5,7,7,12,14,14-Hexamethyl-4,8-diaza-1,11-diazo-niocyclotetra-deca-4,11-diene diiodide dihydrate.

The asymmetric unit of the title compound, C(16)H(34)N(4) (2+)·2I(-)·2H(2)O, contains one half-cation, one iodide anion and one water mol-ecule. The cation has crystallographically imposed centrosymmetric symmetry. Despite some differences in the unit-cell dimensions, packing analysis on a cluster of 15 cations and a comparison of the hydrogen bonding suggests that this compound is isostructural with its bromide analogue. Inter-molecular hydrogen bonding forms eight-membered [H-O-H⋯I](2) and [H-N-H⋯I](2) rings and creates a sheet structure.

Related literature

For the preparation and structure of the equivalent bromide salt, see: Rohovec et al. (1999 ▶). For the structure of the perchlorate salt, see: Bi et al. (2008 ▶). For structures of representative transition metal complexes, see: Bieńko et al. (2007 ▶); Yang (2005 ▶); Ballester et al. (2000 ▶); Endicott et al. (1981 ▶); Wester et al. (1977 ▶); Goedken et al. (1973 ▶). Macrocyclic metal complexes have been studied extensively owing to their similarity to metallobiomolecules, and in order to further understanding of biological mechanisms, see: Merrell et al. (1977 ▶). The packing analysis was performed with Mercury (Macrae et al., 2008 ▶).

Experimental

Crystal data

C16H34N4 2+·2I−·2H2O

M = 572.30

Triclinic,

a = 8.4098 (3) Å

b = 8.7252 (2) Å

c = 8.7724 (3) Å

α = 74.673 (2)°

β = 66.267 (1)°

γ = 75.809 (2)°

V = 561.24 (3) Å3

Z = 1

Mo Kα radiation

μ = 2.82 mm−1

T = 120 K

0.20 × 0.14 × 0.10 mm

Data collection

Bruker–Nonius Roper CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.673, T max = 0.746

12010 measured reflections

2563 independent reflections

2478 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.046

S = 1.18

2563 reflections

127 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.99 e Å−3

Δρmin = −0.75 e Å−3

Data collection: COLLECT (Hooft, 1988 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT ; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005848/rk2263sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005848/rk2263Isup2.hkl

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

C16H34N42+·2I−·2H2O	Z = 1
Mr = 572.30	F(000) = 284
Triclinic, P1	Dx = 1.693 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4098 (3) Å	Cell parameters from 10421 reflections
b = 8.7252 (2) Å	θ = 2.9–27.5°
c = 8.7724 (3) Å	µ = 2.82 mm−1
α = 74.673 (2)°	T = 120 K
β = 66.267 (1)°	Block, colourless
γ = 75.809 (2)°	0.20 × 0.14 × 0.10 mm
V = 561.24 (3) Å3

Bruker–Nonius Roper CCD diffractometer	2563 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2478 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.2°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −11→11
Tmin = 0.673, Tmax = 0.746	l = −11→11
12010 measured reflections

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)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.046	w = 1/[σ2(Fo2) + (0.0124P)2 + 0.33P] where P = (Fo2 + 2Fc2)/3
S = 1.18	(Δ/σ)max = 0.001
2563 reflections	Δρmax = 0.99 e Å−3
127 parameters	Δρmin = −0.75 e Å−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0243 (13)

Experimental. Southampton NCS collection 2010src0073

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 > 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
I1	0.214555 (16)	0.460869 (15)	0.757490 (15)	0.02330 (8)
O1W	0.6274 (2)	0.21795 (19)	0.5780 (2)	0.0336 (4)
H1W	0.525 (3)	0.270 (3)	0.633 (3)	0.050*
H2W	0.671 (3)	0.295 (3)	0.496 (3)	0.050*
N1	0.7414 (2)	0.60362 (18)	−0.1726 (2)	0.0139 (3)
N2	0.6077 (2)	0.29338 (18)	0.0038 (2)	0.0165 (3)
C1	0.7419 (3)	0.4771 (2)	−0.2576 (2)	0.0185 (4)
H1A	0.8389	0.4822	−0.3694	0.022*
H1B	0.6296	0.4954	−0.2762	0.022*
C2	0.7653 (3)	0.3134 (2)	−0.1486 (3)	0.0209 (4)
H2A	0.7880	0.2286	−0.2140	0.025*
H2B	0.8680	0.3019	−0.1159	0.025*
C3	0.6167 (3)	0.1933 (2)	0.1357 (3)	0.0174 (4)
C4	0.4514 (3)	0.1743 (2)	0.2906 (2)	0.0182 (4)
H4A	0.4494	0.2381	0.3696	0.022*
H4B	0.4604	0.0599	0.3474	0.022*
C5	0.2753 (3)	0.2226 (2)	0.2659 (2)	0.0158 (4)
C6	0.7788 (3)	0.0876 (3)	0.1592 (3)	0.0275 (5)
H6A	0.7804	−0.0226	0.1507	0.041*
H6B	0.7780	0.0881	0.2711	0.041*
H6C	0.8836	0.1283	0.0712	0.041*
C7	0.2617 (3)	0.1223 (2)	0.1546 (3)	0.0214 (4)
H7A	0.1452	0.1527	0.1456	0.032*
H7B	0.2788	0.0079	0.2052	0.032*
H7C	0.3523	0.1417	0.0414	0.032*
C8	0.1260 (3)	0.2045 (2)	0.4379 (3)	0.0235 (4)
H8A	0.1421	0.2616	0.5118	0.035*
H8B	0.1266	0.0902	0.4895	0.035*
H8C	0.0134	0.2502	0.4230	0.035*
H1N	0.649 (3)	0.599 (3)	−0.076 (3)	0.020 (6)*
H2N	0.829 (4)	0.584 (3)	−0.149 (3)	0.029 (7)*

	U11	U22	U33	U12	U13	U23
I1	0.01952 (10)	0.03155 (11)	0.01896 (10)	−0.00480 (6)	−0.00879 (7)	−0.00124 (6)
O1W	0.0384 (10)	0.0238 (8)	0.0371 (10)	−0.0029 (7)	−0.0157 (8)	−0.0017 (7)
N1	0.0139 (8)	0.0133 (7)	0.0155 (8)	−0.0038 (6)	−0.0075 (7)	0.0007 (6)
N2	0.0160 (8)	0.0143 (7)	0.0190 (8)	−0.0048 (6)	−0.0052 (7)	−0.0025 (6)
C1	0.0213 (10)	0.0168 (9)	0.0173 (10)	−0.0052 (7)	−0.0053 (8)	−0.0036 (7)
C2	0.0180 (10)	0.0141 (9)	0.0256 (11)	−0.0041 (7)	−0.0017 (8)	−0.0040 (8)
C3	0.0173 (9)	0.0153 (9)	0.0240 (10)	−0.0027 (7)	−0.0105 (8)	−0.0055 (7)
C4	0.0197 (10)	0.0172 (9)	0.0185 (9)	−0.0036 (7)	−0.0101 (8)	0.0011 (7)
C5	0.0190 (10)	0.0118 (8)	0.0171 (9)	−0.0053 (7)	−0.0092 (8)	0.0031 (7)
C6	0.0221 (11)	0.0293 (11)	0.0303 (12)	0.0028 (8)	−0.0137 (9)	−0.0038 (9)
C7	0.0261 (11)	0.0155 (9)	0.0284 (11)	−0.0071 (8)	−0.0154 (9)	−0.0012 (8)
C8	0.0212 (11)	0.0219 (10)	0.0218 (11)	−0.0070 (8)	−0.0055 (8)	0.0044 (8)

O1W—H1W	0.877 (17)	C4—C5	1.524 (3)
O1W—H2W	0.873 (17)	C4—H4A	0.9900
N1—C1	1.485 (2)	C4—H4B	0.9900
N1—C5i	1.524 (2)	C5—N1i	1.524 (2)
N1—H1N	0.89 (3)	C5—C8	1.524 (3)
N1—H2N	0.81 (3)	C5—C7	1.524 (3)
N2—C3	1.269 (3)	C6—H6A	0.9800
N2—C2	1.462 (2)	C6—H6B	0.9800
C1—C2	1.512 (3)	C6—H6C	0.9800
C1—H1A	0.9900	C7—H7A	0.9800
C1—H1B	0.9900	C7—H7B	0.9800
C2—H2A	0.9900	C7—H7C	0.9800
C2—H2B	0.9900	C8—H8A	0.9800
C3—C6	1.504 (3)	C8—H8B	0.9800
C3—C4	1.510 (3)	C8—H8C	0.9800
H1W—O1W—H2W	101 (2)	C5—C4—H4B	107.8
C1—N1—C5i	117.45 (15)	H4A—C4—H4B	107.1
C1—N1—H1N	107.0 (15)	N1i—C5—C4	109.64 (15)
C5i—N1—H1N	105.9 (15)	N1i—C5—C8	109.95 (16)
C1—N1—H2N	109.8 (18)	C4—C5—C8	109.65 (16)
C5i—N1—H2N	108.5 (18)	N1i—C5—C7	105.81 (15)
H1N—N1—H2N	108 (2)	C4—C5—C7	111.51 (16)
C3—N2—C2	120.48 (17)	C8—C5—C7	110.21 (16)
N1—C1—C2	109.64 (16)	C3—C6—H6A	109.5
N1—C1—H1A	109.7	C3—C6—H6B	109.5
C2—C1—H1A	109.7	H6A—C6—H6B	109.5
N1—C1—H1B	109.7	C3—C6—H6C	109.5
C2—C1—H1B	109.7	H6A—C6—H6C	109.5
H1A—C1—H1B	108.2	H6B—C6—H6C	109.5
N2—C2—C1	110.39 (16)	C5—C7—H7A	109.5
N2—C2—H2A	109.6	C5—C7—H7B	109.5
C1—C2—H2A	109.6	H7A—C7—H7B	109.5
N2—C2—H2B	109.6	C5—C7—H7C	109.5
C1—C2—H2B	109.6	H7A—C7—H7C	109.5
H2A—C2—H2B	108.1	H7B—C7—H7C	109.5
N2—C3—C6	127.05 (19)	C5—C8—H8A	109.5
N2—C3—C4	119.23 (17)	C5—C8—H8B	109.5
C6—C3—C4	113.71 (17)	H8A—C8—H8B	109.5
C3—C4—C5	118.10 (16)	C5—C8—H8C	109.5
C3—C4—H4A	107.8	H8A—C8—H8C	109.5
C5—C4—H4A	107.8	H8B—C8—H8C	109.5
C3—C4—H4B	107.8
C5i—N1—C1—C2	178.16 (16)	N2—C3—C4—C5	23.3 (3)
C3—N2—C2—C1	−156.80 (17)	C6—C3—C4—C5	−157.41 (17)
N1—C1—C2—N2	69.8 (2)	C3—C4—C5—N1i	−55.5 (2)
C2—N2—C3—C6	1.3 (3)	C3—C4—C5—C8	−176.29 (16)
C2—N2—C3—C4	−179.47 (16)	C3—C4—C5—C7	61.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2i	0.89 (3)	2.04 (3)	2.744 (2)	136 (2)
O1W—H1W···I1	0.88 (2)	2.71 (2)	3.5753 (18)	171 (3)
O1W—H2W···I1ii	0.87 (2)	2.68 (2)	3.5494 (17)	176 (3)
N1—H2N···I1ii	0.81 (3)	3.23 (3)	3.6895 (17)	119 (2)
N1—H2N···I1iii	0.81 (3)	2.99 (3)	3.7110 (18)	149 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2i	0.89 (3)	2.04 (3)	2.744 (2)	136 (2)
O1W—H1W⋯I1	0.88 (2)	2.71 (2)	3.5753 (18)	171 (3)
O1W—H2W⋯I1ii	0.87 (2)	2.68 (2)	3.5494 (17)	176 (3)
N1—H2N⋯I1ii	0.81 (3)	3.23 (3)	3.6895 (17)	119 (2)
N1—H2N⋯I1iii	0.81 (3)	2.99 (3)	3.7110 (18)	149 (2)

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