Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045205/gg2029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045205/gg2029Isup2.hkl |
CCDC reference: 663796
The 0.047 g (~ 0.1 mM) of the macrocyclic amine (Borowiak, Dutkiewicz et al., 2005a; Borowiak, Kubicki et al., 2005b), was dissolved in 2 ml of ethanol. Then 0.025 g (~0.1 mM) of pyromellitic acid dissolved in 1 ml of water was added. The white precipitate was not dissolved after refluxing the reaction mixture. The 1 ml of formamide was added to the mixture and was warmed until dissolution of the product. The solution was cooled down slowly and after two days colorless crystals were deposited. We expected the adduct of macrocyclic amine and pyromellitic acid, instead crystals comprised both pyromellitic anion and ammonium cation. It can be explained in this way that formamide was hydrolyzed in slightly basic conditions to form ammonia that substituted for the macrocyclic amine cation.
Initial trials to refine the structural model of (I) in the centrosymmetric space group C2/m (No. 12) provided a solution that did not provide a satisfactory refinement convergence. A satisfactory convergence was achieved in the non-centrosymmetric space group C2 (No. 5).
Hydrogen atoms were located in difference Fourier maps and refined except for the hydrogen atoms of the water molecule, which were constrained to ride on their parent O atom.
The compound (I) crystallizes in the space group C2, with two water molecules of crystallization. The crystal structure of the tetrahydrate was determined previously (Bergstrom et al., 2000).
The asymmetric unit of (I) (Fig. 1) contains two cations, one half-anion, and a water molecule; the anion lies on a twofold axis of symmetry. All carboxylic H atoms are transferred to the N atoms, thus forming ammonium cations. The conformation of pyromellitate anion is similar to that in the crystal structures determined previously (Bergstrom et al., 2000; Zheng et al., 2002; Wang et al., 2005; Ejsmont & Zaleski, 2006; Rafizadeh et al., 2006) where one pair of carboxylate groups is almost coplanar with the aromatic ring (8.1°) while the other one is almost perpendicular (82.6°).
The molecules form two different types of hydrogen-bonded layers. In one of them each ammonium cation is connected to four pyromellitate anions via four distinct N1+—H···O- hydrogen bonds (Table 1) that make a kind of a patchwork (Fig. 2, Fig. 3). The second type is formed via three different hydrogen bonds: N—H···O-carboxylate, N—H···Owater, Owater—H···O-carboxylate (Fig. 4). These layers are parallel to the ab crystallographic plane.
The two kinds of layers are placed alternately, thus forming the supramolecular structure (Fig. 5).
For related literature, see: Allen (2002); Bergstrom et al. (2000); Borowiak, Dutkiewicz et al. (2005); Borowiak, Kubicki et al. (2005); Ejsmont & Zaleski (2006); Rafizadeh et al. (2006); Wang et al. (2005); Zheng et al. (2002).
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens 1989); Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
4NH4+·C10H2O84−·2H2O | F(000) = 380 |
Mr = 358.32 | Dx = 1.482 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6054 (10) Å | Cell parameters from 2581 reflections |
b = 6.7122 (6) Å | θ = 2.4–29.1° |
c = 10.5718 (8) Å | µ = 0.13 mm−1 |
β = 102.821 (7)° | T = 130 K |
V = 802.99 (12) Å3 | Block, colourless |
Z = 2 | 0.5 × 0.2 × 0.1 mm |
Kuma KM-4 CCD diffractometer | 1088 independent reflections |
Radiation source: fine-focus sealed tube | 1042 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
Detector resolution: 8.1929 pixels mm-1 | θmax = 29.1°, θmin = 3.5° |
ω–scan | h = −15→15 |
Absorption correction: multi-scan [empirical (using intensity measurements) absorption correction (CrysAlis RED; Oxford Diffraction, 2007)] | k = −9→6 |
Tmin = 0.972, Tmax = 1.000 | l = −14→13 |
3224 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.094P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1088 reflections | Δρmax = 0.28 e Å−3 |
147 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: [Flack, H. D. (1983). Acta Cryst. A39, 876–881] |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (12) |
4NH4+·C10H2O84−·2H2O | V = 802.99 (12) Å3 |
Mr = 358.32 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 11.6054 (10) Å | µ = 0.13 mm−1 |
b = 6.7122 (6) Å | T = 130 K |
c = 10.5718 (8) Å | 0.5 × 0.2 × 0.1 mm |
β = 102.821 (7)° |
Kuma KM-4 CCD diffractometer | 1088 independent reflections |
Absorption correction: multi-scan [empirical (using intensity measurements) absorption correction (CrysAlis RED; Oxford Diffraction, 2007)] | 1042 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 1.000 | Rint = 0.011 |
3224 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | Δρmax = 0.28 e Å−3 |
S = 1.11 | Δρmin = −0.20 e Å−3 |
1088 reflections | Absolute structure: [Flack, H. D. (1983). Acta Cryst. A39, 876–881] |
147 parameters | Absolute structure parameter: 0.1 (12) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.71490 (12) | 0.5340 (3) | 0.39876 (13) | 0.0140 (3) | |
O1 | 0.70464 (10) | 0.50819 (19) | 0.27848 (11) | 0.0194 (3) | |
O2 | 0.81107 (9) | 0.5530 (2) | 0.47862 (10) | 0.0221 (3) | |
C2 | 0.60214 (11) | 0.5412 (3) | 0.44879 (12) | 0.0124 (3) | |
C3 | 0.61053 (11) | 0.5420 (3) | 0.58230 (12) | 0.0130 (3) | |
H3 | 0.6911 (17) | 0.541 (4) | 0.6365 (18) | 0.014 (4)* | |
C4 | 0.51014 (12) | 0.5424 (2) | 0.63515 (13) | 0.0122 (3) | |
C5 | 0.53202 (12) | 0.5467 (3) | 0.78232 (12) | 0.0137 (3) | |
O3 | 0.55778 (11) | 0.38518 (19) | 0.84174 (11) | 0.0187 (3) | |
O4 | 0.53126 (12) | 0.71429 (19) | 0.83520 (11) | 0.0208 (3) | |
N1 | 0.51699 (11) | 1.0495 (3) | 0.67757 (12) | 0.0167 (3) | |
H11 | 0.444 (2) | 1.058 (4) | 0.619 (2) | 0.027 (5)* | |
H12 | 0.519 (2) | 0.936 (4) | 0.726 (2) | 0.021 (6)* | |
H13 | 0.580 (2) | 1.041 (5) | 0.632 (2) | 0.035 (6)* | |
H14 | 0.531 (2) | 1.166 (5) | 0.733 (3) | 0.034 (7)* | |
N2 | 0.68683 (14) | 0.7804 (3) | 0.07294 (14) | 0.0221 (3) | |
H21 | 0.618 (2) | 0.744 (5) | −0.005 (3) | 0.038 (7)* | |
H22 | 0.687 (2) | 0.701 (5) | 0.138 (3) | 0.037 (7)* | |
H23 | 0.664 (3) | 0.901 (6) | 0.091 (3) | 0.041 (8)* | |
H24 | 0.766 (3) | 0.775 (6) | 0.052 (3) | 0.066 (10)* | |
O5 | 0.65381 (12) | 0.1966 (2) | 0.10908 (16) | 0.0304 (3) | |
H51 | 0.6910 | 0.2740 | 0.1752 | 0.088 (13)* | |
H52 | 0.5839 | 0.2424 | 0.1195 | 0.101 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0131 (6) | 0.0137 (6) | 0.0161 (6) | 0.0009 (6) | 0.0050 (5) | 0.0016 (7) |
O1 | 0.0190 (5) | 0.0253 (7) | 0.0154 (5) | 0.0009 (5) | 0.0071 (4) | −0.0001 (5) |
O2 | 0.0127 (5) | 0.0342 (7) | 0.0191 (5) | −0.0008 (6) | 0.0032 (4) | −0.0011 (6) |
C2 | 0.0126 (6) | 0.0125 (6) | 0.0124 (6) | 0.0000 (6) | 0.0035 (4) | 0.0002 (6) |
C3 | 0.0121 (6) | 0.0145 (6) | 0.0120 (6) | −0.0003 (6) | 0.0016 (4) | 0.0007 (6) |
C4 | 0.0142 (6) | 0.0113 (6) | 0.0111 (5) | 0.0001 (6) | 0.0029 (4) | −0.0001 (6) |
C5 | 0.0119 (6) | 0.0178 (7) | 0.0111 (6) | −0.0006 (6) | 0.0019 (4) | −0.0003 (6) |
O3 | 0.0235 (6) | 0.0183 (6) | 0.0146 (6) | 0.0035 (5) | 0.0047 (4) | 0.0033 (4) |
O4 | 0.0325 (7) | 0.0166 (6) | 0.0129 (5) | −0.0024 (5) | 0.0039 (4) | −0.0018 (5) |
N1 | 0.0145 (6) | 0.0179 (6) | 0.0178 (6) | 0.0003 (6) | 0.0036 (4) | 0.0021 (6) |
N2 | 0.0292 (8) | 0.0211 (7) | 0.0164 (6) | −0.0028 (6) | 0.0059 (6) | 0.0008 (6) |
O5 | 0.0254 (7) | 0.0240 (7) | 0.0425 (8) | 0.0017 (6) | 0.0089 (5) | −0.0101 (6) |
C1—O1 | 1.2625 (18) | N1—H11 | 0.94 (2) |
C1—O2 | 1.2476 (18) | N1—H12 | 0.91 (3) |
C1—C2 | 1.5172 (17) | N1—H13 | 0.96 (2) |
C2—C3 | 1.3931 (17) | N1—H14 | 0.97 (3) |
C2—C4i | 1.4043 (18) | N2—H21 | 1.04 (3) |
C3—C4 | 1.3994 (18) | N2—H22 | 0.87 (3) |
C3—H3 | 0.98 (2) | N2—H23 | 0.88 (4) |
C4—C5 | 1.5202 (17) | N2—H24 | 0.99 (4) |
C5—O3 | 1.256 (2) | O5—H51 | 0.90 |
C5—O4 | 1.257 (2) | O5—H52 | 0.90 |
O1—C1—O2 | 124.46 (13) | O4—C5—C4 | 117.15 (15) |
O2—C1—C2 | 118.18 (12) | H11—N1—H12 | 109 (2) |
O1—C1—C2 | 117.36 (12) | H11—N1—H13 | 110.2 (18) |
C3—C2—C4i | 119.12 (12) | H12—N1—H13 | 108 (2) |
C1—C2—C3 | 118.79 (12) | H11—N1—H14 | 111 (2) |
C4i—C2—C1 | 122.08 (11) | H12—N1—H14 | 110.7 (18) |
C2—C3—C4 | 121.82 (12) | H13—N1—H14 | 108 (2) |
C2—C3—H3 | 115.8 (11) | H21—N2—H22 | 110 (2) |
C4—C3—H3 | 122.4 (11) | H21—N2—H23 | 100 (3) |
C3—C4—C2i | 119.06 (12) | H22—N2—H23 | 109 (3) |
C3—C4—C5 | 116.35 (11) | H21—N2—H24 | 114 (2) |
C2i—C4—C5 | 124.58 (12) | H22—N2—H24 | 108 (3) |
O3—C5—O4 | 125.08 (12) | H23—N2—H24 | 115 (3) |
O3—C5—C4 | 117.55 (15) | H51—O5—H52 | 90 |
O2—C1—C2—C3 | −8.4 (2) | C2—C3—C4—C2i | 0.2 (2) |
O1—C1—C2—C3 | 171.32 (16) | C2—C3—C4—C5 | −179.04 (16) |
O2—C1—C2—C4i | 173.12 (16) | C3—C4—C5—O3 | −80.29 (19) |
O1—C1—C2—C4i | −7.2 (2) | C2i—C4—C5—O3 | 100.51 (18) |
C4i—C2—C3—C4 | 0.5 (2) | C3—C4—C5—O4 | 94.68 (18) |
C1—C2—C3—C4 | −178.02 (16) | C2i—C4—C5—O4 | −84.5 (2) |
Symmetry code: (i) −x+1, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O2ii | 0.94 (2) | 1.88 (2) | 2.8114 (16) | 170 (2) |
N1—H12···O4 | 0.91 (3) | 1.87 (3) | 2.783 (2) | 175 (2) |
N1—H13···O2iii | 0.96 (2) | 1.91 (2) | 2.8585 (16) | 171 (2) |
N1—H14···O3iv | 0.97 (3) | 1.85 (3) | 2.819 (2) | 179 (3) |
N2—H21···O4v | 1.04 (3) | 1.78 (3) | 2.786 (2) | 163 (2) |
N2—H22···O1 | 0.87 (3) | 1.94 (3) | 2.811 (2) | 172 (3) |
N2—H23···O5iv | 0.88 (4) | 2.00 (4) | 2.857 (2) | 162 (3) |
N2—H24···O5vi | 0.99 (4) | 2.18 (3) | 3.003 (2) | 139 (2) |
N2—H24···O3iii | 0.99 (4) | 2.23 (3) | 2.984 (2) | 132 (3) |
O5—H51···O1 | 0.90 | 1.90 | 2.7313 (18) | 153 |
O5—H52···O3i | 0.90 | 2.02 | 2.9102 (18) | 170 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x−1/2, y+1/2, z; (iii) −x+3/2, y+1/2, −z+1; (iv) x, y+1, z; (v) x, y, z−1; (vi) −x+3/2, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | 4NH4+·C10H2O84−·2H2O |
Mr | 358.32 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 130 |
a, b, c (Å) | 11.6054 (10), 6.7122 (6), 10.5718 (8) |
β (°) | 102.821 (7) |
V (Å3) | 802.99 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.5 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Kuma KM-4 CCD |
Absorption correction | Multi-scan [empirical (using intensity measurements) absorption correction (CrysAlis RED; Oxford Diffraction, 2007)] |
Tmin, Tmax | 0.972, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3224, 1088, 1042 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.684 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.076, 1.11 |
No. of reflections | 1088 |
No. of parameters | 147 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.20 |
Absolute structure | [Flack, H. D. (1983). Acta Cryst. A39, 876–881] |
Absolute structure parameter | 0.1 (12) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation (Siemens 1989); Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O2i | 0.94 (2) | 1.88 (2) | 2.8114 (16) | 170 (2) |
N1—H12···O4 | 0.91 (3) | 1.87 (3) | 2.783 (2) | 175 (2) |
N1—H13···O2ii | 0.96 (2) | 1.91 (2) | 2.8585 (16) | 171 (2) |
N1—H14···O3iii | 0.97 (3) | 1.85 (3) | 2.819 (2) | 179 (3) |
N2—H21···O4iv | 1.04 (3) | 1.78 (3) | 2.786 (2) | 163 (2) |
N2—H22···O1 | 0.87 (3) | 1.94 (3) | 2.811 (2) | 172 (3) |
N2—H23···O5iii | 0.88 (4) | 2.00 (4) | 2.857 (2) | 162 (3) |
N2—H24···O5v | 0.99 (4) | 2.18 (3) | 3.003 (2) | 139 (2) |
N2—H24···O3ii | 0.99 (4) | 2.23 (3) | 2.984 (2) | 132 (3) |
O5—H51···O1 | 0.90 | 1.90 | 2.7313 (18) | 153 |
O5—H52···O3vi | 0.90 | 2.02 | 2.9102 (18) | 170 |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+3/2, y+1/2, −z+1; (iii) x, y+1, z; (iv) x, y, z−1; (v) −x+3/2, y+1/2, −z; (vi) −x+1, y, −z+1. |
The compound (I) crystallizes in the space group C2, with two water molecules of crystallization. The crystal structure of the tetrahydrate was determined previously (Bergstrom et al., 2000).
The asymmetric unit of (I) (Fig. 1) contains two cations, one half-anion, and a water molecule; the anion lies on a twofold axis of symmetry. All carboxylic H atoms are transferred to the N atoms, thus forming ammonium cations. The conformation of pyromellitate anion is similar to that in the crystal structures determined previously (Bergstrom et al., 2000; Zheng et al., 2002; Wang et al., 2005; Ejsmont & Zaleski, 2006; Rafizadeh et al., 2006) where one pair of carboxylate groups is almost coplanar with the aromatic ring (8.1°) while the other one is almost perpendicular (82.6°).
The molecules form two different types of hydrogen-bonded layers. In one of them each ammonium cation is connected to four pyromellitate anions via four distinct N1+—H···O- hydrogen bonds (Table 1) that make a kind of a patchwork (Fig. 2, Fig. 3). The second type is formed via three different hydrogen bonds: N—H···O-carboxylate, N—H···Owater, Owater—H···O-carboxylate (Fig. 4). These layers are parallel to the ab crystallographic plane.
The two kinds of layers are placed alternately, thus forming the supramolecular structure (Fig. 5).