Hydrogen-bonding behaviour of benzene-1,2,4,5-tetracarboxylic acid: supramolecular structures of different dimensionality in the 2:1 adducts formed with 4,4′-bipyridyl and hexamethylenetetramine

Co-crystallization of benzene-1,2,4,5-tetracarboxylic acid, C₁₀H₆O₈, with 4,4′-bipyridyl, C₁₀H₈N₂, or with hexamethylene­tetramine, C₆H₁₂N₄, from methanol solutions yields in each case a 2:1 salt, [(C₁₀H₉N₂)⁺]₂·[(C₁₀H₄O₈)²⁻] (1) and [(C₆H₁₃N₄)⁺]₂·[(C₁₀H₄O₈)²⁻] (2). In (1) the carboxylate anions lie across centres of inversion, but they contain no intramolecular O—H...O hydrogen bonds: the cations and anions are linked by strong O—H...N and N—H...O hydrogen bonds into a chain-of-rings, and these chains are further linked into a three-dimensional framework structure by means of C—H...O hydrogen bonds and aromatic π...π stacking interactions. Compound (2) contains two independent three-molecule aggregates, comprising a central anion and two cations, linked to the anion by means of short N—H...O hydrogen bonds. One of these aggregates is centrosymmetric, but the other is not, and the two types of anion both form two intramolecular O—H...O hydrogen bonds. The two types of three-molecule aggregate, in which all the anions are virtually parallel, are linked by short C—H...O hydrogen bonds into a molecular staircase.

Computing details

For both compounds, data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997b); molecular graphics: NRCVAX96, ORTEP (Johnson, 1976), PLATON (Spek, 1999); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

(1) Benzene-1,2,4,5-tetracarboxylic acid–4,4'-bipyridyl (1/2)

Crystal data

C10H4O8·2(C10H9N2)	Z = 1
Mr = 566.52	F(000) = 294
Triclinic, P1	Dx = 1.515 Mg m^−3
a = 7.3974 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6352 (4) Å	Cell parameters from 2832 reflections
c = 10.1688 (3) Å	θ = 2.9–27.5°
α = 64.872 (2)°	µ = 0.11 mm^−1
β = 72.375 (2)°	T = 100 K
γ = 76.612 (2)°	Block, colourless
V = 620.92 (4) Å^3	0.35 × 0.27 × 0.25 mm

Data collection

Kappa-CCD diffractometer	2832 independent reflections
Radiation source: fine-focus sealed X-ray tube	2272 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→9
Tmin = 0.962, Tmax = 0.973	k = −11→12
9749 measured reflections	l = −12→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0668P)^2 + 0.0415P] where P = (Fo^2 + 2Fc^2)/3
2832 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.9544(0.0011) x + 4.5295(0.0046) y + 1.8768(0.0040) z = 8.0515(0.0055)

* 0.0091(0.0008) N11 * -0.0033(0.0009) C12 * -0.0034(0.0010) C13 * 0.0019(0.0010) C14 * -0.0014(0.0010) C15 * -0.0053(0.0009) C16 * 0.0024(0.0007) C24

Rms deviation of fitted atoms = 0.0045

6.8559(0.0012) x + 4.9937(0.0043) y + 2.1405(0.0039) z = 8.3597(0.0060)

Angle to previous plane(with approximate e.s.d.) = 3.2 (1)

* 0.0067(0.0008) N21 * -0.0028(0.0008) C22 * -0.0026(0.0009) C23 * -0.0009(0.0010) C24 * -0.0055(0.0009) C25 * 0.0002(0.0009) C26 * 0.0049(0.0007) C14

Rms deviation of fitted atoms = 0.0040

0.0579(0.0050) x + 9.2788(0.0020) y + 5.0640(0.0067) z = 7.2019(0.0050)

Angle to previous plane(with approximate e.s.d.) = 73.5 (1)

* -0.0015(0.0005) CEN # CEN is the inversion centre at 1/2, 1/2, 0.5 * 0.0015(0.0005) C1 * -0.0015(0.0005) C2 * 0.0015(0.0005) C3 0.0509(0.0023) C4 - 0.1197(0.0024) C5 - 0.5393(0.0026) O1 0.7625(0.0026) O2 - 1.1494(0.0027) O3 0.9539(0.0028) O4

Rms deviation of fitted atoms = 0.0015

2.8800(0.0042) x + 8.9939(0.0021) y + 1.6222(0.0065) z = 6.6984(0.0069)

Angle to previous plane(with approximate e.s.d.) = 35.8 (1)

* 0.0014(0.0003) C1 * -0.0052(0.0010) C4 * 0.0020(0.0004) O1 * 0.0018(0.0003) O2

Rms deviation of fitted atoms = 0.0030

0.0579(0.0050) x + 9.2788(0.0020) y + 5.0640(0.0067) z = 7.2019(0.0050)

Angle to previous plane (with approximate e.s.d.) = 35.8 (1)

* -0.0015(0.0005) CEN * 0.0015(0.0005) C1 * -0.0015(0.0005) C2 * 0.0015(0.0005) C3 0.0509(0.0023) C4 - 0.1197(0.0024) C5 - 0.5393(0.0026) O1 0.7625(0.0026) O2 - 1.1494(0.0027) O3 0.9539(0.0028) O4

Rms deviation of fitted atoms = 0.0015

6.6746(0.0018) x + 4.7769(0.0051) y + 6.6873(0.0045) z = 9.1104(0.0035)

Angle to previous plane (with approximate e.s.d.) = 69.7 (1)

* -0.0010(0.0003) C2 * 0.0037(0.0009) C5 * -0.0014(0.0004) O3 * -0.0013(0.0003) O4

Rms deviation of fitted atoms = 0.0021

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.89461 (12)	0.33319 (11)	0.69494 (10)	0.0244 (2)
O2	0.62864 (13)	0.39029 (10)	0.85042 (9)	0.0224 (2)
O3	0.37571 (14)	0.18225 (10)	0.85695 (10)	0.0263 (2)
O4	0.19766 (12)	0.39660 (10)	0.88158 (9)	0.0205 (2)
C1	0.60774 (17)	0.44064 (13)	0.60813 (13)	0.0164 (3)
C2	0.41449 (17)	0.41918 (13)	0.64906 (12)	0.0161 (3)
C3	0.30717 (17)	0.47916 (14)	0.54099 (13)	0.0164 (2)
C4	0.72470 (17)	0.38134 (13)	0.72521 (13)	0.0167 (3)
C5	0.32697 (17)	0.32045 (14)	0.80765 (13)	0.0175 (3)
N11	0.71608 (14)	0.22555 (12)	1.09709 (11)	0.0192 (2)
C12	0.64796 (19)	0.28313 (15)	1.20399 (14)	0.0213 (3)
C13	0.66643 (18)	0.19471 (14)	1.34885 (14)	0.0206 (3)
C14	0.75572 (16)	0.04318 (14)	1.38655 (13)	0.0164 (3)
C15	0.82308 (18)	−0.01395 (15)	1.27304 (14)	0.0216 (3)
C16	0.79949 (18)	0.08063 (15)	1.13010 (14)	0.0227 (3)
N21	0.81740 (15)	−0.23338 (12)	1.83499 (11)	0.0198 (2)
C22	0.89003 (17)	−0.28840 (14)	1.72634 (13)	0.0200 (3)
C23	0.87378 (17)	−0.20332 (14)	1.57999 (13)	0.0194 (3)
C24	0.77721 (16)	−0.05421 (14)	1.54222 (13)	0.0167 (3)
C25	0.70016 (18)	0.00166 (15)	1.65650 (13)	0.0211 (3)
C26	0.72364 (18)	−0.09065 (15)	1.79933 (14)	0.0216 (3)
H4	0.1829	0.3445	0.9737	0.031*
H3	0.1759	0.4653	0.5691	0.020*
H11	0.692 (3)	0.306 (2)	0.972 (2)	0.066 (6)*
H12	0.5862	0.3859	1.1801	0.026*
H13	0.6179	0.2376	1.4232	0.025*
H15	0.8845	−0.1166	1.2934	0.026*
H16	0.8442	0.0407	1.0536	0.027*
H22	0.9555	−0.3901	1.7505	0.024*
H23	0.9281	−0.2464	1.5061	0.023*
H25	0.6322	0.1023	1.6363	0.025*
H26	0.6707	−0.0508	1.8757	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0205 (5)	0.0308 (5)	0.0208 (5)	0.0039 (4)	−0.0078 (4)	−0.0103 (4)
O2	0.0252 (5)	0.0264 (5)	0.0141 (4)	0.0061 (4)	−0.0088 (3)	−0.0080 (4)
O3	0.0396 (6)	0.0170 (5)	0.0163 (4)	−0.0017 (4)	−0.0029 (4)	−0.0042 (4)
O4	0.0221 (5)	0.0223 (5)	0.0115 (4)	0.0021 (4)	−0.0031 (3)	−0.0042 (3)
C1	0.0204 (6)	0.0144 (6)	0.0146 (6)	0.0016 (4)	−0.0066 (4)	−0.0060 (4)
C2	0.0209 (6)	0.0133 (6)	0.0130 (5)	0.0003 (5)	−0.0039 (4)	−0.0052 (4)
C3	0.0166 (6)	0.0167 (6)	0.0156 (6)	0.0000 (5)	−0.0045 (4)	−0.0064 (5)
C4	0.0195 (6)	0.0148 (6)	0.0151 (5)	0.0005 (5)	−0.0061 (5)	−0.0049 (4)
C5	0.0194 (6)	0.0186 (6)	0.0140 (5)	−0.0016 (5)	−0.0053 (4)	−0.0052 (5)
N11	0.0207 (5)	0.0202 (6)	0.0159 (5)	−0.0011 (4)	−0.0072 (4)	−0.0047 (4)
C12	0.0263 (7)	0.0175 (6)	0.0192 (6)	0.0005 (5)	−0.0094 (5)	−0.0051 (5)
C13	0.0264 (7)	0.0190 (6)	0.0170 (6)	0.0009 (5)	−0.0074 (5)	−0.0077 (5)
C14	0.0161 (6)	0.0174 (6)	0.0149 (6)	−0.0022 (5)	−0.0057 (4)	−0.0039 (5)
C15	0.0260 (7)	0.0176 (6)	0.0195 (6)	0.0038 (5)	−0.0083 (5)	−0.0066 (5)
C16	0.0267 (7)	0.0234 (7)	0.0170 (6)	0.0034 (5)	−0.0074 (5)	−0.0085 (5)
N21	0.0200 (5)	0.0205 (6)	0.0154 (5)	−0.0019 (4)	−0.0039 (4)	−0.0040 (4)
C22	0.0208 (6)	0.0181 (6)	0.0173 (6)	0.0015 (5)	−0.0058 (5)	−0.0043 (5)
C23	0.0210 (6)	0.0197 (6)	0.0160 (6)	0.0007 (5)	−0.0048 (5)	−0.0066 (5)
C24	0.0156 (6)	0.0173 (6)	0.0154 (6)	−0.0026 (5)	−0.0043 (4)	−0.0038 (5)
C25	0.0255 (7)	0.0177 (6)	0.0176 (6)	0.0006 (5)	−0.0060 (5)	−0.0053 (5)
C26	0.0259 (7)	0.0214 (7)	0.0154 (6)	0.0002 (5)	−0.0051 (5)	−0.0064 (5)

Geometric parameters (Å, º)

O1—C4	1.228 (2)	C12—C13	1.3844 (17)
O2—C4	1.285 (2)	C13—C14	1.3951 (18)
O3—C5	1.214 (2)	C14—C15	1.3956 (17)
O4—C5	1.314 (2)	C14—C24	1.4945 (16)
C1—C3^i	1.3946 (16)	C15—C16	1.3888 (16)
C1—C2	1.4011 (17)	N21—C26	1.338 (2)
C1—C4	1.5197 (15)	N21—C22	1.340 (2)
C2—C3	1.3958 (16)	C22—C23	1.3885 (16)
C2—C5	1.5083 (15)	C23—C24	1.3944 (17)
C3—C1^i	1.3946 (16)	C24—C25	1.3975 (16)
N11—C16	1.331 (2)	C25—C26	1.3838 (17)
N11—C12	1.340 (2)
C3—C1—C2	119.8 (1)	C12—C13—C14	120.52 (12)
C3—C1—C4	119.5 (1)	C15—C14—C13	117.22 (11)
C2—C1—C4	120.7 (1)	C15—C14—C24	121.40 (11)
C3—C2—C1	120.0 (1)	C13—C14—C24	121.37 (11)
C3—C2—C5	120.0 (1)	C16—C15—C14	119.39 (11)
C1—C2—C5	119.8 (1)	N11—C16—C15	121.98 (11)
C1—C3—C2	120.2 (2)	C26—N21—C22	117.8 (1)
O1—C4—O2	126.4 (1)	N21—C22—C23	122.89 (11)
O1—C4—C1	120.24 (10)	C22—C23—C24	119.51 (11)
O2—C4—C1	113.39 (10)	C23—C24—C25	117.23 (11)
O3—C5—O4	125.3 (1)	C23—C24—C14	121.98 (11)
O3—C5—C2	120.35 (11)	C25—C24—C14	120.79 (11)
O4—C5—C2	114.40 (10)	C26—C25—C24	119.51 (12)
C16—N11—C12	120.0 (1)	N21—C26—C25	123.10 (11)
N11—C12—C13	120.84 (12)
C3^i—C1—C2—C3	−0.58 (19)	C12—C13—C14—C24	179.98 (11)
C4—C1—C2—C3	177.69 (10)	C13—C14—C15—C16	0.21 (18)
C3^i—C1—C2—C5	174.53 (10)	C24—C14—C15—C16	179.83 (11)
C4—C1—C2—C5	−7.20 (16)	C12—N11—C16—C15	−1.54 (19)
C1—C2—C3—C1^i	0.59 (19)	C14—C15—C16—N11	0.76 (19)
C5—C2—C3—C1^i	−174.52 (10)	C26—N21—C22—C23	0.80 (18)
C3^i—C1—C4—O1	−35.92 (17)	N21—C22—C23—C24	−0.41 (19)
C2—C1—C4—O1	145.8 (2)	C22—C23—C24—C25	−0.28 (17)
C3^i—C1—C4—O2	143.10 (11)	C22—C23—C24—C14	179.75 (11)
C2—C1—C4—O2	−35.2 (2)	C15—C14—C24—C23	3.39 (18)
C3—C2—C5—O3	107.54 (14)	C13—C14—C24—C23	−177.01 (11)
C1—C2—C5—O3	−67.6 (2)	C15—C14—C24—C25	−176.58 (11)
C3—C2—C5—O4	−71.76 (14)	C13—C14—C24—C25	3.03 (17)
C1—C2—C5—O4	113.1 (2)	C23—C24—C25—C26	0.55 (17)
C16—N11—C12—C13	1.33 (18)	C14—C24—C25—C26	−179.48 (11)
N11—C12—C13—C14	−0.36 (19)	C22—N21—C26—C25	−0.50 (18)
C12—C13—C14—C15	−0.40 (18)	C24—C25—C26—N21	−0.17 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···N21^ii	0.84	1.78	2.6134 (13)	173
N11—H11···O2	1.22 (2)	1.32 (2)	2.5210 (13)	168 (2)
C3—H3···O1^iii	0.95	2.41	3.312 (2)	158
C12—H12···O2^iv	0.95	2.33	3.259 (2)	167
C15—H15···O1^v	0.95	2.32	3.243 (2)	165

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

(2) Benzeme-1,2,4,5-tetracarboxylic acid–hexamethylenetetramine (1/2)

Crystal data

C10H4O8·2(C6H13N4)	Z = 3
Mr = 534.54	F(000) = 846
Triclinic, P1	Dx = 1.577 Mg m^−3
a = 9.7029 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9369 (7) Å	Cell parameters from 6124 reflections
c = 16.7647 (11) Å	θ = 4.1–25.3°
α = 84.271 (3)°	µ = 0.12 mm^−1
β = 79.399 (3)°	T = 100 K
γ = 75.264 (3)°	Block, colourless
V = 1688.55 (19) Å^3	0.25 × 0.25 × 0.20 mm

Data collection

Kappa-CCD diffractometer	6124 independent reflections
Radiation source: fine-focus sealed X-ray tube	2853 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
φ scans and ω scans with κ offsets	θmax = 25.3°, θmin = 4.1°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→11
Tmin = 0.970, Tmax = 0.976	k = −12→13
14292 measured reflections	l = −19→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0392P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.84	(Δ/σ)max < 0.001
6124 reflections	Δρmax = 0.28 e Å^−3
518 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (5)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O11	0.6525 (2)	0.46593 (18)	0.68594 (11)	0.0231 (5)
O12	0.5605 (2)	0.67100 (19)	0.67335 (12)	0.0289 (5)
O13	0.4134 (2)	0.82486 (18)	0.59120 (12)	0.0256 (5)
O14	0.3063 (2)	0.83142 (18)	0.48633 (12)	0.0247 (5)
C11	0.5332 (3)	0.5392 (3)	0.57139 (17)	0.0174 (7)
C12	0.4517 (3)	0.6293 (3)	0.52159 (17)	0.0173 (7)
C13	0.4224 (3)	0.5870 (3)	0.45151 (17)	0.0160 (7)
C14	0.5850 (3)	0.5593 (3)	0.64867 (18)	0.0205 (7)
C15	0.3849 (3)	0.7708 (3)	0.53225 (17)	0.0179 (7)
O21	0.9971 (2)	0.14832 (18)	0.34281 (12)	0.0248 (5)
O22	0.8485 (2)	0.33866 (19)	0.35061 (12)	0.0255 (5)
O23	0.7094 (2)	0.49269 (18)	0.26530 (12)	0.0269 (5)
O24	0.6172 (2)	0.50109 (19)	0.15426 (12)	0.0287 (5)
O25	0.6491 (2)	0.20571 (19)	−0.01045 (12)	0.0267 (5)
O26	0.7811 (2)	0.0084 (2)	−0.01450 (13)	0.0332 (6)
O27	0.9273 (2)	−0.14665 (18)	0.06679 (12)	0.0264 (5)
O28	1.0211 (2)	−0.15767 (19)	0.17811 (12)	0.0262 (5)
C21	0.8502 (3)	0.2107 (3)	0.23954 (17)	0.0180 (7)
C22	0.7654 (3)	0.3005 (3)	0.19042 (17)	0.0167 (7)
C23	0.7437 (3)	0.2593 (3)	0.11873 (17)	0.0183 (7)
C24	0.7914 (3)	0.1354 (3)	0.09396 (17)	0.0175 (7)
C25	0.8750 (3)	0.0450 (3)	0.14332 (17)	0.0180 (7)
C26	0.9009 (3)	0.0866 (3)	0.21431 (17)	0.0182 (7)
C27	0.9017 (3)	0.2334 (3)	0.31619 (17)	0.0188 (7)
C28	0.6920 (3)	0.4398 (3)	0.20329 (18)	0.0197 (7)
C29	0.7380 (3)	0.1160 (3)	0.01743 (17)	0.0222 (7)
C210	0.9476 (3)	−0.0952 (3)	0.12970 (18)	0.0206 (7)
N31	0.7326 (2)	0.5396 (2)	0.81768 (14)	0.0206 (6)
C32	0.6422 (3)	0.6648 (3)	0.85119 (18)	0.0224 (7)
N33	0.7167 (2)	0.7076 (2)	0.90567 (14)	0.0201 (6)
C34	0.7460 (3)	0.6107 (3)	0.97153 (18)	0.0266 (8)
N35	0.8359 (3)	0.4882 (2)	0.94221 (14)	0.0252 (6)
C36	0.7605 (3)	0.4437 (3)	0.88793 (17)	0.0254 (7)
C37	0.8749 (3)	0.5615 (3)	0.77237 (17)	0.0258 (7)
C38	0.8576 (3)	0.7233 (3)	0.86001 (18)	0.0238 (7)
C39	0.9715 (3)	0.5107 (3)	0.89490 (18)	0.0268 (8)
N310	0.9489 (2)	0.6044 (2)	0.82707 (14)	0.0231 (6)
N41	1.0680 (2)	0.1985 (2)	0.48554 (14)	0.0192 (6)
C42	0.9905 (3)	0.3344 (3)	0.50318 (18)	0.0227 (7)
N43	1.0198 (2)	0.3656 (2)	0.57970 (14)	0.0211 (6)
C44	0.9688 (3)	0.2781 (2)	0.64492 (17)	0.0209 (7)
N45	1.0433 (2)	0.1460 (2)	0.63049 (14)	0.0209 (6)
C46	1.0156 (3)	0.1120 (3)	0.55527 (16)	0.0219 (7)
C47	1.2284 (3)	0.1822 (3)	0.48300 (17)	0.0233 (7)
C48	1.1767 (3)	0.3463 (3)	0.57451 (18)	0.0234 (7)
C49	1.1985 (3)	0.1317 (3)	0.62497 (17)	0.0245 (7)
N410	1.2555 (2)	0.2148 (2)	0.55927 (15)	0.0245 (6)
N51	0.5777 (2)	0.1426 (2)	−0.14699 (14)	0.0194 (6)
C52	0.6476 (3)	0.0043 (3)	−0.15880 (17)	0.0228 (7)
N53	0.6299 (2)	−0.0313 (2)	−0.23607 (14)	0.0205 (6)
C54	0.6978 (3)	0.0475 (3)	−0.30024 (17)	0.0234 (7)
N55	0.6318 (2)	0.1835 (2)	−0.29282 (14)	0.0205 (6)
C56	0.6479 (3)	0.2201 (3)	−0.21548 (16)	0.0194 (7)
C57	0.4181 (3)	0.1686 (3)	−0.15277 (18)	0.0254 (8)
C58	0.4745 (3)	−0.0023 (3)	−0.24020 (18)	0.0234 (7)
C59	0.4771 (3)	0.2070 (3)	−0.29595 (17)	0.0214 (7)
N510	0.4026 (2)	0.1326 (2)	−0.23084 (14)	0.0216 (6)
H13	0.4639	0.7701	0.6196	0.038*
H13A	0.3687	0.6479	0.4172	0.019*
H23	0.7624	0.4392	0.2931	0.040*
H27	0.8768	−0.0913	0.0387	0.040*
H23A	0.6922	0.3208	0.0838	0.022*
H26	0.9570	0.0262	0.2478	0.022*
H31	0.6845	0.5110	0.7829	0.025*
H32A	0.6247	0.7290	0.8058	0.027*
H32B	0.5475	0.6536	0.8805	0.027*
H34A	0.6530	0.5979	1.0025	0.032*
H34B	0.7956	0.6416	1.0092	0.032*
H36A	0.6676	0.4298	0.9182	0.031*
H36B	0.8196	0.3620	0.8669	0.031*
H37A	0.9356	0.4817	0.7492	0.031*
H37B	0.8573	0.6257	0.7271	0.031*
H38A	0.8407	0.7878	0.8147	0.029*
H38B	0.9090	0.7546	0.8965	0.029*
H39A	1.0245	0.5400	0.9314	0.032*
H39B	1.0324	0.4298	0.8735	0.032*
H41	1.0501	0.1778	0.4365	0.023*
H42A	1.0236	0.3921	0.4587	0.027*
H42B	0.8852	0.3457	0.5062	0.027*
H44A	0.9855	0.2998	0.6977	0.025*
H44B	0.8636	0.2886	0.6480	0.025*
H46A	0.9108	0.1202	0.5585	0.026*
H46B	1.0665	0.0228	0.5454	0.026*
H47A	1.2799	0.0933	0.4725	0.028*
H47B	1.2657	0.2373	0.4381	0.028*
H48A	1.2122	0.4031	0.5302	0.028*
H48B	1.1970	0.3695	0.6260	0.028*
H49A	1.2494	0.0425	0.6151	0.029*
H49B	1.2183	0.1518	0.6774	0.029*
H51	0.5892	0.1646	−0.0969	0.023*
H52A	0.7518	−0.0123	−0.1561	0.027*
H52B	0.6034	−0.0477	−0.1146	0.027*
H54A	0.8020	0.0310	−0.2973	0.028*
H54B	0.6890	0.0231	−0.3540	0.028*
H56A	0.6019	0.3113	−0.2097	0.023*
H56B	0.7518	0.2062	−0.2126	0.023*
H57A	0.3693	0.1196	−0.1086	0.030*
H57B	0.3723	0.2597	−0.1466	0.030*
H58A	0.4272	−0.0536	−0.1969	0.028*
H58B	0.4620	−0.0270	−0.2932	0.028*
H59A	0.4647	0.1846	−0.3495	0.026*
H59B	0.4317	0.2983	−0.2903	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0302 (12)	0.0198 (12)	0.0207 (12)	−0.0043 (10)	−0.0113 (10)	0.0004 (10)
O12	0.0433 (14)	0.0198 (12)	0.0275 (13)	−0.0046 (11)	−0.0179 (11)	−0.0052 (10)
O13	0.0307 (13)	0.0205 (12)	0.0256 (13)	0.0013 (10)	−0.0121 (10)	−0.0071 (10)
O14	0.0286 (12)	0.0214 (12)	0.0231 (12)	0.0016 (10)	−0.0118 (10)	−0.0027 (10)
C11	0.0165 (15)	0.0216 (18)	0.0153 (17)	−0.0062 (14)	−0.0027 (13)	−0.0022 (14)
C12	0.0163 (16)	0.0201 (17)	0.0163 (18)	−0.0068 (14)	−0.0009 (13)	−0.0011 (14)
C13	0.0114 (14)	0.0176 (17)	0.0183 (17)	−0.0020 (13)	−0.0042 (12)	0.0016 (13)
C14	0.0205 (16)	0.0268 (19)	0.0185 (18)	−0.0128 (15)	−0.0044 (14)	−0.0001 (15)
C15	0.0210 (17)	0.0164 (17)	0.0175 (18)	−0.0071 (14)	−0.0011 (14)	−0.0025 (14)
O21	0.0278 (12)	0.0238 (12)	0.0230 (12)	0.0000 (10)	−0.0121 (10)	−0.0035 (10)
O22	0.0299 (12)	0.0222 (12)	0.0236 (13)	−0.0001 (10)	−0.0054 (10)	−0.0112 (10)
O23	0.0310 (13)	0.0219 (12)	0.0276 (14)	0.0005 (10)	−0.0114 (10)	−0.0064 (11)
O24	0.0377 (13)	0.0223 (12)	0.0223 (13)	0.0020 (10)	−0.0096 (11)	0.0005 (10)
O25	0.0294 (12)	0.0282 (13)	0.0236 (13)	−0.0038 (11)	−0.0119 (10)	−0.0016 (10)
O26	0.0486 (15)	0.0240 (13)	0.0310 (14)	−0.0029 (11)	−0.0224 (11)	−0.0062 (11)
O27	0.0350 (13)	0.0195 (12)	0.0260 (13)	−0.0002 (10)	−0.0154 (10)	−0.0044 (10)
O28	0.0309 (12)	0.0241 (12)	0.0223 (13)	−0.0001 (10)	−0.0106 (10)	−0.0009 (10)
C21	0.0155 (16)	0.0219 (18)	0.0192 (17)	−0.0113 (14)	−0.0002 (13)	−0.0015 (14)
C22	0.0136 (15)	0.0218 (17)	0.0161 (17)	−0.0074 (14)	−0.0018 (12)	−0.0003 (14)
C23	0.0174 (16)	0.0205 (17)	0.0171 (17)	−0.0058 (14)	−0.0029 (13)	0.0013 (14)
C24	0.0158 (15)	0.0211 (17)	0.0145 (17)	−0.0038 (14)	0.0006 (13)	−0.0042 (14)
C25	0.0174 (16)	0.0194 (17)	0.0175 (18)	−0.0078 (14)	0.0023 (13)	−0.0036 (14)
C26	0.0185 (16)	0.0192 (17)	0.0165 (17)	−0.0038 (14)	−0.0030 (13)	−0.0007 (14)
C27	0.0188 (16)	0.0218 (18)	0.0157 (17)	−0.0067 (15)	−0.0013 (13)	0.0014 (15)
C28	0.0209 (17)	0.0173 (17)	0.0180 (18)	−0.0023 (14)	0.0017 (14)	−0.0020 (15)
C29	0.0219 (17)	0.032 (2)	0.0166 (18)	−0.0144 (16)	−0.0025 (14)	0.0016 (16)
C210	0.0204 (17)	0.0254 (18)	0.0186 (18)	−0.0114 (15)	−0.0012 (14)	−0.0026 (15)
N31	0.0234 (14)	0.0176 (14)	0.0234 (15)	−0.0054 (12)	−0.0098 (11)	−0.0017 (12)
C32	0.0196 (16)	0.0196 (17)	0.0281 (19)	−0.0033 (14)	−0.0059 (14)	−0.0027 (14)
N33	0.0222 (13)	0.0219 (14)	0.0175 (14)	−0.0070 (12)	−0.0045 (11)	−0.0001 (11)
C34	0.0296 (18)	0.0278 (18)	0.0248 (19)	−0.0099 (15)	−0.0070 (14)	−0.0005 (15)
N35	0.0290 (15)	0.0224 (15)	0.0253 (16)	−0.0075 (12)	−0.0035 (12)	−0.0054 (12)
C36	0.0326 (18)	0.0165 (16)	0.0282 (19)	−0.0074 (15)	−0.0084 (15)	0.0040 (14)
C37	0.0259 (17)	0.0286 (19)	0.0249 (18)	−0.0098 (15)	−0.0037 (14)	−0.0035 (15)
C38	0.0224 (17)	0.0213 (17)	0.0292 (19)	−0.0064 (14)	−0.0029 (14)	−0.0087 (14)
C39	0.0254 (17)	0.0278 (18)	0.0292 (19)	−0.0062 (15)	−0.0092 (15)	−0.0018 (15)
N310	0.0250 (14)	0.0216 (14)	0.0245 (15)	−0.0044 (12)	−0.0081 (12)	−0.0056 (12)
N41	0.0206 (14)	0.0212 (14)	0.0166 (14)	−0.0038 (11)	−0.0055 (11)	−0.0035 (11)
C42	0.0231 (17)	0.0187 (17)	0.0260 (19)	−0.0018 (14)	−0.0071 (14)	−0.0031 (14)
N43	0.0221 (14)	0.0206 (14)	0.0219 (15)	−0.0064 (12)	−0.0041 (11)	−0.0034 (12)
C44	0.0219 (16)	0.0193 (17)	0.0207 (18)	−0.0035 (14)	−0.0022 (13)	−0.0038 (14)
N45	0.0213 (13)	0.0195 (14)	0.0222 (15)	−0.0016 (11)	−0.0065 (11)	−0.0065 (11)
C46	0.0279 (17)	0.0185 (17)	0.0225 (18)	−0.0096 (15)	−0.0081 (14)	0.0006 (14)
C47	0.0175 (16)	0.0267 (18)	0.0255 (19)	−0.0050 (14)	−0.0011 (14)	−0.0055 (15)
C48	0.0258 (17)	0.0241 (18)	0.0235 (18)	−0.0113 (15)	−0.0032 (14)	−0.0051 (14)
C49	0.0293 (18)	0.0240 (18)	0.0211 (18)	−0.0015 (15)	−0.0111 (14)	−0.0052 (15)
N410	0.0264 (14)	0.0261 (15)	0.0236 (15)	−0.0080 (13)	−0.0055 (12)	−0.0065 (12)
N51	0.0243 (14)	0.0217 (14)	0.0151 (14)	−0.0086 (12)	−0.0065 (11)	−0.0015 (11)
C52	0.0323 (18)	0.0179 (17)	0.0206 (18)	−0.0053 (14)	−0.0115 (14)	−0.0012 (14)
N53	0.0245 (14)	0.0186 (14)	0.0191 (14)	−0.0031 (11)	−0.0086 (11)	−0.0008 (11)
C54	0.0223 (17)	0.0234 (18)	0.0229 (18)	−0.0033 (14)	−0.0014 (14)	−0.0036 (14)
N55	0.0199 (13)	0.0214 (15)	0.0201 (15)	−0.0037 (12)	−0.0055 (11)	−0.0007 (12)
C56	0.0205 (16)	0.0215 (17)	0.0194 (18)	−0.0099 (14)	−0.0060 (13)	0.0016 (14)
C57	0.0187 (16)	0.0326 (19)	0.0259 (19)	−0.0094 (15)	0.0007 (14)	−0.0064 (15)
C58	0.0260 (17)	0.0249 (18)	0.0219 (18)	−0.0075 (15)	−0.0071 (14)	−0.0036 (14)
C59	0.0196 (16)	0.0195 (17)	0.0253 (18)	−0.0040 (14)	−0.0042 (13)	−0.0026 (14)
N510	0.0195 (13)	0.0265 (15)	0.0216 (15)	−0.0082 (12)	−0.0059 (11)	−0.0026 (12)

Geometric parameters (Å, º)

O11—C14	1.243 (3)	N33—C34	1.466 (4)
O12—C14	1.280 (3)	N33—C38	1.481 (3)
O13—C15	1.305 (3)	C34—N35	1.476 (4)
O14—C15	1.212 (3)	N35—C36	1.454 (3)
C11—C12	1.405 (4)	N35—C39	1.471 (3)
C11—C13^i	1.407 (4)	C37—N310	1.441 (3)
C11—C14	1.527 (4)	C38—N310	1.469 (4)
C12—C13	1.405 (4)	C39—N310	1.461 (4)
C12—C15	1.533 (4)	N41—C47	1.515 (3)
C13—C11^i	1.407 (4)	N41—C42	1.517 (3)
O21—C27	1.246 (3)	N41—C46	1.524 (3)
O22—C27	1.283 (3)	C42—N43	1.454 (3)
O23—C28	1.295 (3)	N43—C48	1.470 (3)
O24—C28	1.231 (3)	N43—C44	1.480 (3)
O25—C29	1.245 (3)	C44—N45	1.464 (3)
O26—C29	1.280 (3)	N45—C46	1.438 (3)
O27—C210	1.311 (3)	N45—C49	1.461 (3)
O28—C210	1.220 (3)	C47—N410	1.447 (3)
C21—C26	1.400 (4)	C48—N410	1.470 (4)
C21—C22	1.413 (4)	C49—N410	1.475 (3)
C21—C27	1.525 (4)	N51—C52	1.508 (3)
C22—C23	1.393 (4)	N51—C56	1.521 (3)
C22—C28	1.526 (4)	N51—C57	1.521 (3)
C23—C24	1.395 (4)	C52—N53	1.441 (3)
C24—C25	1.413 (4)	N53—C58	1.472 (3)
C24—C29	1.521 (4)	N53—C54	1.476 (3)
C25—C26	1.401 (4)	C54—N55	1.470 (4)
C25—C210	1.537 (4)	N55—C56	1.441 (3)
N31—C36	1.512 (3)	N55—C59	1.467 (3)
N31—C37	1.512 (3)	C57—N510	1.448 (3)
N31—C32	1.523 (3)	C58—N510	1.473 (4)
C32—N33	1.441 (3)	C59—N510	1.486 (3)
C12—C11—C13^i	118.0 (2)	C36—N35—C39	108.1 (2)
C12—C11—C14	128.6 (3)	C36—N35—C34	108.2 (2)
C13^i—C11—C14	113.5 (3)	C39—N35—C34	107.7 (2)
C11—C12—C13	117.4 (3)	N35—C36—N31	110.3 (2)
C11—C12—C15	129.7 (3)	N310—C37—N31	109.7 (2)
C13—C12—C15	112.8 (3)	N310—C38—N33	112.2 (2)
C12—C13—C11^i	124.6 (3)	N310—C39—N35	113.1 (2)
O11—C14—O12	121.2 (3)	C37—N310—C39	109.5 (2)
O11—C14—C11	118.8 (3)	C37—N310—C38	108.8 (2)
O12—C14—C11	120.0 (3)	C39—N310—C38	108.1 (2)
O14—C15—O13	120.6 (3)	C47—N41—C42	108.9 (2)
O14—C15—C12	120.2 (3)	C47—N41—C46	107.7 (2)
O13—C15—C12	119.3 (3)	C42—N41—C46	108.5 (2)
C26—C21—C22	117.8 (3)	N43—C42—N41	110.0 (2)
C26—C21—C27	114.4 (3)	C42—N43—C48	108.9 (2)
C22—C21—C27	127.7 (3)	C42—N43—C44	108.3 (2)
C23—C22—C21	117.0 (3)	C48—N43—C44	108.5 (2)
C23—C22—C28	113.2 (3)	N45—C44—N43	111.7 (2)
C21—C22—C28	129.7 (3)	C46—N45—C49	109.0 (2)
C22—C23—C24	125.5 (3)	C46—N45—C44	109.8 (2)
C23—C24—C25	117.6 (3)	C49—N45—C44	108.9 (2)
C23—C24—C29	113.5 (3)	N45—C46—N41	109.7 (2)
C25—C24—C29	128.8 (3)	N410—C47—N41	110.3 (2)
C26—C25—C24	117.2 (3)	N410—C48—N43	112.5 (2)
C26—C25—C210	113.5 (3)	N45—C49—N410	112.2 (2)
C24—C25—C210	129.3 (3)	C47—N410—C48	108.9 (2)
C21—C26—C25	124.8 (3)	C47—N410—C49	108.4 (2)
O21—C27—O22	121.9 (3)	C48—N410—C49	108.1 (2)
O21—C27—C21	118.2 (3)	C52—N51—C56	108.3 (2)
O22—C27—C21	119.9 (3)	C52—N51—C57	109.4 (2)
O24—C28—O23	120.5 (3)	C56—N51—C57	107.9 (2)
O24—C28—C22	119.6 (3)	N53—C52—N51	110.9 (2)
O23—C28—C22	119.9 (3)	C52—N53—C58	108.8 (2)
O25—C29—O26	122.2 (3)	C52—N53—C54	107.8 (2)
O25—C29—C24	118.0 (3)	C58—N53—C54	108.1 (2)
O26—C29—C24	119.8 (3)	N55—C54—N53	112.4 (2)
O28—C210—O27	120.9 (3)	C56—N55—C59	108.5 (2)
O28—C210—C25	119.7 (3)	C56—N55—C54	109.3 (2)
O27—C210—C25	119.3 (3)	C59—N55—C54	108.8 (2)
C36—N31—C37	109.2 (2)	N55—C56—N51	109.9 (2)
C36—N31—C32	108.8 (2)	N510—C57—N51	109.5 (2)
C37—N31—C32	107.9 (2)	N53—C58—N510	113.0 (2)
N33—C32—N31	109.9 (2)	N55—C59—N510	112.1 (2)
C32—N33—C34	109.5 (2)	C57—N510—C58	109.2 (2)
C32—N33—C38	108.3 (2)	C57—N510—C59	108.6 (2)
C34—N33—C38	107.6 (2)	C58—N510—C59	107.7 (2)
N33—C34—N35	113.1 (2)
C13^i—C11—C12—C13	−1.0 (4)	C32—N31—C37—N310	60.1 (3)
C14—C11—C12—C13	177.6 (2)	C32—N33—C38—N310	−60.1 (3)
C13^i—C11—C12—C15	177.8 (2)	C34—N33—C38—N310	58.3 (3)
C14—C11—C12—C15	−3.6 (4)	C36—N35—C39—N310	59.4 (3)
C11—C12—C13—C11^i	1.1 (4)	C34—N35—C39—N310	−57.3 (3)
C15—C12—C13—C11^i	−177.9 (2)	N31—C37—N310—C39	58.0 (3)
C12—C11—C14—O11	177.6 (3)	N31—C37—N310—C38	−59.9 (3)
C13^i—C11—C14—O11	−3.7 (3)	N35—C39—N310—C37	−60.1 (3)
C12—C11—C14—O12	−3.3 (4)	N35—C39—N310—C38	58.3 (3)
C13^i—C11—C14—O12	175.3 (2)	N33—C38—N310—C37	60.4 (3)
C11—C12—C15—O14	−173.2 (2)	N33—C38—N310—C39	−58.5 (3)
C13—C12—C15—O14	5.6 (4)	C47—N41—C42—N43	−58.1 (3)
C11—C12—C15—O13	6.7 (4)	C46—N41—C42—N43	58.9 (3)
C13—C12—C15—O13	−174.5 (2)	N41—C42—N43—C48	58.4 (3)
C26—C21—C22—C23	−2.5 (3)	N41—C42—N43—C44	−59.4 (3)
C27—C21—C22—C23	174.0 (2)	C42—N43—C44—N45	60.6 (3)
C26—C21—C22—C28	177.8 (2)	C48—N43—C44—N45	−57.5 (3)
C27—C21—C22—C28	−5.7 (4)	N43—C44—N45—C46	−61.0 (3)
C21—C22—C23—C24	4.0 (4)	N43—C44—N45—C49	58.3 (3)
C28—C22—C23—C24	−176.2 (2)	C49—N45—C46—N41	−60.1 (3)
C22—C23—C24—C25	−3.4 (4)	C44—N45—C46—N41	59.1 (3)
C22—C23—C24—C29	173.8 (2)	C47—N41—C46—N45	59.5 (3)
C23—C24—C25—C26	1.3 (4)	C42—N41—C46—N45	−58.2 (3)
C29—C24—C25—C26	−175.5 (2)	C42—N41—C47—N410	58.2 (3)
C23—C24—C25—C210	−176.8 (2)	C46—N41—C47—N410	−59.3 (3)
C29—C24—C25—C210	6.4 (4)	C42—N43—C48—N410	−60.2 (3)
C22—C21—C26—C25	0.7 (4)	C44—N43—C48—N410	57.5 (3)
C27—C21—C26—C25	−176.2 (2)	C46—N45—C49—N410	61.0 (3)
C24—C25—C26—C21	−0.1 (4)	C44—N45—C49—N410	−58.8 (3)
C210—C25—C26—C21	178.3 (2)	N41—C47—N410—C48	−58.4 (3)
C26—C21—C27—O21	9.6 (3)	N41—C47—N410—C49	59.0 (3)
C22—C21—C27—O21	−166.9 (2)	N43—C48—N410—C47	60.2 (3)
C26—C21—C27—O22	−171.5 (2)	N43—C48—N410—C49	−57.5 (3)
C22—C21—C27—O22	11.9 (4)	N45—C49—N410—C47	−60.1 (3)
C23—C22—C28—O24	3.3 (4)	N45—C49—N410—C48	57.9 (3)
C21—C22—C28—O24	−177.0 (2)	C56—N51—C52—N53	−59.4 (3)
C23—C22—C28—O23	−176.4 (2)	C57—N51—C52—N53	58.1 (3)
C21—C22—C28—O23	3.3 (4)	N51—C52—N53—C58	−57.4 (3)
C23—C24—C29—O25	−6.6 (3)	N51—C52—N53—C54	59.5 (3)
C25—C24—C29—O25	170.3 (2)	C52—N53—C54—N55	−60.2 (3)
C23—C24—C29—O26	175.8 (2)	C58—N53—C54—N55	57.2 (3)
C25—C24—C29—O26	−7.3 (4)	N53—C54—N55—C56	60.3 (3)
C26—C25—C210—O28	−1.1 (3)	N53—C54—N55—C59	−57.9 (3)
C24—C25—C210—O28	177.1 (3)	C59—N55—C56—N51	60.2 (3)
C26—C25—C210—O27	177.6 (2)	C54—N55—C56—N51	−58.2 (3)
C24—C25—C210—O27	−4.2 (4)	C52—N51—C56—N55	58.0 (3)
C36—N31—C32—N33	58.2 (3)	C57—N51—C56—N55	−60.4 (3)
C37—N31—C32—N33	−60.2 (3)	C52—N51—C57—N510	−57.9 (3)
N31—C32—N33—C34	−57.8 (3)	C56—N51—C57—N510	59.8 (3)
N31—C32—N33—C38	59.3 (3)	C52—N53—C58—N510	58.9 (3)
C32—N33—C34—N35	59.7 (3)	C54—N53—C58—N510	−57.8 (3)
C38—N33—C34—N35	−57.9 (3)	C56—N55—C59—N510	−60.6 (3)
N33—C34—N35—C36	−59.4 (3)	C54—N55—C59—N510	58.2 (3)
N33—C34—N35—C39	57.3 (3)	N51—C57—N510—C58	58.0 (3)
C39—N35—C36—N31	−57.9 (3)	N51—C57—N510—C59	−59.2 (3)
C34—N35—C36—N31	58.5 (3)	N53—C58—N510—C57	−59.8 (3)
C37—N31—C36—N35	58.6 (3)	N53—C58—N510—C59	58.0 (3)
C32—N31—C36—N35	−59.0 (3)	N55—C59—N510—C57	60.4 (3)
C36—N31—C37—N310	−58.0 (3)	N55—C59—N510—C58	−57.8 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O12	0.84	1.57	2.409 (3)	178
O23—H23···O22	0.84	1.57	2.404 (3)	175
O27—H27···O26	0.84	1.56	2.402 (3)	178
N31—H31···O11	0.93	1.85	2.727 (3)	157
N41—H41···O21	0.93	1.82	2.750 (3)	174
N51—H51···O25	0.93	1.79	2.709 (3)	168
C46—H46A···O14^i	0.99	2.28	3.218 (4)	157
C56—H56B···O28^ii	0.99	2.30	3.273 (4)	168

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