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The title compound, C6H9N2O2+·Cl·C6H8N2O2·H2O, con­tains one 2-(3-methyl-1H-imidazol-3-ium-1-yl)acetate inner salt mol­ecule, one 1-carb­oxy­methyl-3-methyl-1H-imidazol-3-ium cation, one chloride ion and one water mol­ecule. In the extended structure, chloride anions and water mol­ecules are linked via O—H...Cl hydrogen bonds, forming an infinite one-dimensional chain. The chloride anions are also linked by two weak C—H...Cl inter­actions to neighbouring methyl­ene groups and imidazole rings. Two imidazolium moieties form a homoconjugated cation through a strong and asymmetric O—H...O hydrogen bond of 2.472 (2) Å. The IR spectrum shows a continuous D-type absorption in the region below 1300 cm−1 and is different to that of 1-carb­oxy­methyl-3-methyl­imid­azolium chloride [Xuan, Wang & Xue (2012). Spectrochim. Acta Part A, 96, 436–443].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023676/ku3105sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023676/ku3105Isup2.hkl
Contains datablock I

CCDC reference: 924050

Introduction top

Functionalized ionic liquids (ILs) have become increasingly popular in recent years as their properties can be widely designed by a reasonable combination of cations, anions and substituents. Multidenate carb­oxy­lic acids are excellent ligands for the metal–organic frameworks, coordination polymers and cocrystals with special topologies and characterizations (Cui et al., 2011). Introduction of carb­oxy­lic acid groups into the cation of ILs can open up a new pathway for the preparation of novel materials. A series of imidazolium salts with one or two carboxyl groups have been prepared (Fei et al. 2004) and found application in the soft material [not clear?] (Li et al., 2008), catalysis (Li et al., 2007; Han et al., 2011) and electrochemistry (Abbott et al., 2011).

Experimental top

Synthesis and crystallization top

The title compound was prepared according to a previously reported procedure (Xuan et al., 2012). Crystals are grown from a water–CCl4 (20:1 v/v) mixture. FT–IR spectra were recorded on a Nicolet Nexus FT–IR spectrometer using the KBr pellet technique with a resolution of 2 cm-1. Geometry optimization, calculation of inter­action energy, and charge analysis have been carried out using the GAUSSIAN09 program (Frisch et al., 2010). Since hydrogen bonding is a kind of van der Waals inter­action, additional dispersion function with density functional theory, ωB97XD (Chai & Head-Gordon, 2008), at the 6–311++G(d,p) basis set, was used in this work.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methyl­ene H atoms, and C—H = 0.97 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The water H atoms were derived from difference Fourier maps and refined in the riding-model approximation, with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O). The hy­droxy groups were derived from difference Fourier maps and refined in the riding-model approximation, with O—H = 0.?? Å and Uiso(H) = 1.5Ueq(O).

Results and discussion top

In our previous work (Xuan et al., 2012), 1-carb­oxy­methyl-3-methyl­imidazolium chloride, (II), was synthesized and its structure determined by single-crystal diffraction. Also, a reliable assignment of the observed IR and Raman bands was made by calculations based on density functional theory (DFT). In the crystal packing of (II), the chloride ion inter­acts with four cations through O—H···Cl and C—H···Cl hydrogen bonds and C···Cl short contacts. Recently, 1-carb­oxy­methyl-3-methyl-1H-imidazol-3-ium chloride 2-(3-methyl-1H-imidazol-3-ium-1-yl)acetate monohydrate, (I) (Fig. 1), was obtained accidentally as crystals from an aqueous solution containing small amounts of carbon tetra­chloride. In the crystal structure of (I), chloride ions and water molecules are linked into a one-dimensional zigzag chain through conventional O—H···Cl hydrogen bonds lying parallel to the b axis (Fig. 2). Two weak C—H···Cl hydrogen bonds are found around the chloride ion in the crystal (Table 2). Additionally, C···Cl short contacts found in (II) are not present in (I). It should be pointed out that the C—H···Cl inter­action in the crystal structure of (I) cannot be neglected since it can produce a multiple and complex network (Table 2). In this case, the C7—H7···Cl1 hydrogen bond including an imidazolium-ring C(2) site H atom is shorter, with a C7···Cl1 distance of 3.414 (2) Å. This type of hydrogen bond, which is considerably different from conventional hydrogen bonds, is generally present in imidazolium ionic liquids (Dong et al., 2006). Experiments have confirmed that it is important inter­action in controlling the structures and physical properties of ionic liquids (Gonfa et al. 2011). This inter­action is even stronger than the isolated O—H···Cl inter­action to a certain extent. For example, we calculated the structures and energies of the ion pairs (Fig. 3) between the chloride ion and the 1-carb­oxy­methyl-3-methyl­imidazolium cation formed through two C—H···Cl (model a) and one O—H···Cl (model b) hydrogen bond, respectively. In model a, two C—H···Cl hydrogen bonds connect the anion and anion, and this structure is about 38.42 kJ mol-1 more stable than model b. This shows that C—H···Cl hydrogen bonds play an important role in the three-dimensional hydrogen-bonded network of imidazolium ionic liquids. In addition, the structural investigation of two typical ionic liquids (Dong et al. 2012) indicates that the strength of hydrogen-bonding inter­actions is greatly enhanced if the Lewis base is an anion and the Lewis acid is a cation. A the possible proton transfer occurs in model b, which agrees with the our NBO (natural bond order?) charge analysis and the crystal structure of (II), and the O—H···Cl hydrogen bond is also stronger than a conventional O—H···Cl hydrogen bond.

It can be seen in Fig. 2 that the title hydrate shows a novel homoconjugated cationic structure stabilized by O—H···O hydrogen bonding since only one proton is present between two 1-carb­oxy­methyl-3-methyl­imidazolium cations. The location of the H atom, which is involved in an O—H···O hydrogen bond, can be determined clearly from a difference Fourier map. In the homoconjugated cation, the H3···O2i and O3···O2i distances are, respectively, 1.402 (3) and 2.472 (2) Å [symmetry code: (i) x, y+1, z]. Moreover, the O3—H3D distance [1.070 (2) Å] is longer than the typical O—H bond length, and this hydrogen bond is almost linear [177 (2)°]. These features show that the O—H···O hydrogen bond in the homoconjugated cation is a very strong inter­action. This is significantly different from the crystal structure of (II), in which the chloride anion inter­acts with the H atom of the carb­oxy­lic acid group of the cation, forming a classical O—H···Cl hydrogen bond. Since electrostatic attraction plays a major role in this ionic compound, the inter­action between the chloride anion and the positively charged N atom of the homoconjugated cation leads to the change in charge distribution. DFT calculations at the ωB97XD/6–311++G(d,p) level show that the NBO charges on the methyl­ene H atom and the whole imidazole ring change markedly when the chloride anion inter­acts with the 1-carb­oxy­methyl-3-methyl­imidazolium cation through C—H···Cl hydrogen bonds (model a), but those on the carbonyl group remain constant. The positive charge is still mainly on the imidazole ring N atom bonded to the –CH2COOH group. Considering the position of the chloride anion in the crystal, the O—H···O hydrogen bond is asymmetric and the proton is not centred. Therefore, these two 1-carb­oxy­methyl-3-methyl­imidazolium cations are not equivalent, and one of them is deprotonated (Table 1) and forms an inner salt. According to the classification of Gilli et al. (1994), the title compound belongs to the positive charge-assisted hydrogen-bonding group. A systematic search of the Cambridge Structural Database (CSD, Version 5.33; Allen, 2002) showed that reports of similar structures of homoconjugated cations were limited, except for the amino acids and their derivatives. The most relevant inner salts are (1-decyl-1H-imidazol-3-ium-3-yl)acetate dihydrate (Lin et al., 2011) and [1-(2,6-diiso­propyl­phenyl)-1H-imidazol-3-ium-3-yl]acetate (Danopoulos et al., 2008). The former, however, is packed by O—H···O hydrogen bonds involving water molecules, and the latter by inter­molecular C—H···O hydrogen bonds. Other reports of homoconjugated cations are based on different heterocyclic compounds, such as betaine (Baran et al., 1995, 1997; Dega-Szafran et al., 2006; Ghaza­ryan et al., 2010; Nockemann et al., 2006; Ratajczak et al., 1994; Szafran et al., 2005; Rodrigues et al., 2001), morpholine (Dega-Szafran et al., 2002), quinuclidine (Dega-Szafran et al., 2010) and 1,4-diazo­niabi­cyclo­[2.2.2]o­ctane (Barczyński et al., 2009). Among these compounds, the O···O distances of the O—H···O hydrogen bonds in the homoconjugated cation are usually in the range 2.41–2.64 Å, with O—H···O angles ranging from 158 to ~179°.

According to our previous assignment of observed bands (Xuan et al., 2012), the IR spectra of (I) and (II) (Fig. 4) describe clearly the difference between the structures of (I) and (II). A sharp band at 3412 cm-1 with a shoulder at 3383 cm-1 for (I) is assigned to the O—H stretching band of water. Its position is much lower than that of free water molecules, and shows that the water molecules are associated via hydrogen bonds (Cammarata et al., 2001). This is also supported by a water O—H bending band at 1666 cm-1. In Fig. 4, the broad absorption in the range 3000–2200 cm-1 is a typical combination containing resonance, overtone, and hydrogen-bond O—H and C—H vibration modes. This is consistent with the short nonbonding contacts of chloride anions with C—H protons shown by X-ray determination. The strong band at 2885 cm-1 in the IR spectrum of (II) is ascribed to the O—H···Cl inter­action. No corresponding band was observed in the IR spectrum of (I), indicating the different inter­action between the carb­oxy­lic acid group and the chloride anion in (I) and (II). Another strong band at 1735 cm-1 in the IR spectrum of (II) is attributed to the CO stretching band. However, this band for (I) shifts to 1729 cm-1, and dramatically increases in half-band-width due to the strong O—H···O hydrogen bonds. IR D-type bands of (I) in the 1300–400 cm-1 region were assigned to the stretching vibrations of the protons in the strong hydrogen bonds (Hadži, 1965). This type of band was also observed for the zwitterionic 1,3-bis­(carb­oxy­methyl)­imidazole (Barczyński et al., 2008; Kratochvíl et al., 1988).

The fact that 1-carb­oxy­methyl-3-methyl­imidazolium chloride crystallizes in different forms from aqueous solution with and without CCl4 is the result of ion solvation. In aqueous solution, 1-carb­oxy­methyl-3-methyl­imidazolium chloride is totally dissociated and all of the cations and anions are completely solvated by water molecules. Addition of CCl4 strongly decreases the solubility of 1-carb­oxy­methyl-3-methyl­imidazolium chloride and leads to the association of two 1-carb­oxy­methyl-3-methyl­imidazolium cations. But the chloride ion is still fully solvated by water molecules due to the stronger inter­action. Apparently, the water content affects the ion solvation and the crystal growth, and leads to the different crystal structures. In addition, one carb­oxy­lic acid group of (I) in a crystal unit is deprotonated to yield a negatively charged carboxyl­ate group; therefore, the presence of the additional H+ could affect the crystallization process.

In summary, in the crystal of (I), two non-equivalent imidazolium cations form a homoconjugated cation by a short and asymmetric O—H···O hydrogen bond of 2.472 (2) Å. This is further confirmed by the broad D-type absorption in its IR spectrum. The chloride anion, solvated by water molecules, inter­acts electrostatically with the positively charged N atom of the homoconjugated cations. The C—H···Cl and C—H···O hydrogen bonds are also very important for the crystal packing. The structure of (I)is different to that of a previous report of 1-carb­oxy­methyl-3-methyl­imidazolium chloride due to the effect of water content on ion solvation.

Related literature top

(type here to add)

For related literature, see: Abbott et al. (2011); Baran et al. (1995, 1997); Barczyński et al. (2008, 2009); Cammarata et al. (2001); Cui et al. (2011); Danopoulos et al. (2008); Dega-Szafran, Dulewicz, Dutkiewicz & Kosturkiewicz (2006); Dega-Szafran, Katrusiak & Szafran (2010); Dong et al. (2006); Fei et al. (2004); Ghazaryan et al. (2010); Hadži (1965); Han et al. (2011); Kratochvíl et al. (1988); Li et al. (2007, 2008); Lin et al. (2011); Nockemann et al. (2006); Ratajczak et al. (1994); Rodrigues et al. (2001); Szafran et al. (2005); Xuan et al. (2012).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SMART (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the packing of O—H···O and C—H···Cl hydrogen bonds in the structure of (I). H atoms not involved in hydrogen bonds have been omitted for clarity. The imidazolium cation is shown in darker shading (blue in the electronic version of the paper) and its inner salt is shown in lighter shading (orange). Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, y-1, z; (ii) x, -y+1, z+1/2; (iii) x, y+1, z.]
[Figure 3] Fig. 3. The optimized structures of ion pairs between chloride and 1-carboxymethyl-3-methylimidazolium at the ωB97XD/6–311++G(d,p) level.
[Figure 4] Fig. 4. The IR spectra of (I) and 1-carboxymethyl-3-methylimidazolium chloride, (II).
1-Carboxymethyl-3-methyl-1H-imidazol-3-ium chloride 2-(3-methyl-1H-imidazol-3-ium-1-yl)acetate monohydrate top
Crystal data top
C6H9N2O2+·Cl·C6H8N2O2·H2OF(000) = 1408
Mr = 334.76Dx = 1.394 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2411 reflections
a = 33.661 (7) Åθ = 2.7–22.6°
b = 5.1236 (11) ŵ = 0.27 mm1
c = 20.232 (4) ÅT = 296 K
β = 113.930 (2)°Block, colourless
V = 3189.4 (12) Å30.38 × 0.27 × 0.15 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
2975 independent reflections
Radiation source: fine-focus sealed tube2218 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
phi and ω scansθmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 4039
Tmin = 0.905, Tmax = 0.961k = 66
11488 measured reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0377P)2 + 2.314P]
where P = (Fo2 + 2Fc2)/3
2975 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C6H9N2O2+·Cl·C6H8N2O2·H2OV = 3189.4 (12) Å3
Mr = 334.76Z = 8
Monoclinic, C2/cMo Kα radiation
a = 33.661 (7) ŵ = 0.27 mm1
b = 5.1236 (11) ÅT = 296 K
c = 20.232 (4) Å0.38 × 0.27 × 0.15 mm
β = 113.930 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2975 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2218 reflections with I > 2σ(I)
Tmin = 0.905, Tmax = 0.961Rint = 0.031
11488 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.04Δρmax = 0.16 e Å3
2975 reflectionsΔρmin = 0.26 e Å3
201 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell esds are taken

into account individually in the estimation of esds in distances, angles

and torsion angles; correlations between esds in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
C10.24185 (6)0.3985 (4)0.59072 (10)0.0402 (5)
H10.24130.52520.55750.048*
C20.22334 (7)0.0746 (4)0.64242 (11)0.0504 (6)
H20.20750.06100.65050.061*
C30.26308 (7)0.1549 (4)0.68765 (11)0.0496 (5)
H30.27990.08580.73300.060*
C40.16904 (6)0.2095 (4)0.51944 (11)0.0438 (5)
H4A0.16520.36250.48920.053*
H4B0.14570.20710.53580.053*
C50.16604 (6)0.0332 (4)0.47469 (10)0.0363 (4)
C60.31546 (7)0.5007 (5)0.68390 (12)0.0627 (7)
H6A0.33780.39650.67900.094*
H6B0.32320.53810.73410.094*
H6C0.31240.66120.65780.094*
C70.01660 (6)0.5302 (4)0.12712 (10)0.0402 (5)
H70.03240.67350.12290.048*
C80.00161 (6)0.1707 (4)0.16580 (11)0.0434 (5)
H80.00020.02290.19330.052*
C90.03585 (6)0.2497 (4)0.10714 (11)0.0461 (5)
H90.06270.16720.08640.055*
C100.07388 (6)0.3470 (4)0.23750 (11)0.0444 (5)
H10A0.09590.36010.21830.053*
H10B0.07800.18210.26300.053*
C110.07992 (6)0.5678 (4)0.29037 (10)0.0350 (4)
C120.05155 (8)0.6277 (5)0.01990 (11)0.0609 (7)
H12A0.07450.70840.02910.091*
H12B0.06380.51480.02130.091*
H12C0.03430.76010.01050.091*
Cl10.097469 (18)0.91074 (11)0.11794 (3)0.05696 (19)
N10.21054 (5)0.2299 (3)0.58221 (8)0.0377 (4)
N20.27420 (5)0.3573 (3)0.65456 (8)0.0416 (4)
N30.03101 (5)0.3492 (3)0.17767 (8)0.0371 (4)
N40.02401 (5)0.4746 (3)0.08329 (8)0.0410 (4)
O10.19845 (4)0.1604 (3)0.48322 (7)0.0490 (4)
O20.12741 (4)0.0774 (3)0.42887 (7)0.0489 (4)
O30.11747 (4)0.5555 (3)0.34433 (7)0.0495 (4)
H3D0.12240.71690.38030.074*
O40.05268 (4)0.7320 (3)0.28154 (8)0.0530 (4)
O50.15802 (5)0.4055 (3)0.15370 (9)0.0696 (5)
H1W0.14050.27820.14550.104*
H2W0.14210.54030.14710.104*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0368 (11)0.0424 (11)0.0359 (11)0.0002 (9)0.0089 (9)0.0004 (9)
C20.0520 (13)0.0523 (13)0.0413 (12)0.0099 (11)0.0130 (10)0.0057 (10)
C30.0518 (13)0.0535 (13)0.0344 (11)0.0008 (11)0.0080 (10)0.0063 (10)
C40.0312 (10)0.0479 (12)0.0416 (11)0.0023 (9)0.0039 (9)0.0087 (10)
C50.0319 (11)0.0421 (11)0.0316 (10)0.0007 (9)0.0096 (9)0.0016 (8)
C60.0393 (13)0.0805 (17)0.0535 (14)0.0170 (12)0.0036 (11)0.0009 (13)
C70.0389 (11)0.0390 (11)0.0429 (11)0.0074 (9)0.0166 (9)0.0090 (9)
C80.0453 (12)0.0354 (11)0.0493 (12)0.0087 (9)0.0188 (10)0.0072 (9)
C90.0347 (11)0.0439 (13)0.0545 (13)0.0094 (9)0.0126 (10)0.0152 (10)
C100.0328 (10)0.0454 (12)0.0471 (12)0.0041 (9)0.0078 (9)0.0106 (10)
C110.0311 (10)0.0325 (10)0.0392 (11)0.0014 (8)0.0120 (9)0.0007 (8)
C120.0636 (15)0.0589 (15)0.0440 (13)0.0098 (12)0.0051 (11)0.0051 (11)
Cl10.0576 (4)0.0443 (3)0.0722 (4)0.0078 (3)0.0297 (3)0.0071 (3)
N10.0314 (8)0.0412 (9)0.0345 (9)0.0016 (7)0.0072 (7)0.0036 (7)
N20.0330 (9)0.0491 (10)0.0350 (9)0.0042 (8)0.0059 (7)0.0007 (8)
N30.0316 (8)0.0359 (9)0.0400 (9)0.0017 (7)0.0105 (7)0.0071 (7)
N40.0394 (10)0.0404 (10)0.0378 (9)0.0007 (7)0.0100 (8)0.0074 (7)
O10.0373 (8)0.0561 (9)0.0451 (8)0.0122 (7)0.0081 (7)0.0057 (7)
O20.0311 (7)0.0566 (9)0.0480 (8)0.0021 (6)0.0047 (6)0.0175 (7)
O30.0354 (8)0.0474 (9)0.0485 (8)0.0046 (6)0.0009 (7)0.0112 (7)
O40.0441 (8)0.0455 (9)0.0537 (9)0.0138 (7)0.0035 (7)0.0112 (7)
O50.0484 (9)0.0571 (10)0.0855 (12)0.0023 (8)0.0089 (9)0.0124 (9)
Geometric parameters (Å, º) top
C1—N11.319 (2)C7—H70.9300
C1—N21.326 (2)C8—C91.338 (3)
C1—H10.9300C8—N31.373 (2)
C2—C31.343 (3)C8—H80.9300
C2—N11.370 (2)C9—N41.370 (3)
C2—H20.9300C9—H90.9300
C3—N21.366 (3)C10—N31.460 (2)
C3—H30.9300C10—C111.513 (3)
C4—N11.461 (2)C10—H10A0.9700
C4—C51.517 (3)C10—H10B0.9700
C4—H4A0.9700C11—O41.203 (2)
C4—H4B0.9700C11—O31.294 (2)
C5—O11.222 (2)C12—N41.468 (3)
C5—O21.274 (2)C12—H12A0.9600
C6—N21.467 (2)C12—H12B0.9600
C6—H6A0.9600C12—H12C0.9600
C6—H6B0.9600O3—H3D1.0688
C6—H6C0.9600O5—H1W0.8499
C7—N31.318 (2)O5—H2W0.8500
C7—N41.324 (2)
N1—C1—N2108.66 (18)C8—C9—H9126.3
N1—C1—H1125.7N4—C9—H9126.3
N2—C1—H1125.7N3—C10—C11112.62 (15)
C3—C2—N1107.17 (19)N3—C10—H10A109.1
C3—C2—H2126.4C11—C10—H10A109.1
N1—C2—H2126.4N3—C10—H10B109.1
C2—C3—N2107.08 (18)C11—C10—H10B109.1
C2—C3—H3126.5H10A—C10—H10B107.8
N2—C3—H3126.5O4—C11—O3125.74 (18)
N1—C4—C5112.70 (16)O4—C11—C10122.82 (17)
N1—C4—H4A109.1O3—C11—C10111.44 (16)
C5—C4—H4A109.1N4—C12—H12A109.5
N1—C4—H4B109.1N4—C12—H12B109.5
C5—C4—H4B109.1H12A—C12—H12B109.5
H4A—C4—H4B107.8N4—C12—H12C109.5
O1—C5—O2126.66 (18)H12A—C12—H12C109.5
O1—C5—C4120.91 (17)H12B—C12—H12C109.5
O2—C5—C4112.41 (16)C1—N1—C2108.53 (16)
N2—C6—H6A109.5C1—N1—C4126.28 (17)
N2—C6—H6B109.5C2—N1—C4125.19 (17)
H6A—C6—H6B109.5C1—N2—C3108.55 (17)
N2—C6—H6C109.5C1—N2—C6125.68 (18)
H6A—C6—H6C109.5C3—N2—C6125.75 (17)
H6B—C6—H6C109.5C7—N3—C8108.44 (16)
N3—C7—N4108.86 (17)C7—N3—C10125.29 (17)
N3—C7—H7125.6C8—N3—C10126.23 (18)
N4—C7—H7125.6C7—N4—C9108.31 (17)
C9—C8—N3107.07 (19)C7—N4—C12125.79 (19)
C9—C8—H8126.5C9—N4—C12125.91 (18)
N3—C8—H8126.5C11—O3—H3D111.4
C8—C9—N4107.32 (17)H1W—O5—H2W104.5
N1—C2—C3—N20.2 (2)N1—C1—N2—C6178.75 (19)
N1—C4—C5—O114.3 (3)C2—C3—N2—C10.0 (2)
N1—C4—C5—O2167.11 (17)C2—C3—N2—C6178.5 (2)
N3—C8—C9—N40.3 (2)N4—C7—N3—C80.0 (2)
N3—C10—C11—O43.0 (3)N4—C7—N3—C10177.78 (16)
N3—C10—C11—O3177.45 (16)C9—C8—N3—C70.2 (2)
N2—C1—N1—C20.3 (2)C9—C8—N3—C10177.57 (17)
N2—C1—N1—C4179.75 (17)C11—C10—N3—C766.7 (2)
C3—C2—N1—C10.4 (2)C11—C10—N3—C8110.7 (2)
C3—C2—N1—C4179.73 (18)N3—C7—N4—C90.2 (2)
C5—C4—N1—C1109.0 (2)N3—C7—N4—C12179.70 (18)
C5—C4—N1—C270.9 (2)C8—C9—N4—C70.3 (2)
N1—C1—N2—C30.2 (2)C8—C9—N4—C12179.60 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···Cl1i0.852.303.1475 (17)174
O5—H2W···Cl10.852.343.1910 (18)175
O3—H3D···O2ii1.07 (1)1.40 (1)2.472 (2)177 (2)
C1—H1···O1ii0.932.273.065 (2)143
C1—H1···O1iii0.932.573.243 (3)129
C2—H2···O5iv0.932.453.368 (3)172
C3—H3···O5iii0.932.403.246 (3)152
C4—H4B···Cl1v0.972.823.748 (2)161
C7—H7···Cl10.932.543.414 (2)156
C8—H8···O4i0.932.453.225 (3)141
C8—H8···O4vi0.932.523.260 (2)137
C9—H9···O2vii0.932.423.319 (2)162
C10—H10B···O4i0.972.543.428 (3)152
C12—H12A···O2viii0.962.513.468 (3)172
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+1; (iv) x, y, z+1/2; (v) x, y+1, z+1/2; (vi) x, y1, z+1/2; (vii) x, y, z+1/2; (viii) x, y+1, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H9N2O2+·Cl·C6H8N2O2·H2O
Mr334.76
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)33.661 (7), 5.1236 (11), 20.232 (4)
β (°) 113.930 (2)
V3)3189.4 (12)
Z8
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.38 × 0.27 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.905, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections
11488, 2975, 2218
Rint0.031
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.097, 1.04
No. of reflections2975
No. of parameters201
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.26

Computer programs: SMART (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···Cl1i0.852.303.1475 (17)173.8
O5—H2W···Cl10.852.343.1910 (18)174.8
O3—H3D···O2ii1.070 (2)1.402 (3)2.472 (2)177 (2)
C1—H1···O1ii0.932.273.065 (2)142.5
C1—H1···O1iii0.932.573.243 (3)129.3
C2—H2···O5iv0.932.453.368 (3)171.7
C3—H3···O5iii0.932.403.246 (3)151.8
C4—H4B···Cl1v0.972.823.748 (2)160.9
C7—H7···Cl10.932.543.414 (2)156.1
C8—H8···O4i0.932.453.225 (3)141.1
C8—H8···O4vi0.932.523.260 (2)137.2
C9—H9···O2vii0.932.423.319 (2)162.3
C10—H10B···O4i0.972.543.428 (3)152.4
C12—H12A···O2viii0.962.513.468 (3)172.1
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+1; (iv) x, y, z+1/2; (v) x, y+1, z+1/2; (vi) x, y1, z+1/2; (vii) x, y, z+1/2; (viii) x, y+1, z+1/2.
 

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