3,14-Diethyl-2,13-di-aza-6,17-diazonia-tri-cyclo-[16.4.0.0(7,12)]docosane dichloride tetra-hydrate from synchrotron radiation.

The asymmetric unit of title hydrated salt, C22H46N4 (2+)·2Cl(-)·4H2O, comprises half a centrosymmetric dication, one Cl(-) anion and two water mol-ecules of crystallization. The structure determination reveals that protonation has occurred at diagonally opposite amine N atoms, and that the dication features intra-molecular N-H⋯N hydrogen bonds. In the crystal, a three-dimensional artchitecture is formed by O-H⋯Cl/N and N-H⋯Cl/O hydrogen bonds.

Related literature

For background to the coordination chemistry of tetra­aza­macrocycles, see: Choi et al. (2010 ▶); De Clercq (2010 ▶). For the synthesis of the precursor macrocycle, see: Lim et al. (2006 ▶). For related structures, see: Choi et al. (2006 ▶, 2011 ▶).

Experimental

Crystal data

C22H46N4 2+·2Cl−·4H2O

M = 509.59

Monoclinic,

a = 22.122 (4) Å

b = 13.616 (3) Å

c = 10.565 (2) Å

β = 115.23 (3)°

V = 2878.5 (10) Å3

Z = 4

Synchrotron radiation

λ = 0.72000 Å

μ = 0.27 mm−1

T = 95 K

0.31 × 0.28 × 0.25 mm

Data collection

ADSC Q210 CCD area-detector diffractometer

Absorption correction: empirical (using intensity measurements) (HKL-3000 ; Otwinowski & Minor, 1997 ▶) T min = 0.922, T max = 0.937

13046 measured reflections

3663 independent reflections

3446 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.079

S = 1.05

3663 reflections

178 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.35 e Å−3

Data collection: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983 ▶); cell refinement: HKL3000sm (Otwinowski & Minor, 1997 ▶); data reduction: HKL3000sm; program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013; molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813027232/tk5261sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027232/tk5261Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813027232/tk5261Isup3.cml

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

C22H46N42+·2Cl−·4H2O	F(000) = 1120
Mr = 509.59	Dx = 1.176 Mg m−3
Monoclinic, C2/c	Synchrotron radiation, λ = 0.72000 Å
a = 22.122 (4) Å	Cell parameters from 31113 reflections
b = 13.616 (3) Å	θ = 1.3–66.4°
c = 10.565 (2) Å	µ = 0.27 mm−1
β = 115.23 (3)°	T = 95 K
V = 2878.5 (10) Å3	Block, colourless
Z = 4	0.31 × 0.28 × 0.25 mm

ADSC Q210 CCD area-detector diffractometer	3663 independent reflections
Radiation source: PLSII 2D bending magnet	3446 reflections with I > 2σ(I)
Si(111) double crystal monochromator	Rint = 0.028
ω scan	θmax = 29.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (HKL-3000 SCALEPACK; Otwinowski & Minor, 1997)	h = −29→29
Tmin = 0.922, Tmax = 0.937	k = −18→18
13046 measured reflections	l = −14→14

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0412P)2 + 2.157P] where P = (Fo2 + 2Fc2)/3
3663 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.35 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	Occ. (<1)
N1	0.24338 (3)	0.30241 (5)	0.30460 (7)	0.00545 (13)
H1N1	0.2484 (6)	0.3678 (10)	0.3234 (13)	0.013 (3)*
H2N1	0.2370 (6)	0.2756 (9)	0.3766 (13)	0.014 (3)*
N2	0.34493 (3)	0.23871 (5)	0.55886 (7)	0.00584 (14)
H1N2	0.3460 (6)	0.1738 (10)	0.5533 (13)	0.012 (3)*
C1	0.18207 (4)	0.28405 (6)	0.17163 (8)	0.00738 (15)
H1A	0.1831	0.2160	0.1398	0.009*
H1B	0.1819	0.3293	0.0981	0.009*
C2	0.30641 (4)	0.26138 (6)	0.30527 (8)	0.00612 (15)
H2	0.3004	0.1891	0.2872	0.007*
C3	0.32229 (4)	0.30822 (7)	0.19167 (8)	0.01049 (16)
H3A	0.3289	0.3798	0.2083	0.013*
H3B	0.2844	0.2980	0.0990	0.013*
C4	0.38574 (4)	0.26195 (8)	0.19333 (9)	0.01451 (18)
H4A	0.3775	0.1916	0.1680	0.017*
H4B	0.3971	0.2947	0.1226	0.017*
C5	0.44453 (4)	0.27145 (8)	0.33736 (9)	0.01465 (18)
H5A	0.4836	0.2358	0.3377	0.018*
H5B	0.4569	0.3415	0.3572	0.018*
C6	0.42661 (4)	0.22968 (7)	0.45105 (9)	0.01216 (17)
H6A	0.4645	0.2403	0.5436	0.015*
H6B	0.4194	0.1580	0.4370	0.015*
C7	0.36367 (4)	0.27744 (6)	0.44987 (8)	0.00632 (15)
H7	0.3718	0.3497	0.4651	0.008*
C8	0.39051 (4)	0.27036 (6)	0.70259 (8)	0.00656 (15)
H8	0.4375	0.2635	0.7134	0.008*
C9	0.38146 (4)	0.20090 (6)	0.80803 (8)	0.00776 (15)
H9A	0.3820	0.1324	0.7770	0.009*
H9B	0.4203	0.2089	0.8998	0.009*
C10	0.37854 (4)	0.37876 (6)	0.72406 (9)	0.01032 (16)
H10A	0.3825	0.4182	0.6492	0.012*
H10B	0.3324	0.3865	0.7153	0.012*
C11	0.42749 (5)	0.41859 (7)	0.86611 (10)	0.01776 (19)
H11A	0.4227	0.3815	0.9408	0.027*
H11B	0.4179	0.4881	0.8734	0.027*
H11C	0.4733	0.4117	0.8753	0.027*
Cl1	0.256487 (11)	0.526092 (15)	0.35905 (2)	0.01378 (8)
O1W	0.16965 (4)	0.51673 (5)	0.02378 (8)	0.01737 (15)
H1O1	0.1926 (9)	0.5195 (12)	0.110 (2)	0.038 (4)*
H2O1	0.1952 (8)	0.5022 (12)	−0.0111 (17)	0.033 (4)*
O2W	0.52804 (5)	0.02912 (8)	0.40229 (12)	0.0354 (2)
H1O2	0.5693 (11)	0.0172 (13)	0.4382 (19)	0.044 (5)*
H2O2	0.512 (2)	0.016 (3)	0.328 (5)	0.062 (14)*	0.50
H3O2	0.5140 (19)	0.015 (3)	0.457 (4)	0.041 (10)*	0.50

	U11	U22	U33	U12	U13	U23
N1	0.0030 (3)	0.0080 (3)	0.0048 (3)	−0.0006 (2)	0.0011 (2)	−0.0001 (2)
N2	0.0045 (3)	0.0083 (3)	0.0045 (3)	−0.0011 (2)	0.0017 (2)	−0.0001 (2)
C1	0.0037 (3)	0.0124 (4)	0.0044 (3)	−0.0012 (3)	0.0001 (3)	0.0005 (3)
C2	0.0030 (3)	0.0095 (3)	0.0061 (3)	0.0000 (3)	0.0021 (3)	−0.0009 (3)
C3	0.0072 (4)	0.0190 (4)	0.0057 (3)	−0.0013 (3)	0.0032 (3)	0.0007 (3)
C4	0.0084 (4)	0.0291 (5)	0.0080 (4)	−0.0005 (3)	0.0054 (3)	−0.0023 (3)
C5	0.0058 (4)	0.0308 (5)	0.0093 (4)	−0.0008 (3)	0.0050 (3)	−0.0001 (3)
C6	0.0050 (3)	0.0232 (4)	0.0093 (4)	0.0032 (3)	0.0040 (3)	0.0019 (3)
C7	0.0032 (3)	0.0109 (4)	0.0049 (3)	−0.0011 (3)	0.0018 (3)	0.0000 (3)
C8	0.0036 (3)	0.0099 (4)	0.0053 (3)	−0.0008 (3)	0.0010 (3)	−0.0002 (3)
C9	0.0041 (3)	0.0111 (4)	0.0069 (3)	0.0010 (3)	0.0012 (3)	0.0023 (3)
C10	0.0131 (4)	0.0091 (4)	0.0081 (3)	−0.0011 (3)	0.0039 (3)	−0.0007 (3)
C11	0.0209 (5)	0.0151 (4)	0.0129 (4)	−0.0049 (4)	0.0030 (3)	−0.0055 (3)
Cl1	0.01970 (12)	0.00834 (11)	0.01508 (12)	−0.00076 (7)	0.00912 (9)	0.00064 (7)
O1W	0.0187 (3)	0.0182 (3)	0.0168 (3)	0.0023 (3)	0.0092 (3)	0.0010 (3)
O2W	0.0226 (5)	0.0488 (6)	0.0330 (5)	0.0101 (4)	0.0101 (4)	0.0081 (4)

N1—C2	1.4995 (10)	C6—C7	1.5320 (11)
N1—C1	1.5003 (12)	C6—H6A	0.9900
N1—H1N1	0.909 (13)	C6—H6B	0.9900
N1—H2N1	0.907 (13)	C7—H7	1.0000
N2—C7	1.4774 (10)	C8—C10	1.5333 (12)
N2—C8	1.4842 (11)	C8—C9	1.5381 (11)
N2—H1N2	0.887 (13)	C8—H8	1.0000
C1—C9i	1.5234 (11)	C9—C1i	1.5233 (11)
C1—H1A	0.9900	C9—H9A	0.9900
C1—H1B	0.9900	C9—H9B	0.9900
C2—C3	1.5264 (11)	C10—C11	1.5276 (13)
C2—C7	1.5285 (12)	C10—H10A	0.9900
C2—H2	1.0000	C10—H10B	0.9900
C3—C4	1.5318 (12)	C11—H11A	0.9800
C3—H3A	0.9900	C11—H11B	0.9800
C3—H3B	0.9900	C11—H11C	0.9800
C4—C5	1.5286 (13)	O1W—H1O1	0.833 (19)
C4—H4A	0.9900	O1W—H2O1	0.820 (18)
C4—H4B	0.9900	O2W—H1O2	0.84 (2)
C5—C6	1.5262 (12)	O2W—H2O2	0.73 (4)
C5—H5A	0.9900	O2W—H3O2	0.78 (4)
C5—H5B	0.9900
C2—N1—C1	114.20 (6)	C5—C6—H6A	109.2
C2—N1—H1N1	109.7 (8)	C7—C6—H6A	109.2
C1—N1—H1N1	110.2 (8)	C5—C6—H6B	109.2
C2—N1—H2N1	108.8 (8)	C7—C6—H6B	109.2
C1—N1—H2N1	108.5 (8)	H6A—C6—H6B	107.9
H1N1—N1—H2N1	105.0 (11)	N2—C7—C2	109.85 (6)
C7—N2—C8	113.56 (6)	N2—C7—C6	113.46 (7)
C7—N2—H1N2	106.2 (8)	C2—C7—C6	108.08 (7)
C8—N2—H1N2	109.4 (8)	N2—C7—H7	108.4
N1—C1—C9i	111.44 (7)	C2—C7—H7	108.4
N1—C1—H1A	109.3	C6—C7—H7	108.4
C9i—C1—H1A	109.3	N2—C8—C10	110.24 (6)
N1—C1—H1B	109.3	N2—C8—C9	108.72 (6)
C9i—C1—H1B	109.3	C10—C8—C9	113.61 (7)
H1A—C1—H1B	108.0	N2—C8—H8	108.0
N1—C2—C3	111.46 (7)	C10—C8—H8	108.0
N1—C2—C7	108.91 (7)	C9—C8—H8	108.0
C3—C2—C7	110.83 (7)	C1i—C9—C8	115.61 (7)
N1—C2—H2	108.5	C1i—C9—H9A	108.4
C3—C2—H2	108.5	C8—C9—H9A	108.4
C7—C2—H2	108.5	C1i—C9—H9B	108.4
C2—C3—C4	109.63 (7)	C8—C9—H9B	108.4
C2—C3—H3A	109.7	H9A—C9—H9B	107.4
C4—C3—H3A	109.7	C11—C10—C8	113.10 (7)
C2—C3—H3B	109.7	C11—C10—H10A	109.0
C4—C3—H3B	109.7	C8—C10—H10A	109.0
H3A—C3—H3B	108.2	C11—C10—H10B	109.0
C5—C4—C3	111.30 (7)	C8—C10—H10B	109.0
C5—C4—H4A	109.4	H10A—C10—H10B	107.8
C3—C4—H4A	109.4	C10—C11—H11A	109.5
C5—C4—H4B	109.4	C10—C11—H11B	109.5
C3—C4—H4B	109.4	H11A—C11—H11B	109.5
H4A—C4—H4B	108.0	C10—C11—H11C	109.5
C6—C5—C4	110.83 (7)	H11A—C11—H11C	109.5
C6—C5—H5A	109.5	H11B—C11—H11C	109.5
C4—C5—H5A	109.5	H1O1—O1W—H2O1	106.6 (16)
C6—C5—H5B	109.5	H1O2—O2W—H2O2	111 (4)
C4—C5—H5B	109.5	H1O2—O2W—H3O2	108 (3)
H5A—C5—H5B	108.1	H2O2—O2W—H3O2	124 (5)
C5—C6—C7	112.06 (7)
C2—N1—C1—C9i	162.93 (7)	C3—C2—C7—N2	175.38 (6)
C1—N1—C2—C3	62.08 (9)	N1—C2—C7—C6	176.69 (7)
C1—N1—C2—C7	−175.33 (6)	C3—C2—C7—C6	−60.34 (9)
N1—C2—C3—C4	−178.28 (7)	C5—C6—C7—N2	−179.94 (7)
C7—C2—C3—C4	60.24 (9)	C5—C6—C7—C2	57.97 (9)
C2—C3—C4—C5	−56.36 (10)	C7—N2—C8—C10	73.59 (8)
C3—C4—C5—C6	54.06 (11)	C7—N2—C8—C9	−161.26 (6)
C4—C5—C6—C7	−55.52 (11)	N2—C8—C9—C1i	−75.02 (9)
C8—N2—C7—C2	−167.13 (6)	C10—C8—C9—C1i	48.13 (9)
C8—N2—C7—C6	71.78 (9)	N2—C8—C10—C11	−175.53 (7)
N1—C2—C7—N2	52.42 (8)	C9—C8—C10—C11	62.15 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···Cl1	0.909 (13)	2.182 (14)	3.0900 (9)	177.3 (12)
N1—H2N1···N2i	0.907 (13)	2.200 (13)	2.9348 (11)	137.6 (10)
N2—H1N2···O1Wii	0.887 (13)	2.262 (13)	3.1242 (12)	164.1 (11)
O1W—H1O1···Cl1	0.833 (19)	2.400 (19)	3.2329 (14)	178.6 (17)
O1W—H2O1···Cl1iii	0.820 (18)	2.335 (18)	3.1479 (10)	171.1 (15)
O2W—H1O2···O1Wiv	0.84 (2)	2.06 (2)	2.9021 (15)	178.1 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯Cl1	0.909 (13)	2.182 (14)	3.0900 (9)	177.3 (12)
N1—H2N1⋯N2i	0.907 (13)	2.200 (13)	2.9348 (11)	137.6 (10)
N2—H1N2⋯O1W ii	0.887 (13)	2.262 (13)	3.1242 (12)	164.1 (11)
O1W—H1O1⋯Cl1	0.833 (19)	2.400 (19)	3.2329 (14)	178.6 (17)
O1W—H2O1⋯Cl1iii	0.820 (18)	2.335 (18)	3.1479 (10)	171.1 (15)
O2W—H1O2⋯O1W iv	0.84 (2)	2.06 (2)	2.9021 (15)	178.1 (18)

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