X-ray studies on crystalline complexes involving amino acids and peptides. XXXIX. Crystal structures of malonic acid complexes of DL- and L-histidine. Preservation of aggregation pattern on reversal of chirality

The malonic acid complexes of DL- and L-histidine are made up of zwitterionic positively charged histidinium ions and semimalonate (hydrogen malonate) ions. They crystallise in space groups P2₁/n and P2₁, respectively, with nearly the same unit-cell parameters. The molecules aggregate in the two complexes in a remarkably similar manner. The two sets of crystallographically independent molecules are related by a pseudo-glide plane. This pseudo-symmetry is almost exact except in the case of the α-carboxylate group and, to some extent, the α-C and the α-N atoms. Preservation of the aggregation pattern to such an extent on the reversal of chirality of half the amino-acid molecules is observed for the first time in amino-acid complexes. This is achieved at the cost of considerable conformational strain in one of the two histidinium ions in the L-histidine complex.

Computing details

For both compounds, data collection: CAD4; cell refinement: CAD4; data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP III; software used to prepare material for publication: MSWORD.

Figures

(DL)

Crystal data

<C9H13N3O6>	F(000) = 544
Mr = 259.1	Dx = 1.533 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
a = 5.3643 (10) Å	Cell parameters from 25 reflections
b = 25.3538 (6) Å	θ = 18–30°
c = 8.3043 (14) Å	µ = 1.13 mm^−1
β = 96.202 (15)°	T = 293 K
V = 1122.8 (3) Å^3	Platy, colourless
Z = 4	0.30 × 0.08 × 0.05 mm

Data collection

CAD4 diffractometer	1760 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 69.9°, θmin = 3.5°
ω–2θ scans	h = 0→6
Absorption correction: empirical North et al .. 1968	k = 0→30
Tmin = 0.904, Tmax = 0.999	l = −10→10
2364 measured reflections	2 standard reflections every 60 min
2135 independent reflections

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0514P)^2 + 0.4527P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2135 reflections	Δρmax = 0.24 e Å^−3
169 parameters	Δρmin = −0.20 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: 0.0025 (5)

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
N1	0.5439 (2)	0.29043 (5)	0.52630 (17)	0.0266 (3)
H1C	0.5899	0.3199	0.5798	0.040*
H1B	0.3798	0.2856	0.5271	0.040*
H1A	0.5797	0.2931	0.4244	0.040*
O1	1.0343 (2)	0.29041 (5)	0.52482 (17)	0.0427 (4)
O2	1.1043 (2)	0.22355 (5)	0.69650 (15)	0.0370 (3)
C1	0.9647 (3)	0.25382 (6)	0.61043 (19)	0.0261 (3)
C2	0.6814 (3)	0.24489 (6)	0.60554 (19)	0.0242 (3)
H2	0.6379	0.2417	0.7167	0.029*
C3	0.6030 (3)	0.19410 (7)	0.5128 (2)	0.0313 (4)
H3A	0.4215	0.1924	0.4949	0.038*
H3B	0.6667	0.1949	0.4079	0.038*
C4	0.6992 (3)	0.14633 (6)	0.6025 (2)	0.0313 (4)
N5	0.8803 (3)	0.11401 (6)	0.55008 (19)	0.0359 (4)
H5	0.9476	0.1180	0.4615	0.043*
C6	0.9346 (4)	0.07596 (8)	0.6566 (3)	0.0449 (5)
H6	1.0507	0.0491	0.6484	0.054*
N7	0.7957 (3)	0.08264 (6)	0.7767 (2)	0.0456 (4)
H7	0.7981	0.0629	0.8612	0.055*
C8	0.6472 (4)	0.12603 (7)	0.7449 (2)	0.0399 (5)
H8	0.5310	0.1392	0.8099	0.048*
O31	0.6264 (3)	0.00988 (6)	0.29379 (19)	0.0541 (4)
H31	0.477 (6)	0.0265 (12)	0.352 (4)	0.093 (10)*
O32	0.7722 (3)	0.02915 (6)	0.06424 (18)	0.0506 (4)
C33	0.6247 (3)	0.03763 (7)	0.1635 (2)	0.0357 (4)
C34	0.4283 (4)	0.08052 (7)	0.1375 (2)	0.0388 (4)
H34A	0.3209	0.0724	0.0391	0.047*
H34B	0.5133	0.1134	0.1190	0.047*
C35	0.2624 (3)	0.08971 (7)	0.2711 (2)	0.0344 (4)
O36	0.2827 (3)	0.05827 (6)	0.38959 (17)	0.0542 (4)
O37	0.1150 (3)	0.12762 (5)	0.25967 (17)	0.0443 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0182 (6)	0.0277 (7)	0.0344 (7)	−0.0010 (5)	0.0055 (5)	−0.0033 (6)
O1	0.0208 (6)	0.0483 (8)	0.0596 (8)	−0.0042 (5)	0.0067 (6)	0.0199 (7)
O2	0.0237 (6)	0.0487 (7)	0.0384 (7)	0.0039 (5)	0.0028 (5)	0.0092 (6)
C1	0.0187 (7)	0.0315 (8)	0.0287 (8)	−0.0012 (6)	0.0057 (6)	−0.0041 (7)
C2	0.0189 (7)	0.0267 (8)	0.0277 (8)	−0.0003 (6)	0.0060 (6)	−0.0008 (6)
C3	0.0261 (8)	0.0299 (8)	0.0380 (9)	−0.0022 (7)	0.0035 (7)	−0.0045 (7)
C4	0.0282 (8)	0.0271 (8)	0.0399 (9)	−0.0025 (7)	0.0098 (7)	−0.0057 (7)
N5	0.0376 (8)	0.0323 (8)	0.0402 (8)	0.0043 (6)	0.0153 (7)	−0.0008 (6)
C6	0.0499 (12)	0.0332 (9)	0.0534 (12)	0.0074 (8)	0.0142 (10)	0.0020 (9)
N7	0.0575 (11)	0.0351 (8)	0.0468 (10)	−0.0006 (7)	0.0175 (8)	0.0080 (7)
C8	0.0443 (11)	0.0334 (9)	0.0456 (10)	−0.0012 (8)	0.0206 (9)	−0.0015 (8)
O31	0.0577 (9)	0.0553 (9)	0.0529 (9)	0.0271 (7)	0.0221 (7)	0.0222 (7)
O32	0.0521 (9)	0.0520 (9)	0.0521 (9)	0.0132 (7)	0.0255 (7)	0.0042 (7)
C33	0.0385 (10)	0.0327 (9)	0.0369 (9)	0.0025 (7)	0.0095 (8)	0.0022 (7)
C34	0.0505 (11)	0.0340 (9)	0.0344 (9)	0.0093 (8)	0.0158 (8)	0.0070 (7)
C35	0.0376 (9)	0.0325 (9)	0.0342 (9)	0.0028 (8)	0.0096 (7)	0.0014 (7)
O36	0.0641 (10)	0.0589 (9)	0.0447 (8)	0.0240 (8)	0.0285 (7)	0.0214 (7)
O37	0.0499 (8)	0.0388 (7)	0.0472 (8)	0.0149 (6)	0.0193 (6)	0.0082 (6)

Geometric parameters (Å, º)

N1—C2	1.485 (2)	C6—N7	1.319 (3)
O1—C1	1.250 (2)	N7—C8	1.367 (3)
O2—C1	1.243 (2)	O31—C33	1.289 (2)
C1—C2	1.533 (2)	O32—C33	1.222 (2)
C2—C3	1.536 (2)	C33—C34	1.513 (2)
C3—C4	1.485 (2)	C34—C35	1.513 (2)
C4—C8	1.346 (3)	C35—O37	1.242 (2)
C4—N5	1.377 (2)	C35—O36	1.262 (2)
N5—C6	1.320 (3)
O2—C1—O1	125.94 (15)	N7—C6—N5	108.11 (17)
O2—C1—C2	117.26 (14)	C6—N7—C8	108.80 (16)
O1—C1—C2	116.78 (14)	C4—C8—N7	107.81 (16)
N1—C2—C1	109.91 (12)	O32—C33—O31	121.57 (17)
N1—C2—C3	109.51 (12)	O32—C33—C34	121.44 (16)
C1—C2—C3	110.74 (13)	O31—C33—C34	116.97 (16)
C4—C3—C2	111.78 (14)	C33—C34—C35	117.49 (15)
C8—C4—N5	105.69 (15)	O37—C35—O36	123.28 (17)
C8—C4—C3	131.20 (16)	O37—C35—C34	118.91 (16)
N5—C4—C3	123.07 (15)	O36—C35—C34	117.80 (16)
C6—N5—C4	109.59 (15)
O2—C1—C2—N1	168.30 (14)	O32—C33—C34—C35	−177.13 (19)
O1—C1—C2—N1	−13.0 (2)	O31—C33—C34—C35	4.0 (3)
O2—C1—C2—C3	−70.58 (18)	C33—C34—C35—O37	173.65 (17)
O1—C1—C2—C3	108.15 (17)	C33—C34—C35—O36	−6.0 (3)
N1—C2—C3—C4	−169.85 (12)	H1A—N1—C2—H2	−178.7
C1—C2—C3—C4	68.79 (17)	H1B—N1—C2—C1	−177.9
C2—C3—C4—C8	65.3 (2)	H1C—N1—C2—C3	−179.8
C2—C3—C4—N5	−111.96 (18)	O1—C1—C2—N1	−13.0 (2)
C8—C4—N5—C6	−0.1 (2)	O2—C1—C2—N1	168.30 (14)
C3—C4—N5—C6	177.76 (17)	O32—C33—C34—C35	−177.13 (19)
C4—N5—C6—N7	−0.2 (2)	O37—C35—C34—C33	173.65 (17)
N5—C6—N7—C8	0.5 (2)	N1—C2—C3—C4	−169.85 (12)
N5—C4—C8—N7	0.3 (2)	C2—C3—C4—N5	−111.96 (18)
C3—C4—C8—N7	−177.24 (17)	O31—C33—C34—C35	4.0 (3)
C6—N7—C8—C4	−0.5 (2)	O36—C35—C34—C33	−6.0 (3)

(L)

Crystal data

<C9H13N3O6>	F(000) = 544
Mr = 259.1	Dx = 1.547 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54180 Å
a = 5.3287 (15) Å	Cell parameters from 25 reflections
b = 25.534 (3) Å	θ = 18–30°
c = 8.2421 (15) Å	µ = 1.14 mm^−1
β = 97.00 (2)°	T = 293 K
V = 1113.1 (4) Å^3	Platy, colourless
Z = 4	0.28 × 0.04 × 0.03 mm

Data collection

CAD4 diffractometer	1657 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 69.9°, θmin = 3.5°
ω–2θ scans	h = −6→6
Absorption correction: empirical North et al .. 1968	k = −19→31
Tmin = 0.941, Tmax = 0.997	l = −10→9
2376 measured reflections	2 standard reflections every 60 min
2147 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0641P)^2 + 0.6228P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.137	(Δ/σ)max = 0.003
S = 1.03	Δρmax = 0.23 e Å^−3
2147 reflections	Δρmin = −0.21 e Å^−3
336 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0033 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (5)

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
N1	0.8157 (8)	0.2906 (2)	0.7721 (5)	0.0259 (10)
H1C	0.8642	0.3196	0.8274	0.039*
H1B	0.6492	0.2867	0.7690	0.039*
H1A	0.8557	0.2932	0.6707	0.039*
O1	1.3101 (8)	0.2872 (2)	0.7789 (5)	0.0432 (12)
O2	1.3675 (8)	0.22012 (19)	0.9527 (5)	0.0350 (10)
C1	1.2317 (9)	0.2515 (2)	0.8634 (6)	0.0260 (11)
C2	0.9461 (10)	0.2445 (2)	0.8543 (6)	0.0239 (11)
H2	0.9006	0.2422	0.9658	0.029*
C3	0.8572 (12)	0.1941 (3)	0.7605 (8)	0.0315 (15)
H3A	0.6738	0.1932	0.7441	0.038*
H3B	0.9165	0.1945	0.6538	0.038*
C4	0.9529 (12)	0.1464 (3)	0.8502 (8)	0.0291 (14)
N5	1.1303 (10)	0.1140 (2)	0.7975 (6)	0.0355 (14)
H5	1.1960	0.1178	0.7080	0.043*
C6	1.1862 (15)	0.0758 (3)	0.9055 (9)	0.0408 (18)
H6	1.3026	0.0491	0.8981	0.049*
N7	1.0454 (13)	0.0829 (3)	1.0256 (8)	0.0449 (16)
H7	1.0451	0.0630	1.1098	0.054*
C8	0.9005 (15)	0.1269 (3)	0.9946 (10)	0.0414 (18)
H8	0.7872	0.1407	1.0606	0.050*
N11	0.4090 (9)	0.2092 (2)	0.2890 (6)	0.0273 (11)
H11A	0.3444	0.2059	0.1848	0.041*
H11C	0.3649	0.1816	0.3454	0.041*
H11B	0.5767	0.2109	0.2959	0.041*
O11	−0.0770 (8)	0.2107 (2)	0.3078 (6)	0.0477 (12)
O12	−0.0761 (8)	0.2866 (2)	0.4406 (5)	0.0385 (11)
C11	0.0274 (10)	0.2513 (2)	0.3690 (6)	0.0273 (11)
C12	0.3113 (10)	0.2573 (2)	0.3570 (6)	0.0260 (12)
H12	0.3990	0.2624	0.4674	0.031*
C13	0.3683 (12)	0.3041 (2)	0.2522 (7)	0.0286 (14)
H13A	0.4997	0.2943	0.1864	0.034*
H13B	0.2178	0.3124	0.1781	0.034*
C14	0.4504 (12)	0.3520 (3)	0.3466 (7)	0.0272 (14)
N15	0.6256 (9)	0.3860 (2)	0.2930 (6)	0.0301 (12)
H15	0.6926	0.3828	0.2037	0.036*
C16	0.6729 (13)	0.4239 (3)	0.4014 (9)	0.0387 (17)
H16	0.7823	0.4518	0.3927	0.046*
N17	0.5408 (12)	0.4158 (2)	0.5229 (7)	0.0400 (14)
H17	0.5437	0.4350	0.6087	0.048*
C18	0.3964 (13)	0.3714 (3)	0.4910 (9)	0.0361 (16)
H18	0.2830	0.3573	0.5566	0.043*
O21	0.8808 (10)	0.0087 (2)	0.5430 (6)	0.0498 (14)
H21	0.729 (18)	0.029 (4)	0.600 (11)	0.09 (3)*
O22	1.0257 (10)	0.0296 (2)	0.3138 (6)	0.0486 (14)
C23	0.8794 (13)	0.0379 (3)	0.4131 (8)	0.0333 (15)
C24	0.6886 (14)	0.0810 (3)	0.3930 (8)	0.0347 (16)
H24A	0.5829	0.0755	0.2900	0.042*
H24B	0.7787	0.1137	0.3834	0.042*
C25	0.5158 (14)	0.0882 (3)	0.5245 (8)	0.0341 (16)
O26	0.5315 (11)	0.0557 (2)	0.6388 (6)	0.0497 (14)
O27	0.3666 (10)	0.12613 (19)	0.5147 (6)	0.0421 (13)
O31	0.3715 (10)	0.4914 (2)	0.0365 (6)	0.0477 (14)
H31	0.217 (12)	0.484 (2)	0.081 (7)	0.023 (15)*
O32	0.5215 (10)	0.4714 (2)	−0.1917 (6)	0.0464 (13)
C33	0.3733 (14)	0.4630 (3)	−0.0925 (9)	0.0380 (16)
C34	0.1796 (14)	0.4190 (3)	−0.1179 (8)	0.0383 (17)
H34A	0.0712	0.4257	−0.2192	0.046*
H34B	0.2694	0.3866	−0.1321	0.046*
C35	0.0134 (13)	0.4106 (3)	0.0151 (8)	0.0325 (15)
O36	0.0275 (10)	0.4429 (2)	0.1333 (6)	0.0517 (15)
O37	−0.1326 (9)	0.3728 (2)	0.0035 (7)	0.0427 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.020 (2)	0.028 (3)	0.030 (2)	0.001 (2)	0.0032 (18)	−0.001 (2)
O1	0.025 (2)	0.051 (3)	0.053 (3)	−0.007 (2)	0.0040 (19)	0.023 (2)
O2	0.030 (2)	0.047 (3)	0.027 (2)	0.005 (2)	0.0016 (17)	0.0043 (19)
C1	0.024 (3)	0.031 (3)	0.022 (3)	0.002 (2)	−0.002 (2)	−0.004 (2)
C2	0.027 (3)	0.027 (3)	0.019 (2)	0.000 (2)	0.0050 (19)	−0.001 (2)
C3	0.031 (3)	0.031 (4)	0.033 (3)	−0.003 (3)	0.006 (3)	−0.008 (3)
C4	0.030 (3)	0.026 (3)	0.035 (3)	0.002 (3)	0.015 (3)	−0.005 (3)
N5	0.041 (3)	0.037 (4)	0.032 (3)	0.002 (2)	0.020 (3)	−0.002 (2)
C6	0.052 (5)	0.025 (4)	0.048 (4)	0.011 (3)	0.015 (3)	0.012 (3)
N7	0.059 (4)	0.036 (4)	0.042 (3)	−0.001 (3)	0.014 (3)	0.010 (3)
C8	0.052 (5)	0.032 (4)	0.045 (4)	0.006 (3)	0.026 (3)	0.000 (3)
N11	0.026 (3)	0.027 (3)	0.029 (2)	0.000 (2)	0.0060 (19)	0.003 (2)
O11	0.026 (2)	0.044 (3)	0.075 (3)	−0.007 (2)	0.013 (2)	−0.020 (3)
O12	0.037 (2)	0.046 (3)	0.034 (2)	0.013 (2)	0.0113 (18)	−0.005 (2)
C11	0.024 (3)	0.036 (3)	0.022 (2)	0.000 (3)	0.004 (2)	0.008 (2)
C12	0.030 (3)	0.022 (3)	0.024 (3)	0.003 (2)	0.000 (2)	−0.002 (2)
C13	0.036 (3)	0.025 (3)	0.026 (3)	−0.002 (2)	0.006 (2)	−0.003 (3)
C14	0.030 (3)	0.027 (3)	0.026 (3)	−0.002 (3)	0.009 (2)	0.002 (2)
N15	0.032 (3)	0.027 (3)	0.034 (3)	−0.004 (2)	0.012 (2)	0.003 (2)
C16	0.038 (4)	0.036 (4)	0.042 (4)	−0.012 (3)	0.005 (3)	0.000 (3)
N17	0.052 (4)	0.030 (3)	0.041 (3)	−0.007 (3)	0.016 (3)	−0.009 (3)
C18	0.048 (4)	0.030 (4)	0.033 (4)	−0.004 (3)	0.012 (3)	0.002 (3)
O21	0.061 (3)	0.047 (3)	0.044 (3)	0.027 (3)	0.015 (3)	0.021 (3)
O22	0.055 (3)	0.052 (3)	0.044 (3)	0.014 (3)	0.028 (3)	0.009 (3)
C23	0.042 (4)	0.027 (4)	0.031 (3)	0.004 (3)	0.001 (3)	0.007 (3)
C24	0.045 (4)	0.025 (3)	0.037 (4)	0.009 (3)	0.016 (3)	0.008 (3)
C25	0.044 (4)	0.033 (4)	0.027 (3)	0.002 (3)	0.008 (3)	0.000 (3)
O26	0.071 (4)	0.047 (3)	0.036 (3)	0.016 (3)	0.028 (2)	0.018 (2)
O27	0.055 (3)	0.033 (3)	0.043 (3)	0.011 (2)	0.023 (2)	0.008 (2)
O31	0.052 (3)	0.050 (3)	0.045 (3)	−0.022 (3)	0.022 (2)	−0.017 (3)
O32	0.050 (3)	0.046 (3)	0.046 (3)	−0.013 (2)	0.019 (2)	−0.001 (2)
C33	0.044 (4)	0.038 (4)	0.034 (3)	0.003 (3)	0.008 (3)	0.002 (3)
C34	0.044 (4)	0.042 (4)	0.030 (4)	−0.011 (3)	0.012 (3)	−0.002 (3)
C35	0.039 (4)	0.030 (4)	0.030 (3)	0.002 (3)	0.009 (3)	−0.004 (3)
O36	0.064 (3)	0.056 (4)	0.038 (3)	−0.022 (3)	0.022 (2)	−0.019 (3)
O37	0.045 (3)	0.036 (3)	0.048 (3)	−0.014 (2)	0.013 (2)	−0.008 (2)

Geometric parameters (Å, º)

N1—C2	1.487 (7)	C14—C18	1.352 (9)
O1—C1	1.250 (7)	C14—N15	1.385 (8)
O2—C1	1.256 (7)	N15—C16	1.320 (9)
C1—C2	1.525 (7)	C16—N17	1.309 (9)
C2—C3	1.547 (8)	N17—C18	1.377 (9)
C3—C4	1.483 (9)	O21—C23	1.305 (7)
C4—C8	1.351 (10)	O22—C23	1.216 (8)
C4—N5	1.366 (8)	C23—C24	1.494 (9)
N5—C6	1.330 (9)	C24—C25	1.516 (9)
C6—N7	1.325 (10)	C25—O26	1.250 (8)
N7—C8	1.369 (10)	C25—O27	1.250 (9)
N11—C12	1.471 (7)	O31—C33	1.288 (8)
O11—C11	1.254 (7)	O32—C33	1.223 (8)
O12—C11	1.243 (7)	C33—C34	1.524 (10)
C11—C12	1.535 (7)	C34—C35	1.506 (9)
C12—C13	1.527 (8)	C35—O37	1.236 (8)
C13—C14	1.486 (8)	C35—O36	1.271 (8)
O1—C1—O2	125.8 (5)	C18—C14—N15	106.0 (6)
O1—C1—C2	117.2 (5)	C18—C14—C13	132.9 (6)
O2—C1—C2	117.0 (5)	N15—C14—C13	121.0 (5)
N1—C2—C1	109.8 (4)	C16—N15—C14	108.9 (6)
N1—C2—C3	109.5 (4)	N17—C16—N15	109.0 (6)
C1—C2—C3	111.4 (5)	C16—N17—C18	108.9 (6)
C4—C3—C2	111.7 (5)	C14—C18—N17	107.2 (6)
C8—C4—N5	106.4 (6)	O22—C23—O21	120.8 (6)
C8—C4—C3	130.3 (6)	O22—C23—C24	122.5 (6)
N5—C4—C3	123.2 (5)	O21—C23—C24	116.7 (6)
C6—N5—C4	109.8 (6)	C23—C24—C25	118.3 (6)
N7—C6—N5	107.4 (6)	O26—C25—O27	123.1 (7)
C6—N7—C8	109.2 (6)	O26—C25—C24	117.9 (6)
C4—C8—N7	107.2 (6)	O27—C25—C24	118.9 (6)
O12—C11—O11	126.2 (5)	O32—C33—O31	121.6 (7)
O12—C11—C12	117.2 (5)	O32—C33—C34	121.2 (7)
O11—C11—C12	116.6 (5)	O31—C33—C34	117.1 (6)
N11—C12—C13	109.6 (4)	C35—C34—C33	116.9 (6)
N11—C12—C11	109.8 (5)	O37—C35—O36	122.9 (6)
C13—C12—C11	112.3 (5)	O37—C35—C34	118.3 (6)
C14—C13—C12	114.5 (5)	O36—C35—C34	118.8 (6)
O1—C1—C2—N1	−12.7 (6)	C13—C14—C18—N17	176.2 (7)
O2—C1—C2—N1	168.6 (4)	C16—N17—C18—C14	1.4 (8)
O1—C1—C2—C3	108.7 (6)	O22—C23—C24—C25	−179.8 (7)
O2—C1—C2—C3	−70.0 (6)	O21—C23—C24—C25	1.1 (10)
N1—C2—C3—C4	−171.8 (5)	C23—C24—C25—O26	−4.1 (10)
C1—C2—C3—C4	66.6 (6)	C23—C24—C25—O27	175.4 (6)
C2—C3—C4—C8	66.0 (9)	O32—C33—C34—C35	177.5 (7)
C2—C3—C4—N5	−111.0 (7)	O31—C33—C34—C35	−3.4 (10)
C8—C4—N5—C6	−0.1 (8)	C33—C34—C35—O37	−174.8 (7)
C3—C4—N5—C6	177.6 (6)	C33—C34—C35—O36	5.8 (10)
C4—N5—C6—N7	0.7 (9)	H1A—N1—C2—H2	−180.0
N5—C6—N7—C8	−1.0 (9)	H1B—N1—C2—C1	−178.8
N5—C4—C8—N7	−0.5 (8)	H1C—N1—C2—C3	178.7
C3—C4—C8—N7	−177.9 (7)	H11A—N11—C12—H12	−173.5
C6—N7—C8—C4	0.9 (9)	H11B—N11—C12—C11	−171.7
O12—C11—C12—N11	172.4 (5)	H11C—N11—C12—C13	−175.5
O11—C11—C12—N11	−6.4 (7)	O1—C1—C2—N1	−12.7 (6)
O12—C11—C12—C13	−65.4 (6)	O11—C11—C12—N11	−6.4 (7)
O11—C11—C12—C13	115.8 (6)	O2—C1—C2—N1	168.6 (4)
N11—C12—C13—C14	−139.5 (5)	O12—C11—C12—N11	172.4 (5)
C11—C12—C13—C14	98.2 (6)	O21—C23—C24—C25	1.1 (10)
C12—C13—C14—C18	−30.9 (10)	O31—C33—C34—C35	−3.4 (10)
C12—C13—C14—N15	145.8 (6)	O22—C23—C24—C25	−179.8 (7)
C18—C14—N15—C16	−0.1 (8)	O32—C33—C34—C35	177.5 (7)
C13—C14—N15—C16	−177.5 (6)	O26—C25—C24—C23	−4.1 (10)
C14—N15—C16—N17	1.0 (8)	O36—C35—C34—C33	5.8 (10)
N15—C16—N17—C18	−1.5 (9)	O27—C25—C24—C23	175.4 (7)
N15—C14—C18—N17	−0.8 (8)	O37—C35—C34—C33	−174.8 (7)