O2w^viii	0.86	2.43	3.277 (6)	171

Symmetry codes: (vii) −x+2, −y+1, −z+1; (viii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	[Ni₂(C₁₆H₁₈FN₃O₃)₂(H₂O)₄](NO₃)(OH)
M_r	907.17
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.9633 (2), 9.8121 (2), 13.2119 (3)
α, β, γ (°)	101.504 (2), 106.301 (2), 113.528 (2)
V (Å³)	956.34 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.18 × 0.16 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.686, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	11320, 4304, 2869
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.219, 1.03
No. of reflections	4304
No. of parameters	280
No. of restraints	34
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.65, −0.59

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected bond lengths (Å) top

Ni1—O1	2.022 (3)	Ni2—O2	1.979 (4)
Ni1—O1w	2.103 (4)	Ni2—O3	2.021 (3)
Ni1—N3ⁱ	2.157 (5)	Ni2—O3w	2.108 (6)

Symmetry code: (i) x, y, z+1.

Acknowledgements

We thank Guangdong Ocean University and the University of Malaya for supporting this study.

References

Barbas, R., Prohens, R. & Puigjaner, C. (2007). J. Therm. Anal. Calor. 89, 687–692. Web of Science CSD CrossRef CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2004). APEX2 (Version 2.0.23A) and SAINT (Version 7.23A). Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Florence, A. J., Kennedy, A. R., Shankland, N., Wright, E. & Al-Rubayi, A. (2000). Acta Cryst. C56, 1372–1373. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Goldstein, E. (1987). Am. J. Med. 82, 3–17. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar

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