Optically active derivatives of terephthalic acid: four crystal structures from two powder patterns

A novel important class of nanoporous crystalline solids, metal–organic frameworks (MOFs), composed of organic ligands (linkers) and metal ions, is now considered as a platform for the development of various functional hybrid materials. In order to design new MOF-based asymmetric catalysts, two terephthalic acid derivatives, namely 2-{[1-(1-tert-but­oxy­carbon­yl)-L-prol­yl]amino}­terephthalic acid, C₁₈H₂₂N₂O₇, (1), and 2-(L-prolyl­amino)­terephthalic acid, C₁₃H₁₄N₂O₅, (2), which could find potential applications as chiral linkers for the construction of enanti­oselective MOFs, were synthesized and their powder samples were measured at synchrotron station ID22 (ESRF). Each sample contained two unknown crystalline phases, so four new crystal structures were determined, namely, the 2.24-hydrate of (1), (1a) (space group C222₁), and the 2.08-hydrate of (1), (1b) (P222₁), which are crystallohydrates, and two polymorphs of (2), i.e. (2a) (C222₁) and (2b) (P2₁2₁2₁), and were validated with DFT-d (dispersion-corrected density functional theory) optimizations.

Computing details

For all structures, data collection: local program; cell refinement: MRIA (Zlokazov & Chernyshev, 1992); data reduction: local program; program(s) used to solve structure: MRIA (Zlokazov & Chernyshev, 1992); program(s) used to refine structure: MRIA (Zlokazov & Chernyshev, 1992); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

1-{[1-(1-tert-Butoxycarbonyl)-L-prolyl]amino}terephthalic acid 2.24-hydrate (1a)

Crystal data

C18H22N2O7·2.24H2O	F(000) = 1779
Mr = 418.64	Dx = 1.271 Mg m^−3
Orthorhombic, C2221	Synchrotron radiation, λ = 0.399962(3) Å
Hall symbol: C 2c 2	µ = 0.02 mm^−1
a = 16.3993 (12) Å	T = 295 K
b = 12.5755 (11) Å	Particle morphology: no specific habit
c = 21.2196 (17) Å	colorless
V = 4376.1 (6) Å^3	cylinder, 15 × 1.0 mm
Z = 8	Specimen preparation: Prepared at 295 K and 101 kPa

Data collection

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: ID22 bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θmin = 1.200°, 2θmax = 17.000°, 2θstep = 0.002°
Specimen mounting: Specimen was sealed in a 1.0 mm diameter borosilicate glass capillary

Refinement

Refinement on Inet	334 parameters
Least-squares matrix: full with fixed elements per cycle	210 restraints
Rp = 0.031	86 constraints
Rwp = 0.040	H-atom parameters not refined
Rexp = 0.028	Weighting scheme based on measured s.u.'s
RBragg = 0.100	(Δ/σ)max = 0.004
10534 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986) [Toraya, H. (1986). J. Appl. Cryst. 19, 440–447]	Preferred orientation correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.1288 (7)	0.2342 (8)	0.3907 (5)	0.057 (10)*
H1	1.1313	0.2993	0.3899	0.086*
O2	1.0139 (6)	0.2665 (7)	0.3353 (5)	0.057 (10)*
O3	1.0813 (7)	−0.3145 (8)	0.3746 (5)	0.057 (10)*
O4	0.9631 (7)	−0.2944 (8)	0.3208 (5)	0.057 (10)*
H4	0.9640	−0.3596	0.3217	0.086*
O5	0.8022 (7)	−0.0132 (9)	0.3397 (5)	0.057 (10)*
O6	0.8243 (6)	0.2481 (8)	0.4225 (6)	0.057 (10)*
O7	0.8413 (7)	0.4168 (7)	0.3804 (5)	0.057 (10)*
N1	0.9089 (7)	0.1057 (9)	0.3242 (6)	0.057 (10)*
H1A	0.9193	0.1704	0.3137	0.068*
N2	0.8028 (7)	0.2752 (9)	0.3190 (7)	0.057 (10)*
C1	0.9758 (10)	0.0384 (11)	0.3358 (7)	0.057 (10)*
C2	1.0498 (9)	0.0848 (11)	0.3584 (7)	0.057 (10)*
C3	1.1156 (9)	0.0179 (13)	0.3750 (7)	0.057 (10)*
H3	1.1646	0.0481	0.3879	0.068*
C4	1.1086 (10)	−0.0910 (12)	0.3724 (7)	0.057 (10)*
H4A	1.1525	−0.1339	0.3835	0.068*
C5	1.0343 (10)	−0.1372 (11)	0.3528 (8)	0.057 (10)*
C6	0.9677 (10)	−0.0731 (11)	0.3368 (8)	0.057 (10)*
H6	0.9179	−0.1042	0.3268	0.068*
C7	1.0606 (10)	0.2015 (12)	0.3600 (7)	0.057 (10)*
C8	1.0297 (10)	−0.2555 (11)	0.3516 (7)	0.057 (10)*
C9	0.8270 (11)	0.0761 (12)	0.3283 (8)	0.057 (9)*
C10	0.7677 (10)	0.1676 (10)	0.3140 (9)	0.057 (10)*
H10	0.7207	0.1623	0.3423	0.068*
C11	0.7376 (10)	0.1625 (9)	0.2451 (11)	0.057 (10)*
H11A	0.7789	0.1318	0.2179	0.068*
H11B	0.6882	0.1205	0.2419	0.068*
C12	0.7213 (10)	0.2785 (11)	0.2276 (9)	0.057 (10)*
H12A	0.7259	0.2891	0.1825	0.068*
H12B	0.6674	0.3004	0.2412	0.068*
C13	0.7873 (10)	0.3398 (9)	0.2627 (9)	0.057 (10)*
H13A	0.8362	0.3464	0.2372	0.068*
H13B	0.7684	0.4103	0.2741	0.068*
C14	0.8240 (11)	0.3217 (13)	0.3754 (8)	0.057 (10)*
C15	0.8450 (8)	0.2768 (12)	0.4883 (9)	0.057 (10)*
C16	0.9321 (8)	0.3203 (11)	0.4922 (10)	0.057 (10)*
H16A	0.9694	0.2689	0.4752	0.086*
H16B	0.9457	0.3341	0.5354	0.086*
H16C	0.9358	0.3851	0.4684	0.086*
C17	0.8390 (9)	0.1697 (11)	0.5224 (8)	0.057 (10)*
H17A	0.8787	0.1216	0.5054	0.086*
H17B	0.7854	0.1406	0.5166	0.086*
H17C	0.8491	0.1798	0.5666	0.086*
C18	0.7821 (9)	0.3548 (11)	0.5147 (10)	0.057 (10)*
H18A	0.7286	0.3244	0.5113	0.085*
H18B	0.7841	0.4200	0.4912	0.085*
H18C	0.7941	0.3690	0.5582	0.085*
O1W	0.9683 (6)	0.4874 (8)	0.3227 (5)	0.061 (7)*
H1W1	0.9254	0.4860	0.3454	0.091*
H1W2	0.9816	0.4218	0.3166	0.091*
O2W	1.1463 (7)	0.4351 (8)	0.3852 (4)	0.061 (7)*
H2W1	1.1052	0.4533	0.3623	0.091*
H2W2	1.1871	0.4323	0.3601	0.091*
O3W	1.1105 (18)	0.5000	0.5000	0.061 (7)*	0.48 (2)
H3W	1.1410	0.4700	0.4728	0.092*	0.48

Geometric parameters (Å, º)

O1—C7	1.36 (2)	C10—C11	1.54 (3)
O1—H1	0.8200	C10—H10	0.9800
O2—C7	1.237 (19)	C11—C12	1.529 (19)
O3—C8	1.227 (19)	C11—H11A	0.9700
O4—C8	1.364 (19)	C11—H11B	0.9700
O4—H4	0.8200	C12—C13	1.52 (2)
O5—C9	1.219 (19)	C12—H12A	0.9700
O6—C14	1.36 (2)	C12—H12B	0.9700
O6—C15	1.48 (2)	C13—H13A	0.9700
O7—C14	1.234 (19)	C13—H13B	0.9700
N1—C9	1.40 (2)	C15—C18	1.53 (2)
N1—C1	1.41 (2)	C15—C16	1.53 (2)
N1—H1A	0.8600	C15—C17	1.53 (2)
N2—C14	1.38 (2)	C16—H16A	0.9600
N2—C13	1.47 (2)	C16—H16B	0.9600
N2—C10	1.474 (18)	C16—H16C	0.9600
C1—C6	1.41 (2)	C17—H17A	0.9600
C1—C2	1.43 (2)	C17—H17B	0.9600
C2—C3	1.41 (2)	C17—H17C	0.9600
C2—C7	1.48 (2)	C18—H18A	0.9600
C3—C4	1.38 (2)	C18—H18B	0.9600
C3—H3	0.9300	C18—H18C	0.9600
C4—C5	1.41 (2)	O1W—H1W1	0.8528
C4—H4A	0.9300	O1W—H1W2	0.8631
C5—C6	1.40 (2)	O2W—H2W1	0.8619
C5—C8	1.490 (19)	O2W—H2W2	0.8559
C6—H6	0.9300	O3W—H3W	0.8518
C9—C10	1.54 (2)
C7—O1—H1	109.5	C12—C11—H11B	110.9
C8—O4—H4	109.5	C10—C11—H11B	110.9
C14—O6—C15	121.8 (12)	H11A—C11—H11B	108.9
C9—N1—C1	125.4 (12)	C13—C12—C11	103.9 (13)
C9—N1—H1A	117.3	C13—C12—H12A	111.0
C1—N1—H1A	117.3	C11—C12—H12A	111.0
C14—N2—C13	121.1 (12)	C13—C12—H12B	111.0
C14—N2—C10	123.4 (14)	C11—C12—H12B	111.0
C13—N2—C10	112.5 (13)	H12A—C12—H12B	109.0
N1—C1—C6	121.9 (14)	N2—C13—C12	103.9 (11)
N1—C1—C2	118.4 (13)	N2—C13—H13A	111.0
C6—C1—C2	118.8 (14)	C12—C13—H13A	111.0
C3—C2—C1	119.3 (13)	N2—C13—H13B	111.0
C3—C2—C7	119.6 (14)	C12—C13—H13B	111.0
C1—C2—C7	121.0 (13)	H13A—C13—H13B	109.0
C4—C3—C2	121.3 (14)	O7—C14—O6	126.5 (15)
C4—C3—H3	119.4	O7—C14—N2	123.0 (14)
C2—C3—H3	119.4	O6—C14—N2	110.5 (13)
C3—C4—C5	119.6 (14)	O6—C15—C18	110.3 (13)
C3—C4—H4A	120.2	O6—C15—C16	110.6 (14)
C5—C4—H4A	120.2	C18—C15—C16	112.3 (13)
C6—C5—C4	120.5 (13)	O6—C15—C17	102.5 (12)
C6—C5—C8	122.1 (14)	C18—C15—C17	110.3 (13)
C4—C5—C8	117.4 (14)	C16—C15—C17	110.4 (12)
C5—C6—C1	120.2 (14)	C15—C16—H16A	109.5
C5—C6—H6	119.9	C15—C16—H16B	109.5
C1—C6—H6	119.9	H16A—C16—H16B	109.5
O2—C7—O1	120.9 (14)	C15—C16—H16C	109.5
O2—C7—C2	124.9 (14)	H16A—C16—H16C	109.5
O1—C7—C2	114.2 (13)	H16B—C16—H16C	109.5
O3—C8—O4	121.8 (13)	C15—C17—H17A	109.5
O3—C8—C5	124.2 (14)	C15—C17—H17B	109.5
O4—C8—C5	114.0 (13)	H17A—C17—H17B	109.5
O5—C9—N1	125.4 (15)	C15—C17—H17C	109.5
O5—C9—C10	121.2 (15)	H17A—C17—H17C	109.5
N1—C9—C10	113.4 (13)	H17B—C17—H17C	109.5
N2—C10—C9	115.2 (13)	C15—C18—H18A	109.5
N2—C10—C11	103.4 (12)	C15—C18—H18B	109.5
C9—C10—C11	111.0 (13)	H18A—C18—H18B	109.5
N2—C10—H10	109.0	C15—C18—H18C	109.5
C9—C10—H10	109.0	H18A—C18—H18C	109.5
C11—C10—H10	109.0	H18B—C18—H18C	109.5
C12—C11—C10	104.3 (13)	H1W1—O1W—H1W2	105.9
C12—C11—H11A	110.9	H2W1—O2W—H2W2	105.7
C10—C11—H11A	110.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2W	0.82	1.73	2.545 (14)	174
O1W—H1W1···O7	0.85	1.79	2.574 (15)	152
N1—H1A···O2	0.86	2.02	2.666 (15)	131
N1—H1A···N2	0.86	2.32	2.754 (16)	111
O1W—H1W2···O2	0.86	2.06	2.889 (13)	160
O2W—H2W1···O1W	0.86	2.44	3.273 (15)	164
O4—H4···O1W^i	0.82	1.93	2.746 (14)	179
O2W—H2W2···O5^ii	0.86	2.05	2.809 (16)	147

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

1-{[1-(1-tert-Butoxycarbonyl)-L-prolyl]amino}terephthalic acid 2.08-hydrate (1b)

Crystal data

C18H22N2O7·2.08H2O	F(000) = 1767
Mr = 415.89	Dx = 1.271 Mg m^−3
Orthorhombic, P2221	Synchrotron radiation, λ = 0.399962(3) Å
Hall symbol: P 2c 2	µ = 0.02 mm^−1
a = 16.4332 (13) Å	T = 295 K
b = 12.3817 (12) Å	Particle morphology: no specific habit
c = 21.3581 (17) Å	colorless
V = 4345.8 (6) Å^3	cylinder, 15 × 1.0 mm
Z = 8	Specimen preparation: Prepared at 295 K and 101 kPa

Data collection

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: ID22 bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θmin = 1.200°, 2θmax = 17.000°, 2θstep = 0.002°
Specimen mounting: Specimen was sealed in a 1.0 mm diameter borosilicate glass capillary

Refinement

Refinement on Inet	334 parameters
Least-squares matrix: full with fixed elements per cycle	210 restraints
Rp = 0.031	86 constraints
Rwp = 0.040	H-atom parameters not refined
Rexp = 0.028	Weighting scheme based on measured s.u.'s
RBragg = 0.100	(Δ/σ)max = 0.004
10534 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986) [Toraya, H. (1986). J. Appl. Cryst. 19, 440–447]	Preferred orientation correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1A	0.6126 (7)	0.7311 (11)	0.6636 (8)	0.053 (12)*
H1A	0.6106	0.6650	0.6656	0.080*
O2A	0.4764 (7)	0.7121 (11)	0.6697 (7)	0.053 (12)*
O3A	0.5965 (7)	1.2927 (10)	0.6553 (8)	0.053 (12)*
O4A	0.4630 (7)	1.2865 (10)	0.6815 (7)	0.053 (12)*
H4A	0.4683	1.3523	0.6820	0.079*
O5A	0.2856 (6)	1.0132 (13)	0.6474 (8)	0.053 (12)*
O6A	0.3214 (6)	0.7606 (10)	0.5675 (9)	0.053 (12)*
O7A	0.3147 (7)	0.5820 (9)	0.5990 (9)	0.053 (12)*
N1A	0.3857 (9)	0.8906 (11)	0.6765 (9)	0.053 (12)*
H1A1	0.3909	0.8264	0.6914	0.064*
N2A	0.2744 (9)	0.7208 (14)	0.6634 (11)	0.053 (12)*
C1A	0.4577 (11)	0.9487 (17)	0.6698 (9)	0.053 (12)*
C2A	0.5326 (11)	0.8918 (14)	0.6613 (9)	0.053 (12)*
C3A	0.6052 (10)	0.9510 (15)	0.6546 (11)	0.053 (12)*
H3A	0.6542	0.9142	0.6501	0.064*
C4A	0.6054 (10)	1.0632 (14)	0.6545 (12)	0.053 (12)*
H4A1	0.6538	1.1010	0.6491	0.064*
C5A	0.5316 (11)	1.1191 (13)	0.6626 (10)	0.053 (12)*
C6A	0.4586 (11)	1.0629 (16)	0.6698 (9)	0.053 (12)*
H6A	0.4102	1.1008	0.6746	0.064*
C7A	0.5359 (10)	0.7720 (17)	0.6647 (11)	0.053 (12)*
C8A	0.5349 (10)	1.2398 (16)	0.6649 (11)	0.053 (12)*
C9A	0.3071 (11)	0.9219 (16)	0.6625 (11)	0.053 (12)*
C10A	0.2436 (11)	0.8316 (16)	0.6704 (12)	0.053 (12)*
H10A	0.1993	0.8432	0.6404	0.064*
C11A	0.2081 (13)	0.8323 (15)	0.7376 (13)	0.053 (12)*
H11A	0.2481	0.8577	0.7676	0.064*
H11B	0.1603	0.8780	0.7400	0.064*
C12A	0.1861 (14)	0.7142 (14)	0.7499 (14)	0.053 (12)*
H12A	0.1332	0.6967	0.7324	0.064*
H12B	0.1856	0.6987	0.7944	0.064*
C13A	0.2538 (10)	0.6515 (14)	0.7167 (12)	0.053 (12)*
H13A	0.3004	0.6415	0.7440	0.064*
H13B	0.2346	0.5814	0.7027	0.064*
C14A	0.3046 (11)	0.6790 (15)	0.6087 (13)	0.053 (12)*
C15A	0.3550 (8)	0.7360 (19)	0.5045 (15)	0.053 (12)*
C16A	0.4313 (9)	0.6658 (12)	0.5102 (13)	0.053 (12)*
H16A	0.4705	0.7017	0.5362	0.080*
H16B	0.4541	0.6541	0.4694	0.080*
H16C	0.4171	0.5976	0.5285	0.080*
C17A	0.3769 (10)	0.8485 (13)	0.4798 (12)	0.053 (12)*
H17A	0.4180	0.8800	0.5060	0.080*
H17B	0.3293	0.8935	0.4801	0.080*
H17C	0.3971	0.8425	0.4378	0.080*
C18A	0.2895 (10)	0.6839 (14)	0.4635 (13)	0.053 (12)*
H18A	0.2430	0.7307	0.4613	0.079*
H18B	0.2737	0.6159	0.4813	0.079*
H18C	0.3107	0.6725	0.4221	0.079*
O1B	1.1029 (7)	0.7440 (10)	0.4323 (8)	0.059 (13)*
H1B	1.1041	0.8101	0.4347	0.089*
O2B	0.9950 (6)	0.7809 (11)	0.3707 (10)	0.059 (13)*
O3B	1.0689 (7)	0.1910 (10)	0.4092 (8)	0.059 (13)*
O4B	0.9652 (7)	0.2066 (11)	0.3399 (8)	0.059 (13)*
H4B	0.9671	0.1405	0.3411	0.089*
O5B	0.7959 (7)	0.4773 (13)	0.3247 (7)	0.059 (13)*
O6B	0.7879 (7)	0.7385 (11)	0.4139 (9)	0.059 (13)*
O7B	0.8235 (7)	0.9092 (9)	0.3796 (9)	0.059 (13)*
N1B	0.8932 (9)	0.6065 (11)	0.3500 (9)	0.059 (13)*
H1B1	0.8977	0.6750	0.3556	0.071*
N2B	0.7938 (10)	0.7721 (13)	0.3107 (10)	0.059 (13)*
C1B	0.9604 (10)	0.5440 (18)	0.3667 (12)	0.059 (13)*
C2B	1.0330 (11)	0.5946 (14)	0.3878 (12)	0.059 (13)*
C3B	1.1006 (9)	0.5300 (15)	0.4048 (10)	0.059 (12)*
H3B	1.1468	0.5627	0.4213	0.071*
C4B	1.0991 (10)	0.4191 (13)	0.3973 (12)	0.059 (13)*
H4B1	1.1456	0.3782	0.4047	0.071*
C5B	1.0262 (11)	0.3690 (13)	0.3783 (13)	0.059 (13)*
C6B	0.9580 (11)	0.4301 (15)	0.3627 (11)	0.059 (13)*
H6B	0.9106	0.3958	0.3496	0.071*
C7B	1.0396 (10)	0.7132 (16)	0.3947 (13)	0.059 (13)*
C8B	1.0246 (9)	0.2483 (15)	0.3773 (15)	0.059 (13)*
C9B	0.8197 (11)	0.5707 (17)	0.3253 (10)	0.059 (13)*
C10B	0.7676 (10)	0.6615 (15)	0.2968 (12)	0.059 (13)*
H10B	0.7112	0.6525	0.3108	0.071*
C11B	0.7699 (11)	0.6561 (15)	0.2243 (12)	0.059 (13)*
H11C	0.8208	0.6253	0.2098	0.071*
H11D	0.7252	0.6129	0.2083	0.071*
C12B	0.7618 (10)	0.7736 (16)	0.2035 (12)	0.059 (13)*
H12C	0.7052	0.7958	0.2025	0.071*
H12D	0.7855	0.7844	0.1624	0.071*
C13B	0.8093 (14)	0.8358 (15)	0.2538 (15)	0.059 (13)*
H13C	0.8669	0.8381	0.2441	0.071*
H13D	0.7890	0.9090	0.2582	0.071*
C14B	0.8029 (11)	0.8150 (16)	0.3692 (13)	0.059 (13)*
C15B	0.7923 (9)	0.7667 (17)	0.4814 (15)	0.059 (13)*
C16B	0.8699 (9)	0.8307 (12)	0.4951 (13)	0.059 (13)*
H16D	0.9164	0.7898	0.4818	0.088*
H16E	0.8736	0.8445	0.5392	0.088*
H16F	0.8684	0.8980	0.4729	0.088*
C17B	0.7958 (10)	0.6553 (13)	0.5126 (14)	0.059 (13)*
H17D	0.7467	0.6163	0.5035	0.089*
H17E	0.8012	0.6639	0.5571	0.089*
H17F	0.8417	0.6159	0.4967	0.089*
C18B	0.7152 (10)	0.8270 (14)	0.5014 (14)	0.059 (13)*
H18D	0.6683	0.7838	0.4919	0.088*
H18E	0.7118	0.8943	0.4792	0.088*
H18F	0.7171	0.8407	0.5456	0.088*
O1W	0.9645 (7)	−0.0192 (12)	0.3266 (6)	0.063 (12)*
H1WA	0.9897	−0.0798	0.3230	0.095*
H1WB	0.9186	−0.0316	0.3441	0.095*
O2W	1.1242 (7)	0.9468 (9)	0.4223 (7)	0.063 (12)*
H2WA	1.1676	0.9712	0.4024	0.094*
H2WB	1.0928	1.0033	0.4259	0.094*
O3W	0.4320 (6)	1.4894 (13)	0.6802 (7)	0.063 (12)*
H3WA	0.4523	1.5518	0.6864	0.094*
H3WB	0.3917	1.4951	0.6552	0.094*
O4W	0.6199 (6)	0.5366 (11)	0.6256 (9)	0.063 (12)*
H4WA	0.5980	0.4828	0.6432	0.094*
H4WB	0.6719	0.5327	0.6290	0.094*
O5W	0.662 (3)	0.5000	0.5000	0.063 (12)*	0.32 (3)
HW5	0.6328	0.5080	0.5324	0.095*	0.32

Geometric parameters (Å, º)

O1A—C7A	1.36 (2)	O4B—H4B	0.8200
O1A—H1A	0.8200	O5B—C9B	1.22 (3)
O2A—C7A	1.23 (2)	O6B—C14B	1.37 (3)
O3A—C8A	1.22 (2)	O6B—C15B	1.49 (4)
O4A—C8A	1.36 (2)	O7B—C14B	1.23 (2)
O4A—H4A	0.8200	N1B—C9B	1.39 (2)
O5A—C9A	1.23 (3)	N1B—C1B	1.39 (2)
O6A—C14A	1.37 (3)	N1B—H1B1	0.8600
O6A—C15A	1.49 (4)	N2B—C14B	1.37 (3)
O7A—C14A	1.23 (2)	N2B—C10B	1.47 (2)
N1A—C9A	1.38 (2)	N2B—C13B	1.47 (3)
N1A—C1A	1.39 (2)	C1B—C6B	1.41 (3)
N1A—H1A1	0.8600	C1B—C2B	1.42 (3)
N2A—C14A	1.37 (3)	C2B—C3B	1.42 (3)
N2A—C13A	1.47 (3)	C2B—C7B	1.48 (3)
N2A—C10A	1.47 (3)	C3B—C4B	1.38 (2)
C1A—C6A	1.41 (3)	C3B—H3B	0.9300
C1A—C2A	1.43 (3)	C4B—C5B	1.41 (3)
C2A—C3A	1.41 (3)	C4B—H4B1	0.9300
C2A—C7A	1.49 (3)	C5B—C6B	1.39 (3)
C3A—C4A	1.39 (3)	C5B—C8B	1.49 (2)
C3A—H3A	0.9300	C6B—H6B	0.9300
C4A—C5A	1.41 (2)	C9B—C10B	1.54 (3)
C4A—H4A1	0.9300	C10B—C11B	1.55 (4)
C5A—C6A	1.40 (3)	C10B—H10B	0.9800
C5A—C8A	1.50 (3)	C11B—C12B	1.53 (3)
C6A—H6A	0.9300	C11B—H11C	0.9700
C9A—C10A	1.54 (3)	C11B—H11D	0.9700
C10A—C11A	1.55 (4)	C12B—C13B	1.54 (3)
C10A—H10A	0.9800	C12B—H12C	0.9700
C11A—C12A	1.53 (3)	C12B—H12D	0.9700
C11A—H11A	0.9700	C13B—H13C	0.9700
C11A—H11B	0.9700	C13B—H13D	0.9700
C12A—C13A	1.53 (3)	C15B—C16B	1.53 (2)
C12A—H12A	0.9700	C15B—C18B	1.53 (3)
C12A—H12B	0.9700	C15B—C17B	1.53 (3)
C13A—H13A	0.9700	C16B—H16D	0.9600
C13A—H13B	0.9700	C16B—H16E	0.9600
C15A—C18A	1.53 (3)	C16B—H16F	0.9600
C15A—C16A	1.53 (2)	C17B—H17D	0.9600
C15A—C17A	1.53 (3)	C17B—H17E	0.9600
C16A—H16A	0.9600	C17B—H17F	0.9600
C16A—H16B	0.9600	C18B—H18D	0.9600
C16A—H16C	0.9600	C18B—H18E	0.9600
C17A—H17A	0.9600	C18B—H18F	0.9600
C17A—H17B	0.9600	O1W—H1WA	0.8605
C17A—H17C	0.9600	O1W—H1WB	0.8557
C18A—H18A	0.9600	O2W—H2WA	0.8835
C18A—H18B	0.9600	O2W—H2WB	0.8727
C18A—H18C	0.9600	O3W—H3WA	0.8519
O1B—C7B	1.37 (3)	O3W—H3WB	0.8536
O1B—H1B	0.8200	O4W—H4WA	0.8453
O2B—C7B	1.23 (2)	O4W—H4WB	0.8590
O3B—C8B	1.22 (3)	O5W—HW5	0.8526
O4B—C8B	1.36 (3)
C7A—O1A—H1A	109.5	C14B—O6B—C15B	120.4 (16)
C8A—O4A—H4A	109.5	C9B—N1B—C1B	127.4 (16)
C14A—O6A—C15A	120.4 (16)	C9B—N1B—H1B1	116.3
C9A—N1A—C1A	128.9 (16)	C1B—N1B—H1B1	116.3
C9A—N1A—H1A1	115.6	C14B—N2B—C10B	125.5 (19)
C1A—N1A—H1A1	115.6	C14B—N2B—C13B	121.9 (17)
C14A—N2A—C13A	121.6 (17)	C10B—N2B—C13B	112.6 (19)
C14A—N2A—C10A	124 (2)	N1B—C1B—C6B	121.1 (16)
C13A—N2A—C10A	112.8 (18)	N1B—C1B—C2B	120.1 (18)
N1A—C1A—C6A	121.7 (16)	C6B—C1B—C2B	118.9 (17)
N1A—C1A—C2A	119.3 (17)	C3B—C2B—C1B	119.4 (17)
C6A—C1A—C2A	118.9 (16)	C3B—C2B—C7B	118.5 (17)
C3A—C2A—C1A	119.1 (16)	C1B—C2B—C7B	122.1 (17)
C3A—C2A—C7A	119.6 (16)	C4B—C3B—C2B	121.1 (16)
C1A—C2A—C7A	121.1 (16)	C4B—C3B—H3B	119.4
C4A—C3A—C2A	121.5 (16)	C2B—C3B—H3B	119.4
C4A—C3A—H3A	119.2	C3B—C4B—C5B	119.1 (15)
C2A—C3A—H3A	119.2	C3B—C4B—H4B1	120.5
C3A—C4A—C5A	119.3 (15)	C5B—C4B—H4B1	120.5
C3A—C4A—H4A1	120.3	C6B—C5B—C4B	120.9 (16)
C5A—C4A—H4A1	120.3	C6B—C5B—C8B	121.7 (16)
C6A—C5A—C4A	120.6 (16)	C4B—C5B—C8B	117.3 (15)
C6A—C5A—C8A	121.7 (16)	C5B—C6B—C1B	120.3 (17)
C4A—C5A—C8A	117.7 (15)	C5B—C6B—H6B	119.8
C5A—C6A—C1A	120.5 (16)	C1B—C6B—H6B	119.8
C5A—C6A—H6A	119.7	O2B—C7B—O1B	120.6 (18)
C1A—C6A—H6A	119.7	O2B—C7B—C2B	126.4 (19)
O2A—C7A—O1A	120.9 (18)	O1B—C7B—C2B	113.0 (17)
O2A—C7A—C2A	125.2 (16)	O3B—C8B—O4B	122.2 (17)
O1A—C7A—C2A	113.9 (15)	O3B—C8B—C5B	124 (2)
O3A—C8A—O4A	122.3 (17)	O4B—C8B—C5B	113.6 (18)
O3A—C8A—C5A	124.0 (16)	O5B—C9B—N1B	125.7 (18)
O4A—C8A—C5A	113.6 (15)	O5B—C9B—C10B	120.6 (17)
O5A—C9A—N1A	125.8 (17)	N1B—C9B—C10B	113.6 (16)
O5A—C9A—C10A	120.2 (16)	N2B—C10B—C9B	116.0 (17)
N1A—C9A—C10A	114.0 (16)	N2B—C10B—C11B	103.6 (17)
N2A—C10A—C9A	115.7 (15)	C9B—C10B—C11B	110.5 (16)
N2A—C10A—C11A	103.2 (17)	N2B—C10B—H10B	108.8
C9A—C10A—C11A	110.7 (18)	C9B—C10B—H10B	108.8
N2A—C10A—H10A	109.0	C11B—C10B—H10B	108.8
C9A—C10A—H10A	109.0	C12B—C11B—C10B	104.3 (17)
C11A—C10A—H10A	109.0	C12B—C11B—H11C	110.9
C12A—C11A—C10A	104.1 (19)	C10B—C11B—H11C	110.9
C12A—C11A—H11A	110.9	C12B—C11B—H11D	110.9
C10A—C11A—H11A	110.9	C10B—C11B—H11D	110.9
C12A—C11A—H11B	110.9	H11C—C11B—H11D	108.9
C10A—C11A—H11B	110.9	C11B—C12B—C13B	103.3 (18)
H11A—C11A—H11B	109.0	C11B—C12B—H12C	111.1
C11A—C12A—C13A	103.5 (18)	C13B—C12B—H12C	111.1
C11A—C12A—H12A	111.1	C11B—C12B—H12D	111.1
C13A—C12A—H12A	111.1	C13B—C12B—H12D	111.1
C11A—C12A—H12B	111.1	H12C—C12B—H12D	109.1
C13A—C12A—H12B	111.1	N2B—C13B—C12B	102.8 (16)
H12A—C12A—H12B	109.0	N2B—C13B—H13C	111.2
N2A—C13A—C12A	103.3 (16)	C12B—C13B—H13C	111.2
N2A—C13A—H13A	111.1	N2B—C13B—H13D	111.2
C12A—C13A—H13A	111.1	C12B—C13B—H13D	111.2
N2A—C13A—H13B	111.1	H13C—C13B—H13D	109.1
C12A—C13A—H13B	111.1	O7B—C14B—N2B	124 (2)
H13A—C13A—H13B	109.1	O7B—C14B—O6B	125 (2)
O7A—C14A—O6A	126 (2)	N2B—C14B—O6B	110.5 (17)
O7A—C14A—N2A	124 (2)	O6B—C15B—C16B	110.4 (19)
O6A—C14A—N2A	110.0 (17)	O6B—C15B—C18B	110.2 (18)
O6A—C15A—C18A	110.1 (14)	C16B—C15B—C18B	112.6 (18)
O6A—C15A—C16A	110 (2)	O6B—C15B—C17B	102.3 (18)
C18A—C15A—C16A	112.5 (19)	C16B—C15B—C17B	110.6 (17)
O6A—C15A—C17A	102.3 (18)	C18B—C15B—C17B	110.4 (19)
C18A—C15A—C17A	111 (2)	C15B—C16B—H16D	109.5
C16A—C15A—C17A	110.6 (13)	C15B—C16B—H16E	109.5
C15A—C16A—H16A	109.5	H16D—C16B—H16E	109.5
C15A—C16A—H16B	109.5	C15B—C16B—H16F	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16F	109.5
C15A—C16A—H16C	109.5	H16E—C16B—H16F	109.5
H16A—C16A—H16C	109.5	C15B—C17B—H17D	109.5
H16B—C16A—H16C	109.5	C15B—C17B—H17E	109.5
C15A—C17A—H17A	109.5	H17D—C17B—H17E	109.5
C15A—C17A—H17B	109.5	C15B—C17B—H17F	109.5
H17A—C17A—H17B	109.5	H17D—C17B—H17F	109.5
C15A—C17A—H17C	109.5	H17E—C17B—H17F	109.5
H17A—C17A—H17C	109.5	C15B—C18B—H18D	109.5
H17B—C17A—H17C	109.5	C15B—C18B—H18E	109.5
C15A—C18A—H18A	109.5	H18D—C18B—H18E	109.5
C15A—C18A—H18B	109.5	C15B—C18B—H18F	109.5
H18A—C18A—H18B	109.5	H18D—C18B—H18F	109.5
C15A—C18A—H18C	109.5	H18E—C18B—H18F	109.5
H18A—C18A—H18C	109.5	H1WA—O1W—H1WB	107.9
H18B—C18A—H18C	109.5	H2WA—O2W—H2WB	104.2
C7B—O1B—H1B	109.5	H3WA—O3W—H3WB	109.0
C8B—O4B—H4B	109.5	H4WA—O4W—H4WB	110.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O2A	0.86	2.05	2.670 (19)	129
N1A—H1A1···N2A	0.86	2.39	2.80 (2)	109
O1A—H1A···O4W	0.82	1.81	2.54 (2)	148
O1B—H1B···O2W	0.82	1.74	2.544 (17)	164
N1B—H1B1···O2B	0.86	2.09	2.767 (19)	135
N1B—H1B1···O6B	0.86	2.33	2.74 (2)	110
N1B—H1B1···N2B	0.86	2.30	2.75 (2)	113
O4A—H4A···O3W	0.82	1.80	2.56 (2)	154
O4B—H4B···O1W	0.82	2.00	2.81 (2)	169
O1W—H1WA···O2B^i	0.86	2.01	2.70 (2)	137
O1W—H1WB···O7B^i	0.86	1.89	2.727 (18)	167
O2W—H2WA···O5A^ii	0.88	2.22	3.082 (17)	165
O2W—H2WB···O3B^iii	0.87	2.38	3.170 (17)	150
O3W—H3WA···O2A^iii	0.85	2.06	2.86 (2)	158
O3W—H3WB···O7A^iii	0.85	2.05	2.84 (2)	153
O4W—H4WA···O3A^i	0.85	2.37	3.110 (19)	147
O4W—H4WB···O5B^iv	0.86	2.27	3.086 (17)	159

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

1-(L-Prolylamino)terephthalic acid (2a)

Crystal data

C13H14N2O5	F(000) = 1168
Mr = 278.26	Dx = 1.479 Mg m^−3
Orthorhombic, C2221	Synchrotron radiation, λ = 0.399962(3) Å
Hall symbol: C 2c 2	µ = 0.03 mm^−1
a = 7.6220 (8) Å	T = 295 K
b = 18.8180 (11) Å	Particle morphology: no specific habit
c = 17.4277 (10) Å	colorless
V = 2499.7 (3) Å^3	cylinder, 15 × 1.0 mm
Z = 8	Specimen preparation: Prepared at 295 K and 101 kPa

Data collection

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: ID22 bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θmin = 2.000°, 2θmax = 22.001°, 2θstep = 0.002°
Specimen mounting: Specimen was sealed in a 1.0 mm diameter borosilicate glass capillary

Refinement

Refinement on Inet	222 parameters
Least-squares matrix: full with fixed elements per cycle	116 restraints
Rp = 0.033	0 constraints
Rwp = 0.041	H-atom parameters not refined
Rexp = 0.023	Weighting scheme based on measured s.u.'s
RBragg = 0.088	(Δ/σ)max = 0.001
13335 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986) [Toraya, H. (1986). J. Appl. Cryst. 19, 440–447]	Preferred orientation correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2436 (8)	0.6434 (2)	0.9178 (2)	0.044 (2)*
O2	0.2204 (7)	0.6661 (3)	0.7922 (2)	0.050 (2)*
O3	0.2166 (7)	0.2785 (3)	0.8490 (3)	0.050 (2)*
O4	0.2660 (8)	0.2983 (2)	0.7244 (2)	0.046 (2)*
H4	0.2669	0.2547	0.7230	0.069*
O5	0.3583 (6)	0.4982 (3)	0.5925 (3)	0.045 (2)*
N1	0.2801 (9)	0.5656 (3)	0.6962 (3)	0.050 (3)*
H1	0.2613	0.6092	0.7083	0.060*
N2	0.4589 (9)	0.6153 (3)	0.5093 (3)	0.057 (3)*
H2A	0.4520	0.5709	0.4904	0.068*
H2B	0.5699	0.6233	0.5247	0.068*
C1	0.2553 (9)	0.5178 (4)	0.7577 (4)	0.059 (3)*
C2	0.2203 (11)	0.5450 (4)	0.8325 (4)	0.061 (3)*
C3	0.1882 (10)	0.4969 (5)	0.8915 (4)	0.057 (3)*
H3	0.1665	0.5145	0.9404	0.068*
C4	0.1870 (11)	0.4239 (4)	0.8806 (4)	0.055 (3)*
H4A	0.1604	0.3931	0.9207	0.066*
C5	0.2268 (12)	0.3982 (5)	0.8080 (3)	0.060 (3)*
C6	0.2485 (10)	0.4444 (4)	0.7467 (5)	0.055 (3)*
H6	0.2587	0.4261	0.6973	0.066*
C7	0.2268 (12)	0.6229 (4)	0.8488 (4)	0.058 (4)*
C8	0.2332 (12)	0.3196 (5)	0.7951 (3)	0.063 (3)*
C9	0.3271 (11)	0.5566 (4)	0.6225 (4)	0.057 (3)*
C10	0.3349 (12)	0.6244 (4)	0.5747 (4)	0.059 (4)*
H10	0.3707	0.6647	0.6067	0.071*
C11	0.1566 (12)	0.6404 (4)	0.5349 (4)	0.062 (4)*
H11A	0.0983	0.5969	0.5192	0.074*
H11B	0.0794	0.6672	0.5683	0.074*
C12	0.2129 (12)	0.6848 (4)	0.4650 (4)	0.063 (4)*
H12A	0.1423	0.6725	0.4206	0.076*
H12B	0.1979	0.7350	0.4755	0.076*
C13	0.4065 (12)	0.6681 (4)	0.4497 (4)	0.060 (3)*
H13A	0.4215	0.6483	0.3987	0.072*
H13B	0.4771	0.7108	0.4539	0.072*

Geometric parameters (Å, º)

O1—C7	1.270 (8)	C3—H3	0.9303
O2—C7	1.279 (8)	C4—C5	1.388 (10)
O3—C8	1.223 (9)	C4—H4A	0.9302
O4—C8	1.320 (8)	C5—C6	1.387 (11)
O4—H4	0.8200	C5—C8	1.497 (13)
O5—C9	1.241 (9)	C6—H6	0.9295
N1—C9	1.344 (9)	C9—C10	1.525 (10)
N1—C1	1.412 (9)	C10—C11	1.555 (12)
N1—H1	0.8603	C10—H10	0.9802
N2—C10	1.491 (10)	C11—C12	1.538 (10)
N2—C13	1.492 (9)	C11—H11A	0.9700
N2—H2A	0.8997	C11—H11B	0.9703
N2—H2B	0.9004	C12—C13	1.532 (13)
C1—C6	1.396 (10)	C12—H12A	0.9696
C1—C2	1.425 (11)	C12—H12B	0.9702
C2—C3	1.392 (11)	C13—H13A	0.9700
C2—C7	1.494 (10)	C13—H13B	0.9702
C3—C4	1.386 (12)
C8—O4—H4	109.5	O3—C8—O4	123.0 (8)
C9—N1—C1	132.9 (6)	O3—C8—C5	120.4 (6)
C9—N1—H1	113.5	O4—C8—C5	116.5 (6)
C1—N1—H1	113.5	O5—C9—N1	124.4 (7)
C10—N2—C13	106.6 (6)	O5—C9—C10	120.2 (6)
C10—N2—H2A	110.4	N1—C9—C10	115.3 (6)
C13—N2—H2A	110.4	N2—C10—C9	110.3 (6)
C10—N2—H2B	110.4	N2—C10—C11	103.6 (5)
C13—N2—H2B	110.4	C9—C10—C11	111.8 (7)
H2A—N2—H2B	108.6	N2—C10—H10	110.3
C6—C1—N1	122.1 (7)	C9—C10—H10	110.3
C6—C1—C2	118.3 (7)	C11—C10—H10	110.3
N1—C1—C2	119.4 (6)	C12—C11—C10	102.4 (7)
C3—C2—C1	118.4 (7)	C12—C11—H11A	111.3
C3—C2—C7	120.2 (7)	C10—C11—H11A	111.3
C1—C2—C7	121.3 (7)	C12—C11—H11B	111.3
C4—C3—C2	123.0 (7)	C10—C11—H11B	111.3
C4—C3—H3	118.5	H11A—C11—H11B	109.2
C2—C3—H3	118.5	C13—C12—C11	107.2 (6)
C3—C4—C5	117.9 (7)	C13—C12—H12A	110.3
C3—C4—H4A	121.0	C11—C12—H12A	110.3
C5—C4—H4A	121.0	C13—C12—H12B	110.2
C6—C5—C4	120.6 (8)	C11—C12—H12B	110.3
C6—C5—C8	120.0 (6)	H12A—C12—H12B	108.6
C4—C5—C8	119.2 (7)	N2—C13—C12	105.9 (6)
C5—C6—C1	121.2 (8)	N2—C13—H13A	110.6
C5—C6—H6	119.4	C12—C13—H13A	110.6
C1—C6—H6	119.4	N2—C13—H13B	110.6
O1—C7—O2	122.8 (6)	C12—C13—H13B	110.6
O1—C7—C2	118.8 (6)	H13A—C13—H13B	108.7
O2—C7—C2	118.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.84	2.566 (7)	141
N2—H2A···O5^i	0.90	2.07	2.881 (8)	149
N2—H2B···O1^ii	0.90	1.78	2.653 (9)	163
O4—H4···O2^iii	0.82	1.69	2.507 (7)	172

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

1-(L-Prolylamino)terephthalic acid (2b)

Crystal data

C13H14N2O5	F(000) = 584
Mr = 278.26	Dx = 1.536 Mg m^−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.399962(3) Å
Hall symbol: P 2ac 2ab	µ = 0.03 mm^−1
a = 17.4407 (13) Å	T = 295 K
b = 9.7795 (9) Å	Particle morphology: no specific habit
c = 7.0567 (7) Å	colorless
V = 1203.60 (19) Å^3	cylinder, 15 × 1.0 mm
Z = 4	Specimen preparation: Prepared at 295 K and 101 kPa

Data collection

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: ID22 bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θmin = 2.000°, 2θmax = 22.001°, 2θstep = 0.002°
Specimen mounting: Specimen was sealed in a 1.0 mm diameter borosilicate glass capillary

Refinement

Refinement on Inet	222 parameters
Least-squares matrix: full with fixed elements per cycle	116 restraints
Rp = 0.033	0 constraints
Rwp = 0.041	H-atom parameters not refined
Rexp = 0.023	Weighting scheme based on measured s.u.'s
RBragg = 0.088	(Δ/σ)max = 0.001
13335 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986) [Toraya, H. (1986). J. Appl. Cryst. 19, 440–447]	Preferred orientation correction: March-Dollase (Dollase, 1986); direction of preferred orientation [100], texture parameter r=1.10(1). [Dollase, W. A. (1986). J. Appl. Cryst. 19, 267–272]

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2661 (3)	1.2085 (4)	0.0340 (11)	0.053 (3)*
O2	0.1455 (3)	1.1372 (5)	0.0157 (10)	0.048 (3)*
O3	0.2463 (3)	0.4535 (5)	0.0180 (9)	0.049 (2)*
H3	0.2617	0.3748	0.0306	0.073*
O4	0.3660 (2)	0.5040 (5)	0.1155 (10)	0.052 (3)*
O5	0.4936 (3)	0.9092 (5)	0.1141 (9)	0.055 (3)*
N1	0.3790 (3)	1.0264 (7)	0.0829 (11)	0.052 (3)*
H1	0.3622	1.1091	0.0850	0.062*
N2	0.5759 (3)	1.1220 (6)	0.0165 (11)	0.053 (3)*
H2A	0.6069	1.1947	0.0325	0.064*
H2B	0.5958	1.0500	0.0788	0.064*
C1	0.3216 (4)	0.9261 (9)	0.0638 (16)	0.063 (4)*
C2	0.2436 (5)	0.9669 (8)	0.0349 (15)	0.060 (4)*
C3	0.1884 (4)	0.8644 (8)	0.0080 (16)	0.057 (4)*
H3A	0.1378	0.8895	−0.0155	0.068*
C4	0.2071 (5)	0.7271 (8)	0.0153 (17)	0.062 (4)*
H4	0.1692	0.6608	0.0019	0.074*
C5	0.2832 (5)	0.6891 (7)	0.0430 (18)	0.059 (4)*
C6	0.3398 (4)	0.7869 (9)	0.0743 (17)	0.061 (4)*
H6	0.3896	0.7598	0.1022	0.073*
C7	0.2172 (4)	1.1116 (7)	0.0258 (15)	0.058 (4)*
C8	0.3028 (4)	0.5407 (8)	0.0596 (17)	0.064 (4)*
C9	0.4557 (4)	1.0150 (9)	0.0984 (15)	0.062 (4)*
C10	0.4967 (4)	1.1527 (8)	0.0850 (14)	0.057 (4)*
H10	0.4962	1.2035	0.2047	0.068*
C11	0.4634 (5)	1.2355 (9)	−0.0822 (15)	0.063 (4)*
H11A	0.4078	1.2361	−0.0786	0.076*
H11B	0.4819	1.3290	−0.0803	0.076*
C12	0.4929 (4)	1.1591 (9)	−0.2572 (15)	0.064 (5)*
H12A	0.4559	1.0919	−0.3000	0.077*
H12B	0.5036	1.2221	−0.3600	0.077*
C13	0.5661 (5)	1.0902 (9)	−0.1883 (14)	0.059 (4)*
H13A	0.5626	0.9921	−0.2066	0.071*
H13B	0.6098	1.1238	−0.2596	0.071*

Geometric parameters (Å, º)

O1—C7	1.276 (8)	C3—H3A	0.9298
O2—C7	1.277 (8)	C4—C5	1.393 (12)
O3—C8	1.336 (9)	C4—H4	0.9296
O3—H3	0.8202	C5—C6	1.392 (11)
O4—C8	1.224 (9)	C5—C8	1.495 (11)
O5—C9	1.233 (10)	C6—H6	0.9301
N1—C9	1.347 (9)	C9—C10	1.528 (11)
N1—C1	1.408 (10)	C10—C11	1.544 (13)
N1—H1	0.8601	C10—H10	0.9802
N2—C13	1.488 (13)	C11—C12	1.532 (14)
N2—C10	1.494 (10)	C11—H11A	0.9704
N2—H2A	0.8999	C11—H11B	0.9700
N2—H2B	0.9002	C12—C13	1.523 (12)
C1—C6	1.400 (12)	C12—H12A	0.9702
C1—C2	1.432 (11)	C12—H12B	0.9700
C2—C3	1.403 (11)	C13—H13A	0.9702
C2—C7	1.490 (11)	C13—H13B	0.9698
C3—C4	1.383 (11)
C8—O3—H3	109.5	O4—C8—O3	123.2 (7)
C9—N1—C1	131.0 (7)	O4—C8—C5	121.0 (7)
C9—N1—H1	114.5	O3—C8—C5	115.7 (6)
C1—N1—H1	114.5	O5—C9—N1	127.6 (7)
C13—N2—C10	104.5 (6)	O5—C9—C10	119.6 (6)
C13—N2—H2A	110.9	N1—C9—C10	112.8 (7)
C10—N2—H2A	110.8	N2—C10—C9	106.0 (6)
C13—N2—H2B	110.9	N2—C10—C11	101.8 (7)
C10—N2—H2B	110.8	C9—C10—C11	109.5 (7)
H2A—N2—H2B	108.9	N2—C10—H10	112.9
C6—C1—N1	120.7 (6)	C9—C10—H10	112.9
C6—C1—C2	119.6 (7)	C11—C10—H10	113.0
N1—C1—C2	119.7 (7)	C12—C11—C10	103.6 (7)
C3—C2—C1	118.2 (7)	C12—C11—H11A	111.1
C3—C2—C7	117.4 (7)	C10—C11—H11A	111.0
C1—C2—C7	124.4 (7)	C12—C11—H11B	111.1
C4—C3—C2	121.8 (7)	C10—C11—H11B	111.0
C4—C3—H3A	119.1	H11A—C11—H11B	109.0
C2—C3—H3A	119.1	C13—C12—C11	103.9 (8)
C3—C4—C5	119.3 (7)	C13—C12—H12A	111.0
C3—C4—H4	120.4	C11—C12—H12A	111.0
C5—C4—H4	120.3	C13—C12—H12B	111.0
C4—C5—C6	121.0 (7)	C11—C12—H12B	111.0
C4—C5—C8	119.2 (7)	H12A—C12—H12B	109.0
C6—C5—C8	119.5 (7)	N2—C13—C12	108.3 (7)
C5—C6—C1	119.9 (7)	N2—C13—H13A	110.0
C5—C6—H6	120.0	C12—C13—H13A	110.0
C1—C6—H6	120.0	N2—C13—H13B	110.0
O1—C7—O2	120.8 (6)	C12—C13—H13B	110.1
O1—C7—C2	119.8 (6)	H13A—C13—H13B	108.4
O2—C7—C2	119.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.97	2.677 (8)	139
N2—H2A···O2^i	0.90	1.81	2.659 (8)	157
N2—H2B···O4^ii	0.90	2.30	3.017 (10)	136
O3—H3···O1^iii	0.82	1.63	2.423 (6)	163

Symmetry codes: (i) x+1/2, −y+5/2, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) x, y−1, z.