Trimesic acid bis(N,N-di­methyl­form­amide) solvate at 150 K

The crystal structure of the title compound, C₁₅H₂₀N₂O₈, has been redetermined using low-temperature single-crystal X-ray diffraction.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.134
• Data-to-parameter ratio = 12.8

checkCIF results

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 Alert Level B:



PLAT_031  Alert B Refined Extinction Parameter within Range ....       1.25 Sigma


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

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S1. Comment

The title compound was originally synthesized by Chatterjee et al. (2000) by the crystallization of trimesic acid (TMA) from N,N-dimethylformamide (DMF) in the presence of benzene, and characterized using single-crystal X-ray diffraction at room temperature.

We have now synthesized the same 1:2 T MA:DMF adduct, (I), in the absence of benzene, characterizing the compound using low-temperature single-crystal X-ray diffraction. The same structure is found in both cases, ruling out the benzene co-solvent as an essential templating agent in the previous synthesis (Chatterjee et al., 2000). Carboxylic acid–DMF R²₂(7) ring motifs (Etter, 1990; Etter & MacDonald, 1990; Bernstein et al., 1995), utilizing strong O—H···O and weaker C—H···O hydrogen bonding (Desiraju & Steiner, 1999), exist at two of the three carboxylic acid groups, preventing the formation of the carboxylic acid head-to-tail R²₂(8) dimer motif.

The determination at low-temperature (150 K) gives a slight improvement in the final R value (5.14% compared to 5.87%), with reductions of 1.5, 0.4 and 2.2% in the a, b and c unit-cell dimensions, resulting in an overall 4.1% contraction in the unit-cell volume compared to that determined at room temperature.

S2. Experimental

The title compound was prepared as X-ray quality colourless crystals by the slow evaporation of an N,N-dimethylformamide solution of trimesic acid at room temperature.

S3. Refinement

H atoms were positioned geometrically. The coordinates of those attached to oxygen were refined freely; allother H atoms were refined using a riding model. U_iso values were set to be 1.2 times U_eq for aryl and aldehyde H, and 1.5 times U_eq for methyl and hydroxy H atoms.

Computing details

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures

Fig. 1. View of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size. Hydrogen bonding between TMA and DMF molecules is indicated by dashed lines.

Trimesic acid bis(N,N-dimethylformamide) solvate

Crystal data

C15H20N2O8	F(000) = 752
Mr = 356.33	Dx = 1.364 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.6529 (18) Å	Cell parameters from 1416 reflections
b = 14.4143 (16) Å	θ = 2.5–26.4°
c = 7.2310 (8) Å	µ = 0.11 mm^−1
β = 90.719 (2)°	T = 150 K
V = 1735.6 (3) Å^3	Block, colourless
Z = 4	0.27 × 0.16 × 0.02 mm

Data collection

Bruker SMART 1000 CCD diffractometer	3064 independent reflections
Radiation source: sealed tube	1664 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ω rotation with narrow frames scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −19→19
Tmin = 0.971, Tmax = 0.998	k = −9→17
8644 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: All non-H atoms found by direct methods
Least-squares matrix: full	Hydrogen site location: Geom except OH coords freely refined
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0475P)^2 + 0.6362P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3064 reflections	Δρmax = 0.23 e Å^−3
240 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0005 (4)

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	0.33564 (17)	0.6428 (2)	−0.0696 (4)	0.0220 (7)
C2	0.27185 (17)	0.6966 (2)	−0.0084 (4)	0.0208 (7)
H2	0.2242	0.6673	0.0326	0.025*
C3	0.27729 (17)	0.7922 (2)	−0.0067 (4)	0.0206 (7)
C4	0.34667 (17)	0.8353 (2)	−0.0695 (4)	0.0234 (7)
H4	0.3502	0.9010	−0.0704	0.028*
C5	0.41113 (18)	0.7819 (2)	−0.1313 (4)	0.0223 (7)
C6	0.40506 (17)	0.6859 (2)	−0.1303 (4)	0.0220 (7)
H6	0.4488	0.6493	−0.1715	0.026*
C7	0.33008 (18)	0.5389 (2)	−0.0747 (4)	0.0251 (8)
O1	0.38163 (13)	0.48977 (15)	−0.1405 (3)	0.0345 (6)
O2	0.26379 (13)	0.50821 (15)	−0.0014 (3)	0.0316 (6)
H2A	0.260 (2)	0.455 (3)	−0.019 (5)	0.047*
C8	0.21036 (18)	0.8513 (2)	0.0593 (4)	0.0238 (8)
O3	0.14420 (13)	0.80494 (16)	0.0989 (3)	0.0328 (6)
H3	0.105 (2)	0.839 (3)	0.135 (5)	0.049*
O4	0.21653 (13)	0.93499 (15)	0.0756 (3)	0.0319 (6)
C9	0.48552 (19)	0.8249 (2)	−0.2024 (4)	0.0270 (8)
O5	0.48175 (14)	0.91764 (16)	−0.2115 (3)	0.0375 (6)
H5	0.527 (2)	0.936 (3)	−0.252 (5)	0.056*
O6	0.54328 (13)	0.78065 (16)	−0.2484 (3)	0.0418 (7)
O7	0.23200 (13)	0.33931 (16)	−0.0409 (3)	0.0399 (7)
C10	0.2856 (2)	0.2795 (2)	−0.0544 (5)	0.0332 (9)
H10	0.3399	0.2995	−0.0583	0.040*
N1	0.27062 (16)	0.18998 (18)	−0.0638 (4)	0.0321 (7)
C11	0.3350 (2)	0.1219 (2)	−0.0824 (5)	0.0428 (10)
H11A	0.3861	0.1542	−0.0996	0.064*
H11B	0.3238	0.0822	−0.1897	0.064*
H11C	0.3382	0.0837	0.0295	0.064*
C12	0.1889 (2)	0.1561 (3)	−0.0598 (6)	0.0538 (11)
H12A	0.1556	0.1995	0.0100	0.081*
H12B	0.1878	0.0951	−0.0002	0.081*
H12C	0.1678	0.1508	−0.1866	0.081*
O8	0.02931 (13)	0.91508 (17)	0.2006 (3)	0.0419 (7)
C13	0.0486 (2)	0.9956 (3)	0.2403 (5)	0.0366 (9)
H13	0.1039	1.0114	0.2333	0.044*
N2	−0.00169 (16)	1.0615 (2)	0.2917 (4)	0.0336 (7)
C14	−0.0872 (2)	1.0426 (3)	0.3040 (6)	0.0569 (12)
H14A	−0.1149	1.0677	0.1947	0.085*
H14B	−0.1084	1.0718	0.4156	0.085*
H14C	−0.0958	0.9754	0.3100	0.085*
C15	0.0248 (3)	1.1553 (3)	0.3322 (6)	0.0626 (13)
H15A	0.0836	1.1580	0.3287	0.094*
H15B	0.0066	1.1732	0.4555	0.094*
H15C	0.0021	1.1979	0.2398	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0220 (17)	0.0214 (18)	0.0225 (18)	0.0018 (14)	0.0016 (14)	0.0002 (15)
C2	0.0224 (17)	0.0224 (18)	0.0177 (17)	−0.0023 (14)	0.0015 (14)	−0.0012 (14)
C3	0.0232 (17)	0.0190 (18)	0.0197 (17)	−0.0005 (14)	0.0051 (14)	0.0010 (14)
C4	0.0296 (18)	0.0192 (18)	0.0212 (17)	−0.0024 (15)	−0.0016 (14)	−0.0006 (15)
C5	0.0221 (17)	0.0243 (19)	0.0203 (17)	−0.0015 (14)	−0.0007 (14)	0.0001 (15)
C6	0.0222 (17)	0.0249 (19)	0.0191 (18)	0.0036 (15)	0.0029 (14)	−0.0041 (15)
C7	0.0229 (18)	0.0251 (19)	0.0274 (19)	−0.0006 (15)	0.0045 (15)	−0.0029 (16)
O1	0.0295 (12)	0.0233 (13)	0.0510 (15)	0.0017 (11)	0.0133 (11)	−0.0098 (12)
O2	0.0335 (13)	0.0161 (12)	0.0455 (15)	0.0001 (11)	0.0133 (11)	−0.0016 (12)
C8	0.0249 (18)	0.023 (2)	0.0235 (19)	−0.0002 (16)	−0.0004 (14)	0.0003 (16)
O3	0.0258 (13)	0.0240 (13)	0.0490 (16)	0.0010 (11)	0.0150 (12)	−0.0027 (12)
O4	0.0333 (13)	0.0178 (14)	0.0448 (15)	0.0011 (11)	0.0041 (11)	0.0000 (11)
C9	0.0252 (18)	0.027 (2)	0.029 (2)	−0.0030 (16)	0.0042 (15)	−0.0014 (17)
O5	0.0307 (14)	0.0258 (14)	0.0562 (17)	−0.0071 (12)	0.0125 (12)	0.0020 (13)
O6	0.0300 (14)	0.0351 (15)	0.0608 (17)	−0.0037 (12)	0.0180 (13)	−0.0018 (13)
O7	0.0386 (14)	0.0196 (13)	0.0619 (18)	−0.0030 (12)	0.0142 (12)	−0.0018 (13)
C10	0.032 (2)	0.026 (2)	0.041 (2)	−0.0041 (18)	0.0091 (17)	−0.0013 (18)
N1	0.0368 (17)	0.0194 (16)	0.0403 (18)	−0.0025 (13)	0.0030 (14)	0.0032 (14)
C11	0.054 (3)	0.024 (2)	0.050 (2)	0.0022 (18)	0.003 (2)	0.0005 (19)
C12	0.045 (2)	0.029 (2)	0.087 (3)	−0.0134 (19)	0.004 (2)	0.002 (2)
O8	0.0334 (14)	0.0361 (16)	0.0565 (17)	0.0044 (12)	0.0088 (12)	−0.0096 (14)
C13	0.034 (2)	0.035 (2)	0.040 (2)	0.0037 (19)	0.0128 (17)	0.0026 (19)
N2	0.0332 (16)	0.0341 (18)	0.0336 (17)	0.0077 (14)	0.0074 (13)	−0.0021 (15)
C14	0.033 (2)	0.065 (3)	0.072 (3)	0.018 (2)	−0.011 (2)	−0.030 (2)
C15	0.069 (3)	0.030 (2)	0.090 (3)	0.002 (2)	0.037 (3)	−0.005 (2)

Geometric parameters (Å, º)

C1—C6	1.388 (4)	C10—N1	1.316 (4)
C1—C2	1.392 (4)	C10—H10	0.9500
C1—C7	1.500 (4)	N1—C12	1.447 (4)
C2—C3	1.382 (4)	N1—C11	1.460 (4)
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.393 (4)	C11—H11B	0.9800
C3—C8	1.486 (4)	C11—H11C	0.9800
C4—C5	1.398 (4)	C12—H12A	0.9800
C4—H4	0.9500	C12—H12B	0.9800
C5—C6	1.388 (4)	C12—H12C	0.9800
C5—C9	1.483 (4)	O8—C13	1.238 (4)
C6—H6	0.9500	C13—N2	1.323 (4)
C7—O1	1.215 (4)	C13—H13	0.9500
C7—O2	1.308 (4)	N2—C15	1.451 (5)
O2—H2A	0.79 (4)	N2—C14	1.453 (4)
C8—O4	1.217 (4)	C14—H14A	0.9800
C8—O3	1.323 (4)	C14—H14B	0.9800
O3—H3	0.85 (4)	C14—H14C	0.9800
C9—O6	1.204 (4)	C15—H15A	0.9800
C9—O5	1.340 (4)	C15—H15B	0.9800
O5—H5	0.86 (4)	C15—H15C	0.9800
O7—C10	1.245 (4)
C6—C1—C2	119.5 (3)	C10—N1—C12	120.5 (3)
C6—C1—C7	119.3 (3)	C10—N1—C11	121.7 (3)
C2—C1—C7	121.1 (3)	C12—N1—C11	117.9 (3)
C3—C2—C1	120.6 (3)	N1—C11—H11A	109.5
C3—C2—H2	119.7	N1—C11—H11B	109.5
C1—C2—H2	119.7	H11A—C11—H11B	109.5
C2—C3—C4	119.8 (3)	N1—C11—H11C	109.5
C2—C3—C8	121.7 (3)	H11A—C11—H11C	109.5
C4—C3—C8	118.6 (3)	H11B—C11—H11C	109.5
C3—C4—C5	120.2 (3)	N1—C12—H12A	109.5
C3—C4—H4	119.9	N1—C12—H12B	109.5
C5—C4—H4	119.9	H12A—C12—H12B	109.5
C6—C5—C4	119.4 (3)	N1—C12—H12C	109.5
C6—C5—C9	118.6 (3)	H12A—C12—H12C	109.5
C4—C5—C9	122.0 (3)	H12B—C12—H12C	109.5
C1—C6—C5	120.6 (3)	O8—C13—N2	125.1 (3)
C1—C6—H6	119.7	O8—C13—H13	117.5
C5—C6—H6	119.7	N2—C13—H13	117.5
O1—C7—O2	124.4 (3)	C13—N2—C15	122.2 (3)
O1—C7—C1	123.2 (3)	C13—N2—C14	120.5 (3)
O2—C7—C1	112.3 (3)	C15—N2—C14	117.3 (3)
C7—O2—H2A	109 (3)	N2—C14—H14A	109.5
O4—C8—O3	123.3 (3)	N2—C14—H14B	109.5
O4—C8—C3	122.4 (3)	H14A—C14—H14B	109.5
O3—C8—C3	114.3 (3)	N2—C14—H14C	109.5
C8—O3—H3	115 (2)	H14A—C14—H14C	109.5
O6—C9—O5	123.5 (3)	H14B—C14—H14C	109.5
O6—C9—C5	123.3 (3)	N2—C15—H15A	109.5
O5—C9—C5	113.2 (3)	N2—C15—H15B	109.5
C9—O5—H5	106 (3)	H15A—C15—H15B	109.5
O7—C10—N1	123.2 (3)	N2—C15—H15C	109.5
O7—C10—H10	118.4	H15A—C15—H15C	109.5
N1—C10—H10	118.4	H15B—C15—H15C	109.5
C6—C1—C2—C3	−0.4 (5)	C6—C1—C7—O2	175.5 (3)
C7—C1—C2—C3	−179.1 (3)	C2—C1—C7—O2	−5.8 (4)
C1—C2—C3—C4	1.0 (5)	C2—C3—C8—O4	174.0 (3)
C1—C2—C3—C8	−179.5 (3)	C4—C3—C8—O4	−6.5 (5)
C2—C3—C4—C5	−1.0 (5)	C2—C3—C8—O3	−5.8 (4)
C8—C3—C4—C5	179.5 (3)	C4—C3—C8—O3	173.6 (3)
C3—C4—C5—C6	0.4 (4)	C6—C5—C9—O6	−5.0 (5)
C3—C4—C5—C9	178.9 (3)	C4—C5—C9—O6	176.5 (3)
C2—C1—C6—C5	−0.3 (5)	C6—C5—C9—O5	174.6 (3)
C7—C1—C6—C5	178.4 (3)	C4—C5—C9—O5	−4.0 (4)
C4—C5—C6—C1	0.3 (5)	O7—C10—N1—C12	0.5 (5)
C9—C5—C6—C1	−178.3 (3)	O7—C10—N1—C11	179.1 (3)
C6—C1—C7—O1	−4.7 (5)	O8—C13—N2—C15	−178.5 (4)
C2—C1—C7—O1	174.0 (3)	O8—C13—N2—C14	−0.5 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O7	0.79 (4)	1.73 (4)	2.507 (3)	168 (4)
O3—H3···O8	0.85 (4)	1.75 (4)	2.599 (3)	176 (4)
O5—H5···O1^i	0.86 (4)	1.88 (4)	2.732 (3)	171 (4)

Symmetry code: (i) −x+1, y+1/2, −z−1/2.