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

The title compound, 4C(9)H(6)O(6)·C(6)H(8)N(6)·2H(2)O, crystallizes in a layer structure where each sheet is composed of anellated hydrogen-bonded rings of six distinct sizes: R(2) (2)(16), R(3) (3)(18), R(4) (4)(12), R(4) (4)(18), R(4) (4)(22) and R(4) (4)(25). The two largest rings, viz. R(4) (4)(22) and R(4) (4)(25), are associated with O-H⋯N bonds from the carboxyl groups to the triazole rings. The typical head-to-tail carbox-yl-carboxyl R(2) (2)(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 = 1040.76

Triclinic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.105

S = 1.02

4824 reflections

359 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.24 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

4C9H6O6·C6H8N6·2H2O	Z = 1
Mr = 1040.76	F000 = 538
Triclinic, P1	Dx = 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 = 2.2–31.5º
c = 12.6578 (2) Å	µ = 0.13 mm−1
α = 108.801 (1)º	T = 203 (2) K
β = 98.737 (1)º	Needle, colourless
γ = 113.340 (1)º	0.37 × 0.05 × 0.02 mm
V = 1097.44 (3) Å3

Bruker APEXII CCD area-detector diffractometer	4824 independent reflections
Radiation source: fine-focus sealed tube	3452 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.036
T = 203(2) K	θmax = 27.1º
ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.952, Tmax = 0.997	k = −13→13
20984 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0562P)2 + 0.0985P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
4824 reflections	Δρmax = 0.25 e Å−3
359 parameters	Δρmin = −0.24 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. IR (KBr) 3512m (νCOO-H), 3427m (νCOO-H), 3122m, 1886m, 1704 s, (νasymCO2), 1539m (νasymCO2),1452 s (νsymCO2), 1356w (νsymCO2), 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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···N2iv	0.90 (2)	1.76 (2)	2.644 (2)	167 (2)
O13—H13A···O10v	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)

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⋯O10iv	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) ; (ii) ; (iii) ; (iv) .