Benzene-1,3,5-tricarboxylic acid–1,2-bis­(1,2,4-triazol-4-yl)ethane–water (4/1/2)

Habib, H.A.; Janiak, C.

doi:10.1107/S1600536808015808

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1199

doi:10.1107/S1600536808015808

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Benzene-1,3,5-tricarboxylic acid–1,2-bis(1,2,4-triazol-4-yl)ethane–water (4/1/2)

Hesham A. Habib ^a and Christoph Janiak ^a ^*

^aInstitut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
^*Correspondence e-mail: janiak@uni-freiburg.de

(Received 1 March 2008; accepted 26 May 2008; online 7 June 2008)

The title compound, 4C₉H₆O₆·C₆H₈N₆·2H₂O, crystallizes in a layer structure where each sheet is composed of anellated hydrogen-bonded rings of six distinct sizes: R₂²(16), R₃³(18), R₄⁴(12), R₄⁴(18), R₄⁴(22) and R₄⁴(25). The two largest rings, viz. R₄⁴(22) and R₄⁴(25), are associated with O—H⋯N bonds from the carboxyl groups to the triazole rings. The typical head-to-tail carboxyl–carboxyl R₂²(8) motif is not observed.

Related literature

For related literature, see: Althoff et al. (2006 ); Dale & Elsegood (2004 ); Dale et al. (2004 ); Dorn et al. (2005 , 2006 ); Du et al. (2005 ); Etter et al. (1990 ); Fan et al. (2005 ); Goldberg & Bernstein (2007 ); Janiak (2000 ); Shattock et al. (2005 ); Turner et al. (2008 ); Wang & Wang (2005 ); Wisser & Janiak (2007a ,b ).

Experimental

Crystal data

4C₉H₆O₆·C₆H₈N₆·2H₂O
M_r = 1040.76
Triclinic, $[P \overline 1]$
a = 9.7989 (1) Å
b = 10.7511 (2) Å
c = 12.6578 (2) Å
α = 108.801 (1)°
β = 98.737 (1)°
γ = 113.340 (1)°
V = 1097.44 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 203 (2) K
0.37 × 0.05 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.952, T_max = 0.997
20984 measured reflections
4824 independent reflections
3452 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.105
S = 1.02
4824 reflections
359 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O11ⁱ	0.92 (2)	1.67 (2)	2.594 (2)	175 (2)
O4—H4⋯O8	0.88 (2)	1.75 (2)	2.626 (2)	174 (2)
O6—H6⋯O1ⁱⁱ	0.91 (2)	1.84 (2)	2.699 (2)	157 (2)
O7—H7⋯N1	0.96 (2)	1.75 (2)	2.703 (2)	172 (2)
O9—H9⋯O13	0.91 (3)	1.63 (3)	2.531 (2)	170 (2)
O12—H12⋯N2ⁱⁱⁱ	0.90 (2)	1.76 (2)	2.644 (2)	167 (2)
O13—H13A⋯O10^iv	0.91 (2)	1.81 (3)	2.711 (2)	171 (2)
O13—H13B⋯O5	0.85 (3)	1.92 (3)	2.751 (2)	167 (2)
Symmetry codes: (i) x+1, y, z-1; (ii) -x+3, -y+2, -z+1; (iii) -x, -y, -z+1; (iv) -x+2, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015808/kj2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015808/kj2089Isup2.hkl

checkCIF report

Comment top

Hydrogen bonding within crystalline systems is of timely interest for the rational design of organized solids (Althoff et al., 2006; Dorn et al., 2005; Dorn et al. 2006; Wisser & Janiak, 2007a,b). Co-crystallization of benzene-di, -tri- and -tetra-carboxylic acids, like trimesic acid or hemimellitic acid with solvent molecules or nitrogen bases is the focus of permanent and recent research activities (Dale & Elsegood, 2004; Dale et al., 2004; Du et al., 2005; Fan et al., 2005; Goldberg & Bernstein, 2007; Shattock et al., 2005; Turner et al., 2008; Wang & Wang, 2005). Co-crystal structures of trimesic acid (benzene-1,3,5-tricarboxylic acid) have been reported with 2,5-bis(3- and 4-pyridyl)-1,3,4-oxadiazole (two-dimensional sheet, Du et al., 2005), 3,6-bis(3'-pyridyl)-1,2,4,5-tetrazine (one-dimensional ribbon, Wang & Wang, 2005), 1,2-bis(4-pyridyl)ethane (two-dimensional 6,3- and 10,3-network with interpenetration, Shattock et al., 2005), mono- and bis(methanol) (one-dimensional tape, Dale et al., 2004), acetic acid (Goldberg & Bernstein, 2007) and dihydrate (three-dimensional network, Fan et al., 2005).

The hydrogen-bonded sheet in the title compound contains several different motifs that engage all of the strong hydrogen bond donors and acceptors available (Fig. 1 and 2). The hydrogen bond distances in the sheet are spread over a narrow range, with D···A distances from 2.53 to 2.75 Å. The sheet is constructed of six distinct hydrogen-bonded rings of sizes R₂²(16), R₃³(18), R₄⁴(12), R₄⁴(18), R₄⁴(22) and R₄⁴(25), using Etter's graph set analysis (Etter et al., 1990). The two largest rings R₄⁴(22) and R₄⁴(25) are associated with the O—H···N bonds from the carboxylic acid groups to the triazole rings. All N1 and N2 nitrogen atoms of the 1,2-bis(1,2,4-triazol-4-yl)ethane molecule act as hydrogen-bond acceptors. The smallest ring R₄⁴(12) incorporates two water molecules and two carboxylic acid groups. The 18-membered R₃³(18) and R₄⁴(18) rings are constructed from one water molecule in combination with three and four carboxylic acid groups, respectively. These water and carboxylic acid containing motifs are different from those seen in the structure of the trimesic acid dihydrate (Fan et al., 2005). Also, formation of the common R₂²(8) head-to-tail carboxylic acid–acid graph-set motif is apparently prevented in the structure of the title compound by the water and the bis-triazole molecule. No relevant π–π or C—H···π interactions are found between molecules in adjacent sheets (Fig. 3) (Janiak, 2000).

Related literature top

For related literature, see: Althoff et al. (2006); Dale & Elsegood (2004); Dale et al. (2004); Dorn et al. (2005, 2006); Du et al. (2005); Etter et al. (1990); Fan et al. (2005); Goldberg & Bernstein (2007); Janiak (2000); Shattock et al. (2005); Turner et al. (2008); Wang & Wang (2005); Wisser & Janiak (2007a,b).

Experimental top

A mixture of trimesic acid, H₃btc (210 mg, 1.00 mmol), 1,2-bis(1,2,4-triazol-4-yl)ethane, btre (164 mg, 1.00 mmol) and water (15 ml) was stirred for 30 min at room temperature, transferred to a Teflon-lined stainless-steel autoclave and heated at 453 K for 3 d. Then the autoclave was cooled to room temperature at a rate of 2.8 K h^-1. A colorless crystalline product was filtered off, washed with distilled water and dried in air (yield 135 mg, 52% based on H₃btc). Elemental analysis C₂₁H₁₈N₃O₁₃ (520.38) calcd. C 48.47, H 3.49, N 8.07; found: C 47.84, H 3.49, N 8.02%.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2006); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Fully labelled displacement ellipsoid diagram (at 50% probability) of the asymmetric unit. Symmetry code (v) 1-x, -y, -z.
	Fig. 2. The hydrogen-bonded sheet in the structure of 2(C₆H₃-1,3,5-(COOH)₃).0.5(C₆H₈N₆).H₂O with graph set pattern of hydrogen-bonded rings in violet. Hydrogen bond data is given in Table 1. Additional symmetry code (v) 1-x, -y, -z.
	Fig. 3. Packing of the hydrogen-bonded sheets parallel to the (-2,3,-2)-plane with a d-spacing (distance of neighboring sheets) of 3.155 Å.

benzene-1,3,5-tricarboxylic acid–1,2-bis(1,2,4-triazol-4-yl)ethane–water (4/1/2) top

Crystal data top

4C₉H₆O₆·C₆H₈N₆·2H₂O	Z = 1
M_r = 1040.76	F(000) = 538
Triclinic, P1	D_x = 1.575 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7989 (1) Å	Cell parameters from 5028 reflections
b = 10.7511 (2) Å	θ = 2.2–31.5°
c = 12.6578 (2) Å	µ = 0.13 mm⁻¹
α = 108.801 (1)°	T = 203 K
β = 98.737 (1)°	Needle, colourless
γ = 113.340 (1)°	0.37 × 0.05 × 0.02 mm
V = 1097.44 (3) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4824 independent reflections
Radiation source: fine-focus sealed tube	3452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.952, T_max = 0.997	k = −13→13
20984 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0562P)² + 0.0985P] where P = (F_o² + 2F_c²)/3
4824 reflections	(Δ/σ)_max < 0.001
359 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

4C₉H₆O₆·C₆H₈N₆·2H₂O	γ = 113.340 (1)°
M_r = 1040.76	V = 1097.44 (3) Å³
Triclinic, P1	Z = 1
a = 9.7989 (1) Å	Mo Kα radiation
b = 10.7511 (2) Å	µ = 0.13 mm⁻¹
c = 12.6578 (2) Å	T = 203 K
α = 108.801 (1)°	0.37 × 0.05 × 0.02 mm
β = 98.737 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4824 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3452 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.997	R_int = 0.036
20984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.25 e Å⁻³
4824 reflections	Δρ_min = −0.24 e Å⁻³
359 parameters

Special details top

Experimental. IR (KBr) 3512m (νCOO-H), 3427m (νCOO-H), 3122m, 1886m, 1704 s, (ν_asymCO₂), 1539m (ν_asymCO₂),1452 s (ν_symCO₂), 1356w (ν_symCO₂), 1320w (δOH···O),1285m, 1225m, 1190m, 1071m, 1020m, 986m, 936m (γOH···O), 905m, 870w, 844w, 814w, 745 s, 683 s, 666 s, 936m, 605w, 570w, 510m, 448m cm^-1.

Thermogravimetric analysis (simultaneous thermoanalysis apparatus STA 409 C from Netzsch under nitrogen with a heating rate of 10 K min^-1 in the range of 323 to 920 K): A sample of the compound shows the first weight loss in the temperature range 450–490 K which corresponds to the removal of the water molecule (obs. 3.67, calcd. 3.45%). From 550 to 610 K a less well resolved weight loss of about 17% occurs which is assigned to the half btre molecule (calcd. 15.8%). A third weight loss in the range 610–650 K of around 40% is assigned to the removal of one H~3~btc molecule (calcd. 40.3%). A weight loss continues to 920 K where 18.6% of the original mass is retained.

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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

	x	y	z	U_iso*/U_eq
O1	1.35077 (13)	0.71622 (12)	0.20868 (9)	0.0281 (3)
O2	1.12433 (15)	0.50380 (13)	0.11195 (10)	0.0342 (3)
H2	1.169 (2)	0.490 (2)	0.0526 (19)	0.051*
O3	0.72628 (14)	0.32810 (13)	0.28747 (10)	0.0357 (3)
O4	0.75183 (14)	0.47603 (13)	0.46864 (10)	0.0295 (3)
H4	0.658 (3)	0.402 (2)	0.4509 (17)	0.044*
O5	1.23563 (17)	0.97506 (14)	0.69889 (11)	0.0479 (4)
O6	1.41605 (14)	1.03213 (13)	0.61107 (11)	0.0335 (3)
H6	1.473 (3)	1.117 (2)	0.6791 (19)	0.050*
C1	1.15857 (19)	0.65177 (17)	0.30595 (13)	0.0226 (3)
C2	1.01588 (19)	0.54260 (17)	0.29865 (13)	0.0241 (4)
H2A	0.9603	0.4520	0.2306	0.031 (5)*
C3	0.95434 (19)	0.56593 (17)	0.39110 (13)	0.0224 (3)
C4	1.03774 (18)	0.69911 (17)	0.49313 (13)	0.0230 (3)
H4A	0.9963	0.7159	0.5555	0.028*
C5	1.18299 (19)	0.80705 (17)	0.50200 (13)	0.0228 (3)
C6	1.24244 (19)	0.78375 (17)	0.40836 (13)	0.0230 (3)
H6A	1.3397	0.8576	0.4144	0.028*
C7	1.22269 (19)	0.62928 (17)	0.20573 (13)	0.0235 (3)
C8	0.79976 (19)	0.44429 (17)	0.37606 (14)	0.0237 (3)
C9	1.2777 (2)	0.94488 (18)	0.61364 (14)	0.0260 (4)
O7	0.23309 (14)	0.11931 (13)	0.42638 (10)	0.0327 (3)
H7	0.230 (2)	0.064 (2)	0.349 (2)	0.049*
O8	0.47138 (14)	0.26410 (13)	0.43007 (10)	0.0369 (3)
O9	0.82100 (16)	0.72343 (14)	0.77430 (11)	0.0405 (3)
H9	0.916 (3)	0.808 (3)	0.814 (2)	0.061*
O10	0.75891 (16)	0.79239 (14)	0.93837 (11)	0.0487 (4)
O11	0.23548 (16)	0.46243 (14)	0.93776 (11)	0.0443 (4)
O12	0.10133 (15)	0.22723 (13)	0.79990 (11)	0.0360 (3)
H12	0.029 (3)	0.214 (2)	0.8372 (19)	0.054*
C11	0.40237 (18)	0.33372 (17)	0.60392 (13)	0.0226 (3)
C12	0.54215 (19)	0.46733 (17)	0.66014 (14)	0.0248 (4)
H12A	0.6137	0.4932	0.6193	0.030*
C13	0.57695 (19)	0.56305 (17)	0.77641 (14)	0.0252 (4)
C14	0.47026 (19)	0.52582 (17)	0.83609 (14)	0.0259 (4)
H14A	0.4929	0.5908	0.9144	0.031*
C15	0.33011 (19)	0.39277 (17)	0.78027 (14)	0.0242 (4)
C16	0.29563 (19)	0.29562 (17)	0.66414 (13)	0.0226 (3)
H16A	0.2012	0.2052	0.6267	0.027*
C17	0.37241 (19)	0.23634 (17)	0.47946 (14)	0.0255 (4)
C18	0.7287 (2)	0.70561 (18)	0.83851 (15)	0.0295 (4)
C19	0.2168 (2)	0.36255 (19)	0.84716 (14)	0.0276 (4)
O13	1.09496 (16)	0.94370 (15)	0.86765 (12)	0.0442 (4)
H13A	1.134 (3)	1.031 (3)	0.932 (2)	0.066*
H13B	1.129 (3)	0.959 (3)	0.813 (2)	0.066*
C21	0.2033 (2)	−0.17823 (19)	0.03864 (14)	0.0307 (4)
H21A	0.1519	−0.2613	−0.0349	0.037*
C22	0.3793 (2)	0.02501 (18)	0.18472 (14)	0.0277 (4)
H22A	0.4747	0.1115	0.2332	0.033*
C23	0.4714 (2)	−0.0680 (2)	0.01332 (16)	0.0338 (4)
H23A	0.4241	−0.1585	−0.0605	0.041*
H23B	0.5608	−0.0657	0.0623	0.041*
N1	0.25099 (16)	−0.01876 (15)	0.21283 (12)	0.0281 (3)
N2	0.13810 (16)	−0.14927 (15)	0.11899 (12)	0.0293 (3)
N3	0.35506 (16)	−0.07258 (15)	0.07521 (11)	0.0272 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0239 (6)	0.0268 (6)	0.0238 (6)	0.0049 (5)	0.0126 (5)	0.0063 (5)
O2	0.0292 (7)	0.0311 (7)	0.0215 (6)	0.0013 (6)	0.0140 (5)	0.0010 (5)
O3	0.0264 (7)	0.0300 (7)	0.0276 (7)	−0.0011 (6)	0.0100 (5)	0.0032 (6)
O4	0.0195 (6)	0.0265 (6)	0.0300 (6)	0.0014 (5)	0.0130 (5)	0.0073 (5)
O5	0.0467 (9)	0.0343 (7)	0.0338 (7)	0.0005 (6)	0.0268 (7)	−0.0017 (6)
O6	0.0236 (7)	0.0270 (6)	0.0248 (6)	−0.0018 (5)	0.0099 (5)	−0.0015 (5)
C1	0.0207 (8)	0.0239 (8)	0.0197 (8)	0.0080 (7)	0.0084 (7)	0.0075 (7)
C2	0.0208 (9)	0.0237 (8)	0.0187 (8)	0.0054 (7)	0.0065 (7)	0.0049 (7)
C3	0.0187 (8)	0.0223 (8)	0.0225 (8)	0.0070 (7)	0.0074 (7)	0.0081 (7)
C4	0.0209 (8)	0.0235 (8)	0.0221 (8)	0.0079 (7)	0.0111 (7)	0.0082 (7)
C5	0.0207 (9)	0.0219 (8)	0.0228 (8)	0.0079 (7)	0.0091 (7)	0.0078 (7)
C6	0.0178 (8)	0.0226 (8)	0.0229 (8)	0.0050 (7)	0.0093 (7)	0.0076 (7)
C7	0.0211 (9)	0.0219 (8)	0.0209 (8)	0.0058 (7)	0.0084 (7)	0.0065 (7)
C8	0.0191 (8)	0.0245 (8)	0.0240 (8)	0.0069 (7)	0.0083 (7)	0.0100 (7)
C9	0.0248 (9)	0.0218 (8)	0.0250 (8)	0.0062 (7)	0.0131 (7)	0.0065 (7)
O7	0.0237 (7)	0.0300 (6)	0.0214 (6)	−0.0013 (5)	0.0110 (5)	0.0004 (5)
O8	0.0273 (7)	0.0332 (7)	0.0261 (6)	−0.0017 (6)	0.0167 (6)	0.0013 (5)
O9	0.0282 (7)	0.0291 (7)	0.0359 (7)	−0.0047 (6)	0.0161 (6)	0.0014 (6)
O10	0.0416 (8)	0.0347 (7)	0.0305 (7)	−0.0044 (6)	0.0152 (6)	−0.0049 (6)
O11	0.0399 (8)	0.0402 (8)	0.0307 (7)	0.0046 (6)	0.0237 (6)	0.0018 (6)
O12	0.0269 (7)	0.0324 (7)	0.0349 (7)	0.0026 (6)	0.0202 (6)	0.0079 (6)
C11	0.0199 (9)	0.0220 (8)	0.0225 (8)	0.0073 (7)	0.0090 (7)	0.0081 (7)
C12	0.0223 (9)	0.0240 (8)	0.0255 (8)	0.0077 (7)	0.0123 (7)	0.0095 (7)
C13	0.0234 (9)	0.0218 (8)	0.0242 (8)	0.0072 (7)	0.0094 (7)	0.0063 (7)
C14	0.0243 (9)	0.0239 (8)	0.0220 (8)	0.0075 (7)	0.0101 (7)	0.0051 (7)
C15	0.0223 (9)	0.0251 (8)	0.0245 (8)	0.0096 (7)	0.0109 (7)	0.0101 (7)
C16	0.0197 (8)	0.0208 (8)	0.0223 (8)	0.0060 (7)	0.0083 (7)	0.0072 (7)
C17	0.0219 (9)	0.0237 (8)	0.0240 (8)	0.0051 (7)	0.0104 (7)	0.0082 (7)
C18	0.0273 (10)	0.0236 (9)	0.0274 (9)	0.0054 (8)	0.0115 (8)	0.0060 (7)
C19	0.0242 (9)	0.0311 (9)	0.0227 (8)	0.0092 (8)	0.0109 (7)	0.0094 (7)
O13	0.0374 (8)	0.0341 (7)	0.0289 (7)	−0.0054 (6)	0.0157 (6)	0.0019 (6)
C21	0.0262 (9)	0.0272 (9)	0.0209 (8)	0.0011 (7)	0.0097 (7)	0.0032 (7)
C22	0.0236 (9)	0.0258 (8)	0.0229 (8)	0.0040 (7)	0.0103 (7)	0.0062 (7)
C23	0.0336 (10)	0.0365 (10)	0.0329 (9)	0.0138 (8)	0.0233 (8)	0.0144 (8)
N1	0.0233 (8)	0.0249 (7)	0.0228 (7)	0.0023 (6)	0.0103 (6)	0.0049 (6)
N2	0.0223 (8)	0.0280 (7)	0.0234 (7)	0.0022 (6)	0.0105 (6)	0.0053 (6)
N3	0.0239 (8)	0.0268 (7)	0.0235 (7)	0.0055 (6)	0.0132 (6)	0.0079 (6)

Geometric parameters (Å, º) top

O1—C7	1.2182 (19)	O12—C19	1.298 (2)
O2—C7	1.3221 (19)	O12—H12	0.90 (2)
O2—H2	0.92 (2)	C11—C12	1.390 (2)
O3—C8	1.2147 (19)	C11—C16	1.395 (2)
O4—C8	1.3217 (19)	C11—C17	1.489 (2)
O4—H4	0.88 (2)	C12—C13	1.391 (2)
O5—C9	1.2065 (19)	C12—H12A	0.9400
O6—C9	1.3204 (19)	C13—C14	1.388 (2)
O6—H6	0.91 (2)	C13—C18	1.497 (2)
C1—C2	1.390 (2)	C14—C15	1.389 (2)
C1—C6	1.391 (2)	C14—H14A	0.9400
C1—C7	1.492 (2)	C15—C16	1.395 (2)
C2—C3	1.393 (2)	C15—C19	1.494 (2)
C2—H2A	0.9400	C16—H16A	0.9400
C3—C4	1.395 (2)	O13—H13A	0.91 (2)
C3—C8	1.491 (2)	O13—H13B	0.85 (3)
C4—C5	1.394 (2)	C21—N2	1.300 (2)
C4—H4A	0.9400	C21—N3	1.353 (2)
C5—C6	1.393 (2)	C21—H21A	0.9400
C5—C9	1.489 (2)	C22—N1	1.306 (2)
C6—H6A	0.9400	C22—N3	1.358 (2)
O7—C17	1.3090 (19)	C22—H22A	0.9400
O7—H7	0.96 (2)	C23—N3	1.472 (2)
O8—C17	1.2230 (18)	C23—C23ⁱ	1.513 (3)
O9—C18	1.304 (2)	C23—H23A	0.9800
O9—H9	0.91 (3)	C23—H23B	0.9800
O10—C18	1.210 (2)	N1—N2	1.3784 (18)
O11—C19	1.2201 (19)

C7—O2—H2	110.6 (13)	C14—C13—C12	119.73 (15)
C8—O4—H4	107.2 (13)	C14—C13—C18	119.44 (14)
C9—O6—H6	112.6 (13)	C12—C13—C18	120.83 (14)
C2—C1—C6	119.32 (14)	C13—C14—C15	120.10 (15)
C2—C1—C7	120.95 (14)	C13—C14—H14A	120.0
C6—C1—C7	119.73 (14)	C15—C14—H14A	120.0
C1—C2—C3	120.72 (14)	C14—C15—C16	120.34 (14)
C1—C2—H2A	119.6	C14—C15—C19	117.53 (14)
C3—C2—H2A	119.6	C16—C15—C19	122.06 (15)
C2—C3—C4	119.85 (14)	C15—C16—C11	119.51 (15)
C2—C3—C8	117.56 (14)	C15—C16—H16A	120.2
C4—C3—C8	122.59 (14)	C11—C16—H16A	120.2
C5—C4—C3	119.53 (14)	O8—C17—O7	122.24 (14)
C5—C4—H4A	120.2	O8—C17—C11	122.17 (15)
C3—C4—H4A	120.2	O7—C17—C11	115.59 (13)
C6—C5—C4	120.21 (14)	O10—C18—O9	125.16 (16)
C6—C5—C9	119.87 (14)	O10—C18—C13	121.74 (15)
C4—C5—C9	119.88 (13)	O9—C18—C13	113.10 (14)
C1—C6—C5	120.34 (14)	O11—C19—O12	125.08 (15)
C1—C6—H6A	119.8	O11—C19—C15	120.02 (15)
C5—C6—H6A	119.8	O12—C19—C15	114.90 (14)
O1—C7—O2	123.19 (14)	H13A—O13—H13B	110 (2)
O1—C7—C1	124.36 (15)	N2—C21—N3	110.82 (14)
O2—C7—C1	112.45 (13)	N2—C21—H21A	124.6
O3—C8—O4	123.84 (15)	N3—C21—H21A	124.6
O3—C8—C3	123.02 (14)	N1—C22—N3	110.10 (15)
O4—C8—C3	113.14 (14)	N1—C22—H22A	124.9
O5—C9—O6	122.58 (16)	N3—C22—H22A	124.9
O5—C9—C5	124.55 (15)	N3—C23—C23ⁱ	111.15 (18)
O6—C9—C5	112.86 (13)	N3—C23—H23A	109.4
C17—O7—H7	107.8 (13)	C23ⁱ—C23—H23A	109.4
C18—O9—H9	112.4 (14)	N3—C23—H23B	109.4
C19—O12—H12	113.6 (14)	C23ⁱ—C23—H23B	109.4
C12—C11—C16	119.86 (14)	H23A—C23—H23B	108.0
C12—C11—C17	117.73 (14)	C22—N1—N2	107.37 (13)
C16—C11—C17	122.41 (14)	C21—N2—N1	106.94 (13)
C11—C12—C13	120.45 (14)	C21—N3—C22	104.77 (13)
C11—C12—H12A	119.8	C21—N3—C23	127.89 (14)
C13—C12—H12A	119.8	C22—N3—C23	127.25 (14)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O11ⁱⁱ	0.92 (2)	1.67 (2)	2.594 (2)	175 (2)
O4—H4···O8	0.88 (2)	1.75 (2)	2.626 (2)	174 (2)
O6—H6···O1ⁱⁱⁱ	0.91 (2)	1.84 (2)	2.699 (2)	157 (2)
O7—H7···N1	0.96 (2)	1.75 (2)	2.703 (2)	172 (2)
O9—H9···O13	0.91 (3)	1.63 (3)	2.531 (2)	170 (2)
O12—H12···N2^iv	0.90 (2)	1.76 (2)	2.644 (2)	167 (2)
O13—H13A···O10^v	0.91 (2)	1.81 (3)	2.711 (2)	171 (2)
O13—H13B···O5	0.85 (3)	1.92 (3)	2.751 (2)	167 (2)

Symmetry codes: (ii) x+1, y, z−1; (iii) −x+3, −y+2, −z+1; (iv) −x, −y, −z+1; (v) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	4C₉H₆O₆·C₆H₈N₆·2H₂O
M_r	1040.76
Crystal system, space group	Triclinic, P1
Temperature (K)	203
a, b, c (Å)	9.7989 (1), 10.7511 (2), 12.6578 (2)
α, β, γ (°)	108.801 (1), 98.737 (1), 113.340 (1)
V (Å³)	1097.44 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.37 × 0.05 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.952, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	20984, 4824, 3452
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.105, 1.02
No. of reflections	4824
No. of parameters	359
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2006), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O11ⁱ	0.92 (2)	1.67 (2)	2.594 (2)	175 (2)
O4—H4···O8	0.88 (2)	1.75 (2)	2.626 (2)	174 (2)
O6—H6···O1ⁱⁱ	0.91 (2)	1.84 (2)	2.699 (2)	157 (2)
O7—H7···N1	0.96 (2)	1.75 (2)	2.703 (2)	172 (2)
O9—H9···O13	0.91 (3)	1.63 (3)	2.531 (2)	170 (2)
O12—H12···N2ⁱⁱⁱ	0.90 (2)	1.76 (2)	2.644 (2)	167 (2)
O13—H13A···O10^iv	0.91 (2)	1.81 (3)	2.711 (2)	171 (2)
O13—H13B···O5	0.85 (3)	1.92 (3)	2.751 (2)	167 (2)

Symmetry codes: (i) x+1, y, z−1; (ii) −x+3, −y+2, −z+1; (iii) −x, −y, −z+1; (iv) −x+2, −y+2, −z+2.

Acknowledgements

Support through DFG grant No. Ja466/14-1 is acknowledged.

References

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Volume 64| Part 7| July 2008| Page o1199

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Benzene-1,3,5-tri­carboxylic acid–1,2-bis­­(1,2,4-triazol-4-yl)ethane–water (4/1/2)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Benzene-1,3,5-tricarboxylic acid–1,2-bis(1,2,4-triazol-4-yl)ethane–water (4/1/2)