Transition metal complexes with pyrazole-based ligands. XIX. Di­aqua­bis(3,5-di­methyl-1H-pyrazole-1-carbox­amidine-κ2N,N′)­metal(II) ­dinitrate, with metal = Co and Ni

Jaćimović, Ž.K.; Leovac, V.; Mészáros Szécsényi, K.; Howard, J.A.K.; Radosavljević Evans, I.

doi:10.1107/S0108270104017433

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 10| October 2004| Pages m467-m470

doi:10.1107/S0108270104017433

Transition metal complexes with pyrazole-based ligands. XIX. Diaquabis(3,5-dimethyl-1H-pyrazole-1-carboxamidine-κ²N,N′)metal(II) dinitrate, with metal = Co and Ni

Željko K. Jaćimović,^a Vukadin Leovac,^b Katalin Mészáros Szécsényi,^b Judith A. K. Howard ^c and Ivana Radosavljević Evans ^c ^*

^aFaculty of Metallurgy and Technology, University of Montenegro, 81000 Podgorica, Serbia and Montenegro, ^bFaculty of Sciences, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad, Serbia and Montenegro, and ^cDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: ivana.radosavljevic@durham.ac.uk

(Received 27 May 2004; accepted 15 July 2004; online 4 September 2004)

The two title isostructural and isomorphous complexes, [M(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂ (M is Co or Ni), contain the transition metal in a distorted octahedral geometry, coordinated by four N atoms of two neutral bidentate organic ligands in the equatorial plane and two water O atoms molecules in the axial positions. The cation is centrosymmetric, with the transition metal located on an inversion centre. The structures are stabilized by a three-dimensional network of hydrogen bonding.

Comment

Transition metal complexes with pyrazole-derived ligands exhibit interesting coordination chemistry and have attracted the research interest of numerous authors (Trofimenko, 1972 , 1986 , 1993 , and references therein). These compounds find application in antipyretics and antirheumatics, in herbicides and fungicides, and also as metal ion extractants (Ding et al., 1994 ; Goslar et al., 1988 ). A more recent area of research activity has focused on the biocoordination chemistry of pyrazole and its macrocyclic derivatives (Bienvenue et al., 1995 ; Gupta et al., 1996 ).

We have synthesized and characterized a number of pyrazole-derived ligands and their metal complexes, with the aim of investigating the influence of the pyrazole ring substituents on complex formation (Jaćimović et al., 1999 , 2003 ; Tomić et al., 2000 ; Mészáros Szécsényi et al., 2001 , 2003 ). We report here the crystal structures of the isomorphous Co and Ni complexes of the ligand 3,5-dimethyl-1H-pyrazole-1-carboxamidine nitrate (Khudoyarov et al., 1995 ). The Co complex, (I), has been prepared for the first time, while the structure of the Ni analogue, (II), has been determined previously (Podder et al., 1986 ). However, the geometry and orientation of the water molecules in the previously reported structure were implausible. For example, the O—H bond lengths were 0.64 and 0.90 Å, the H—O—H bond angle was 96°, and the molecule was oriented in such a way that one of the H atoms was only 1.4 Å from the Ni centre. Clearly, such an incorrect model does not permit an accurate description of the hydrogen-bonding interactions, which play a significant role in the stability of this complex and which will be discussed below.

The asymmetric units of (I) and (II) contains half an [M(C₆H₁₀N₄)₂(H₂O)₂]²⁺ cation, located on an inversion centre, and an NO₃⁻ anion. The Co^II and Ni^II cations are found in a distorted octahedral environment, coordinated to the ligand in the equatorial plane through pyrazole ring N atoms and the adjacent amidinium group N atoms. The coordination sphere is completed by two O atoms belonging to water molecules in axial positions (Fig. 1).

In (I), the equatorial bond lengths are Co—N2 = 2.0871 (8) Å and Co—N3 2.0842 (9) Å, and the ligand bite angle is 76.46 (3)°. The axial Co—O4 bond length is 2.1737 (7) Å. The corresponding parameters for (II) are 2.0474 (11) and 2.0552 (12) Å, 77.67 (4)°, and 2.1520 (10) Å. In both cases, the ligand ring system is essentially planar, with the amidinium group tilted relative to the substituted pyrazole ring by 3.7° in (I) and by 2.2° in (II). This is in contrast to the molecular structure of the ligand itself (Khudoyarov et al., 1995), where a significant departure from planarity exists, with the amidinium group twisted at an angle of 34° relative to the plane of the pyrazole ring. In the formation of complexes (I) and (II), the geometry of the ligand is adjusted to accommodate the coordination requirements of the transition metal.

Packing diagrams for the title complexes are shown in Fig. 2. The cations pack in such a way that molecules lying parallel form layers of alternating orientation. Layers of cations are separated by layers of nitrate anions. This arrangement gives rise to a system of hydrogen bonding involving the N atoms of the amino group and the water O atoms as donors, and the O atoms of the nitrate groups as acceptors. Two O atoms of a given nitrate group form hydrogen bonds to two cations in the layer above (with the amino group of one molecule and water in the other), while the third forms a bifurcated hydrogen bond to two cations in the layer below. The adjacent nitrate group forms the same number and types of hydrogen bonds, but in the opposite orientation, as shown in Fig. 2. Details of the hydrogen-bonding geometries for the two complexes are given in Tables 2 and 4. This three-dimensional pattern of hydrogen bonding imparts stability to the crystal structures of these two complexes.

Figure 1
Views of the (a) the Co complex, (I

), and (b) the Ni complex, (II

), with their atom-numbering schemes. Each asymmetric unit consists of half a cation, with the metal on an inversion centre, and one nitrate anion. Displacement ellipsoids are shown at the 50% probability level.

Figure 2
Views of the packing and hydrogen-bonding schemes for (a) complex (I

) and (b) complex (II

Experimental

For the preparation of (I), an ethanol solution (5 ml) of Co(OAc)₂·4H₂O (0.06 g, 0.25 mmol) was added to an ethanol solution (5 ml) of the ligand 3,5-dimethylpyrazole-1-carboxamidine nitrate (0.1 g, 0.5 mmol) and the mixture was gently heated. After 48 h, orange crystals of (I) were filtered off and washed with ethanol (yield 0.18 g, 65%). Elemental analysis, found (calculated): C 28.89 (29.08), N 28.30 (28.27), H 4.96% (4.89%). For the preparation of (II), an ethanol solution (5 ml) of Ni(OAc)₂·4H₂O (0.06 g, 0.25 mmol) was added to an ethanol solution (5 ml) of the ligand 3,5-dimethylpyrazole-1-carboxamidine nitrate (0.1 g, 0.5 mmol) and the mixture was gently heated. After 60 h, purple crystals of (II) were filtered off and washed with ethanol (yield 0.18 g, 65%). Elemental analysis, found (calculated): C 28.93 (29.10), N 28.30 (28.29), H 4.96% (4.89%).

Compound (I)

Crystal data

[Co(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂
M_r = 495.32
Monoclinic, P2₁/n
a = 9.1067 (11) Å
b = 10.9344 (13) Å
c = 10.4425 (13) Å
β = 107.602 (2)°
V = 991.1 (2) Å³
Z = 2
D_x = 1.660 Mg m⁻³
Mo Kα radiation
Cell parameters from 7486 reflections
θ = 5.2–61.7°
μ = 0.93 mm⁻¹
T = 120 K
Rectangular prism, orange
0.24 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.840, T_max = 0.911
13 055 measured reflections
2975 independent reflections
2920 reflections with I > 2σ(I)
R_int = 0.02
θ_max = 30.9°
h = −12 → 13
k = −15 → 15
l = −15 → 14

Refinement

Refinement on F²
R(F) = 0.027
wR(F²) = 0.062
S = 0.98
2920 reflections
190 parameters
All H-atom parameters refined
Weighting scheme: method, part 1, Chebychev polynomial (Watkin, 1994 ; Prince, 1982 ), [weight] = 1/[A₀T₀(x) + A₁T₁(x) + … + A_n−1T_n−1(x)], where A_i are the Chebychev coefficients 1.62, 2.12 and 0.556, and x = F_calc/F_max. Method = robust weighting (Prince, 1982), W = [weight] × [1−(ΔF/6σF)²]²
(Δ/σ)_max = 0.001
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for (I)

Co1—N2	2.0871 (8)
Co1—N3	2.0842 (9)
Co1—O4	2.1737 (7)
N1—N2	1.3778 (10)
N1—C1	1.4176 (12)
N1—C5	1.3731 (12)
N2—C3	1.3256 (12)
N3—C1	1.2890 (12)
N5—O1	1.2408 (11)
N5—O2	1.2582 (11)
N5—O3	1.2546 (11)
N4—C1	1.3361 (12)
C2—C3	1.4918 (13)
C3—C4	1.4104 (12)
C4—C5	1.3717 (13)
C5—C6	1.4860 (13)

N2—Co1—N3	76.46 (3)
N2—Co1—O4	91.79 (3)
N3—Co1—O4	87.79 (3)

Table 2
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H9⋯O1ⁱ	0.84 (2)	2.249 (18)	2.8572 (13)	129.7 (16)
N4—H10⋯O2ⁱⁱ	0.811 (18)	2.114 (18)	2.9136 (13)	168.8 (18)
O4—H11⋯O2	0.772 (19)	2.081 (19)	2.8539 (12)	179.5 (14)
O4—H12⋯O3ⁱⁱⁱ	0.85 (2)	2.14 (2)	2.9799 (12)	169.6 (18)
Symmetry codes: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ ; (ii) 3-x,1-y,2-z; (iii) $[{\script{5\over 2}}-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ .

Compound (II)

Crystal data

[Ni(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂
M_r = 495.10
Monoclinic, P2₁/n
a = 9.077 (3) Å
b = 10.866 (4) Å
c = 10.456 (3) Å
β = 107.251 (15)°
V = 985.0 (6) Å³
Z = 2
D_x = 1.669 Mg m⁻³
Mo Kα radiation
Cell parameters from 6757 reflections
θ = 5.2–62.2°
μ = 1.05 mm⁻¹
T = 120 K
Rectangular prism, purple
0.20 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.803, T_max = 0.881
13 257 measured reflections
2990 independent reflections
2617 reflections with I > 2σ(I)
R_int = 0.02
θ_max = 31.0°
h = −12 → 12
k = −15 → 15
l = −14 → 14

Refinement

Refinement on F²
R(F) = 0.026
wR(F²) = 0.062
S = 0.98
2617 reflections
190 parameters
All H-atom parameters refined
Weighting scheme, method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982), [weight] = 1/[A₀T₀(x) + A₁T₁(x) + … + A_n−1T_n−1(x)], where A_i are the Chebychev coefficients 1.85, 2.44 and 0.676, and x = F_calc/F_max. Method = robust weighting (Prince, 1982), W = [weight] × [1−(ΔF/6σF)²]²
(Δ/σ)_max = 0.001
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 3
Selected geometric parameters (Å, °) for (II)

Ni1—N2	2.0474 (11)
Ni1—N3	2.0552 (12)
Ni1—O4	2.1520 (10)
N1—N2	1.3776 (12)
N1—C2	1.4186 (14)
N1—C5	1.3753 (14)
N2—C3	1.3275 (14)
N3—C2	1.2833 (14)
N4—C2	1.3402 (14)
N5—O1	1.2402 (13)
N5—O2	1.2589 (13)
N5—O3	1.2548 (13)
C1—C3	1.4919 (16)
C3—C4	1.4106 (14)
C4—C5	1.3701 (16)
C5—C6	1.4863 (15)

N2—Ni1—N3	77.67 (4)
N2—Ni1—O4	91.05 (4)
N3—Ni1—O4	88.43 (4)

Table 4
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H9⋯O1ⁱ	0.83 (2)	2.256 (19)	2.8604 (18)	130.0 (17)
N4—H10⋯O2ⁱⁱ	0.818 (19)	2.113 (19)	2.9171 (18)	167.5 (18)
O4—H12⋯O2	0.76 (2)	2.09 (2)	2.8537 (16)	179 (2)
O4—H11⋯O3ⁱⁱⁱ	0.82 (2)	2.17 (2)	2.9849 (17)	169.9 (18)
Symmetry codes: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ ; (ii) 3-x,1-y,2-z; (iii) $[{\script{5\over 2}}-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ .

H atoms were located in difference Fourier maps and refined isotropically. Refined distance ranges are as follows: C—H = 0.91 (2)–0.99 (2) Å, N—H = 0.74 (2)–0.84 (2) Å and O—H = 0.76 (2)–0.85 (2) Å.

For both compounds, data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ATOMS (Dowty, 2000 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270104017433/bm1571sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104017433/bm1571Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104017433/bm1571IIsup3.hkl

Comment top

Transition metal complexes with pyrazole-derived ligands exhibit interesting coordination chemistry and have attracted the research interest of numerous authors (Trofimenko, 1972, 1986, 1993, and references therein). These phases find applications in antipyretics and antirheumatics, in herbicides and fungicides, and also as metal ion extragents [extractants?] (Ding et al., 1994; Goslar et al., 1988). A more recent area of research activity has focused on the biocoordination chemistry of pyrazole and its macrocyclic derivatives (Bienvenue et al., 1995; Gupta et al., 1996).

We have synthesized and characterized a number of pyrazole-derived ligands and their metal complexes, with the aim of investigating the influence of the pyrazole ring substituents on complex formation (Jaćimović et al., 1999, 2003; Tomić et al., 2000; Mészáros Szécsényi et al., 2001, 2003). We report here the crystal structures of the isomorphous Co and Ni complexes of the ligand 3,5-dimethylpyrazole-1-carboxamidine nitrate (Khudoyarov et al., 1995). The Co complex, (I), has been prepared for the first time, while the structure of the Ni analogue, (II), has been determined previously (Podder et al., 1986). However, the geometry and orientation of the water molecules in that reported structure was implausible. For example, the O—H bond lengths are 0.64 and 0.90 Å, the H—O—H bond angle is 96°, and the molecule is oriented in such a way that one of the H atoms lies only 1.4 Å away from the Ni centre. Clearly, such an incorrect model does not permit an accurate description of the hydrogen-bonding interactions, which play a significant role in the stability of this complex and which will be discussed below. \sch

The asymmetric unit of (I) and (II) contains half an (MC₁₂N₈O₂H₂₄)²⁺ cation, located on an inversion centre, and an NO₃⁻ anion. The Co^II and Ni^II cations are found in a distorted octahedral environment, coordinated to the ligand in the equatorial plane through the pyrazole ring N atoms and the adjacent amidinium group N atoms. The coordination sphere is completed by two O atoms belonging to water molecules in axial positions (Fig. 1).

In (I), the equatorial bond lengths are Co—N2 2.0871 (8) and Co—N3 2.0842 (9) Å, and the ligand bite angle is 76.46 (3)°. The axial Co—O4 bond length is 2.1737 (7) Å. The corresponding parameters for (II) are 2.0474 (11) and 2.0552 (12) Å, 77.67 (4)°, and 2.1520 (10) Å. In both cases, the ligand ring system is essentially planar, with the amidinium group tilted relative to the substituted pyrazole ring by 3.7° in (I) and by 2.2° in (II). This is in contrast with the molecular structure of the ligand itself (Khudoyarov et al., 1995), where a significant departure from planarity exists, with the amidinium group twisted at an angle of 34° relative to the plane of the pyrazole ring. In the formation of complexes (I) and (II), the geometry of the ligand is adjusted to accommodate the coordination requirements of the transition metal.

Packing diagrams for the title complexes are shown in Fig. 2. The cations pack in such a way that molecules lying parallel form layers of alternating orientation. Layers of cations are separated by layers of nitrate anions. This arrangement gives rise to a system of hydrogen bonding involving the N atoms of the amino group and the water O atoms as donors, and the O atoms of the nitrate groups as acceptors. Two O atoms of a given nitrate group form hydrogen bonds to two cations in the layer above (with the amino group on one molecule and water on the other), while the third forms a bifurcated hydrogen bond to two cations in the layer below. The adjacent nitrate group forms the same number and types of hydrogen bonds, but in the opposite orientation, as shown in Fig. 2. Details of the hydrogen-bonding geometries for the two complexes are given in Tables 2 and 4. This three-dimensional pattern of hydrogen bonding imparts stability to the crystal structures of these two complexes.

Experimental top

For the preparation of (I), 5 ml of an ethanolic solution of Co(OAc)₂.4 H₂O (0.06 g, 0.25 mmol) was added to 5 ml of an ethanolic solution of the ligand 3,5-dimethylpyrazole-1-carboxamidine nitrate (0.1 g, 0.5 mmol) and the mixture was gently heated. After 48 h, orange crystals of (I) were filtered off and washed with ethanol (yield 0.08 g). Elemental analysis, found (calculated): C 28.89 (29.08), N 28.30 (28.27), H 4.96 (4.89)%. For the preparation of (II), 5 ml of an ethanolic solution of Ni(OAc)₂.4 H₂O (0.06 g, (0.25 mmol) was added to 5 ml of an ethanolic solution of the ligand 3,5-dimethylpyrazole-1-carboxamidine nitrate (0.1 g, 0.5 mmol) and the mixture was gently heated. After 60 h, purple crystals of (II) were filtered off and washed with ethanol (yield 0.18 g). Elemental analysis, found (calculated): C 28.93 (29.10), N 28.30 (28.29), H 4.96 (4.89)%.

Computing details top

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS.

Figures top

Fig. 1. Views of the Co and Ni complexes, (I) and (II), repsectively, with their and atom-numbering schemes. The asymmetric unit consists of half a cation, with the metal on an inversion centre, and one nitrate anion. Displacement ellipsoids are shown at the 50% probability level. From the Coeditor: Please check the above text, and make sure you have sent in a copy of the ellipsoid plot for the Ni structure.

Fig. 2. Views of the packing and hydrogen-bonding schemes for (a) complex (I) and (b) complex (II).

(I) Diaquabis(3,5-dimethylpyrazole-1-carboxamidine-κ²N,N')cobalt(II) dinitrate top

Crystal data top

[Co(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂	F(000) = 514
M_r = 495.32	D_x = 1.660 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7486 reflections
a = 9.1067 (11) Å	θ = 5.2–61.7°
b = 10.9344 (13) Å	µ = 0.93 mm⁻¹
c = 10.4425 (13) Å	T = 120 K
β = 107.602 (2)°	Rectangular prism, orange
V = 991.1 (2) Å³	0.24 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2920 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.02
ω scans	θ_max = 30.9°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.840, T_max = 0.911	k = −15→15
13055 measured reflections	l = −15→14
2975 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	All H-atom parameters refined
wR(F²) = 0.062	Method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982), [weight] = 1/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1T_n-1(x)], where A_i are the Chebychev coefficients listed below and x = F /F_max Method = robust weighting (Prince, 1982), W = [weight] × [1-(ΔF/6σF)²]². A_i are 1.62, 2.12 and 0.556
S = 0.98	(Δ/σ)_max = 0.001
2920 reflections	Δρ_max = 0.44 e Å⁻³
190 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints

Crystal data top

[Co(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂	V = 991.1 (2) Å³
M_r = 495.32	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1067 (11) Å	µ = 0.93 mm⁻¹
b = 10.9344 (13) Å	T = 120 K
c = 10.4425 (13) Å	0.24 × 0.10 × 0.10 mm
β = 107.602 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2975 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2920 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.911	R_int = 0.02
13055 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.062	All H-atom parameters refined
S = 0.98	Δρ_max = 0.44 e Å⁻³
2920 reflections	Δρ_min = −0.38 e Å⁻³
190 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	1.0000	0.5000	1.0000	0.0127
N1	1.20636 (9)	0.29222 (7)	1.00939 (8)	0.0146
N2	1.05102 (8)	0.31803 (7)	0.97054 (8)	0.0151
N3	1.23936 (10)	0.49253 (7)	1.07683 (9)	0.0161
N4	1.45759 (10)	0.37046 (9)	1.09871 (9)	0.0204
N5	1.33613 (9)	0.34672 (8)	0.74332 (8)	0.0171
C1	1.30604 (10)	0.39099 (9)	1.06510 (9)	0.0151
C2	0.80811 (11)	0.20551 (9)	0.87785 (11)	0.0206
C3	0.97959 (10)	0.21337 (8)	0.92762 (9)	0.0157
C4	1.08791 (11)	0.11904 (8)	0.93680 (10)	0.0178
C5	1.23080 (11)	0.17100 (8)	0.98816 (9)	0.0165
C6	1.38285 (12)	0.11031 (10)	1.01281 (12)	0.0231
O1	1.23276 (9)	0.27136 (8)	0.69350 (9)	0.0309
O2	1.30401 (9)	0.45101 (7)	0.77817 (8)	0.0219
O3	1.47423 (9)	0.31926 (8)	0.75900 (9)	0.0275
O4	1.02884 (8)	0.55437 (7)	0.80883 (7)	0.0183
H1	1.297 (2)	0.5397 (17)	1.1074 (16)	0.027 (4)*
H2	1.0670 (17)	0.0377 (15)	0.9125 (14)	0.020 (3)*
H3	0.7762 (19)	0.1272 (17)	0.8487 (16)	0.035 (4)*
H4	0.7637 (18)	0.2253 (16)	0.9478 (15)	0.029 (4)*
H5	0.765 (2)	0.2578 (16)	0.8001 (17)	0.032 (4)*
H6	1.362 (2)	0.030 (2)	0.9825 (19)	0.041 (5)*
H7	1.4387 (19)	0.1133 (16)	1.1032 (16)	0.029 (4)*
H8	1.4425 (19)	0.1488 (15)	0.9590 (15)	0.027 (4)*
H9	1.4919 (19)	0.2992 (18)	1.1012 (16)	0.034 (4)*
H10	1.514 (2)	0.4268 (17)	1.1324 (16)	0.028 (4)*
H11	1.103 (2)	0.5260 (18)	0.8003 (18)	0.035 (4)*
H12	1.037 (2)	0.6309 (19)	0.7992 (18)	0.042 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00943 (9)	0.01169 (9)	0.01636 (9)	0.00113 (5)	0.00285 (6)	−0.00073 (5)
N1	0.0107 (3)	0.0139 (3)	0.0182 (3)	0.0025 (3)	0.0027 (2)	−0.0004 (3)
N2	0.0092 (3)	0.0150 (3)	0.0201 (3)	0.0017 (3)	0.0030 (3)	−0.0015 (3)
N3	0.0120 (4)	0.0142 (3)	0.0207 (4)	−0.0004 (3)	0.0030 (3)	−0.0022 (3)
N4	0.0109 (3)	0.0188 (4)	0.0287 (4)	0.0027 (3)	0.0018 (3)	−0.0028 (3)
N5	0.0137 (3)	0.0192 (4)	0.0179 (3)	−0.0011 (3)	0.0039 (3)	0.0008 (3)
C1	0.0125 (4)	0.0167 (4)	0.0153 (4)	0.0000 (3)	0.0029 (3)	−0.0003 (3)
C2	0.0129 (4)	0.0195 (4)	0.0281 (4)	−0.0023 (3)	0.0043 (3)	−0.0061 (4)
C3	0.0140 (4)	0.0148 (4)	0.0182 (4)	−0.0001 (3)	0.0048 (3)	−0.0010 (3)
C4	0.0175 (4)	0.0141 (4)	0.0222 (4)	0.0016 (3)	0.0065 (3)	−0.0010 (3)
C5	0.0160 (4)	0.0146 (4)	0.0188 (4)	0.0036 (3)	0.0052 (3)	0.0006 (3)
C6	0.0170 (4)	0.0185 (4)	0.0323 (5)	0.0065 (3)	0.0049 (4)	−0.0014 (4)
O1	0.0190 (4)	0.0276 (4)	0.0434 (5)	−0.0085 (3)	0.0052 (3)	−0.0082 (4)
O2	0.0180 (3)	0.0188 (3)	0.0299 (4)	0.0016 (3)	0.0087 (3)	−0.0005 (3)
O3	0.0131 (3)	0.0275 (4)	0.0416 (4)	0.0013 (3)	0.0078 (3)	−0.0087 (3)
O4	0.0161 (3)	0.0183 (3)	0.0216 (3)	0.0018 (3)	0.0072 (2)	0.0016 (2)

Geometric parameters (Å, º) top

Co1—N2	2.0871 (8)	N4—H10	0.809 (18)
Co1—N3	2.0842 (9)	C2—C3	1.4918 (13)
Co1—O4	2.1737 (7)	C2—H3	0.926 (18)
N1—N2	1.3778 (10)	C2—H4	0.960 (16)
N1—C1	1.4176 (12)	C2—H5	0.973 (17)
N1—C5	1.3731 (12)	C3—C4	1.4104 (12)
N2—C3	1.3256 (12)	C4—C5	1.3717 (13)
N3—C1	1.2890 (12)	C4—H2	0.929 (16)
N3—H1	0.734 (19)	C5—C6	1.4860 (13)
N5—O1	1.2408 (11)	C6—H6	0.93 (2)
N5—O2	1.2582 (11)	C6—H7	0.927 (16)
N5—O3	1.2546 (11)	C6—H8	0.986 (16)
N4—C1	1.3361 (12)	O4—H11	0.78 (2)
N4—H9	0.837 (19)	O4—H12	0.85 (2)

N2—Co1—N3	76.46 (3)	H3—C2—H4	107.2 (14)
N2—Co1—O4	91.79 (3)	C3—C2—H5	111.8 (10)
N3—Co1—O4	87.79 (3)	H3—C2—H5	105.2 (14)
N2—N1—C1	115.97 (7)	H4—C2—H5	110.2 (14)
N2—N1—C5	110.63 (7)	C2—C3—N2	121.50 (8)
C1—N1—C5	133.37 (8)	C2—C3—C4	128.21 (8)
Co1—N2—N1	113.98 (6)	N2—C3—C4	110.29 (8)
Co1—N2—C3	139.86 (6)	C3—C4—C5	106.56 (8)
N1—N2—C3	106.14 (7)	C3—C4—H2	126.9 (9)
Co1—N3—C1	117.72 (7)	C5—C4—H2	126.5 (9)
Co1—N3—H1	131.5 (14)	N1—C5—C4	106.38 (8)
C1—N3—H1	110.7 (14)	N1—C5—C6	126.24 (9)
O1—N5—O2	120.66 (8)	C4—C5—C6	127.36 (9)
O1—N5—O3	119.95 (9)	C5—C6—H6	106.2 (12)
O2—N5—O3	119.39 (8)	C5—C6—H7	110.9 (10)
C1—N4—H9	120.7 (12)	H6—C6—H7	111.7 (15)
C1—N4—H10	116.9 (12)	C5—C6—H8	110.8 (9)
H9—N4—H10	120.9 (16)	H6—C6—H8	107.3 (15)
N1—C1—N4	117.53 (8)	H7—C6—H8	109.8 (14)
N1—C1—N3	115.70 (8)	Co1—O4—H11	110.4 (14)
N4—C1—N3	126.77 (9)	Co1—O4—H12	114.7 (12)
C3—C2—H3	111.1 (10)	H11—O4—H12	105.7 (18)
C3—C2—H4	111.1 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H9···O1ⁱ	0.84 (2)	2.249 (18)	2.8572 (13)	129.7 (16)
N4—H10···O2ⁱⁱ	0.811 (18)	2.114 (18)	2.9136 (13)	168.8 (18)
O4—H11···O2	0.772 (19)	2.081 (19)	2.8539 (12)	179.5 (14)
O4—H12···O3ⁱⁱⁱ	0.85 (2)	2.14 (2)	2.9799 (12)	169.6 (18)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2; (iii) −x+5/2, y+1/2, −z+3/2.

(II) Diaquabis(3,5-dimethylpyrazole-1-carboxamidine-κ²N,N')nickel(II) dinitrate top

Crystal data top

[Ni(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂	F(000) = 516
M_r = 495.10	D_x = 1.669 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6757 reflections
a = 9.077 (3) Å	θ = 5.2–62.2°
b = 10.866 (4) Å	µ = 1.05 mm⁻¹
c = 10.456 (3) Å	T = 120 K
β = 107.251 (15)°	Rectangular prism, purple
V = 985.0 (6) Å³	0.20 × 0.20 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.02
ω scans	θ_max = 31.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.803, T_max = 0.881	k = −15→15
13257 measured reflections	l = −14→14
2990 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	All H-atom parameters refined
wR(F²) = 0.062	Method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982), [weight] = 1/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1T_n-1(x)], where A_i are the Chebychev coefficients listed below and x = F /F_max Method = robust weighting (Prince, 1982), W = [weight] × [1-(ΔF/6σF)²]². A_i are: 1.85, 2.44 and 0.676
S = 0.98	(Δ/σ)_max = 0.001
2617 reflections	Δρ_max = 0.47 e Å⁻³
190 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints

Crystal data top

[Ni(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂	V = 985.0 (6) Å³
M_r = 495.10	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.077 (3) Å	µ = 1.05 mm⁻¹
b = 10.866 (4) Å	T = 120 K
c = 10.456 (3) Å	0.20 × 0.20 × 0.12 mm
β = 107.251 (15)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2990 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2617 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.881	R_int = 0.02
13257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.062	All H-atom parameters refined
S = 0.98	Δρ_max = 0.47 e Å⁻³
2617 reflections	Δρ_min = −0.47 e Å⁻³
190 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	1.0000	0.5000	1.0000	0.0117
N1	1.20472 (10)	0.29438 (8)	1.00897 (9)	0.0135
N2	1.04915 (10)	0.32015 (8)	0.97087 (9)	0.0138
N3	1.23645 (11)	0.49587 (8)	1.07451 (10)	0.0149
N4	1.45618 (11)	0.37327 (10)	1.09870 (11)	0.0190
N5	1.33536 (10)	0.34503 (9)	0.74153 (9)	0.0160
C1	0.80616 (12)	0.20587 (11)	0.87690 (12)	0.0195
C2	1.30392 (11)	0.39416 (10)	1.06429 (10)	0.0138
C3	0.97774 (12)	0.21492 (10)	0.92694 (10)	0.0148
C4	1.08685 (13)	0.12043 (10)	0.93566 (11)	0.0165
C5	1.22977 (12)	0.17245 (10)	0.98690 (10)	0.0151
C6	1.38240 (13)	0.11188 (11)	1.01099 (13)	0.0214
O1	1.23263 (11)	0.26895 (9)	0.69137 (10)	0.0288
O2	1.30235 (10)	0.44931 (8)	0.77778 (9)	0.0210
O3	1.47384 (10)	0.31817 (9)	0.75619 (10)	0.0262
O4	1.02480 (9)	0.55069 (8)	0.80849 (8)	0.0169
H1	1.295 (2)	0.544 (2)	1.1051 (18)	0.027 (4)*
H2	1.064 (2)	0.0411 (19)	0.9098 (16)	0.024 (4)*
H3	0.760 (2)	0.2269 (17)	0.9444 (17)	0.027 (4)*
H4	0.777 (2)	0.1244 (19)	0.8476 (18)	0.035 (5)*
H5	0.767 (2)	0.2570 (18)	0.7992 (19)	0.030 (4)*
H6	1.360 (2)	0.031 (2)	0.9824 (19)	0.032 (5)*
H7	1.439 (2)	0.1114 (17)	1.1021 (18)	0.028 (4)*
H8	1.444 (2)	0.1498 (17)	0.9580 (16)	0.022 (4)*
H9	1.490 (2)	0.302 (2)	1.1036 (19)	0.040 (5)*
H10	1.513 (2)	0.4310 (18)	1.1309 (17)	0.024 (4)*
H11	1.035 (2)	0.625 (2)	0.799 (2)	0.041 (5)*
H12	1.099 (2)	0.524 (2)	0.800 (2)	0.030 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00923 (9)	0.01014 (9)	0.01518 (9)	0.00126 (6)	0.00284 (7)	−0.00069 (6)
N1	0.0094 (4)	0.0131 (4)	0.0167 (4)	0.0023 (3)	0.0020 (3)	−0.0005 (3)
N2	0.0089 (4)	0.0130 (4)	0.0186 (4)	0.0016 (3)	0.0027 (3)	−0.0005 (3)
N3	0.0118 (4)	0.0126 (4)	0.0193 (4)	−0.0005 (3)	0.0029 (3)	−0.0016 (3)
N4	0.0102 (4)	0.0169 (4)	0.0272 (5)	0.0021 (3)	0.0013 (3)	−0.0028 (4)
N5	0.0135 (4)	0.0171 (4)	0.0171 (4)	−0.0006 (3)	0.0040 (3)	0.0012 (3)
C1	0.0125 (4)	0.0175 (5)	0.0273 (5)	−0.0017 (4)	0.0043 (4)	−0.0056 (4)
C2	0.0117 (4)	0.0149 (4)	0.0142 (4)	0.0001 (3)	0.0027 (3)	−0.0002 (3)
C3	0.0138 (4)	0.0132 (4)	0.0174 (4)	−0.0002 (3)	0.0046 (3)	−0.0013 (4)
C4	0.0165 (4)	0.0119 (4)	0.0211 (5)	0.0014 (4)	0.0056 (4)	−0.0009 (4)
C5	0.0151 (4)	0.0130 (4)	0.0176 (4)	0.0031 (3)	0.0051 (3)	0.0005 (3)
C6	0.0161 (5)	0.0163 (5)	0.0299 (6)	0.0060 (4)	0.0042 (4)	−0.0021 (4)
O1	0.0177 (4)	0.0256 (5)	0.0403 (5)	−0.0090 (3)	0.0041 (4)	−0.0086 (4)
O2	0.0180 (4)	0.0175 (4)	0.0286 (4)	0.0014 (3)	0.0086 (3)	−0.0007 (3)
O3	0.0126 (4)	0.0253 (4)	0.0401 (5)	0.0015 (3)	0.0071 (3)	−0.0080 (4)
O4	0.0148 (3)	0.0164 (4)	0.0204 (4)	0.0013 (3)	0.0067 (3)	0.0012 (3)

Geometric parameters (Å, º) top

Ni1—N2	2.0474 (11)	N5—O3	1.2548 (13)
Ni1—N3	2.0552 (12)	C1—C3	1.4919 (16)
Ni1—O4	2.1520 (10)	C1—H3	0.948 (17)
N1—N2	1.3776 (12)	C1—H4	0.95 (2)
N1—C2	1.4186 (14)	C1—H5	0.961 (19)
N1—C5	1.3753 (14)	C3—C4	1.4106 (14)
N2—C3	1.3275 (14)	C4—C5	1.3701 (16)
N3—C2	1.2833 (14)	C4—H2	0.91 (2)
N3—H1	0.75 (2)	C5—C6	1.4863 (15)
N4—C2	1.3402 (14)	C6—H6	0.93 (2)
N4—H9	0.83 (2)	C6—H7	0.939 (18)
N4—H10	0.817 (19)	C6—H8	0.983 (17)
N5—O1	1.2402 (13)	O4—H11	0.83 (2)
N5—O2	1.2589 (13)	O4—H12	0.76 (2)

N2—Ni1—N3	77.67 (4)	H4—C1—H5	105.6 (16)
N2—Ni1—O4	91.05 (4)	N1—C2—N4	117.35 (10)
N3—Ni1—O4	88.43 (4)	N1—C2—N3	115.55 (9)
N2—N1—C2	115.77 (8)	N4—C2—N3	127.10 (10)
N2—N1—C5	110.71 (8)	C1—C3—N2	122.00 (9)
C2—N1—C5	133.49 (9)	C1—C3—C4	127.92 (10)
N1—N2—Ni1	113.64 (7)	N2—C3—C4	110.08 (9)
N1—N2—C3	106.16 (8)	C3—C4—C5	106.87 (10)
Ni1—N2—C3	140.19 (7)	C3—C4—H2	125.4 (11)
Ni1—N3—C2	117.24 (7)	C5—C4—H2	127.7 (11)
Ni1—N3—H1	132.7 (15)	N1—C5—C4	106.18 (9)
C2—N3—H1	109.9 (15)	N1—C5—C6	126.18 (10)
C2—N4—H9	120.7 (14)	C4—C5—C6	127.62 (10)
C2—N4—H10	116.8 (13)	C5—C6—H6	104.9 (12)
H9—N4—H10	121.0 (18)	C5—C6—H7	112.3 (11)
O1—N5—O2	120.74 (10)	H6—C6—H7	108.8 (16)
O1—N5—O3	119.80 (10)	C5—C6—H8	111.8 (10)
O2—N5—O3	119.46 (9)	H6—C6—H8	108.8 (16)
C3—C1—H3	111.5 (10)	H7—C6—H8	109.9 (15)
C3—C1—H4	109.6 (12)	Ni1—O4—H11	114.0 (14)
H3—C1—H4	108.9 (16)	Ni1—O4—H12	110.5 (15)
C3—C1—H5	109.9 (11)	H11—O4—H12	103 (2)
H3—C1—H5	111.0 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H9···O1ⁱ	0.83 (2)	2.256 (19)	2.8604 (18)	130.0 (17)
N4—H10···O2ⁱⁱ	0.818 (19)	2.113 (19)	2.9171 (18)	167.5 (18)
O4—H12···O2	0.76 (2)	2.09 (2)	2.8537 (16)	179 (2)
O4—H11···O3ⁱⁱⁱ	0.82 (2)	2.17 (2)	2.9849 (17)	169.9 (18)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2; (iii) −x+5/2, y+1/2, −z+3/2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Co(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂	[Ni(C₆H₁₀N₄)₂(H₂O)₂](NO₃)₂
M_r	495.32	495.10
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	120	120
a, b, c (Å)	9.1067 (11), 10.9344 (13), 10.4425 (13)	9.077 (3), 10.866 (4), 10.456 (3)
β (°)	107.602 (2)	107.251 (15)
V (Å³)	991.1 (2)	985.0 (6)
Z	2	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.93	1.05
Crystal size (mm)	0.24 × 0.10 × 0.10	0.20 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.840, 0.911	0.803, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	13055, 2975, 2920	13257, 2990, 2617
R_int	0.02	0.02
(sin θ/λ)_max (Å⁻¹)	0.723	0.726

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.062, 0.98	0.026, 0.062, 0.98
No. of reflections	2920	2617
No. of parameters	190	190
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.38	0.47, −0.47

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ATOMS (Dowty, 2000), CRYSTALS.

Selected geometric parameters (Å, º) for (I) top

Co1—N2	2.0871 (8)	N5—O1	1.2408 (11)
Co1—N3	2.0842 (9)	N5—O2	1.2582 (11)
Co1—O4	2.1737 (7)	N5—O3	1.2546 (11)
N1—N2	1.3778 (10)	N4—C1	1.3361 (12)
N1—C1	1.4176 (12)	C2—C3	1.4918 (13)
N1—C5	1.3731 (12)	C3—C4	1.4104 (12)
N2—C3	1.3256 (12)	C4—C5	1.3717 (13)
N3—C1	1.2890 (12)	C5—C6	1.4860 (13)

N2—Co1—N3	76.46 (3)	N3—Co1—O4	87.79 (3)
N2—Co1—O4	91.79 (3)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H9···O1ⁱ	0.84 (2)	2.249 (18)	2.8572 (13)	129.7 (16)
N4—H10···O2ⁱⁱ	0.811 (18)	2.114 (18)	2.9136 (13)	168.8 (18)
O4—H11···O2	0.772 (19)	2.081 (19)	2.8539 (12)	179.5 (14)
O4—H12···O3ⁱⁱⁱ	0.85 (2)	2.14 (2)	2.9799 (12)	169.6 (18)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2; (iii) −x+5/2, y+1/2, −z+3/2.

Selected geometric parameters (Å, º) for (II) top

Ni1—N2	2.0474 (11)	N4—C2	1.3402 (14)
Ni1—N3	2.0552 (12)	N5—O1	1.2402 (13)
Ni1—O4	2.1520 (10)	N5—O2	1.2589 (13)
N1—N2	1.3776 (12)	N5—O3	1.2548 (13)
N1—C2	1.4186 (14)	C1—C3	1.4919 (16)
N1—C5	1.3753 (14)	C3—C4	1.4106 (14)
N2—C3	1.3275 (14)	C4—C5	1.3701 (16)
N3—C2	1.2833 (14)	C5—C6	1.4863 (15)

N2—Ni1—N3	77.67 (4)	N3—Ni1—O4	88.43 (4)
N2—Ni1—O4	91.05 (4)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H9···O1ⁱ	0.83 (2)	2.256 (19)	2.8604 (18)	130.0 (17)
N4—H10···O2ⁱⁱ	0.818 (19)	2.113 (19)	2.9171 (18)	167.5 (18)
O4—H12···O2	0.76 (2)	2.09 (2)	2.8537 (16)	179 (2)
O4—H11···O3ⁱⁱⁱ	0.82 (2)	2.17 (2)	2.9849 (17)	169.9 (18)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2; (iii) −x+5/2, y+1/2, −z+3/2.

Acknowledgements

The purchase of the Bruker AXS SMART diffractometer with a Bede Microsource was facilitated by grant No. HEFCE/JR00DUHOEQ. This work was financed in part by the Ministry for Science and Technology of the Republic of Serbia (Project No. 1318 – `Physicochemical, structural and biological investigation of complex compounds').

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Volume 60| Part 10| October 2004| Pages m467-m470

doi:10.1107/S0108270104017433

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