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In the title compound, {[NiCl2(C19H17N5O2)2]·4C3H7NO}n, the NiII atom is located on an inversion centre and is in a six-coordinated octa­hedral geometry, formed by four pyridine N atoms from four N2,N6-bis­[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide (BPDA) ligands occupying the equatorial plane and two chloride anions at the axial sites. The bidentate bridging BPDA ligands link the NiII atoms into a two-dimensional corrugated grid-like flexible layer with a (4,4)-connected topology, which consists of left- and right-handed helical chains sharing the common NiII atoms. Investigation of the thermal stability shows that the network is stable up to 573 K.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011203750X/fn3111sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011203750X/fn3111Isup2.hkl
Contains datablock I

CCDC reference: 720624

Comment top

Owing to their intriguing architectures and potential applications in many areas, such as catalysis, sensing, magnetism, gas storage and separation, metal–organic frameworks have been widely investigated in the last decade (Bradshaw et al., 2005). U-Shaped symmetric bis(amidopyridine) ligands are frequently used, based on benzene-1,2-diamine, pyridine-2,6-diamine and pyridine-2,6-dicarboxylic acid, which combine a rigid aromatic group in the centre and flexible binding arms on each side. These compounds have flexible conformations and excellent self-assembly, through coordination bonds and hydrogen bonds occurring from the amide substitutes. These spacers can construct novel metal-containing structural motifs, such as isolated macrocycles, helicates and dynamic porous frameworks (Pan et al., 2010; Uemura et al., 2002; Burchell et al., 2006). For example, from reactions of a bis(pyridyl)-bis(amide) ligand, N2,N6-bis(pyridin-3-yl)pyridine-2,6-dicarboxamide, with nickel(II) and cobalt(II) salts, Li et al. (2012) produced a tetragonal molecular cage and a one-dimensional polymeric macrocyclic complex. Herein, we report the reaction of the multifunctional ligand N2,N6-bis[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide (BPDA), in which each binding arm is elongated by one methylene unit compared with the analogous ligand N2,N6-bis(pyridin-3-yl)pyridine-2,6-dicarboxamide, and we report a novel nickel(II) coordination polymer of BPDA, the title compound, {[NiCl2(BPDA)2].4DMF}n, (I) (DMF is N,N-dimethylformamide).

In (I), the NiII atom is located on an inversion centre in a six-coordinated octahedral geometry, with four pyridine N atoms of four BPDA ligands occupying the equatorial plane and two chloride anions at the axial sites (Fig. 1). The four coordinated pyridine N atoms are almost coplanar with the NiII atom. The four pyridine rings are arranged around the NiII atom in the well known paddlewheel pattern, with Ni—N bond lengths of 2.212 (2) (Ni1—N3) and 2.149 (2) Å [Ni1—N5i; symmetry code: (i) -x, y - 1/2, -z + 1/2]. The two chloride anions located at the axial sites are almost perpendicular to the equatorial plane. The Ni—Cl distance is 2.4450 (7) Å.

In (I), the U-shaped BPDA ligands lower the C2v symmetry into pseudo-C2 symmetry and adopt a helical conformation, with the pyridin-3-yl arms obviously twisted from the central pyridine ring [the dihedral angles between the pyridin-3-yl arms and the central pyridine are 78.3(s.u.?) and 84.1(s.u.?)°]. The helical conformation of BPDA is very similar to that of the isomer N,N'-bis[(pyridin-2-yl)methyl]pyridine-2,6-dicarboxamide found in AgI polymers (Wu et al., 2010). Bidentate bridging BPDA ligands link the NiII atoms into a two-dimensional corrugated sheet in the bc plane (Fig. 2), with a uniform (4,4)-connected topology. The layer structure of (I) is entwined along the b axis through left- and right-handed helical chains sharing the common NiII atoms, with a long pitch of 19.039 Å. Within this net, there are two types of helical chain which partially overlap with the adjacent central BPDA pyridine rings, resulting in two equal nano-squares which form one-dimensional channels as described below. The separation of adjacent Ni nodes bridged by BPDA is 13.508(s.u.?) Å.

In (I), the two-dimensional networks align through ππ stacking interactions between pyridine rings in adjacent layers, with the centroid-to-centroid distance being 3.72 (6) Å, and are thus extended into a three-dimensional supramolecular architecture with intriguing one-dimensional channels along the a axis (Fig. 3). The DMF molecules interact through N—H···O hydrogen-bonding interactions between the NH groups of the BPDA ligands and the DMF O atoms, or they occupy the channels. The percentage of effective free volume in (I) is 38.2% [total potential solvent volume of 1020.5(s.u.?) Å3 out of the unit-cell volume of 2674.8(s.u.?) Å3] calculated using PLATON (Spek, 2003) with the DMF molecules removed from the model, indicating that the network structure of (I) could potentially provide a porous material for [ion?] absorption and exchange.

Thermogravimetric analysis (TGA) of (I) was carried out under an air atmosphere from 303 to 1023 K at a heating rate of 10 K min-1 using a crystalline sample. As shown in Fig. 4, there are three weight-loss steps on heating. In the range 308–463 K, a weight loss of 22.52% occurs, corresponding to the loss of the four solvent DMF molecules. On heating above 573 K, a second weight-loss step is observed in the temperature range 573–688 K with a weight loss of 32.78%. This step indicates the decomposition of the framework in (I). A successive mass loss of 37.84% occurs in the temperature range 688–973 K, indicating the complete decomposition of the complex. The remaining 6.86% may be NiO, in good agreement with the theoretical value of 6.62%. These TGA results indicate that the two-dimensional network structure of (I) is stable up to 573 K.

Related literature top

For related literature, see: Bradshaw et al. (2005); Burchell et al. (2006); Li et al. (2012); Pan et al. (2010); Spek (2003); Uemura et al. (2002); Wu et al. (2010); Yang et al. (2012).

Experimental top

BPDA was synthesised according to the method of Yang et al. (2012). For the preparation of the title compound, a solution of BPDA (69.4 mg, 0.2 mmol) in DMF (6 ml) was added dropwise to a solution of NiCl2.6H2O (23.8 mg, 0.1 mmol) in methanol (6 ml). The resulting mixture was stirred for 30 min and then filtered. The filtrate was allowed to evaporate at room temperature for a period of one month, producing green crystals of (I) in 56% yield. Selected IR data (KBr pellet, ν, cm-1): 3268 (m), 3059 (w), 2930 (w), 1665 (vs), 1534 (vs), 1435 (s), 1382 (m), 1104 (m), 711 (m), 679 (m).

Refinement top

H atoms bonded to C atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (methylene), and with Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) otherwise. The positions of the H atoms bonded to N atoms were refined with Uiso(H) = 1.2Ueq(C25).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The coordination environment of the NiII atoms in (I). [Symmetry codes: (i) -x, y - 1/2, -z + 1/2; (ii) x, -y - 1/2, z + 1/2; (iii) -x, -y - 1, -z + 1.]
[Figure 2] Fig. 2. A view of the two-dimensional corrugated sheet of (I) (middle), formed by left- (left) and right-handed (right) helical chains sharing the common NiII atoms.
[Figure 3] Fig. 3. A view of the straight stacking of the layers in (I), with intriguing one-dimensional channels along the a axis being occupied by guest DMF molecules.
[Figure 4] Fig. 4. The TGA curve of (I).
Poly[[bis{µ2-N2,N6-bis[(pyridin-3-yl)methyl]pyridine- 2,6-dicarboxamide}dichloridonickel(II)] N,N-dimethylformamide tetrasolvate] top
Crystal data top
[NiCl2(C19H17N5O2)2]·4C3H7NOF(000) = 1172
Mr = 1116.75Dx = 1.387 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybcCell parameters from 2607 reflections
a = 7.6822 (8) Åθ = 2.8–22.7°
b = 19.039 (2) ŵ = 0.53 mm1
c = 19.1684 (18) ÅT = 293 K
β = 107.432 (4)°Prism, green
V = 2674.8 (5) Å30.31 × 0.24 × 0.11 mm
Z = 2
Data collection top
Siemens SMART CCD area-detector
diffractometer
3382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 25.0°, θmin = 2.4°
ω scansh = 99
18986 measured reflectionsk = 2222
4712 independent reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0518P)2 + 0.0123P]
where P = (Fo2 + 2Fc2)/3
4712 reflections(Δ/σ)max < 0.001
350 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
[NiCl2(C19H17N5O2)2]·4C3H7NOV = 2674.8 (5) Å3
Mr = 1116.75Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.6822 (8) ŵ = 0.53 mm1
b = 19.039 (2) ÅT = 293 K
c = 19.1684 (18) Å0.31 × 0.24 × 0.11 mm
β = 107.432 (4)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3382 reflections with I > 2σ(I)
18986 measured reflectionsRint = 0.056
4712 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.35 e Å3
4712 reflectionsΔρmin = 0.24 e Å3
350 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
xyzUiso*/Ueq
Ni10.00000.50000.50000.03094 (16)
Cl10.29339 (9)0.44213 (4)0.55473 (4)0.0395 (2)
O10.0909 (3)0.12612 (11)0.58282 (11)0.0605 (6)
O20.4275 (3)0.13157 (11)0.31366 (11)0.0555 (6)
O30.1777 (4)0.11447 (13)0.30310 (14)0.0870 (9)
O40.7336 (4)0.22197 (15)0.36157 (15)0.0881 (9)
N10.2586 (3)0.01407 (11)0.42927 (12)0.0342 (5)
N20.1097 (3)0.14252 (12)0.46427 (13)0.0415 (6)
N30.1430 (3)0.39819 (11)0.49317 (12)0.0345 (5)
N40.3411 (3)0.02348 (13)0.28741 (13)0.0398 (6)
N50.0180 (3)0.02437 (11)0.10711 (12)0.0341 (5)
N60.2511 (5)0.20905 (16)0.22920 (16)0.0683 (9)
N70.7526 (4)0.19078 (16)0.24524 (15)0.0669 (8)
C10.1336 (4)0.10497 (15)0.51957 (15)0.0389 (7)
C20.2166 (4)0.03320 (14)0.49941 (14)0.0353 (7)
C30.2428 (4)0.01018 (16)0.55336 (16)0.0451 (8)
H30.21010.00500.60280.054*
C40.3171 (4)0.07555 (17)0.53410 (16)0.0504 (8)
H40.33660.10640.57000.060*
C50.3629 (4)0.09585 (16)0.46163 (16)0.0435 (7)
H50.41670.14040.44670.052*
C60.3289 (3)0.05000 (14)0.41134 (14)0.0323 (6)
C70.3711 (4)0.07215 (15)0.33260 (15)0.0368 (7)
C80.0152 (4)0.20960 (15)0.47661 (17)0.0438 (7)
H8A0.08320.20730.52370.053*
H8B0.04320.21690.43760.053*
C90.1338 (4)0.27255 (14)0.47823 (14)0.0355 (7)
C100.3199 (4)0.26881 (15)0.46779 (16)0.0440 (7)
H100.38160.22500.45820.053*
C110.4144 (4)0.32972 (16)0.47151 (16)0.0473 (8)
H110.54170.32810.46540.057*
C120.3233 (4)0.39237 (15)0.48413 (15)0.0402 (7)
H120.39020.43380.48660.048*
C130.0544 (4)0.33824 (14)0.48939 (14)0.0350 (7)
H130.07240.34130.49480.042*
C140.3636 (4)0.03758 (17)0.21066 (14)0.0415 (7)
H14A0.42930.08260.19680.050*
H14B0.43890.00000.18050.050*
C150.1824 (3)0.04147 (14)0.19447 (14)0.0331 (6)
C160.0250 (4)0.06378 (15)0.24615 (15)0.0407 (7)
H160.02670.07690.29380.049*
C170.1352 (4)0.06667 (16)0.22728 (15)0.0450 (8)
H170.24500.08250.26160.054*
C180.1334 (4)0.04617 (15)0.15787 (15)0.0407 (7)
H180.24440.04760.14570.049*
C190.1722 (4)0.02244 (14)0.12611 (14)0.0334 (6)
H190.28080.00710.09060.040*
C200.2059 (7)0.1441 (2)0.2437 (2)0.0897 (14)
H200.19320.11630.20440.108*
C210.2747 (8)0.2423 (3)0.1592 (2)0.126 (2)
H21A0.24110.20930.12620.189*
H21B0.40250.25630.13820.189*
H21C0.19650.28400.16580.189*
C220.2702 (6)0.2536 (2)0.2878 (2)0.0913 (14)
H22A0.15270.27580.31250.137*
H22B0.36160.29000.26760.137*
H22C0.30920.22510.32300.137*
C230.7580 (5)0.2355 (2)0.2968 (2)0.0708 (11)
H230.78340.28310.28240.085*
C240.7856 (8)0.2117 (3)0.1698 (2)0.1121 (18)
H24A0.81190.26210.16490.168*
H24B0.67720.20160.15460.168*
H24C0.89000.18550.13870.168*
C250.7108 (8)0.1183 (2)0.2631 (3)0.1151 (18)
H25A0.81200.09630.27630.173*
H25B0.69290.09400.22070.173*
H25C0.59910.11500.30440.173*
H20.143 (6)0.121 (3)0.421 (3)0.138*
H4A0.289 (7)0.015 (2)0.306 (3)0.138*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0304 (3)0.0331 (3)0.0307 (3)0.0005 (2)0.0112 (2)0.0028 (2)
Cl10.0349 (4)0.0406 (4)0.0421 (4)0.0019 (3)0.0100 (3)0.0015 (3)
O10.0940 (18)0.0542 (14)0.0314 (12)0.0054 (13)0.0158 (12)0.0099 (10)
O20.0734 (16)0.0477 (14)0.0452 (13)0.0194 (12)0.0174 (11)0.0081 (11)
O30.154 (3)0.0560 (16)0.0536 (16)0.0120 (16)0.0349 (17)0.0107 (13)
O40.108 (2)0.100 (2)0.0580 (18)0.0199 (17)0.0277 (16)0.0097 (15)
N10.0360 (13)0.0359 (14)0.0315 (13)0.0054 (10)0.0114 (10)0.0021 (10)
N20.0537 (16)0.0319 (14)0.0385 (14)0.0033 (12)0.0131 (13)0.0038 (11)
N30.0377 (14)0.0345 (14)0.0326 (13)0.0006 (11)0.0125 (10)0.0055 (10)
N40.0447 (15)0.0458 (16)0.0322 (13)0.0026 (12)0.0164 (12)0.0021 (11)
N50.0327 (13)0.0371 (13)0.0325 (13)0.0005 (10)0.0097 (11)0.0016 (10)
N60.103 (3)0.0512 (19)0.0540 (19)0.0052 (17)0.0288 (18)0.0085 (15)
N70.094 (2)0.055 (2)0.0505 (19)0.0024 (17)0.0198 (17)0.0003 (15)
C10.0467 (18)0.0355 (17)0.0348 (18)0.0078 (14)0.0128 (14)0.0020 (14)
C20.0392 (16)0.0370 (17)0.0317 (16)0.0087 (13)0.0140 (13)0.0026 (13)
C30.056 (2)0.049 (2)0.0295 (16)0.0043 (15)0.0120 (14)0.0017 (14)
C40.066 (2)0.051 (2)0.0389 (18)0.0011 (17)0.0225 (16)0.0106 (15)
C50.0464 (18)0.0411 (18)0.0448 (19)0.0004 (14)0.0164 (15)0.0039 (14)
C60.0298 (15)0.0345 (16)0.0341 (15)0.0028 (12)0.0118 (12)0.0020 (13)
C70.0346 (16)0.0404 (18)0.0365 (16)0.0024 (13)0.0122 (13)0.0004 (14)
C80.0492 (19)0.0349 (17)0.0460 (18)0.0002 (14)0.0123 (15)0.0054 (14)
C90.0409 (17)0.0361 (16)0.0297 (15)0.0023 (13)0.0108 (13)0.0031 (12)
C100.0448 (19)0.0353 (17)0.0516 (19)0.0082 (14)0.0142 (15)0.0053 (14)
C110.0347 (17)0.047 (2)0.061 (2)0.0054 (15)0.0159 (15)0.0083 (16)
C120.0412 (18)0.0394 (18)0.0429 (18)0.0026 (14)0.0171 (14)0.0018 (14)
C130.0344 (16)0.0378 (17)0.0334 (16)0.0008 (13)0.0109 (13)0.0035 (13)
C140.0398 (17)0.058 (2)0.0283 (15)0.0038 (15)0.0118 (13)0.0015 (14)
C150.0344 (16)0.0367 (16)0.0269 (15)0.0026 (13)0.0071 (12)0.0014 (12)
C160.0422 (18)0.0498 (19)0.0288 (15)0.0024 (14)0.0088 (13)0.0046 (13)
C170.0345 (17)0.060 (2)0.0349 (17)0.0067 (14)0.0021 (13)0.0078 (14)
C180.0294 (16)0.0516 (19)0.0403 (17)0.0018 (14)0.0090 (13)0.0051 (14)
C190.0297 (15)0.0389 (16)0.0301 (15)0.0018 (12)0.0067 (12)0.0004 (12)
C200.143 (4)0.064 (3)0.068 (3)0.011 (3)0.042 (3)0.003 (2)
C210.203 (6)0.116 (4)0.076 (3)0.047 (4)0.068 (4)0.045 (3)
C220.123 (4)0.069 (3)0.075 (3)0.016 (3)0.019 (3)0.002 (2)
C230.081 (3)0.059 (2)0.068 (3)0.009 (2)0.017 (2)0.002 (2)
C240.171 (5)0.113 (4)0.051 (3)0.001 (3)0.031 (3)0.007 (2)
C250.191 (6)0.064 (3)0.098 (4)0.023 (3)0.055 (4)0.005 (3)
Geometric parameters (Å, º) top
Ni1—N32.212 (2)C6—C71.506 (4)
Ni1—N5i2.149 (2)C8—C91.512 (4)
Ni1—N5ii2.149 (2)C8—H8A0.9900
Ni1—N3iii2.212 (2)C8—H8B0.9900
Ni1—Cl12.4450 (7)C9—C131.380 (4)
Ni1—Cl1iii2.4450 (7)C9—C101.385 (4)
O1—C11.225 (3)C10—C111.382 (4)
O2—C71.227 (3)C10—H100.9500
O3—C201.230 (4)C11—C121.367 (4)
O4—C231.226 (4)C11—H110.9500
N1—C61.336 (3)C12—H120.9500
N1—C21.336 (3)C13—H130.9500
N2—C11.336 (3)C14—C151.516 (4)
N2—C81.453 (4)C14—H14A0.9900
N2—H20.89 (5)C14—H14B0.9900
N3—C131.342 (3)C15—C161.380 (4)
N3—C121.348 (3)C15—C191.384 (3)
N4—C71.335 (3)C16—C171.384 (4)
N4—C141.454 (3)C16—H160.9500
N4—H4A0.86 (5)C17—C181.383 (4)
N5—C191.340 (3)C17—H170.9500
N5—C181.340 (3)C18—H180.9500
N5—Ni1iv2.149 (2)C19—H190.9500
N6—C201.292 (5)C20—H200.9500
N6—C211.445 (5)C21—H21A0.9800
N6—C221.450 (5)C21—H21B0.9800
N7—C231.314 (4)C21—H21C0.9800
N7—C251.436 (5)C22—H22A0.9800
N7—C241.448 (4)C22—H22B0.9800
C1—C21.509 (4)C22—H22C0.9800
C2—C31.384 (4)C23—H230.9500
C3—C41.373 (4)C24—H24A0.9800
C3—H30.9500C24—H24B0.9800
C4—C51.382 (4)C24—H24C0.9800
C4—H40.9500C25—H25A0.9800
C5—C61.382 (4)C25—H25B0.9800
C5—H50.9500C25—H25C0.9800
N5i—Ni1—N5ii180.00 (11)C11—C10—C9119.0 (3)
N5i—Ni1—N385.83 (8)C11—C10—H10120.5
N5ii—Ni1—N394.17 (8)C9—C10—H10120.5
N5i—Ni1—N3iii94.17 (8)C12—C11—C10119.5 (3)
N5ii—Ni1—N3iii85.83 (8)C12—C11—H11120.3
N3—Ni1—N3iii180.0C10—C11—H11120.3
N5i—Ni1—Cl189.87 (6)N3—C12—C11123.1 (3)
N5ii—Ni1—Cl190.13 (6)N3—C12—H12118.4
N3—Ni1—Cl190.46 (6)C11—C12—H12118.4
N3iii—Ni1—Cl189.54 (6)N3—C13—C9124.9 (3)
N5i—Ni1—Cl1iii90.13 (6)N3—C13—H13117.6
N5ii—Ni1—Cl1iii89.87 (6)C9—C13—H13117.6
N3—Ni1—Cl1iii89.54 (6)N4—C14—C15112.2 (2)
N3iii—Ni1—Cl1iii90.46 (6)N4—C14—H14A109.2
Cl1—Ni1—Cl1iii180.00 (3)C15—C14—H14A109.2
C6—N1—C2117.7 (2)N4—C14—H14B109.2
C1—N2—C8121.5 (2)C15—C14—H14B109.2
C1—N2—H2115 (3)H14A—C14—H14B107.9
C8—N2—H2123 (3)C16—C15—C19118.3 (2)
C13—N3—C12116.2 (2)C16—C15—C14121.9 (2)
C13—N3—Ni1119.85 (17)C19—C15—C14119.8 (2)
C12—N3—Ni1123.54 (18)C15—C16—C17118.7 (3)
C7—N4—C14122.5 (2)C15—C16—H16120.6
C7—N4—H4A119 (3)C17—C16—H16120.6
C14—N4—H4A118 (3)C18—C17—C16119.2 (3)
C19—N5—C18117.2 (2)C18—C17—H17120.4
C19—N5—Ni1iv124.67 (18)C16—C17—H17120.4
C18—N5—Ni1iv118.05 (18)N5—C18—C17122.8 (3)
C20—N6—C21124.8 (4)N5—C18—H18118.6
C20—N6—C22118.4 (3)C17—C18—H18118.6
C21—N6—C22116.7 (3)N5—C19—C15123.7 (2)
C23—N7—C25120.0 (3)N5—C19—H19118.1
C23—N7—C24122.5 (4)C15—C19—H19118.1
C25—N7—C24117.5 (3)O3—C20—N6126.9 (4)
O1—C1—N2123.3 (3)O3—C20—H20116.6
O1—C1—C2121.2 (3)N6—C20—H20116.6
N2—C1—C2115.4 (2)N6—C21—H21A109.5
N1—C2—C3122.9 (3)N6—C21—H21B109.5
N1—C2—C1117.4 (2)H21A—C21—H21B109.5
C3—C2—C1119.6 (2)N6—C21—H21C109.5
C4—C3—C2118.8 (3)H21A—C21—H21C109.5
C4—C3—H3120.6H21B—C21—H21C109.5
C2—C3—H3120.6N6—C22—H22A109.5
C3—C4—C5118.9 (3)N6—C22—H22B109.5
C3—C4—H4120.5H22A—C22—H22B109.5
C5—C4—H4120.5N6—C22—H22C109.5
C6—C5—C4118.7 (3)H22A—C22—H22C109.5
C6—C5—H5120.7H22B—C22—H22C109.5
C4—C5—H5120.7O4—C23—N7126.5 (4)
N1—C6—C5122.9 (3)O4—C23—H23116.7
N1—C6—C7117.5 (2)N7—C23—H23116.7
C5—C6—C7119.5 (3)N7—C24—H24A109.5
O2—C7—N4124.2 (3)N7—C24—H24B109.5
O2—C7—C6120.4 (2)H24A—C24—H24B109.5
N4—C7—C6115.4 (2)N7—C24—H24C109.5
N2—C8—C9115.2 (2)H24A—C24—H24C109.5
N2—C8—H8A108.5H24B—C24—H24C109.5
C9—C8—H8A108.5N7—C25—H25A109.5
N2—C8—H8B108.5N7—C25—H25B109.5
C9—C8—H8B108.5H25A—C25—H25B109.5
H8A—C8—H8B107.5N7—C25—H25C109.5
C13—C9—C10117.3 (3)H25A—C25—H25C109.5
C13—C9—C8118.7 (2)H25B—C25—H25C109.5
C10—C9—C8124.0 (3)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y1/2, z+1/2; (iii) x, y1, z+1; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O30.89 (5)2.20 (5)3.023 (3)154 (4)
N4—H4A···O30.86 (5)2.08 (5)2.887 (3)156 (4)

Experimental details

Crystal data
Chemical formula[NiCl2(C19H17N5O2)2]·4C3H7NO
Mr1116.75
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.6822 (8), 19.039 (2), 19.1684 (18)
β (°) 107.432 (4)
V3)2674.8 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.53
Crystal size (mm)0.31 × 0.24 × 0.11
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
18986, 4712, 3382
Rint0.056
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.111, 1.08
No. of reflections4712
No. of parameters350
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.24

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Siemens, 1994).

Selected geometric parameters (Å, º) top
Ni1—N32.212 (2)Ni1—Cl12.4450 (7)
Ni1—N5i2.149 (2)
N5i—Ni1—N5ii180.00 (11)N3—Ni1—Cl190.46 (6)
N5i—Ni1—N385.83 (8)N3iii—Ni1—Cl189.54 (6)
N5ii—Ni1—N394.17 (8)N5i—Ni1—Cl1iii90.13 (6)
N5i—Ni1—N3iii94.17 (8)N5ii—Ni1—Cl1iii89.87 (6)
N5ii—Ni1—N3iii85.83 (8)N3—Ni1—Cl1iii89.54 (6)
N3—Ni1—N3iii180.0N3iii—Ni1—Cl1iii90.46 (6)
N5i—Ni1—Cl189.87 (6)Cl1—Ni1—Cl1iii180.00 (3)
N5ii—Ni1—Cl190.13 (6)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y1/2, z+1/2; (iii) x, y1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O30.89 (5)2.20 (5)3.023 (3)154 (4)
N4—H4A···O30.86 (5)2.08 (5)2.887 (3)156 (4)
 

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