organic compounds
Bis(dimethylammonium) 3,3′-dicarboxy-5,5′-(5,7,12,14-tetraoxo-6,13-diazatetracyclo[6.6.2.04,16.011,15]hexadeca-1,3,8,10,15-pentaene-6,13-diyl)dibenzoate dihydrate
aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, People's Republic of China, and bState Key Laboratory of Structural, Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China
*Correspondence e-mail: hanlei@nbu.edu.cn
The title compound, 2C2H8N+·C30H12N2O122−·2H2O, comprises dimethylammonium cations, 3,3′-dicarboxy-5,5′-(5,7,12,14-tetraoxo-6,13-diazatetracyclo[6.6.2.04,16.011,15]hexadeca-1,3,8,10,15-pentaene-6,13-diyl)dibenzoate dianions and water molecules. The dianion is situated on a crystallographic inversion centre. Two very strong symmetry-restricted O⋯H⋯O hydrogen bonds are present which are situated about the crystallographic inversion centres. In one of these hydrogen bonds, the H atom is situated at its centre, while in the other one the H atom is disordered about its centre. Both H atoms are involved in the chain-like C22(16) motif, and not in a more common motif R22(8) that is composed of a pair of hydrogen carboxylates with the H atoms situated about the centre between the pair of O atoms. In the crystal, interaction of these hydrogen bonds results in formation of anionic layers of dianions parallel to (-111). The water molecules donate their H atoms to one of two of the carboxylate O atoms, forming strong hydrogen bonds. The dimethylammonium donates a bifurcated hydrogen bond to an oxo group of the dianion, forming weak hydrogen bonds. All the hydrogen bonds form a three-dimensional hydrogen-bonded network.
Related literature
For organic supramolecular solids, see: Pantos et al. (2007). For multi-component molecular crystals or organic co-crystals, see: Bond (2007); MacGillivray (2008); Yan et al. (2011). For prediction of organic crystal structures, see: Pigge (2011). For organic structures based on naphthalaleneteracarboxylic diimide derivatives, see: Xu et al. (2011). For hydrogen carboxylates forming chain-like motifs with very strong O—H⋯O hydrogen bonds, see: Foces-Foces et al. (1996); Hsu et al. (2006); Aciro et al. (2009). For in situ hydrolysis of dimethylformamide molecules, see: Jain et al. (2008). For classification of hydrogen bonds, see: Desiraju & Steiner (1999). For graph-set motifs, see: Etter et al. (1990). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku/MSC, 2008); cell CrystalClear; data reduction: CrystalClear; 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: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812025470/fb2246sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025470/fb2246Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812025470/fb2246Isup3.cml
A mixture of 5,5-[naphthalene-1,8:4,5- bis(dicarboximide)-N,N-diyl]bis(benzene-1,3-dicarboxylic acid) (59.4 mg, 0.1 mmol), 1,10-phenanthroline (35.9 mg, 0.2 mmol) in dimethylformamide (3 ml) was sealed in a 25 ml teflon-lined stainless steel reactor and heated at 393 K for 72 h. Colourless and cube-like single crystals of the title compound were obtained after cooling to room temperature. The yield equals to 50 weight %.
All the hydrogens were discernible in the difference electron density maps. Notably in the final stages of the
it turned out that the hydrogens H1 and H2 involved in the symmetry restricted strong hydrogen bonds were situated just at the centre or disorded about it, respectively. The positional as well as the displacement parameters of these hydrogens have been refined. The positional parameters of the water hydrogens H3 and H4 were refined using the following restraints: The O7—H3 and O7—H4 distances equal to 0.965 (20) Å while for the angle was used restraint DANG 1.5555 (400) (SHELXL97; Sheldrick, 2008) which corresponds to the average angle H—Ow—H (107.407°) retrieved from the Cambridge Structural Database (CSD) (Allen, 2002) from the structures determined by neutron diffraction. The isotropic displacement parameters of these hydrogens (H3 and H4) were constrained as Uiso(H) = 1.5Ueq(O). Other H atoms were allowed to ride on their respective parent atoms at distances of C—H(phenyl) = 0.93 Å with Uiso(H) = 1.2 Ueq(C), C—H(methyl) = 0.96 Å with Uiso(H) = 1.5Ueq(C), N—H(ammonium) = 0.90 Å with Uiso(H) = 1.2Ueq(N).Assemblies of functionalised organic molecules in the solid state have attracted much interest in crystal engineering and materials science (Pantos et al., 2007). Recently, much attention has been paid to formation of multi-component molecular crystals or organic co-crystals as a means of modification of properties of organic molecules in the solid state (Bond, 2007; MacGillivray, 2008; Yan et al., 2011). However, an effective strategy for tuning functionality of
solids still remains challenging (Pigge, 2011).We have been interested in utilizing acid-functionalized naphthalaleneteracarboxylic diimide derivatives as starting materials in crystal engineering of a series of functional organic
materials (Xu et al., 2011). Herein we report an organic salt, 2(C2H8N)+.(C30H12N2O12)2-.2H2O, which has been prepared under solvothermal reaction from 5,5-[naphthalene-1,8:4,5- bis(dicarboximide)-N,N-diyl]bis(benzene-1,3-dicarboxylic acid) and 1,10-phenanthroline in dimethylformamide (DMF). The dimethylammonium cations in the title structure were formed by in situ hydrolysis of the dimethylformamide molecules (Jain et al., 2008).Single-crystal X-ray
has indicated that the title structure is composed dimethylammonium cations, 3,3-dicarboxy-5,5-[naphthalene-1,8:4,5- bis(dicarboximide)-N,N-diyl]bis(benzene-1-carboxylate) anion and water molecules. As shown in Fig. 1, the anion is situated on the crystallographic inversion centre.The most prominent as well as unusual feature of the title structure is presence of two different very strong symmetry restricted hydrogen bonds (Table 1; for the terminology of the hydrogen bonds, see Desiraju & Steiner, 1999). One of the hydrogens (H1) is situated at its centre while the other one (H4) is disordered about it as revealed the difference electron density maps. These hydrogens form a chain-like motif C22(16) (Etter et al., 1990). The atoms involved in this motif are as follows: H2···O4-C5-C4-C3-C2-C1-O1···H1···O1i-C1i-C2i-C3i-C4i-C5i-O4i···, where the symmetry code i = 1-x, 1-y, 1-z. This is only a fourth known example (Cambridge Structural Database (Allen, 2002; version 5.33)) of a chain motif in the hydrogen carboxylates with a strong or very strong hydrogen bond (up to 2.55Å for O···O) in contrast to 11 structures with a motif R22(8) with the same type of the hydrogen bonds (up to 2.55Å for O···O) between the hydrogen carboxylates. The structures with the chain motif are as follows: (RABNEN, 4-(3,5-dimethylpyrazol-4-yl)benzoic acid trifluoroacetate, Foces-Foces et al. (1996); SERYUK, sesquikis(3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine) trimesic acid dehydrate, Hsu et al. (2006); POYXOR, hemikis((1RS,2RS,3RS)-3-N,N-dibenzylaminocyclohexane -1,2-diol N-oxide) 3-chlorobenzoic acid, Aciro et al. (2009).
In the title structure, these short hydrogen bonds form 2D-layers (Fig. 2). The 2D-framework is extended to a 3D network by involvement of water which donates strong O—H···O hydrogen bonds to the oxo-groups of the hydrogen carboxylates. Dimethylammonium donates a weak bifurcated hydrogen bond to the oxo-group O5.
For organic supramolecular solids, see: Pantos et al. (2007). For multi-component molecular crystals or organic co-crystals, see: Bond (2007); MacGillivray (2008); Yan et al. (2011). For prediction of organic crystal structures, see: Pigge (2011). For organic structures based on naphthalaleneteracarboxylic diimide derivatives, see: Xu et al. (2011). For hydrogen carboxylates forming chain-like motifs with very strong O—H···O hydrogen bonds, see: Foces-Foces et al. (1996); Hsu et al. (2006); Aciro et al. (2009). For in situ hydrolysis of dimethylformamide molecules, see: Jain et al. (2008). For classification of hydrogen bonds, see: Desiraju & Steiner (1999). For graph-set motifs, see: Etter et al. (1990). For a description of the Cambridge Structural Database, see: Allen (2002).
Data collection: CrystalClear (Rigaku/MSC, 2008); cell
CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); 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: SHELXL97 (Sheldrick, 2008.Fig. 1. The title molecule with the displacement ellipsoids drawn at the 30% probability level and with the labelling scheme. The H atoms are shown as small spheres of arbitrary radii. (Symmetry code: i -x+1, -y+2, -z.) | |
Fig. 2. View of the anionic layer with very strong symmetry-restricted hydrogen bonds. |
2C2H8N+·C30H12N2O122−·2H2O | F(000) = 752 |
Mr = 720.64 | Dx = 1.443 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3435 reflections |
a = 10.428 (13) Å | θ = 2.2–27.6° |
b = 8.651 (10) Å | µ = 0.11 mm−1 |
c = 18.40 (2) Å | T = 293 K |
β = 91.956 (16)° | Cube-like, colourless |
V = 1659 (4) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 2 |
Rigaku Saturn70 diffractometer | 3780 independent reflections |
Radiation source: fine-focus sealed tube | 2137 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
CCD_Profile_fitting scans | h = −13→13 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008) | k = −11→11 |
Tmin = 0.788, Tmax = 1.000 | l = −23→21 |
12286 measured reflections |
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)] = 0.081 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.266 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.1621P)2] where P = (Fo2 + 2Fc2)/3 |
3780 reflections | (Δ/σ)max < 0.001 |
248 parameters | Δρmax = 0.43 e Å−3 |
3 restraints | Δρmin = −0.36 e Å−3 |
0 constraints |
2C2H8N+·C30H12N2O122−·2H2O | V = 1659 (4) Å3 |
Mr = 720.64 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.428 (13) Å | µ = 0.11 mm−1 |
b = 8.651 (10) Å | T = 293 K |
c = 18.40 (2) Å | 0.20 × 0.20 × 0.20 mm |
β = 91.956 (16)° |
Rigaku Saturn70 diffractometer | 3780 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008) | 2137 reflections with I > 2σ(I) |
Tmin = 0.788, Tmax = 1.000 | Rint = 0.051 |
12286 measured reflections |
R[F2 > 2σ(F2)] = 0.081 | 3 restraints |
wR(F2) = 0.266 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.43 e Å−3 |
3780 reflections | Δρmin = −0.36 e Å−3 |
248 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 | Occ. (<1) | |
N1 | 0.6155 (2) | 0.9195 (3) | 0.17822 (12) | 0.0435 (6) | |
C3 | 0.7165 (3) | 0.7875 (3) | 0.39335 (14) | 0.0430 (6) | |
H3A | 0.7380 | 0.7588 | 0.4409 | 0.052* | |
O6 | 0.7771 (2) | 0.7754 (3) | 0.13324 (12) | 0.0697 (7) | |
C6 | 0.7610 (3) | 0.9351 (3) | 0.28630 (15) | 0.0473 (7) | |
H6A | 0.8123 | 1.0043 | 0.2617 | 0.057* | |
C12 | 0.5244 (2) | 0.9859 (3) | 0.03593 (13) | 0.0402 (6) | |
C7 | 0.6535 (3) | 0.8733 (3) | 0.25224 (13) | 0.0415 (6) | |
C8 | 0.5761 (3) | 0.7673 (3) | 0.28718 (14) | 0.0425 (6) | |
H8A | 0.5040 | 0.7259 | 0.2633 | 0.051* | |
O5 | 0.4661 (3) | 1.0808 (3) | 0.22384 (12) | 0.0720 (8) | |
O3 | 0.9850 (2) | 1.0402 (3) | 0.36519 (13) | 0.0745 (8) | |
C14 | 0.5140 (3) | 1.0235 (3) | 0.17045 (14) | 0.0459 (7) | |
C4 | 0.7929 (3) | 0.8936 (3) | 0.35776 (14) | 0.0442 (7) | |
C13 | 0.4669 (3) | 1.0575 (3) | 0.09499 (14) | 0.0444 (7) | |
O1 | 0.5588 (3) | 0.5959 (3) | 0.46612 (13) | 0.0822 (9) | |
H1 | 0.5000 | 0.5000 | 0.5000 | 0.17 (4)* | |
C2 | 0.6085 (3) | 0.7243 (3) | 0.35853 (14) | 0.0409 (6) | |
C9 | 0.6833 (3) | 0.8543 (4) | 0.12086 (15) | 0.0473 (7) | |
C1 | 0.5278 (3) | 0.6114 (4) | 0.39882 (16) | 0.0538 (8) | |
C10 | 0.6314 (3) | 0.8857 (3) | 0.04610 (14) | 0.0452 (7) | |
C15 | 0.3628 (3) | 1.1555 (4) | 0.08394 (16) | 0.0569 (8) | |
H15A | 0.3255 | 1.2033 | 0.1232 | 0.068* | |
C5 | 0.9058 (3) | 0.9650 (4) | 0.39769 (17) | 0.0555 (8) | |
C11 | 0.6858 (3) | 0.8183 (4) | −0.01297 (16) | 0.0590 (8) | |
H11A | 0.7565 | 0.7538 | −0.0058 | 0.071* | |
N2 | 0.3624 (5) | 0.1938 (5) | 0.3549 (2) | 0.1119 (15) | |
H2A | 0.4089 | 0.2749 | 0.3401 | 0.134* | |
H2B | 0.3412 | 0.1375 | 0.3152 | 0.134* | |
C16 | 0.2451 (4) | 0.2531 (6) | 0.3843 (3) | 0.0923 (13) | |
H16A | 0.1929 | 0.2981 | 0.3459 | 0.138* | |
H16B | 0.2656 | 0.3303 | 0.4203 | 0.138* | |
H16C | 0.1990 | 0.1701 | 0.4062 | 0.138* | |
C17 | 0.4449 (5) | 0.0987 (6) | 0.4027 (3) | 0.1022 (15) | |
H17A | 0.5121 | 0.0541 | 0.3752 | 0.153* | |
H17B | 0.3950 | 0.0178 | 0.4235 | 0.153* | |
H17C | 0.4819 | 0.1619 | 0.4409 | 0.153* | |
O2 | 0.4408 (3) | 0.5385 (3) | 0.36690 (14) | 0.0844 (10) | |
O4 | 0.9083 (2) | 0.9425 (3) | 0.46707 (12) | 0.0759 (8) | |
H2 | 0.965 (5) | 1.036 (6) | 0.500 (3) | 0.040 (16)* | 0.50 |
O7 | 0.6740 (4) | 0.5344 (6) | 0.7689 (2) | 0.1276 (14) | |
H3 | 0.620 (6) | 0.552 (9) | 0.725 (2) | 0.191* | |
H4 | 0.611 (6) | 0.540 (9) | 0.808 (3) | 0.191* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0534 (13) | 0.0541 (13) | 0.0224 (11) | −0.0007 (10) | −0.0079 (9) | 0.0064 (9) |
C3 | 0.0529 (15) | 0.0514 (15) | 0.0242 (13) | −0.0022 (12) | −0.0059 (11) | 0.0043 (11) |
O6 | 0.0693 (14) | 0.1023 (18) | 0.0368 (13) | 0.0242 (13) | −0.0068 (10) | 0.0118 (12) |
C6 | 0.0531 (15) | 0.0600 (17) | 0.0282 (14) | −0.0161 (13) | −0.0071 (11) | 0.0086 (12) |
C12 | 0.0476 (14) | 0.0478 (14) | 0.0249 (14) | −0.0043 (12) | −0.0036 (11) | 0.0055 (10) |
C7 | 0.0525 (14) | 0.0500 (15) | 0.0214 (13) | −0.0042 (12) | −0.0082 (11) | 0.0021 (10) |
C8 | 0.0495 (14) | 0.0488 (15) | 0.0285 (14) | −0.0065 (12) | −0.0082 (11) | 0.0037 (11) |
O5 | 0.0876 (17) | 0.1009 (19) | 0.0271 (12) | 0.0284 (14) | −0.0023 (11) | −0.0034 (11) |
O3 | 0.0663 (14) | 0.111 (2) | 0.0455 (14) | −0.0401 (14) | −0.0119 (11) | 0.0173 (13) |
C14 | 0.0555 (16) | 0.0581 (16) | 0.0238 (14) | −0.0009 (13) | −0.0035 (11) | 0.0045 (11) |
C4 | 0.0467 (14) | 0.0576 (16) | 0.0277 (14) | −0.0103 (12) | −0.0087 (11) | 0.0040 (11) |
C13 | 0.0514 (15) | 0.0588 (16) | 0.0226 (13) | −0.0014 (13) | −0.0049 (11) | 0.0043 (11) |
O1 | 0.1009 (19) | 0.107 (2) | 0.0378 (13) | −0.0553 (16) | −0.0163 (13) | 0.0252 (13) |
C2 | 0.0485 (14) | 0.0443 (14) | 0.0294 (14) | −0.0070 (11) | −0.0032 (11) | 0.0035 (11) |
C9 | 0.0530 (15) | 0.0601 (17) | 0.0286 (14) | 0.0031 (14) | −0.0032 (12) | 0.0076 (12) |
C1 | 0.0645 (18) | 0.0637 (18) | 0.0327 (16) | −0.0190 (15) | −0.0064 (13) | 0.0127 (13) |
C10 | 0.0502 (15) | 0.0582 (16) | 0.0269 (14) | −0.0009 (13) | −0.0047 (11) | 0.0084 (11) |
C15 | 0.0705 (19) | 0.074 (2) | 0.0262 (14) | 0.0165 (16) | −0.0010 (13) | −0.0003 (13) |
C5 | 0.0581 (18) | 0.075 (2) | 0.0327 (16) | −0.0185 (16) | −0.0135 (13) | 0.0072 (14) |
C11 | 0.0644 (18) | 0.079 (2) | 0.0332 (16) | 0.0206 (16) | −0.0042 (13) | 0.0068 (14) |
N2 | 0.180 (4) | 0.084 (2) | 0.075 (3) | 0.040 (3) | 0.051 (3) | 0.013 (2) |
C16 | 0.083 (3) | 0.096 (3) | 0.098 (4) | −0.009 (3) | 0.002 (2) | 0.004 (2) |
C17 | 0.099 (3) | 0.109 (3) | 0.098 (4) | 0.019 (3) | −0.007 (3) | −0.019 (3) |
O2 | 0.0893 (18) | 0.106 (2) | 0.0561 (16) | −0.0564 (16) | −0.0266 (13) | 0.0311 (14) |
O4 | 0.0778 (16) | 0.115 (2) | 0.0328 (12) | −0.0436 (15) | −0.0197 (11) | 0.0107 (12) |
O7 | 0.128 (3) | 0.165 (4) | 0.090 (3) | −0.030 (3) | 0.017 (2) | −0.026 (3) |
N1—C14 | 1.393 (4) | C2—C1 | 1.501 (4) |
N1—C9 | 1.408 (4) | C9—C10 | 1.486 (4) |
N1—C7 | 1.461 (3) | C1—O2 | 1.237 (4) |
C3—C2 | 1.389 (4) | C10—C11 | 1.373 (4) |
C3—C4 | 1.394 (4) | C15—C11i | 1.403 (4) |
C3—H3A | 0.9300 | C15—H15A | 0.9300 |
O6—C9 | 1.208 (4) | C5—O4 | 1.291 (4) |
C6—C7 | 1.374 (4) | C11—C15i | 1.403 (4) |
C6—C4 | 1.393 (4) | C11—H11A | 0.9300 |
C6—H6A | 0.9300 | N2—C16 | 1.448 (6) |
C12—C13 | 1.403 (4) | N2—C17 | 1.463 (6) |
C12—C10 | 1.421 (4) | N2—H2A | 0.9000 |
C12—C12i | 1.421 (5) | N2—H2B | 0.9000 |
C7—C8 | 1.393 (4) | C16—H16A | 0.9600 |
C8—C2 | 1.395 (4) | C16—H16B | 0.9600 |
C8—H8A | 0.9300 | C16—H16C | 0.9600 |
O5—C14 | 1.222 (4) | C17—H17A | 0.9600 |
O3—C5 | 1.224 (4) | C17—H17B | 0.9600 |
C14—C13 | 1.486 (4) | C17—H17C | 0.9600 |
C4—C5 | 1.499 (4) | O4—H2 | 1.15 (6) |
C13—C15 | 1.387 (4) | O7—H3 | 0.98 (2) |
O1—C1 | 1.276 (4) | O7—H4 | 0.98 (2) |
O1—H1 | 1.216 (2) | ||
C14—N1—C9 | 125.5 (2) | O2—C1—C2 | 120.8 (3) |
C14—N1—C7 | 117.0 (2) | O1—C1—C2 | 114.8 (2) |
C9—N1—C7 | 117.5 (2) | C11—C10—C12 | 119.9 (2) |
C2—C3—C4 | 120.7 (2) | C11—C10—C9 | 120.5 (3) |
C2—C3—H3A | 119.7 | C12—C10—C9 | 119.5 (3) |
C4—C3—H3A | 119.7 | C13—C15—C11i | 119.4 (3) |
C7—C6—C4 | 119.7 (3) | C13—C15—H15A | 120.3 |
C7—C6—H6A | 120.2 | C11i—C15—H15A | 120.3 |
C4—C6—H6A | 120.2 | O3—C5—O4 | 124.9 (3) |
C13—C12—C10 | 121.5 (2) | O3—C5—C4 | 120.8 (3) |
C13—C12—C12i | 119.8 (3) | O4—C5—C4 | 114.3 (3) |
C10—C12—C12i | 118.8 (3) | C10—C11—C15i | 121.5 (3) |
C6—C7—C8 | 121.5 (2) | C10—C11—H11A | 119.3 |
C6—C7—N1 | 120.6 (2) | C15i—C11—H11A | 119.3 |
C8—C7—N1 | 117.9 (2) | C16—N2—C17 | 117.5 (4) |
C7—C8—C2 | 119.0 (2) | C16—N2—H2A | 107.9 |
C7—C8—H8A | 120.5 | C17—N2—H2A | 107.9 |
C2—C8—H8A | 120.5 | C16—N2—H2B | 107.9 |
O5—C14—N1 | 120.6 (3) | C17—N2—H2B | 107.9 |
O5—C14—C13 | 122.7 (3) | H2A—N2—H2B | 107.2 |
N1—C14—C13 | 116.7 (2) | N2—C16—H16A | 109.5 |
C6—C4—C3 | 119.4 (2) | N2—C16—H16B | 109.5 |
C6—C4—C5 | 121.0 (3) | H16A—C16—H16B | 109.5 |
C3—C4—C5 | 119.6 (2) | N2—C16—H16C | 109.5 |
C15—C13—C12 | 120.6 (3) | H16A—C16—H16C | 109.5 |
C15—C13—C14 | 119.3 (3) | H16B—C16—H16C | 109.5 |
C12—C13—C14 | 120.0 (3) | N2—C17—H17A | 109.5 |
C1—O1—H1 | 117.0 (2) | N2—C17—H17B | 109.5 |
C3—C2—C8 | 119.7 (2) | H17A—C17—H17B | 109.5 |
C3—C2—C1 | 119.2 (2) | N2—C17—H17C | 109.5 |
C8—C2—C1 | 121.1 (2) | H17A—C17—H17C | 109.5 |
O6—C9—N1 | 120.6 (3) | H17B—C17—H17C | 109.5 |
O6—C9—C10 | 123.0 (3) | C5—O4—H2 | 114 (3) |
N1—C9—C10 | 116.4 (2) | H3—O7—H4 | 102 (4) |
O2—C1—O1 | 124.4 (3) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1ii | 1.22 (1) | 1.22 (1) | 2.432 (5) | 180 (1) |
O4—H2···O4iii | 1.15 (6) | 1.45 (5) | 2.441 (5) | 139 (4) |
N2—H2B···O5iv | 0.90 | 2.22 | 2.850 (5) | 127 |
O7—H3···O2ii | 0.98 (2) | 1.95 (5) | 2.805 (6) | 144 (6) |
O7—H4···O3v | 0.98 (2) | 1.85 (4) | 2.771 (6) | 154 (7) |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+2, −z+1; (iv) x, y−1, z; (v) x−1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | 2C2H8N+·C30H12N2O122−·2H2O |
Mr | 720.64 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.428 (13), 8.651 (10), 18.40 (2) |
β (°) | 91.956 (16) |
V (Å3) | 1659 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku Saturn70 |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2008) |
Tmin, Tmax | 0.788, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12286, 3780, 2137 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.081, 0.266, 1.01 |
No. of reflections | 3780 |
No. of parameters | 248 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.36 |
Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1i | 1.216 (2) | 1.216 (2) | 2.432 (5) | 180.0 (2) |
O4—H2···O4ii | 1.15 (6) | 1.45 (5) | 2.441 (5) | 139 (4) |
N2—H2B···O5iii | 0.90 | 2.22 | 2.850 (5) | 127.0 |
O7—H3···O2i | 0.98 (2) | 1.95 (5) | 2.805 (6) | 144 (6) |
O7—H4···O3iv | 0.98 (2) | 1.85 (4) | 2.771 (6) | 154 (7) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) x, y−1, z; (iv) x−1/2, −y+3/2, z+1/2. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21071087, 91122012) and the K. C. Wong Magna Fund in Ningbo University.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Assemblies of functionalised organic molecules in the solid state have attracted much interest in crystal engineering and materials science (Pantos et al., 2007). Recently, much attention has been paid to formation of multi-component molecular crystals or organic co-crystals as a means of modification of properties of organic molecules in the solid state (Bond, 2007; MacGillivray, 2008; Yan et al., 2011). However, an effective strategy for tuning functionality of co-crystal solids still remains challenging (Pigge, 2011).
We have been interested in utilizing acid-functionalized naphthalaleneteracarboxylic diimide derivatives as starting materials in crystal engineering of a series of functional organic co-crystal materials (Xu et al., 2011). Herein we report an organic salt, 2(C2H8N)+.(C30H12N2O12)2-.2H2O, which has been prepared under solvothermal reaction from 5,5-[naphthalene-1,8:4,5- bis(dicarboximide)-N,N-diyl]bis(benzene-1,3-dicarboxylic acid) and 1,10-phenanthroline in dimethylformamide (DMF). The dimethylammonium cations in the title structure were formed by in situ hydrolysis of the dimethylformamide molecules (Jain et al., 2008).
Single-crystal X-ray diffraction analysis has indicated that the title structure is composed dimethylammonium cations, 3,3-dicarboxy-5,5-[naphthalene-1,8:4,5- bis(dicarboximide)-N,N-diyl]bis(benzene-1-carboxylate) anion and water molecules. As shown in Fig. 1, the anion is situated on the crystallographic inversion centre.
The most prominent as well as unusual feature of the title structure is presence of two different very strong symmetry restricted hydrogen bonds (Table 1; for the terminology of the hydrogen bonds, see Desiraju & Steiner, 1999). One of the hydrogens (H1) is situated at its centre while the other one (H4) is disordered about it as revealed the difference electron density maps. These hydrogens form a chain-like motif C22(16) (Etter et al., 1990). The atoms involved in this motif are as follows: H2···O4-C5-C4-C3-C2-C1-O1···H1···O1i-C1i-C2i-C3i-C4i-C5i-O4i···, where the symmetry code i = 1-x, 1-y, 1-z. This is only a fourth known example (Cambridge Structural Database (Allen, 2002; version 5.33)) of a chain motif in the hydrogen carboxylates with a strong or very strong hydrogen bond (up to 2.55Å for O···O) in contrast to 11 structures with a motif R22(8) with the same type of the hydrogen bonds (up to 2.55Å for O···O) between the hydrogen carboxylates. The structures with the chain motif are as follows: (RABNEN, 4-(3,5-dimethylpyrazol-4-yl)benzoic acid trifluoroacetate, Foces-Foces et al. (1996); SERYUK, sesquikis(3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine) trimesic acid dehydrate, Hsu et al. (2006); POYXOR, hemikis((1RS,2RS,3RS)-3-N,N-dibenzylaminocyclohexane -1,2-diol N-oxide) 3-chlorobenzoic acid, Aciro et al. (2009).
In the title structure, these short hydrogen bonds form 2D-layers (Fig. 2). The 2D-framework is extended to a 3D network by involvement of water which donates strong O—H···O hydrogen bonds to the oxo-groups of the hydrogen carboxylates. Dimethylammonium donates a weak bifurcated hydrogen bond to the oxo-group O5.