5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazo-niacyclo-tetra-deca-4,11-diene dichloride trihydrate.

In the title compound, C(16)H(34)N(4) (2+)·2Cl(-)·3H(2)O, 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 ▶); n class="Disease">Curtis et al. (1975 ▶). For applications of macrocyclic compounds, see: Mittal et al. (2008 ▶); Yatsimirskii (1990 ▶).

Experimental

Crystal data

C16H34N4 2+·2Cl−·3H2O

M = 407.42

Triclinic,

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[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.136

S = 1.07

3987 reflections

248 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.16 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016649/hg5196sup1.cif

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

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

C16H34N42+·2Cl−·3H2O	Z = 2
Mr = 407.42	F(000) = 444
Triclinic, P1	Dx = 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

Bruker SMART APEX CCD area-detector diffractometer	3987 independent reflections
Radiation source: fine-focus sealed tube	2878 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 83.66 pixels mm-1	θmax = 25.0°, θmin = 1.6°
ω scan	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→12
Tmin = 0.897, Tmax = 0.961	l = −15→15
11977 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)] = 0.055	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(Fo2) + (0.0559P)2 + 0.1922P] where P = (Fo2 + 2Fc2)/3
3987 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.16 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
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*

	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)

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)

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

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) .