Diaqua­(1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)nickel(II) fumarate tetra­hydrate

Lim, S.L.; Ng, C.H.; Teoh, S.G.; Loh, W.-S.; Fun, H.-K.

doi:10.1107/S1600536810020064

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m737-m738

doi:10.1107/S1600536810020064

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Diaqua(1,4,8,11-tetraazacyclotetradecane)nickel(II) fumarate tetrahydrate

Shao Liang Lim,^a Chew Hee Ng,^a Siang Guan Teoh,^b Wan-Sin Loh ^c ‡ and Hoong-Kun Fun ^c ^*§

^aFaculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia, ^bSchool of Chemical Science, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 13 May 2010; accepted 27 May 2010; online 5 June 2010)

The asymmetric unit of the title complex salt, [Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O, comprises half of a nickel(II) complex dication, half of a fumarate dianion and two water molecules. Both the Ni^II cation and fumarate anion lie on a crystallographic inversion center. The Ni^II ion in the cyclam complex is six-coordinated within a distorted N₄O₂ octahedral geometry, with the four cyclam N atoms in the equatorial plane and the two water molecules in apical positions. The six-membered metalla ring adopts a chair conformation, whereas the five-membered ring exists in a twisted form. In the crystal packing, intermolecular O—H⋯O hydrogen bonds between the water molecules and the carboxyl groups of the fumarate anions lead to the formation of layers with R₄²(8) ring motifs. Ni^II complex cations are sandwiched between two such layers, being held in place by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, consolidating a three-dimensional network.

Related literature

For the background to and the biological activity of cyclam, see: Kim et al. (2006 ); Hunter et al. (2006 ); Gerlach et al. (2003 ); Paisey & Sadler (2004 ). For a related structure, see: Panneerselvam et al. (1999 ). For puckering parameters, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

[Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O
M_r = 481.19
Triclinic, $[P \overline 1]$
a = 6.9913 (5) Å
b = 8.8313 (7) Å
c = 9.3147 (8) Å
α = 73.165 (2)°
β = 79.207 (2)°
γ = 85.227 (2)°
V = 540.47 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 100 K
0.47 × 0.44 × 0.24 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.665, T_max = 0.805
12800 measured reflections
4295 independent reflections
4219 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.133
S = 1.30
4295 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.27 e Å⁻³
Δρ_min = −1.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O3W	0.85	2.17	2.8047 (14)	131
O2W—H1W2⋯O2ⁱ	0.85	1.98	2.7026 (14)	142
O2W—H2W2⋯O2ⁱⁱ	0.85	1.91	2.7000 (15)	154
O3W—H1W3⋯O1ⁱⁱⁱ	0.85	1.96	2.7633 (14)	157
O3W—H2W3⋯O1	0.85	2.06	2.7968 (14)	144
N1—H1N1⋯O2W^iv	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2⋯O3W^iv	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B⋯O1^v	0.97	2.60	3.3850 (18)	138
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) -x+2, -y+1, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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 PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020064/tk2677sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020064/tk2677Isup2.hkl

checkCIF report

Comment top

The antiviral properties of cyclam (1,4,8,11-tetraazacyclotetradecane) have stimulated interest in metal complexes of this ligand (Kim et al., 2006). Besides its antiviral property, [Ni(cyclam)(OAc)₂] also has protein recognition potential (Hunter et al., 2006). Amongst the metal ions investigated, coordination of Ni^II to cyclam rings bridged by 1,4-dimethylene(phenylene) was reported to result in greatest enhancement of its antiviral property (Gerlach et al., 2003). However, the rate of complexation of Ni^II to cyclam is the poorest compared to Cu^II, Zn^II and Co^II (Paisey et al., 2004). In this paper, we report the crystal structure of the title compound, obtained by the reaction of a nickel(II) salt, cyclam and sodium fumarate.

The title compound, Fig. 1, consists of one nickel(II) complex cation, one fumarate anion and four water molecules. Both Ni^II ion and fumarate anion lie on a crystallographic inversion center, generated by the symmetry codes -x+2, -y+1, -z and -x+1, -y, -z+1, respectively. The Ni^II complex of cyclam has six-coordination in a distorted octahedral geometry, with the four ligand N atoms (N1/N2/N1A/N2A) almost coplanar with the Ni^II ion and the two water molecules (O1W & O1WA) in apical positions. The six-membered ring (Ni1/N1/C1–C3/N2) exists in a chair conformation with the puckering parameters (Cremer & Pople, 1975) Q = 0.5900 (14) Å; Θ = 9.05 (13)° and ϕ = 192.1 (9)°. In the five-membered ring, Ni1/N1/C5/C4A/N2A is twisted about the C5–C4A bond with the puckering parameters (Cremer & Pople, 1975) Q = 0.4382 (14) Å and ϕ = 271.34 (14)°. This structure is comparable to a closely related structure (Panneerselvam et al., 1999).

In the crystal packing (Fig. 2), intermolecular O_water—H···O_carboxylate, hydrogen bonds (Table 1) link with the carboxyl groups of the fumarate anions into a two-dimensional layers with R²₄(8) ring motifs (Bernstein et al., 1995). The Ni^II complex cations are linked to these layers by O_aquo—H···O_water, N_amine—H···O_water, C3—H3B···O_carboxylate hydrogen bonds (Table 1) to form a three-dimensional network.

Related literature top

For the background to and the biological activity of cyclam, see: Kim et al. (2006); Hunter et al. (2006); Gerlach et al. (2003); Paisey et al. (2004). For a related structure, see: Panneerselvam et al. (1999). For puckering parameters, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

Nickel chloride hexahydrate (0.24 g, 1 mmol), cyclam (0.22 g, 1 mmol) and sodium fumarate (0.16 g, 1 mmol) were dissolved in water and heated overnight in a water bath at 313 K. Purple crystals were obtained from the yellow solution.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Symmetry-related atoms of the Ni^II complex ion and fumarate anion are generated by the symmetry codes -x+2, -y+1, -z and -x+1, -y, -z+1, respectively.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the a axis, showing the three-dimensional network. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Diaqua(1,4,8,11-tetraazacyclotetradecane)nickel(II) fumarate tetrahydrate top

Crystal data top

[Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O	Z = 1
M_r = 481.19	F(000) = 258
Triclinic, P1	D_x = 1.478 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9913 (5) Å	Cell parameters from 9982 reflections
b = 8.8313 (7) Å	θ = 3.8–35.1°
c = 9.3147 (8) Å	µ = 0.95 mm⁻¹
α = 73.165 (2)°	T = 100 K
β = 79.207 (2)°	Block, purple
γ = 85.227 (2)°	0.47 × 0.44 × 0.24 mm
V = 540.47 (7) Å³

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	4295 independent reflections
Radiation source: fine-focus sealed tube	4219 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 34.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.665, T_max = 0.805	k = −13→13
12800 measured reflections	l = −14→14

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0892P)² + 0.062P] where P = (F_o² + 2F_c²)/3
S = 1.30	(Δ/σ)_max < 0.001
4295 reflections	Δρ_max = 1.27 e Å⁻³
142 parameters	Δρ_min = −1.18 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.75 (4)

Crystal data top

[Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O	γ = 85.227 (2)°
M_r = 481.19	V = 540.47 (7) Å³
Triclinic, P1	Z = 1
a = 6.9913 (5) Å	Mo Kα radiation
b = 8.8313 (7) Å	µ = 0.95 mm⁻¹
c = 9.3147 (8) Å	T = 100 K
α = 73.165 (2)°	0.47 × 0.44 × 0.24 mm
β = 79.207 (2)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	4295 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4219 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.805	R_int = 0.017
12800 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	Δρ_max = 1.27 e Å⁻³
4295 reflections	Δρ_min = −1.18 e Å⁻³
142 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Ni1	1.0000	0.5000	0.0000	0.00889 (11)
O1W	0.70136 (13)	0.43457 (11)	0.07879 (11)	0.01471 (17)
H1W1	0.5819	0.4284	0.1199	0.022*
H2W1	0.7631	0.3578	0.1313	0.022*
N1	0.90487 (15)	0.73294 (12)	−0.04325 (12)	0.01220 (18)
N2	0.97429 (15)	0.48188 (12)	−0.21216 (12)	0.01229 (18)
C1	0.97192 (19)	0.83674 (14)	−0.19756 (15)	0.0160 (2)
H1A	1.1117	0.8476	−0.2125	0.019*
H1B	0.9108	0.9411	−0.2068	0.019*
C2	0.9231 (2)	0.77130 (15)	−0.32091 (15)	0.0188 (2)
H2A	0.7853	0.7497	−0.2980	0.023*
H2B	0.9461	0.8528	−0.4173	0.023*
C3	1.0368 (2)	0.62134 (16)	−0.34023 (14)	0.0168 (2)
H3A	1.0178	0.6032	−0.4344	0.020*
H3B	1.1746	0.6357	−0.3474	0.020*
C4	1.08394 (18)	0.33580 (15)	−0.22827 (14)	0.0154 (2)
H4A	1.2220	0.3563	−0.2578	0.018*
H4B	1.0424	0.3011	−0.3070	0.018*
C5	0.95195 (18)	0.79227 (14)	0.07821 (15)	0.0144 (2)
H5A	0.8713	0.8855	0.0855	0.017*
H5B	1.0873	0.8217	0.0545	0.017*
O1	0.52695 (16)	0.26163 (11)	0.55707 (11)	0.01632 (18)
O2	0.52311 (19)	0.08177 (12)	0.78098 (11)	0.0224 (2)
C11	0.51455 (17)	0.12258 (13)	0.64080 (13)	0.0124 (2)
C12	0.48943 (17)	−0.00891 (13)	0.57443 (12)	0.0121 (2)
H12A	0.4574	−0.1080	0.6408	0.014*
O2W	0.52940 (14)	0.20503 (11)	0.01387 (11)	0.01441 (17)
H1W2	0.5831	0.1689	−0.0597	0.022*
H2W2	0.5251	0.1297	0.0954	0.022*
O3W	0.42354 (14)	0.50357 (11)	0.31238 (11)	0.01463 (18)
H1W3	0.4170	0.5898	0.3362	0.022*
H2W3	0.3993	0.4291	0.3948	0.022*
H1N1	0.779 (3)	0.719 (3)	−0.034 (3)	0.018 (5)*
H1N2	0.849 (3)	0.463 (3)	−0.210 (3)	0.015 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00948 (13)	0.00806 (13)	0.00991 (13)	−0.00033 (7)	−0.00201 (7)	−0.00347 (8)
O1W	0.0114 (4)	0.0161 (4)	0.0187 (4)	−0.0023 (3)	−0.0003 (3)	−0.0089 (3)
N1	0.0115 (4)	0.0103 (4)	0.0151 (4)	−0.0006 (3)	−0.0026 (3)	−0.0038 (3)
N2	0.0125 (4)	0.0134 (4)	0.0120 (4)	−0.0008 (3)	−0.0025 (3)	−0.0047 (3)
C1	0.0183 (5)	0.0108 (4)	0.0175 (5)	−0.0020 (4)	−0.0043 (4)	−0.0006 (4)
C2	0.0237 (6)	0.0158 (5)	0.0163 (5)	−0.0013 (4)	−0.0087 (4)	−0.0003 (4)
C3	0.0212 (5)	0.0180 (5)	0.0111 (4)	−0.0034 (4)	−0.0030 (4)	−0.0029 (4)
C4	0.0170 (5)	0.0161 (5)	0.0153 (5)	−0.0003 (4)	−0.0011 (4)	−0.0089 (4)
C5	0.0143 (5)	0.0117 (4)	0.0193 (5)	−0.0008 (3)	−0.0023 (4)	−0.0080 (4)
O1	0.0251 (5)	0.0105 (4)	0.0131 (4)	−0.0020 (3)	−0.0028 (3)	−0.0029 (3)
O2	0.0434 (6)	0.0145 (4)	0.0110 (4)	−0.0018 (4)	−0.0080 (4)	−0.0041 (3)
C11	0.0158 (5)	0.0113 (4)	0.0110 (4)	−0.0002 (3)	−0.0017 (3)	−0.0050 (3)
C12	0.0153 (5)	0.0107 (4)	0.0105 (4)	−0.0004 (3)	−0.0019 (3)	−0.0037 (3)
O2W	0.0174 (4)	0.0131 (4)	0.0146 (4)	−0.0020 (3)	−0.0032 (3)	−0.0061 (3)
O3W	0.0175 (4)	0.0144 (4)	0.0134 (4)	−0.0017 (3)	−0.0034 (3)	−0.0052 (3)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.0564 (10)	C2—H2B	0.9700
Ni1—N1	2.0565 (10)	C3—H3A	0.9700
Ni1—N2	2.0699 (10)	C3—H3B	0.9700
Ni1—N2ⁱ	2.0699 (10)	C4—C5ⁱ	1.5153 (18)
Ni1—O1W	2.1478 (9)	C4—H4A	0.9700
Ni1—O1Wⁱ	2.1478 (9)	C4—H4B	0.9700
O1W—H1W1	0.8499	C5—C4ⁱ	1.5153 (18)
O1W—H2W1	0.8506	C5—H5A	0.9700
N1—C5	1.4747 (16)	C5—H5B	0.9700
N1—C1	1.4772 (17)	O1—C11	1.2496 (14)
N1—H1N1	0.88 (2)	O2—C11	1.2615 (14)
N2—C3	1.4745 (16)	C11—C12	1.5007 (16)
N2—C4	1.4761 (16)	C12—C12ⁱⁱ	1.330 (2)
N2—H1N2	0.90 (2)	C12—H12A	0.9300
C1—C2	1.5279 (19)	O2W—H1W2	0.8501
C1—H1A	0.9700	O2W—H2W2	0.8496
C1—H1B	0.9700	O3W—H1W3	0.8482
C2—C3	1.5253 (19)	O3W—H2W3	0.8537
C2—H2A	0.9700

N1ⁱ—Ni1—N1	180.0	C2—C1—H1B	109.2
N1ⁱ—Ni1—N2	85.49 (4)	H1A—C1—H1B	107.9
N1—Ni1—N2	94.51 (4)	C3—C2—C1	115.74 (11)
N1ⁱ—Ni1—N2ⁱ	94.51 (4)	C3—C2—H2A	108.3
N1—Ni1—N2ⁱ	85.49 (4)	C1—C2—H2A	108.3
N2—Ni1—N2ⁱ	179.999 (1)	C3—C2—H2B	108.3
N1ⁱ—Ni1—O1W	91.94 (4)	C1—C2—H2B	108.3
N1—Ni1—O1W	88.06 (4)	H2A—C2—H2B	107.4
N2—Ni1—O1W	88.73 (4)	N2—C3—C2	111.79 (10)
N2ⁱ—Ni1—O1W	91.27 (4)	N2—C3—H3A	109.3
N1ⁱ—Ni1—O1Wⁱ	88.06 (4)	C2—C3—H3A	109.3
N1—Ni1—O1Wⁱ	91.94 (4)	N2—C3—H3B	109.3
N2—Ni1—O1Wⁱ	91.27 (4)	C2—C3—H3B	109.3
N2ⁱ—Ni1—O1Wⁱ	88.73 (4)	H3A—C3—H3B	107.9
O1W—Ni1—O1Wⁱ	180.0	N2—C4—C5ⁱ	109.50 (10)
Ni1—O1W—H1W1	165.2	N2—C4—H4A	109.8
Ni1—O1W—H2W1	77.0	C5ⁱ—C4—H4A	109.8
H1W1—O1W—H2W1	107.7	N2—C4—H4B	109.8
C5—N1—C1	113.05 (9)	C5ⁱ—C4—H4B	109.8
C5—N1—Ni1	106.83 (7)	H4A—C4—H4B	108.2
C1—N1—Ni1	116.66 (8)	N1—C5—C4ⁱ	109.30 (9)
C5—N1—H1N1	112.6 (16)	N1—C5—H5A	109.8
C1—N1—H1N1	108.2 (16)	C4ⁱ—C5—H5A	109.8
Ni1—N1—H1N1	98.8 (16)	N1—C5—H5B	109.8
C3—N2—C4	112.55 (10)	C4ⁱ—C5—H5B	109.8
C3—N2—Ni1	114.93 (8)	H5A—C5—H5B	108.3
C4—N2—Ni1	105.98 (7)	O1—C11—O2	124.55 (11)
C3—N2—H1N2	109.8 (15)	O1—C11—C12	119.64 (10)
C4—N2—H1N2	105.3 (14)	O2—C11—C12	115.81 (10)
Ni1—N2—H1N2	107.8 (15)	C12ⁱⁱ—C12—C11	123.39 (13)
N1—C1—C2	111.84 (10)	C12ⁱⁱ—C12—H12A	118.3
N1—C1—H1A	109.2	C11—C12—H12A	118.3
C2—C1—H1A	109.2	H1W2—O2W—H2W2	107.7
N1—C1—H1B	109.2	H1W3—O3W—H2W3	107.5

N2—Ni1—N1—C5	−166.65 (8)	O1W—Ni1—N2—C4	−106.83 (7)
N2ⁱ—Ni1—N1—C5	13.35 (8)	O1Wⁱ—Ni1—N2—C4	73.17 (7)
O1W—Ni1—N1—C5	104.78 (8)	C5—N1—C1—C2	179.36 (10)
O1Wⁱ—Ni1—N1—C5	−75.22 (8)	Ni1—N1—C1—C2	54.91 (12)
N2—Ni1—N1—C1	−39.09 (9)	N1—C1—C2—C3	−69.36 (15)
N2ⁱ—Ni1—N1—C1	140.91 (9)	C4—N2—C3—C2	−179.50 (10)
O1W—Ni1—N1—C1	−127.66 (8)	Ni1—N2—C3—C2	−58.06 (12)
O1Wⁱ—Ni1—N1—C1	52.34 (8)	C1—C2—C3—N2	71.78 (14)
N1ⁱ—Ni1—N2—C3	−139.74 (9)	C3—N2—C4—C5ⁱ	166.48 (10)
N1—Ni1—N2—C3	40.26 (9)	Ni1—N2—C4—C5ⁱ	40.06 (11)
O1W—Ni1—N2—C3	128.21 (9)	C1—N1—C5—C4ⁱ	−168.52 (10)
O1Wⁱ—Ni1—N2—C3	−51.79 (9)	Ni1—N1—C5—C4ⁱ	−38.86 (11)
N1ⁱ—Ni1—N2—C4	−14.78 (7)	O1—C11—C12—C12ⁱⁱ	11.2 (2)
N1—Ni1—N2—C4	165.22 (7)	O2—C11—C12—C12ⁱⁱ	−168.24 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3W	0.85	2.17	2.8047 (14)	131
O2W—H1W2···O2ⁱⁱⁱ	0.85	1.98	2.7026 (14)	142
O2W—H2W2···O2ⁱⁱ	0.85	1.91	2.7000 (15)	154
O3W—H1W3···O1^iv	0.85	1.96	2.7633 (14)	157
O3W—H2W3···O1	0.85	2.06	2.7968 (14)	144
N1—H1N1···O2W^v	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2···O3W^v	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B···O1ⁱ	0.97	2.60	3.3850 (18)	138

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

Experimental details

Crystal data
Chemical formula	[Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O
M_r	481.19
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.9913 (5), 8.8313 (7), 9.3147 (8)
α, β, γ (°)	73.165 (2), 79.207 (2), 85.227 (2)
V (Å³)	540.47 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.47 × 0.44 × 0.24

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.665, 0.805
No. of measured, independent and observed [I > 2σ(I)] reflections	12800, 4295, 4219
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.787

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.133, 1.30
No. of reflections	4295
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.27, −1.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3W	0.8500	2.1700	2.8047 (14)	131.00
O2W—H1W2···O2ⁱ	0.8500	1.9800	2.7026 (14)	142.00
O2W—H2W2···O2ⁱⁱ	0.8500	1.9100	2.7000 (15)	154.00
O3W—H1W3···O1ⁱⁱⁱ	0.8500	1.9600	2.7633 (14)	157.00
O3W—H2W3···O1	0.8500	2.0600	2.7968 (14)	144.00
N1—H1N1···O2W^iv	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2···O3W^iv	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B···O1^v	0.9700	2.6000	3.3850 (18)	138.00

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

Footnotes

‡Thomson Reuters ResearcherID: C-7581-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

SLL, CHN and SGT thank the Malaysian Government and the Ministry of Science, Technology and Innovation (MOSTI) (eSc 02–02-11-SF0033). CHN and SLL also thank the UTAR Research Fund. HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). WSL also thanks the Malaysian Government and USM for the award of Research Fellowship.

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