Download citation
Download citation
link to html
The title compounds, C10H10N22+·C8Cl4O42−·2H2O, (I), and 2C12H9N2+·C8Cl4O42−·C8H2Cl4O4·3H2O, (II), both crystallize as charge-transfer organic salts with the dianionic or neutral acid components lying on inversion centres. The acid and base subunits in (I) arrange alternately to generate a linear tape motif via N—H...O hydrogen bonds; these tapes are further combined into a three-dimensional architecture through multiple O—H...O and C—H...O inter­actions involving solvent water mol­ecules. In contrast, the neutral and anionic acid components in (II) are linked to form a zigzag chain by means of O—H...O hydrogen bonds between acid groups, with dangling 1,10-phenanthrolinium units connected to these chains by carboxyl­ate–pyridinium inter­actions with R22(7) hydrogen-bond notation. Adjacent chains are further extended to result in a two-dimensional corrugated layer network via π–π inter­actions. Inter-ion Cl...O inter­actions are also found in both (I) and (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109037500/fg3128sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109037500/fg3128Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109037500/fg3128IIsup3.hkl
Contains datablock II

CCDC references: 755986; 755987

Comment top

The supramolecular synthon approach has been widely applied to tailor desired supramolecules and molecular solids by using previously identified robust intermolecular interactions since it offers a considerable simplification in the design of crystal structures (Desiraju, 1995; Nangia & Desiraju, 1998). For the co-crystal structures of carboxylic acids with pyridyl building blocks, strong hydrogen bonds, such as O—H···N or charge-assisted N—H···O, are always essential, usually combining auxiliary weak C—H···O interactions, leading to the most familiar carboxyl/pyridyl heterosynthon [R22(7); Etter, 1990] (Shan et al., 2002). In this context, although aromatic dicarboxylic acids have been proven to be excellent building blocks in binary co-crystal assemblies with bipyridine-type components, terephthalic acid (H2tp) has been less well studied than phthalic acid and isophthalic acid in this respect owing to the mismatched solubility with base components, especially because of its poor solubility (Du et al., 2005). Related efforts on its derivatives have been rare so far. Notably, it can be forecast that the substituent groups will influence the structural assemblies, since they may display different hydrogen-bonding capability and potential steric/electronic effects. A search of the Cambridge Structural Database (CSD; Version 5.30 of November 2009, plus two updates; Allen, 2002) reveals that no organic structure based on a halogen functional terephthalic acid has been reported to date, except a supramolecular adduct of triethylammonium with tetrachloroterephthalic acid (H2tpCl4; Lan et al., 2008). In this present work, two charge-transfer crystalline products, that is [(H2bipy)][tpCl4].2H2O], (I) (bipy = 4,4'-bipyridine), and [(Hphen)2(H2tpCl4)(tpCl4).3H2O], (II) (phen = 1,10-phenanthroline), were prepared.

Compound (I) is shown to be a proton-transfer organic binary salt, in which the asymmetric unit is composed of half of a tpCl42- anion, half of an H2bipy2+ cation (both lying about independent inversion centres) and one solvent water molecule in a general position (Fig. 1). Proton transfer from the tetrachloroterephthalic acid to the 4,4'-bipyridine moiety was unequivocally established from difference map plots, and the resulting cation and anion dimensions are normal and fully in accord with this proton transfer scheme. Because the two pyridylium rings are related by an inversion centre, the dihedral angle between then is exactly 0°. In the centrosymmetric tpCl42- ion the unique carboxyl group is nearly perpendicular [87.4 (2)°] to the aromatic ring as influenced by the stereo hindrance of the adjacent chloro substituents. The aromatic ring of the tpCl42- anion is inclined at 3.96 (9)° to the bipy component.

In the crystal structure of (I) (Fig. 2), linear tapes are generated through strong N1—H1···O1 hydrogen bonds (Table 1) between carboxylate and pyridinium groups; these tapes run along the crystallographic [211] direction with a graph-set notation C22(18) (Etter, 1990). Notably, the anticipated R22(7) synthon of N—H···O/C—H···O is absent owing to the approximately perpendicular dihedral angle [83.52 (13)°] between the carboxylate and pyridinium groups. The solvent water molecule is involved in two strong hydrogen bonds (O3—H3A···O2 and O3—H3B···O2iii; symmetry codes and geometric parameters are given in Table 1) with carboxylate atom O2 of tpCl42-, which leads to an eight-membered hydrogen-bonded R42(8) ring and gives rise to a linear [(tpCl4)2-.2H2O]n chain extending along the c-axis direction. Such hydrogen-bonding interactions connect neighboring tapes, resulting in a two-dimensional layer, as shown in Fig. 2. These layers align parallel to the (120) plane with some offset to fulfill the final three-dimensional hydrogen-bonding framework which is generated via weak C—H···O interactions (C6—H6···O3iv and C8—H8···O3v; Table 1) between bipyridinium cations and water molecules from adjacent layers. Additionally, intermolecular C4—Cl2···O3vi [symmetry code: (vi) x + 1, y, z - 1] interactions link water molecules to further consolidate the three-dimensional assembly, with a Cl···O distance of 3.040 (2) Å, modestly shorter than the van der Waals distance (3.12 Å) suggested by Nyburg & Faerman (1985).

Crystallization of tetrachloroterephthalic acid with phenanthroline also yields a proton-transfer organic salt, (II). The crystal structure of (II) exhibits a two-dimensional supramolecular host network with the inclusion of disordered guest water molecules (Fig. 3). The asymmetric unit is composed of half of an H2tpCl4 molecule, half of a tpCl42- anion, (both lying about independent inversion centres), one monoprotonated Hphen+ cation in a general position and 1.5 disordered guest water molecules lying about another inversion centre. Proton transfer from a tetrachloroterephthalic acid molecule to the phen molecule was unequivocally established from difference map plots and the resulting cation and anion dimensions are normal and fully in accord with this proton transfer scheme.

As shown in Fig. 3, within each centrosymmetric acidic unit, the rotation angles of the the carboxylate/carboxyl groups relative to the tetrachlorinated aromatic rings are 77.8 (2)° for tpCl42- and 89.9 (1)° for H2tpCl4, respectively. The rotation angle in the dianion moiety is smaller than the corresponding values for other polychlorinated carboxylate compounds [80.6 (4) and 89.7 (3)° (Maspoch et al., 2004), and 81.88 (13)–90.0 (1)° (Chen et al., 2008)]. Analysis of the crystal packing of (II) shows that the neutral and dianionic acid moieties are connected to by intermolecular O1—H1'···O3 hydrogen bonds to form a one-dimensional zigzag chain structure extending in the (101) direction. Meanwhile, each tpCl42- dianion is linked to monoprotonated Hphen+ cations with an R22(7) ring pattern via N1—H1A···O3 and C10—H10···O4 hydrogen bonds (Table 2). Adjacent inversion-related Hphen+ ions take part in ππ interactions; the centroid (Cg1) of the N1/C7–C10/C12 ring is 3.556 (2) Å from the centroid (Cg2) of the C4–C7/C11/C12 ring at (1 - x,2 - y,1 - z); this also allows a further C6—H6···O2iv (Table 2) interaction and expands the one-dimensional zigzag motif into a two-dimensional hydrogen-bonding network (Fig. 5). The disordered solvent water subunits are captured in the two-dimensional supramolecular layer with partial-occupancy water atom O52 lying 2.765 (7) Å from the adjacent carboxylate atom O4. Adjoining two-dimensional layers are further extended to a three-dimensional arrangement through intermolecular C20—Cl4···O4v [Cl···O =3.265 (2) Å and C—Cl···O 144.42 (10)°; symmetry code: (v) x + 1, y, z] interactions.

In conclusion, this work demonstrates the first example of H2tpCl4 as a good participant in cocrystallization with aromatic diamines. When cocrystallizing with the rod-like 4,4'-bipyridine building block, the H2tpCl4 subunits reliably form N—H···O interactions, while in the case of 2,2'-bipyridine-type moieties, only one of the phenanthroline N-atom donors forms an R22(7) heterosynthon with anionic tpCl4 as a result of the stereochemistry effect of the phen molecule. Both the acid–base adducts show organic binary salts behaving as charge-assisted hydrogen-bonding structures of considerable multiplicity. This result offers a new challenge in the seeking of true neutral cocrystals based on such halogen-substituted terephthalic acids.

Related literature top

For related literature, see: Allen (2002); Chen et al. (2007, 2008); Desiraju (1995); Du et al. (2005); Etter (1990); Lan et al. (2008); Maspoch et al. (2004); Nangia & Desiraju (1998); Nyburg & Faerman (1985); Shan et al. (2002).

Experimental top

All the reagents and solvents for synthesis were commercially available and used as received, except for H2tpCl4, which was prepared according to the literature procedures (Chen et al., 2007). For the preparation of (I), to a methanol/water (2:1 v/v) solution (6 ml) of H2tpCl4 was added a solution of bipy (15.8 mg, 0.1 mmol) in methanol (5 ml). After stirring for ca 10 min, the reaction mixture was filtered and left to stand at ambient temperature. Colorless block crystals of (I) suitable for X-ray diffraction were obtained through 5 d evaporation of the filtrate with a yield of 90% (44.6 mg, based on bipy). Analysis calculated for C18H14Cl4N2O6: C 43.58, H 2.84, N 5.65%; found: C 43.58, H 2.96, N 5.56%.

For the preparation of (II), the same synthetic procedure as that for (I) was used except that bipy was replaced by phen (18.0 mg, 0.1 mmol), affording colorless block crystals of (II) in 85% yield (43.4 mg, based on phen). Analysis calculated for C40H26Cl8N4O11: C 47.00, H 2.56, N 5.48%; found: C 47.03, H 2.61, N 5.45%.

Refinement top

H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with Uiso(H) set at 1.2Ueq(C). In (II), a study of the electron-density maps showed that the water molecule O5 is disordered unequally over two sites, consistent with occupancies of 0.6 and 0.4; the water molecule O6 has electron density consistent with it being a half-occupancy O atom disordered equally over two sites. It was not possible to locate any of these water H atoms. All of the other water and amine H atoms were located in difference maps and allowed for as riding with Uiso(H) value of 1.5Ueq(O,N).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids. Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x, -y + 2, -z + 2.]
[Figure 2] Fig. 2. The two-dimensional hydrogen-bonded layer of (I). Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x, -y + 2, -z + 2; (iii) -x + 2, -y + 1, -z + 2.]
[Figure 3] Fig. 3. The molecular structure of (II), drawn with 30% probability displacement ellipsoids. Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z; (iii) -x, -y + 2, -z.]
[Figure 4] Fig. 4. A partial view of the one-dimensional zigzag motif of (II). Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z.]
[Figure 5] Fig. 5. The two-dimensional hydrogen-bonded layer of (II), with hydrogen bonds indicated as dashed lines. The disordered water guests within the cavities have been omitted for clarity.
(I) 4,4'-bipyridinium tetrachloroterephthalate dihydrate top
Crystal data top
C10H10N22+·C8Cl4O42·2H2OZ = 1
Mr = 496.11F(000) = 252
Triclinic, P1Dx = 1.643 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.306 (2) ÅCell parameters from 3073 reflections
b = 9.325 (3) Åθ = 2.3–27.6°
c = 10.040 (4) ŵ = 0.63 mm1
α = 62.508 (3)°T = 296 K
β = 86.763 (4)°Block, colorless
γ = 73.842 (4)°0.18 × 0.15 × 0.12 mm
V = 501.3 (3) Å3
Data collection top
Bruker APEXII? CCD area-detector
diffractometer
1732 independent reflections
Radiation source: fine-focus sealed tube1590 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
phi and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 77
Tmin = 0.895, Tmax = 0.928k = 1111
3529 measured reflectionsl = 1111
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0928P)2 + 0.2018P]
where P = (Fo2 + 2Fc2)/3
1732 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.47 e Å3
Crystal data top
C10H10N22+·C8Cl4O42·2H2Oγ = 73.842 (4)°
Mr = 496.11V = 501.3 (3) Å3
Triclinic, P1Z = 1
a = 6.306 (2) ÅMo Kα radiation
b = 9.325 (3) ŵ = 0.63 mm1
c = 10.040 (4) ÅT = 296 K
α = 62.508 (3)°0.18 × 0.15 × 0.12 mm
β = 86.763 (4)°
Data collection top
Bruker APEXII? CCD area-detector
diffractometer
1732 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1590 reflections with I > 2σ(I)
Tmin = 0.895, Tmax = 0.928Rint = 0.033
3529 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.00Δρmax = 0.40 e Å3
1732 reflectionsΔρmin = 0.47 e Å3
136 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
O10.6388 (3)0.8256 (2)0.58191 (18)0.0333 (4)
C10.7975 (4)0.6971 (3)0.6556 (2)0.0255 (5)
C20.9041 (3)0.5942 (3)0.5747 (2)0.0221 (5)
C31.0746 (4)0.6338 (3)0.4826 (2)0.0233 (5)
C41.1701 (3)0.5396 (3)0.4087 (2)0.0227 (5)
Cl11.16530 (10)0.80187 (7)0.46194 (6)0.0333 (2)
Cl21.38021 (9)0.58890 (7)0.29182 (6)0.0308 (2)
O20.8747 (3)0.6456 (2)0.78608 (19)0.0432 (5)
C50.3642 (4)1.0521 (3)0.7790 (3)0.0315 (5)
H50.45331.12240.72950.038*
C60.2182 (4)1.0860 (3)0.8760 (3)0.0296 (5)
H60.21111.17740.89250.036*
C70.0822 (4)0.9831 (3)0.9485 (2)0.0243 (5)
C80.1036 (5)0.8457 (3)0.9214 (3)0.0371 (6)
H80.01600.77340.96810.045*
C90.2546 (5)0.8177 (3)0.8253 (3)0.0366 (6)
H90.26980.72510.80890.044*
N10.3792 (3)0.9207 (2)0.7556 (2)0.0281 (5)
H10.47590.89870.69330.042*
O30.7331 (3)0.6041 (2)1.07034 (19)0.0391 (5)
H3A0.72530.63290.97980.059*
H3B0.84120.53181.12640.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0346 (10)0.0339 (9)0.0283 (8)0.0003 (8)0.0076 (7)0.0181 (7)
C10.0266 (12)0.0316 (11)0.0220 (10)0.0083 (10)0.0085 (9)0.0160 (9)
C20.0188 (11)0.0278 (11)0.0191 (10)0.0010 (9)0.0022 (8)0.0137 (9)
C30.0212 (11)0.0269 (11)0.0225 (10)0.0036 (9)0.0026 (9)0.0139 (9)
C40.0181 (11)0.0292 (11)0.0197 (10)0.0026 (9)0.0050 (8)0.0131 (9)
Cl10.0361 (4)0.0370 (4)0.0384 (4)0.0161 (3)0.0122 (3)0.0249 (3)
Cl20.0284 (4)0.0379 (4)0.0302 (4)0.0116 (3)0.0147 (2)0.0194 (3)
O20.0468 (11)0.0565 (11)0.0283 (9)0.0000 (9)0.0012 (8)0.0290 (8)
C50.0340 (13)0.0342 (12)0.0333 (12)0.0141 (11)0.0130 (10)0.0201 (10)
C60.0317 (13)0.0321 (12)0.0351 (12)0.0121 (10)0.0122 (10)0.0232 (10)
C70.0254 (12)0.0283 (11)0.0212 (10)0.0059 (9)0.0042 (9)0.0145 (9)
C80.0486 (16)0.0415 (13)0.0399 (13)0.0253 (12)0.0219 (12)0.0292 (11)
C90.0456 (16)0.0386 (13)0.0412 (14)0.0174 (12)0.0174 (12)0.0297 (11)
N10.0280 (11)0.0315 (10)0.0265 (10)0.0041 (8)0.0084 (8)0.0180 (8)
O30.0405 (11)0.0465 (10)0.0348 (9)0.0103 (8)0.0109 (8)0.0246 (8)
Geometric parameters (Å, º) top
O1—C11.258 (3)C6—C71.389 (3)
C1—O21.243 (3)C6—H60.9300
C1—C21.527 (3)C7—C81.399 (3)
C2—C4i1.388 (3)C7—C7ii1.497 (4)
C2—C31.394 (3)C8—C91.377 (4)
C3—C41.393 (3)C8—H80.9300
C3—Cl11.735 (2)C9—N11.329 (3)
C4—C2i1.388 (3)C9—H90.9300
C4—Cl21.734 (2)N1—H10.9000
C5—N11.329 (3)O3—H3A0.8202
C5—C61.384 (4)O3—H3B0.8202
C5—H50.9300
O2—C1—O1127.0 (2)C5—C6—H6120.1
O2—C1—C2117.3 (2)C7—C6—H6120.1
O1—C1—C2115.72 (18)C6—C7—C8117.4 (2)
C4i—C2—C3119.2 (2)C6—C7—C7ii121.8 (2)
C4i—C2—C1120.03 (19)C8—C7—C7ii120.8 (3)
C3—C2—C1120.7 (2)C9—C8—C7119.8 (2)
C4—C3—C2120.3 (2)C9—C8—H8120.1
C4—C3—Cl1120.83 (18)C7—C8—H8120.1
C2—C3—Cl1118.85 (17)N1—C9—C8121.2 (2)
C2i—C4—C3120.4 (2)N1—C9—H9119.4
C2i—C4—Cl2118.66 (17)C8—C9—H9119.4
C3—C4—Cl2120.89 (18)C5—N1—C9120.7 (2)
N1—C5—C6121.1 (2)C5—N1—H1120.5
N1—C5—H5119.5C9—N1—H1118.7
C6—C5—H5119.5H3A—O3—H3B121.3
C5—C6—C7119.8 (2)
O2—C1—C2—C4i87.5 (3)C2—C3—C4—Cl2179.20 (15)
O1—C1—C2—C4i92.1 (2)Cl1—C3—C4—Cl20.8 (3)
O2—C1—C2—C393.1 (3)N1—C5—C6—C71.0 (4)
O1—C1—C2—C387.3 (3)C5—C6—C7—C81.2 (3)
C4i—C2—C3—C40.3 (3)C5—C6—C7—C7ii178.5 (3)
C1—C2—C3—C4179.72 (18)C6—C7—C8—C90.3 (4)
C4i—C2—C3—Cl1179.73 (15)C7ii—C7—C8—C9179.5 (3)
C1—C2—C3—Cl10.3 (3)C7—C8—C9—N11.0 (4)
C2—C3—C4—C2i0.3 (3)C6—C5—N1—C90.3 (4)
Cl1—C3—C4—C2i179.73 (15)C8—C9—N1—C51.3 (4)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.901.722.609 (3)169
O3—H3A···O20.822.082.824 (3)151
O3—H3B···O2iii0.821.982.778 (3)165
C6—H6···O3iv0.932.353.269 (4)169
C8—H8···O3v0.932.573.492 (4)172
Symmetry codes: (iii) x+2, y+1, z+2; (iv) x+1, y+2, z+2; (v) x1, y, z.
(II) bis(1,10-phenanthrolinium) tetrachloroterephthalate tetrachloroterephthalic acid trihydrate top
Crystal data top
2C12H9N2+·C8Cl4O42·C8H2Cl4O4·3H2OZ = 1
Mr = 1022.25F(000) = 518
Triclinic, P1Dx = 1.610 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2931 (11) ÅCell parameters from 4670 reflections
b = 12.0916 (16) Åθ = 2.1–27.5°
c = 12.3108 (16) ŵ = 0.60 mm1
α = 102.127 (2)°T = 295 K
β = 109.454 (1)°Block, colorless
γ = 106.072 (2)°0.28 × 0.22 × 0.15 mm
V = 1054.4 (2) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3677 independent reflections
Radiation source: fine-focus sealed tube3201 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
phi and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 99
Tmin = 0.850, Tmax = 0.915k = 1414
7609 measured reflectionsl = 1414
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.085P)2 + 0.8354P]
where P = (Fo2 + 2Fc2)/3
3677 reflections(Δ/σ)max < 0.001
288 parametersΔρmax = 0.73 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
2C12H9N2+·C8Cl4O42·C8H2Cl4O4·3H2Oγ = 106.072 (2)°
Mr = 1022.25V = 1054.4 (2) Å3
Triclinic, P1Z = 1
a = 8.2931 (11) ÅMo Kα radiation
b = 12.0916 (16) ŵ = 0.60 mm1
c = 12.3108 (16) ÅT = 295 K
α = 102.127 (2)°0.28 × 0.22 × 0.15 mm
β = 109.454 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3677 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3201 reflections with I > 2σ(I)
Tmin = 0.850, Tmax = 0.915Rint = 0.020
7609 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.07Δρmax = 0.73 e Å3
3677 reflectionsΔρmin = 0.38 e Å3
288 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*/UeqOcc. (<1)
C130.8004 (4)0.6428 (2)0.3931 (3)0.0349 (6)
C140.9036 (4)0.5691 (2)0.4489 (2)0.0327 (6)
C150.9437 (4)0.4846 (3)0.3768 (2)0.0354 (6)
C161.0369 (4)0.4155 (2)0.4264 (2)0.0345 (6)
C170.3805 (4)0.6728 (2)0.1275 (2)0.0328 (6)
C180.4441 (3)0.5832 (2)0.0631 (2)0.0310 (6)
C190.5945 (4)0.6239 (2)0.0353 (2)0.0337 (6)
C200.6511 (3)0.5427 (2)0.0266 (2)0.0316 (6)
Cl10.87168 (13)0.46445 (9)0.22274 (7)0.0581 (3)
Cl21.08249 (13)0.30984 (8)0.33555 (7)0.0551 (3)
Cl30.71191 (12)0.78008 (7)0.07764 (8)0.0540 (3)
Cl40.84232 (11)0.59513 (7)0.05612 (9)0.0551 (3)
O10.6217 (3)0.58790 (18)0.3543 (2)0.0429 (5)
H1'0.56920.62790.32110.064*
O20.8792 (3)0.7397 (2)0.3880 (3)0.0637 (7)
O30.4225 (3)0.68953 (18)0.24061 (17)0.0389 (5)
O40.2923 (3)0.7218 (2)0.06687 (19)0.0474 (5)
C10.4661 (4)0.6718 (3)0.5789 (3)0.0478 (7)
H10.49550.60560.55120.057*
C20.4929 (5)0.7087 (3)0.7015 (3)0.0552 (8)
H20.54050.66850.75310.066*
C30.4483 (5)0.8047 (3)0.7442 (3)0.0530 (8)
H30.46510.83060.82530.064*
C40.3759 (4)0.8639 (3)0.6632 (3)0.0426 (7)
C50.3258 (5)0.9656 (3)0.6993 (3)0.0494 (8)
H50.33700.99330.77890.059*
C60.2628 (4)1.0217 (3)0.6203 (3)0.0432 (7)
H60.23201.08780.64620.052*
C70.2427 (4)0.9811 (2)0.4973 (3)0.0369 (6)
C80.1782 (4)1.0353 (3)0.4106 (3)0.0449 (7)
H80.14651.10190.43270.054*
C90.1613 (5)0.9916 (3)0.2938 (3)0.0489 (7)
H90.11631.02720.23650.059*
C100.2122 (4)0.8929 (3)0.2614 (3)0.0464 (7)
H100.20140.86280.18220.056*
C110.3581 (4)0.8207 (2)0.5431 (3)0.0361 (6)
C120.2910 (3)0.8807 (2)0.4601 (3)0.0342 (6)
N10.2759 (3)0.8421 (2)0.3436 (2)0.0389 (5)
H1A0.30700.77800.32140.058*
N20.4023 (3)0.7248 (2)0.5005 (2)0.0423 (6)
O510.2373 (14)0.9245 (9)0.0266 (9)0.095 (3)*0.40
O520.3445 (8)0.9208 (5)0.0130 (5)0.0779 (14)*0.60
O610.023 (2)0.9425 (14)0.0330 (15)0.103 (5)*0.25
O620.022 (2)0.8996 (14)0.0653 (14)0.093 (4)*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C130.0356 (14)0.0339 (14)0.0365 (14)0.0191 (12)0.0129 (12)0.0098 (11)
C140.0313 (13)0.0345 (14)0.0345 (14)0.0175 (11)0.0124 (11)0.0108 (11)
C150.0339 (14)0.0413 (15)0.0296 (13)0.0188 (12)0.0089 (11)0.0100 (11)
C160.0328 (14)0.0368 (14)0.0342 (14)0.0188 (11)0.0123 (11)0.0074 (11)
C170.0324 (14)0.0352 (14)0.0297 (13)0.0167 (11)0.0116 (11)0.0059 (11)
C180.0325 (14)0.0361 (14)0.0272 (13)0.0183 (11)0.0123 (11)0.0089 (11)
C190.0371 (14)0.0301 (13)0.0329 (14)0.0134 (11)0.0146 (12)0.0073 (11)
C200.0286 (13)0.0383 (14)0.0304 (13)0.0154 (11)0.0139 (11)0.0098 (11)
Cl10.0725 (6)0.0879 (6)0.0315 (4)0.0536 (5)0.0208 (4)0.0236 (4)
Cl20.0693 (5)0.0635 (5)0.0435 (4)0.0480 (4)0.0228 (4)0.0093 (4)
Cl30.0559 (5)0.0309 (4)0.0732 (6)0.0106 (3)0.0360 (4)0.0061 (4)
Cl40.0508 (5)0.0479 (4)0.0822 (6)0.0189 (4)0.0475 (5)0.0183 (4)
O10.0373 (11)0.0443 (11)0.0526 (13)0.0243 (9)0.0139 (10)0.0226 (10)
O20.0476 (13)0.0464 (13)0.100 (2)0.0221 (11)0.0222 (13)0.0385 (14)
O30.0457 (11)0.0493 (11)0.0304 (10)0.0326 (9)0.0161 (9)0.0096 (9)
O40.0563 (13)0.0586 (13)0.0450 (12)0.0406 (11)0.0228 (10)0.0229 (10)
C10.0466 (17)0.0391 (16)0.065 (2)0.0236 (14)0.0247 (16)0.0179 (15)
C20.058 (2)0.0472 (18)0.065 (2)0.0242 (16)0.0251 (18)0.0245 (17)
C30.064 (2)0.0506 (18)0.0454 (18)0.0231 (16)0.0236 (16)0.0144 (15)
C40.0403 (16)0.0368 (15)0.0467 (17)0.0130 (12)0.0185 (13)0.0071 (13)
C50.0549 (19)0.0441 (17)0.0492 (18)0.0217 (15)0.0262 (15)0.0037 (14)
C60.0436 (16)0.0352 (15)0.0524 (18)0.0186 (13)0.0251 (14)0.0043 (13)
C70.0277 (13)0.0293 (13)0.0494 (17)0.0098 (11)0.0172 (12)0.0046 (12)
C80.0401 (16)0.0348 (15)0.062 (2)0.0204 (13)0.0216 (15)0.0111 (14)
C90.0491 (18)0.0493 (18)0.0549 (19)0.0275 (15)0.0212 (15)0.0187 (15)
C100.0486 (18)0.0525 (18)0.0444 (17)0.0278 (15)0.0201 (14)0.0149 (14)
C110.0300 (13)0.0313 (13)0.0450 (16)0.0121 (11)0.0172 (12)0.0056 (12)
C120.0257 (13)0.0282 (13)0.0437 (15)0.0087 (10)0.0153 (12)0.0030 (11)
N10.0358 (12)0.0370 (12)0.0436 (14)0.0188 (10)0.0167 (11)0.0059 (11)
N20.0445 (14)0.0349 (12)0.0514 (15)0.0207 (11)0.0227 (12)0.0095 (11)
Geometric parameters (Å, º) top
C13—O21.200 (4)C3—C41.416 (5)
C13—O11.310 (3)C3—H30.9300
C13—C141.512 (4)C4—C111.403 (4)
C14—C151.395 (4)C4—C51.435 (4)
C14—C16i1.400 (4)C5—C61.347 (5)
C15—C161.388 (4)C5—H50.9300
C15—Cl11.727 (3)C6—C71.427 (4)
C16—C14i1.400 (4)C6—H60.9300
C16—Cl21.724 (3)C7—C81.401 (4)
C17—O41.227 (3)C7—C121.414 (4)
C17—O31.273 (3)C8—C91.368 (5)
C17—C181.522 (3)C8—H80.9300
C18—C191.389 (4)C9—C101.397 (4)
C18—C20ii1.398 (4)C9—H90.9300
C19—C201.395 (4)C10—N11.329 (4)
C19—Cl31.737 (3)C10—H100.9300
C20—C18ii1.398 (4)C11—N21.364 (3)
C20—Cl41.724 (3)C11—C121.427 (4)
O1—H1'0.8200C12—N11.364 (4)
C1—N21.314 (4)N1—H1A0.9000
C1—C21.402 (5)O51—O520.864 (10)
C1—H10.9300O51—O621.603 (18)
C2—C31.368 (5)O61—O620.831 (19)
C2—H20.9300O61—O61iii1.33 (3)
O2—C13—O1126.5 (3)C11—C4—C3116.9 (3)
O2—C13—C14121.8 (3)C11—C4—C5119.8 (3)
O1—C13—C14111.7 (2)C3—C4—C5123.3 (3)
C15—C14—C16i118.4 (2)C6—C5—C4121.3 (3)
C15—C14—C13120.4 (2)C6—C5—H5119.3
C16i—C14—C13121.2 (2)C4—C5—H5119.3
C16—C15—C14121.1 (3)C5—C6—C7120.8 (3)
C16—C15—Cl1119.9 (2)C5—C6—H6119.6
C14—C15—Cl1119.0 (2)C7—C6—H6119.6
C15—C16—C14i120.5 (2)C8—C7—C12117.8 (3)
C15—C16—Cl2120.6 (2)C8—C7—C6123.7 (3)
C14i—C16—Cl2118.9 (2)C12—C7—C6118.5 (3)
O4—C17—O3125.5 (2)C9—C8—C7120.9 (3)
O4—C17—C18117.9 (2)C9—C8—H8119.6
O3—C17—C18116.6 (2)C7—C8—H8119.6
C19—C18—C20ii118.1 (2)C8—C9—C10119.5 (3)
C19—C18—C17121.1 (2)C8—C9—H9120.3
C20ii—C18—C17120.8 (2)C10—C9—H9120.3
C18—C19—C20121.7 (2)N1—C10—C9120.0 (3)
C18—C19—Cl3118.7 (2)N1—C10—H10120.0
C20—C19—Cl3119.6 (2)C9—C10—H10120.0
C19—C20—C18ii120.2 (2)N2—C11—C4124.0 (3)
C19—C20—Cl4120.9 (2)N2—C11—C12117.6 (3)
C18ii—C20—Cl4118.85 (19)C4—C11—C12118.4 (2)
C13—O1—H1'109.5N1—C12—C7119.3 (3)
N2—C1—C2124.3 (3)N1—C12—C11119.6 (2)
N2—C1—H1117.9C7—C12—C11121.1 (3)
C2—C1—H1117.9C10—N1—C12122.6 (2)
C3—C2—C1119.1 (3)C10—N1—H1A119.2
C3—C2—H2120.4C12—N1—H1A118.2
C1—C2—H2120.4C1—N2—C11116.7 (3)
C2—C3—C4119.0 (3)O52—O51—O62167.4 (13)
C2—C3—H3120.5O62—O61—O61iii139 (3)
C4—C3—H3120.5O61—O62—O51127 (2)
O2—C13—C14—C1589.7 (4)C3—C4—C5—C6177.9 (3)
O1—C13—C14—C1590.7 (3)C4—C5—C6—C70.4 (5)
O2—C13—C14—C16i89.5 (4)C5—C6—C7—C8179.9 (3)
O1—C13—C14—C16i90.1 (3)C5—C6—C7—C120.2 (4)
C16i—C14—C15—C161.3 (5)C12—C7—C8—C90.6 (4)
C13—C14—C15—C16179.5 (2)C6—C7—C8—C9179.7 (3)
C16i—C14—C15—Cl1179.9 (2)C7—C8—C9—C101.2 (5)
C13—C14—C15—Cl10.7 (4)C8—C9—C10—N10.2 (5)
C14—C15—C16—C14i1.3 (5)C3—C4—C11—N21.5 (4)
Cl1—C15—C16—C14i179.9 (2)C5—C4—C11—N2180.0 (3)
C14—C15—C16—Cl2179.0 (2)C3—C4—C11—C12178.1 (3)
Cl1—C15—C16—Cl20.3 (3)C5—C4—C11—C120.4 (4)
O4—C17—C18—C1977.1 (3)C8—C7—C12—N11.0 (4)
O3—C17—C18—C19103.6 (3)C6—C7—C12—N1178.8 (2)
O4—C17—C18—C20ii100.9 (3)C8—C7—C12—C11179.9 (2)
O3—C17—C18—C20ii78.5 (3)C6—C7—C12—C110.1 (4)
C20ii—C18—C19—C200.3 (4)N2—C11—C12—N10.9 (4)
C17—C18—C19—C20178.3 (2)C4—C11—C12—N1178.7 (2)
C20ii—C18—C19—Cl3178.91 (19)N2—C11—C12—C7179.8 (2)
C17—C18—C19—Cl30.9 (3)C4—C11—C12—C70.2 (4)
C18—C19—C20—C18ii0.3 (4)C9—C10—N1—C121.4 (5)
Cl3—C19—C20—C18ii178.9 (2)C7—C12—N1—C102.0 (4)
C18—C19—C20—Cl4178.0 (2)C11—C12—N1—C10179.1 (3)
Cl3—C19—C20—Cl42.8 (3)C2—C1—N2—C110.8 (5)
N2—C1—C2—C31.0 (5)C4—C11—N2—C10.5 (4)
C1—C2—C3—C40.1 (5)C12—C11—N2—C1179.1 (3)
C2—C3—C4—C111.2 (5)O61iii—O61—O62—O5124 (6)
C2—C3—C4—C5179.7 (3)O52—O51—O62—O61155 (5)
C11—C4—C5—C60.5 (5)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1, z; (iii) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O30.821.742.550 (3)170
N1—H1A···O30.901.952.788 (4)154
C6—H6···O2iv0.932.563.413 (5)152
C10—H10···O40.932.433.193 (4)139
Symmetry code: (iv) x+1, y+2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H10N22+·C8Cl4O42·2H2O2C12H9N2+·C8Cl4O42·C8H2Cl4O4·3H2O
Mr496.111022.25
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)296295
a, b, c (Å)6.306 (2), 9.325 (3), 10.040 (4)8.2931 (11), 12.0916 (16), 12.3108 (16)
α, β, γ (°)62.508 (3), 86.763 (4), 73.842 (4)102.127 (2), 109.454 (1), 106.072 (2)
V3)501.3 (3)1054.4 (2)
Z11
Radiation typeMo KαMo Kα
µ (mm1)0.630.60
Crystal size (mm)0.18 × 0.15 × 0.120.28 × 0.22 × 0.15
Data collection
DiffractometerBruker APEXII? CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.895, 0.9280.850, 0.915
No. of measured, independent and
observed [I > 2σ(I)] reflections
3529, 1732, 1590 7609, 3677, 3201
Rint0.0330.020
(sin θ/λ)max1)0.5940.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.128, 1.00 0.044, 0.147, 1.07
No. of reflections17323677
No. of parameters136288
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.470.73, 0.38

Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.901.722.609 (3)169
O3—H3A···O20.822.082.824 (3)151
O3—H3B···O2i0.821.982.778 (3)165
C6—H6···O3ii0.932.353.269 (4)169
C8—H8···O3iii0.932.573.492 (4)172
Symmetry codes: (i) x+2, y+1, z+2; (ii) x+1, y+2, z+2; (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1'···O30.821.742.550 (3)170
N1—H1A···O30.901.952.788 (4)154
C6—H6···O2i0.932.563.413 (5)152
C10—H10···O40.932.433.193 (4)139
Symmetry code: (i) x+1, y+2, z+1.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds