4,4′-(1,2-Di­aza­niumyl­ethane-1,2-di­yl)dibenzoate trihydrate

Numata, T.; Ikenomoto, S.; Akitsu, T.

doi:10.1107/S2414314616002522

4,4′-(1,2-Diazaniumylethane-1,2-diyl)dibenzoate trihydrate

The title compound, C₁₆H₁₆N₂O₄·3H₂O, was synthesized from (1R,2R)-1,2-bis(2-hydroxyphenyl)ethylenediamine and terephthalaldehydic acid. The compound crystallizes from water as a double zwitterion with protonated amine groups and deprotonated carboxylate groups. The dihedral angle formed by the aromatic rings is 3.86 (11)°. In the crystal, N—H

O and O—H

O hydrogen bonds link molecules into a three-dimensional network.

Keywords: crystal structure; double zwitterion; hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2414314616002522/rz4001sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2414314616002522/rz4001Isup2.hkl Contains datablock I

CCDC reference: 1452936

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.004 Å
R factor = 0.038
wR factor = 0.103
Data-to-parameter ratio = 8.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......      0.948 Note
PLAT915_ALERT_3_B Low Friedel Pair Coverage ....(No Flack x Check)         12 %

Alert level C
STRVA01_ALERT_4_C           Flack test results are meaningless.
           From the CIF: _refine_ls_abs_structure_Flack   -0.200
           From the CIF: _refine_ls_abs_structure_Flack_su    1.000
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       7.15 Note
PLAT213_ALERT_2_C Atom O4              has ADP max/min Ratio .....        3.2 oblate
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.8 Note
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2C    ..  H21     ..       2.12 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         37 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          6 Report
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High .      1.000 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.006 Degree
PLAT791_ALERT_4_G The Model has Chirality at C8      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C9      (Chiral SPGR)          S Verify
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         63 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density          10 Note

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4,4'-(1,2-Diazaniumylethane-1,2-diyl)dibenzoate trihydrate top

Crystal data top

C₁₆H₁₆N₂O₄·3H₂O	Z = 1
M_r = 354.35	F(000) = 188
Triclinic, P1	D_x = 1.422 Mg m⁻³
a = 6.778 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.953 (3) Å	Cell parameters from 2325 reflections
c = 9.458 (4) Å	θ = 2.3–27.5°
α = 109.182 (6)°	µ = 0.11 mm⁻¹
β = 93.369 (6)°	T = 173 K
γ = 98.437 (6)°	Prism, colourless
V = 413.7 (3) Å³	0.49 × 0.34 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2030 independent reflections
Radiation source: fine-forcus sealed tube	1969 reflections with I > 2σ(I)
Detector resolution: 8.333 pixels mm^-1	R_int = 0.019
φ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −8→8
T_min = 0.946, T_max = 0.990	k = −8→9
2325 measured reflections	l = −12→6

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0632P)² + 0.1469P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.103	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.37 e Å⁻³
2030 reflections	Δρ_min = −0.21 e Å⁻³
253 parameters	Extinction correction: SHELXL2014 (Sheldrick 2015)
3 restraints	Extinction coefficient: 0.061 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 217 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.2 (10)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C2	0.2668 (4)	−0.0431 (4)	0.0660 (3)	0.0148 (5)
C14	0.6379 (4)	0.5409 (4)	1.0399 (3)	0.0186 (6)
H14	0.7642	0.6159	1.0928	0.022*
C10	0.4424 (4)	0.3099 (4)	0.8089 (3)	0.0150 (5)
C13	0.4672 (4)	0.5516 (4)	1.1153 (3)	0.0154 (5)
C4	0.4811 (4)	0.1770 (4)	0.2925 (3)	0.0165 (5)
H4	0.6097	0.2517	0.3405	0.02*
C15	0.6259 (4)	0.4219 (4)	0.8886 (3)	0.0180 (5)
H15	0.7439	0.4169	0.8389	0.022*
C9	0.4215 (4)	0.1817 (4)	0.6422 (3)	0.0155 (5)
H9	0.3206	0.054	0.6262	0.019*
C1	0.2389 (4)	−0.1709 (4)	−0.1001 (3)	0.0177 (5)
C12	0.2827 (4)	0.4406 (4)	1.0366 (3)	0.0166 (5)
H12	0.1651	0.4459	1.0866	0.02*
C8	0.3387 (4)	0.2978 (4)	0.5438 (3)	0.0145 (5)
H8	0.2001	0.3148	0.5703	0.017*
C6	0.1036 (4)	−0.0325 (4)	0.1485 (3)	0.0189 (6)
H6	−0.0263	−0.1009	0.0992	0.023*
C5	0.1280 (4)	0.0772 (4)	0.3027 (3)	0.0188 (6)
H5	0.0154	0.0814	0.3582	0.023*
C3	0.4556 (4)	0.0630 (4)	0.1388 (3)	0.0156 (5)
H3	0.5681	0.0577	0.0831	0.019*
C16	0.4895 (4)	0.6773 (4)	1.2817 (3)	0.0167 (5)
C11	0.2706 (4)	0.3217 (4)	0.8846 (3)	0.0170 (5)
H11	0.1441	0.2476	0.8315	0.02*
C7	0.3178 (4)	0.1811 (4)	0.3758 (3)	0.0151 (5)
O4	0.0625 (3)	−0.2489 (3)	−0.1609 (2)	0.0281 (5)
O1	0.6571 (3)	0.7863 (3)	1.3418 (2)	0.0245 (5)
O3	0.3929 (3)	−0.1941 (3)	−0.1665 (2)	0.0240 (5)
O2	0.3413 (3)	0.6659 (3)	1.3551 (2)	0.0223 (4)
O6	0.7705 (4)	0.9702 (4)	0.8108 (3)	0.0346 (6)
O5	0.8755 (3)	0.4606 (3)	0.5889 (2)	0.0230 (4)
O7	0.9441 (4)	0.5415 (4)	0.3428 (3)	0.0338 (5)
N1	0.4571 (3)	0.5128 (3)	0.5815 (2)	0.0161 (4)
H1A	0.5904	0.5072	0.5822	0.024*
H1B	0.4329	0.5936	0.674	0.024*
H1C	0.4195	0.5676	0.5112	0.024*
N2	0.6159 (3)	0.1137 (3)	0.5979 (2)	0.0162 (4)
H2A	0.7043	0.2233	0.5941	0.024*
H2B	0.5935	0.0126	0.5057	0.024*
H2C	0.6677	0.064	0.6671	0.024*
H19	0.875 (7)	0.639 (7)	0.346 (5)	0.050 (13)*
H18	1.071 (6)	0.586 (5)	0.333 (4)	0.026 (9)*
H20	0.867 (8)	0.900 (8)	0.812 (6)	0.057 (14)*
H17	0.903 (8)	0.478 (8)	0.507 (7)	0.068 (16)*
H21	0.667 (8)	0.937 (8)	0.842 (6)	0.057 (15)*
H16	0.951 (6)	0.543 (7)	0.664 (5)	0.042 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0215 (12)	0.0117 (12)	0.0079 (11)	0.0007 (10)	−0.0062 (9)	0.0012 (9)
C14	0.0207 (13)	0.0203 (13)	0.0111 (12)	−0.0028 (10)	−0.0045 (9)	0.0044 (10)
C10	0.0225 (13)	0.0138 (12)	0.0079 (12)	0.0023 (10)	−0.0030 (9)	0.0036 (9)
C13	0.0209 (13)	0.0143 (12)	0.0112 (12)	0.0017 (10)	−0.0029 (9)	0.0058 (9)
C4	0.0168 (12)	0.0181 (13)	0.0102 (12)	−0.0016 (10)	−0.0060 (9)	0.0025 (9)
C15	0.0186 (13)	0.0217 (12)	0.0121 (12)	0.0000 (10)	−0.0009 (9)	0.0056 (10)
C9	0.0218 (12)	0.0165 (12)	0.0068 (11)	0.0016 (10)	−0.0028 (9)	0.0036 (9)
C1	0.0261 (14)	0.0130 (11)	0.0107 (12)	0.0028 (10)	−0.0067 (10)	0.0014 (9)
C12	0.0191 (13)	0.0184 (12)	0.0118 (12)	0.0012 (10)	−0.0018 (9)	0.0058 (10)
C8	0.0141 (11)	0.0162 (11)	0.0085 (11)	−0.0018 (9)	−0.0051 (8)	0.0012 (9)
C6	0.0157 (12)	0.0208 (13)	0.0146 (13)	−0.0025 (10)	−0.0078 (10)	0.0025 (10)
C5	0.0181 (13)	0.0213 (13)	0.0122 (12)	−0.0016 (10)	−0.0026 (10)	0.0023 (10)
C3	0.0176 (12)	0.0176 (12)	0.0102 (12)	0.0023 (10)	−0.0025 (9)	0.0040 (9)
C16	0.0226 (13)	0.0163 (12)	0.0116 (12)	0.0049 (10)	−0.0041 (9)	0.0056 (9)
C11	0.0189 (12)	0.0173 (12)	0.0119 (12)	−0.0012 (10)	−0.0053 (10)	0.0043 (10)
C7	0.0183 (12)	0.0156 (11)	0.0098 (12)	0.0019 (9)	−0.0049 (9)	0.0039 (9)
O4	0.0273 (10)	0.0318 (11)	0.0135 (10)	0.0040 (8)	−0.0128 (8)	−0.0049 (8)
O1	0.0239 (10)	0.0266 (10)	0.0143 (9)	0.0012 (8)	−0.0055 (7)	−0.0017 (8)
O3	0.0285 (10)	0.0241 (10)	0.0122 (9)	0.0006 (8)	−0.0014 (8)	−0.0010 (7)
O2	0.0245 (10)	0.0304 (10)	0.0128 (9)	0.0078 (8)	0.0013 (7)	0.0072 (7)
O6	0.0288 (12)	0.0487 (15)	0.0387 (13)	0.0121 (11)	0.0036 (10)	0.0291 (11)
O5	0.0235 (10)	0.0246 (10)	0.0129 (9)	−0.0058 (8)	−0.0052 (8)	0.0012 (8)
O7	0.0253 (12)	0.0523 (14)	0.0305 (12)	0.0073 (11)	0.0019 (9)	0.0229 (10)
N1	0.0210 (10)	0.0164 (10)	0.0089 (9)	0.0013 (8)	−0.0033 (8)	0.0034 (7)
N2	0.0227 (10)	0.0157 (9)	0.0086 (9)	0.0036 (8)	−0.0041 (7)	0.0030 (8)

Geometric parameters (Å, º) top

C2—C6	1.387 (4)	C8—C7	1.516 (3)
C2—C3	1.393 (3)	C8—H8	1.0
C2—C1	1.514 (3)	C6—C5	1.393 (4)
C14—C13	1.393 (4)	C6—H6	0.95
C14—C15	1.389 (4)	C5—C7	1.396 (3)
C14—H14	0.95	C5—H5	0.95
C10—C15	1.394 (4)	C3—H3	0.95
C10—C11	1.401 (4)	C16—O1	1.255 (3)
C10—C9	1.521 (3)	C16—O2	1.262 (3)
C13—C12	1.394 (3)	C11—H11	0.95
C13—C16	1.514 (3)	O6—H20	0.88 (6)
C4—C7	1.394 (4)	O6—H21	0.81 (6)
C4—C3	1.395 (3)	O5—H17	0.85 (6)
C4—H4	0.95	O5—H16	0.83 (5)
C15—H15	0.95	O7—H19	0.87 (5)
C9—N2	1.501 (4)	O7—H18	0.89 (4)
C9—C8	1.549 (3)	N1—H1A	0.91
C9—H9	1.0	N1—H1B	0.91
C1—O4	1.256 (3)	N1—H1C	0.91
C1—O3	1.252 (4)	N2—H2A	0.91
C12—C11	1.394 (4)	N2—H2B	0.91
C12—H12	0.95	N2—H2C	0.91
C8—N1	1.507 (3)

C6—C2—C3	119.0 (2)	C9—C8—H8	106.4
C6—C2—C1	120.1 (2)	C2—C6—C5	120.8 (2)
C3—C2—C1	120.9 (2)	C2—C6—H6	119.6
C13—C14—C15	120.9 (2)	C5—C6—H6	119.6
C13—C14—H14	119.5	C6—C5—C7	120.1 (2)
C15—C14—H14	119.5	C6—C5—H5	120.0
C15—C10—C11	118.5 (2)	C7—C5—H5	120.0
C15—C10—C9	122.3 (2)	C2—C3—C4	120.7 (2)
C11—C10—C9	119.1 (2)	C2—C3—H3	119.7
C14—C13—C12	119.0 (2)	C4—C3—H3	119.7
C14—C13—C16	118.8 (2)	O1—C16—O2	122.6 (2)
C12—C13—C16	122.1 (2)	O1—C16—C13	118.3 (2)
C7—C4—C3	120.0 (2)	O2—C16—C13	119.1 (2)
C7—C4—H4	120.0	C12—C11—C10	120.9 (2)
C3—C4—H4	120.0	C12—C11—H11	119.5
C14—C15—C10	120.6 (2)	C10—C11—H11	119.5
C14—C15—H15	119.7	C4—C7—C5	119.4 (2)
C10—C15—H15	119.7	C4—C7—C8	122.0 (2)
N2—C9—C10	110.8 (2)	C5—C7—C8	118.6 (2)
N2—C9—C8	112.81 (19)	H20—O6—H21	118 (5)
C10—C9—C8	111.31 (19)	H17—O5—H16	113 (4)
N2—C9—H9	107.2	H19—O7—H18	109 (4)
C10—C9—H9	107.2	C8—N1—H1A	109.5
C8—C9—H9	107.2	C8—N1—H1B	109.5
O4—C1—O3	124.7 (2)	H1A—N1—H1B	109.5
O4—C1—C2	117.4 (2)	C8—N1—H1C	109.5
O3—C1—C2	117.9 (2)	H1A—N1—H1C	109.5
C11—C12—C13	120.1 (2)	H1B—N1—H1C	109.5
C11—C12—H12	119.9	C9—N2—H2A	109.5
C13—C12—H12	119.9	C9—N2—H2B	109.5
N1—C8—C7	110.9 (2)	H2A—N2—H2B	109.5
N1—C8—C9	111.91 (18)	C9—N2—H2C	109.5
C7—C8—C9	114.34 (19)	H2A—N2—H2C	109.5
N1—C8—H8	106.4	H2B—N2—H2C	109.5
C7—C8—H8	106.4

C15—C14—C13—C12	0.1 (4)	C1—C2—C6—C5	177.3 (2)
C15—C14—C13—C16	177.8 (2)	C2—C6—C5—C7	1.1 (4)
C13—C14—C15—C10	−0.2 (4)	C6—C2—C3—C4	0.5 (4)
C11—C10—C15—C14	0.6 (4)	C1—C2—C3—C4	−178.6 (2)
C9—C10—C15—C14	178.5 (2)	C7—C4—C3—C2	1.7 (4)
C15—C10—C9—N2	26.1 (3)	C14—C13—C16—O1	8.0 (4)
C11—C10—C9—N2	−155.9 (2)	C12—C13—C16—O1	−174.4 (2)
C15—C10—C9—C8	−100.3 (3)	C14—C13—C16—O2	−170.7 (2)
C11—C10—C9—C8	77.7 (3)	C12—C13—C16—O2	7.0 (4)
C6—C2—C1—O4	6.4 (4)	C13—C12—C11—C10	0.6 (4)
C3—C2—C1—O4	−174.5 (2)	C15—C10—C11—C12	−0.8 (4)
C6—C2—C1—O3	−172.6 (3)	C9—C10—C11—C12	−178.8 (2)
C3—C2—C1—O3	6.6 (4)	C3—C4—C7—C5	−2.5 (4)
C14—C13—C12—C11	−0.3 (4)	C3—C4—C7—C8	178.3 (2)
C16—C13—C12—C11	−177.9 (2)	C6—C5—C7—C4	1.2 (4)
N2—C9—C8—N1	−73.5 (2)	C6—C5—C7—C8	−179.6 (2)
C10—C9—C8—N1	51.7 (3)	N1—C8—C7—C4	47.4 (3)
N2—C9—C8—C7	53.6 (3)	C9—C8—C7—C4	−80.3 (3)
C10—C9—C8—C7	178.8 (2)	N1—C8—C7—C5	−131.8 (2)
C3—C2—C6—C5	−1.9 (4)	C9—C8—C7—C5	100.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5	0.91	2.01	2.911 (3)	173
N1—H1B···O3ⁱ	0.91	1.80	2.686 (3)	165
N1—H1C···O2ⁱⁱ	0.91	1.90	2.807 (3)	176
N2—H2A···O5	0.91	1.89	2.798 (3)	177
N2—H2B···O1ⁱⁱⁱ	0.91	1.93	2.787 (3)	156
N2—H2C···O6^iv	0.91	1.83	2.744 (4)	178
O7—H19···O1ⁱⁱ	0.87 (5)	1.92 (5)	2.768 (4)	162 (5)
O7—H18···O2^v	0.89 (4)	1.81 (4)	2.688 (3)	166 (4)
O6—H20···O4^vi	0.87 (6)	1.85 (6)	2.720 (4)	172 (5)
O5—H17···O7	0.85 (7)	1.77 (7)	2.619 (4)	172 (6)
O6—H21···O3ⁱ	0.81 (6)	1.93 (5)	2.696 (3)	157 (5)
O5—H16···O4^vi	0.84 (4)	1.83 (4)	2.654 (2)	166 (4)

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

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4,4′-(1,2-Di­aza­niumyl­ethane-1,2-di­yl)dibenzoate trihydrate

Supporting information

Key indicators

checkCIF/PLATON results

4,4′-(1,2-Diazaniumylethane-1,2-diyl)dibenzoate trihydrate