Tetra­ammonium benzene-1,2,4,5-tetra­carboxyl­ate dihydrate

In the crystal structure of 4NH₄⁺·C₁₀H₂O₈⁴⁻·2H₂O, the tetra­carboxyl­ate anion resides on a twofold crystallographic axis. The supra­molecular structure arises from eight N—H...O [N...O ranges from 2.783 (2) to 3.003 (2) Å] and two O—H...O [O...O distances of 2.7313 (18) and 2.9102 (18) Å] hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 130 K
• Mean [sigma](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

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S1. Comment

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···O_water, O_water—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).

Related literature

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).

S2. Experimental

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.

S3. Refinement

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.

Computing details

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).

Figures

	Fig. 1. The asymmetric unit of (I) with 50% probability displacement ellipsoids (Siemens, 1989).
	Fig. 2. The molecular layer in (I) generated by four N1^+—H(11,12,13,14)···O^- hydrogen bonds with a view along the c axis (Macrae et al., 2006).
	Fig. 3. The molecular layer in (I) generated by four N1^+—H(11,12,13,14)···O^- hydrogen bonds with a view along the a axis (Macrae et al., 2006).
	Fig. 4. A second type of the molecular layer in (I) generated by N—H···O^-carboxylate, N—H···Owater, Owater—H···O^-carboxylate hydrogen bonds with a view along the a axis (Macrae et al., 2006).
	Fig. 5. Three types of hydrogen bonds: N—H···O^-carboxylate, N—H···Owater, Owater—H···O^-carboxylate connect layers (see Fig. 2a, 2 b, 2c) into the supramolecular structure (Macrae et al., 2006).

Tetraammonium benzene-1,2,4,5-tetracarboxylate dihydrate

Crystal data

4NH4^+·C10H2O8^4^−·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) Å^3	Block, colourless
Z = 2	0.5 × 0.2 × 0.1 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 0.094P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C4^i	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—C4^i	119.12 (12)	H12—N1—H13	108 (2)
C1—C2—C3	118.79 (12)	H11—N1—H14	111 (2)
C4^i—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—C2^i	119.06 (12)	H22—N2—H23	109 (3)
C3—C4—C5	116.35 (11)	H21—N2—H24	114 (2)
C2^i—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—C2^i	0.2 (2)
O1—C1—C2—C3	171.32 (16)	C2—C3—C4—C5	−179.04 (16)
O2—C1—C2—C4^i	173.12 (16)	C3—C4—C5—O3	−80.29 (19)
O1—C1—C2—C4^i	−7.2 (2)	C2^i—C4—C5—O3	100.51 (18)
C4^i—C2—C3—C4	0.5 (2)	C3—C4—C5—O4	94.68 (18)
C1—C2—C3—C4	−178.02 (16)	C2^i—C4—C5—O4	−84.5 (2)

Symmetry code: (i) −x+1, y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2^ii	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···O2^iii	0.96 (2)	1.91 (2)	2.8585 (16)	171 (2)
N1—H14···O3^iv	0.97 (3)	1.85 (3)	2.819 (2)	179 (3)
N2—H21···O4^v	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···O5^iv	0.88 (4)	2.00 (4)	2.857 (2)	162 (3)
N2—H24···O5^vi	0.99 (4)	2.18 (3)	3.003 (2)	139 (2)
N2—H24···O3^iii	0.99 (4)	2.23 (3)	2.984 (2)	132 (3)
O5—H51···O1	0.90	1.90	2.7313 (18)	153
O5—H52···O3^i	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.