1-Carboxymethyl-1′-carboxylatomethyl-3,3′-[p-phenylenebis(oxymethylene)]dipyridinium bromide dihydrate

Lian, H.-L.; Pan, W.-C.

doi:10.1107/S1600536810037748

organic compounds

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doi:10.1107/S1600536810037748

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1-Carboxymethyl-1′-carboxylatomethyl-3,3′-[p-phenylenebis(oxymethylene)]dipyridinium bromide dihydrate

Hong-Lei Lian ^a ^* and Wei-Cheng Pan ^b

^aCollege of Chemical Engineering, Zhengzhou University, Zhengzhou, Henan 450001, People's Republic of China, and ^bCollege of Chemical Engineering and Foods, Zhongzhou University, Zhengzhou, Henan 450044, People's Republic of China
^*Correspondence e-mail: zzulhl@yahoo.com.cn

(Received 12 August 2010; accepted 21 September 2010; online 30 September 2010)

In the crystal structure of the title salt, C₂₂H₂₁N₂O₆⁺·Br⁻·2H₂O, pairs of betaine molecules are bridged by protons (the bridging proton is disordered), forming strong and symmetrical O—H⋯O hydrogen bonds, leading to an infinite chain along the b axis. The water molecules are linked to the betaine molecule and the bromide ion through O—H⋯O and O—H⋯Br interactions. The central ring, located on an inversion centre, makes dihedral angles of 1.2 (2)° with the outer rings. One of the carboxylic acid groups is deprotonated.

Related literature

For a related structure, see: Zhang et al. (2004 ).

Experimental

Crystal data

C₂₂H₂₁N₂O₆⁺·Br⁻·2H₂O
M_r = 525.35
Monoclinic, C 2/c
a = 20.605 (4) Å
b = 7.9612 (12) Å
c = 15.233 (4) Å
β = 113.845 (16)°
V = 2285.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.85 mm⁻¹
T = 293 K
0.49 × 0.43 × 0.36 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.464, T_max = 0.556
2537 measured reflections
2009 independent reflections
1520 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.090
S = 1.09
2009 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.82	1.65	2.459 (5)	168
O4—H4B⋯Br1	0.85	2.72	3.496 (3)	152
O4—H4C⋯O2ⁱⁱ	0.85	2.25	3.040 (4)	155
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037748/pb2040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037748/pb2040Isup2.hkl

checkCIF report

Comment top

The design and synthesis of substrates for the ultimate preparation of supramolecular species has received much attention in recent years. Double betaines are a class of zwitterionic compounds possessing pairs of carboxylate groups and quaternary ammonium or pyridinium moieties. The carboxylate group is basic, so betaines are good proton acceptors that easily form complexes with Bronsted acids.

The synthesis and crystal structure of 1:2 salt of 1,4-bis(3-picolyloxyl)benzene-N,N^'– diacetic acid with HBr has been reported, here we will describe the preparation and structure of the 1:1 salt.

In the crystal structure of the title compound, the phenylene ring of the title double betaine is located at an inversion center, making a dihedra angle of 1.2 degree. Pairs of the betaine molecules are bridged by protons to form strong and symmetrical O···O hydrogen bonds, leading to an infinite chain. The bromide ion is connected to the betaine molecule through hydrogen bonding at O1W—H1WB···Br1 152.2 °, O1W···Br1 3.491 (4) Å, O1W—H1WA···O2 3.037 (4) Å,O1W···O2 154.5 °(Fig. 1).

Related literature top

For a related structure, see: Zhang et al. (2004)

Experimental top

1,4-bis(3-Picolyloxyl)benzene (2.92 g, 10 mmol) was dissolved in methanol (30 ml) to give a light yellow solution, to which ethyl bromoacetate (3 ml, 27 mmol, Aldrich) was added. The resulting solution was refluxed for 3 days. After the methanol was removed by rotary evaporation under reduced pressure, hydrobromic acid (12.5 ml, 4.8% (w/v)) was added to the yellow residue. The mixture was refluxed for 24 h to give a yellow solution. Removal of solvent afforded a light yellow powdery product. Yield: 46%. It was re-crystallized in water to obtain suitable single crystals for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. Ellipsoid plot.
	Fig. 2. A portion of the infinite chain of the title compound viewed along the a direction, with atom labels of 30% probability displacement ellipsoids. Hydrogen bonds are displayed with dashed lines.

1-Carboxymethyl-1'-carboxylatomethyl-3,3'-[p- phenylenebis(oxymethylene)]dipyridinium bromide dihydrate top

Crystal data top

C₂₂H₂₁N₂O₆⁺·Br⁻·2H₂O	F(000) = 1080
M_r = 525.35	D_x = 1.527 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.605 (4) Å	Cell parameters from 186 reflections
b = 7.9612 (12) Å	θ = 2.0–27.6°
c = 15.233 (4) Å	µ = 1.85 mm⁻¹
β = 113.845 (16)°	T = 293 K
V = 2285.6 (8) Å³	Block, light yellow
Z = 4	0.49 × 0.43 × 0.36 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2009 independent reflections
Radiation source: fine-focus sealed tube	1520 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −1→24
T_min = 0.464, T_max = 0.556	k = −1→9
2537 measured reflections	l = −18→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0331P)² + 1.7877P] where P = (F_o² + 2F_c²)/3
2009 reflections	(Δ/σ)_max < 0.001
150 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₂₂H₂₁N₂O₆⁺·Br⁻·2H₂O	V = 2285.6 (8) Å³
M_r = 525.35	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.605 (4) Å	µ = 1.85 mm⁻¹
b = 7.9612 (12) Å	T = 293 K
c = 15.233 (4) Å	0.49 × 0.43 × 0.36 mm
β = 113.845 (16)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2009 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1520 reflections with I > 2σ(I)
T_min = 0.464, T_max = 0.556	R_int = 0.047
2537 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.09	Δρ_max = 0.52 e Å⁻³
2009 reflections	Δρ_min = −0.33 e Å⁻³
150 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	Occ. (<1)
Br1	0.0000	0.04115 (8)	0.2500	0.0454 (2)
O1	0.20052 (13)	−0.2950 (4)	0.42592 (16)	0.0527 (7)
H1	0.2364	−0.2608	0.4703	0.079*	0.50
O2	0.26011 (13)	−0.2308 (4)	0.33644 (16)	0.0519 (7)
O3	0.05771 (12)	0.1842 (3)	0.05634 (16)	0.0410 (6)
N1	0.14157 (13)	−0.2645 (3)	0.16985 (17)	0.0307 (6)
C1	0.20678 (19)	−0.2737 (4)	0.3465 (2)	0.0351 (8)
C2	0.13832 (18)	−0.3130 (5)	0.2610 (2)	0.0366 (8)
H2A	0.1288	−0.4324	0.2600	0.044*
H2B	0.0995	−0.2538	0.2679	0.044*
C3	0.17237 (18)	−0.3677 (5)	0.1291 (2)	0.0398 (9)
H3A	0.1902	−0.4708	0.1572	0.048*
C4	0.17744 (18)	−0.3203 (5)	0.0454 (3)	0.0454 (10)
H4A	0.1982	−0.3922	0.0161	0.054*
C5	0.15208 (18)	−0.1677 (5)	0.0053 (2)	0.0410 (9)
H5A	0.1561	−0.1351	−0.0509	0.049*
C6	0.12032 (16)	−0.0615 (4)	0.0482 (2)	0.0304 (8)
C7	0.11602 (16)	−0.1142 (4)	0.1314 (2)	0.0303 (8)
H7A	0.0951	−0.0448	0.1617	0.036*
C8	0.09107 (19)	0.1032 (4)	0.0026 (2)	0.0367 (8)
H8A	0.1291	0.1732	0.0008	0.044*
H8B	0.0569	0.0855	−0.0628	0.044*
C9	0.02970 (17)	0.3417 (4)	0.0252 (2)	0.0327 (8)
C10	0.02951 (18)	0.4206 (4)	−0.0558 (2)	0.0368 (9)
H10A	0.0492	0.3675	−0.0937	0.044*
C11	−0.00005 (18)	0.4215 (4)	0.0802 (2)	0.0367 (9)
H11A	−0.0003	0.3684	0.1344	0.044*
O4	0.15569 (16)	0.2619 (4)	0.28766 (19)	0.0738 (9)
H4B	0.1174	0.2082	0.2578	0.111*
H4C	0.1662	0.2720	0.2395	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0537 (4)	0.0565 (4)	0.0345 (3)	0.000	0.0266 (2)	0.000
O1	0.0496 (16)	0.081 (2)	0.0317 (13)	−0.0026 (15)	0.0210 (12)	−0.0007 (13)
O2	0.0408 (15)	0.075 (2)	0.0394 (14)	−0.0151 (14)	0.0154 (12)	0.0005 (13)
O3	0.0565 (16)	0.0336 (15)	0.0416 (13)	0.0120 (12)	0.0289 (12)	0.0107 (11)
N1	0.0294 (15)	0.0312 (17)	0.0302 (14)	0.0004 (13)	0.0108 (12)	−0.0002 (13)
C1	0.039 (2)	0.032 (2)	0.0343 (18)	0.0022 (17)	0.0150 (16)	0.0015 (16)
C2	0.037 (2)	0.035 (2)	0.0370 (19)	−0.0008 (17)	0.0145 (16)	0.0067 (16)
C3	0.038 (2)	0.033 (2)	0.043 (2)	0.0067 (17)	0.0109 (17)	0.0006 (18)
C4	0.045 (2)	0.049 (3)	0.045 (2)	0.014 (2)	0.0218 (19)	−0.009 (2)
C5	0.044 (2)	0.051 (3)	0.0335 (18)	0.0026 (19)	0.0206 (17)	−0.0030 (18)
C6	0.0294 (17)	0.032 (2)	0.0280 (16)	−0.0034 (16)	0.0100 (14)	−0.0026 (16)
C7	0.0305 (18)	0.0292 (19)	0.0310 (16)	−0.0007 (16)	0.0122 (15)	−0.0046 (15)
C8	0.048 (2)	0.037 (2)	0.0305 (17)	0.0007 (18)	0.0209 (16)	0.0008 (16)
C9	0.0351 (19)	0.029 (2)	0.0335 (17)	−0.0007 (17)	0.0129 (15)	0.0052 (16)
C10	0.048 (2)	0.036 (2)	0.0313 (17)	0.0031 (17)	0.0207 (16)	0.0016 (16)
C11	0.046 (2)	0.036 (2)	0.0317 (17)	0.0028 (17)	0.0192 (16)	0.0097 (15)
O4	0.076 (2)	0.094 (2)	0.0528 (17)	−0.0131 (19)	0.0270 (16)	−0.0071 (17)

Geometric parameters (Å, º) top

Br1—Br1	0.0000 (12)	C5—C6	1.385 (4)
O1—C1	1.279 (4)	C5—H5A	0.9300
O1—H1	0.8200	C6—C7	1.372 (4)
O2—C1	1.218 (4)	C6—C8	1.492 (5)
O3—C9	1.382 (4)	C7—H7A	0.9300
O3—C8	1.419 (4)	C8—H8A	0.9700
N1—C3	1.335 (4)	C8—H8B	0.9700
N1—C7	1.342 (4)	C9—C11	1.376 (4)
N1—C2	1.469 (4)	C9—C10	1.383 (4)
C1—C2	1.516 (5)	C10—C11ⁱ	1.380 (5)
C2—H2A	0.9700	C10—H10A	0.9300
C2—H2B	0.9700	C11—C10ⁱ	1.380 (5)
C3—C4	1.373 (5)	C11—H11A	0.9300
C3—H3A	0.9300	O4—H4B	0.8498
C4—C5	1.366 (5)	O4—H4C	0.8494
C4—H4A	0.9300

C1—O1—H1	109.5	C7—C6—C5	118.0 (3)
C9—O3—C8	116.5 (2)	C7—C6—C8	122.3 (3)
C3—N1—C7	121.5 (3)	C5—C6—C8	119.7 (3)
C3—N1—C2	119.3 (3)	N1—C7—C6	121.0 (3)
C7—N1—C2	119.1 (3)	N1—C7—H7A	119.5
O2—C1—O1	126.7 (3)	C6—C7—H7A	119.5
O2—C1—C2	121.6 (3)	O3—C8—C6	109.2 (2)
O1—C1—C2	111.7 (3)	O3—C8—H8A	109.8
N1—C2—C1	112.0 (3)	C6—C8—H8A	109.8
N1—C2—H2A	109.2	O3—C8—H8B	109.8
C1—C2—H2A	109.2	C6—C8—H8B	109.8
N1—C2—H2B	109.2	H8A—C8—H8B	108.3
C1—C2—H2B	109.2	C11—C9—O3	115.9 (3)
H2A—C2—H2B	107.9	C11—C9—C10	119.4 (3)
N1—C3—C4	119.4 (3)	O3—C9—C10	124.6 (3)
N1—C3—H3A	120.3	C11ⁱ—C10—C9	119.7 (3)
C4—C3—H3A	120.3	C11ⁱ—C10—H10A	120.1
C5—C4—C3	120.1 (3)	C9—C10—H10A	120.1
C5—C4—H4A	119.9	C9—C11—C10ⁱ	120.8 (3)
C3—C4—H4A	119.9	C9—C11—H11A	119.6
C4—C5—C6	120.0 (3)	C10ⁱ—C11—H11A	119.6
C4—C5—H5A	120.0	H4B—O4—H4C	95.3
C6—C5—H5A	120.0

C3—N1—C2—C1	82.2 (4)	C5—C6—C7—N1	−0.3 (5)
C7—N1—C2—C1	−95.1 (3)	C8—C6—C7—N1	178.7 (3)
O2—C1—C2—N1	−10.1 (5)	C9—O3—C8—C6	177.9 (3)
O1—C1—C2—N1	171.3 (3)	C7—C6—C8—O3	−2.4 (4)
C7—N1—C3—C4	−0.7 (5)	C5—C6—C8—O3	176.5 (3)
C2—N1—C3—C4	−178.0 (3)	C8—O3—C9—C11	−177.6 (3)
N1—C3—C4—C5	1.0 (5)	C8—O3—C9—C10	2.8 (5)
C3—C4—C5—C6	−0.9 (5)	C11—C9—C10—C11ⁱ	0.5 (6)
C4—C5—C6—C7	0.5 (5)	O3—C9—C10—C11ⁱ	−180.0 (3)
C4—C5—C6—C8	−178.5 (3)	O3—C9—C11—C10ⁱ	179.9 (3)
C3—N1—C7—C6	0.4 (5)	C10—C9—C11—C10ⁱ	−0.5 (6)
C2—N1—C7—C6	177.6 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱⁱ	0.82	1.65	2.459 (5)	168
O4—H4B···Br1	0.85	2.72	3.496 (3)	152
O4—H4C···O2ⁱⁱⁱ	0.85	2.25	3.040 (4)	155

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₁N₂O₆⁺·Br⁻·2H₂O
M_r	525.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.605 (4), 7.9612 (12), 15.233 (4)
β (°)	113.845 (16)
V (Å³)	2285.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.85
Crystal size (mm)	0.49 × 0.43 × 0.36

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.464, 0.556
No. of measured, independent and observed [I > 2σ(I)] reflections	2537, 2009, 1520
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.090, 1.09
No. of reflections	2009
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.33

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	1.65	2.459 (5)	167.6
O4—H4B···Br1	0.85	2.72	3.496 (3)	152.4
O4—H4C···O2ⁱⁱ	0.85	2.25	3.040 (4)	154.8

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

Acknowledgements

Financial support from Zhengzhou University is greatly appreciated.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, L.-P., Lam, C.-K., Song, H.-B. & Mak, T. C. W. (2004). Polyhedron, 23, 2413–2425. Web of Science CSD CrossRef CAS Google Scholar

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doi:10.1107/S1600536810037748

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1-Carboxymethyl-1′-carboxylato­methyl-3,3′-[p-phenylenebis(oxymethylene)]dipyridinium bromide dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-Carboxymethyl-1′-carboxylatomethyl-3,3′-[p-phenylenebis(oxymethylene)]dipyridinium bromide dihydrate