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The reaction of N1,N1′-(ethane-1,2-di­yl)bis­(propane-1,3-di­amine) (bapen), K2[Ni(CN)4]·H2O and di­methyl­formamide in the presence of Gd(NO3)3·6H2O under solvothermal conditions yielded yellow crystals of dicyanido(2,3,4,6,7,9,10,11-octahydro­pyrimido[2′,1′:3,4]pyrazino[1,2-a]py­rimi­dine)­nickel(II) hemihydrate, [Ni(CN)2(C10H16N4)]·0.5H2O, (I), the crystal structure of which is composed of [Ni(CN)2(pdpm)] mol­ecules (pdpm is 2,3,4,6,7,9,10,11-octahydro­py­rim­ido[2′,1′:3,4]pyrazino[1,2-a]pyrimidine) on general positions linked by O—H...N hydrogen bonds to water mol­ecules located on twofold axes. This structural unit is further linked by nonclassical C—H...N inter­actions to form a warped two-dimensional net perpendicular to the unit-cell b axis. The nets are stacked, with C—H...O contacts joining successive units. The NiII cation is coordinated with square-planar geometry by a chelating pdpm ligand and two cyanide ligands in mutually cis positions. Complex (I) is stable up to 360 K, at which point dehydration takes place; the ligands start to decompose at 558 K.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113010585/ku3094sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010585/ku3094Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S0108270113010585/ku3094Isup3.cdx
Supplementary material

CCDC reference: 950395

Comment top

The formation of new ligands by the reaction of organic compounds in the presence of metal cations, leading to the isolation of new solid coordination compounds, is commonly observed in solvothermal preparations. Examples include the in situ reduction of pyridine-2-carboxaldehyde to (pyridin-2-yl)methanol during the synthesis of tetranuclear NiII and dinuclear FeIII complexes (Sun et al., 2011), or the transformation of the mono Schiff base 4-chloro-2-[(3-cyclohexylaminopropylimino)methyl]phenol in the presence of ZnII cations to 4-chloro-2-{[3-(5-chloro-2-hydroxybenzyl)aminopropylimino]methyl}phenol with a newly formed C—N single bond (You et al., 2012).

Within our broader studies of 3d–4f complexes, we have reacted Gd(NO3)3.6H2O, N1,N1'-(ethane-1,2-diyl)bis(propane-1,3-diamine) (bapen), K2[Ni(CN)4].H2O and dimethylformamide (DMF) under solvothermal conditions. The formation of 3d–4f complexes based on GdIII and [Ni(CN)4]2- has already been reported (Du et al., 2001), so our goal was to isolate a compound based on GdIII, bapen and [Ni(CN)4]2-. However, the synthetic procedure unexpectedly produced the title nickel complex, [Ni(CN)2(pdpm)].0.5H2O (pdpm is 2,3,4,6,7,9,10,11-octahydropyrimido[2',1':3,4]pyrazino[1,2-a]pyrimidine), (I), the structure of which was established by single-crystal X-ray diffraction. The result indicates that in situ formation of the pdpm ligand has occurred. The newly synthesized complex was further characterized by CHN analysis, as well as by its spectroscopic and thermal properties.

The synthesis of (I) itself merits comment. From the system bapen–K2[Ni(CN)4].H2O–Gd(NO3)3.6H2O (4:3:2) with DMF (in excess) as solvent under solvothermal conditions, yellow crystals of (I) were isolated in low yield. Crystals of the same compound were obtained after lowering the content of the GdIII salt to give ratios of 4:3:0.5. However, in the absence of the GdIII salt no crystals of (I) were produced, suggesting a possible catalytic role for GdIII. A previously reported preparation of pdpm involved reaction of dithiooxamide with bapen in absolute ethanol under an N2 atmosphere, followed by azeotropic distillation with toluene (Li et al., 2010).

The most prominent feature in the IR spectrum of (I) (Fig. 1, top) is the strong sharp absorption band at 2118 cm-1 which, in accord with the literature (Nakamoto, 1997), was assigned to the stretching vibrations of the terminal cyanide groups. A further easily identifiable absorption band is observed at 3500 cm-1, signalling the presence of the interstitial water molecule. Additionally, several weak-to-medium absorption bands observed below 3000 cm-1 can be attributed to the ν(CH) vibrations of the methylene groups. A broad strong absorption due to the NC—CN fragment is observed at 1616 cm-1; this band was observed at 1601 cm-1 in the free pdpm ligand and between 1525 and 1670 cm-1 in the spectra of various complexes containing pdpm as a ligand (Li et al., 2010).

Compound (I) forms molecular crystals of a hemihydrate, in which the Ni-centred complex resides on a general position while the solvent water sits on a crystallographic twofold axis. The central NiII cation is coordinated in a square-planar fashion (Fig. 2) by two cyanide ligands cis to each other and with the two remaining mutually-cis positions occupied by N atoms of the pdpm ligand. A search of the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002) reveals no square-planar NiII complexes with mutually cis cyanide ligands and two N-bound ligands. Thus, complex (I) is the first example of a square-planar NiII complex with this coordination set. In contrast, there have been a few examples reported of square-planar NiII complexes with C2P2 donor sets, e.g. cis-[Ni(CN)2(dppe)] [dppe = 1,2-bis(diphenylphosphino)ethene; Oberhauser et al., 1998] or trans-[Ni(CN)2(chp)2] (chp = tricyclohexylphosphine; Xia et al., 2002), and with a C2NS donor set, e.g. cis-[Ni(CN)2(Htsc)2].H2O (Htsc = thiosemicarbazide; Dunaj-Jurčo et al., 1992).

The mean Ni—C bond length of 1.847 (3) Å (Table 1) is close to the typical value of 1.859 Å for this bond in square-planar complexes (Orpen et al., 1989). The other geometric parameters associated with the cyanide ligands are also as expected (Ray et al., 2008). The Ni—C distances in (I) are also similar to those found in a five-coordinate Ni complex with a cis-[Ni(CN)2N3] coordination set (Li et al., 2006), but are significantly shorter than those found for a six-coordinate Ni compound with cis-[Ni(CN)2N4] coordination (Jiang et al., 2005). The Ni—N bonds to the chelating pdpm ligand [1.902 (2) and 1.909 (3) Å] are longer, but similar to the value of 1.923 (2) Å found for the square-planar complex cis-[Ni(CN)2(Htsc)2].H2O (Dunaj-Jurčo et al., 1992). The geometric parameters associated with the pdpm ligand are similar to those found in analogous complexes, e.g. in [Zn(pdpm)3](ClO4)2 (Li et al., 2010).

The water molecule does not enter the coordination environment of the NiII cation, but it nevertheless has an important role in the crystal structure. Each water molecule forms two O—H···N(C) hydrogen bonds (Table 2) linking two molecules of the complex (Fig. 3). Weak C—H···N hydrogen bonds link neighbouring units of this aggregate to form a slightly warped two-dimensional net perpendicular to the b axis and centred at y = 1/4, 3/4. The net is composed of R44(25) and R42(16) rings (Bernstein et al., 1995) (Fig. 4, denoted A and B). A crystallographic twofold axis parallel to b goes through the water molecule at the edge of ring A, while another twofold axis in the same direction goes through the middle of ring B. The three-dimensional structure is completed by stacking of the two-dimensional nets along [010]. C—H···O contacts (Table 2 and Fig. 5) stabilize the third dimension.

In order to study the thermal stability of complex (I), its thermogravimetric (TG) and differential thermogravimetric (DTG) curves were recorded (see Supplementary materials). The complex starts to dehydrate at 360 K. The observed weight loss of 2.7% corresponds well to the calculated value of 2.8% for the water content. The IR spectrum of the dehydrated sample, (Ia) (heated to 423 K) (Fig. 1, bottom), does not show the absorption band due to the ν(OH) vibration, which appears at 3501 cm-1 in the spectrum of the hydrate. The anhydrous complex (Ia) thus formed is stable up to 558 K, at which point a complicated three-step decomposition process takes place. The weight of the solid residue (26.6%) is consistent with any of several interpretations, but it clearly does not contain any species relevant to the characterization of complex (I).

In conclusion, under solvothermal conditions the organic compound bapen reacts to form pdpm, which binds to NiII giving the title square-planar complex [Ni(CN)2(pdpm)].0.5H2O as yellow crystals. The present complex is, to the best of our knowledge, the first structurally characterized NiII complex with a cis-C2N2 donor set. The solvent water molecule is hydrogen-bonded to two molecules of the complex, and C—H···O contacts further unite this structural unit into two-dimensional nets, which are stacked along [010]. The complex is stable up to 360 K, at which point dehydration takes place; the dehydrated product is stable up to 558 K.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Du et al. (2001); Dunaj-Jurčo, Kožíšek, Cagáň, Melník & Šramko (1992); Jiang et al. (2005); Li et al. (2006, 2010); Nakamoto (1997); Oberhauser et al. (1998); Orpen et al. (1989); Ray et al. (2008); Sun et al. (2011); Xia et al. (2002); You et al. (2012).

Experimental top

N1,N1'-(Ethane-1,2-diyl)bis(propane-1,3-diamine) (bapen; 94%, Aldrich), potassium tetracyanidonickelate(II) monohydrate (Aldrich), gadolinium(III) nitrate hexahydrate (99.9%, Aldrich) and N,N-dimethylformamide (DMF; 99.8%, Aldrich) were used as received.

A mixture of solid Gd(NO3)3.6H2O (0.914 g, 2 mmol), bapen (0.78 ml, 4 mmol), solid K2[Ni(CN)4].H2O (0.774 g, 3 mmol) and DMF (5 ml, 65 mmol) was placed in a stainless steel reactor with a Teflon liner. The reactor was heated linearly to 453 K at a heating rate of 78 K h-1. After 8 h of reaction at 453 K, the reactor was cooled to room temperature at a cooling rate of 11 K h-1. The light-brown powder (0.275 g) which had formed was removed by filtration and the dark-orange filtrate was left for crystallization at room temperature. Yellow crystals of (I) formed within 3 d; these were isolated by filtration, and washed with DMF and hexane (yield 8%, 0.07 g). Analysis, calculated for C12H17N6NiO0.5: C 46.20, H 5.49, N 26.94%; found: C 46.54, H 5.59, N 26.96%. Thermogravimetric analysis (TA), water: expected 2.7%, calculated 2.8%.

Refinement top

Atom C5 of the pdpm ligand was found to be disordered over two positions. The occupancies refined to values of 0.601 (12) for atom C5A and 0.399 (12) for atom C5B, and these were fixed at 0.60 and 0.40, respectively, for the final refinement. H atoms attached to C atoms were placed at calculated positions, with C—H = 0.99 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C). The pivot atom C4 was assigned two sets of H atoms, corresponding to idealized geometries for the two congeners of C5. The unique H atom of the water molecule, atom O1 of which sits on a twofold axis, was located in a difference Fourier map and refined freely with an isotropic displacement parameter.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The IR spectra of (I) (top) and (Ia) (bottom). See Comment for details.
[Figure 2] Fig. 2. A view of the structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The H atoms of the minor disorder component at atoms C4 and C5 have been omitted. The dashed line represents a hydrogen bond.
[Figure 3] Fig. 3. The O—H···N(C) hydrogen bonds (dashed lines) linking the water and two molecules of the complex. H atoms not involved in hydrogen bonding, and one disordered position of atom C5 of the pdpm ligand, are not shown. [Symmetry code: (iv) -x+1, y, -z+3/2.]
[Figure 4] Fig. 4. The two-dimensional net in (I), perpendicular to the b axis. [Symmetry codes: (iv) -x+1, y, -z+3/2; (v) x-1/2, -y+3/2, -z+1; (vi) -x+3/2, -y+3/2, z-1/2; (vii) -x+1, y, -z+1/2.]
[Figure 5] Fig. 5. The stacking of layers along the b direction in (I), with C—H···O contacts (dashed lines) bridging adjoining layers. [Symmetry code: (viii) -x+1, -y+1, -z+1.]
Dicyanido(2,3,4,6,7,9,10,11-octahydropyrimido[2',1':3,4]pyrazino[1,2-a]pyrimidine)nickel(II) hemihydrate top
Crystal data top
[Ni(CN)2(C10H16N4)]·0.5H2ODx = 1.583 Mg m3
Mr = 312.03Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 8937 reflections
a = 20.4120 (4) Åθ = 4.1–28.8°
b = 7.1730 (2) ŵ = 1.48 mm1
c = 17.8858 (4) ÅT = 150 K
V = 2618.75 (11) Å3Plate, yellow
Z = 80.19 × 0.17 × 0.03 mm
F(000) = 1304
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
2994 independent reflections
Radiation source: Enhance (Mo) X-ray Source2304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
Detector resolution: 16.0655 pixels mm-1θmax = 27.5°, θmin = 4.1°
ω scansh = 2626
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 99
Tmin = 0.835, Tmax = 1.000l = 2323
42018 measured reflections
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) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0357P)2 + 3.9675P]
where P = (Fo2 + 2Fc2)/3
2994 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
[Ni(CN)2(C10H16N4)]·0.5H2OV = 2618.75 (11) Å3
Mr = 312.03Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 20.4120 (4) ŵ = 1.48 mm1
b = 7.1730 (2) ÅT = 150 K
c = 17.8858 (4) Å0.19 × 0.17 × 0.03 mm
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
2994 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2304 reflections with I > 2σ(I)
Tmin = 0.835, Tmax = 1.000Rint = 0.052
42018 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.54 e Å3
2994 reflectionsΔρmin = 0.29 e Å3
190 parameters
Special details top

Experimental. Elemental analyses were performed on a Perkin–Elmer 2400 CHNS instrument. IR spectra were recorded on a Perkin–Elmer Spectrum 100 FT–IR spectrophotometer with UATR accessory in the range of 4000–300 cm-1. The TG and DTG curves were recorded on a 2960 SDT V3.0 F instrument under the following conditions: sample weight = 1.8945 mg, heating rate = 10° min-1, nitrogen atmosphere, temperature range 20–700°C, aluminium crucibles.

IR (cm-1): 3501 (m), 2981 (w), 2931 (w), 2874 (w), 2118 (s), 1616 (s), 1530 (w), 1484 (m), 1428 (w), 1385 (m), 1360 (s), 1317 (s), 1219 (m), 1201 (m), 1172 (m), 1127 (w), 1105 (m), 1082 (m), 1017 (s), 976 (w), 943 (m), 801 (w), 764 (m), 577 (m), 568 (m), 511 (s), 411 (s), 394 (s), 337 (m), 298 (m).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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*/UeqOcc. (<1)
Ni10.720296 (16)0.74617 (5)0.557303 (19)0.02275 (13)
C10.78102 (14)0.6524 (4)0.70851 (16)0.0280 (6)
H1A0.78080.51490.71350.034*
H1B0.73890.70020.72810.034*
C20.83706 (14)0.7328 (4)0.75409 (16)0.0297 (6)
H2A0.83520.87060.75280.036*
H2B0.83310.69210.80680.036*
C30.90153 (14)0.6671 (5)0.72241 (16)0.0305 (7)
H3A0.93800.73670.74590.037*
H3B0.90760.53290.73330.037*
C40.96506 (15)0.7087 (7)0.60409 (19)0.0505 (11)
H4A0.99760.75970.63960.061*0.60
H4B0.97920.58090.59070.061*0.60
H4C0.98450.83210.61500.061*0.40
H4D0.99430.61320.62610.061*0.40
C5A0.9654 (2)0.8212 (10)0.5378 (3)0.0360 (12)0.60
H5A1.00620.79680.50930.043*0.60
H5B0.96520.95450.55210.043*0.60
C5B0.9644 (4)0.6831 (16)0.5237 (4)0.038 (2)0.40
H5C0.96150.54840.51210.045*0.40
H5D1.00570.73130.50220.045*0.40
C60.91205 (15)0.8205 (6)0.40855 (18)0.0424 (9)
H6A0.94970.75230.38690.051*
H6B0.91920.95550.40040.051*
C70.85057 (16)0.7615 (5)0.37072 (17)0.0376 (7)
H7A0.84910.62370.36830.045*
H7B0.85040.80970.31890.045*
C80.79102 (14)0.8313 (5)0.41094 (16)0.0323 (7)
H8A0.78850.96860.40580.039*
H8B0.75140.77730.38760.039*
C90.84943 (13)0.7647 (4)0.52216 (16)0.0244 (6)
C100.84659 (13)0.7184 (4)0.60346 (16)0.0239 (6)
C110.65737 (14)0.7888 (4)0.48561 (17)0.0284 (6)
C120.65114 (14)0.7112 (4)0.62294 (17)0.0285 (6)
N10.78732 (11)0.7029 (3)0.62914 (13)0.0236 (5)
N20.90211 (11)0.6977 (4)0.64140 (13)0.0288 (6)
N30.90782 (11)0.7820 (4)0.48908 (14)0.0317 (6)
N40.79239 (11)0.7818 (3)0.49086 (13)0.0257 (5)
N50.61745 (13)0.8148 (4)0.44083 (15)0.0381 (7)
N60.60749 (13)0.6917 (4)0.66256 (16)0.0409 (7)
O10.50000.5297 (6)0.75000.0529 (11)
H1W0.5254 (18)0.592 (6)0.729 (2)0.054 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01569 (18)0.0297 (2)0.0229 (2)0.00265 (15)0.00032 (13)0.00025 (15)
C10.0240 (15)0.0376 (16)0.0224 (14)0.0016 (12)0.0023 (12)0.0033 (12)
C20.0309 (15)0.0369 (16)0.0213 (13)0.0008 (13)0.0010 (12)0.0005 (13)
C30.0227 (15)0.0463 (18)0.0226 (15)0.0014 (13)0.0041 (12)0.0024 (13)
C40.0196 (15)0.101 (3)0.0304 (18)0.0060 (18)0.0020 (13)0.0058 (19)
C5A0.017 (2)0.060 (4)0.031 (3)0.003 (3)0.004 (2)0.000 (3)
C5B0.014 (4)0.073 (6)0.025 (4)0.002 (4)0.002 (3)0.009 (4)
C60.0264 (16)0.073 (2)0.0279 (17)0.0014 (16)0.0068 (13)0.0106 (17)
C70.0403 (18)0.0493 (19)0.0231 (15)0.0022 (16)0.0018 (13)0.0039 (15)
C80.0243 (15)0.0492 (19)0.0233 (15)0.0082 (13)0.0029 (12)0.0066 (14)
C90.0195 (13)0.0276 (14)0.0259 (14)0.0029 (12)0.0002 (11)0.0016 (12)
C100.0194 (13)0.0277 (15)0.0246 (14)0.0009 (11)0.0000 (11)0.0003 (11)
C110.0204 (14)0.0349 (17)0.0300 (15)0.0052 (12)0.0040 (12)0.0000 (12)
C120.0239 (15)0.0339 (16)0.0278 (15)0.0006 (12)0.0029 (12)0.0016 (12)
N10.0192 (12)0.0310 (13)0.0205 (12)0.0022 (9)0.0004 (9)0.0004 (9)
N20.0186 (12)0.0448 (15)0.0230 (12)0.0002 (10)0.0022 (10)0.0013 (11)
N30.0185 (12)0.0535 (18)0.0232 (13)0.0065 (11)0.0013 (9)0.0032 (11)
N40.0200 (12)0.0355 (14)0.0215 (12)0.0057 (10)0.0015 (9)0.0016 (10)
N50.0200 (13)0.0593 (18)0.0349 (15)0.0057 (12)0.0023 (11)0.0059 (13)
N60.0249 (14)0.0549 (18)0.0428 (17)0.0008 (12)0.0103 (13)0.0016 (14)
O10.039 (2)0.052 (2)0.067 (3)0.0000.026 (2)0.000
Geometric parameters (Å, º) top
Ni1—C111.841 (3)C5A—H5B0.9900
Ni1—C121.853 (3)C5B—N31.490 (9)
Ni1—N11.902 (2)C5B—H5C0.9900
Ni1—N41.909 (2)C5B—H5D0.9900
C1—N11.471 (3)C6—N31.469 (4)
C1—C21.518 (4)C6—C71.487 (4)
C1—H1A0.9900C6—H6A0.9900
C1—H1B0.9900C6—H6B0.9900
C2—C31.508 (4)C7—C81.499 (4)
C2—H2A0.9900C7—H7A0.9900
C2—H2B0.9900C7—H7B0.9900
C3—N21.466 (4)C8—N41.473 (4)
C3—H3A0.9900C8—H8A0.9900
C3—H3B0.9900C8—H8B0.9900
C4—C5A1.435 (7)C9—N41.298 (3)
C4—C5B1.449 (9)C9—N31.336 (3)
C4—N21.450 (4)C9—C101.493 (4)
C4—H4A0.9900C10—N11.299 (3)
C4—H4B0.9900C10—N21.329 (4)
C4—H4C0.9900C11—N51.158 (4)
C4—H4D0.9900C12—N61.147 (4)
C5A—N31.490 (6)O1—H1Wi0.78 (4)
C5A—H5A0.9900O1—H1W0.78 (4)
C11—Ni1—C1286.12 (13)C4—C5B—H5D109.4
C11—Ni1—N1178.27 (11)N3—C5B—H5D109.4
C12—Ni1—N195.61 (11)H5C—C5B—H5D108.0
C11—Ni1—N494.70 (11)N3—C6—C7110.1 (3)
C12—Ni1—N4179.17 (11)N3—C6—H6A109.7
N1—Ni1—N483.57 (10)C7—C6—H6A109.7
N1—C1—C2111.0 (2)N3—C6—H6B109.7
N1—C1—H1A109.4C7—C6—H6B109.7
C2—C1—H1A109.4H6A—C6—H6B108.2
N1—C1—H1B109.4C6—C7—C8111.8 (3)
C2—C1—H1B109.4C6—C7—H7A109.3
H1A—C1—H1B108.0C8—C7—H7A109.3
C3—C2—C1109.7 (2)C6—C7—H7B109.3
C3—C2—H2A109.7C8—C7—H7B109.3
C1—C2—H2A109.7H7A—C7—H7B107.9
C3—C2—H2B109.7N4—C8—C7111.7 (2)
C1—C2—H2B109.7N4—C8—H8A109.3
H2A—C2—H2B108.2C7—C8—H8A109.3
N2—C3—C2109.4 (2)N4—C8—H8B109.3
N2—C3—H3A109.8C7—C8—H8B109.3
C2—C3—H3A109.8H8A—C8—H8B107.9
N2—C3—H3B109.8N4—C9—N3126.9 (3)
C2—C3—H3B109.8N4—C9—C10114.0 (2)
H3A—C3—H3B108.2N3—C9—C10119.1 (2)
C5A—C4—N2114.6 (3)N1—C10—N2127.1 (3)
C5B—C4—N2116.2 (4)N1—C10—C9113.6 (2)
C5A—C4—H4A108.6N2—C10—C9119.3 (2)
N2—C4—H4A108.6N5—C11—Ni1179.5 (3)
C5A—C4—H4B108.6N6—C12—Ni1178.5 (3)
N2—C4—H4B108.6C10—N1—C1116.4 (2)
H4A—C4—H4B107.6C10—N1—Ni1114.64 (19)
C5B—C4—H4C108.2C1—N1—Ni1129.00 (18)
N2—C4—H4C108.2C10—N2—C4121.0 (2)
C5B—C4—H4D108.2C10—N2—C3121.0 (2)
N2—C4—H4D108.2C4—N2—C3118.1 (2)
H4C—C4—H4D107.4C9—N3—C6120.3 (2)
C4—C5A—N3111.9 (4)C9—N3—C5A117.6 (3)
C4—C5A—H5A109.2C6—N3—C5A119.4 (3)
N3—C5A—H5A109.2C9—N3—C5B117.5 (4)
C4—C5A—H5B109.2C6—N3—C5B116.8 (4)
N3—C5A—H5B109.2C9—N4—C8117.3 (2)
H5A—C5A—H5B107.9C9—N4—Ni1114.24 (19)
C4—C5B—N3111.1 (6)C8—N4—Ni1128.45 (18)
C4—C5B—H5C109.4H1Wi—O1—H1W110 (6)
N3—C5B—H5C109.4
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N60.78 (4)2.18 (4)2.934 (3)164 (4)
C2—H2B···N5ii0.992.603.483 (4)148
C3—H3A···O1iii0.992.453.324 (5)146
C5A—H5A···N5iv0.992.573.275 (6)128
Symmetry codes: (ii) x+3/2, y+3/2, z+1/2; (iii) x+1/2, y+1/2, z+3/2; (iv) x+1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[Ni(CN)2(C10H16N4)]·0.5H2O
Mr312.03
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)150
a, b, c (Å)20.4120 (4), 7.1730 (2), 17.8858 (4)
V3)2618.75 (11)
Z8
Radiation typeMo Kα
µ (mm1)1.48
Crystal size (mm)0.19 × 0.17 × 0.03
Data collection
DiffractometerAgilent Xcalibur Sapphire3
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.835, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
42018, 2994, 2304
Rint0.052
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.107, 1.14
No. of reflections2994
No. of parameters190
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.54, 0.29

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top
Ni1—C111.841 (3)C6—N31.469 (4)
Ni1—C121.853 (3)C8—N41.473 (4)
Ni1—N11.902 (2)C9—N41.298 (3)
Ni1—N41.909 (2)C9—N31.336 (3)
C1—N11.471 (3)C9—C101.493 (4)
C1—C21.518 (4)C10—N11.299 (3)
C3—N21.466 (4)C10—N21.329 (4)
N4—C9—C10114.0 (2)N6—C12—Ni1178.5 (3)
N1—C10—N2127.1 (3)C10—N1—Ni1114.64 (19)
N5—C11—Ni1179.5 (3)C1—N1—Ni1129.00 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N60.78 (4)2.18 (4)2.934 (3)164 (4)
C2—H2B···N5i0.992.603.483 (4)148.3
C3—H3A···O1ii0.992.453.324 (5)146.3
C5A—H5A···N5iii0.992.573.275 (6)128.3
Symmetry codes: (i) x+3/2, y+3/2, z+1/2; (ii) x+1/2, y+1/2, z+3/2; (iii) x+1/2, y+3/2, z+1.
 

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