Triaqua-(1,4,7-triaza-cyclo-nonane-κN,N,N)nickel(II) bromide nitrate.

In the title half-sandwich compound, [Ni(C(6)H(15)N(3))(H(2)O)(3)]Br(NO(3)), the central Ni(II) ion, lying on a threefold rotation axis, is six-coordinated by three amine N atoms from the face-capping triaza macrocycle and three water O atoms in a slightly distorted octa-hedral geometry. In the crystal, O-H⋯O hydrogen bonding and weak O-H⋯Br inter-actions associate the Ni(II) cations and the counter-ions into a three-dimensional supra-molecular network.

Related literature

For the preparation of 1,4,7-triaza­cyclo­nonane trihydro­bromide, see: Koyama & Yoshino (1972 ▶). For the applications of metal complexes containing 1,4,7-triaza­cyclo­nonane as small-mol­ecule models of metalloenzymes and metalloproteins and as mol­ecule-based magnets, see: Berseth et al. (2000 ▶); Chaudhury et al. (1985 ▶); Cheng et al. (2004 ▶); Deal et al. (1996 ▶); Hegg & Burstyn (1995 ▶); Hegg et al. (1997 ▶); Lin et al. (2001 ▶); Poganiuch et al. (1991 ▶); Williams et al. (1999 ▶). For related NiII complexes with 1,4,7-triaza­cyclo­nonane, see: Bencini et al. (1990 ▶); Stranger et al. (1992 ▶); Wang et al. (2003 ▶, 2005 ▶); Zompa & Margulis (1978 ▶).

Experimental

Crystal data

[Ni(C6H15N3)(H2O)3]Br(NO3)

M = 383.89

Cubic,

a = 11.300 (1) Å

V = 1442.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.14 mm−1

T = 298 K

0.29 × 0.27 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.320, T max = 0.480

15223 measured reflections

1110 independent reflections

985 reflections with I > 2σ(I)

R int = 0.080

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.072

S = 1.03

1110 reflections

61 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.47 e Å−3

Absolute structure: Flack (1983 ▶), 475 Friedel pairs

Flack parameter: 0.01 (3)

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681001620X/pb2027sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001620X/pb2027Isup2.hkl

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

[Ni(C6H15N3)(H2O)3]Br(NO3)	Dx = 1.767 Mg m−3
Mr = 383.89	Mo Kα radiation, λ = 0.71073 Å
Cubic, P213	Cell parameters from 13409 reflections
Hall symbol: P 2ac 2ab 3	θ = 3.1–27.4°
a = 11.300 (1) Å	µ = 4.14 mm−1
V = 1442.9 (3) Å3	T = 298 K
Z = 4	Plate, green
F(000) = 784	0.29 × 0.27 × 0.18 mm

Bruker APEXII CCD area-detector diffractometer	1110 independent reflections
Radiation source: fine-focus sealed tube	985 reflections with I > 2σ(I)
graphite	Rint = 0.080
φ and ω scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −14→14
Tmin = 0.320, Tmax = 0.480	k = −14→14
15223 measured reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.072	w = 1/[σ2(Fo2) + (0.0232P)2 + 1.6516P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
8717 reflections	Δρmax = 0.36 e Å−3
61 parameters	Δρmin = −0.46 e Å−3
0 restraints	Absolute structure: Flack (1983), 475 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (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 > 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	1.06169 (4)	0.56169 (4)	0.93831 (4)	0.02729 (19)
Br1	0.25347 (4)	0.24653 (4)	0.75347 (4)	0.0437 (2)
C1	0.8566 (4)	0.4233 (4)	0.8872 (4)	0.0437 (11)
H1A	0.8123	0.3498	0.8858	0.052*
H1B	0.8438	0.4636	0.8125	0.052*
C2	1.0118 (4)	0.3128 (4)	0.9995 (4)	0.0449 (11)
H2A	1.0326	0.2365	0.9660	0.054*
H2B	0.9417	0.3022	1.0478	0.054*
N1	0.9850 (3)	0.3973 (3)	0.9019 (3)	0.0353 (8)
H3	1.0226	0.3631	0.8407	0.053*
N2	0.9466 (3)	0.9466 (3)	0.9466 (3)	0.0316 (11)
O1	1.0196 (3)	0.6447 (3)	0.7786 (3)	0.0391 (8)
O2	0.8854 (3)	1.0345 (3)	0.9196 (3)	0.0577 (9)
H4B	0.947 (5)	0.659 (4)	0.765 (4)	0.050 (14)*
H4A	1.040 (4)	0.598 (4)	0.723 (4)	0.050 (14)*

	U11	U22	U33	U12	U13	U23
Ni1	0.02729 (19)	0.02729 (19)	0.02729 (19)	−0.0011 (2)	0.0011 (2)	0.0011 (2)
Br1	0.0437 (2)	0.0437 (2)	0.0437 (2)	−0.0012 (2)	0.0012 (2)	−0.0012 (2)
C1	0.041 (2)	0.042 (3)	0.049 (3)	−0.016 (2)	−0.009 (2)	0.005 (2)
C2	0.054 (3)	0.027 (2)	0.054 (3)	−0.0022 (19)	0.010 (2)	0.0063 (19)
N1	0.0365 (19)	0.0349 (19)	0.0346 (19)	−0.0022 (14)	0.0050 (14)	−0.0021 (14)
N2	0.0316 (11)	0.0316 (11)	0.0316 (11)	0.0002 (15)	0.0002 (15)	0.0002 (15)
O1	0.0424 (18)	0.0419 (18)	0.0330 (18)	0.0052 (14)	−0.0007 (13)	0.0024 (12)
O2	0.055 (2)	0.054 (2)	0.065 (2)	0.0156 (16)	0.0149 (17)	0.0133 (18)

Ni1—O1i	2.089 (3)	C2—N1	1.490 (5)
Ni1—O1	2.089 (3)	C2—C1ii	1.520 (6)
Ni1—O1ii	2.089 (3)	C2—H2A	0.9700
Ni1—N1	2.091 (3)	C2—H2B	0.9700
Ni1—N1ii	2.091 (3)	N1—H3	0.8987
Ni1—N1i	2.091 (3)	N2—O2iii	1.248 (3)
C1—N1	1.490 (6)	N2—O2iv	1.248 (3)
C1—C2i	1.520 (6)	N2—O2	1.248 (3)
C1—H1A	0.9700	O1—H4B	0.85 (5)
C1—H1B	0.9700	O1—H4A	0.84 (4)
O1i—Ni1—O1	84.90 (14)	H1A—C1—H1B	108.1
O1i—Ni1—O1ii	84.90 (14)	N1—C2—C1ii	111.7 (3)
O1—Ni1—O1ii	84.90 (14)	N1—C2—H2A	109.3
O1i—Ni1—N1	177.00 (13)	C1ii—C2—H2A	109.3
O1—Ni1—N1	97.72 (13)	N1—C2—H2B	109.3
O1ii—Ni1—N1	93.87 (12)	C1ii—C2—H2B	109.3
O1i—Ni1—N1ii	93.87 (12)	H2A—C2—H2B	108.0
O1—Ni1—N1ii	177.00 (13)	C1—N1—C2	114.0 (3)
O1ii—Ni1—N1ii	97.72 (12)	C1—N1—Ni1	104.5 (3)
N1—Ni1—N1ii	83.58 (14)	C2—N1—Ni1	109.8 (3)
O1i—Ni1—N1i	97.72 (12)	C1—N1—H3	117.3
O1—Ni1—N1i	93.87 (12)	C2—N1—H3	101.4
O1ii—Ni1—N1i	177.00 (13)	Ni1—N1—H3	109.7
N1—Ni1—N1i	83.58 (14)	O2iii—N2—O2iv	119.999 (2)
N1ii—Ni1—N1i	83.58 (14)	O2iii—N2—O2	120.000 (3)
N1—C1—C2i	110.3 (4)	O2iv—N2—O2	120.000 (2)
N1—C1—H1A	109.6	Ni1—O1—H4B	117 (4)
C2i—C1—H1A	109.6	Ni1—O1—H4A	107 (4)
N1—C1—H1B	109.6	H4B—O1—H4A	104 (5)
C2i—C1—H1B	109.6
C2i—C1—N1—C2	72.1 (5)	N1ii—Ni1—N1—C1	114.6 (2)
C2i—C1—N1—Ni1	−47.8 (4)	N1i—Ni1—N1—C1	30.4 (3)
C1ii—C2—N1—C1	−133.2 (4)	O1—Ni1—N1—C2	174.6 (3)
C1ii—C2—N1—Ni1	−16.3 (4)	O1ii—Ni1—N1—C2	89.3 (3)
O1—Ni1—N1—C1	−62.7 (3)	N1ii—Ni1—N1—C2	−8.1 (3)
O1ii—Ni1—N1—C1	−148.0 (3)	N1i—Ni1—N1—C2	−92.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H4A···O2v	0.84 (4)	1.95 (5)	2.776 (5)	162 (4)
O1—H4B···Br1vi	0.85 (5)	2.48 (5)	3.312 (3)	167 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H4A⋯O2i	0.84 (4)	1.95 (5)	2.776 (5)	162 (4)
O1—H4B⋯Br1ii	0.85 (5)	2.48 (5)	3.312 (3)	167 (4)

Symmetry codes: (i) ; (ii) .