(2-Amino-7-methyl-4-oxidopteridine-6-carboxyl­ato-κ3O4,N5,O6)(ethane-1,2-diamine-κ2N,N′)(1H-imidazole-κN3)nickel(II) dihydrate

Baisya, S.S.; Roy, P.S.

doi:10.1107/S1600536813005898

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Pages m193-m194

doi:10.1107/S1600536813005898

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(2-Amino-7-methyl-4-oxidopteridine-6-carboxylato-κ³O⁴,N⁵,O⁶)(ethane-1,2-diamine-κ²N,N′)(1H-imidazole-κN³)nickel(II) dihydrate

Siddhartha S. Baisya ^a and Parag S. Roy ^a ^*

^aDepartment of Chemistry, University of North Bengal, Siliguri 734 013, India
^*Correspondence e-mail: psrnbu@gmail.com

(Received 23 February 2013; accepted 28 February 2013; online 9 March 2013)

In the title complex, [Ni(C₈H₅N₅O₃)(C₂H₈N₂)(C₃N₂H₄)]·2H₂O, a tridentate 2-amino-7-methyl-4-oxidopteridine-6-carboxylate (pterin) ligand, a bidentate ancillary ethane-1,2-diamine (en) ligand and a monodentate 1H-imidazole (im) ligand complete a distorted octahedral geometry around the Ni^II atom. The pterin ligand forms two chelate rings. Both the en and im ligands are arranged nearly orthogonally relative to the pterin ligand [dihedral angles between the mean planes of the en and pterin ligands and of the im and pterin ligands are 84.62 (9) and 85.14 (9)°, respectively]. N—H⋯N, N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds link the complex molecules and lattice water molecules into a three-dimensional network.

Related literature

For the importance of pterin in metalloenzymes, see: Basu & Burgmayer (2011 ); Burgmayer (1998 ); Fitzpatrick (2003 ); Fukuzumi & Kojima (2008 ); Kaim et al. (1999 ). For the structures of related nickel complexes, see: Baisya & Roy (2013 ); Crispini et al. (2005 ). For the structures of related copper complexes, see: Odani et al. (1992 ). For the electron-shuffling ability of the pterin unit as well as its donor groups and the effect on the geometric parameters of related complexes, see: Beddoes et al. (1993 ); Kohzuma et al. (1988 ); Russell et al. (1992 ). For the synthesis of the pterin ligand, see: Wittle et al. (1947 ). For refinement of H atoms, see: Cooper et al. (2010 ).

Experimental

Crystal data

[Ni(C₈H₅N₅O₃)(C₂H₈N₂)(C₃H₄N₂)]·2H₂O
M_r = 442.08
Orthorhombic, P b c n
a = 13.484 (2) Å
b = 8.8741 (15) Å
c = 29.959 (5) Å
V = 3584.9 (10) Å³
Z = 8
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 293 K
0.24 × 0.24 × 0.03 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.77, T_max = 0.97
19640 measured reflections
4231 independent reflections
3521 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.091
S = 0.95
4231 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H171⋯O4ⁱ	0.84	2.50	3.193 (3)	140
N5—H172⋯N4ⁱⁱ	0.85	2.13	2.984 (3)	177
N6—H182⋯O5	0.88	2.28	3.099 (3)	154
N7—H211⋯N2ⁱⁱⁱ	0.90	2.41	3.298 (2)	173
N7—H212⋯O4^iv	0.87	2.53	3.210 (3)	136
N9—H241⋯O5^v	0.89	2.15	3.024 (3)	168
O4—H271⋯N3^vi	0.82	2.02	2.837 (2)	169
O4—H272⋯O3	0.81	2.07	2.859 (2)	167
O5—H281⋯O2^vii	0.83	2.00	2.822 (2)	170
O5—H282⋯O1	0.81	2.14	2.789 (2)	138
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) -x+1, -y+1, -z+1; (v) x, y-1, z; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (vii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813005898/hy2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005898/hy2617Isup2.hkl

checkCIF report

Comment top

Increasing attention is being paid nowadays towards the metalloenzymes requiring both a pterin and a transition metal (Basu & Burgmayer, 2011; Burgmayer, 1998; Fitzpatrick, 2003; Fukuzumi & Kojima, 2008; Kaim et al., 1999). This has, in turn, catalysed research work on the coordination chemistry of the bicyclic N-heterocycles called pteridines in general, and an important member of this family named pterin in particular. Literature survey reveals the existence of only a couple of structurally characterized Ni(II)–pterin complexes (Baisya & Roy, 2013; Crispini et al., 2005) and no related quaternary complex. The present effort is concerned with the title quaternary complex, possessing a tridentate pterin ligand, a bidentate σ-donor ligand like en and a monodentate σ-donor ligand like im.

The molecular structure (Fig. 1) represents a mononuclear Ni^II centre in a distorted octahedral coordination geometry, with two N atoms (N6 and N7) of the en ligand, a pyrazine ring N atom (N1) of the pterin ligand and an imidazole ring N atom (N8), forming the equatorial plane. The two pterin O atoms (O1 and O3) occupy the longer axial positions, with the phenolate O3 constituting the longest axial bond [2.2722 (14) Å]. The pterin ligand forms two five-membered chelate rings having small bite angles [75.91 (6) and 77.50 (6)°], instead of only one per pterin ligand for an earlier case (Crispini et al., 2005). This factor is responsible to a large extent for the observed distortion here from regular octahedral geometry. Accordingly, the O1—Ni1—O3 axis shows maximum deviation [153.37 (5)°] from linearity. Again, closest approach to linearity [174.10 (7)°] is observed for the N7—Ni1—N8 axis, which is associated with both the im and en ligands. Here each such ligand tries to achieve near orthogonality with respect to the pterin ligand [dihedral angles between the mean planes of the en and pterin ligands and of the im and pterin ligands are 84.62 (9) and 85.14 (9)°, respectively], for minimizing the steric repulsion. In line with the earlier observations on related copper complexes (Odani et al., 1992), the pyrazine ring N atom (N1) is located in the equatorial plane. The corresponding short Ni1—N1 distance [1.9787 (16) Å] indicates dπ–pπ interaction between the pterin ring and the Ni^II atom (d⁸), with further assistance from the nearby π-donating phenolate and carboxylate O atoms (Kohzuma et al., 1988). The pterin ligand is coordinated in its binegative form as an O,N,O-donor, as evident from the charge balance of this Ni(II) complex. The significantly shorter nature of the O3—C6 [1.271 (2) Å] and N5—C5 [1.332 (2) Å] bonds could be rationalized in terms of electron-shuffling ability of the pterin ring (Baisya & Roy, 2013; Beddoes et al., 1993; Russell et al., 1992).

In the crystal, intermolecular N—H···N, N—H···O, O—H···N and O—H···O hydrogen bonds (Table 1) link the complex molecules and lattice water molecules into a three-dimensional network (Fig 2). The lattice water molecules play a decisive role for the crystal packing.

Related literature top

For the importance of pterin in metalloenzymes, see: Basu & Burgmayer (2011); Burgmayer (1998); Fitzpatrick (2003); Fukuzumi & Kojima (2008); Kaim et al. (1999). For the structures of related nickel complexes, see: Baisya & Roy (2013); Crispini et al. (2005). For the structures of related copper complexes, see: Odani et al. (1992). For the electron-shuffling ability of the pterin unit as well as its donor groups and the affect on the geometric parameters of related complexes, see: Beddoes et al. (1993); Kohzuma et al. (1988); Russell et al. (1992). For the synthesis of the pterin ligand, see: Wittle et al. (1947). For refinement of H atoms, see: Cooper et al. (2010).

Experimental top

2-Amino-4–hydroxy-7-methylpteridine-6-carboxylic acid sesquihydrate (C₈H₇N₅O₃.1.5H₂O) was obtained by published procedure (Wittle et al., 1947). The title complex was synthesized by the dropwise addition of an aqueous alkaline solution (NaOH: 11 mg, 0.275 mmol) of the pterin ligand (31 mg, 0.125 mmol) to a warm (311 K; paraffin oil bath) aqueous reaction mixture containing NiSO₄.7H₂O (35 mg, 0.125 mmol), ethane-1,2-diamine (7.5 mg, 0.125 mmol) and 1H-imidazole (14 mg, 0.2 mmol); final volume was 45 ml. The pH value was adjusted to 10.3 and the mixture was stirred for 3 h; final pH was 9.7. The orange coloured solution was transferred to a 100 ml beaker and allowed to stand at room temperature. Orange crystals appeared after 4 days (yield: 40%), which were suitable for single-crystal X-ray diffraction. Sample for analytical purpose could be obtained by filtration, repeated washing with small quantities of water and drying in vacuo over silica gel. Analysis, calculated for C₁₃H₂₁N₉NiO₅: C 35.31, H 4.80, N 28.52%; found: C 35.72, H 4.70, N 28.07%.

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: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing diagram of the title compound, viewed along the a axis. Dotted lines indicate hydrogen bonds.

(2-Amino-7-methyl-4-oxidopteridine-6-carboxylato-κ³O⁴,N⁵,O⁶)(ethane-1,2-diamine-κ²N,N')(1H-imidazole-κN³)nickel(II) dihydrate top

Crystal data top

[Ni(C₈H₅N₅O₃)(C₂H₈N₂)(C₃H₄N₂)]·2H₂O	F(000) = 1840
M_r = 442.08	D_x = 1.638 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4231 reflections
a = 13.484 (2) Å	θ = 1.4–28.3°
b = 8.8741 (15) Å	µ = 1.13 mm⁻¹
c = 29.959 (5) Å	T = 293 K
V = 3584.9 (10) Å³	Plate, orange
Z = 8	0.24 × 0.24 × 0.03 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3521 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
T_min = 0.77, T_max = 0.97	k = −11→11
19640 measured reflections	l = −24→38
4231 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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.091	Method = Modified Sheldrick w = 1/[σ²(F²) + (0.04P)² + 3.53P], where P = [max(F_o²,0) + 2F_c²]/3
S = 0.95	(Δ/σ)_max = 0.001
4231 reflections	Δρ_max = 0.62 e Å⁻³
253 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints

Crystal data top

[Ni(C₈H₅N₅O₃)(C₂H₈N₂)(C₃H₄N₂)]·2H₂O	V = 3584.9 (10) Å³
M_r = 442.08	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 13.484 (2) Å	µ = 1.13 mm⁻¹
b = 8.8741 (15) Å	T = 293 K
c = 29.959 (5) Å	0.24 × 0.24 × 0.03 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4231 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3521 reflections with I > 2σ(I)
T_min = 0.77, T_max = 0.97	R_int = 0.030
19640 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 0.95	Δρ_max = 0.62 e Å⁻³
4231 reflections	Δρ_min = −0.32 e Å⁻³
253 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.461327 (17)	0.49322 (3)	0.372395 (8)	0.0275
O1	0.54402 (10)	0.60856 (16)	0.32134 (5)	0.0335
C1	0.63525 (15)	0.5742 (2)	0.31846 (6)	0.0292
O2	0.69402 (11)	0.62442 (18)	0.29021 (5)	0.0423
C2	0.67092 (14)	0.4597 (2)	0.35277 (6)	0.0262
N1	0.59680 (11)	0.40936 (17)	0.37761 (5)	0.0254
C7	0.61252 (13)	0.3066 (2)	0.40867 (6)	0.0252
C4	0.70658 (13)	0.2460 (2)	0.41611 (6)	0.0246
N2	0.78491 (11)	0.29914 (18)	0.39231 (5)	0.0286
C3	0.76772 (14)	0.4043 (2)	0.36124 (6)	0.0273
C8	0.85670 (16)	0.4622 (2)	0.33676 (8)	0.0407
H111	0.9180	0.4284	0.3494	0.0629*
H113	0.8523	0.4298	0.3069	0.0630*
H112	0.8565	0.5676	0.3363	0.0619*
N3	0.71925 (12)	0.13478 (18)	0.44623 (5)	0.0293
C5	0.63537 (14)	0.0864 (2)	0.46626 (6)	0.0297
N4	0.54093 (12)	0.14309 (19)	0.46268 (5)	0.0312
C6	0.52732 (13)	0.2575 (2)	0.43450 (6)	0.0268
O3	0.44423 (10)	0.32158 (16)	0.42815 (5)	0.0329
N5	0.64372 (14)	−0.0319 (2)	0.49338 (6)	0.0414
H172	0.5918	−0.0634	0.5068	0.0504*
H171	0.7003	−0.0668	0.4983	0.0503*
N6	0.32580 (14)	0.6051 (2)	0.36971 (7)	0.0478
C9	0.3190 (2)	0.7106 (3)	0.40720 (9)	0.0610
C10	0.4178 (2)	0.7830 (3)	0.41328 (10)	0.0556
N7	0.49397 (14)	0.66577 (19)	0.41780 (6)	0.0367
H211	0.5548	0.7039	0.4136	0.0564*
H212	0.4950	0.6335	0.4452	0.0559*
H202	0.4167	0.8476	0.4384	0.0688*
H201	0.4317	0.8402	0.3867	0.0695*
H192	0.2669	0.7839	0.4035	0.0736*
H191	0.3043	0.6540	0.4352	0.0746*
H181	0.2742	0.5434	0.3674	0.0732*
H182	0.3228	0.6546	0.3442	0.0727*
N8	0.41434 (14)	0.3313 (2)	0.32768 (6)	0.0383
C11	0.41880 (17)	0.1814 (2)	0.33182 (8)	0.0416
N9	0.38881 (18)	0.1135 (3)	0.29413 (9)	0.0652
C12	0.3599 (3)	0.2243 (3)	0.26639 (9)	0.0699
C13	0.3786 (3)	0.3547 (3)	0.28659 (9)	0.0733
H261	0.3671	0.4468	0.2743	0.0892*
H251	0.3344	0.2134	0.2406	0.0848*
H241	0.3806	0.0153	0.2892	0.0825*
H231	0.4395	0.1296	0.3568	0.0527*
O4	0.37876 (13)	0.4892 (2)	0.50415 (6)	0.0543
H271	0.3379	0.4436	0.5195	0.0824*
H272	0.3890	0.4340	0.4833	0.0825*
O5	0.38933 (16)	0.7745 (2)	0.28388 (6)	0.0685
H281	0.3645	0.7400	0.2605	0.1040*
H282	0.4446	0.7401	0.2817	0.1049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02605 (14)	0.02545 (14)	0.03107 (14)	0.00016 (9)	−0.00317 (9)	0.00076 (9)
O1	0.0339 (7)	0.0321 (7)	0.0344 (7)	−0.0011 (6)	−0.0042 (6)	0.0073 (6)
C1	0.0361 (10)	0.0262 (9)	0.0253 (9)	−0.0028 (8)	−0.0023 (7)	0.0001 (7)
O2	0.0456 (9)	0.0479 (9)	0.0334 (7)	−0.0033 (7)	0.0059 (6)	0.0132 (7)
C2	0.0310 (9)	0.0226 (8)	0.0250 (8)	−0.0023 (7)	0.0013 (7)	−0.0009 (7)
N1	0.0259 (7)	0.0252 (8)	0.0250 (7)	0.0000 (6)	−0.0009 (6)	0.0005 (6)
C7	0.0274 (9)	0.0237 (8)	0.0245 (8)	−0.0002 (7)	0.0010 (7)	−0.0007 (7)
C4	0.0271 (9)	0.0238 (8)	0.0228 (8)	−0.0001 (7)	0.0000 (7)	−0.0030 (7)
N2	0.0280 (8)	0.0257 (8)	0.0320 (8)	0.0009 (6)	0.0034 (6)	−0.0004 (6)
C3	0.0297 (10)	0.0236 (8)	0.0286 (9)	−0.0025 (7)	0.0039 (7)	−0.0027 (7)
C8	0.0323 (10)	0.0358 (11)	0.0541 (13)	0.0004 (9)	0.0119 (9)	0.0109 (10)
N3	0.0282 (8)	0.0304 (8)	0.0293 (8)	0.0033 (6)	0.0010 (6)	0.0046 (6)
C5	0.0340 (10)	0.0275 (9)	0.0275 (9)	0.0017 (8)	0.0013 (7)	0.0023 (7)
N4	0.0290 (8)	0.0321 (8)	0.0324 (8)	−0.0002 (6)	0.0042 (6)	0.0064 (7)
C6	0.0263 (9)	0.0281 (9)	0.0258 (8)	−0.0016 (7)	0.0007 (7)	−0.0003 (7)
O3	0.0255 (6)	0.0372 (7)	0.0359 (7)	0.0023 (6)	0.0030 (5)	0.0058 (6)
N5	0.0376 (10)	0.0412 (10)	0.0454 (10)	0.0058 (8)	0.0078 (8)	0.0188 (8)
N6	0.0336 (10)	0.0475 (11)	0.0624 (13)	0.0043 (8)	−0.0076 (9)	0.0034 (9)
C9	0.0523 (15)	0.0690 (18)	0.0617 (16)	0.0258 (14)	0.0095 (13)	0.0033 (14)
C10	0.0660 (17)	0.0399 (13)	0.0610 (16)	0.0132 (12)	−0.0007 (13)	−0.0132 (11)
N7	0.0413 (10)	0.0360 (9)	0.0329 (9)	−0.0008 (8)	−0.0013 (7)	−0.0027 (7)
N8	0.0422 (10)	0.0324 (9)	0.0402 (9)	−0.0059 (8)	−0.0084 (8)	−0.0020 (7)
C11	0.0428 (12)	0.0323 (11)	0.0498 (13)	−0.0009 (9)	−0.0073 (10)	−0.0025 (9)
N9	0.0756 (16)	0.0430 (12)	0.0769 (16)	−0.0070 (11)	−0.0090 (13)	−0.0200 (11)
C12	0.112 (3)	0.0476 (15)	0.0503 (15)	−0.0073 (16)	−0.0420 (16)	−0.0115 (12)
C13	0.122 (3)	0.0437 (14)	0.0544 (16)	−0.0051 (16)	−0.0438 (17)	0.0012 (12)
O4	0.0545 (10)	0.0558 (11)	0.0525 (10)	−0.0125 (8)	0.0175 (8)	−0.0034 (8)
O5	0.0879 (14)	0.0667 (12)	0.0509 (10)	0.0327 (11)	−0.0241 (10)	−0.0153 (9)

Geometric parameters (Å, º) top

Ni1—O1	2.1519 (14)	N5—H172	0.853
Ni1—N1	1.9787 (16)	N5—H171	0.837
Ni1—O3	2.2722 (14)	N6—C9	1.465 (3)
Ni1—N6	2.0812 (19)	N6—H181	0.888
Ni1—N7	2.0949 (17)	N6—H182	0.881
Ni1—N8	2.0638 (17)	C9—C10	1.491 (4)
O1—C1	1.270 (2)	C9—H192	0.964
C1—O2	1.242 (2)	C9—H191	0.997
C1—C2	1.523 (3)	C10—N7	1.468 (3)
C2—N1	1.324 (2)	C10—H202	0.945
C2—C3	1.418 (3)	C10—H201	0.962
N1—C7	1.320 (2)	N7—H211	0.896
C7—C4	1.395 (2)	N7—H212	0.869
C7—C6	1.452 (2)	N8—C11	1.338 (3)
C4—N2	1.359 (2)	N8—C13	1.338 (3)
C4—N3	1.348 (2)	C11—N9	1.342 (3)
N2—C3	1.338 (2)	C11—H231	0.922
C3—C8	1.497 (3)	N9—C12	1.346 (4)
C8—H111	0.957	N9—H241	0.890
C8—H113	0.940	C12—C13	1.329 (4)
C8—H112	0.936	C12—H251	0.850
N3—C5	1.351 (2)	C13—H261	0.910
C5—N4	1.373 (2)	O4—H271	0.825
C5—N5	1.332 (2)	O4—H272	0.807
N4—C6	1.333 (2)	O5—H281	0.834
C6—O3	1.271 (2)	O5—H282	0.808

O1—Ni1—N1	75.91 (6)	C7—C6—O3	118.92 (16)
O1—Ni1—O3	153.37 (5)	N4—C6—O3	123.85 (16)
N1—Ni1—O3	77.50 (6)	Ni1—O3—C6	108.69 (11)
O1—Ni1—N6	101.58 (7)	C5—N5—H172	118.4
N1—Ni1—N6	173.26 (7)	C5—N5—H171	118.4
O3—Ni1—N6	105.01 (7)	H172—N5—H171	122.9
O1—Ni1—N7	90.29 (6)	Ni1—N6—C9	109.29 (15)
N1—Ni1—N7	91.70 (7)	Ni1—N6—H181	113.4
O3—Ni1—N7	91.95 (6)	C9—N6—H181	113.8
N6—Ni1—N7	82.01 (8)	Ni1—N6—H182	108.1
O1—Ni1—N8	91.65 (7)	C9—N6—H182	110.0
N1—Ni1—N8	94.18 (7)	H181—N6—H182	101.8
O3—Ni1—N8	88.82 (7)	N6—C9—C10	108.2 (2)
N6—Ni1—N8	92.13 (8)	N6—C9—H192	112.9
N7—Ni1—N8	174.10 (7)	C10—C9—H192	112.0
Ni1—O1—C1	115.85 (12)	N6—C9—H191	109.6
O1—C1—O2	125.32 (18)	C10—C9—H191	107.0
O1—C1—C2	114.83 (16)	H192—C9—H191	107.0
O2—C1—C2	119.84 (17)	C9—C10—N7	109.3 (2)
C1—C2—N1	111.47 (16)	C9—C10—H202	110.1
C1—C2—C3	130.01 (16)	N7—C10—H202	111.5
N1—C2—C3	118.51 (16)	C9—C10—H201	107.5
C2—N1—Ni1	121.72 (13)	N7—C10—H201	108.3
C2—N1—C7	120.55 (16)	H202—C10—H201	110.0
Ni1—N1—C7	117.63 (12)	C10—N7—Ni1	108.13 (14)
N1—C7—C4	121.65 (16)	C10—N7—H211	111.1
N1—C7—C6	117.12 (16)	Ni1—N7—H211	112.2
C4—C7—C6	121.23 (16)	C10—N7—H212	109.4
C7—C4—N2	119.28 (16)	Ni1—N7—H212	112.0
C7—C4—N3	120.28 (16)	H211—N7—H212	104.0
N2—C4—N3	120.44 (16)	Ni1—N8—C11	128.20 (15)
C4—N2—C3	118.19 (16)	Ni1—N8—C13	126.88 (17)
C2—C3—N2	121.72 (16)	C11—N8—C13	104.8 (2)
C2—C3—C8	122.07 (17)	N8—C11—N9	110.8 (2)
N2—C3—C8	116.19 (17)	N8—C11—H231	125.8
C3—C8—H111	113.0	N9—C11—H231	123.4
C3—C8—H113	108.0	C11—N9—C12	106.2 (2)
H111—C8—H113	109.6	C11—N9—H241	128.0
C3—C8—H112	110.4	C12—N9—H241	125.3
H111—C8—H112	108.7	N9—C12—C13	107.5 (2)
H113—C8—H112	107.0	N9—C12—H251	126.4
C4—N3—C5	115.09 (15)	C13—C12—H251	126.1
N3—C5—N4	128.71 (17)	N8—C13—C12	110.6 (2)
N3—C5—N5	116.80 (17)	N8—C13—H261	124.9
N4—C5—N5	114.49 (17)	C12—C13—H261	124.4
C5—N4—C6	117.14 (16)	H271—O4—H272	104.5
C7—C6—N4	117.19 (16)	H281—O5—H282	99.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H171···O4ⁱ	0.84	2.50	3.193 (3)	140
N5—H172···N4ⁱⁱ	0.85	2.13	2.984 (3)	177
N6—H182···O5	0.88	2.28	3.099 (3)	154
N7—H211···N2ⁱⁱⁱ	0.90	2.41	3.298 (2)	173
N7—H212···O4^iv	0.87	2.53	3.210 (3)	136
N9—H241···O5^v	0.89	2.15	3.024 (3)	168
O4—H271···N3^vi	0.82	2.02	2.837 (2)	169
O4—H272···O3	0.81	2.07	2.859 (2)	167
O5—H281···O2^vii	0.83	2.00	2.822 (2)	170
O5—H282···O1	0.81	2.14	2.789 (2)	138

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

Experimental details

Crystal data
Chemical formula	[Ni(C₈H₅N₅O₃)(C₂H₈N₂)(C₃H₄N₂)]·2H₂O
M_r	442.08
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	13.484 (2), 8.8741 (15), 29.959 (5)
V (Å³)	3584.9 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.13
Crystal size (mm)	0.24 × 0.24 × 0.03

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.77, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	19640, 4231, 3521
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.091, 0.95
No. of reflections	4231
No. of parameters	253
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H171···O4ⁱ	0.84	2.50	3.193 (3)	140
N5—H172···N4ⁱⁱ	0.85	2.13	2.984 (3)	177
N6—H182···O5	0.88	2.28	3.099 (3)	154
N7—H211···N2ⁱⁱⁱ	0.90	2.41	3.298 (2)	173
N7—H212···O4^iv	0.87	2.53	3.210 (3)	136
N9—H241···O5^v	0.89	2.15	3.024 (3)	168
O4—H271···N3^vi	0.82	2.02	2.837 (2)	169
O4—H272···O3	0.81	2.07	2.859 (2)	167
O5—H281···O2^vii	0.83	2.00	2.822 (2)	170
O5—H282···O1	0.81	2.14	2.789 (2)	138

Acknowledgements

The authors are grateful to the UGC, New Delhi, for financial assistance (SAP–DRS program). Thanks are due to the CSMCRI, Bhavnagar, Gujrat, India, for the X-ray structural data and elemental analysis data, and the University of North Bengal for infrastructure.

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