Ethane-1,2-diaminium 2,2′-[tereph­thal­oyl­bis(aza­nedi­yl)]di­acetate tetrahydrate

In the title salt hydrate, C₂H₁₀N₂²⁺·C₁₂H₁₀N₂O₆²⁻·4H₂O, each of the ions is located about a centre of inversion and the asymmetric unit is completed by two water molecules in general positons. In the crystal, the cations, anions and water mol­ecules are connected by O—H...O and N—H...O hydrogen bonding into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.096
• Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.823 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT128_ALERT_4_G Alternate Setting for Input Space-Group  P21/c        P21/n Note
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Recently, the inter­est in constructing metal-organic coordination polymers continuously rises due to their facinating structures and properties with potential application as functional materials. For the synthesis of such compounds frequently relatively rigid ligands with several coordination centers are used. In this context the title compound was prepared, which should be used as a precursor in the synthesis of new coordination polymers.

The crystal structure of the title compound consists of 2,2'-(terephthaloylbis(aza­nediyl))di­acetate anions that are located on centers of inversion as well as of ethyl­enediaminium cations and water molecules in general positions (Fig. 1). The ethyl­enedi­amine cations are connected to the anions by N—H···O hydrogen bonding between the carboxyl­ate O atom and the ammonium H atoms. The anions and cations are additionally linked to water molecules via N—H···O and O—H···O hydrogen bonding into a three-dimensional network (Fig. 2 and Table 1). Furthermore, the compound shows luminescence under excitation with ultraviolet light.

S2. Experimental

The starting material, 2,2'-(benzene-1,4-dicarboxamido)­diacetatic acid, was prepared by the method of Cleaver & Pratt (Cleaver & Pratt, 1955). Single crystals were obtained by slow evaporation from an aqueous solution (40 ml) of 2,2'-terephthaloylbis-(glycine) dihydrate (630 mg) and ethyl­enedi­amine (3 ml) at room temperature. Colorless block shaped crystals appeared after a few days.

S2.1. Refinement

All hydrogen atoms were located the difference Fourier map and were refined isotropically with no restraints.

Related literature

For related organic structures, see: Armelin et al. (2001); Ray et al. (2006). For crystal strucutres of d-block elements with 2,2'-(terephthaloylbis(azanediyl))diacetate and similar ligands, see: Duan et al. (2010); Kostakis et al. (2005, 2011); Wisser et al. (2008); Zhang & You (2005); Zhang et al. (2006). The starting material, 2,2'-(benzene-1,4-dicarboxamido)diacetatic acid, was prepared by the method of Cleaver & Pratt (1955).

Computing details

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. View of the asymmetric unit of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. The dashed lines indicate N—H···O and O—H···O hydrogen bonds (see Table 1 for details). Symmetry codes: (i) -x - 1, -y - 1, -1 - z; (ii) -x + 1, -y - 1, -z.
	Fig. 2. Crystal structure of the title compound viewed along the a axis. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonding is shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Ethane-1,2-diaminium 2,2'-[terephthaloylbis(azanediyl)]diacetate tetrahydrate

Crystal data

C2H10N2^2+·C12H10N2O6^2^−·4H2O	F(000) = 440
Mr = 412.40	Dx = 1.443 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1859 reflections
a = 7.3710 (11) Å	θ = 1.0–26.0°
b = 9.0675 (11) Å	µ = 0.12 mm^−1
c = 14.704 (2) Å	T = 223 K
β = 105.041 (11)°	Block, colorless
V = 949.1 (2) Å^3	0.28 × 0.25 × 0.22 mm
Z = 2

Data collection

Stoe IPDS 2 diffractometer	1633 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.099
Graphite monochromator	θmax = 26.0°, θmin = 2.7°
ω–scans	h = −9→9
9883 measured reflections	k = −11→11
1859 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.2529P] where P = (Fo^2 + 2Fc^2)/3
1859 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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
O1	0.49836 (13)	0.43561 (11)	0.11941 (7)	0.0248 (2)
O2	0.67537 (15)	0.79044 (11)	0.17064 (7)	0.0293 (3)
O3	0.87997 (14)	0.70796 (12)	0.30002 (8)	0.0307 (3)
O4	1.16417 (16)	0.83739 (12)	0.24811 (9)	0.0304 (3)
H4A	1.250 (3)	0.875 (3)	0.2948 (17)	0.052 (6)*
H4B	1.067 (3)	0.806 (3)	0.2678 (16)	0.050 (6)*
O5	0.57247 (18)	0.30272 (13)	0.50636 (9)	0.0387 (3)
H5A	0.505 (3)	0.294 (3)	0.4449 (19)	0.058 (7)*
H5B	0.539 (4)	0.227 (3)	0.534 (2)	0.073 (8)*
N1	0.39210 (16)	0.60948 (13)	0.20250 (8)	0.0216 (3)
H1	0.302 (3)	0.670 (2)	0.2048 (14)	0.037 (5)*
N2	1.13211 (18)	0.50461 (14)	0.40607 (9)	0.0256 (3)
H2A	1.234 (3)	0.561 (2)	0.4374 (14)	0.035 (5)*
H2B	1.039 (3)	0.560 (2)	0.3615 (15)	0.041 (5)*
H2C	1.183 (3)	0.434 (3)	0.3741 (16)	0.053 (6)*
C1	0.17640 (18)	0.50869 (14)	0.06420 (9)	0.0192 (3)
C2	0.01507 (19)	0.54693 (15)	0.09178 (10)	0.0218 (3)
H2	0.023 (2)	0.5766 (19)	0.1573 (13)	0.028 (4)*
C3	0.16018 (19)	0.46137 (15)	−0.02754 (10)	0.0220 (3)
H3	0.268 (2)	0.4371 (18)	−0.0461 (12)	0.021 (4)*
C4	0.36832 (18)	0.51552 (14)	0.13090 (9)	0.0194 (3)
C5	0.56927 (18)	0.62239 (15)	0.27321 (10)	0.0215 (3)
H51	0.625 (2)	0.527 (2)	0.2943 (12)	0.025 (4)*
H52	0.544 (3)	0.673 (2)	0.3279 (14)	0.033 (5)*
C6	0.71953 (19)	0.71403 (14)	0.24383 (10)	0.0205 (3)
C7	1.0404 (2)	0.43916 (16)	0.47572 (11)	0.0275 (3)
H7A	1.135 (3)	0.384 (2)	0.5210 (14)	0.036 (5)*
H7B	0.937 (3)	0.375 (2)	0.4412 (13)	0.033 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0196 (5)	0.0265 (5)	0.0275 (5)	0.0040 (4)	0.0048 (4)	−0.0023 (4)
O2	0.0294 (6)	0.0305 (5)	0.0258 (6)	−0.0051 (4)	0.0034 (4)	0.0053 (4)
O3	0.0208 (5)	0.0308 (6)	0.0363 (6)	−0.0048 (4)	−0.0001 (4)	0.0053 (4)
O4	0.0237 (6)	0.0322 (6)	0.0349 (6)	−0.0038 (4)	0.0070 (5)	−0.0053 (5)
O5	0.0466 (7)	0.0325 (6)	0.0307 (7)	−0.0133 (5)	−0.0010 (5)	0.0009 (5)
N1	0.0157 (5)	0.0219 (6)	0.0266 (6)	0.0004 (4)	0.0041 (5)	−0.0026 (4)
N2	0.0255 (6)	0.0263 (6)	0.0237 (6)	0.0008 (5)	0.0040 (5)	−0.0018 (5)
C1	0.0180 (6)	0.0154 (6)	0.0237 (7)	−0.0017 (5)	0.0047 (5)	0.0024 (5)
C2	0.0204 (7)	0.0224 (7)	0.0230 (7)	−0.0017 (5)	0.0065 (5)	−0.0016 (5)
C3	0.0170 (6)	0.0226 (7)	0.0281 (7)	−0.0007 (5)	0.0087 (5)	−0.0016 (5)
C4	0.0189 (6)	0.0177 (6)	0.0227 (7)	−0.0011 (5)	0.0070 (5)	0.0033 (5)
C5	0.0201 (7)	0.0229 (7)	0.0204 (7)	−0.0011 (5)	0.0033 (5)	−0.0010 (6)
C6	0.0202 (7)	0.0181 (6)	0.0228 (7)	−0.0006 (5)	0.0050 (5)	−0.0038 (5)
C7	0.0358 (8)	0.0206 (7)	0.0260 (8)	0.0025 (6)	0.0076 (6)	−0.0010 (6)

Geometric parameters (Å, º)

O1—C4	1.2476 (16)	C1—C3	1.391 (2)
O2—C6	1.2500 (18)	C1—C2	1.3961 (19)
O3—C6	1.2558 (17)	C1—C4	1.4990 (18)
O4—H4A	0.87 (3)	C2—C3^i	1.390 (2)
O4—H4B	0.89 (3)	C2—H2	0.987 (19)
O5—H5A	0.92 (3)	C3—C2^i	1.390 (2)
O5—H5B	0.86 (3)	C3—H3	0.931 (17)
N1—C4	1.3301 (18)	C5—C6	1.5337 (18)
N1—C5	1.4476 (17)	C5—H51	0.977 (18)
N1—H1	0.87 (2)	C5—H52	0.98 (2)
N2—C7	1.489 (2)	C6—O3	1.2558 (17)
N2—H2A	0.93 (2)	C7—C7^ii	1.517 (3)
N2—H2B	0.96 (2)	C7—H7A	0.97 (2)
N2—H2C	0.93 (2)	C7—H7B	0.98 (2)
H4A—O4—H4B	110 (2)	O1—C4—N1	122.09 (12)
H5A—O5—H5B	104 (2)	O1—C4—C1	121.01 (12)
C4—N1—C5	121.96 (12)	N1—C4—C1	116.90 (11)
C4—N1—H1	119.3 (13)	N1—C5—C6	115.11 (12)
C5—N1—H1	118.6 (13)	N1—C5—H51	112.5 (10)
C7—N2—H2A	109.4 (12)	C6—C5—H51	107.3 (10)
C7—N2—H2B	108.1 (12)	N1—C5—H52	107.5 (11)
H2A—N2—H2B	113.2 (17)	C6—C5—H52	106.3 (11)
C7—N2—H2C	112.9 (14)	H51—C5—H52	107.8 (15)
H2A—N2—H2C	104.4 (18)	O2—C6—O3	125.53 (13)
H2B—N2—H2C	108.9 (18)	O2—C6—O3	125.53 (13)
C3—C1—C2	119.54 (13)	O2—C6—C5	119.81 (12)
C3—C1—C4	118.45 (12)	O3—C6—C5	114.62 (12)
C2—C1—C4	122.01 (13)	O3—C6—C5	114.62 (12)
C3^i—C2—C1	120.03 (14)	N2—C7—C7^ii	109.72 (15)
C3^i—C2—H2	119.1 (10)	N2—C7—H7A	107.8 (12)
C1—C2—H2	120.9 (10)	C7^ii—C7—H7A	110.7 (12)
C2^i—C3—C1	120.43 (13)	N2—C7—H7B	107.9 (11)
C2^i—C3—H3	120.1 (10)	C7^ii—C7—H7B	109.0 (11)
C1—C3—H3	119.5 (10)	H7A—C7—H7B	111.6 (16)
C3—C1—C2—C3^i	−0.5 (2)	C3—C1—C4—N1	154.93 (12)
C4—C1—C2—C3^i	−179.87 (12)	C2—C1—C4—N1	−25.66 (18)
C2—C1—C3—C2^i	0.5 (2)	C4—N1—C5—C6	79.20 (16)
C4—C1—C3—C2^i	179.89 (12)	O3—O3—C6—O2	0.00 (17)
C5—N1—C4—O1	−1.6 (2)	O3—O3—C6—C5	0.00 (13)
C5—N1—C4—C1	177.93 (11)	N1—C5—C6—O2	11.70 (18)
C3—C1—C4—O1	−25.48 (18)	N1—C5—C6—O3	−170.64 (12)
C2—C1—C4—O1	153.92 (13)	N1—C5—C6—O3	−170.64 (12)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O3	0.89 (3)	1.80 (3)	2.6792 (16)	169 (2)
N2—H2B···O3	0.96 (2)	1.85 (2)	2.7896 (17)	164.3 (18)
O4—H4A···O1^iii	0.87 (3)	2.03 (3)	2.8741 (16)	162 (2)
O5—H5A···O2^iv	0.92 (3)	1.87 (3)	2.7669 (17)	168 (2)
O5—H5B···O1^v	0.86 (3)	2.01 (3)	2.8641 (17)	169 (3)
N1—H1···O4^vi	0.87 (2)	2.02 (2)	2.8509 (17)	159.8 (18)
N2—H2A···O5^ii	0.93 (2)	1.91 (2)	2.8278 (18)	172.6 (18)
N2—H2C···O2^vii	0.93 (2)	1.89 (2)	2.8086 (17)	169 (2)

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2; (vi) x−1, y, z; (vii) −x+2, y−1/2, −z+1/2.