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
Key indicators
- Single-crystal X-ray study
- T = 130 K
- Mean (C-C) = 0.002 Å
- R factor = 0.026
- wR factor = 0.076
- Data-to-parameter ratio = 7.4
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT113_ALERT_2_A ADDSYM Suggests Possible Pseudo/New Spacegroup . C2/m
Author Response: `see _publ_section_exptl_refinement' |
Alert level B PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 100 PerFi
Alert level C STRVA01_ALERT_4_C Flack test results are meaningless. From the CIF: _refine_ls_abs_structure_Flack 0.100 From the CIF: _refine_ls_abs_structure_Flack_su 1.200 PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 1.20 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.40 PLAT353_ALERT_3_C Long N-H Bond (0.87A) N2 - H21 ... 1.04 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.987 Tmax scaled 0.987 Tmin scaled 0.959 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 29.09 From the CIF: _reflns_number_total 1088 Count of symmetry unique reflns 1161 Completeness (_total/calc) 93.71% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
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. |
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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).