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Acta Cryst. (2009). E65, m1141    [ doi:10.1107/S1600536809033820 ]

Diaqua(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) tetracyanidonickelate(II)

Q. Zhang, X.-P. Shen and H. Zhou

Abstract top

In the title complex, [Ni(C16H36N4)(H2O)2][Ni(CN)4], the [Ni(teta)(H2O)2]2+ cations (teta = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) and [Ni(CN)4]2- anions are arranged in an alternating fashion through electrostatic and N-H...N and O-H...N hydrogen-bonding interactions, forming a two-dimensional layered structure. Adjacent layers are linked through weak van der Waals interactions, resulting in a three-dimensional supramolecular network.

Comment top

In the past decades, there has been a continuous interest in the utilization of cyano-containing building blocks for constructing either ion-paired or cyano-bridged assemblies due to their potential applications and intriguing architectures (Lescouëzec et al., 2005; Liu et al., 2008; Xu et al., 2009). It has been found that cyano-bridged bimetallic assemblies, derived from tailored cyanometalate entities [MLp(CN)q]n- (L = polydentate ligand) and unsaturated coordinated complex [M'(L)]m+, possess extraordinarily excellent magnetic properties such as SMM (single molecular magnets) and SCM (single chain magnets). Recently, we had expected to obtain such low-dimensional system using [Cr(salen)(CN)2]- (Yamada et al., 1969; Ni et al., 2008) and [Ni(teta)]2+ as the building blocks. However, an unexpected tetracyanonickel(II)-based complex of [Ni(teta)(H2O)2][Ni(CN)4] instead of any [Cr(salen)(CN)2]--based complex was obtained. So far, Jiang et al. (Jiang et al., 2005; 2007) have reported several complexes based on the direct assembly of [Ni(CN)4]2- and [Ni(teta)]2+ building blocks, and they found that all these complexes showed cyano-bridged structures. In contrast to these reported complexes, the title complex of [Ni(teta)(H2O)2][Ni(CN)4] is ion-paired and its crystal structure is reported here.

The title complex consists of [Ni(teta)(H2O)2]2+ cation and [Ni(CN)4]2- anion (Fig. 1). In [Ni(teta)(H2O)2]2+ cation, the NiII ion assumes a distorted octahedral coordination geometry, in which the equatorial sites are occupied by four nitrogen atoms of the macrocyclic ligand teta with the Ni(2)—N bond distances of 2.067 (3) and 2.100 (3) Å, while the axial positions are occupied by two oxygen atoms of water molecules with Ni(2)—O distance of 2.183 (2) Å. As usual, [Ni(CN)4]2- anion exhibits a square planar structure, where all four cyano groups are terminal ones, with Ni(1)—C(1) and Ni(1)—C(2) distances of 1.862 (3) and 1.869 (3) Å, respectively. The Ni(1)—C—N bonds deviate slightly from linearity with the bond angles 177.2 (3) and 178.1 (3)°. [Ni(teta)(H2O)2]2+ and [Ni(CN)4]2- are arranged in an alternating fashion, forming a two-dimensional layered structure through electrostatic and hydrogen bonding interactions (Fig. 2). Furthermore, adjacent layers are linked through weak van der Waals interactions, resulting in a three-dimensional supramolecular network (Fig. 3).

Related literature top

For background to cyanide-bridged complexes, see: Lescouëzec et al. (2005); Liu et al. (2008); Xu et al. (2009). For related structures, see: Jiang et al. (2005, 2007); Ni et al. (2008); Yamada & Iwasaki (1969).

Experimental top

A solution of Ni(teta)(ClO4)2 (0.05 mmol) in DMF (10 ml) was added to a solution of K[Cr(salen)(CN)2].H2O (0.05 mmol) in MeOH/H2O (1/1(V/V),10 ml) mixture. The resulting solution was filtrated and the filtrate was left to allow slow evaporation in dark at room temperature. Pink prism crystals of the title complex were obtained after two weeks, washed with MeOH and H2O, respectively, and dried in air. Anal. Calc. for C20H40Ni2N8O2: C, 44.32; H, 7.44; N, 20.68; Ni, 21.66%. Found: C, 44.28; H, 7.49; N, 20.71; Ni, 21.52%.

Refinement top

All non-H atoms were refined anisotropically. The C(H) atoms of the teta ligands were placed incalculated position [C-H = 0.99 Å or 0.98 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C). The N(H) atoms were located from the difference Fourier maps, and refined as riding with Uiso(H) = 1.2Ueq(N). The O(H) atoms of the coordinated water molecules were located in a difference Fourier map and refined as riding [O-H = 0.84 Å], with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title complex. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. Projection of the title complex viewed from the a-axis, showing the two-dimensional structure. Hydrogen bonds are shown as dashed lines. Symmetry codes: (i) x, -y-0.5, z+0.5; (ii) -x, y+0.5, -z+0.5.
[Figure 3] Fig. 3. The three-dimensional supramolecular network of the title complex.
Diaqua(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) tetracyanidonickelate(II) top
Crystal data top
[Ni(C16H36N4)(H2O)2][Ni(CN)4]F(000) = 576
Mr = 542.02Dx = 1.389 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4392 reflections
a = 8.065 (8) Åθ = 2.3–26.0°
b = 13.255 (12) ŵ = 1.48 mm−1
c = 13.559 (10) ÅT = 173 K
β = 116.59 (4)°Prism, pink
V = 1296 (2) Å30.58 × 0.16 × 0.12 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer		1576 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.047
φ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −9→9
Tmin = 0.808, Tmax = 0.888k = −16→15
9778 measured reflectionsl = −16→16
2530 independent 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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0423P)2 + 0.2883P]
where P = (Fo2 + 2Fc2)/3
2530 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.73 e Å−3
2 restraintsΔρmin = −0.51 e Å−3
Crystal data top
[Ni(C16H36N4)(H2O)2][Ni(CN)4]V = 1296 (2) Å3
Mr = 542.02Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.065 (8) ŵ = 1.48 mm−1
b = 13.255 (12) ÅT = 173 K
c = 13.559 (10) Å0.58 × 0.16 × 0.12 mm
β = 116.59 (4)°
Data collection top
Bruker SMART APEX
diffractometer		2530 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		1576 reflections with I > 2σ(I)
Tmin = 0.808, Tmax = 0.888Rint = 0.047
9778 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093Δρmax = 0.73 e Å−3
S = 1.01Δρmin = −0.51 e Å−3
2530 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ni10.00000.00000.00000.02563 (16)
Ni20.00000.00000.50000.02354 (15)
O10.1715 (3)0.08968 (15)0.44654 (15)0.0298 (5)
H1A0.153 (5)0.1515 (9)0.449 (3)0.045*
H1B0.146 (4)0.086 (2)0.3803 (10)0.045*
N1−0.1059 (5)−0.2055 (2)0.0474 (2)0.0537 (8)
N20.0522 (4)0.0799 (2)0.2194 (2)0.0477 (7)
N3−0.1760 (3)−0.02613 (18)0.33256 (18)0.0278 (6)
H3−0.120 (4)0.012 (2)0.303 (2)0.033*
N40.1362 (3)−0.12904 (18)0.49057 (19)0.0282 (6)
H40.097 (4)−0.176 (2)0.513 (2)0.034*
C1−0.0637 (4)−0.1267 (2)0.0321 (2)0.0358 (7)
C20.0293 (4)0.0502 (2)0.1355 (2)0.0321 (7)
C3−0.4969 (4)−0.0695 (3)0.3047 (2)0.0441 (8)
H3A−0.5060−0.13290.26550.066*
H3B−0.6212−0.04100.28060.066*
H3C−0.4408−0.08230.38420.066*
C4−0.3767 (4)0.0051 (2)0.2793 (2)0.0368 (8)
C5−0.4462 (5)0.0123 (3)0.1536 (3)0.0538 (10)
H5A−0.37790.06540.13710.081*
H5B−0.57880.02830.11810.081*
H5C−0.4261−0.05240.12560.081*
C6−0.1359 (4)−0.1309 (2)0.3117 (2)0.0368 (8)
H6A−0.1808−0.14160.23160.044*
H6B−0.2009−0.17910.33820.044*
C70.0699 (4)−0.1490 (2)0.3712 (2)0.0348 (7)
H7A0.0977−0.21970.36010.042*
H7B0.1344−0.10390.34130.042*
C80.4289 (5)−0.2269 (3)0.5442 (3)0.0530 (10)
H8A0.3772−0.28380.56740.080*
H8B0.5634−0.22420.59010.080*
H8C0.4023−0.23550.46680.080*
C90.3411 (4)−0.1285 (2)0.5574 (2)0.0348 (7)
H90.3932−0.07130.53190.042*
C100.3891 (4)−0.1115 (2)0.6794 (2)0.0412 (8)
H10A0.3070−0.15580.69690.049*
H10B0.5175−0.13580.72380.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0380 (3)0.0219 (3)0.0229 (3)−0.0001 (2)0.0188 (2)0.0007 (2)
Ni20.0290 (3)0.0228 (3)0.0216 (3)0.0012 (2)0.0138 (2)0.0004 (2)
O10.0416 (12)0.0258 (12)0.0265 (10)0.0003 (11)0.0195 (9)−0.0004 (10)
N10.093 (2)0.0286 (16)0.069 (2)−0.0054 (17)0.0625 (19)−0.0004 (15)
N20.078 (2)0.0434 (17)0.0344 (14)−0.0084 (16)0.0364 (15)−0.0043 (13)
N30.0293 (14)0.0323 (15)0.0234 (12)−0.0030 (11)0.0134 (11)0.0006 (10)
N40.0342 (15)0.0242 (14)0.0339 (13)0.0020 (12)0.0221 (11)0.0032 (11)
C10.052 (2)0.0330 (19)0.0348 (16)0.0011 (16)0.0302 (16)−0.0012 (14)
C20.0469 (19)0.0269 (18)0.0293 (15)0.0004 (15)0.0232 (14)0.0052 (13)
C30.0329 (18)0.058 (2)0.0374 (17)−0.0086 (17)0.0117 (14)0.0059 (16)
C40.0325 (17)0.046 (2)0.0281 (15)−0.0030 (16)0.0100 (13)0.0061 (14)
C50.048 (2)0.076 (3)0.0265 (16)−0.0072 (19)0.0068 (15)0.0096 (17)
C60.052 (2)0.0327 (19)0.0296 (15)−0.0100 (16)0.0220 (15)−0.0087 (14)
C70.049 (2)0.0287 (18)0.0381 (17)0.0009 (15)0.0300 (15)−0.0054 (13)
C80.052 (2)0.042 (2)0.078 (3)0.0205 (17)0.040 (2)0.0140 (18)
C90.0366 (18)0.0316 (18)0.0446 (17)0.0071 (15)0.0258 (15)0.0087 (14)
C100.0329 (18)0.048 (2)0.0398 (17)0.0071 (16)0.0133 (14)0.0166 (15)
Geometric parameters (Å, °) top
Ni1—C11.863 (4)C3—H3B0.9800
Ni1—C1i1.863 (4)C3—H3C0.9800
Ni1—C2i1.867 (3)C4—C10ii1.537 (5)
Ni1—C21.867 (3)C4—C51.541 (4)
Ni2—N42.067 (3)C5—H5A0.9800
Ni2—N4ii2.067 (3)C5—H5B0.9800
Ni2—N3ii2.099 (3)C5—H5C0.9800
Ni2—N32.099 (3)C6—C71.505 (4)
Ni2—O1ii2.179 (2)C6—H6A0.9900
Ni2—O12.179 (2)C6—H6B0.9900
O1—H1A0.835 (10)C7—H7A0.9900
O1—H1B0.830 (10)C7—H7B0.9900
N1—C11.146 (4)C8—C91.532 (4)
N2—C21.137 (3)C8—H8A0.9800
N3—C61.482 (4)C8—H8B0.9800
N3—C41.505 (4)C8—H8C0.9800
N3—H30.88 (3)C9—C101.538 (4)
N4—C71.484 (4)C9—H91.0000
N4—C91.487 (4)C10—C4ii1.537 (5)
N4—H40.81 (3)C10—H10A0.9900
C3—C41.528 (4)C10—H10B0.9900
C3—H3A0.9800
C1—Ni1—C1i180.0 (2)H3B—C3—H3C109.5
C1—Ni1—C2i88.96 (13)N3—C4—C3111.6 (3)
C1i—Ni1—C2i91.04 (13)N3—C4—C10ii108.0 (2)
C1—Ni1—C291.04 (13)C3—C4—C10ii111.1 (3)
C1i—Ni1—C288.96 (13)N3—C4—C5109.2 (3)
C2i—Ni1—C2180.0 (3)C3—C4—C5109.6 (3)
N4—Ni2—N4ii180.00 (14)C10ii—C4—C5107.2 (3)
N4—Ni2—N3ii94.74 (10)C4—C5—H5A109.5
N4ii—Ni2—N3ii85.26 (10)C4—C5—H5B109.5
N4—Ni2—N385.26 (10)H5A—C5—H5B109.5
N4ii—Ni2—N394.74 (10)C4—C5—H5C109.5
N3ii—Ni2—N3180.0H5A—C5—H5C109.5
N4—Ni2—O1ii90.18 (10)H5B—C5—H5C109.5
N4ii—Ni2—O1ii89.82 (10)N3—C6—C7109.3 (2)
N3ii—Ni2—O1ii87.30 (10)N3—C6—H6A109.8
N3—Ni2—O1ii92.70 (10)C7—C6—H6A109.8
N4—Ni2—O189.82 (10)N3—C6—H6B109.8
N4ii—Ni2—O190.18 (10)C7—C6—H6B109.8
N3ii—Ni2—O192.70 (10)H6A—C6—H6B108.3
N3—Ni2—O187.30 (10)N4—C7—C6109.2 (2)
O1ii—Ni2—O1180.0N4—C7—H7A109.8
Ni2—O1—H1A112 (2)C6—C7—H7A109.8
Ni2—O1—H1B116 (2)N4—C7—H7B109.8
H1A—O1—H1B98 (3)C6—C7—H7B109.8
C6—N3—C4116.5 (2)H7A—C7—H7B108.3
C6—N3—Ni2105.14 (17)C9—C8—H8A109.5
C4—N3—Ni2122.34 (18)C9—C8—H8B109.5
C6—N3—H3105.1 (19)H8A—C8—H8B109.5
C4—N3—H3106 (2)C9—C8—H8C109.5
Ni2—N3—H399 (2)H8A—C8—H8C109.5
C7—N4—C9115.1 (2)H8B—C8—H8C109.5
C7—N4—Ni2105.86 (18)N4—C9—C8111.8 (3)
C9—N4—Ni2115.77 (19)N4—C9—C10109.4 (2)
C7—N4—H4105 (2)C8—C9—C10110.1 (3)
C9—N4—H4107 (2)N4—C9—H9108.5
Ni2—N4—H4107 (2)C8—C9—H9108.5
N1—C1—Ni1177.2 (3)C10—C9—H9108.5
N2—C2—Ni1178.0 (3)C4ii—C10—C9120.0 (2)
C4—C3—H3A109.5C4ii—C10—H10A107.3
C4—C3—H3B109.5C9—C10—H10A107.3
H3A—C3—H3B109.5C4ii—C10—H10B107.3
C4—C3—H3C109.5C9—C10—H10B107.3
H3A—C3—H3C109.5H10A—C10—H10B106.9
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1iii0.81 (3)2.46 (3)3.250 (4)164 (3)
N3—H3···N20.88 (3)2.34 (3)3.201 (4)167 (3)
O1—H1B···N20.83 (1)1.96 (1)2.789 (4)172 (3)
O1—H1A···N1iv0.84 (1)1.94 (1)2.775 (4)179 (3)
Symmetry codes: (iii) x, −y−1/2, z+1/2; (iv) −x, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.81 (3)2.46 (3)3.250 (4)164 (3)
N3—H3···N20.88 (3)2.34 (3)3.201 (4)167 (3)
O1—H1B···N20.83 (1)1.96 (1)2.789 (4)172 (3)
O1—H1A···N1ii0.84 (1)1.94 (1)2.775 (4)179 (3)
Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) −x, y+1/2, −z+1/2.
Acknowledgements top

The authors thank the Natural Science Foundation of Jiangsu Province and the Foundation of the State Key Laboratory of Coordination Chemistry (China) for financial support.

references
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