(IUCr) Crystallography Journals Online

Abstract top

The title compound, C₂₄H₄₆N₄O₈²⁺·2Cl^-·2H₂O, was synthesized by the hydrolysis of tetraethyl 2,2',2'',2'''-(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetraacetate in hydrochloric acid solution. The crystal structure of the title compound consists of a 14-membered C₁₀N₄ centrosymmetric cationic macrocycle which interacts with the chloride ions and water molecules of crystallization to give a three-dimensional hydrogen-bonded network.

1,4,8,11-Tetrakis(carboxymethyl)-5,5,7,12,12,14-hexamethyl- 4,11-diaza-1,8-diazoniacyclotetradecane dichloride dihydrate top

Crystal data top

C₂₄H₄₆N₄O₈²⁺·2Cl^–·2H₂O	F₀₀₀ = 672
M_r = 625.58	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 17651 reflections
a = 9.977 (5) Å	θ = 2.4–24.9º
b = 13.475 (7) Å	µ = 0.27 mm⁻¹
c = 11.572 (6) Å	T = 293 (2) K
β = 104.220 (9)º	BLOCK, colorless
V = 1508.1 (13) Å³	0.10 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2036 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.143
Monochromator: graphite	θ_max = 26.0º
T = 293(2) K	θ_min = 2.4º
φ and ω scans	h = −12→12
Absorption correction: none	k = −16→16
15242 measured reflections	l = −14→14
2946 independent reflections

Refinement top

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0715P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.032
2946 reflections	Δρ_max = 0.63 e Å⁻³
194 parameters	Δρ_min = −0.37 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Crystal data top

C₂₄H₄₆N₄O₈²⁺·2Cl^–·2H₂O	V = 1508.1 (13) Å³
M_r = 625.58	Z = 2
Monoclinic, P2₁/n	Mo Kα
a = 9.977 (5) Å	µ = 0.27 mm⁻¹
b = 13.475 (7) Å	T = 293 (2) K
c = 11.572 (6) Å	0.10 × 0.10 × 0.08 mm
β = 104.220 (9)º

Data collection top

Bruker SMART CCD area-detector diffractometer	2946 independent reflections
Absorption correction: none	2036 reflections with I > 2σ(I)
15242 measured reflections	R_int = 0.143

Refinement top

R[F² > 2σ(F²)] = 0.056	194 parameters
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.63 e Å⁻³
2946 reflections	Δρ_min = −0.37 e Å⁻³

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.

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
C1	0.5351 (3)	0.98193 (17)	−0.1532 (2)	0.0292 (6)
H1A	0.4667	0.9400	−0.1306	0.035*
H1B	0.5360	0.9664	−0.2348	0.035*
C2	0.7189 (3)	0.85672 (17)	−0.0818 (2)	0.0335 (6)
H2	0.8150	0.8530	−0.0349	0.040*
C3	0.6370 (3)	0.78525 (17)	−0.0239 (2)	0.0323 (6)
H3A	0.6485	0.7189	−0.0525	0.039*
H3B	0.5398	0.8021	−0.0511	0.039*
C4	0.6741 (3)	0.78252 (17)	0.1120 (2)	0.0319 (6)
C5	0.5034 (2)	0.90943 (16)	0.1443 (2)	0.0285 (6)
H5A	0.4752	0.8726	0.2064	0.034*
H5B	0.4516	0.8836	0.0682	0.034*
C6	0.7192 (4)	0.8235 (2)	−0.2076 (3)	0.0495 (8)
H6A	0.6257	0.8156	−0.2537	0.074*
H6B	0.7673	0.7614	−0.2041	0.074*
H6C	0.7649	0.8726	−0.2444	0.074*
C7	0.8226 (3)	0.7482 (2)	0.1616 (3)	0.0422 (7)
H7A	0.8371	0.6866	0.1248	0.063*
H7B	0.8394	0.7391	0.2462	0.063*
H7C	0.8850	0.7974	0.1450	0.063*
C8	0.5799 (3)	0.70891 (19)	0.1556 (3)	0.0442 (7)
H8A	0.6022	0.6425	0.1369	0.066*
H8B	0.4851	0.7228	0.1169	0.066*
H8C	0.5933	0.7154	0.2403	0.066*
C9	0.7378 (2)	0.91341 (19)	0.2780 (2)	0.0328 (6)
H9A	0.7422	0.8550	0.3278	0.039*
H9B	0.6935	0.9660	0.3121	0.039*
C10	0.8828 (3)	0.94509 (17)	0.2765 (2)	0.0303 (6)
C11	0.7806 (3)	1.03008 (17)	−0.0922 (2)	0.0338 (6)
H11A	0.7562	1.0512	−0.1749	0.041*
H11B	0.8669	0.9937	−0.0793	0.041*
C12	0.8052 (3)	1.12186 (18)	−0.0142 (2)	0.0319 (6)
Cl1	0.27157 (7)	0.97170 (5)	0.43440 (7)	0.0480 (3)
N1	0.6734 (2)	0.96203 (13)	−0.07355 (18)	0.0270 (5)
H1N	0.6660	0.9714	0.0025	0.032*
N2	0.6540 (2)	0.89074 (14)	0.15548 (17)	0.0275 (5)
O1	0.74179 (19)	1.14840 (14)	0.05549 (17)	0.0405 (5)
O2	0.9133 (2)	1.17039 (15)	−0.0337 (2)	0.0572 (6)
H2A	0.9260	1.2212	0.0065	0.086*
O3	0.9143 (2)	0.97572 (14)	0.19069 (18)	0.0449 (5)
O4	0.96439 (19)	0.93712 (15)	0.38441 (16)	0.0434 (5)
H4	1.0409	0.9596	0.3849	0.065*
O1W	0.5390 (3)	0.84981 (16)	0.4486 (2)	0.0519 (6)
H2W	0.594 (4)	0.887 (2)	0.479 (3)	0.042 (10)*
H1W	0.457 (5)	0.877 (3)	0.443 (4)	0.092 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0262 (13)	0.0260 (12)	0.0318 (13)	0.0029 (10)	0.0005 (11)	0.0006 (10)
C2	0.0304 (14)	0.0251 (12)	0.0417 (15)	0.0084 (11)	0.0026 (12)	−0.0014 (11)
C3	0.0336 (14)	0.0220 (12)	0.0357 (14)	0.0030 (11)	−0.0019 (11)	−0.0050 (10)
C4	0.0332 (14)	0.0217 (12)	0.0356 (14)	0.0055 (10)	−0.0012 (11)	−0.0029 (10)
C5	0.0218 (12)	0.0263 (12)	0.0340 (14)	−0.0011 (10)	0.0002 (11)	0.0031 (10)
C6	0.070 (2)	0.0378 (15)	0.0471 (18)	0.0086 (15)	0.0258 (16)	−0.0046 (13)
C7	0.0435 (17)	0.0368 (14)	0.0398 (15)	0.0101 (13)	−0.0021 (13)	−0.0001 (12)
C8	0.0569 (19)	0.0261 (13)	0.0446 (16)	−0.0013 (13)	0.0031 (14)	0.0076 (12)
C9	0.0271 (13)	0.0387 (14)	0.0279 (13)	0.0018 (11)	−0.0022 (11)	−0.0041 (11)
C10	0.0298 (14)	0.0239 (12)	0.0324 (14)	0.0020 (10)	−0.0017 (11)	−0.0037 (10)
C11	0.0292 (13)	0.0320 (13)	0.0405 (15)	−0.0007 (11)	0.0094 (12)	−0.0045 (11)
C12	0.0279 (14)	0.0287 (13)	0.0365 (14)	−0.0008 (11)	0.0029 (12)	0.0030 (11)
Cl1	0.0331 (4)	0.0426 (4)	0.0634 (5)	−0.0038 (3)	0.0023 (3)	0.0034 (3)
N1	0.0249 (11)	0.0246 (10)	0.0298 (11)	0.0013 (8)	0.0036 (9)	−0.0025 (8)
N2	0.0248 (11)	0.0229 (10)	0.0298 (11)	0.0027 (8)	−0.0025 (9)	−0.0029 (8)
O1	0.0330 (10)	0.0486 (11)	0.0384 (11)	−0.0090 (9)	0.0060 (9)	−0.0126 (9)
O2	0.0537 (14)	0.0430 (12)	0.0839 (17)	−0.0206 (10)	0.0339 (13)	−0.0177 (11)
O3	0.0393 (12)	0.0501 (12)	0.0415 (12)	−0.0057 (9)	0.0023 (9)	0.0060 (9)
O4	0.0286 (10)	0.0547 (12)	0.0392 (11)	−0.0042 (9)	−0.0065 (9)	−0.0003 (9)
O1W	0.0484 (15)	0.0327 (11)	0.0759 (17)	0.0025 (11)	0.0176 (13)	0.0018 (11)

Geometric parameters (Å, °) top

C1—N1	1.483 (3)	C7—H7B	0.9600
C1—C5ⁱ	1.523 (3)	C7—H7C	0.9600
C1—H1A	0.9700	C8—H8A	0.9600
C1—H1B	0.9700	C8—H8B	0.9600
C2—N1	1.500 (3)	C8—H8C	0.9600
C2—C3	1.521 (4)	C9—N2	1.490 (3)
C2—C6	1.524 (4)	C9—C10	1.513 (4)
C2—H2	0.9800	C9—H9A	0.9700
C3—C4	1.525 (4)	C9—H9B	0.9700
C3—H3A	0.9700	C10—O3	1.186 (3)
C3—H3B	0.9700	C10—O4	1.317 (3)
C4—C7	1.523 (4)	C11—N1	1.465 (3)
C4—C8	1.535 (4)	C11—C12	1.515 (4)
C4—N2	1.571 (3)	C11—H11A	0.9700
C5—N2	1.497 (3)	C11—H11B	0.9700
C5—C1ⁱ	1.523 (3)	C12—O1	1.196 (3)
C5—H5A	0.9700	C12—O2	1.327 (3)
C5—H5B	0.9700	N1—H1N	0.9100
C6—H6A	0.9600	O2—H2A	0.8200
C6—H6B	0.9600	O4—H4	0.8200
C6—H6C	0.9600	O1W—H2W	0.76 (3)
C7—H7A	0.9600	O1W—H1W	0.88 (5)

N1—C1—C5ⁱ	110.10 (18)	C4—C7—H7C	109.5
N1—C1—H1A	109.6	H7A—C7—H7C	109.5
C5ⁱ—C1—H1A	109.6	H7B—C7—H7C	109.5
N1—C1—H1B	109.6	C4—C8—H8A	109.5
C5ⁱ—C1—H1B	109.6	C4—C8—H8B	109.5
H1A—C1—H1B	108.2	H8A—C8—H8B	109.5
N1—C2—C3	111.5 (2)	C4—C8—H8C	109.5
N1—C2—C6	114.2 (2)	H8A—C8—H8C	109.5
C3—C2—C6	111.3 (2)	H8B—C8—H8C	109.5
N1—C2—H2	106.4	N2—C9—C10	111.2 (2)
C3—C2—H2	106.4	N2—C9—H9A	109.4
C6—C2—H2	106.4	C10—C9—H9A	109.4
C2—C3—C4	116.7 (2)	N2—C9—H9B	109.4
C2—C3—H3A	108.1	C10—C9—H9B	109.4
C4—C3—H3A	108.1	H9A—C9—H9B	108.0
C2—C3—H3B	108.1	O3—C10—O4	126.4 (3)
C4—C3—H3B	108.1	O3—C10—C9	123.9 (2)
H3A—C3—H3B	107.3	O4—C10—C9	109.6 (2)
C7—C4—C3	111.3 (2)	N1—C11—C12	116.1 (2)
C7—C4—C8	107.3 (2)	N1—C11—H11A	108.3
C3—C4—C8	110.0 (2)	C12—C11—H11A	108.3
C7—C4—N2	110.47 (19)	N1—C11—H11B	108.3
C3—C4—N2	106.86 (18)	C12—C11—H11B	108.3
C8—C4—N2	111.0 (2)	H11A—C11—H11B	107.4
N2—C5—C1ⁱ	114.86 (19)	O1—C12—O2	123.7 (2)
N2—C5—H5A	108.6	O1—C12—C11	127.7 (2)
C1ⁱ—C5—H5A	108.6	O2—C12—C11	108.7 (2)
N2—C5—H5B	108.6	C11—N1—C1	113.39 (19)
C1ⁱ—C5—H5B	108.6	C11—N1—C2	109.8 (2)
H5A—C5—H5B	107.5	C1—N1—C2	112.43 (18)
C2—C6—H6A	109.5	C11—N1—H1N	106.9
C2—C6—H6B	109.5	C1—N1—H1N	106.9
H6A—C6—H6B	109.5	C2—N1—H1N	106.9
C2—C6—H6C	109.5	C9—N2—C5	111.37 (19)
H6A—C6—H6C	109.5	C9—N2—C4	114.14 (17)
H6B—C6—H6C	109.5	C5—N2—C4	109.45 (17)
C4—C7—H7A	109.5	C12—O2—H2A	109.5
C4—C7—H7B	109.5	C10—O4—H4	109.5
H7A—C7—H7B	109.5	H2W—O1W—H1W	107 (3)

N1—C2—C3—C4	−75.6 (3)	C6—C2—N1—C11	−71.7 (3)
C6—C2—C3—C4	155.6 (2)	C3—C2—N1—C1	−71.7 (3)
C2—C3—C4—C7	−62.6 (3)	C6—C2—N1—C1	55.5 (3)
C2—C3—C4—C8	178.6 (2)	C10—C9—N2—C5	−151.36 (19)
C2—C3—C4—N2	58.1 (3)	C10—C9—N2—C4	84.1 (2)
N2—C9—C10—O3	20.5 (3)	C1ⁱ—C5—N2—C9	67.6 (3)
N2—C9—C10—O4	−162.1 (2)	C1ⁱ—C5—N2—C4	−165.3 (2)
N1—C11—C12—O1	−5.1 (4)	C7—C4—N2—C9	−34.3 (3)
N1—C11—C12—O2	174.1 (2)	C3—C4—N2—C9	−155.5 (2)
C12—C11—N1—C1	92.6 (3)	C8—C4—N2—C9	84.6 (2)
C12—C11—N1—C2	−140.7 (2)	C7—C4—N2—C5	−159.9 (2)
C5ⁱ—C1—N1—C11	−52.7 (3)	C3—C4—N2—C5	78.9 (2)
C5ⁱ—C1—N1—C2	−178.0 (2)	C8—C4—N2—C5	−41.0 (2)
C3—C2—N1—C11	161.1 (2)

Symmetry codes: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···Cl1ⁱⁱ	0.82	2.24	3.012 (3)	158
O2—H2A···O1Wⁱⁱⁱ	0.82	1.82	2.610 (3)	162
O1W—H2W···Cl1^iv	0.76 (3)	2.40 (3)	3.152 (3)	169 (3)

Symmetry codes: (ii) x+1, y, z; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z+1.

Table 1
Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···Cl1ⁱ	0.82	2.24	3.012 (3)	158
O2—H2A···O1Wⁱⁱ	0.82	1.82	2.610 (3)	162
O1W—H2W···Cl1ⁱⁱⁱ	0.76 (3)	2.40 (3)	3.152 (3)	169 (3)

Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z+1.

supplementary materials

1,4,8,11-Tetrakis(carboxymethyl)-5,5,7,12,12,14-hexamethyl-4,11-diaza-1,8-diazoniacyclotetradecane dichloride dihydrate

S.-F. Wang, H.-Q. Liu, X.-M. Yao, K. Yang and X.-H. Li

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry code: (a) 1-x, 2-y, -z.
	Fig. 2. A view of the hydrogen bonding. Dashed lines indicate hydrogen bonds.