μ-Squarato-κ2O1:O2-bis­{[2-(2-amino­ethyl)pyridine-κ2N,N′]aqua­nickel(II)} squarate 0.25-hydrate

Bekdemir, Y.; Uçar, I.; Büyükgüngör, O.

doi:10.1107/S1600536808030808

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1344-m1345

doi:10.1107/S1600536808030808

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μ-Squarato-κ²O¹:O²-bis{[2-(2-aminoethyl)pyridine-κ²N,N′]aquanickel(II)} squarate 0.25-hydrate

Yunus Bekdemir,^a Ibrahim Uçar ^b ^* and Orhan Büyükgüngör ^b

^aOndokuz Mayıs University, Art and Science Faculty, Department of Chemistry, 55139 Samsun, Turkey, and ^bOndokuz Mayıs University, Art and Science Faculty, Department of Physics, 55139 Samsun, Turkey
^*Correspondence e-mail: iucar@omu.edu.tr

(Received 15 August 2008; accepted 24 September 2008; online 27 September 2008)

The asymmetric unit of title compound, [Ni₂(C₄O₄)(C₇H₁₀N₂)₄(H₂O)₂]C₄O₄·0.25H₂O, contains one-half of a squarate ligand, one-half of an uncoordinated squarate dianion, two 2-(2-aminoethyl)pyridine ligands and one aqua ligand, all coordinated to an Ni^II ion. The compound also contains 0.25 solvent water molecules. The Ni^II ion has distorted octahedral geometry. The squarate ligand adopts a μ-1,2 coordination mode, the intradimer Ni^II⋯Ni^II separation being 7.1442 (7) Å, while the other squarate unit acts as a counter-anion. The crystal structure is stabilized by intermolecular O—H⋯O and N—H⋯O hydrogen-bond interactions, forming a three-dimensional network.

Related literature

For general background, see: Bernardinelli et al. (1989 ); Bulut et al. (2004 ); Castro et al. (1995 , 1997 ); Crispini et al. (2000 ); Kirchmaier et al. (2003 ); Lee et al. (1996 ); Milet et al. (2003 ); Solans et al. (1990 ); Spek (2003 ); Trombe et al. (2002 ); Uçar (2008 ); Uçar et al. (2006 , 2007 ); Yang et al. (2003 ).

Experimental

Crystal data

[Ni₂(C₄O₄)(C₇H₁₀N₂)₄(H₂O)₂]C₄O₄·0.25H₂O
M_r = 870.16
Monoclinic, C 2/c
a = 28.037 (3) Å
b = 8.0409 (5) Å
c = 17.7752 (16) Å
β = 103.572 (7)°
V = 3895.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 297 (2) K
0.3 × 0.2 × 0.1 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.49, T_max = 0.81
12243 measured reflections
3809 independent reflections
3148 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.03
3809 reflections
282 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O4ⁱ	0.81 (3)	1.93 (3)	2.716 (2)	163 (3)
N2—H2A⋯O3ⁱ	0.90 (2)	2.09 (2)	2.935 (2)	157 (2)
O5—H5B⋯O2	0.81 (3)	1.87 (3)	2.675 (2)	172 (3)
N4—H4B⋯O2ⁱⁱ	0.88 (2)	2.52 (2)	3.078 (2)	122.6 (18)
N4—H4B⋯O6	0.88 (2)	2.52 (3)	3.350 (2)	158 (2)
N4—H4A⋯O4ⁱⁱⁱ	0.86 (2)	2.27 (2)	3.091 (2)	161 (2)
N2—H2B⋯O3^iv	0.83 (2)	2.14 (3)	2.963 (2)	169 (2)
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030808/pk2116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030808/pk2116Isup2.hkl

checkCIF report

Comment top

Squarate acts as a bridge between two or more metal atoms in mono- or polydentate coordination modes when acting as a ligand towards first row transition metal ions [Trombe et al., 2002; Milet et al., 2003]. It coordinates to Fe(II), Fe(III), Ni^II and Cu(II) complexes in a µ-1,3 fashion, giving binuclear [Bernardinelli et al., 1989; Lee et al., 1996] and chain structures [Solans et al., 1990; Yang et al.,2003], whereas the µ-1,2 coordination mode has been reported for binuclear and chain complexes of Cu(II) and Pd(II) [Castro et al., 1997; Crispini et al., 2000]. It is also observed that the squarate anion, with Cu(II) and Ni^II, acts as a tetramonodentate ligand and forms polynuclear compounds [Castro et al., 1995].

In our ongoing research on squaric acid, we have synthesized some mixed–ligand metal(II) complexes of squaric acid, and their structures have been reported [Uçar et al., 2006; Uçar et al. 2007;]. In these compounds, squaric acid behaves as a monodentate ligand [Bulut et al., 2004] or acts as both a monodentate and bidentate ligand, or has a µ-1,3 coordination, while in this study, it has µ-1,2 bis(monodentate) coordination between the metal ions.

The title compound consists of an apparently centrosymmetric binuclear [Ni₂(aepy)₄(H₂O)₂(C₄O₄)]²⁺ [aepy: 2(2-aminoethyl)pyridine] complex cation, one squarate counter anion (C₄O₄)^2-and 0.25 water molecule. In the crystal structure one of the squarates adopts a bridging position between the metal atoms, coordinating via two of its O atoms in a µ-1,2 fashion, forming a dimeric metal unit, while the other squarate acts as a counter anion (Fig.1). The geometry about Ni^II ion centre is a slightly distorted octahedron, the six coordination sites being occupied by four N atoms from two chelating aepy ligands and two O atoms from squarate and aqua ligands. The observed Ni1–N, Ni1–O bond distances and N–Ni1–N, N–Ni1–O and O–Ni1–O bond angles are generally consistent with those observed in related Ni^II squarate complexes [Uçar, 2008; Kirchmaier et al., 2003].

The crystal packing is formed by intermolecular hydrogen bonding interactions (Fig. 2). The aqua ligands and amine hydrogen atoms link the complex cation to counter the squarate anion through hydrogen bonding interactions. The intradimer Ni1(II)···Ni1 (-x, y, -z + 1/2) distance is 7.1442 (7) Å.

Related literature top

For related literature, see: Bernardinelli et al. (1989); Bulut et al. (2004); Castro et al. (1995, 1997); Crispini et al. (2000); Kirchmaier et al. (2003); Lee et al. (1996); Milet et al. (2003); Solans et al. (1990); Spek (2003); Trombe et al. (2002); Uçar (2008); Uçar et al. (2006, 2007); Yang et al. (2003).

Experimental top

Squaric acid (0.57 g, 5 mmol), dissolved in 25 ml water was neutralized with NaOH (0.40 g, 10 mmol) and was added to a hot solution of the NiCl₂.6H₂O (1.19 g, 5 mmol) dissolved in 100 ml water. The mixture was refluxed at 353 K for 12 h and then cooled to room temperature. The blue crystals that formed were filtered and washed with water and alcohol and dried in vacuum. A solution of 2(2-aminoethyl)pyridine) (0.25 g, 2 mmol) in ethanol (50 ml) was added dropwise with stirring to a suspension of the NiSq.2H₂O (0.207 g, 1 mmol) in water (100 ml). A few days later, well formed blue crystals were selected for X-ray studies.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. : ORTEPIII (Burnett & Johnson, 1996) plot of the [Ni₂(aepy)₄(sq)(H₂O)₂].sq 0.25H₂O. Non-H atoms are drawn with displacement ellipsoids at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) -x, y, -z + 1/2; (ii) -x + 1/2, -y + 1.5, -z]
	Fig. 2. : Showing of intermolecular hydrogen bonding interactions (dashed lines) in the unitcell.

µ-Squarato-κ²O¹:O²-bis{[2-(2-aminoethyl)pyridine- κ²N,N']aquanickel(II)} squarate 0.25-hydrate top

Crystal data top

[Ni₂(C₄O₄)(C₇H₁₀N₂)₄(H₂O)₂]C₄O₄·0.25H₂O	F(000) = 1816
M_r = 870.16	D_x = 1.484 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 24222 reflections
a = 28.037 (3) Å	θ = 1.7–28.0°
b = 8.0409 (5) Å	µ = 1.03 mm⁻¹
c = 17.7752 (16) Å	T = 297 K
β = 103.572 (7)°	Prism, blue
V = 3895.3 (5) Å³	0.3 × 0.2 × 0.1 mm
Z = 4

Data collection top

Stoe IPDS-II diffractometer	3809 independent reflections
Radiation source: fine-focus sealed tube	3148 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 2.4°
ω scans	h = −34→34
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −9→9
T_min = 0.49, T_max = 0.81	l = −21→21
12243 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0385P)² + 0.9229P] where P = (F_o² + 2F_c²)/3
3809 reflections	(Δ/σ)_max = 0.001
282 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Ni₂(C₄O₄)(C₇H₁₀N₂)₄(H₂O)₂]C₄O₄·0.25H₂O	V = 3895.3 (5) Å³
M_r = 870.16	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 28.037 (3) Å	µ = 1.03 mm⁻¹
b = 8.0409 (5) Å	T = 297 K
c = 17.7752 (16) Å	0.3 × 0.2 × 0.1 mm
β = 103.572 (7)°

Data collection top

Stoe IPDS-II diffractometer	3809 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	3148 reflections with I > 2σ(I)
T_min = 0.49, T_max = 0.81	R_int = 0.042
12243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.29 e Å⁻³
3809 reflections	Δρ_min = −0.26 e Å⁻³
282 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)
C1	0.01456 (9)	0.6924 (3)	0.42515 (16)	0.0615 (6)
H1	0.0078	0.6622	0.3732	0.074*
C2	−0.02378 (11)	0.7007 (4)	0.4607 (2)	0.0880 (9)
H2	−0.0557	0.6790	0.4331	0.106*
C3	−0.01433 (14)	0.7411 (5)	0.5371 (3)	0.1052 (12)
H3	−0.0396	0.7486	0.5627	0.126*
C4	0.03335 (14)	0.7707 (4)	0.5755 (2)	0.0885 (10)
H4	0.0406	0.7952	0.6281	0.106*
C5	0.07099 (10)	0.7643 (3)	0.53672 (15)	0.0568 (6)
C6	0.12298 (10)	0.7973 (3)	0.57849 (13)	0.0590 (6)
H6A	0.1253	0.7886	0.6337	0.071*
H6B	0.1311	0.9109	0.5679	0.071*
C7	0.16091 (9)	0.6827 (3)	0.55784 (13)	0.0535 (5)
H7A	0.1905	0.6846	0.5990	0.064*
H7B	0.1485	0.5697	0.5529	0.064*
C8	0.18856 (8)	0.9557 (3)	0.32778 (14)	0.0528 (5)
H8	0.1919	1.0099	0.3749	0.063*
C9	0.21215 (9)	1.0213 (3)	0.27497 (17)	0.0667 (7)
H9	0.2311	1.1169	0.2865	0.080*
C10	0.20735 (10)	0.9436 (3)	0.20518 (17)	0.0685 (7)
H10	0.2223	0.9864	0.1679	0.082*
C11	0.17984 (9)	0.8010 (3)	0.19165 (14)	0.0586 (6)
H11	0.1759	0.7462	0.1445	0.070*
C12	0.15786 (8)	0.7380 (2)	0.24758 (12)	0.0445 (4)
C13	0.13096 (9)	0.5757 (3)	0.23578 (13)	0.0539 (5)
H13A	0.1395	0.5175	0.1929	0.065*
H13B	0.0960	0.5978	0.2216	0.065*
C14	0.14211 (8)	0.4629 (2)	0.30683 (13)	0.0498 (5)
H14A	0.1344	0.3488	0.2908	0.060*
H14B	0.1768	0.4686	0.3313	0.060*
C15	0.02527 (7)	0.9053 (2)	0.27139 (11)	0.0361 (4)
C16	0.02560 (8)	1.0864 (2)	0.27195 (12)	0.0452 (5)
C17	0.24949 (7)	0.8704 (2)	0.01973 (11)	0.0375 (4)
C18	0.21239 (7)	0.7408 (2)	−0.00476 (11)	0.0375 (4)
N1	0.06135 (7)	0.7253 (2)	0.46111 (11)	0.0472 (4)
N2	0.17263 (6)	0.7340 (2)	0.48476 (10)	0.0404 (4)
N3	0.16111 (6)	0.81826 (19)	0.31494 (9)	0.0396 (4)
N4	0.11369 (7)	0.51155 (19)	0.36278 (11)	0.0407 (4)
O1	0.05537 (5)	0.79065 (16)	0.29572 (8)	0.0449 (3)
O2	0.05610 (6)	1.19590 (18)	0.29910 (11)	0.0663 (5)
O3	0.24837 (5)	1.01589 (15)	0.04408 (9)	0.0487 (4)
O4	0.16716 (5)	0.73117 (15)	−0.01038 (9)	0.0470 (3)
O5	0.10943 (6)	1.01843 (17)	0.41638 (11)	0.0479 (4)
O6	0.0000	0.4863 (13)	0.2500	0.121 (6)	0.25
Ni1	0.114036 (8)	0.76294 (2)	0.391260 (13)	0.03314 (8)
H5A	0.1284 (10)	1.079 (3)	0.4454 (16)	0.062 (8)*
H5B	0.0958 (10)	1.073 (3)	0.3792 (16)	0.062 (8)*
H2A	0.1897 (8)	0.829 (3)	0.4946 (13)	0.050 (6)*
H4B	0.0829 (9)	0.485 (3)	0.3435 (14)	0.052 (6)*
H4A	0.1238 (8)	0.454 (3)	0.4042 (13)	0.043 (6)*
H2B	0.1917 (9)	0.666 (3)	0.4725 (14)	0.051 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0446 (13)	0.0681 (13)	0.0736 (17)	−0.0058 (11)	0.0174 (12)	0.0051 (12)
C2	0.0501 (17)	0.107 (2)	0.115 (3)	−0.0029 (15)	0.0356 (18)	0.005 (2)
C3	0.077 (2)	0.125 (3)	0.135 (3)	0.0032 (19)	0.069 (2)	−0.012 (2)
C4	0.096 (2)	0.102 (2)	0.085 (2)	0.0014 (18)	0.0552 (19)	−0.0172 (17)
C5	0.0688 (15)	0.0494 (11)	0.0581 (14)	0.0021 (10)	0.0271 (12)	−0.0041 (10)
C6	0.0784 (18)	0.0595 (12)	0.0405 (12)	−0.0028 (12)	0.0168 (12)	−0.0056 (10)
C7	0.0616 (15)	0.0523 (11)	0.0414 (12)	0.0008 (10)	0.0017 (10)	0.0058 (9)
C8	0.0499 (12)	0.0523 (11)	0.0573 (14)	−0.0113 (10)	0.0150 (10)	−0.0018 (10)
C9	0.0566 (14)	0.0622 (13)	0.086 (2)	−0.0107 (11)	0.0271 (14)	0.0122 (13)
C10	0.0680 (16)	0.0727 (15)	0.0763 (18)	0.0119 (13)	0.0403 (14)	0.0257 (14)
C11	0.0643 (15)	0.0691 (14)	0.0469 (13)	0.0177 (12)	0.0221 (11)	0.0091 (11)
C12	0.0422 (11)	0.0507 (10)	0.0412 (10)	0.0092 (8)	0.0109 (9)	0.0028 (9)
C13	0.0606 (14)	0.0580 (12)	0.0442 (12)	−0.0021 (10)	0.0148 (10)	−0.0159 (10)
C14	0.0523 (12)	0.0358 (9)	0.0623 (14)	0.0000 (8)	0.0152 (10)	−0.0090 (9)
C15	0.0335 (10)	0.0379 (9)	0.0354 (10)	−0.0017 (7)	0.0048 (8)	−0.0008 (7)
C16	0.0482 (12)	0.0399 (9)	0.0420 (11)	−0.0030 (8)	−0.0004 (9)	0.0023 (8)
C17	0.0379 (10)	0.0355 (8)	0.0371 (10)	0.0011 (7)	0.0046 (9)	0.0034 (7)
C18	0.0391 (10)	0.0341 (8)	0.0368 (9)	0.0013 (7)	0.0036 (8)	0.0045 (7)
N1	0.0442 (10)	0.0479 (9)	0.0529 (10)	−0.0028 (7)	0.0181 (8)	−0.0007 (8)
N2	0.0373 (9)	0.0374 (8)	0.0429 (9)	0.0007 (7)	0.0023 (7)	−0.0019 (7)
N3	0.0379 (9)	0.0415 (8)	0.0390 (9)	−0.0037 (6)	0.0085 (7)	0.0004 (7)
N4	0.0386 (10)	0.0356 (8)	0.0447 (10)	−0.0031 (7)	0.0033 (8)	−0.0010 (7)
O1	0.0379 (7)	0.0416 (7)	0.0484 (8)	0.0058 (6)	−0.0039 (6)	−0.0029 (6)
O2	0.0651 (11)	0.0435 (7)	0.0744 (12)	−0.0173 (7)	−0.0155 (9)	0.0054 (7)
O3	0.0471 (8)	0.0340 (6)	0.0627 (10)	0.0011 (6)	0.0083 (7)	−0.0049 (6)
O4	0.0369 (7)	0.0426 (7)	0.0590 (9)	0.0006 (6)	0.0061 (7)	0.0018 (6)
O5	0.0455 (8)	0.0366 (7)	0.0543 (9)	0.0007 (6)	−0.0032 (7)	−0.0056 (7)
O6	0.081 (8)	0.056 (6)	0.196 (16)	0.000	−0.027 (9)	0.000
Ni1	0.03027 (13)	0.03237 (12)	0.03530 (13)	−0.00067 (9)	0.00469 (9)	−0.00121 (9)

Geometric parameters (Å, º) top

C1—N1	1.344 (3)	C13—C14	1.527 (3)
C1—C2	1.371 (4)	C13—H13A	0.9700
C1—H1	0.9300	C13—H13B	0.9700
C2—C3	1.361 (5)	C14—N4	1.466 (3)
C2—H2	0.9300	C14—H14A	0.9700
C3—C4	1.371 (5)	C14—H14B	0.9700
C3—H3	0.9300	C15—O1	1.256 (2)
C4—C5	1.391 (4)	C15—C15ⁱ	1.442 (4)
C4—H4	0.9300	C15—C16	1.456 (3)
C5—N1	1.344 (3)	C16—O2	1.243 (2)
C5—C6	1.496 (4)	C16—C16ⁱ	1.464 (4)
C6—C7	1.516 (3)	C17—O3	1.250 (2)
C6—H6A	0.9700	C17—C18	1.465 (2)
C6—H6B	0.9700	C17—C18ⁱⁱ	1.465 (3)
C7—N2	1.471 (3)	C18—O4	1.251 (2)
C7—H7A	0.9700	C18—C17ⁱⁱ	1.465 (3)
C7—H7B	0.9700	N1—Ni1	2.1624 (17)
C8—N3	1.336 (3)	N2—Ni1	2.0576 (17)
C8—C9	1.374 (3)	N2—H2A	0.90 (2)
C8—H8	0.9300	N2—H2B	0.83 (2)
C9—C10	1.367 (4)	N3—Ni1	2.1495 (16)
C9—H9	0.9300	N4—Ni1	2.0833 (15)
C10—C11	1.372 (4)	N4—H4B	0.88 (2)
C10—H10	0.9300	N4—H4A	0.86 (2)
C11—C12	1.383 (3)	O1—Ni1	2.0803 (13)
C11—H11	0.9300	O5—Ni1	2.1126 (14)
C12—N3	1.344 (3)	O5—H5A	0.81 (3)
C12—C13	1.497 (3)	O5—H5B	0.81 (3)

N1—C1—C2	123.7 (3)	C13—C14—H14B	109.4
N1—C1—H1	118.2	H14A—C14—H14B	108.0
C2—C1—H1	118.2	O1—C15—C15ⁱ	132.78 (10)
C3—C2—C1	118.8 (3)	O1—C15—C16	136.79 (18)
C3—C2—H2	120.6	C15ⁱ—C15—C16	90.42 (11)
C1—C2—H2	120.6	O2—C16—C15	135.5 (2)
C2—C3—C4	118.5 (3)	O2—C16—C16ⁱ	134.90 (12)
C2—C3—H3	120.8	C15—C16—C16ⁱ	89.58 (11)
C4—C3—H3	120.8	O3—C17—C18	134.03 (18)
C3—C4—C5	120.7 (3)	O3—C17—C18ⁱⁱ	135.44 (18)
C3—C4—H4	119.6	C18—C17—C18ⁱⁱ	90.52 (15)
C5—C4—H4	119.6	O4—C18—C17ⁱⁱ	135.81 (17)
N1—C5—C4	120.4 (3)	O4—C18—C17	134.71 (17)
N1—C5—C6	118.8 (2)	C17ⁱⁱ—C18—C17	89.48 (15)
C4—C5—C6	120.8 (3)	C1—N1—C5	117.8 (2)
C5—C6—C7	115.41 (19)	C1—N1—Ni1	118.46 (16)
C5—C6—H6A	108.4	C5—N1—Ni1	122.50 (15)
C7—C6—H6A	108.4	C7—N2—Ni1	116.32 (14)
C5—C6—H6B	108.4	C7—N2—H2A	106.6 (15)
C7—C6—H6B	108.4	Ni1—N2—H2A	110.4 (14)
H6A—C6—H6B	107.5	C7—N2—H2B	109.6 (17)
N2—C7—C6	110.98 (18)	Ni1—N2—H2B	107.7 (17)
N2—C7—H7A	109.4	H2A—N2—H2B	106 (2)
C6—C7—H7A	109.4	C8—N3—C12	117.74 (18)
N2—C7—H7B	109.4	C8—N3—Ni1	118.55 (14)
C6—C7—H7B	109.4	C12—N3—Ni1	122.65 (13)
H7A—C7—H7B	108.0	C14—N4—Ni1	116.85 (12)
N3—C8—C9	123.5 (2)	C14—N4—H4B	108.3 (15)
N3—C8—H8	118.3	Ni1—N4—H4B	106.0 (14)
C9—C8—H8	118.3	C14—N4—H4A	108.5 (14)
C10—C9—C8	119.0 (2)	Ni1—N4—H4A	109.3 (14)
C10—C9—H9	120.5	H4B—N4—H4A	108 (2)
C8—C9—H9	120.5	C15—O1—Ni1	134.29 (12)
C9—C10—C11	118.2 (2)	Ni1—O5—H5A	131.0 (18)
C9—C10—H10	120.9	Ni1—O5—H5B	113.3 (18)
C11—C10—H10	120.9	H5A—O5—H5B	108 (3)
C10—C11—C12	120.5 (2)	N2—Ni1—O1	179.19 (7)
C10—C11—H11	119.8	N2—Ni1—N4	92.52 (7)
C12—C11—H11	119.8	O1—Ni1—N4	87.01 (6)
N3—C12—C11	121.1 (2)	N2—Ni1—O5	90.91 (7)
N3—C12—C13	118.03 (18)	O1—Ni1—O5	89.58 (6)
C11—C12—C13	120.9 (2)	N4—Ni1—O5	176.22 (7)
C12—C13—C14	113.80 (18)	N2—Ni1—N3	92.36 (7)
C12—C13—H13A	108.8	O1—Ni1—N3	86.99 (6)
C14—C13—H13A	108.8	N4—Ni1—N3	90.91 (7)
C12—C13—H13B	108.8	O5—Ni1—N3	90.53 (6)
C14—C13—H13B	108.8	N2—Ni1—N1	92.52 (7)
H13A—C13—H13B	107.7	O1—Ni1—N1	88.16 (7)
N4—C14—C13	111.35 (17)	N4—Ni1—N1	92.23 (7)
N4—C14—H14A	109.4	O5—Ni1—N1	86.03 (6)
C13—C14—H14A	109.4	N3—Ni1—N1	174.08 (6)
N4—C14—H14B	109.4

N1—C1—C2—C3	−1.4 (5)	C13—C12—N3—C8	174.5 (2)
C1—C2—C3—C4	−0.5 (5)	C11—C12—N3—Ni1	164.32 (16)
C2—C3—C4—C5	1.9 (5)	C13—C12—N3—Ni1	−17.4 (3)
C3—C4—C5—N1	−1.5 (4)	C13—C14—N4—Ni1	−48.4 (2)
C3—C4—C5—C6	179.7 (3)	C15ⁱ—C15—O1—Ni1	−148.2 (2)
N1—C5—C6—C7	−40.5 (3)	C16—C15—O1—Ni1	33.2 (4)
C4—C5—C6—C7	138.4 (2)	C7—N2—Ni1—N4	−85.75 (15)
C5—C6—C7—N2	79.8 (3)	C7—N2—Ni1—O5	92.66 (15)
N3—C8—C9—C10	0.4 (4)	C7—N2—Ni1—N3	−176.77 (14)
C8—C9—C10—C11	−1.3 (4)	C7—N2—Ni1—N1	6.59 (15)
C9—C10—C11—C12	−0.3 (4)	C15—O1—Ni1—N4	168.45 (19)
C10—C11—C12—N3	2.9 (3)	C15—O1—Ni1—O5	−9.92 (19)
C10—C11—C12—C13	−175.3 (2)	C15—O1—Ni1—N3	−100.47 (19)
N3—C12—C13—C14	−42.1 (3)	C15—O1—Ni1—N1	76.12 (19)
C11—C12—C13—C14	136.1 (2)	C14—N4—Ni1—N2	−92.56 (16)
C12—C13—C14—N4	80.6 (2)	C14—N4—Ni1—O1	86.78 (16)
O1—C15—C16—O2	−2.4 (5)	C14—N4—Ni1—N3	−0.16 (16)
C15ⁱ—C15—C16—O2	178.7 (3)	C14—N4—Ni1—N1	174.82 (16)
O1—C15—C16—C16ⁱ	178.5 (2)	C8—N3—Ni1—N2	−64.13 (16)
C15ⁱ—C15—C16—C16ⁱ	−0.4 (2)	C12—N3—Ni1—N2	127.95 (16)
O3—C17—C18—O4	0.7 (4)	C8—N3—Ni1—O1	116.36 (16)
C18ⁱⁱ—C17—C18—O4	−179.9 (3)	C12—N3—Ni1—O1	−51.57 (15)
O3—C17—C18—C17ⁱⁱ	−179.4 (3)	C8—N3—Ni1—N4	−156.69 (16)
C18ⁱⁱ—C17—C18—C17ⁱⁱ	0.0	C12—N3—Ni1—N4	35.39 (16)
C2—C1—N1—C5	1.8 (4)	C8—N3—Ni1—O5	26.81 (16)
C2—C1—N1—Ni1	−165.8 (2)	C12—N3—Ni1—O5	−141.12 (16)
C4—C5—N1—C1	−0.4 (3)	C1—N1—Ni1—N2	−164.45 (17)
C6—C5—N1—C1	178.5 (2)	C5—N1—Ni1—N2	28.56 (17)
C4—C5—N1—Ni1	166.70 (19)	C1—N1—Ni1—O1	15.11 (16)
C6—C5—N1—Ni1	−14.4 (3)	C5—N1—Ni1—O1	−151.88 (17)
C6—C7—N2—Ni1	−52.9 (2)	C1—N1—Ni1—N4	−71.83 (17)
C9—C8—N3—C12	2.1 (3)	C5—N1—Ni1—N4	121.19 (17)
C9—C8—N3—Ni1	−166.43 (19)	C1—N1—Ni1—O5	104.81 (17)
C11—C12—N3—C8	−3.7 (3)	C5—N1—Ni1—O5	−62.18 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱⁱⁱ	0.81 (3)	1.93 (3)	2.716 (2)	163 (3)
N2—H2A···O3ⁱⁱⁱ	0.90 (2)	2.09 (2)	2.935 (2)	157 (2)
O5—H5B···O2	0.81 (3)	1.87 (3)	2.675 (2)	172 (3)
N4—H4B···O2^iv	0.88 (2)	2.52 (2)	3.078 (2)	122.6 (18)
N4—H4B···O6	0.88 (2)	2.52 (3)	3.350 (2)	158 (2)
N4—H4A···O4^v	0.86 (2)	2.27 (2)	3.091 (2)	161 (2)
N2—H2B···O3^vi	0.83 (2)	2.14 (3)	2.963 (2)	169 (2)

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

Experimental details

Crystal data
Chemical formula	[Ni₂(C₄O₄)(C₇H₁₀N₂)₄(H₂O)₂]C₄O₄·0.25H₂O
M_r	870.16
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	297
a, b, c (Å)	28.037 (3), 8.0409 (5), 17.7752 (16)
β (°)	103.572 (7)
V (Å³)	3895.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.49, 0.81
No. of measured, independent and observed [I > 2σ(I)] reflections	12243, 3809, 3148
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.03
No. of reflections	3809
No. of parameters	282
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱ	0.81 (3)	1.93 (3)	2.716 (2)	163 (3)
N2—H2A···O3ⁱ	0.90 (2)	2.09 (2)	2.935 (2)	157 (2)
O5—H5B···O2	0.81 (3)	1.87 (3)	2.675 (2)	172 (3)
N4—H4B···O2ⁱⁱ	0.88 (2)	2.52 (2)	3.078 (2)	122.6 (18)
N4—H4B···O6	0.88 (2)	2.52 (3)	3.350 (2)	158 (2)
N4—H4A···O4ⁱⁱⁱ	0.86 (2)	2.27 (2)	3.091 (2)	161 (2)
N2—H2B···O3^iv	0.83 (2)	2.14 (3)	2.963 (2)	169 (2)

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

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