Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023676/ku3105sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023676/ku3105Isup2.hkl |
CCDC reference: 924050
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).
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.
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).
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 C═O 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.
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).
C6H9N2O2+·Cl−·C6H8N2O2·H2O | F(000) = 1408 |
Mr = 334.76 | Dx = 1.394 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2411 reflections |
a = 33.661 (7) Å | θ = 2.7–22.6° |
b = 5.1236 (11) Å | µ = 0.27 mm−1 |
c = 20.232 (4) Å | T = 296 K |
β = 113.930 (2)° | Block, colourless |
V = 3189.4 (12) Å3 | 0.38 × 0.27 × 0.15 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 2975 independent reflections |
Radiation source: fine-focus sealed tube | 2218 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
phi and ω scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −40→39 |
Tmin = 0.905, Tmax = 0.961 | k = −6→6 |
11488 measured reflections | l = −24→24 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-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 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C6H9N2O2+·Cl−·C6H8N2O2·H2O | V = 3189.4 (12) Å3 |
Mr = 334.76 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.661 (7) Å | µ = 0.27 mm−1 |
b = 5.1236 (11) Å | T = 296 K |
c = 20.232 (4) Å | 0.38 × 0.27 × 0.15 mm |
β = 113.930 (2)° |
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 = 0.961 | Rint = 0.031 |
11488 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.16 e Å−3 |
2975 reflections | Δρmin = −0.26 e Å−3 |
201 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.24185 (6) | 0.3985 (4) | 0.59072 (10) | 0.0402 (5) | |
H1 | 0.2413 | 0.5252 | 0.5575 | 0.048* | |
C2 | 0.22334 (7) | 0.0746 (4) | 0.64242 (11) | 0.0504 (6) | |
H2 | 0.2075 | −0.0610 | 0.6505 | 0.061* | |
C3 | 0.26308 (7) | 0.1549 (4) | 0.68765 (11) | 0.0496 (5) | |
H3 | 0.2799 | 0.0858 | 0.7330 | 0.060* | |
C4 | 0.16904 (6) | 0.2095 (4) | 0.51944 (11) | 0.0438 (5) | |
H4A | 0.1652 | 0.3625 | 0.4892 | 0.053* | |
H4B | 0.1457 | 0.2071 | 0.5358 | 0.053* | |
C5 | 0.16604 (6) | −0.0332 (4) | 0.47469 (10) | 0.0363 (4) | |
C6 | 0.31546 (7) | 0.5007 (5) | 0.68390 (12) | 0.0627 (7) | |
H6A | 0.3378 | 0.3965 | 0.6790 | 0.094* | |
H6B | 0.3232 | 0.5381 | 0.7341 | 0.094* | |
H6C | 0.3124 | 0.6612 | 0.6578 | 0.094* | |
C7 | 0.01660 (6) | 0.5302 (4) | 0.12712 (10) | 0.0402 (5) | |
H7 | 0.0324 | 0.6735 | 0.1229 | 0.048* | |
C8 | −0.00161 (6) | 0.1707 (4) | 0.16580 (11) | 0.0434 (5) | |
H8 | −0.0002 | 0.0229 | 0.1933 | 0.052* | |
C9 | −0.03585 (6) | 0.2497 (4) | 0.10714 (11) | 0.0461 (5) | |
H9 | −0.0627 | 0.1672 | 0.0864 | 0.055* | |
C10 | 0.07388 (6) | 0.3470 (4) | 0.23750 (11) | 0.0444 (5) | |
H10A | 0.0959 | 0.3601 | 0.2183 | 0.053* | |
H10B | 0.0780 | 0.1821 | 0.2630 | 0.053* | |
C11 | 0.07992 (6) | 0.5678 (4) | 0.29037 (10) | 0.0350 (4) | |
C12 | −0.05155 (8) | 0.6277 (5) | 0.01990 (11) | 0.0609 (7) | |
H12A | −0.0745 | 0.7084 | 0.0291 | 0.091* | |
H12B | −0.0638 | 0.5148 | −0.0213 | 0.091* | |
H12C | −0.0343 | 0.7601 | 0.0105 | 0.091* | |
Cl1 | 0.097469 (18) | 0.91074 (11) | 0.11794 (3) | 0.05696 (19) | |
N1 | 0.21054 (5) | 0.2299 (3) | 0.58221 (8) | 0.0377 (4) | |
N2 | 0.27420 (5) | 0.3573 (3) | 0.65456 (8) | 0.0416 (4) | |
N3 | 0.03101 (5) | 0.3492 (3) | 0.17767 (8) | 0.0371 (4) | |
N4 | −0.02401 (5) | 0.4746 (3) | 0.08329 (8) | 0.0410 (4) | |
O1 | 0.19845 (4) | −0.1604 (3) | 0.48322 (7) | 0.0490 (4) | |
O2 | 0.12741 (4) | −0.0774 (3) | 0.42887 (7) | 0.0489 (4) | |
O3 | 0.11747 (4) | 0.5555 (3) | 0.34433 (7) | 0.0495 (4) | |
H3D | 0.1224 | 0.7169 | 0.3803 | 0.074* | |
O4 | 0.05268 (4) | 0.7320 (3) | 0.28154 (8) | 0.0530 (4) | |
O5 | 0.15802 (5) | 0.4055 (3) | 0.15370 (9) | 0.0696 (5) | |
H1W | 0.1405 | 0.2782 | 0.1455 | 0.104* | |
H2W | 0.1421 | 0.5403 | 0.1471 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0368 (11) | 0.0424 (11) | 0.0359 (11) | 0.0002 (9) | 0.0089 (9) | 0.0004 (9) |
C2 | 0.0520 (13) | 0.0523 (13) | 0.0413 (12) | −0.0099 (11) | 0.0130 (10) | 0.0057 (10) |
C3 | 0.0518 (13) | 0.0535 (13) | 0.0344 (11) | −0.0008 (11) | 0.0080 (10) | 0.0063 (10) |
C4 | 0.0312 (10) | 0.0479 (12) | 0.0416 (11) | 0.0023 (9) | 0.0039 (9) | −0.0087 (10) |
C5 | 0.0319 (11) | 0.0421 (11) | 0.0316 (10) | −0.0007 (9) | 0.0096 (9) | 0.0016 (8) |
C6 | 0.0393 (13) | 0.0805 (17) | 0.0535 (14) | −0.0170 (12) | 0.0036 (11) | 0.0009 (13) |
C7 | 0.0389 (11) | 0.0390 (11) | 0.0429 (11) | −0.0074 (9) | 0.0166 (9) | −0.0090 (9) |
C8 | 0.0453 (12) | 0.0354 (11) | 0.0493 (12) | −0.0087 (9) | 0.0188 (10) | −0.0072 (9) |
C9 | 0.0347 (11) | 0.0439 (13) | 0.0545 (13) | −0.0094 (9) | 0.0126 (10) | −0.0152 (10) |
C10 | 0.0328 (10) | 0.0454 (12) | 0.0471 (12) | 0.0041 (9) | 0.0078 (9) | −0.0106 (10) |
C11 | 0.0311 (10) | 0.0325 (10) | 0.0392 (11) | −0.0014 (8) | 0.0120 (9) | 0.0007 (8) |
C12 | 0.0636 (15) | 0.0589 (15) | 0.0440 (13) | 0.0098 (12) | 0.0051 (11) | −0.0051 (11) |
Cl1 | 0.0576 (4) | 0.0443 (3) | 0.0722 (4) | −0.0078 (3) | 0.0297 (3) | −0.0071 (3) |
N1 | 0.0314 (8) | 0.0412 (9) | 0.0345 (9) | −0.0016 (7) | 0.0072 (7) | −0.0036 (7) |
N2 | 0.0330 (9) | 0.0491 (10) | 0.0350 (9) | −0.0042 (8) | 0.0059 (7) | −0.0007 (8) |
N3 | 0.0316 (8) | 0.0359 (9) | 0.0400 (9) | −0.0017 (7) | 0.0105 (7) | −0.0071 (7) |
N4 | 0.0394 (10) | 0.0404 (10) | 0.0378 (9) | 0.0007 (7) | 0.0100 (8) | −0.0074 (7) |
O1 | 0.0373 (8) | 0.0561 (9) | 0.0451 (8) | 0.0122 (7) | 0.0081 (7) | −0.0057 (7) |
O2 | 0.0311 (7) | 0.0566 (9) | 0.0480 (8) | −0.0021 (6) | 0.0047 (6) | −0.0175 (7) |
O3 | 0.0354 (8) | 0.0474 (9) | 0.0485 (8) | 0.0046 (6) | −0.0009 (7) | −0.0112 (7) |
O4 | 0.0441 (8) | 0.0455 (9) | 0.0537 (9) | 0.0138 (7) | 0.0035 (7) | −0.0112 (7) |
O5 | 0.0484 (9) | 0.0571 (10) | 0.0855 (12) | −0.0023 (8) | 0.0089 (9) | 0.0124 (9) |
C1—N1 | 1.319 (2) | C7—H7 | 0.9300 |
C1—N2 | 1.326 (2) | C8—C9 | 1.338 (3) |
C1—H1 | 0.9300 | C8—N3 | 1.373 (2) |
C2—C3 | 1.343 (3) | C8—H8 | 0.9300 |
C2—N1 | 1.370 (2) | C9—N4 | 1.370 (3) |
C2—H2 | 0.9300 | C9—H9 | 0.9300 |
C3—N2 | 1.366 (3) | C10—N3 | 1.460 (2) |
C3—H3 | 0.9300 | C10—C11 | 1.513 (3) |
C4—N1 | 1.461 (2) | C10—H10A | 0.9700 |
C4—C5 | 1.517 (3) | C10—H10B | 0.9700 |
C4—H4A | 0.9700 | C11—O4 | 1.203 (2) |
C4—H4B | 0.9700 | C11—O3 | 1.294 (2) |
C5—O1 | 1.222 (2) | C12—N4 | 1.468 (3) |
C5—O2 | 1.274 (2) | C12—H12A | 0.9600 |
C6—N2 | 1.467 (2) | C12—H12B | 0.9600 |
C6—H6A | 0.9600 | C12—H12C | 0.9600 |
C6—H6B | 0.9600 | O3—H3D | 1.0688 |
C6—H6C | 0.9600 | O5—H1W | 0.8499 |
C7—N3 | 1.318 (2) | O5—H2W | 0.8500 |
C7—N4 | 1.324 (2) | ||
N1—C1—N2 | 108.66 (18) | C8—C9—H9 | 126.3 |
N1—C1—H1 | 125.7 | N4—C9—H9 | 126.3 |
N2—C1—H1 | 125.7 | N3—C10—C11 | 112.62 (15) |
C3—C2—N1 | 107.17 (19) | N3—C10—H10A | 109.1 |
C3—C2—H2 | 126.4 | C11—C10—H10A | 109.1 |
N1—C2—H2 | 126.4 | N3—C10—H10B | 109.1 |
C2—C3—N2 | 107.08 (18) | C11—C10—H10B | 109.1 |
C2—C3—H3 | 126.5 | H10A—C10—H10B | 107.8 |
N2—C3—H3 | 126.5 | O4—C11—O3 | 125.74 (18) |
N1—C4—C5 | 112.70 (16) | O4—C11—C10 | 122.82 (17) |
N1—C4—H4A | 109.1 | O3—C11—C10 | 111.44 (16) |
C5—C4—H4A | 109.1 | N4—C12—H12A | 109.5 |
N1—C4—H4B | 109.1 | N4—C12—H12B | 109.5 |
C5—C4—H4B | 109.1 | H12A—C12—H12B | 109.5 |
H4A—C4—H4B | 107.8 | N4—C12—H12C | 109.5 |
O1—C5—O2 | 126.66 (18) | H12A—C12—H12C | 109.5 |
O1—C5—C4 | 120.91 (17) | H12B—C12—H12C | 109.5 |
O2—C5—C4 | 112.41 (16) | C1—N1—C2 | 108.53 (16) |
N2—C6—H6A | 109.5 | C1—N1—C4 | 126.28 (17) |
N2—C6—H6B | 109.5 | C2—N1—C4 | 125.19 (17) |
H6A—C6—H6B | 109.5 | C1—N2—C3 | 108.55 (17) |
N2—C6—H6C | 109.5 | C1—N2—C6 | 125.68 (18) |
H6A—C6—H6C | 109.5 | C3—N2—C6 | 125.75 (17) |
H6B—C6—H6C | 109.5 | C7—N3—C8 | 108.44 (16) |
N3—C7—N4 | 108.86 (17) | C7—N3—C10 | 125.29 (17) |
N3—C7—H7 | 125.6 | C8—N3—C10 | 126.23 (18) |
N4—C7—H7 | 125.6 | C7—N4—C9 | 108.31 (17) |
C9—C8—N3 | 107.07 (19) | C7—N4—C12 | 125.79 (19) |
C9—C8—H8 | 126.5 | C9—N4—C12 | 125.91 (18) |
N3—C8—H8 | 126.5 | C11—O3—H3D | 111.4 |
C8—C9—N4 | 107.32 (17) | H1W—O5—H2W | 104.5 |
N1—C2—C3—N2 | −0.2 (2) | N1—C1—N2—C6 | 178.75 (19) |
N1—C4—C5—O1 | −14.3 (3) | C2—C3—N2—C1 | 0.0 (2) |
N1—C4—C5—O2 | 167.11 (17) | C2—C3—N2—C6 | −178.5 (2) |
N3—C8—C9—N4 | 0.3 (2) | N4—C7—N3—C8 | 0.0 (2) |
N3—C10—C11—O4 | −3.0 (3) | N4—C7—N3—C10 | −177.78 (16) |
N3—C10—C11—O3 | 177.45 (16) | C9—C8—N3—C7 | −0.2 (2) |
N2—C1—N1—C2 | −0.3 (2) | C9—C8—N3—C10 | 177.57 (17) |
N2—C1—N1—C4 | 179.75 (17) | C11—C10—N3—C7 | 66.7 (2) |
C3—C2—N1—C1 | 0.4 (2) | C11—C10—N3—C8 | −110.7 (2) |
C3—C2—N1—C4 | −179.73 (18) | N3—C7—N4—C9 | 0.2 (2) |
C5—C4—N1—C1 | 109.0 (2) | N3—C7—N4—C12 | −179.70 (18) |
C5—C4—N1—C2 | −70.9 (2) | C8—C9—N4—C7 | −0.3 (2) |
N1—C1—N2—C3 | 0.2 (2) | C8—C9—N4—C12 | 179.60 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1W···Cl1i | 0.85 | 2.30 | 3.1475 (17) | 174 |
O5—H2W···Cl1 | 0.85 | 2.34 | 3.1910 (18) | 175 |
O3—H3D···O2ii | 1.07 (1) | 1.40 (1) | 2.472 (2) | 177 (2) |
C1—H1···O1ii | 0.93 | 2.27 | 3.065 (2) | 143 |
C1—H1···O1iii | 0.93 | 2.57 | 3.243 (3) | 129 |
C2—H2···O5iv | 0.93 | 2.45 | 3.368 (3) | 172 |
C3—H3···O5iii | 0.93 | 2.40 | 3.246 (3) | 152 |
C4—H4B···Cl1v | 0.97 | 2.82 | 3.748 (2) | 161 |
C7—H7···Cl1 | 0.93 | 2.54 | 3.414 (2) | 156 |
C8—H8···O4i | 0.93 | 2.45 | 3.225 (3) | 141 |
C8—H8···O4vi | 0.93 | 2.52 | 3.260 (2) | 137 |
C9—H9···O2vii | 0.93 | 2.42 | 3.319 (2) | 162 |
C10—H10B···O4i | 0.97 | 2.54 | 3.428 (3) | 152 |
C12—H12A···O2viii | 0.96 | 2.51 | 3.468 (3) | 172 |
Symmetry codes: (i) x, y−1, 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, y−1, −z+1/2; (vii) −x, y, −z+1/2; (viii) −x, y+1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H9N2O2+·Cl−·C6H8N2O2·H2O |
Mr | 334.76 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 33.661 (7), 5.1236 (11), 20.232 (4) |
β (°) | 113.930 (2) |
V (Å3) | 3189.4 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.38 × 0.27 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.905, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11488, 2975, 2218 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.097, 1.04 |
No. of reflections | 2975 |
No. of parameters | 201 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.26 |
Computer programs: SMART (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1W···Cl1i | 0.85 | 2.30 | 3.1475 (17) | 173.8 |
O5—H2W···Cl1 | 0.85 | 2.34 | 3.1910 (18) | 174.8 |
O3—H3D···O2ii | 1.070 (2) | 1.402 (3) | 2.472 (2) | 177 (2) |
C1—H1···O1ii | 0.93 | 2.27 | 3.065 (2) | 142.5 |
C1—H1···O1iii | 0.93 | 2.57 | 3.243 (3) | 129.3 |
C2—H2···O5iv | 0.93 | 2.45 | 3.368 (3) | 171.7 |
C3—H3···O5iii | 0.93 | 2.40 | 3.246 (3) | 151.8 |
C4—H4B···Cl1v | 0.97 | 2.82 | 3.748 (2) | 160.9 |
C7—H7···Cl1 | 0.93 | 2.54 | 3.414 (2) | 156.1 |
C8—H8···O4i | 0.93 | 2.45 | 3.225 (3) | 141.1 |
C8—H8···O4vi | 0.93 | 2.52 | 3.260 (2) | 137.2 |
C9—H9···O2vii | 0.93 | 2.42 | 3.319 (2) | 162.3 |
C10—H10B···O4i | 0.97 | 2.54 | 3.428 (3) | 152.4 |
C12—H12A···O2viii | 0.96 | 2.51 | 3.468 (3) | 172.1 |
Symmetry codes: (i) x, y−1, 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, y−1, −z+1/2; (vii) −x, y, −z+1/2; (viii) −x, y+1, −z+1/2. |