Propane-1,2-diammonium bis­(pyridine-2,6-dicarboxyl­ato-κ3O,N,O′)nickelate(II) tetra­hydrate

Aghabozorg, H.; Heidari, M.; Bagheri, S.; Attar Gharamaleki, J.; Ghadermazi, M.

doi:10.1107/S1600536808016309

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m874-m875

doi:10.1107/S1600536808016309

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Propane-1,2-diammonium bis(pyridine-2,6-dicarboxylato-κ³O,N,O′)nickelate(II) tetrahydrate

Hossein Aghabozorg,^a ^* Mohammad Heidari,^a Sara Bagheri,^b Jafar Attar Gharamaleki ^a and Mohammad Ghadermazi ^c

^aFaculty of Chemistry, Tarbiat Moallem University, 49 Mofateh Avenue, Tehran, Iran, ^bDepartment of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, and ^cDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 28 April 2008; accepted 29 May 2008; online 7 June 2008)

The reaction of nickel(II) nitrate hexahydrate, propane-1,2-diamine and pyridine-2,6-dicarboxylic acid in a 1:2:2 molar ratio in aqueous solution resulted in the formation of the title compound, (C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O or (p-1,2-daH₂)[Ni(pydc)₂]·4H₂O (where p-1,2-da is propane-1,2-diamine and pydcH₂ is pyridine-2,6-dicarboxylic acid). The geometry of the resulting NiN₂O₄ coordination can be described as distorted octahedral. Considerable C=O⋯π stacking interactions are observed between the carboxylate C=O groups and the pyridine rings of the (pydc)²⁻ fragments, with O⋯π distances of 3.1563 (12) and 3.2523 (12) Å and C=O⋯π angles of 95.14 (8) and 94.64 (8)°. In the crystal structure, a wide range of non-covalent interactions, consisting of hydrogen bonding [O—H⋯O, N—H⋯O and C—H⋯O, with D⋯A distances ranging from 2.712 (2) to 3.484 (2) Å], ion pairing, π–π [centroid-to-centroid distance = 3.4825 (8) Å] and C=O⋯π stacking, connect the various components to form a supramolecular structure.

Related literature

For related literature, see: Aghabozorg et al. (2007 ); Aghabozorg, Ghadermazi & Attar Gharamaleki (2006 ); Aghabozorg, Ghadermazi & Ramezanipour (2006 ); Aghabozorg, Heidari et al. (2008 ); Aghabozorg, Manteghi & Sheshmani (2008 ).

Experimental

Crystal data

(C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O
M_r = 537.13
Orthorhombic, P n a 2₁
a = 20.7598 (6) Å
b = 8.2582 (2) Å
c = 12.7242 (4) Å
V = 2181.42 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 100 (2) K
0.26 × 0.22 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.781, T_max = 0.898
36654 measured reflections
6379 independent reflections
6016 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.059
S = 1.01
6379 reflections
310 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 2846 Friedel pairs
Flack parameter: 0.004 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4W	0.82	1.97	2.788 (2)	173
O1W—H1WB⋯O2	0.82	2.47	3.109 (2)	135
O1W—H1WB⋯O6	0.82	2.21	2.912 (2)	144
O2W—H2WA⋯O3	0.82	2.21	2.759 (2)	125
N3—H3B⋯O4ⁱ	0.91	1.90	2.795 (2)	168
N3—H3C⋯O1W	0.91	1.91	2.763 (2)	155
N3—H3D⋯O8ⁱⁱ	0.91	1.88	2.783 (2)	176
O2W—H2WB⋯O1ⁱⁱⁱ	0.82	2.07	2.849 (2)	160
N4—H4B⋯O3Wⁱⁱ	0.91	1.92	2.812 (2)	165
N4—H4C⋯O1	0.91	1.92	2.813 (2)	168
N4—H4D⋯O4W^iv	0.91	1.91	2.777 (2)	160
O3W—H3WA⋯O8	0.82	2.03	2.771 (2)	149
O3W—H3WB⋯O4^v	0.82	1.99	2.787 (2)	166
O4W—H4WA⋯O2Wⁱ	0.82	1.99	2.749 (2)	153
O4W—H4WB⋯O5	0.82	1.90	2.712 (2)	171
C10—H10A⋯O6^vi	0.95	2.54	3.289 (2)	136
C11—H11A⋯O1W^vi	0.95	2.58	3.484 (2)	160
C15—H15B⋯O5^vii	0.99	2.30	3.268 (2)	164
C16—H16A⋯O7ⁱⁱ	1.00	2.49	3.291 (2)	137
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[-x, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016309/su2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016309/su2054Isup2.hkl

checkCIF report

Comment top

Recently, we have defined a plan to prepare water soluble proton transfer compounds as novel self-assembled systems that can function as suitable ligands in the synthesis of metal complexes. In this regard, we have reported cases in which proton transfers from pyridine-2,6-dicarboxylic acid (pydcH₂), and benzene-1,2,4,5-tetracarboxylic acid (btcH₄), to propane-1,3-diamine (pda), propane-1,2-diamine (p-1,2-da) and 1,10-phenanthroline, (phen). This work has resulted in the formation of some novel proton transfer compounds such as (pdaH₂)(pydc).(pydcH₂).2.5H₂O (Aghabozorg, Ghadermazi & Ramezanipour, 2006), (pdaH₂)₂(btc).2H₂O (Aghabozorg et al., 2007), (p-1,2-daH₂)(pydcH)₂.2H₂O (Aghabozorg, Heidari et al., 2008) and (phenH)₄(btcH₃)₂(btcH₂) (Aghabozorg, Ghadermazi & Attar Gharamaleki, 2006). For more details and related literature see our recent review article (Aghabozorg, Manteghi & Sheshmani, 2008).

The molecular structure and crystal packing diagram of the title compound are presented in Figs. 1 and 2, respectively. The Ni^II atom is six-coordinated by two pyridine-2,6-dicarboxylate, or (pydc)^2-, groups, i.e. each (pydc)^2- ligand is coordinated through one pyridine N atom and two carboxylate O atoms. As it can be seen, atoms N1 and N2 of the two (pydc)^2- fragments occupy the axial positions, while atoms O2, O3, O6 and O7 form the equatorial plane [with Ni—O distances ranging from 2.1178 (11) to 2.1477 (10) Å]. The N1—Ni1—N2 angle [176.17 (5)°] deviates from linearity. Therefore, the geometry of the resulting NiN₂O₄ coordination can be described as distorted octahedral. The O2—Ni1—O6 and O3—Ni1—O7 bond angles are equal to 87.26 (4)° and 90.55 (4)°, respectively. On the other hand, the torsion angles O3—Ni1—O7—C14 and O7—Ni1—O3—C7 are 92.68 (10)° and 95.05 (10)°, respectively, indicating that the two (pydc)^2- units are almost perpendicular to one another. The O2—Ni1—O3 [155.41 (4)°] and O6—Ni1—O7 [155.96 (4)°] bond angles indicate that the four carboxylate groups of the two dianions are oriented in a flattened tetrahedral arrangement around the Ni1 atom.

It is interesting to note that the crystal packing shows a layered structure. The space between the layers of [Ni(pydc)₂]^2- units is occupied by (p-1,2-daH₂)²⁺ cations and uncoordinated water molecules, which bridge the [Ni(pydc)₂]^2- units via hydrogen bonds (Fig 3 and Table 1). A noticeable feature of the title compound is the presence of C═O···π stacking interactions, between C═O groups of the carboxylate with aromatic rings of pyridine-2,6-dicarboxylate, with O···π distances of 3.1563 (12) Å for C13–O5···Cg1 (1/2 - x, 1/2 + y, -1/2 + z) and 3.2523 (12) Å for C6–O1···Cg2 (1/2 - x, -1/2 + y, 1/2 + z) [Cg1 and Cg2 are the centroids of the rings N1/C1–C5 and N2/C8–C12, respectively]. There is also considerable π–π stacking interactions between the two aromatic rings of the (pydc)^2- units, with a centorid–centroid distance of 3.4825 (8) Å (1/2 - x, -1/2 + y, -1/2 + z) [see Fig. 4]. In the crystal structure, a wide range of non-covalent interactions consisting of hydrogen bonding (of the type O—H···O, N—H···O and C—H···O with D···A ranging from 2.712 (2) Å to 3.484 (2) Å), ion pairing, π···π and C═ O···π stacking connect the various components to form a supramolecular structure.

Related literature top

For related literature, see: Aghabozorg et al. (2007); Aghabozorg, Ghadermazi & Attar Gharamaleki (2006); Aghabozorg, Ghadermazi & Ramezanipour (2006); Aghabozorg, Heidari et al. (2008); Aghabozorg, Manteghi & Sheshmani (2008).

Experimental top

An aqueous solution of Ni(NO₃)₂.6H₂O (290 mg, 1 mmol), propane-1,2-diamine (80 mg, 2 mmol) and pyridine-2,6-dicarboxylic acid (360 mg, 2 mmol) was added to each other in a 1:2:2 molar ratio, and the reaction mixture was heated at about 40°C for 5 h. Green crystals of the title compound were obtained from the solution after four weeks at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of the title compound as viewed approximately down b, with the hydrogen bonds shown as dashed lines.
	Fig. 3. A layered packing diagram of the title compound. The space between the two layers of [Ni(pydc)₂]^2- fragments is filled with a layer of (p-1,2-daH₂)²⁺ cations and water molecules.
	Fig. 4. π–π Stacking interaction between two aromatic rings of (pydc)^2- units, with centorid–centroid distance of 3.4825 (8) Å (1/2 - x, -1/2 + y, -1/2 + z); C–O···π Stacking interactions between C═O groups of carboxylate and the aromatic rings of pyridine-2,6-dicarboxylate with O···π distances of 3.1563 (12) Å for C13—O5···Cg1 (1/2 - x, 1/2 + y, -1/2 + z) and 3.2523 (12) Å for C6—O1···Cg2 (1/2 - x, -1/2 + y, 1/2 + z) [Cg1 and Cg2 are the centroids for rings N1/C1–C5 and N2/C8–C12, respectively].

Propane-1,2-diammonium bis(pyridine-2,6-dicarboxylato-κ³O,N,O')nickelate(II) tetrahydrate top

Crystal data top

(C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O	F(000) = 1120
M_r = 537.13	D_x = 1.635 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 410 reflections
a = 20.7598 (6) Å	θ = 3–29°
b = 8.2582 (2) Å	µ = 0.96 mm⁻¹
c = 12.7242 (4) Å	T = 100 K
V = 2181.42 (11) Å³	Prism, light-green
Z = 4	0.26 × 0.22 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	6379 independent reflections
Radiation source: fine-focus sealed tube	6016 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 30.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→29
T_min = 0.781, T_max = 0.898	k = −11→11
36654 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.03P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
6379 reflections	Δρ_max = 0.34 e Å⁻³
310 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (7)

Crystal data top

(C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O	V = 2181.42 (11) Å³
M_r = 537.13	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 20.7598 (6) Å	µ = 0.96 mm⁻¹
b = 8.2582 (2) Å	T = 100 K
c = 12.7242 (4) Å	0.26 × 0.22 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	6379 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6016 reflections with I > 2σ(I)
T_min = 0.781, T_max = 0.898	R_int = 0.035
36654 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.059	Δρ_max = 0.34 e Å⁻³
S = 1.01	Δρ_min = −0.33 e Å⁻³
6379 reflections	Absolute structure: Flack (1983), with how many Friedel pairs?
310 parameters	Absolute structure parameter: 0.004 (7)
1 restraint

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
Ni1	0.230880 (7)	0.50781 (2)	0.25665 (2)	0.00841 (4)
O1	0.36657 (5)	0.27840 (12)	0.44207 (8)	0.0123 (2)
O2	0.30848 (5)	0.35043 (12)	0.30169 (8)	0.0110 (2)
O3	0.15872 (5)	0.68763 (13)	0.28120 (8)	0.0131 (2)
O4	0.10593 (5)	0.81657 (13)	0.41025 (9)	0.0133 (2)
O5	0.35128 (5)	0.74395 (13)	0.04995 (8)	0.0128 (2)
O6	0.30178 (5)	0.66991 (13)	0.19960 (8)	0.0113 (2)
O7	0.15889 (5)	0.32530 (12)	0.24551 (9)	0.0120 (2)
O8	0.09570 (5)	0.20477 (13)	0.12645 (9)	0.0146 (2)
N1	0.23302 (5)	0.53498 (17)	0.41041 (11)	0.0085 (2)
N2	0.22246 (6)	0.48264 (15)	0.10356 (12)	0.0090 (3)
C1	0.27701 (7)	0.45504 (17)	0.46722 (12)	0.0087 (2)
C2	0.28041 (8)	0.47344 (19)	0.57519 (13)	0.0109 (3)
H2A	0.3120	0.4178	0.6153	0.013*
C3	0.23594 (7)	0.57630 (18)	0.62343 (12)	0.0112 (3)
H3A	0.2371	0.5909	0.6975	0.013*
C4	0.18997 (7)	0.65754 (17)	0.56366 (11)	0.0102 (3)
H4A	0.1593	0.7270	0.5958	0.012*
C5	0.19040 (7)	0.63384 (17)	0.45558 (11)	0.0088 (2)
C6	0.32098 (6)	0.35197 (16)	0.39952 (12)	0.0096 (2)
C7	0.14761 (7)	0.71970 (17)	0.37710 (11)	0.0102 (3)
C8	0.26305 (6)	0.56135 (18)	0.04015 (12)	0.0095 (3)
C9	0.26076 (7)	0.5380 (2)	−0.06858 (12)	0.0105 (3)
H9A	0.2901	0.5919	−0.1140	0.013*
C10	0.21417 (7)	0.43328 (18)	−0.10826 (11)	0.0121 (3)
H10A	0.2116	0.4147	−0.1818	0.015*
C11	0.17109 (7)	0.35526 (17)	−0.04071 (12)	0.0110 (3)
H11A	0.1385	0.2857	−0.0673	0.013*
C12	0.17748 (6)	0.38260 (17)	0.06599 (12)	0.0097 (2)
C13	0.30969 (6)	0.66803 (17)	0.10021 (12)	0.0101 (3)
C14	0.14033 (7)	0.29812 (17)	0.15243 (12)	0.0108 (3)
N3	0.54006 (6)	0.43977 (15)	0.30200 (10)	0.0123 (2)
H3B	0.5651	0.5201	0.3289	0.018*
H3C	0.5010	0.4809	0.2837	0.018*
H3D	0.5595	0.3971	0.2442	0.018*
N4	0.44676 (5)	0.16524 (15)	0.27970 (10)	0.0118 (2)
H4B	0.4502	0.2393	0.2270	0.018*
H4C	0.4162	0.1982	0.3263	0.018*
H4D	0.4354	0.0676	0.2523	0.018*
C15	0.53120 (7)	0.31041 (17)	0.38271 (12)	0.0130 (3)
H15A	0.4983	0.3459	0.4340	0.016*
H15B	0.5722	0.2949	0.4212	0.016*
C16	0.51052 (7)	0.14977 (17)	0.33504 (12)	0.0113 (2)
H16A	0.5437	0.1154	0.2827	0.014*
C17	0.50526 (8)	0.01962 (18)	0.41937 (13)	0.0174 (3)
H17A	0.4940	−0.0840	0.3866	0.026*
H17B	0.4718	0.0499	0.4700	0.026*
H17C	0.5466	0.0091	0.4558	0.026*
O1W	0.42220 (5)	0.59529 (14)	0.30653 (9)	0.0169 (2)
H1WA	0.4295	0.6786	0.2735	0.020*
H1WB	0.3837	0.5823	0.2945	0.020*
O2W	0.06395 (6)	0.74698 (19)	0.13415 (10)	0.0297 (3)
H2WA	0.0821	0.6693	0.1612	0.036*
H2WB	0.0882	0.7755	0.0867	0.036*
O3W	−0.03481 (5)	0.15335 (15)	0.09506 (9)	0.0199 (2)
H3WA	0.0027	0.1743	0.0800	0.024*
H3WB	−0.0520	0.1482	0.0372	0.024*
O4W	0.44262 (5)	0.86620 (13)	0.18005 (9)	0.0158 (2)
H4WA	0.4731	0.8280	0.1474	0.019*
H4WB	0.4180	0.8294	0.1357	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00786 (7)	0.01104 (7)	0.00634 (7)	0.00044 (6)	−0.00030 (7)	−0.00050 (7)
O1	0.0097 (4)	0.0146 (5)	0.0125 (5)	0.0032 (4)	−0.0006 (4)	0.0011 (4)
O2	0.0123 (4)	0.0127 (5)	0.0082 (5)	0.0015 (4)	−0.0003 (4)	−0.0013 (4)
O3	0.0121 (5)	0.0174 (5)	0.0097 (5)	0.0037 (4)	−0.0006 (4)	0.0003 (4)
O4	0.0125 (5)	0.0146 (5)	0.0129 (5)	0.0047 (4)	0.0020 (4)	0.0016 (4)
O5	0.0110 (5)	0.0154 (5)	0.0121 (5)	−0.0025 (4)	0.0019 (4)	−0.0005 (4)
O6	0.0106 (5)	0.0139 (5)	0.0092 (5)	−0.0009 (4)	−0.0003 (4)	−0.0009 (4)
O7	0.0115 (4)	0.0165 (4)	0.0081 (5)	−0.0015 (3)	0.0002 (4)	0.0010 (4)
O8	0.0131 (5)	0.0173 (5)	0.0134 (5)	−0.0049 (4)	−0.0003 (4)	−0.0013 (4)
N1	0.0095 (6)	0.0079 (5)	0.0080 (6)	−0.0005 (4)	−0.0004 (4)	−0.0014 (5)
N2	0.0081 (5)	0.0099 (5)	0.0088 (6)	0.0014 (4)	0.0000 (5)	0.0009 (5)
C1	0.0084 (6)	0.0083 (6)	0.0095 (6)	−0.0008 (5)	−0.0002 (5)	0.0010 (5)
C2	0.0123 (6)	0.0093 (6)	0.0111 (7)	−0.0004 (5)	−0.0004 (5)	0.0009 (5)
C3	0.0136 (6)	0.0122 (6)	0.0080 (6)	−0.0017 (5)	0.0010 (5)	−0.0003 (5)
C4	0.0106 (6)	0.0110 (6)	0.0090 (6)	−0.0010 (5)	0.0032 (5)	−0.0012 (5)
C5	0.0074 (6)	0.0098 (6)	0.0094 (6)	−0.0007 (5)	0.0001 (5)	0.0019 (5)
C6	0.0084 (6)	0.0084 (6)	0.0121 (6)	−0.0010 (4)	0.0012 (5)	−0.0001 (5)
C7	0.0090 (6)	0.0102 (6)	0.0114 (6)	−0.0010 (5)	−0.0005 (5)	0.0012 (5)
C8	0.0080 (6)	0.0096 (6)	0.0108 (7)	0.0008 (5)	0.0000 (5)	−0.0010 (5)
C9	0.0135 (6)	0.0098 (6)	0.0081 (7)	0.0006 (5)	0.0003 (5)	0.0022 (5)
C10	0.0171 (7)	0.0122 (6)	0.0071 (6)	0.0015 (5)	−0.0011 (5)	−0.0013 (5)
C11	0.0112 (6)	0.0105 (6)	0.0112 (6)	0.0007 (5)	−0.0015 (5)	−0.0004 (5)
C12	0.0073 (6)	0.0098 (6)	0.0121 (6)	0.0011 (5)	0.0001 (5)	−0.0004 (5)
C13	0.0083 (6)	0.0096 (6)	0.0125 (6)	0.0015 (5)	−0.0007 (5)	−0.0010 (5)
C14	0.0088 (6)	0.0116 (6)	0.0119 (6)	0.0010 (5)	0.0022 (5)	0.0001 (5)
N3	0.0108 (5)	0.0121 (5)	0.0141 (6)	−0.0006 (4)	−0.0012 (4)	−0.0033 (5)
N4	0.0106 (5)	0.0127 (5)	0.0122 (6)	0.0001 (4)	−0.0016 (4)	−0.0010 (4)
C15	0.0127 (6)	0.0143 (6)	0.0119 (6)	−0.0011 (5)	−0.0011 (5)	−0.0020 (5)
C16	0.0099 (6)	0.0127 (6)	0.0113 (6)	0.0003 (5)	−0.0007 (5)	−0.0006 (5)
C17	0.0204 (7)	0.0153 (7)	0.0164 (7)	0.0027 (5)	−0.0024 (6)	0.0026 (6)
O1W	0.0118 (5)	0.0196 (5)	0.0193 (6)	0.0011 (4)	−0.0009 (4)	0.0034 (4)
O2W	0.0140 (5)	0.0595 (9)	0.0155 (6)	−0.0035 (6)	−0.0019 (4)	0.0121 (6)
O3W	0.0142 (5)	0.0318 (6)	0.0138 (5)	0.0009 (5)	−0.0037 (4)	−0.0011 (5)
O4W	0.0139 (5)	0.0171 (5)	0.0163 (5)	−0.0014 (4)	−0.0006 (4)	−0.0047 (4)

Geometric parameters (Å, º) top

Ni1—N2	1.9668 (15)	C9—H9A	0.9500
Ni1—N1	1.9698 (14)	C10—C11	1.398 (2)
Ni1—O6	2.1178 (11)	C10—H10A	0.9500
Ni1—O7	2.1273 (10)	C11—C12	1.383 (2)
Ni1—O3	2.1324 (10)	C11—H11A	0.9500
Ni1—O2	2.1477 (10)	C12—C14	1.514 (2)
O1—C6	1.2483 (17)	N3—C15	1.4932 (19)
O2—C6	1.2717 (18)	N3—H3B	0.9100
O3—C7	1.2697 (18)	N3—H3C	0.9100
O4—C7	1.2516 (17)	N3—H3D	0.9100
O5—C13	1.2441 (18)	N4—C16	1.5048 (17)
O6—C13	1.2754 (19)	N4—H4B	0.9100
O7—C14	1.2655 (19)	N4—H4C	0.9100
O8—C14	1.2498 (18)	N4—H4D	0.9100
N1—C5	1.3340 (19)	C15—C16	1.5205 (19)
N1—C1	1.3387 (19)	C15—H15A	0.9900
N2—C12	1.335 (2)	C15—H15B	0.9900
N2—C8	1.335 (2)	C16—C17	1.523 (2)
C1—C2	1.384 (2)	C16—H16A	1.0000
C1—C6	1.516 (2)	C17—H17A	0.9800
C2—C3	1.397 (2)	C17—H17B	0.9800
C2—H2A	0.9500	C17—H17C	0.9800
C3—C4	1.393 (2)	O1W—H1WA	0.8201
C3—H3A	0.9500	O1W—H1WB	0.8200
C4—C5	1.389 (2)	O2W—H2WA	0.8201
C4—H4A	0.9500	O2W—H2WB	0.8198
C5—C7	1.5130 (19)	O3W—H3WA	0.8200
C8—C9	1.398 (2)	O3W—H3WB	0.8201
C8—C13	1.516 (2)	O4W—H4WA	0.8201
C9—C10	1.392 (2)	O4W—H4WB	0.8201

N2—Ni1—N1	176.17 (5)	C8—C9—H9A	121.0
N2—Ni1—O6	77.83 (5)	C9—C10—C11	120.52 (14)
N1—Ni1—O6	104.64 (5)	C9—C10—H10A	119.7
N2—Ni1—O7	78.27 (5)	C11—C10—H10A	119.7
N1—Ni1—O7	99.37 (5)	C12—C11—C10	117.85 (14)
O6—Ni1—O7	155.96 (4)	C12—C11—H11A	121.1
N2—Ni1—O3	98.99 (5)	C10—C11—H11A	121.1
N1—Ni1—O3	77.94 (5)	N2—C12—C11	121.31 (14)
O6—Ni1—O3	95.64 (4)	N2—C12—C14	112.42 (14)
O7—Ni1—O3	90.55 (4)	C11—C12—C14	126.11 (13)
N2—Ni1—O2	105.48 (5)	O5—C13—O6	126.37 (14)
N1—Ni1—O2	77.70 (5)	O5—C13—C8	118.49 (13)
O6—Ni1—O2	87.29 (4)	O6—C13—C8	115.14 (12)
O7—Ni1—O2	96.66 (4)	O8—C14—O7	125.63 (14)
O3—Ni1—O2	155.41 (4)	O8—C14—C12	118.02 (13)
C6—O2—Ni1	114.09 (9)	O7—C14—C12	116.31 (12)
C7—O3—Ni1	114.43 (9)	C15—N3—H3B	109.5
C13—O6—Ni1	114.94 (9)	C15—N3—H3C	109.5
C14—O7—Ni1	113.70 (9)	H3B—N3—H3C	109.5
C5—N1—C1	121.44 (14)	C15—N3—H3D	109.5
C5—N1—Ni1	118.86 (10)	H3B—N3—H3D	109.5
C1—N1—Ni1	119.70 (10)	H3C—N3—H3D	109.5
C12—N2—C8	121.75 (15)	C16—N4—H4B	109.5
C12—N2—Ni1	118.82 (11)	C16—N4—H4C	109.5
C8—N2—Ni1	119.39 (11)	H4B—N4—H4C	109.5
N1—C1—C2	121.11 (14)	C16—N4—H4D	109.5
N1—C1—C6	112.38 (13)	H4B—N4—H4D	109.5
C2—C1—C6	126.50 (14)	H4C—N4—H4D	109.5
C1—C2—C3	117.99 (14)	N3—C15—C16	112.62 (12)
C1—C2—H2A	121.0	N3—C15—H15A	109.1
C3—C2—H2A	121.0	C16—C15—H15A	109.1
C4—C3—C2	120.40 (14)	N3—C15—H15B	109.1
C4—C3—H3A	119.8	C16—C15—H15B	109.1
C2—C3—H3A	119.8	H15A—C15—H15B	107.8
C5—C4—C3	117.93 (13)	N4—C16—C15	111.16 (11)
C5—C4—H4A	121.0	N4—C16—C17	109.06 (12)
C3—C4—H4A	121.0	C15—C16—C17	110.80 (12)
N1—C5—C4	121.13 (14)	N4—C16—H16A	108.6
N1—C5—C7	113.07 (13)	C15—C16—H16A	108.6
C4—C5—C7	125.70 (13)	C17—C16—H16A	108.6
O1—C6—O2	125.06 (13)	C16—C17—H17A	109.5
O1—C6—C1	118.90 (13)	C16—C17—H17B	109.5
O2—C6—C1	116.03 (12)	H17A—C17—H17B	109.5
O4—C7—O3	125.65 (13)	C16—C17—H17C	109.5
O4—C7—C5	118.88 (13)	H17A—C17—H17C	109.5
O3—C7—C5	115.46 (12)	H17B—C17—H17C	109.5
N2—C8—C9	120.62 (14)	H1WA—O1W—H1WB	101.2
N2—C8—C13	112.42 (13)	H2WA—O2W—H2WB	104.5
C9—C8—C13	126.95 (13)	H3WA—O3W—H3WB	102.4
C10—C9—C8	117.93 (14)	H4WA—O4W—H4WB	89.5
C10—C9—H9A	121.0

N2—Ni1—O2—C6	179.68 (10)	Ni1—N1—C5—C4	−179.84 (10)
N1—Ni1—O2—C6	−2.52 (10)	C1—N1—C5—C7	176.61 (12)
O6—Ni1—O2—C6	103.10 (10)	Ni1—N1—C5—C7	−3.14 (16)
O7—Ni1—O2—C6	−100.70 (10)	C3—C4—C5—N1	0.7 (2)
O3—Ni1—O2—C6	5.46 (16)	C3—C4—C5—C7	−175.52 (13)
N2—Ni1—O3—C7	173.26 (10)	Ni1—O2—C6—O1	−175.13 (11)
N1—Ni1—O3—C7	−4.41 (10)	Ni1—O2—C6—C1	3.57 (15)
O6—Ni1—O3—C7	−108.21 (10)	N1—C1—C6—O1	175.89 (13)
O7—Ni1—O3—C7	95.05 (10)	C2—C1—C6—O1	−2.4 (2)
O2—Ni1—O3—C7	−12.39 (16)	N1—C1—C6—O2	−2.89 (18)
N2—Ni1—O6—C13	−4.98 (10)	C2—C1—C6—O2	178.85 (14)
N1—Ni1—O6—C13	178.04 (10)	Ni1—O3—C7—O4	−177.39 (11)
O7—Ni1—O6—C13	1.20 (16)	Ni1—O3—C7—C5	4.04 (15)
O3—Ni1—O6—C13	−102.99 (10)	N1—C5—C7—O4	−179.55 (13)
O2—Ni1—O6—C13	101.50 (10)	C4—C5—C7—O4	−3.0 (2)
N2—Ni1—O7—C14	−6.39 (10)	N1—C5—C7—O3	−0.87 (18)
N1—Ni1—O7—C14	170.54 (10)	C4—C5—C7—O3	175.64 (13)
O6—Ni1—O7—C14	−12.55 (15)	C12—N2—C8—C9	−1.7 (2)
O3—Ni1—O7—C14	92.68 (10)	Ni1—N2—C8—C9	176.03 (11)
O2—Ni1—O7—C14	−110.88 (10)	C12—N2—C8—C13	179.89 (12)
O6—Ni1—N1—C5	96.77 (11)	Ni1—N2—C8—C13	−2.41 (16)
O7—Ni1—N1—C5	−84.54 (11)	N2—C8—C9—C10	1.3 (2)
O3—Ni1—N1—C5	4.01 (11)	C13—C8—C9—C10	179.52 (14)
O2—Ni1—N1—C5	−179.38 (12)	C8—C9—C10—C11	0.3 (2)
O6—Ni1—N1—C1	−83.00 (12)	C9—C10—C11—C12	−1.6 (2)
O7—Ni1—N1—C1	95.70 (11)	C8—N2—C12—C11	0.3 (2)
O3—Ni1—N1—C1	−175.75 (12)	Ni1—N2—C12—C11	−177.38 (10)
O2—Ni1—N1—C1	0.86 (11)	C8—N2—C12—C14	175.92 (12)
O6—Ni1—N2—C12	−178.35 (11)	Ni1—N2—C12—C14	−1.80 (16)
O7—Ni1—N2—C12	4.21 (10)	C10—C11—C12—N2	1.3 (2)
O3—Ni1—N2—C12	−84.47 (11)	C10—C11—C12—C14	−173.67 (13)
O2—Ni1—N2—C12	97.96 (11)	Ni1—O6—C13—O5	−174.76 (11)
O6—Ni1—N2—C8	3.88 (10)	Ni1—O6—C13—C8	5.13 (15)
O7—Ni1—N2—C8	−173.56 (11)	N2—C8—C13—O5	177.84 (12)
O3—Ni1—N2—C8	97.75 (11)	C9—C8—C13—O5	−0.5 (2)
O2—Ni1—N2—C8	−79.81 (11)	N2—C8—C13—O6	−2.06 (18)
C5—N1—C1—C2	−0.8 (2)	C9—C8—C13—O6	179.62 (14)
Ni1—N1—C1—C2	179.00 (11)	Ni1—O7—C14—O8	−174.94 (12)
C5—N1—C1—C6	−179.12 (12)	Ni1—O7—C14—C12	7.30 (15)
Ni1—N1—C1—C6	0.63 (16)	N2—C12—C14—O8	178.05 (12)
N1—C1—C2—C3	0.9 (2)	C11—C12—C14—O8	−6.6 (2)
C6—C1—C2—C3	179.00 (13)	N2—C12—C14—O7	−4.02 (18)
C1—C2—C3—C4	−0.2 (2)	C11—C12—C14—O7	171.32 (14)
C2—C3—C4—C5	−0.6 (2)	N3—C15—C16—N4	−61.32 (15)
C1—N1—C5—C4	−0.1 (2)	N3—C15—C16—C17	177.24 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4W	0.82	1.97	2.788 (2)	173
O1W—H1WB···O2	0.82	2.47	3.109 (2)	135
O1W—H1WB···O6	0.82	2.21	2.912 (2)	144
O2W—H2WA···O3	0.82	2.21	2.759 (2)	125
N3—H3B···O4ⁱ	0.91	1.90	2.795 (2)	168
N3—H3C···O1W	0.91	1.91	2.763 (2)	155
N3—H3D···O8ⁱⁱ	0.91	1.88	2.783 (2)	176
O2W—H2WB···O1ⁱⁱⁱ	0.82	2.07	2.849 (2)	160
N4—H4B···O3Wⁱⁱ	0.91	1.92	2.812 (2)	165
N4—H4C···O1	0.91	1.92	2.813 (2)	168
N4—H4D···O4W^iv	0.91	1.91	2.777 (2)	160
O3W—H3WA···O8	0.82	2.03	2.771 (2)	149
O3W—H3WB···O4^v	0.82	1.99	2.787 (2)	166
O4W—H4WA···O2Wⁱ	0.82	1.99	2.749 (2)	153
O4W—H4WB···O5	0.82	1.90	2.712 (2)	171
C10—H10A···O6^vi	0.95	2.54	3.289 (2)	136
C11—H11A···O1W^vi	0.95	2.58	3.484 (2)	160
C15—H15B···O5^vii	0.99	2.30	3.268 (2)	164
C16—H16A···O7ⁱⁱ	1.00	2.49	3.291 (2)	137

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

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O
M_r	537.13
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	20.7598 (6), 8.2582 (2), 12.7242 (4)
V (Å³)	2181.42 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.26 × 0.22 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.781, 0.898
No. of measured, independent and observed [I > 2σ(I)] reflections	36654, 6379, 6016
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.059, 1.01
No. of reflections	6379
No. of parameters	310
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.33
Absolute structure	Flack (1983), with how many Friedel pairs?
Absolute structure parameter	0.004 (7)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4W	0.82	1.97	2.788 (2)	173
O1W—H1WB···O2	0.82	2.47	3.109 (2)	135
O1W—H1WB···O6	0.82	2.21	2.912 (2)	144
O2W—H2WA···O3	0.82	2.21	2.759 (2)	125
N3—H3B···O4ⁱ	0.91	1.90	2.795 (2)	168
N3—H3C···O1W	0.91	1.91	2.763 (2)	155
N3—H3D···O8ⁱⁱ	0.91	1.88	2.783 (2)	176
O2W—H2WB···O1ⁱⁱⁱ	0.82	2.07	2.849 (2)	160
N4—H4B···O3Wⁱⁱ	0.91	1.92	2.812 (2)	165
N4—H4C···O1	0.91	1.92	2.813 (2)	168
N4—H4D···O4W^iv	0.91	1.91	2.777 (2)	160
O3W—H3WA···O8	0.82	2.03	2.771 (2)	149
O3W—H3WB···O4^v	0.82	1.99	2.787 (2)	166
O4W—H4WA···O2Wⁱ	0.82	1.99	2.749 (2)	153
O4W—H4WB···O5	0.82	1.90	2.712 (2)	171
C10—H10A···O6^vi	0.95	2.54	3.289 (2)	136
C11—H11A···O1W^vi	0.95	2.58	3.484 (2)	160
C15—H15B···O5^vii	0.99	2.30	3.268 (2)	164
C16—H16A···O7ⁱⁱ	1.00	2.49	3.291 (2)	137

References

Aghabozorg, H., Ghadermazi, M. & Attar Gharamaleki, J. (2006). Acta Cryst. E62, o3174–o3176. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Ghadermazi, M. & Ramezanipour, F. (2006). Acta Cryst. E62, o1143–o1146. CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Ghadermazi, M., Sheshmani, S. & Attar Gharamaleki, J. (2007). Acta Cryst. E63, o2985–o2986. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Heidari, M., Ghadermazi, M. & Attar Gharamaleki, J. (2008). Acta Cryst. E64, o1045–o1046. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc. 5, 184–227. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 7| July 2008| Pages m874-m875

doi:10.1107/S1600536808016309

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