(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxyl­ato)bis­(1,10-phenanthroline)nickel(II) 3.5-hydrate

Malinkin, S.; Kapshuk, A.A.; Gumienna-Kontecka, E.; Prisyazhnaya, E.V.; Iskenderov, T.S.

doi:10.1107/S1600536813017194

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m417-m418

https://doi.org/10.1107/S1600536813017194

Open

access

(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxylato)bis(1,10-phenanthroline)nickel(II) 3.5-hydrate

Sergey Malinkin,^a Anatoliy A. Kapshuk,^a Elzbieta Gumienna-Kontecka,^b Elena V. Prisyazhnaya ^c and Turganbay S. Iskenderov ^a ^*

^aDepartment of Chemistry, Kiev National Taras Shevchenko University, Volodymyrska Street 64, 01601 Kiev, Ukraine, ^bFaculty of Chemistry, University of Wrocław, F. Joliot-Curie Street 14, 50-383 Wrocław, Poland, and ^cDepartment of Chemistry, Kyiv National University of Construction and Architecture, Povitroflotsky Avenue 31, 03680 Kiev, Ukraine
^*Correspondence e-mail: tiskenderov@ukr.net

(Received 14 June 2013; accepted 21 June 2013; online 26 June 2013)

The title compound, [Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O, crystallizes as a neutral mononuclear complex with 3.5 solvent water molecules. One of the water molecules lies on an inversion centre, so that its H atoms are disordered over two sites. The coordination environment of Ni^II has a slightly distorted octahedral geometry, which is formed by one O and five N atoms belonging to the N,O-chelating pyrazol-1-ide-5-carboxylate and two N,N′-chelating phenanthroline molecules. In the crystal, O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds involving the solvent water molecules and pyrazole-5-carboxylate ligands form layers parallel to the ab plane. These layers are linked further via weak π–π interactions between two adjacent phenanthroline molecules, with centroid-to-centroid distances in the range 3.886 (2)–4.018 (1) Å, together with C—H⋯π contacts, forming a three-dimensional network.

Related literature

The work presented here continues studies of complexes based on pyrazolate ligands with transition metals, see: Klingele et al. (2009 ); Malinkin et al. (2009 , 2012a ,b ,c ); Ng et al. (2011 ); Penkova et al. (2008 , 2009 ); Meyer & Pritzkow (2000 ); Bauer-Siebenlist et al. (2005 ); Świątek-Kozłowska et al. (2000 ). For related structures, see: Zhong et al. (2009 ); Zheng et al. (2009 ); Bouchene et al. (2013 ); Fang & Wang (2010 ); Fritsky et al. (2004 , 2006 ); Kanderal et al. (2005 ); Moroz et al. (2010 ). For the starting material, see: Sachse et al. (2008 ).

Experimental

Crystal data

[Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O
M_r = 648.29
Triclinic, $[P \overline 1]$
a = 9.865 (3) Å
b = 11.659 (4) Å
c = 13.561 (5) Å
α = 91.91 (3)°
β = 98.85 (3)°
γ = 105.20 (4)°
V = 1482.8 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 170 K
0.23 × 0.18 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.857, T_max = 0.929
12624 measured reflections
6830 independent reflections
3040 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.153
S = 0.85
6830 reflections
405 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—Ni1	2.041 (4)
N3—Ni1	2.085 (4)
N4—Ni1	2.080 (4)
N5—Ni1	2.078 (3)
N6—Ni1	2.093 (4)
O2—Ni1	2.066 (3)

Table 2
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/N2/C2/C3/C4 pyrazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.95	2.31	3.088 (6)	139
O4—H4B⋯N2ⁱ	0.94	2.01	2.906 (6)	157
O5—H5A⋯O4ⁱⁱ	0.86	2.02	2.875 (6)	172
O5—H5B⋯O1	0.90	2.00	2.787 (5)	145
O6—H6D⋯O5	0.87	2.05	2.895 (6)	163
O6—H6E⋯O2	0.88	1.98	2.827 (5)	163
O7—H7D⋯O3	0.89	2.16	2.964 (4)	150
O7—H7E⋯O4	0.89	2.02	2.821 (5)	149
C12—H12⋯Cg1ⁱⁱⁱ	0.93	2.77	3.646 (6)	158
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y+2, -z+2; (iii) -x+1, -y+1, -z+1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: WinGX (Farrugia, 2012 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813017194/sj5334sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813017194/sj5334Isup2.hkl

checkCIF report

Comment top

The bridging nature of pyrazolate provides the possibility to bring metal ions into close proximity, which results in arrays with interesting magnetic and catalytic properties (Klingele et al., 2009; Malinkin et al., 2012b; Ng et al., 2011). Therefore, research focused on pyrazolate complexes with higher nuclearity is of special interest in the field of supramolecular and bioinorganic chemistry (Penkova et al., 2008, 2009; Meyer & Pritzkow, 2000; Bauer-Siebenlist et al., 2005). Mononuclear pyrazolate-based complexes bearing non-coordinated donor groups can potentially be used as building blocks for the synthesis of discrete clusters as well as extended frameworks that offer a wide range of possible applications. On the other hand, phenanthroline is often used in the synthesis of discrete polynuclear complexes in order to prevent formation of coordination polymers by blocking a certain number of vacant sites in the coordination sphere of a metal ion (Fritsky et al., 2004, 2006). Herein we report the synthesis and crystal structure of the title compound, (I), as a continuation of our earlier work devoted to complexes based on non-symmetrical pyrazole ligands (Penkova et al., 2008; Malinkin et al., 2012a,b), in particular, 3-acetyl-4-methyl-1H-pyrazole-5 carboxylic acid (Malinkin et al., 2009, 2012c).

As shown in Figure 1, the Ni^II ion is coordinated by one pyrazolate ligand via N,O-chelating groups and two N,N-chelating phenanthroline molecules forming a slightly distorted octahedral coordination environment. The Ni—N_pz, Ni—N_phen and Ni—O distances are consistent with the reported data for related complexes (Fang & Wang, 2010; Zheng et al., 2009; Zhong et al., 2009; Bouchene et al., 2013).

The coordinated pyrazolate ligand exhibits C—C, C—N, N—N bond lengths which are normal for bridging pyrazolate rings (Penkova et al., 2008; Malinkin et al., 2012a,b; Świątek-Kozłowska et al., 2000). The C—O bond lengths in the deprotonated carboxylic groups differs significantly (1.239 (2) and 1.292 (2) Å) which is typical for monodentate coordinated carboxylates (Malinkin et al., 2012a,b). Also the C—N and C—C bond lengths in the phenanthroline ligand are similar to those separations observed in other 2-substituted pyridine derivatives (Kanderal et al., 2005; Moroz et al., 2010).

In the crystal packing the complex molecules are associated via intermolecular hydrogen bonds (Table 1) that involve O—H and N—H interactions between the donor atoms of pyrazolate ligand and solvate water molecules forming layers which are parallel to the xy plane (Fig. 2). In addition layers are stabilized by a weak π–π interactions between phenanthroline moieties with intercentroid distances of 4.018 (1) Å. Further complex species are united into three-dimensional motif through a π–π interactions found between two adjacent phenanthroline molecules belonging to the different layers (intercentroid distances 3.886 (2) and 3.950 (2) Å) and a C—H(phenanthroline)···π(pyrazole) contacts (the shortest H—centroid separation is around 2.77 Å).

Related literature top

The work presented here continues studies of complexes based on pyrazolate ligands with transition metals, see: Klingele et al. (2009); Malinkin et al. (2009, 2012a,b,c); Ng et al. (2011); Penkova et al. (2008, 2009); Meyer & Pritzkow (2000); Bauer-Siebenlist et al. (2005); Świątek-Kozłowska et al. (2000). For related structures, see: Zhong et al. (2009); Zheng et al. (2009); Bouchene et al. (2013); Fang & Wang (2010); Fritsky et al. (2004, 2006); Kanderal et al. (2005); Moroz et al. (2010). For the starting material, see: Sachse et al. (2008).

Experimental top

The compound was prepared by addition of 4 ml of a methanolic solution containing 0.0360 g (0.2 mmol) of phenanthroline and 0.0366 g (0.1 mmol) Ni(ClO₄)₂.6H₂O to a mixture containing 0.0167 g (0.1 mmol) L (Sachse et al., 2008) and 0.2 ml of aqueous NaOH solution (0.1 M) in 5 ml methanol.

Light-green crystals appeared after several days. Yield: 0.0227 g (35%). Elemental analysis calc. (%) for C₃₁H₂₉N_6NiO_6.5: C 57.38; H 4.47; N 12.96; found: C 57.22; H 4.30; N 13.05.

Structure description top

The work presented here continues studies of complexes based on pyrazolate ligands with transition metals, see: Klingele et al. (2009); Malinkin et al. (2009, 2012a,b,c); Ng et al. (2011); Penkova et al. (2008, 2009); Meyer & Pritzkow (2000); Bauer-Siebenlist et al. (2005); Świątek-Kozłowska et al. (2000). For related structures, see: Zhong et al. (2009); Zheng et al. (2009); Bouchene et al. (2013); Fang & Wang (2010); Fritsky et al. (2004, 2006); Kanderal et al. (2005); Moroz et al. (2010). For the starting material, see: Sachse et al. (2008).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. A portion of the packing, viewed down the y axis. Intermolecular hydrogen bonds link the molecules into a two-dimensional network. Hydrogen bonds and π-interactions are shown as red and black dashed lines, respectively. [Symmetry codes: (i) -x + 1, -y + 1, -z + 2; (ii) -x + 1, -y + 2, -z + 2; (iii) -x + 1, -y + 1, -z + 1.]

(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxylato)bis(1,10-phenanthroline)nickel(II) 3.5-hydrate top

Crystal data top

[Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O	Z = 2
M_r = 648.29	F(000) = 674
Triclinic, P1	D_x = 1.452 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.865 (3) Å	Cell parameters from 11133 reflections
b = 11.659 (4) Å	θ = 3.4–36.5°
c = 13.561 (5) Å	µ = 0.71 mm⁻¹
α = 91.91 (3)°	T = 170 K
β = 98.85 (3)°	Block, light green
γ = 105.20 (4)°	0.23 × 0.18 × 0.11 mm
V = 1482.8 (9) Å³

Data collection top

Nonius KappaCCD diffractometer	6830 independent reflections
Radiation source: fine-focus sealed tube	3040 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.070
Detector resolution: 9 pixels mm^-1	θ_max = 28.6°, θ_min = 3.0°
φ scans and ω scans with κ offset	h = −12→12
Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −15→15
T_min = 0.857, T_max = 0.929	l = −18→18
12624 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 0.85	w = 1/[σ²(F_o²) + (0.0675P)²] where P = (F_o² + 2F_c²)/3
6830 reflections	(Δ/σ)_max = 0.001
405 parameters	Δρ_max = 1.12 e Å⁻³
13 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O	γ = 105.20 (4)°
M_r = 648.29	V = 1482.8 (9) Å³
Triclinic, P1	Z = 2
a = 9.865 (3) Å	Mo Kα radiation
b = 11.659 (4) Å	µ = 0.71 mm⁻¹
c = 13.561 (5) Å	T = 170 K
α = 91.91 (3)°	0.23 × 0.18 × 0.11 mm
β = 98.85 (3)°

Data collection top

Nonius KappaCCD diffractometer	6830 independent reflections
Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	3040 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.929	R_int = 0.070
12624 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	13 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 0.85	Δρ_max = 1.12 e Å⁻³
6830 reflections	Δρ_min = −0.59 e Å⁻³
405 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)
N1	0.6503 (4)	0.6632 (3)	0.7897 (2)	0.0294 (9)
N2	0.5838 (4)	0.5594 (3)	0.8208 (2)	0.0322 (10)
N3	0.7221 (4)	0.6920 (3)	0.5843 (3)	0.0331 (10)
N4	0.8913 (4)	0.5870 (3)	0.6988 (2)	0.0303 (9)
N5	0.9485 (4)	0.7889 (3)	0.8732 (2)	0.0293 (9)
N6	1.0125 (4)	0.8544 (3)	0.6950 (2)	0.0299 (9)
O1	0.5691 (4)	0.9471 (3)	0.7919 (2)	0.0416 (9)
O2	0.7478 (3)	0.8848 (3)	0.7411 (2)	0.0318 (8)
O3	0.2663 (4)	0.4867 (3)	0.9303 (3)	0.0518 (10)
Ni1	0.82850 (7)	0.73904 (5)	0.73104 (4)	0.0312 (2)
C1	0.6312 (6)	0.8686 (4)	0.7797 (3)	0.0316 (12)
C2	0.5759 (5)	0.7458 (4)	0.8088 (3)	0.0315 (11)
C3	0.4603 (5)	0.6920 (4)	0.8544 (3)	0.0332 (12)
C4	0.4690 (5)	0.5759 (4)	0.8588 (3)	0.0287 (11)
C5	0.3683 (6)	0.4731 (4)	0.8924 (3)	0.0365 (13)
C6	0.3883 (6)	0.3506 (4)	0.8784 (4)	0.0508 (15)
H6A	0.4691	0.3442	0.9250	0.076*
H6B	0.4038	0.3372	0.8113	0.076*
H6C	0.3045	0.2922	0.8898	0.076*
C7	0.3526 (5)	0.7476 (4)	0.8889 (4)	0.0431 (13)
H7A	0.3621	0.7487	0.9605	0.065*
H7B	0.2584	0.7018	0.8592	0.065*
H7C	0.3686	0.8277	0.8691	0.065*
C8	0.6363 (5)	0.7446 (4)	0.5314 (3)	0.0383 (13)
H8	0.6268	0.8159	0.5584	0.046*
C9	0.5574 (5)	0.6988 (5)	0.4354 (3)	0.0458 (14)
H9	0.4957	0.7376	0.4009	0.055*
C10	0.5754 (6)	0.5954 (5)	0.3951 (3)	0.0482 (16)
H10	0.5254	0.5635	0.3321	0.058*
C11	0.6679 (5)	0.5375 (4)	0.4475 (3)	0.0382 (13)
C12	0.6942 (6)	0.4303 (5)	0.4122 (4)	0.0501 (16)
H12	0.6486	0.3956	0.3489	0.060*
C13	0.7818 (6)	0.3779 (4)	0.4666 (4)	0.0483 (15)
H13	0.7965	0.3083	0.4404	0.058*
C14	0.8553 (6)	0.4280 (4)	0.5668 (3)	0.0404 (14)
C15	0.9472 (6)	0.3781 (4)	0.6280 (4)	0.0462 (14)
H15	0.9663	0.3088	0.6052	0.055*
C16	1.0106 (5)	0.4308 (4)	0.7228 (4)	0.0425 (13)
H16	1.0728	0.3985	0.7644	0.051*
C17	0.9775 (5)	0.5347 (4)	0.7536 (4)	0.0382 (13)
H17	1.0194	0.5697	0.8174	0.046*
C18	0.7407 (5)	0.5897 (4)	0.5443 (3)	0.0318 (12)
C19	0.8312 (5)	0.5333 (4)	0.6038 (3)	0.0329 (12)
C20	0.9158 (5)	0.7544 (4)	0.9607 (3)	0.0348 (12)
H20	0.8343	0.6925	0.9614	0.042*
C21	1.0000 (5)	0.8078 (4)	1.0528 (3)	0.0360 (12)
H21	0.9734	0.7815	1.1128	0.043*
C22	1.1195 (5)	0.8975 (4)	1.0534 (3)	0.0331 (12)
H22	1.1747	0.9339	1.1138	0.040*
C23	1.1596 (5)	0.9353 (4)	0.9623 (3)	0.0299 (11)
C24	1.2904 (5)	1.0252 (4)	0.9547 (3)	0.0367 (12)
H24	1.3502	1.0638	1.0128	0.044*
C25	1.3267 (5)	1.0535 (4)	0.8642 (3)	0.0390 (13)
H25	1.4124	1.1094	0.8612	0.047*
C26	1.2346 (5)	0.9984 (4)	0.7734 (3)	0.0333 (12)
C27	1.2673 (6)	1.0234 (4)	0.6772 (3)	0.0456 (14)
H27	1.3521	1.0784	0.6704	0.055*
C28	1.1733 (6)	0.9662 (4)	0.5937 (4)	0.0477 (15)
H28	1.1940	0.9816	0.5300	0.057*
C29	1.0464 (5)	0.8846 (4)	0.6058 (3)	0.0373 (12)
H29	0.9819	0.8492	0.5487	0.045*
C30	1.0704 (5)	0.8775 (3)	0.8739 (3)	0.0240 (10)
C31	1.1071 (5)	0.9121 (4)	0.7786 (3)	0.0284 (11)
O4	0.2548 (5)	0.6130 (4)	1.1314 (3)	0.0849 (15)
H4A	0.3056	0.6009	1.0797	0.127*
H4B	0.2955	0.5559	1.1627	0.127*
O5	0.6423 (4)	1.1780 (3)	0.7310 (3)	0.0707 (13)
H5A	0.6793	1.2428	0.7689	0.106*
H5B	0.5979	1.1190	0.7654	0.106*
O6	0.8621 (6)	1.0978 (3)	0.6534 (3)	0.1067 (19)
H6D	0.8036	1.1361	0.6718	0.160*
H6E	0.8406	1.0267	0.6755	0.160*
O7	0.0000	0.5000	1.0000	0.383 (10)
H7D	0.0556	0.4810	0.9600	0.575*	0.50
H7E	0.0563	0.5411	1.0543	0.575*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.040 (2)	0.0185 (19)	0.0159 (17)	−0.0093 (18)	−0.0078 (16)	−0.0005 (14)
N2	0.046 (3)	0.020 (2)	0.0188 (18)	−0.0036 (19)	−0.0079 (18)	0.0005 (15)
N3	0.043 (3)	0.023 (2)	0.027 (2)	−0.0004 (19)	0.0018 (19)	0.0016 (16)
N4	0.041 (3)	0.021 (2)	0.0210 (18)	−0.0037 (18)	0.0042 (17)	0.0008 (15)
N5	0.040 (3)	0.0186 (19)	0.0217 (18)	−0.0043 (17)	0.0037 (17)	−0.0003 (15)
N6	0.040 (2)	0.023 (2)	0.0198 (18)	0.0001 (18)	−0.0009 (17)	−0.0015 (15)
O1	0.054 (2)	0.0216 (18)	0.045 (2)	0.0063 (17)	0.0017 (17)	0.0011 (14)
O2	0.035 (2)	0.0276 (18)	0.0281 (17)	0.0016 (15)	0.0052 (15)	0.0003 (13)
O3	0.054 (3)	0.043 (2)	0.053 (2)	−0.0003 (19)	0.015 (2)	0.0153 (17)
Ni1	0.0433 (4)	0.0227 (3)	0.0173 (3)	−0.0043 (3)	−0.0027 (2)	−0.0026 (2)
C1	0.045 (3)	0.023 (3)	0.021 (2)	0.005 (2)	−0.004 (2)	0.0005 (19)
C2	0.042 (3)	0.023 (2)	0.023 (2)	0.003 (2)	−0.004 (2)	−0.0050 (18)
C3	0.043 (3)	0.025 (3)	0.022 (2)	0.001 (2)	−0.009 (2)	0.0006 (19)
C4	0.032 (3)	0.024 (2)	0.026 (2)	0.004 (2)	−0.002 (2)	−0.0038 (18)
C5	0.044 (3)	0.032 (3)	0.026 (2)	0.001 (2)	0.001 (2)	0.007 (2)
C6	0.068 (4)	0.026 (3)	0.044 (3)	−0.012 (3)	0.008 (3)	0.003 (2)
C7	0.048 (3)	0.029 (3)	0.051 (3)	0.007 (3)	0.008 (3)	0.007 (2)
C8	0.046 (3)	0.034 (3)	0.027 (2)	−0.004 (2)	0.007 (2)	0.003 (2)
C9	0.047 (3)	0.048 (3)	0.028 (2)	−0.007 (3)	−0.004 (2)	0.005 (2)
C10	0.053 (4)	0.053 (3)	0.018 (2)	−0.018 (3)	−0.002 (2)	0.001 (2)
C11	0.045 (3)	0.036 (3)	0.022 (2)	−0.010 (2)	0.007 (2)	−0.005 (2)
C12	0.060 (4)	0.043 (3)	0.031 (3)	−0.016 (3)	0.010 (3)	−0.012 (2)
C13	0.062 (4)	0.031 (3)	0.041 (3)	−0.014 (3)	0.023 (3)	−0.011 (2)
C14	0.054 (4)	0.029 (3)	0.032 (3)	−0.004 (3)	0.016 (3)	−0.002 (2)
C15	0.051 (4)	0.027 (3)	0.056 (3)	−0.004 (3)	0.025 (3)	−0.004 (2)
C16	0.046 (3)	0.033 (3)	0.051 (3)	0.011 (3)	0.014 (3)	0.009 (2)
C17	0.042 (3)	0.030 (3)	0.036 (3)	0.000 (2)	0.005 (2)	0.002 (2)
C18	0.040 (3)	0.025 (2)	0.022 (2)	−0.008 (2)	0.005 (2)	−0.0001 (19)
C19	0.039 (3)	0.025 (2)	0.028 (2)	−0.008 (2)	0.014 (2)	−0.0038 (19)
C20	0.041 (3)	0.030 (3)	0.023 (2)	−0.006 (2)	−0.003 (2)	0.0000 (19)
C21	0.047 (3)	0.029 (3)	0.024 (2)	0.000 (2)	0.001 (2)	−0.0022 (19)
C22	0.042 (3)	0.028 (3)	0.022 (2)	0.005 (2)	−0.006 (2)	−0.0061 (19)
C23	0.037 (3)	0.020 (2)	0.027 (2)	0.004 (2)	−0.001 (2)	−0.0056 (18)
C24	0.040 (3)	0.024 (2)	0.036 (3)	−0.005 (2)	−0.001 (2)	−0.006 (2)
C25	0.043 (3)	0.021 (2)	0.044 (3)	−0.003 (2)	0.002 (2)	−0.002 (2)
C26	0.041 (3)	0.023 (2)	0.030 (2)	−0.002 (2)	0.005 (2)	0.0035 (19)
C27	0.051 (4)	0.035 (3)	0.042 (3)	−0.006 (3)	0.010 (3)	0.004 (2)
C28	0.059 (4)	0.046 (3)	0.030 (3)	−0.002 (3)	0.010 (3)	0.010 (2)
C29	0.045 (3)	0.037 (3)	0.025 (2)	0.002 (2)	0.007 (2)	0.006 (2)
C30	0.031 (3)	0.015 (2)	0.023 (2)	0.0038 (19)	0.0004 (19)	−0.0037 (17)
C31	0.036 (3)	0.018 (2)	0.024 (2)	−0.001 (2)	0.001 (2)	0.0013 (17)
O4	0.101 (4)	0.065 (3)	0.118 (4)	0.042 (3)	0.065 (3)	0.054 (3)
O5	0.067 (3)	0.044 (2)	0.093 (3)	0.008 (2)	−0.002 (2)	0.030 (2)
O6	0.205 (6)	0.043 (3)	0.097 (3)	0.033 (3)	0.098 (4)	0.027 (2)
O7	0.51 (2)	0.397 (17)	0.303 (16)	0.246 (16)	0.044 (14)	0.047 (13)

Geometric parameters (Å, º) top

N1—N2	1.333 (4)	C12—H12	0.9300
N1—Ni1	2.041 (4)	C12—C13	1.333 (7)
N1—C2	1.394 (6)	C13—H13	0.9300
N2—C4	1.368 (6)	C13—C14	1.461 (6)
N3—Ni1	2.085 (4)	C14—C15	1.387 (7)
N3—C8	1.312 (6)	C14—C19	1.401 (6)
N3—C18	1.361 (5)	C15—H15	0.9300
N4—Ni1	2.080 (4)	C15—C16	1.386 (7)
N4—C17	1.324 (6)	C16—H16	0.9300
N4—C19	1.386 (5)	C16—C17	1.401 (6)
N5—Ni1	2.078 (3)	C17—H17	0.9300
N5—C20	1.324 (5)	C18—C19	1.415 (7)
N5—C30	1.363 (5)	C20—H20	0.9300
N6—Ni1	2.093 (4)	C20—C21	1.413 (5)
N6—C29	1.337 (5)	C21—H21	0.9300
N6—C31	1.379 (5)	C21—C22	1.355 (6)
O1—C1	1.247 (5)	C22—H22	0.9300
O2—Ni1	2.066 (3)	C22—C23	1.404 (6)
O2—C1	1.308 (6)	C23—C24	1.453 (6)
O3—C5	1.240 (6)	C23—C30	1.406 (5)
C1—C2	1.482 (6)	C24—H24	0.9300
C2—C3	1.395 (6)	C24—C25	1.358 (6)
C3—C4	1.382 (6)	C25—H25	0.9300
C3—C7	1.503 (7)	C25—C26	1.433 (6)
C4—C5	1.477 (6)	C26—C27	1.413 (6)
C5—C6	1.502 (7)	C26—C31	1.403 (6)
C6—H6A	0.9600	C27—H27	0.9300
C6—H6B	0.9600	C27—C28	1.374 (6)
C6—H6C	0.9600	C28—H28	0.9300
C7—H7A	0.9600	C28—C29	1.396 (6)
C7—H7B	0.9600	C29—H29	0.9300
C7—H7C	0.9600	C30—C31	1.438 (6)
C8—H8	0.9300	O4—H4A	0.9495
C8—C9	1.418 (6)	O4—H4B	0.9445
C9—H9	0.9300	O5—H5A	0.8599
C9—C10	1.371 (7)	O5—H5B	0.9001
C10—H10	0.9300	O6—H6D	0.8749
C10—C11	1.396 (7)	O6—H6E	0.8751
C11—C12	1.424 (7)	O7—H7D	0.8900
C11—C18	1.427 (5)	O7—H7E	0.8900

N2—N1—Ni1	140.1 (3)	C10—C11—C12	125.1 (5)
N2—N1—C2	107.9 (4)	C10—C11—C18	117.2 (5)
C2—N1—Ni1	111.9 (3)	C12—C11—C18	117.7 (5)
N1—N2—C4	107.4 (4)	C11—C12—H12	118.8
C8—N3—Ni1	127.8 (3)	C13—C12—C11	122.3 (5)
C8—N3—C18	118.8 (4)	C13—C12—H12	118.8
C18—N3—Ni1	113.2 (3)	C12—C13—H13	119.4
C17—N4—Ni1	130.8 (3)	C12—C13—C14	121.2 (5)
C17—N4—C19	116.1 (4)	C14—C13—H13	119.4
C19—N4—Ni1	113.1 (3)	C15—C14—C13	124.4 (5)
C20—N5—Ni1	128.9 (3)	C15—C14—C19	117.7 (4)
C20—N5—C30	117.7 (4)	C19—C14—C13	117.9 (5)
C30—N5—Ni1	113.1 (3)	C14—C15—H15	119.8
C29—N6—Ni1	130.3 (3)	C16—C15—C14	120.4 (5)
C29—N6—C31	117.0 (4)	C16—C15—H15	119.8
C31—N6—Ni1	112.6 (3)	C15—C16—H16	121.3
C1—O2—Ni1	116.3 (3)	C15—C16—C17	117.4 (5)
N1—Ni1—N3	92.73 (14)	C17—C16—H16	121.3
N1—Ni1—N4	99.54 (15)	N4—C17—C16	125.1 (4)
N1—Ni1—N5	91.36 (14)	N4—C17—H17	117.4
N1—Ni1—N6	165.31 (14)	C16—C17—H17	117.4
N1—Ni1—O2	80.47 (15)	N3—C18—C11	121.8 (5)
N3—Ni1—N6	96.35 (14)	N3—C18—C19	117.6 (4)
N4—Ni1—N3	79.56 (15)	C19—C18—C11	120.5 (4)
N4—Ni1—N6	93.46 (15)	N4—C19—C14	123.1 (5)
N5—Ni1—N3	175.80 (16)	N4—C19—C18	116.5 (4)
N5—Ni1—N4	98.84 (15)	C14—C19—C18	120.4 (4)
N5—Ni1—N6	79.83 (14)	N5—C20—H20	118.7
O2—Ni1—N3	91.62 (14)	N5—C20—C21	122.5 (4)
O2—Ni1—N4	171.18 (13)	C21—C20—H20	118.7
O2—Ni1—N5	89.97 (13)	C20—C21—H21	120.1
O2—Ni1—N6	87.73 (14)	C22—C21—C20	119.7 (4)
O1—C1—O2	124.6 (4)	C22—C21—H21	120.1
O1—C1—C2	121.4 (5)	C21—C22—H22	120.2
O2—C1—C2	114.0 (5)	C21—C22—C23	119.6 (4)
N1—C2—C1	117.3 (4)	C23—C22—H22	120.2
N1—C2—C3	109.9 (4)	C22—C23—C24	123.8 (4)
C3—C2—C1	132.8 (5)	C22—C23—C30	117.2 (4)
C2—C3—C7	128.1 (4)	C30—C23—C24	118.8 (4)
C4—C3—C2	102.8 (4)	C23—C24—H24	119.5
C4—C3—C7	129.1 (4)	C25—C24—C23	121.0 (4)
N2—C4—C3	112.0 (4)	C25—C24—H24	119.5
N2—C4—C5	119.7 (4)	C24—C25—H25	119.6
C3—C4—C5	128.2 (5)	C24—C25—C26	120.9 (4)
O3—C5—C4	120.8 (5)	C26—C25—H25	119.6
O3—C5—C6	119.8 (5)	C27—C26—C25	123.4 (4)
C4—C5—C6	119.4 (5)	C31—C26—C25	119.3 (4)
C5—C6—H6A	109.5	C31—C26—C27	117.3 (4)
C5—C6—H6B	109.5	C26—C27—H27	120.1
C5—C6—H6C	109.5	C28—C27—C26	119.7 (5)
H6A—C6—H6B	109.5	C28—C27—H27	120.1
H6A—C6—H6C	109.5	C27—C28—H28	120.5
H6B—C6—H6C	109.5	C27—C28—C29	119.1 (4)
C3—C7—H7A	109.5	C29—C28—H28	120.5
C3—C7—H7B	109.5	N6—C29—C28	123.7 (4)
C3—C7—H7C	109.5	N6—C29—H29	118.2
H7A—C7—H7B	109.5	C28—C29—H29	118.2
H7A—C7—H7C	109.5	N5—C30—C23	123.2 (4)
H7B—C7—H7C	109.5	N5—C30—C31	117.3 (3)
N3—C8—H8	118.2	C23—C30—C31	119.5 (4)
N3—C8—C9	123.6 (5)	N6—C31—C26	123.1 (4)
C9—C8—H8	118.2	N6—C31—C30	116.4 (4)
C8—C9—H9	121.2	C26—C31—C30	120.5 (4)
C10—C9—C8	117.7 (5)	H4A—O4—H4B	83.7
C10—C9—H9	121.2	H5A—O5—H5B	111.0
C9—C10—H10	119.6	H6D—O6—H6E	107.9
C9—C10—C11	120.8 (4)	H7D—O7—H7E	107.6
C11—C10—H10	119.6

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/N2/C2/C3/C4 pyrazole ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.95	2.31	3.088 (6)	139
O4—H4B···N2ⁱ	0.94	2.01	2.906 (6)	157
O5—H5A···O4ⁱⁱ	0.86	2.02	2.875 (6)	172
O5—H5B···O1	0.90	2.00	2.787 (5)	145
O6—H6D···O5	0.87	2.05	2.895 (6)	163
O6—H6E···O2	0.88	1.98	2.827 (5)	163
O7—H7D···O3	0.89	2.16	2.964 (4)	150
O7—H7E···O4	0.89	2.02	2.821 (5)	149
C12—H12···Cg1ⁱⁱⁱ	0.93	2.77	3.646 (6)	158

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O
M_r	648.29
Crystal system, space group	Triclinic, P1
Temperature (K)	170
a, b, c (Å)	9.865 (3), 11.659 (4), 13.561 (5)
α, β, γ (°)	91.91 (3), 98.85 (3), 105.20 (4)
V (Å³)	1482.8 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.23 × 0.18 × 0.11

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.857, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	12624, 6830, 3040
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.153, 0.85
No. of reflections	6830
No. of parameters	405
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.59

Computer programs: COLLECT (Nonius, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), WinGX (Farrugia, 2012), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008).

Selected bond lengths (Å) top

N1—Ni1	2.041 (4)	N5—Ni1	2.078 (3)
N3—Ni1	2.085 (4)	N6—Ni1	2.093 (4)
N4—Ni1	2.080 (4)	O2—Ni1	2.066 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/N2/C2/C3/C4 pyrazole ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.95	2.31	3.088 (6)	138.7
O4—H4B···N2ⁱ	0.94	2.01	2.906 (6)	157.1
O5—H5A···O4ⁱⁱ	0.86	2.02	2.875 (6)	172.4
O5—H5B···O1	0.90	2.00	2.787 (5)	144.9
O6—H6D···O5	0.87	2.05	2.895 (6)	162.9
O6—H6E···O2	0.88	1.98	2.827 (5)	162.6
O7—H7D···O3	0.89	2.16	2.964 (4)	149.7
O7—H7E···O4	0.89	2.02	2.821 (5)	149.1
C12—H12···Cg1ⁱⁱⁱ	0.93	2.77	3.646 (6)	157.8

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

Acknowledgements

The authors are grateful for financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program).

References

Bauer-Siebenlist, B., Dechert, S. & Meyer, F. (2005). Chem. Eur. J. 11, 5343–5352. Web of Science PubMed CAS Google Scholar
Bouchene, R., Khadri, A., Bouacida, S., Berrah, F. & Merazig, H. (2013). Acta Cryst. E69, m309–m310. CSD CrossRef CAS IUCr Journals Google Scholar
Fang, Z. & Wang, J. (2010). Acta Cryst. E66, m1285. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fritsky, I. O., Kozłowski, H., Kanderal, O. M., Haukka, M., Świątek-Kozłowska, J., Gumienna-Kontecka, E. & Meyer, F. (2006). Chem. Commun. pp. 4125–4127. Web of Science CSD CrossRef Google Scholar
Fritsky, I. O., Świątek-Kozłowska, J., Dobosz, A., Sliva, T. Y. & Dudarenko, N. M. (2004). Inorg. Chim. Acta, 357, 3746–3752. Web of Science CSD CrossRef CAS Google Scholar
Kanderal, O. M., Kozłowski, H., Dobosz, A., Świątek-Kozłowska, J., Meyer, F. & Fritsky, I. O. (2005). Dalton Trans. pp. 1428–1437. Web of Science CrossRef PubMed Google Scholar
Klingele, J., Dechert, S. & Meyer, F. (2009). Coord. Chem. Rev. 253, 2698–2741. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Malinkin, S. O., Moroz, Y. S., Penkova, L., Haukka, M., Szebesczyk, A., Gumienna-Kontecka, E., Pavlenko, V. A., Nordlander, E., Meyer, F. & Fritsky, I. O. (2012c). Inorg. Chim. Acta, 392, 322–330. Web of Science CSD CrossRef CAS Google Scholar
Malinkin, S. O., Penkova, L., Moroz, Y. S., Bon, V., Gumienna-Kontecka, E., Pekhnyo, V. I., Meyer, F. & Fritsky, I. O. (2012b). Polyhedron, 37, 77–84. Web of Science CSD CrossRef CAS Google Scholar
Malinkin, S., Penkova, L., Moroz, Y. S., Haukka, M., Maciag, A., Gumienna-Kontecka, E., Pavlova, S., Nordlander, E., Fritsky, I. O. & Pavlenko, V. A. (2012a). Eur. J. Inorg. Chem. pp. 1639–1649. Web of Science CSD CrossRef Google Scholar
Malinkin, S., Penkova, L., Pavlenko, V. A., Haukka, M. & Fritsky, I. O. (2009). Acta Cryst. E65, m1247–m1248. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Meyer, F. & Pritzkow, H. (2000). Angew. Chem. Int. Ed. 39, 2112–2115. CrossRef CAS Google Scholar
Moroz, Y. S., Szyrweil, L., Demeshko, S., Kozłowski, H., Meyer, F. & Fritsky, I. O. (2010). Inorg. Chem. 49, 4750–4752. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ng, G. K.-Y., Ziller, J. W. & Borovik, A. S. (2011). Inorg. Chem. 50, 7922–7924. Web of Science CrossRef CAS PubMed Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Penkova, L., Demeshko, S., Haukka, M., Pavlenko, V. A., Meyer, F. & Fritsky, I. O. (2008). Z. Anorg. Allg. Chem. 634, 2428–2436. Web of Science CSD CrossRef CAS Google Scholar
Penkova, L. V., Maciag, A., Rybak-Akimova, E. V., Haukka, M., Pavlenko, V. A., Iskenderov, T. S., Kozlowski, H., Meyer, F. & Fritsky, I. O. (2009). Inorg. Chem. 48, 6960–6971. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sachse, A., Penkova, L., Noel, G., Dechert, S., Varzatskii, O. A., Fritsky, I. O. & Meyer, F. (2008). Synthesis, 5, 800–806. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Świątek-Kozłowska, J., Fritsky, I. O., Dobosz, A., Karaczyn, A., Dudarenko, N. M., Sliva, T. Yu., Gumienna-Kontecka, E. & Jerzykiewicz, L. (2000). J. Chem. Soc. Dalton Trans. pp. 4064–4068. Google Scholar
Zheng, Z.-B., Wu, R.-T., Li, J.-K. & Sun, Y.-F. (2009). J. Mol. Struct. 928, 78–84. Web of Science CSD CrossRef CAS Google Scholar
Zhong, F., Ying, S., Liu, J., Duan, D., Shi, T. & Wang, Q. (2009). Chem. Res. Appl. 21, 385–391. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m417-m418

https://doi.org/10.1107/S1600536813017194

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxyl­ato)bis­­(1,10-phenanthroline)nickel(II) 3.5-hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxylato)bis(1,10-phenanthroline)nickel(II) 3.5-hydrate