Aqua­(propane­dioato-κ2O1,O3)[2-(1H-pyrazol-1-yl-κN2)-1,10-phenanthroline-κ2N,N′]nickel(II) trihydrate

Yan, H.Y.; Hu, T.Q.; Shi, J.M.

doi:10.1107/S1600536809017188

metal-organic compounds

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Volume 65| Part 6| June 2009| Page m647

doi:10.1107/S1600536809017188

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Aqua(propanedioato-κ²O¹,O³)[2-(1H-pyrazol-1-yl-κN²)-1,10-phenanthroline-κ²N,N′]nickel(II) trihydrate

Huai Yi Yan,^a Tai Qiu Hu ^b and Jing Min Shi ^b ^*

^aDepartment of Chemistry, Xinzhou Teacher's University, Shanxi Xinzhou 034000, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: shijingmin1955@yahoo.com.cn

(Received 25 April 2009; accepted 7 May 2009; online 14 May 2009)

In the title mononuclear complex, [Ni(C₃H₂O₄)(C₁₅H₁₀N₄)(H₂O)]·3H₂O, the metal center is coordinated in a distorted NiN₃O₃ geometry. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the components into a two-dimensional network. In addition, there are weak π–π stacking interactions between symmetry-related phenanthroline rings, with a centroid–centroid distance of 3.6253 (17) Å.

Related literature

For a related Ni^II structure with 1,10-phenanthroline, see: Zhang et al. (2008 ).

Experimental

Crystal data

[Ni(C₃H₂O₄)(C₁₅H₁₀N₄)(H₂O)]·3H₂O
M_r = 479.09
Triclinic, $[P \overline 1]$
a = 7.8066 (14) Å
b = 11.639 (2) Å
c = 12.159 (2) Å
α = 109.234 (2)°
β = 103.493 (2)°
γ = 90.601 (2)°
V = 1009.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 298 K
0.31 × 0.21 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.744, T_max = 0.863
5558 measured reflections
3887 independent reflections
3414 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.06
3887 reflections
280 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N1—Ni1	2.186 (2)
N3—Ni1	2.007 (2)
N4—Ni1	2.145 (2)
Ni1—O3	2.0149 (18)
Ni1—O1	2.0427 (17)
Ni1—O5	2.0603 (18)

N3—Ni1—O3	172.30 (8)
N3—Ni1—O1	89.69 (7)
O3—Ni1—O1	89.36 (7)
N3—Ni1—O5	94.60 (8)
O3—Ni1—O5	86.90 (8)
O1—Ni1—O5	174.18 (7)
N3—Ni1—N4	78.21 (8)
O3—Ni1—N4	94.31 (8)
O1—Ni1—N4	96.83 (7)
O5—Ni1—N4	87.90 (8)
N3—Ni1—N1	75.03 (8)
O3—Ni1—N1	112.52 (8)
O1—Ni1—N1	85.91 (8)
O5—Ni1—N1	91.40 (8)
N4—Ni1—N1	153.09 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H2⋯O2ⁱ	0.87	1.77	2.622 (3)	170
O7—H15⋯O8ⁱⁱ	0.82	2.04	2.791 (4)	152
O5—H1⋯O6ⁱⁱⁱ	0.82	1.97	2.773 (3)	167
O6—H12⋯O3^iv	0.89	2.00	2.785 (3)	147
O8—H3⋯O4	0.90	2.13	2.895 (4)	143
O7—H8⋯O4	0.90	1.99	2.836 (4)	155
O6—H11⋯O8	0.76	1.99	2.736 (4)	165
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) x+1, y, z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017188/lh2813sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017188/lh2813Isup2.hkl

checkCIF report

Comment top

Metal complexes containing derivatives of 1,10-phenanthroline as ligands play a pivotal role in the area of modern coordination chemistry. The interest in this area has caused us to synthesize the title complex, and here we report its crystal structure, (I), Fig. 1.

The coordination bond lengths and associated angles (Table 1) indicate that the Ni^II ion assumes a distorted octahedral geometry. All non-hydrogen atoms of the ligand 2-(1H-pyrazol-1-yl)-1,10-phenanthroline define a plane within 0.0368 Å with a maximum deviation of -0.0854 (19) Å for atom N4. In the crystal structure, intermolecular O—H···O hydrogen bonds link the components of the structure into a two-dimensional network (see Fig. 2 and Table 2). In addition, there are weak π–π stacking interactions with Cg1···Cg2ⁱ = 3.6253 (17) Å and Cg1···Cg2ⁱ_perp = 3.411 Å; α is 1.41° [symmetry code: (i) -x, -y, -z; Cg1 and Cg2 are the centroids of C1/C15–C18/N4 ring and C1/C11–C15 ring, respectively; Cg1···Cg2_perp is the perpendicular distance from ring Cg1 to ring Cg2ⁱ; α is the dihedral angle between the Cg1 ring plane and the Cg2 ring plane].

Related literature top

For a related Ni^II structure with 1,10-phenanthroline, see: Zhang et al. (2008).

Experimental top

A 5 ml H₂O solution of hydrated nickel perchlorate (0.1606 g, 0.439 mmol) was added to an ethanol solution containing 2-(1H-pyrazol-1-yl)1,10-phenanthroline (0.1025 g, 0.416 mmol) and the solution was stirred for a few minutes. A 5 ml H₂O solution of sodium propanedioate (0.0714 g, 0.482 mmol) was then added dropwise into the above solution. The solution was stirred for another a few minutes. Blue single crystals were obtained after the filtrate had been allowed to stand at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds drawn as dashed lines.

Aqua(propanedioato-κ²O¹,O³[2-(1H-pyrazol-1-yl- κN²)-1,10-phenanthroline-κ²N,N'])nickel(II) trihydrate top

Crystal data top

[Ni(C₃H₂O₄)(C₁₅H₁₀N₄)(H₂O)]·3H₂O	Z = 2
M_r = 479.09	F(000) = 496
Triclinic, P1	D_x = 1.576 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8066 (14) Å	Cell parameters from 2439 reflections
b = 11.639 (2) Å	θ = 2.7–26.4°
c = 12.159 (2) Å	µ = 1.02 mm⁻¹
α = 109.234 (2)°	T = 298 K
β = 103.493 (2)°	Block, blue
γ = 90.601 (2)°	0.31 × 0.21 × 0.15 mm
V = 1009.8 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3887 independent reflections
Radiation source: fine-focus sealed tube	3414 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.744, T_max = 0.863	k = −10→14
5558 measured reflections	l = −14→12

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0609P)² + 0.1787P] where P = (F_o² + 2F_c²)/3
3887 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.41 e Å⁻³
3 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Ni(C₃H₂O₄)(C₁₅H₁₀N₄)(H₂O)]·3H₂O	γ = 90.601 (2)°
M_r = 479.09	V = 1009.8 (3) Å³
Triclinic, P1	Z = 2
a = 7.8066 (14) Å	Mo Kα radiation
b = 11.639 (2) Å	µ = 1.02 mm⁻¹
c = 12.159 (2) Å	T = 298 K
α = 109.234 (2)°	0.31 × 0.21 × 0.15 mm
β = 103.493 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	3887 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3414 reflections with I > 2σ(I)
T_min = 0.744, T_max = 0.863	R_int = 0.018
5558 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	3 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
3887 reflections	Δρ_min = −0.36 e Å⁻³
280 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
C1	−0.2105 (3)	−0.0069 (3)	0.0485 (2)	0.0402 (6)
C2	0.5533 (3)	0.2194 (2)	0.3192 (2)	0.0317 (5)
C3	0.5634 (4)	0.3565 (2)	0.3449 (3)	0.0481 (7)
H3A	0.6004	0.3975	0.4313	0.058*
H3B	0.6542	0.3783	0.3108	0.058*
C4	0.3933 (3)	0.4043 (2)	0.2967 (3)	0.0391 (6)
C5	0.4542 (4)	0.2600 (3)	0.6200 (2)	0.0501 (7)
H5	0.5037	0.3403	0.6456	0.060*
C6	0.4961 (4)	0.1811 (3)	0.6853 (3)	0.0585 (8)
H6	0.5771	0.1983	0.7594	0.070*
C7	0.3961 (4)	0.0755 (3)	0.6196 (3)	0.0485 (7)
H7	0.3934	0.0053	0.6399	0.058*
C8	0.1738 (3)	0.0109 (2)	0.4191 (2)	0.0349 (5)
C9	0.1191 (4)	−0.1082 (3)	0.4083 (3)	0.0464 (7)
H9	0.1665	−0.1405	0.4681	0.056*
C10	−0.0063 (4)	−0.1753 (3)	0.3072 (3)	0.0500 (7)
H10	−0.0437	−0.2549	0.2977	0.060*
C11	−0.0800 (4)	−0.1258 (2)	0.2169 (3)	0.0423 (6)
C12	−0.0145 (3)	−0.0073 (2)	0.2364 (2)	0.0334 (5)
C13	−0.2146 (4)	−0.1856 (3)	0.1088 (3)	0.0513 (8)
H13	−0.2603	−0.2650	0.0932	0.062*
C14	−0.2756 (4)	−0.1290 (3)	0.0300 (3)	0.0501 (7)
H14	−0.3633	−0.1704	−0.0391	0.060*
C15	−0.0762 (3)	0.0535 (2)	0.1524 (2)	0.0321 (5)
C16	−0.2689 (4)	0.0593 (3)	−0.0293 (2)	0.0490 (7)
H16	−0.3580	0.0242	−0.0994	0.059*
C17	−0.1951 (4)	0.1745 (3)	−0.0018 (2)	0.0506 (7)
H17	−0.2345	0.2190	−0.0523	0.061*
C18	−0.0589 (4)	0.2261 (3)	0.1032 (2)	0.0411 (6)
H18	−0.0085	0.3047	0.1202	0.049*
N1	0.3355 (3)	0.2062 (2)	0.51739 (19)	0.0395 (5)
N2	0.2992 (3)	0.0911 (2)	0.51724 (19)	0.0366 (5)
N3	0.1093 (3)	0.05894 (19)	0.33639 (18)	0.0317 (4)
N4	0.0004 (3)	0.16792 (19)	0.17875 (18)	0.0325 (5)
Ni1	0.19360 (4)	0.22721 (3)	0.34854 (3)	0.02967 (12)
O1	0.4043 (2)	0.15843 (15)	0.28425 (15)	0.0354 (4)
O2	0.6966 (2)	0.17407 (18)	0.3347 (2)	0.0496 (5)
O3	0.2619 (2)	0.38952 (16)	0.33705 (18)	0.0437 (5)
O4	0.3907 (3)	0.4573 (2)	0.2239 (2)	0.0593 (6)
O5	−0.0012 (2)	0.31123 (18)	0.42578 (17)	0.0474 (5)
H2	−0.0974	0.2633	0.3875	0.071*
H1	0.0036	0.3463	0.4970	0.071*
O6	0.9811 (4)	0.5352 (2)	0.3413 (2)	0.0834 (8)
H12	1.0838	0.5098	0.3269	0.125*
H11	0.9107	0.5181	0.2821	0.125*
O7	0.1756 (4)	0.5519 (3)	0.0576 (3)	0.0948 (9)
H8	0.2184	0.5035	0.1004	0.142*
H15	0.2443	0.5350	0.0145	0.142*
O8	0.6999 (4)	0.5114 (3)	0.1500 (3)	0.0967 (10)
H4	0.6894	0.4311	0.1063	0.145*
H3	0.5869	0.5176	0.1541	0.145*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0324 (14)	0.0451 (15)	0.0345 (13)	0.0010 (11)	0.0083 (11)	0.0025 (12)
C2	0.0300 (13)	0.0359 (13)	0.0310 (12)	0.0031 (10)	0.0078 (10)	0.0139 (10)
C3	0.0311 (14)	0.0379 (15)	0.075 (2)	−0.0006 (11)	0.0046 (13)	0.0257 (15)
C4	0.0322 (14)	0.0281 (13)	0.0527 (16)	−0.0026 (10)	0.0022 (12)	0.0142 (12)
C5	0.0474 (17)	0.0535 (18)	0.0400 (15)	−0.0024 (14)	−0.0011 (13)	0.0122 (14)
C6	0.0524 (19)	0.078 (2)	0.0394 (16)	0.0021 (17)	−0.0043 (14)	0.0244 (16)
C7	0.0488 (17)	0.0619 (19)	0.0444 (15)	0.0125 (15)	0.0096 (13)	0.0319 (15)
C8	0.0347 (14)	0.0368 (13)	0.0377 (13)	0.0047 (11)	0.0115 (11)	0.0169 (11)
C9	0.0527 (18)	0.0428 (16)	0.0541 (17)	0.0055 (13)	0.0154 (14)	0.0289 (14)
C10	0.0561 (19)	0.0337 (15)	0.0650 (19)	−0.0046 (13)	0.0204 (15)	0.0197 (14)
C11	0.0445 (16)	0.0366 (14)	0.0471 (15)	−0.0010 (12)	0.0181 (13)	0.0116 (12)
C12	0.0281 (13)	0.0340 (13)	0.0376 (13)	−0.0006 (10)	0.0106 (10)	0.0100 (11)
C13	0.0506 (18)	0.0386 (15)	0.0545 (18)	−0.0165 (13)	0.0142 (14)	0.0026 (14)
C14	0.0416 (17)	0.0502 (17)	0.0418 (15)	−0.0104 (13)	0.0044 (13)	−0.0015 (13)
C15	0.0296 (13)	0.0354 (13)	0.0305 (12)	0.0027 (10)	0.0102 (10)	0.0083 (10)
C16	0.0425 (16)	0.0588 (19)	0.0332 (14)	0.0082 (14)	0.0000 (12)	0.0057 (13)
C17	0.0570 (19)	0.0522 (18)	0.0369 (15)	0.0138 (15)	0.0006 (13)	0.0154 (13)
C18	0.0436 (15)	0.0408 (15)	0.0385 (14)	0.0085 (12)	0.0076 (12)	0.0148 (12)
N1	0.0396 (13)	0.0398 (12)	0.0373 (12)	0.0003 (10)	0.0046 (10)	0.0145 (10)
N2	0.0352 (12)	0.0426 (12)	0.0371 (11)	0.0056 (10)	0.0079 (9)	0.0208 (10)
N3	0.0294 (11)	0.0324 (11)	0.0347 (11)	0.0007 (8)	0.0081 (8)	0.0133 (9)
N4	0.0302 (11)	0.0343 (11)	0.0326 (11)	0.0033 (9)	0.0070 (8)	0.0114 (9)
Ni1	0.02559 (19)	0.02943 (19)	0.03366 (19)	0.00035 (12)	0.00542 (13)	0.01179 (14)
O1	0.0286 (9)	0.0319 (9)	0.0421 (10)	0.0002 (7)	0.0076 (7)	0.0090 (8)
O2	0.0311 (10)	0.0451 (11)	0.0792 (14)	0.0093 (8)	0.0159 (10)	0.0282 (10)
O3	0.0369 (11)	0.0334 (10)	0.0658 (13)	0.0051 (8)	0.0160 (9)	0.0210 (9)
O4	0.0512 (13)	0.0661 (14)	0.0783 (15)	0.0069 (11)	0.0143 (11)	0.0488 (13)
O5	0.0315 (10)	0.0577 (12)	0.0436 (10)	0.0017 (9)	0.0104 (8)	0.0043 (9)
O6	0.0684 (17)	0.0799 (19)	0.0820 (17)	0.0267 (14)	0.0127 (14)	0.0053 (15)
O7	0.090 (2)	0.123 (3)	0.097 (2)	0.0304 (19)	0.0232 (17)	0.070 (2)
O8	0.074 (2)	0.128 (3)	0.105 (2)	0.0108 (18)	0.0367 (17)	0.051 (2)

Geometric parameters (Å, º) top

C1—C15	1.404 (4)	C12—N3	1.351 (3)
C1—C16	1.408 (4)	C12—C15	1.425 (4)
C1—C14	1.432 (4)	C13—C14	1.336 (5)
C2—O2	1.243 (3)	C13—H13	0.9300
C2—O1	1.261 (3)	C14—H14	0.9300
C2—C3	1.519 (4)	C15—N4	1.358 (3)
C3—C4	1.511 (4)	C16—C17	1.356 (4)
C3—H3A	0.9700	C16—H16	0.9300
C3—H3B	0.9700	C17—C18	1.403 (4)
C4—O4	1.231 (3)	C17—H17	0.9300
C4—O3	1.269 (3)	C18—N4	1.317 (3)
C5—N1	1.320 (4)	C18—H18	0.9300
C5—C6	1.395 (4)	N1—N2	1.367 (3)
C5—H5	0.9300	N1—Ni1	2.186 (2)
C6—C7	1.341 (5)	N3—Ni1	2.007 (2)
C6—H6	0.9300	N4—Ni1	2.145 (2)
C7—N2	1.366 (3)	Ni1—O3	2.0149 (18)
C7—H7	0.9300	Ni1—O1	2.0427 (17)
C8—N3	1.311 (3)	Ni1—O5	2.0603 (18)
C8—N2	1.398 (3)	O5—H2	0.8653
C8—C9	1.401 (4)	O5—H1	0.8184
C9—C10	1.367 (4)	O6—H12	0.8934
C9—H9	0.9300	O6—H11	0.7604
C10—C11	1.414 (4)	O7—H8	0.9033
C10—H10	0.9300	O7—H15	0.8159
C11—C12	1.390 (4)	O8—H4	0.9009
C11—C13	1.433 (4)	O8—H3	0.8976

C15—C1—C16	116.2 (3)	N4—C15—C12	117.1 (2)
C15—C1—C14	118.1 (3)	C1—C15—C12	119.0 (2)
C16—C1—C14	125.7 (3)	C17—C16—C1	119.9 (3)
O2—C2—O1	123.8 (2)	C17—C16—H16	120.1
O2—C2—C3	116.5 (2)	C1—C16—H16	120.1
O1—C2—C3	119.7 (2)	C16—C17—C18	119.6 (3)
C4—C3—C2	115.2 (2)	C16—C17—H17	120.2
C4—C3—H3A	108.5	C18—C17—H17	120.2
C2—C3—H3A	108.5	N4—C18—C17	122.8 (3)
C4—C3—H3B	108.5	N4—C18—H18	118.6
C2—C3—H3B	108.5	C17—C18—H18	118.6
H3A—C3—H3B	107.5	C5—N1—N2	104.6 (2)
O4—C4—O3	124.0 (3)	C5—N1—Ni1	144.3 (2)
O4—C4—C3	119.0 (3)	N2—N1—Ni1	110.94 (15)
O3—C4—C3	117.0 (2)	C7—N2—N1	111.0 (2)
N1—C5—C6	111.4 (3)	C7—N2—C8	130.7 (2)
N1—C5—H5	124.3	N1—N2—C8	118.3 (2)
C6—C5—H5	124.3	C8—N3—C12	119.8 (2)
C7—C6—C5	106.2 (3)	C8—N3—Ni1	122.53 (18)
C7—C6—H6	126.9	C12—N3—Ni1	117.64 (16)
C5—C6—H6	126.9	C18—N4—C15	117.5 (2)
C6—C7—N2	106.8 (3)	C18—N4—Ni1	130.64 (19)
C6—C7—H7	126.6	C15—N4—Ni1	111.70 (16)
N2—C7—H7	126.6	N3—Ni1—O3	172.30 (8)
N3—C8—N2	112.9 (2)	N3—Ni1—O1	89.69 (7)
N3—C8—C9	122.4 (2)	O3—Ni1—O1	89.36 (7)
N2—C8—C9	124.7 (2)	N3—Ni1—O5	94.60 (8)
C10—C9—C8	118.0 (3)	O3—Ni1—O5	86.90 (8)
C10—C9—H9	121.0	O1—Ni1—O5	174.18 (7)
C8—C9—H9	121.0	N3—Ni1—N4	78.21 (8)
C9—C10—C11	121.1 (3)	O3—Ni1—N4	94.31 (8)
C9—C10—H10	119.5	O1—Ni1—N4	96.83 (7)
C11—C10—H10	119.5	O5—Ni1—N4	87.90 (8)
C12—C11—C10	116.0 (3)	N3—Ni1—N1	75.03 (8)
C12—C11—C13	117.6 (3)	O3—Ni1—N1	112.52 (8)
C10—C11—C13	126.4 (3)	O1—Ni1—N1	85.91 (8)
N3—C12—C11	122.7 (2)	O5—Ni1—N1	91.40 (8)
N3—C12—C15	115.3 (2)	N4—Ni1—N1	153.09 (8)
C11—C12—C15	122.0 (2)	C2—O1—Ni1	121.73 (15)
C14—C13—C11	121.1 (3)	C4—O3—Ni1	121.25 (16)
C14—C13—H13	119.4	Ni1—O5—H2	105.6
C11—C13—H13	119.4	Ni1—O5—H1	128.8
C13—C14—C1	122.2 (3)	H2—O5—H1	113.1
C13—C14—H14	118.9	H12—O6—H11	109.3
C1—C14—H14	118.9	H8—O7—H15	95.2
N4—C15—C1	124.0 (2)	H4—O8—H3	97.9

O2—C2—C3—C4	165.4 (2)	C15—C12—N3—C8	179.8 (2)
O1—C2—C3—C4	−14.8 (4)	C11—C12—N3—Ni1	178.57 (19)
C2—C3—C4—O4	−120.0 (3)	C15—C12—N3—Ni1	−2.4 (3)
C2—C3—C4—O3	61.9 (3)	C17—C18—N4—C15	−0.4 (4)
N1—C5—C6—C7	−0.8 (4)	C17—C18—N4—Ni1	−176.1 (2)
C5—C6—C7—N2	0.8 (4)	C1—C15—N4—C18	1.7 (3)
N3—C8—C9—C10	0.0 (4)	C12—C15—N4—C18	−178.3 (2)
N2—C8—C9—C10	179.4 (3)	C1—C15—N4—Ni1	178.24 (19)
C8—C9—C10—C11	−0.7 (4)	C12—C15—N4—Ni1	−1.8 (3)
C9—C10—C11—C12	1.4 (4)	C8—N3—Ni1—O1	81.8 (2)
C9—C10—C11—C13	−178.4 (3)	C12—N3—Ni1—O1	−95.92 (18)
C10—C11—C12—N3	−1.4 (4)	C8—N3—Ni1—O5	−94.3 (2)
C13—C11—C12—N3	178.3 (2)	C12—N3—Ni1—O5	88.01 (18)
C10—C11—C12—C15	179.6 (2)	C8—N3—Ni1—N4	178.8 (2)
C13—C11—C12—C15	−0.6 (4)	C12—N3—Ni1—N4	1.12 (17)
C12—C11—C13—C14	−0.4 (4)	C8—N3—Ni1—N1	−4.07 (19)
C10—C11—C13—C14	179.4 (3)	C12—N3—Ni1—N1	178.23 (19)
C11—C13—C14—C1	0.2 (5)	C18—N4—Ni1—N3	176.3 (2)
C15—C1—C14—C13	1.0 (4)	C15—N4—Ni1—N3	0.39 (15)
C16—C1—C14—C13	−179.3 (3)	C18—N4—Ni1—O3	−5.6 (2)
C16—C1—C15—N4	−1.7 (4)	C15—N4—Ni1—O3	178.52 (15)
C14—C1—C15—N4	178.1 (2)	C18—N4—Ni1—O1	−95.4 (2)
C16—C1—C15—C12	178.3 (2)	C15—N4—Ni1—O1	88.65 (16)
C14—C1—C15—C12	−1.9 (4)	C18—N4—Ni1—O5	81.2 (2)
N3—C12—C15—N4	2.8 (3)	C15—N4—Ni1—O5	−94.75 (16)
C11—C12—C15—N4	−178.2 (2)	C18—N4—Ni1—N1	170.1 (2)
N3—C12—C15—C1	−177.2 (2)	C15—N4—Ni1—N1	−5.8 (3)
C11—C12—C15—C1	1.8 (4)	C5—N1—Ni1—N3	178.2 (4)
C15—C1—C16—C17	0.3 (4)	N2—N1—Ni1—N3	4.34 (15)
C14—C1—C16—C17	−179.5 (3)	C5—N1—Ni1—O3	−0.2 (4)
C1—C16—C17—C18	1.0 (4)	N2—N1—Ni1—O3	−174.04 (14)
C16—C17—C18—N4	−1.0 (5)	C5—N1—Ni1—O1	87.4 (3)
C6—C5—N1—N2	0.5 (3)	N2—N1—Ni1—O1	−86.44 (16)
C6—C5—N1—Ni1	−173.6 (2)	C5—N1—Ni1—O5	−87.4 (3)
C6—C7—N2—N1	−0.5 (3)	N2—N1—Ni1—O5	98.73 (16)
C6—C7—N2—C8	−179.5 (3)	C5—N1—Ni1—N4	−175.5 (3)
C5—N1—N2—C7	−0.1 (3)	N2—N1—Ni1—N4	10.6 (3)
Ni1—N1—N2—C7	176.26 (17)	O2—C2—O1—Ni1	143.1 (2)
C5—N1—N2—C8	179.1 (2)	C3—C2—O1—Ni1	−36.7 (3)
Ni1—N1—N2—C8	−4.6 (3)	N3—Ni1—O1—C2	−145.91 (18)
N3—C8—N2—C7	−179.5 (2)	O3—Ni1—O1—C2	41.73 (19)
C9—C8—N2—C7	1.1 (4)	N4—Ni1—O1—C2	136.00 (18)
N3—C8—N2—N1	1.6 (3)	N1—Ni1—O1—C2	−70.90 (18)
C9—C8—N2—N1	−177.9 (2)	O4—C4—O3—Ni1	135.1 (2)
N2—C8—N3—C12	−179.5 (2)	C3—C4—O3—Ni1	−46.9 (3)
C9—C8—N3—C12	0.0 (4)	O1—Ni1—O3—C4	1.6 (2)
N2—C8—N3—Ni1	2.8 (3)	O5—Ni1—O3—C4	177.2 (2)
C9—C8—N3—Ni1	−177.69 (19)	N4—Ni1—O3—C4	−95.2 (2)
C11—C12—N3—C8	0.8 (4)	N1—Ni1—O3—C4	86.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H2···O2ⁱ	0.87	1.77	2.622 (3)	170
O7—H15···O8ⁱⁱ	0.82	2.04	2.791 (4)	152
O5—H1···O6ⁱⁱⁱ	0.82	1.97	2.773 (3)	167
O6—H12···O3^iv	0.89	2.00	2.785 (3)	147
O8—H3···O4	0.90	2.13	2.895 (4)	143
O7—H8···O4	0.90	1.99	2.836 (4)	155
O6—H11···O8	0.76	1.99	2.736 (4)	165

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

Experimental details

Crystal data
Chemical formula	[Ni(C₃H₂O₄)(C₁₅H₁₀N₄)(H₂O)]·3H₂O
M_r	479.09
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.8066 (14), 11.639 (2), 12.159 (2)
α, β, γ (°)	109.234 (2), 103.493 (2), 90.601 (2)
V (Å³)	1009.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.31 × 0.21 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.744, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	5558, 3887, 3414
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.06
No. of reflections	3887
No. of parameters	280
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.36

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

N1—Ni1	2.186 (2)	Ni1—O3	2.0149 (18)
N3—Ni1	2.007 (2)	Ni1—O1	2.0427 (17)
N4—Ni1	2.145 (2)	Ni1—O5	2.0603 (18)

N3—Ni1—O3	172.30 (8)	O1—Ni1—N4	96.83 (7)
N3—Ni1—O1	89.69 (7)	O5—Ni1—N4	87.90 (8)
O3—Ni1—O1	89.36 (7)	N3—Ni1—N1	75.03 (8)
N3—Ni1—O5	94.60 (8)	O3—Ni1—N1	112.52 (8)
O3—Ni1—O5	86.90 (8)	O1—Ni1—N1	85.91 (8)
O1—Ni1—O5	174.18 (7)	O5—Ni1—N1	91.40 (8)
N3—Ni1—N4	78.21 (8)	N4—Ni1—N1	153.09 (8)
O3—Ni1—N4	94.31 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H2···O2ⁱ	0.87	1.77	2.622 (3)	170
O7—H15···O8ⁱⁱ	0.82	2.04	2.791 (4)	152
O5—H1···O6ⁱⁱⁱ	0.82	1.97	2.773 (3)	167
O6—H12···O3^iv	0.89	2.00	2.785 (3)	147
O8—H3···O4	0.90	2.13	2.895 (4)	143
O7—H8···O4	0.90	1.99	2.836 (4)	155
O6—H11···O8	0.76	1.99	2.736 (4)	165

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

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Zhang, S. G., Hu, T. Q. & Li, H. (2008). Acta Cryst. E64, m769. Web of Science CSD CrossRef IUCr Journals Google Scholar

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