5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazo­niacyclo­tetra­deca-4,11-diene dichloride trihydrate

Ismail, W.; Yamin, B.M.; Daran, J.-C.

doi:10.1107/S1600536812016649

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1476-o1477

doi:10.1107/S1600536812016649

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5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazoniacyclotetradeca-4,11-diene dichloride trihydrate

Wafiuddin Ismail,^a Bohari M. Yamin ^a ^* and Jean-Claude Daran ^b

^aLow Carbon Energy Research Group, School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia, and ^bLaboratoire de Chimie de Coordination, UPR5241, 205, route de Narbonne 31077, Toulose Cedex 04, France
^*Correspondence e-mail: bohari@ukm.my

(Received 20 March 2012; accepted 16 April 2012; online 21 April 2012)

In the title compound, C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O, the two protonated N atoms in the macrocyclic ring of the dication are located at diagonally opposite positions. There are two intramolecular N—H⋯N hydrogen bonds in the cation. The crystal structure features O—H⋯Cl, O—H⋯O, C—H⋯Cl and N—H⋯Cl hydrogen bonds.

Related literature

For related structures, see: Bi et al. (2008 ); He et al. (2010 ); Heeg et al. (1981 ); Heinlein & Tebbe (1985 ); Kennedy et al. (2011 ); Rohovec et al. (1999 ). For bond-length data, see: Allen et al. (1987 ). For the preparation, see: Curtis & Hay (1966 ); Curtis et al. (1975 ). For applications of macrocyclic compounds, see: Mittal et al. (2008 ); Yatsimirskii (1990 ).

Experimental

Crystal data

C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O
M_r = 407.42
Triclinic, $[P \overline 1]$
a = 8.576 (4) Å
b = 10.735 (4) Å
c = 13.438 (6) Å
α = 73.752 (9)°
β = 86.085 (9)°
γ = 71.886 (8)°
V = 1128.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 298 K
0.36 × 0.14 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.897, T_max = 0.961
11977 measured reflections
3987 independent reflections
2878 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.136
S = 1.07
3987 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯N1	0.90 (3)	2.02 (3)	2.732 (3)	135.6 (18)
N4—H2N4⋯N3	0.86 (3)	2.03 (3)	2.740 (3)	140 (2)
O1W—H2W1⋯Cl1	0.82	2.54	3.343 (4)	167
O2W—H2W2⋯Cl1	0.82	2.51	3.324 (3)	168
O3W—H1W3⋯Cl1	0.83	2.53	3.298 (3)	156
O3W—H2W3⋯Cl2	0.82	2.32	3.138 (3)	175
N2—H1N2⋯Cl1	0.92 (3)	2.28 (3)	3.201 (3)	177 (3)
N4—H1N4⋯Cl2	0.93 (3)	2.27 (3)	3.178 (3)	167 (2)
O1W—H1W1⋯Cl2ⁱ	0.82	2.49	3.282 (3)	163
O2W—H1W2⋯O3Wⁱ	0.82	2.16	2.955 (4)	161
C9—H9B⋯Cl2ⁱ	0.97	2.75	3.709 (3)	172
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016649/hg5196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016649/hg5196Isup2.hkl

checkCIF report

Comment top

The structures of tetraazacyclotetradeca-4,11-diene macrocyclic complexes with metal such as cobalt, nickel, zinc have been extensively studied (Heeg et al., 1981; He et al., 2010; Heinlein et al., 1985). Some macrocyclic compounds and their complexes have been applied as ionophores for metal ions determination and catalyst for several reactions (Mittal et al., 2008; Yatsimirskii 1990). However, the structure of the macrocyclic salts are still less reported. So far, the macrocyclic salts with perchlorate, bromide and iodide anion have been reported (Rohovec et al., 1999; Kennedy et al., 2011; Bi et al., 2008). The unit-cell parameters for the bromide and iodide salt are similar and the two salts are indeed isostructural. The title compound (I) is similar to those salts but the presence of trihydrate water molecules caused the unit-cell parameters to be different. The unit cell of the salt consists of symmetrically generated macrocyclic dication, two chloride anions atoms and three water molecules of crystallization (Fig.1). The bond lengths are in normal ranges (Allen et al. 2003) and comparable to those in the bromide and iodide salts. There are seven intramolecular hydrogen bonds, two of them are in the macrocyclic ring N2-H1N2..N1 and N4-H2N4..N3 and the other five, O1-H2W1..Cl1, O2-H2W2..Cl1, O3-H1W3..Cl1, O3W-H2W3..Cl2 and N4-H1N4..Cl2 are formed between chlorine atom and hydrogen atom of the water molecule and nitrogen atom of the macrocyclic ring. In the crystal structure, the molecules are linked by intermolecular hydrogen bond, O1W-H1W1..Cl2, O2W-H1W2..O3W and C9—H9B..Cl2 (symmetry as in table 2) together with the OW—H..Cl and N—H..Cl intramolecular hydrogen bonds.

Related literature top

For related structures, see: Bi et al. (2008); He et al. (2010); Heeg et al. (1981); Heinlein & Tebbe (1985); Kennedy et al. (2011); Rohovec et al. (1999). For bond-length data, see: Allen et al. (1987). For the preparation, see: Curtis & Hay (1966); Curtis et al. (1975). For applications of macrocyclic compounds, see: Mittal et al. (2008); Yatsimirskii (1990).

Experimental top

All solvents and chemicals were of analytical grade and were used without purification. The macrocylic compound was prepared according to the literature methods (Curtis et al., 1966; Curtis et al., 1975) but with the addition of stoichiometric amounts of ammonium chloride (0.01 mol, 0.534 g) and ethylenediamine (0.01 mol, 0.601 g) in 30 ml acetone. Single crystals were obtained from the solution after one day of evaporation (yield 82%, m.p 372.1–372.8 K). IR(KBr)v_max, cm^-1: 1667.1 (C=N); 3468.2 (NH); 1227.9 (C—N); 3012.4(CH₃). Elemental analysis: Calc. for C₁₆H₄₀N₄O₃ Cl₂(C: 47.2; N: 13.7; H: 9.4%) Found (C: 46.9; N: 13.26; H: 9.3%). ¹H NMR (p.p.m.,CD₃OH), δ_H: 1.5 (s,12H,C-(CH₃)₂); 2.1 (s,6H,C—CH₃); 2.8 (s,4H,C—CH₂—C); 3.3 (m,4H,CH₂—CH₂); 3.8 (m,4H,CH₂—CH₂); 5.1 (s,2H,NH₂). ¹³C NMR (p.p.m.,CD₃OH), δ_C: 175.9 (N=C—C); 58.4 (C—C—N); 47.4 (C=N—CH₂); 43.91 (N—CH₂—C); 40.0 (C—CH₂—C); 23.47 (N=C—CH₃); 20.65 (C-(CH₃)₂).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsods are drawn at the 50% probability level. The dashed line indicate intramolecular hydrogen bond. The unlabelled atoms are symmetrically generated (1-x, 1-y,-z).

5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazoniacyclotetradeca-4,11-diene dichloride trihydrate top

Crystal data top

C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O	Z = 2
M_r = 407.42	F(000) = 444
Triclinic, P1	D_x = 1.199 Mg m⁻³
Hall symbol: -P 1	Melting point = 372.1–372.8 K
a = 8.576 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.735 (4) Å	Cell parameters from 2072 reflections
c = 13.438 (6) Å	θ = 1.6–25.0°
α = 73.752 (9)°	µ = 0.31 mm⁻¹
β = 86.085 (9)°	T = 298 K
γ = 71.886 (8)°	Block, colourless
V = 1128.7 (8) Å³	0.36 × 0.14 × 0.13 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3987 independent reflections
Radiation source: fine-focus sealed tube	2878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.0°, θ_min = 1.6°
ω scan	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→12
T_min = 0.897, T_max = 0.961	l = −15→15
11977 measured reflections

Refinement top

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0559P)² + 0.1922P] where P = (F_o² + 2F_c²)/3
3987 reflections	(Δ/σ)_max < 0.001
248 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O	γ = 71.886 (8)°
M_r = 407.42	V = 1128.7 (8) Å³
Triclinic, P1	Z = 2
a = 8.576 (4) Å	Mo Kα radiation
b = 10.735 (4) Å	µ = 0.31 mm⁻¹
c = 13.438 (6) Å	T = 298 K
α = 73.752 (9)°	0.36 × 0.14 × 0.13 mm
β = 86.085 (9)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3987 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2878 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.961	R_int = 0.051
11977 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.28 e Å⁻³
3987 reflections	Δρ_min = −0.16 e Å⁻³
248 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.54889 (10)	0.63892 (9)	0.26242 (6)	0.0731 (3)
Cl2	0.91229 (9)	0.98055 (8)	0.24245 (6)	0.0552 (2)
O1W	0.2897 (3)	0.9092 (3)	0.3252 (2)	0.1010 (9)
H1W1	0.2055	0.9197	0.2942	0.151*
H2W1	0.3523	0.8513	0.2998	0.151*
O2W	0.2391 (3)	0.5665 (3)	0.18015 (19)	0.0887 (8)
H1W2	0.1576	0.6126	0.2037	0.133*
H2W2	0.3136	0.5769	0.2095	0.133*
O3W	0.9133 (3)	0.6822 (2)	0.26157 (19)	0.0869 (8)
H1W3	0.8192	0.6909	0.2442	0.130*
H2W3	0.9170	0.7602	0.2532	0.130*
N1	1.1625 (2)	0.3762 (2)	0.45434 (15)	0.0365 (5)
N2	0.8331 (3)	0.4327 (2)	0.42420 (16)	0.0336 (5)
H1N2	0.754 (3)	0.494 (3)	0.377 (2)	0.049 (8)*
H2N2	0.920 (3)	0.463 (2)	0.4218 (17)	0.032 (7)*
N3	0.3084 (2)	1.0996 (2)	0.03415 (16)	0.0394 (5)
N4	0.6102 (3)	1.1063 (2)	0.08282 (16)	0.0335 (5)
H1N4	0.688 (3)	1.061 (3)	0.136 (2)	0.054 (8)*
H2N4	0.542 (3)	1.063 (2)	0.0808 (17)	0.026 (6)*
C1	1.2999 (3)	0.4269 (3)	0.4597 (2)	0.0409 (6)
H1A	1.3631	0.4267	0.3971	0.049*
H1B	1.3712	0.3675	0.5182	0.049*
C2	1.1821 (3)	0.2496 (3)	0.47770 (18)	0.0365 (6)
C3	1.0377 (3)	0.2016 (3)	0.4681 (2)	0.0421 (6)
H3A	0.9935	0.1775	0.5367	0.051*
H3B	1.0785	0.1188	0.4460	0.051*
C4	0.8963 (3)	0.2984 (2)	0.39511 (19)	0.0365 (6)
C5	0.7616 (3)	0.4304 (3)	0.52835 (19)	0.0392 (6)
H5A	0.8443	0.3738	0.5815	0.047*
H5B	0.6717	0.3918	0.5368	0.047*
C6	1.3381 (3)	0.1384 (3)	0.5155 (3)	0.0673 (9)
H6A	1.4014	0.1686	0.5548	0.101*
H6B	1.4000	0.1158	0.4573	0.101*
H6C	1.3131	0.0595	0.5587	0.101*
C7	0.9524 (3)	0.3337 (3)	0.2835 (2)	0.0477 (7)
H7A	1.0376	0.3754	0.2794	0.072*
H7B	0.8613	0.3959	0.2397	0.072*
H7C	0.9936	0.2522	0.2612	0.072*
C8	0.7565 (3)	0.2372 (3)	0.4025 (2)	0.0503 (7)
H8A	0.7280	0.2089	0.4738	0.076*
H8B	0.7904	0.1600	0.3746	0.076*
H8C	0.6629	0.3043	0.3637	0.076*
C9	0.2026 (3)	1.0191 (3)	0.0267 (2)	0.0434 (7)
H9A	0.1299	1.0660	−0.0334	0.052*
H9B	0.1355	1.0093	0.0878	0.052*
C10	0.2476 (3)	1.2250 (3)	0.02649 (19)	0.0392 (6)
C11	0.3598 (3)	1.3067 (3)	0.0326 (2)	0.0446 (7)
H11A	0.2945	1.3883	0.0511	0.054*
H11B	0.4019	1.3353	−0.0360	0.054*
C12	0.5058 (3)	1.2355 (2)	0.10895 (19)	0.0385 (6)
C13	0.6969 (3)	1.1195 (3)	−0.01763 (19)	0.0418 (6)
H13A	0.7678	1.1756	−0.0216	0.050*
H13B	0.6174	1.1634	−0.0745	0.050*
C14	0.0690 (4)	1.3023 (3)	0.0107 (3)	0.0748 (10)
H14A	0.0055	1.2405	0.0349	0.112*
H14B	0.0458	1.3466	−0.0617	0.112*
H14C	0.0409	1.3694	0.0489	0.112*
C15	0.6104 (3)	1.3283 (3)	0.1027 (2)	0.0520 (7)
H15A	0.7093	1.2782	0.1434	0.078*
H15B	0.5504	1.4037	0.1290	0.078*
H15C	0.6378	1.3616	0.0318	0.078*
C16	0.4492 (3)	1.1912 (3)	0.2195 (2)	0.0495 (7)
H16A	0.5431	1.1463	0.2654	0.074*
H16B	0.3871	1.1296	0.2231	0.074*
H16C	0.3818	1.2697	0.2396	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0542 (5)	0.0882 (6)	0.0592 (5)	−0.0075 (4)	−0.0185 (4)	−0.0037 (4)
Cl2	0.0491 (4)	0.0642 (5)	0.0495 (4)	−0.0115 (4)	−0.0061 (3)	−0.0160 (3)
O1W	0.0910 (19)	0.115 (2)	0.105 (2)	−0.0405 (17)	−0.0193 (16)	−0.0280 (17)
O2W	0.0793 (17)	0.102 (2)	0.0905 (18)	−0.0236 (15)	−0.0020 (14)	−0.0391 (15)
O3W	0.0810 (17)	0.0622 (15)	0.112 (2)	−0.0201 (13)	0.0023 (15)	−0.0176 (14)
N1	0.0298 (11)	0.0359 (13)	0.0439 (12)	−0.0045 (9)	−0.0044 (9)	−0.0161 (10)
N2	0.0287 (11)	0.0356 (12)	0.0376 (12)	−0.0097 (10)	−0.0039 (9)	−0.0109 (10)
N3	0.0308 (11)	0.0423 (13)	0.0488 (13)	−0.0118 (10)	−0.0020 (9)	−0.0169 (10)
N4	0.0335 (11)	0.0338 (12)	0.0365 (12)	−0.0138 (10)	−0.0049 (10)	−0.0096 (9)
C1	0.0317 (13)	0.0498 (16)	0.0449 (15)	−0.0112 (12)	0.0008 (11)	−0.0201 (13)
C2	0.0345 (14)	0.0353 (15)	0.0347 (14)	−0.0032 (11)	0.0008 (11)	−0.0101 (11)
C3	0.0444 (15)	0.0318 (14)	0.0508 (16)	−0.0092 (12)	0.0013 (12)	−0.0152 (12)
C4	0.0386 (14)	0.0360 (14)	0.0412 (14)	−0.0130 (11)	−0.0019 (11)	−0.0177 (11)
C5	0.0383 (14)	0.0452 (15)	0.0387 (14)	−0.0180 (12)	0.0040 (11)	−0.0137 (12)
C6	0.0405 (16)	0.0421 (17)	0.100 (3)	0.0022 (14)	−0.0053 (16)	−0.0044 (17)
C7	0.0495 (16)	0.0565 (17)	0.0431 (16)	−0.0176 (14)	0.0012 (13)	−0.0214 (13)
C8	0.0513 (17)	0.0551 (18)	0.0588 (18)	−0.0248 (14)	0.0019 (14)	−0.0283 (15)
C9	0.0345 (14)	0.0575 (17)	0.0491 (16)	−0.0210 (13)	0.0061 (12)	−0.0249 (13)
C10	0.0345 (14)	0.0445 (16)	0.0371 (14)	−0.0064 (12)	−0.0045 (11)	−0.0139 (12)
C11	0.0440 (15)	0.0339 (14)	0.0525 (17)	−0.0050 (12)	−0.0091 (12)	−0.0117 (12)
C12	0.0394 (14)	0.0337 (14)	0.0460 (15)	−0.0102 (11)	−0.0045 (12)	−0.0164 (12)
C13	0.0436 (15)	0.0476 (16)	0.0419 (15)	−0.0244 (13)	0.0028 (12)	−0.0127 (12)
C14	0.0463 (18)	0.063 (2)	0.114 (3)	0.0041 (16)	−0.0190 (18)	−0.041 (2)
C15	0.0553 (17)	0.0420 (16)	0.0684 (19)	−0.0194 (14)	−0.0042 (15)	−0.0239 (14)
C16	0.0498 (16)	0.0545 (17)	0.0488 (17)	−0.0144 (14)	−0.0010 (13)	−0.0226 (14)

Geometric parameters (Å, º) top

O1W—H1W1	0.8197	C6—H6A	0.9600
O1W—H2W1	0.8227	C6—H6B	0.9600
O2W—H1W2	0.8219	C6—H6C	0.9600
O2W—H2W2	0.8240	C7—H7A	0.9600
O3W—H1W3	0.8259	C7—H7B	0.9600
O3W—H2W3	0.8234	C7—H7C	0.9600
N1—C2	1.265 (3)	C8—H8A	0.9600
N1—C1	1.457 (3)	C8—H8B	0.9600
N2—C5	1.486 (3)	C8—H8C	0.9600
N2—C4	1.525 (3)	C9—C13ⁱⁱ	1.504 (4)
N2—H1N2	0.92 (3)	C9—H9A	0.9700
N2—H2N2	0.90 (2)	C9—H9B	0.9700
N3—C10	1.260 (3)	C10—C14	1.495 (4)
N3—C9	1.459 (3)	C10—C11	1.509 (3)
N4—C13	1.489 (3)	C11—C12	1.532 (3)
N4—C12	1.518 (3)	C11—H11A	0.9700
N4—H1N4	0.93 (3)	C11—H11B	0.9700
N4—H2N4	0.86 (2)	C12—C15	1.517 (3)
C1—C5ⁱ	1.508 (3)	C12—C16	1.522 (4)
C1—H1A	0.9700	C13—C9ⁱⁱ	1.504 (4)
C1—H1B	0.9700	C13—H13A	0.9700
C2—C6	1.494 (3)	C13—H13B	0.9700
C2—C3	1.507 (3)	C14—H14A	0.9600
C3—C4	1.523 (3)	C14—H14B	0.9600
C3—H3A	0.9700	C14—H14C	0.9600
C3—H3B	0.9700	C15—H15A	0.9600
C4—C8	1.522 (3)	C15—H15B	0.9600
C4—C7	1.523 (4)	C15—H15C	0.9600
C5—C1ⁱ	1.508 (3)	C16—H16A	0.9600
C5—H5A	0.9700	C16—H16B	0.9600
C5—H5B	0.9700	C16—H16C	0.9600

H1W1—O1W—H2W1	98.0	H7A—C7—H7C	109.5
H1W2—O2W—H2W2	101.4	H7B—C7—H7C	109.5
H1W3—O3W—H2W3	105.5	C4—C8—H8A	109.5
C2—N1—C1	120.7 (2)	C4—C8—H8B	109.5
C5—N2—C4	118.08 (19)	H8A—C8—H8B	109.5
C5—N2—H1N2	106.4 (16)	C4—C8—H8C	109.5
C4—N2—H1N2	109.7 (16)	H8A—C8—H8C	109.5
C5—N2—H2N2	106.5 (15)	H8B—C8—H8C	109.5
C4—N2—H2N2	105.8 (15)	N3—C9—C13ⁱⁱ	110.7 (2)
H1N2—N2—H2N2	110 (2)	N3—C9—H9A	109.5
C10—N3—C9	120.1 (2)	C13ⁱⁱ—C9—H9A	109.5
C13—N4—C12	118.30 (19)	N3—C9—H9B	109.5
C13—N4—H1N4	108.3 (17)	C13ⁱⁱ—C9—H9B	109.5
C12—N4—H1N4	106.2 (16)	H9A—C9—H9B	108.1
C13—N4—H2N4	106.8 (15)	N3—C10—C14	124.9 (2)
C12—N4—H2N4	104.3 (15)	N3—C10—C11	119.1 (2)
H1N4—N4—H2N4	113 (2)	C14—C10—C11	116.0 (2)
N1—C1—C5ⁱ	110.30 (19)	C10—C11—C12	116.8 (2)
N1—C1—H1A	109.6	C10—C11—H11A	108.1
C5ⁱ—C1—H1A	109.6	C12—C11—H11A	108.1
N1—C1—H1B	109.6	C10—C11—H11B	108.1
C5ⁱ—C1—H1B	109.6	C12—C11—H11B	108.1
H1A—C1—H1B	108.1	H11A—C11—H11B	107.3
N1—C2—C6	126.2 (2)	C15—C12—N4	109.0 (2)
N1—C2—C3	119.0 (2)	C15—C12—C16	110.2 (2)
C6—C2—C3	114.9 (2)	N4—C12—C16	106.2 (2)
C2—C3—C4	118.2 (2)	C15—C12—C11	110.4 (2)
C2—C3—H3A	107.8	N4—C12—C11	109.54 (19)
C4—C3—H3A	107.8	C16—C12—C11	111.3 (2)
C2—C3—H3B	107.8	N4—C13—C9ⁱⁱ	109.9 (2)
C4—C3—H3B	107.8	N4—C13—H13A	109.7
H3A—C3—H3B	107.1	C9ⁱⁱ—C13—H13A	109.7
C8—C4—C3	110.6 (2)	N4—C13—H13B	109.7
C8—C4—C7	110.3 (2)	C9ⁱⁱ—C13—H13B	109.7
C3—C4—C7	111.4 (2)	H13A—C13—H13B	108.2
C8—C4—N2	108.9 (2)	C10—C14—H14A	109.5
C3—C4—N2	109.49 (19)	C10—C14—H14B	109.5
C7—C4—N2	106.1 (2)	H14A—C14—H14B	109.5
N2—C5—C1ⁱ	109.9 (2)	C10—C14—H14C	109.5
N2—C5—H5A	109.7	H14A—C14—H14C	109.5
C1ⁱ—C5—H5A	109.7	H14B—C14—H14C	109.5
N2—C5—H5B	109.7	C12—C15—H15A	109.5
C1ⁱ—C5—H5B	109.7	C12—C15—H15B	109.5
H5A—C5—H5B	108.2	H15A—C15—H15B	109.5
C2—C6—H6A	109.5	C12—C15—H15C	109.5
C2—C6—H6B	109.5	H15A—C15—H15C	109.5
H6A—C6—H6B	109.5	H15B—C15—H15C	109.5
C2—C6—H6C	109.5	C12—C16—H16A	109.5
H6A—C6—H6C	109.5	C12—C16—H16B	109.5
H6B—C6—H6C	109.5	H16A—C16—H16B	109.5
C4—C7—H7A	109.5	C12—C16—H16C	109.5
C4—C7—H7B	109.5	H16A—C16—H16C	109.5
H7A—C7—H7B	109.5	H16B—C16—H16C	109.5
C4—C7—H7C	109.5

C2—N1—C1—C5ⁱ	−157.0 (2)	C10—N3—C9—C13ⁱⁱ	169.2 (2)
C1—N1—C2—C6	2.0 (4)	C9—N3—C10—C14	0.6 (4)
C1—N1—C2—C3	−178.3 (2)	C9—N3—C10—C11	−179.0 (2)
N1—C2—C3—C4	22.6 (3)	N3—C10—C11—C12	−37.1 (4)
C6—C2—C3—C4	−157.6 (2)	C14—C10—C11—C12	143.3 (3)
C2—C3—C4—C8	−175.2 (2)	C13—N4—C12—C15	−55.2 (3)
C2—C3—C4—C7	61.8 (3)	C13—N4—C12—C16	−174.0 (2)
C2—C3—C4—N2	−55.2 (3)	C13—N4—C12—C11	65.7 (3)
C5—N2—C4—C8	58.2 (3)	C10—C11—C12—C15	177.6 (2)
C5—N2—C4—C3	−62.8 (3)	C10—C11—C12—N4	57.5 (3)
C5—N2—C4—C7	176.9 (2)	C10—C11—C12—C16	−59.7 (3)
C4—N2—C5—C1ⁱ	−177.59 (19)	C12—N4—C13—C9ⁱⁱ	178.0 (2)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···N1	0.90 (3)	2.02 (3)	2.732 (3)	135.6 (18)
N4—H2N4···N3	0.86 (3)	2.03 (3)	2.740 (3)	140 (2)
O1W—H2W1···Cl1	0.82	2.54	3.343 (4)	167
O2W—H2W2···Cl1	0.82	2.51	3.324 (3)	168
O3W—H1W3···Cl1	0.83	2.53	3.298 (3)	156
O3W—H2W3···Cl2	0.82	2.32	3.138 (3)	175
N2—H1N2···Cl1	0.92 (3)	2.28 (3)	3.201 (3)	177 (3)
N4—H1N4···Cl2	0.93 (3)	2.27 (3)	3.178 (3)	167 (2)
O1W—H1W1···Cl2ⁱⁱⁱ	0.82	2.49	3.282 (3)	163
O2W—H1W2···O3Wⁱⁱⁱ	0.82	2.16	2.955 (4)	161
C9—H9B···Cl2ⁱⁱⁱ	0.97	2.75	3.709 (3)	172

Symmetry code: (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O
M_r	407.42
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.576 (4), 10.735 (4), 13.438 (6)
α, β, γ (°)	73.752 (9), 86.085 (9), 71.886 (8)
V (Å³)	1128.7 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.36 × 0.14 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.897, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	11977, 3987, 2878
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.136, 1.07
No. of reflections	3987
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···N1	0.90 (3)	2.02 (3)	2.732 (3)	135.6 (18)
N4—H2N4···N3	0.86 (3)	2.03 (3)	2.740 (3)	140 (2)
O1W—H2W1···Cl1	0.82	2.54	3.343 (4)	167
O2W—H2W2···Cl1	0.82	2.51	3.324 (3)	168
O3W—H1W3···Cl1	0.83	2.53	3.298 (3)	156
O3W—H2W3···Cl2	0.82	2.32	3.138 (3)	175
N2—H1N2···Cl1	0.92 (3)	2.28 (3)	3.201 (3)	177 (3)
N4—H1N4···Cl2	0.93 (3)	2.27 (3)	3.178 (3)	167 (2)
O1W—H1W1···Cl2ⁱ	0.82	2.49	3.282 (3)	163
O2W—H1W2···O3Wⁱ	0.82	2.16	2.955 (4)	161
C9—H9B···Cl2ⁱ	0.97	2.75	3.709 (3)	172

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for research grant LRGS/BU/2011/USM-UKM/PG/02 and the Ministry of Science and Technology & Inovation (MOSTI) for an NSF scholarship to WI.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bi, J. H., Chen, Y., Huang, Z. X., Cui, M. & Hu, N. L. (2008). Asian J. Chem. 20, 4887–4890. CAS Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Curtis, N. F. & Hay, R. W. (1966). J. Chem. Soc. Chem. Commun. pp. 524–525. Google Scholar
Curtis, N. F., Hay, R. W. & Lawrance, G. A. (1975). J. Chem. Soc. Perkin Trans. 1, pp. 591–593. Google Scholar
He, X. L., Shi, F. & Lu, Y. (2010). Acta Cryst. E66, m1339. Web of Science CSD CrossRef IUCr Journals Google Scholar
Heeg, M. J., Endicott, J. F. & Glick, M. D. (1981). Inorg. Chem. 20, 1196–1201. CSD CrossRef CAS Web of Science Google Scholar
Heinlein, T. & Tebbe, K. F. (1985). Z. Kristallogr. 170, 70–71. Google Scholar
Kennedy, A. R., Lutta, S. T., Morrison, C. A., Okoth, M. O. & Orang'o, D. M. (2011). Acta Cryst. E67, o682–o683. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mittal, S. K., Kumar, S. K., Gupta, N. R., Ocak, M. & Ocak, U. (2008). Indian J. Chem. Sect. A, 47, 1676–1680. Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Rohovec, J., Vojtisek, P. & Lukes, I. (1999). Collect. Czech. Chem. Commun. 64, 73–88. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yatsimirskii, K. B. (1990). Usp. Khim. 59, 1960–1971. CrossRef CAS Google Scholar

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Volume 68| Part 5| May 2012| Pages o1476-o1477

doi:10.1107/S1600536812016649

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5,5,7,12,14,14-Hexa­methyl-1,8-di­aza-4,11-diazo­nia­cyclo­tetra­deca-4,11-diene dichloride trihydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazoniacyclotetradeca-4,11-diene dichloride trihydrate