(meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene)nickel(II) dibromide dihydrate.

The asymmetric unit of the title compound, [Ni(C(16)H(32)N(4))]Br(2)·2H(2)O, consists of one half [Ni(C(16)H(32)N(4))](2+) cation, one Br(-) anion and one water mol-ecule of crystallization. The Ni(II) ion lies on an inversion centre in a square-planar environment formed by the four macrocyclic ligand N atoms. In the crystal structure, the cations, anions and water mol-ecules are linked via inter-molecular N-H⋯Br and O-H⋯Br hydrogen bonds, forming discrete chains with set-graph motif D(2)D(2) (2)(7)D(2) (1)(3)D(3) (2)(8). The water mol-ecules and Br(-) ions are linked with set-graph motif R(4) (2)(8).

Related literature

For related structures, see: Ballester et al. (2000 ▶); Heinlein & Tebbe (1985 ▶); Shen et al. (1999 ▶); Szalda et al. (1989 ▶); Wang et al. (2007 ▶); Whimp et al. (1970 ▶); Yang (2005 ▶). For the preparation of the precursor complex C16H32N4·2HBr·2H2O, see: Hay et al. (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Ni(C16H32N4)]Br2·2H2O

M = 535.02

Monoclinic,

a = 8.0349 (16) Å

b = 15.619 (3) Å

c = 8.9355 (18) Å

β = 99.72 (3)°

V = 1105.3 (4) Å3

Z = 2

Mo Kα radiation

μ = 4.51 mm−1

T = 293 K

0.27 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.831, T max = 0.862

11266 measured reflections

2531 independent reflections

1995 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.099

S = 1.05

2531 reflections

116 parameters

H-atom parameters constrained

Δρmax = 0.74 e Å−3

Δρmin = −0.74 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810033714/bx2296sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033714/bx2296Isup2.hkl

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

[Ni(C16H32N4)]Br2·2H2O	F(000) = 548
Mr = 535.02	Dx = 1.608 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3476 reflections
a = 8.0349 (16) Å	θ = 2.3–27.5°
b = 15.619 (3) Å	µ = 4.51 mm−1
c = 8.9355 (18) Å	T = 293 K
β = 99.72 (3)°	Prism, brown
V = 1105.3 (4) Å3	0.27 × 0.20 × 0.20 mm
Z = 2

Rigaku SCXmini diffractometer	2531 independent reflections
Radiation source: fine-focus sealed tube	1995 reflections with I > 2σ(I)
graphite	Rint = 0.048
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.4°
thin–slice ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
Tmin = 0.831, Tmax = 0.862	l = −11→11
11266 measured 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0317P)2 + 1.6713P] where P = (Fo2 + 2Fc2)/3
2531 reflections	(Δ/σ)max < 0.001
116 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −0.74 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.02894 (16)
Br1	0.69586 (6)	0.10330 (3)	0.63849 (6)	0.06334 (18)
C1	0.8076 (5)	0.5280 (2)	0.7876 (4)	0.0410 (8)
H1B	0.9228	0.5334	0.8406	0.061*
H1C	0.7344	0.5312	0.8633	0.061*
C2	0.7698 (4)	0.6042 (2)	0.6830 (4)	0.0362 (8)
C3	0.5246 (5)	0.6761 (2)	0.5232 (5)	0.0546 (11)
H3A	0.5877	0.6831	0.4405	0.065*
H3B	0.5384	0.7273	0.5854	0.065*
C4	0.3413 (5)	0.6610 (2)	0.4621 (5)	0.0536 (11)
H4A	0.2748	0.6656	0.5429	0.064*
H4B	0.3003	0.7030	0.3846	0.064*
C5	0.2117 (4)	0.5591 (2)	0.2827 (4)	0.0343 (7)
C6	0.8765 (5)	0.6034 (3)	0.5571 (5)	0.0503 (10)
H6A	0.8525	0.5525	0.4972	0.075*
H6B	0.9941	0.6044	0.6013	0.075*
H6C	0.8503	0.6528	0.4937	0.075*
C7	0.8061 (5)	0.6849 (3)	0.7812 (5)	0.0561 (11)
H7A	0.7833	0.7348	0.7184	0.084*
H7B	0.9225	0.6851	0.8290	0.084*
H7C	0.7353	0.6853	0.8576	0.084*
C8	0.0896 (5)	0.6244 (3)	0.2077 (5)	0.0528 (10)
H8A	0.0147	0.5984	0.1252	0.079*
H8B	0.1504	0.6702	0.1695	0.079*
H8C	0.0252	0.6468	0.2802	0.079*
N1	0.5857 (3)	0.60021 (16)	0.6151 (3)	0.0332 (6)
H1A	0.5300	0.6015	0.6957	0.040*
N2	0.3276 (3)	0.57404 (17)	0.3970 (3)	0.0333 (6)
O1	0.6240 (6)	0.8913 (2)	0.6616 (5)	0.0923 (12)
H1E	0.6525	0.9438	0.6665	0.111*
H1F	0.5421	0.8854	0.5885	0.111*

	U11	U22	U33	U12	U13	U23
Ni1	0.0263 (3)	0.0225 (3)	0.0368 (3)	0.0004 (2)	0.0016 (2)	0.0001 (3)
Br1	0.0521 (3)	0.0655 (3)	0.0752 (4)	−0.0076 (2)	0.0189 (2)	−0.0112 (2)
C1	0.041 (2)	0.046 (2)	0.0338 (19)	0.0010 (16)	−0.0019 (16)	−0.0021 (16)
C2	0.0299 (17)	0.0349 (19)	0.042 (2)	−0.0014 (14)	0.0011 (15)	−0.0035 (15)
C3	0.057 (3)	0.0238 (17)	0.075 (3)	−0.0031 (17)	−0.012 (2)	0.0055 (19)
C4	0.050 (2)	0.0277 (19)	0.074 (3)	0.0112 (17)	−0.013 (2)	−0.0055 (19)
C5	0.0321 (17)	0.0398 (19)	0.0319 (18)	0.0022 (14)	0.0079 (14)	0.0059 (15)
C6	0.043 (2)	0.051 (2)	0.061 (3)	−0.0022 (18)	0.021 (2)	0.008 (2)
C7	0.051 (2)	0.041 (2)	0.071 (3)	−0.0062 (18)	−0.004 (2)	−0.012 (2)
C8	0.048 (2)	0.057 (3)	0.048 (2)	0.019 (2)	−0.0043 (19)	0.003 (2)
N1	0.0299 (14)	0.0264 (14)	0.0430 (17)	−0.0001 (11)	0.0051 (12)	−0.0013 (12)
N2	0.0321 (15)	0.0257 (14)	0.0407 (16)	0.0040 (11)	0.0025 (13)	0.0021 (12)
O1	0.103 (3)	0.070 (2)	0.097 (3)	0.013 (2)	−0.001 (2)	0.019 (2)

Ni1—N2	1.916 (3)	C4—H4B	0.9700
Ni1—N2i	1.916 (3)	C5—N2	1.282 (4)
Ni1—N1	1.934 (3)	C5—C8	1.494 (5)
Ni1—N1i	1.934 (3)	C5—C1i	1.494 (5)
C1—C5i	1.494 (5)	C6—H6A	0.9600
C1—C2	1.513 (5)	C6—H6B	0.9600
C1—H1B	0.9700	C6—H6C	0.9600
C1—H1C	0.9700	C7—H7A	0.9600
C2—N1	1.503 (4)	C7—H7B	0.9600
C2—C6	1.525 (5)	C7—H7C	0.9600
C2—C7	1.535 (5)	C8—H8A	0.9600
C3—N1	1.477 (4)	C8—H8B	0.9600
C3—C4	1.501 (5)	C8—H8C	0.9600
C3—H3A	0.9700	N1—H1A	0.9100
C3—H3B	0.9700	O1—H1E	0.8500
C4—N2	1.475 (5)	O1—H1F	0.8500
C4—H4A	0.9700
N2—Ni1—N2i	180.000 (1)	N2—C5—C1i	120.7 (3)
N2—Ni1—N1	86.01 (12)	C8—C5—C1i	114.8 (3)
N2i—Ni1—N1	93.99 (12)	C2—C6—H6A	109.5
N2—Ni1—N1i	93.99 (12)	C2—C6—H6B	109.5
N2i—Ni1—N1i	86.01 (12)	H6A—C6—H6B	109.5
N1—Ni1—N1i	180.0	C2—C6—H6C	109.5
C5i—C1—C2	117.5 (3)	H6A—C6—H6C	109.5
C5i—C1—H1B	107.9	H6B—C6—H6C	109.5
C2—C1—H1B	107.9	C2—C7—H7A	109.5
C5i—C1—H1C	107.9	C2—C7—H7B	109.5
C2—C1—H1C	107.9	H7A—C7—H7B	109.5
H1B—C1—H1C	107.2	C2—C7—H7C	109.5
N1—C2—C1	107.3 (3)	H7A—C7—H7C	109.5
N1—C2—C6	109.9 (3)	H7B—C7—H7C	109.5
C1—C2—C6	111.7 (3)	C5—C8—H8A	109.5
N1—C2—C7	110.1 (3)	C5—C8—H8B	109.5
C1—C2—C7	107.1 (3)	H8A—C8—H8B	109.5
C6—C2—C7	110.6 (3)	C5—C8—H8C	109.5
N1—C3—C4	106.8 (3)	H8A—C8—H8C	109.5
N1—C3—H3A	110.4	H8B—C8—H8C	109.5
C4—C3—H3A	110.4	C3—N1—C2	113.8 (3)
N1—C3—H3B	110.4	C3—N1—Ni1	107.4 (2)
C4—C3—H3B	110.4	C2—N1—Ni1	119.1 (2)
H3A—C3—H3B	108.6	C3—N1—H1A	105.1
N2—C4—C3	106.9 (3)	C2—N1—H1A	105.1
N2—C4—H4A	110.3	Ni1—N1—H1A	105.1
C3—C4—H4A	110.3	C5—N2—C4	118.5 (3)
N2—C4—H4B	110.3	C5—N2—Ni1	129.9 (2)
C3—C4—H4B	110.3	C4—N2—Ni1	111.5 (2)
H4A—C4—H4B	108.6	H1E—O1—H1F	108.1
N2—C5—C8	124.5 (3)
C5i—C1—C2—N1	64.1 (4)	N2—Ni1—N1—C2	−154.2 (3)
C5i—C1—C2—C6	−56.4 (4)	N2i—Ni1—N1—C2	25.8 (3)
C5i—C1—C2—C7	−177.6 (3)	N1i—Ni1—N1—C2	79 (100)
N1—C3—C4—N2	−48.4 (5)	C8—C5—N2—C4	1.2 (5)
C4—C3—N1—C2	179.0 (3)	C1i—C5—N2—C4	180.0 (3)
C4—C3—N1—Ni1	45.0 (4)	C8—C5—N2—Ni1	−176.6 (3)
C1—C2—N1—C3	173.5 (3)	C1i—C5—N2—Ni1	2.2 (5)
C6—C2—N1—C3	−64.9 (4)	C3—C4—N2—C5	−148.4 (4)
C7—C2—N1—C3	57.2 (4)	C3—C4—N2—Ni1	29.8 (4)
C1—C2—N1—Ni1	−58.4 (3)	N2i—Ni1—N2—C5	−65 (100)
C6—C2—N1—Ni1	63.2 (3)	N1—Ni1—N2—C5	173.9 (3)
C7—C2—N1—Ni1	−174.7 (3)	N1i—Ni1—N2—C5	−6.1 (3)
N2—Ni1—N1—C3	−23.2 (3)	N2i—Ni1—N2—C4	117 (100)
N2i—Ni1—N1—C3	156.8 (3)	N1—Ni1—N2—C4	−4.0 (3)
N1i—Ni1—N1—C3	−150 (100)	N1i—Ni1—N2—C4	176.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ii	0.91	2.53	3.413 (3)	164
O1—H1E···Br1iii	0.85	2.53	3.374 (3)	169
O1—H1F···Br1i	0.85	2.55	3.388 (5)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1i	0.91	2.53	3.413 (3)	164
O1—H1E⋯Br1ii	0.85	2.53	3.374 (3)	169
O1—H1F⋯Br1iii	0.85	2.55	3.388 (5)	170

Symmetry codes: (i) ; (ii) ; (iii) .