Diaqua-(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-ne)nickel(II) tetra-cyanidonickelate(II).

In the title complex, [Ni(C(16)H(36)N(4))(H(2)O)(2)][Ni(CN)(4)], the [Ni(teta)(H(2)O)(2)](2+) cations (teta = 5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-ne) and [Ni(CN)(4)](2-) anions are arranged in an alternating fashion through electrostatic and N-H⋯N and O-H⋯N hydrogen-bonding inter-actions, forming a two-dimensional layered structure. Adjacent layers are linked through weak van der Waals inter-actions, resulting in a three-dimensional supra-molecular network.

Related literature

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

Crystal data

[Ni(C16H36N4)(H2O)2][Ni(CN)4]

M = 542.02

Monoclinic,

a = 8.065 (8) Å

b = 13.255 (12) Å

c = 13.559 (10) Å

β = 116.59 (4)°

V = 1296 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.48 mm−1

T = 173 K

0.58 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.808, T max = 0.888

9778 measured reflections

2530 independent reflections

1576 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.093

S = 1.01

2530 reflections

163 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.73 e Å−3

Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033820/at2863sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033820/at2863Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C16H36N4)(H2O)2][Ni(CN)4]	F(000) = 576
Mr = 542.02	Dx = 1.389 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4392 reflections
a = 8.065 (8) Å	θ = 2.3–26.0°
b = 13.255 (12) Å	µ = 1.48 mm−1
c = 13.559 (10) Å	T = 173 K
β = 116.59 (4)°	Prism, pink
V = 1296 (2) Å3	0.58 × 0.16 × 0.12 mm
Z = 2

Bruker SMART APEX diffractometer	1576 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.808, Tmax = 0.888	k = −16→15
9778 measured reflections	l = −16→16
2530 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H 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 parameters	Δρmax = 0.73 e Å−3
2 restraints	Δρmin = −0.51 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.0000	0.0000	0.02563 (16)
Ni2	0.0000	0.0000	0.5000	0.02354 (15)
O1	0.1715 (3)	0.08968 (15)	0.44654 (15)	0.0298 (5)
H1A	0.153 (5)	0.1515 (9)	0.449 (3)	0.045*
H1B	0.146 (4)	0.086 (2)	0.3803 (10)	0.045*
N1	−0.1059 (5)	−0.2055 (2)	0.0474 (2)	0.0537 (8)
N2	0.0522 (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*
N4	0.1362 (3)	−0.12904 (18)	0.49057 (19)	0.0282 (6)
H4	0.097 (4)	−0.176 (2)	0.513 (2)	0.034*
C1	−0.0637 (4)	−0.1267 (2)	0.0321 (2)	0.0358 (7)
C2	0.0293 (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	−0.1329	0.2655	0.066*
H3B	−0.6212	−0.0410	0.2806	0.066*
H3C	−0.4408	−0.0823	0.3842	0.066*
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	−0.3779	0.0654	0.1371	0.081*
H5B	−0.5788	0.0283	0.1181	0.081*
H5C	−0.4261	−0.0524	0.1256	0.081*
C6	−0.1359 (4)	−0.1309 (2)	0.3117 (2)	0.0368 (8)
H6A	−0.1808	−0.1416	0.2316	0.044*
H6B	−0.2009	−0.1791	0.3382	0.044*
C7	0.0699 (4)	−0.1490 (2)	0.3712 (2)	0.0348 (7)
H7A	0.0977	−0.2197	0.3601	0.042*
H7B	0.1344	−0.1039	0.3413	0.042*
C8	0.4289 (5)	−0.2269 (3)	0.5442 (3)	0.0530 (10)
H8A	0.3772	−0.2838	0.5674	0.080*
H8B	0.5634	−0.2242	0.5901	0.080*
H8C	0.4023	−0.2355	0.4668	0.080*
C9	0.3411 (4)	−0.1285 (2)	0.5574 (2)	0.0348 (7)
H9	0.3932	−0.0713	0.5319	0.042*
C10	0.3891 (4)	−0.1115 (2)	0.6794 (2)	0.0412 (8)
H10A	0.3070	−0.1558	0.6969	0.049*
H10B	0.5175	−0.1358	0.7238	0.049*

	U11	U22	U33	U12	U13	U23
Ni1	0.0380 (3)	0.0219 (3)	0.0229 (3)	−0.0001 (2)	0.0188 (2)	0.0007 (2)
Ni2	0.0290 (3)	0.0228 (3)	0.0216 (3)	0.0012 (2)	0.0138 (2)	0.0004 (2)
O1	0.0416 (12)	0.0258 (12)	0.0265 (10)	0.0003 (11)	0.0195 (9)	−0.0004 (10)
N1	0.093 (2)	0.0286 (16)	0.069 (2)	−0.0054 (17)	0.0625 (19)	−0.0004 (15)
N2	0.078 (2)	0.0434 (17)	0.0344 (14)	−0.0084 (16)	0.0364 (15)	−0.0043 (13)
N3	0.0293 (14)	0.0323 (15)	0.0234 (12)	−0.0030 (11)	0.0134 (11)	0.0006 (10)
N4	0.0342 (15)	0.0242 (14)	0.0339 (13)	0.0020 (12)	0.0221 (11)	0.0032 (11)
C1	0.052 (2)	0.0330 (19)	0.0348 (16)	0.0011 (16)	0.0302 (16)	−0.0012 (14)
C2	0.0469 (19)	0.0269 (18)	0.0293 (15)	0.0004 (15)	0.0232 (14)	0.0052 (13)
C3	0.0329 (18)	0.058 (2)	0.0374 (17)	−0.0086 (17)	0.0117 (14)	0.0059 (16)
C4	0.0325 (17)	0.046 (2)	0.0281 (15)	−0.0030 (16)	0.0100 (13)	0.0061 (14)
C5	0.048 (2)	0.076 (3)	0.0265 (16)	−0.0072 (19)	0.0068 (15)	0.0096 (17)
C6	0.052 (2)	0.0327 (19)	0.0296 (15)	−0.0100 (16)	0.0220 (15)	−0.0087 (14)
C7	0.049 (2)	0.0287 (18)	0.0381 (17)	0.0009 (15)	0.0300 (15)	−0.0054 (13)
C8	0.052 (2)	0.042 (2)	0.078 (3)	0.0205 (17)	0.040 (2)	0.0140 (18)
C9	0.0366 (18)	0.0316 (18)	0.0446 (17)	0.0071 (15)	0.0258 (15)	0.0087 (14)
C10	0.0329 (18)	0.048 (2)	0.0398 (17)	0.0071 (16)	0.0133 (14)	0.0166 (15)

Ni1—C1	1.863 (4)	C3—H3B	0.9800
Ni1—C1i	1.863 (4)	C3—H3C	0.9800
Ni1—C2i	1.867 (3)	C4—C10ii	1.537 (5)
Ni1—C2	1.867 (3)	C4—C5	1.541 (4)
Ni2—N4	2.067 (3)	C5—H5A	0.9800
Ni2—N4ii	2.067 (3)	C5—H5B	0.9800
Ni2—N3ii	2.099 (3)	C5—H5C	0.9800
Ni2—N3	2.099 (3)	C6—C7	1.505 (4)
Ni2—O1ii	2.179 (2)	C6—H6A	0.9900
Ni2—O1	2.179 (2)	C6—H6B	0.9900
O1—H1A	0.835 (10)	C7—H7A	0.9900
O1—H1B	0.830 (10)	C7—H7B	0.9900
N1—C1	1.146 (4)	C8—C9	1.532 (4)
N2—C2	1.137 (3)	C8—H8A	0.9800
N3—C6	1.482 (4)	C8—H8B	0.9800
N3—C4	1.505 (4)	C8—H8C	0.9800
N3—H3	0.88 (3)	C9—C10	1.538 (4)
N4—C7	1.484 (4)	C9—H9	1.0000
N4—C9	1.487 (4)	C10—C4ii	1.537 (5)
N4—H4	0.81 (3)	C10—H10A	0.9900
C3—C4	1.528 (4)	C10—H10B	0.9900
C3—H3A	0.9800
C1—Ni1—C1i	180.0 (2)	H3B—C3—H3C	109.5
C1—Ni1—C2i	88.96 (13)	N3—C4—C3	111.6 (3)
C1i—Ni1—C2i	91.04 (13)	N3—C4—C10ii	108.0 (2)
C1—Ni1—C2	91.04 (13)	C3—C4—C10ii	111.1 (3)
C1i—Ni1—C2	88.96 (13)	N3—C4—C5	109.2 (3)
C2i—Ni1—C2	180.0 (3)	C3—C4—C5	109.6 (3)
N4—Ni2—N4ii	180.00 (14)	C10ii—C4—C5	107.2 (3)
N4—Ni2—N3ii	94.74 (10)	C4—C5—H5A	109.5
N4ii—Ni2—N3ii	85.26 (10)	C4—C5—H5B	109.5
N4—Ni2—N3	85.26 (10)	H5A—C5—H5B	109.5
N4ii—Ni2—N3	94.74 (10)	C4—C5—H5C	109.5
N3ii—Ni2—N3	180.0	H5A—C5—H5C	109.5
N4—Ni2—O1ii	90.18 (10)	H5B—C5—H5C	109.5
N4ii—Ni2—O1ii	89.82 (10)	N3—C6—C7	109.3 (2)
N3ii—Ni2—O1ii	87.30 (10)	N3—C6—H6A	109.8
N3—Ni2—O1ii	92.70 (10)	C7—C6—H6A	109.8
N4—Ni2—O1	89.82 (10)	N3—C6—H6B	109.8
N4ii—Ni2—O1	90.18 (10)	C7—C6—H6B	109.8
N3ii—Ni2—O1	92.70 (10)	H6A—C6—H6B	108.3
N3—Ni2—O1	87.30 (10)	N4—C7—C6	109.2 (2)
O1ii—Ni2—O1	180.0	N4—C7—H7A	109.8
Ni2—O1—H1A	112 (2)	C6—C7—H7A	109.8
Ni2—O1—H1B	116 (2)	N4—C7—H7B	109.8
H1A—O1—H1B	98 (3)	C6—C7—H7B	109.8
C6—N3—C4	116.5 (2)	H7A—C7—H7B	108.3
C6—N3—Ni2	105.14 (17)	C9—C8—H8A	109.5
C4—N3—Ni2	122.34 (18)	C9—C8—H8B	109.5
C6—N3—H3	105.1 (19)	H8A—C8—H8B	109.5
C4—N3—H3	106 (2)	C9—C8—H8C	109.5
Ni2—N3—H3	99 (2)	H8A—C8—H8C	109.5
C7—N4—C9	115.1 (2)	H8B—C8—H8C	109.5
C7—N4—Ni2	105.86 (18)	N4—C9—C8	111.8 (3)
C9—N4—Ni2	115.77 (19)	N4—C9—C10	109.4 (2)
C7—N4—H4	105 (2)	C8—C9—C10	110.1 (3)
C9—N4—H4	107 (2)	N4—C9—H9	108.5
Ni2—N4—H4	107 (2)	C8—C9—H9	108.5
N1—C1—Ni1	177.2 (3)	C10—C9—H9	108.5
N2—C2—Ni1	178.0 (3)	C4ii—C10—C9	120.0 (2)
C4—C3—H3A	109.5	C4ii—C10—H10A	107.3
C4—C3—H3B	109.5	C9—C10—H10A	107.3
H3A—C3—H3B	109.5	C4ii—C10—H10B	107.3
C4—C3—H3C	109.5	C9—C10—H10B	107.3
H3A—C3—H3C	109.5	H10A—C10—H10B	106.9

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N1iii	0.81 (3)	2.46 (3)	3.250 (4)	164 (3)
N3—H3···N2	0.88 (3)	2.34 (3)	3.201 (4)	167 (3)
O1—H1B···N2	0.83 (1)	1.96 (1)	2.789 (4)	172 (3)
O1—H1A···N1iv	0.84 (1)	1.94 (1)	2.775 (4)	179 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N1i	0.81 (3)	2.46 (3)	3.250 (4)	164 (3)
N3—H3⋯N2	0.88 (3)	2.34 (3)	3.201 (4)	167 (3)
O1—H1B⋯N2	0.830 (10)	1.964 (11)	2.789 (4)	172 (3)
O1—H1A⋯N1ii	0.835 (10)	1.939 (11)	2.775 (4)	179 (3)

Symmetry codes: (i) ; (ii) .