The formation of the salt and neutral molecule cocrystal from equimolar solution of heli­amine and bi­cyclo­[2.2.1]hept-5-ene-endo-2,3-di­carb­oxy­lic acid

The possible interaction of 6,7-di­meth­oxy-1,2,3,4-tetra­hydro­iso­quinoline (heli­amine) with bi­cyclo­[2.2.1]hept-5-ene-endo-2,3-di­carb­oxy­lic acid anhydride has been studied. Instead of the reaction with heli­amine, the acid anhydride was hydrolyzed into the appropriate di­carb­oxy­lic acid. An equimolar mixture of unreacted heli­amine and in-situ-generated di­carb­oxy­lic acid crystallized in space group P2₁/c. The comprehensive study of the obtained crystals shows that the peculiarities of the crystallization process lead to the formation of the salt-cocrystal structure where the dianion interacts simultaneously with two cations forming a chain as the primary structural motif. The neutral molecules of di­carb­oxy­lic acid link the dianions of the neighbouring chains, forming a layer as the secondary structural motif. As a result, the stronger hydrogen bonds formed by the neutral molecules play a secondary role in the crystal structure formation.

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58); program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2014); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016).

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Crystal data

2(C11H16NO2)·C9H8O4·C9H10O4	F(000) = 1600
Mr = 750.82	Dx = 1.387 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.078 (2) Å	Cell parameters from 808 reflections
b = 30.555 (2) Å	θ = 3.4–18.8°
c = 10.2038 (9) Å	µ = 0.10 mm^−1
β = 107.272 (12)°	T = 100 K
V = 3595.8 (7) Å^3	Plate, colourless
Z = 4	0.30 × 0.20 × 0.05 mm

Data collection

Xcalibur, Sapphire3 diffractometer	6231 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5252 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	Rint = 0.045
ω–scan	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −13→14
Tmin = 0.330, Tmax = 1.000	k = −36→34
17733 measured reflections	l = −10→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0613P)^2 + 4.0263P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
6231 reflections	Δρmax = 0.40 e Å^−3
515 parameters	Δρmin = −0.36 e Å^−3

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
O1A	0.84173 (16)	0.71921 (6)	0.27228 (18)	0.0248 (4)
O2A	0.98432 (16)	0.72673 (6)	0.12790 (19)	0.0274 (4)
N2A	1.0273 (2)	0.52735 (8)	0.1900 (2)	0.0306 (6)
H1NA	0.947 (3)	0.5239 (13)	0.116 (4)	0.060 (11)*
H2NA	1.076 (3)	0.5040 (13)	0.186 (4)	0.052 (10)*
C1A	1.0808 (2)	0.56933 (9)	0.1751 (3)	0.0254 (6)
H1AB	1.089975	0.571217	0.081976	0.030*
H1AA	1.159020	0.570873	0.242356	0.030*
C3A	0.9967 (2)	0.52500 (9)	0.3231 (3)	0.0260 (6)
H3AB	0.966603	0.495522	0.334118	0.031*
H3AA	1.066653	0.530416	0.401557	0.031*
C4A	0.9065 (3)	0.55887 (9)	0.3204 (4)	0.0352 (7)
H4AB	0.899307	0.562011	0.414128	0.042*
H4AA	0.830875	0.548450	0.260089	0.042*
C4AA	0.9316 (2)	0.60317 (9)	0.2709 (3)	0.0229 (6)
C5A	0.8735 (2)	0.64036 (8)	0.2969 (3)	0.0222 (6)
H5A	0.819170	0.637446	0.347231	0.027*
C6A	0.8940 (2)	0.68119 (8)	0.2506 (2)	0.0198 (5)
C7A	0.9711 (2)	0.68540 (8)	0.1721 (2)	0.0203 (5)
C8A	1.0284 (2)	0.64870 (9)	0.1472 (2)	0.0221 (6)
H8A	1.081554	0.651408	0.095178	0.026*
C8AA	1.0095 (2)	0.60754 (8)	0.1971 (2)	0.0200 (5)
C9A	0.7808 (2)	0.71810 (9)	0.3730 (3)	0.0275 (6)
H9AC	0.717014	0.696989	0.345004	0.041*
H9AB	0.749521	0.747229	0.381220	0.041*
H9AA	0.834091	0.709335	0.461776	0.041*
C10A	1.0543 (2)	0.73205 (10)	0.0379 (3)	0.0290 (6)
H10A	1.132811	0.721277	0.083126	0.043*
H10B	1.057723	0.763121	0.015569	0.043*
H10C	1.020366	0.715411	−0.046592	0.043*
O1B	0.67262 (17)	0.56395 (7)	0.47521 (19)	0.0341 (5)
O2B	0.75572 (17)	0.51274 (6)	0.62873 (19)	0.0313 (5)
O3B	0.64864 (16)	0.54223 (6)	0.8486 (2)	0.0290 (4)
O4B	0.82615 (17)	0.51740 (7)	0.9603 (2)	0.0328 (5)
C1B	0.7688 (2)	0.63468 (9)	0.6462 (3)	0.0285 (6)
H1B	0.784705	0.646649	0.562411	0.034*
C2B	0.8096 (2)	0.58675 (8)	0.6846 (2)	0.0212 (5)
H2B	0.890713	0.584405	0.679352	0.025*
C3B	0.8162 (2)	0.58431 (8)	0.8406 (2)	0.0200 (5)
H3B	0.899957	0.582824	0.894782	0.024*
C4B	0.7699 (2)	0.63040 (8)	0.8661 (3)	0.0239 (6)
H4B	0.785737	0.639150	0.964364	0.029*
C5B	0.6452 (2)	0.63464 (8)	0.7774 (3)	0.0273 (6)
H5B	0.578962	0.635267	0.809291	0.033*
C6B	0.6446 (2)	0.63733 (9)	0.6475 (3)	0.0304 (7)
H6B	0.578224	0.640353	0.569762	0.036*
C7B	0.8305 (2)	0.65803 (9)	0.7812 (3)	0.0278 (6)
H7BB	0.811142	0.689536	0.779923	0.033*
H7BA	0.915662	0.653912	0.809727	0.033*
C8B	0.7380 (2)	0.55247 (9)	0.5887 (2)	0.0222 (6)
C9B	0.7555 (2)	0.54553 (8)	0.8830 (2)	0.0216 (6)
O1C	0.19069 (19)	0.53645 (7)	0.6290 (2)	0.0404 (6)
O2C	0.34211 (17)	0.54131 (7)	0.5511 (2)	0.0322 (5)
H2OC	0.301 (3)	0.5194 (13)	0.484 (4)	0.058 (11)*
O3C	0.10204 (16)	0.57628 (7)	0.86339 (19)	0.0293 (5)
O4C	0.26872 (15)	0.53861 (6)	0.93112 (19)	0.0279 (4)
H4OC	0.223 (4)	0.5157 (16)	0.978 (5)	0.087 (14)*
C1C	0.3078 (2)	0.63562 (8)	0.6236 (3)	0.0226 (6)
H1C	0.358657	0.639644	0.563005	0.027*
C2C	0.3313 (2)	0.59327 (8)	0.7153 (2)	0.0193 (5)
H2C	0.416832	0.589102	0.755933	0.023*
C3C	0.2770 (2)	0.60634 (8)	0.8307 (2)	0.0199 (5)
H3C	0.343470	0.612441	0.914293	0.024*
C4C	0.2192 (2)	0.65137 (9)	0.7815 (3)	0.0258 (6)
H4C	0.195519	0.668815	0.851688	0.031*
C5C	0.1264 (2)	0.64464 (9)	0.6456 (3)	0.0305 (6)
H5C	0.045043	0.646044	0.630728	0.037*
C6C	0.1786 (2)	0.63651 (9)	0.5518 (3)	0.0270 (6)
H6C	0.141899	0.632019	0.456644	0.032*
C7C	0.3161 (3)	0.67137 (9)	0.7309 (3)	0.0275 (6)
H7CB	0.296389	0.700806	0.690088	0.033*
H7CA	0.392138	0.671958	0.802577	0.033*
C8C	0.2801 (2)	0.55381 (8)	0.6293 (3)	0.0205 (5)
C9C	0.2040 (2)	0.57215 (9)	0.8720 (2)	0.0217 (6)
O1D	0.48984 (16)	0.73668 (6)	0.12089 (19)	0.0275 (4)
O2D	0.34205 (16)	0.72312 (6)	0.25603 (18)	0.0248 (4)
N2D	0.4993 (2)	0.53114 (7)	0.2670 (2)	0.0235 (5)
H1ND	0.565 (3)	0.5363 (11)	0.344 (3)	0.040 (9)*
H2ND	0.466 (3)	0.5044 (12)	0.262 (3)	0.039 (9)*
C1D	0.4086 (2)	0.56367 (8)	0.2700 (3)	0.0223 (6)
H1DB	0.399876	0.564534	0.363432	0.027*
H1DA	0.333620	0.554268	0.205811	0.027*
C3D	0.5376 (2)	0.53484 (9)	0.1421 (3)	0.0238 (6)
H3DA	0.470265	0.530601	0.059534	0.029*
H3DB	0.595056	0.511662	0.142908	0.029*
C4D	0.5912 (2)	0.57935 (9)	0.1357 (3)	0.0238 (6)
H4DB	0.668641	0.580500	0.204677	0.029*
H4DA	0.602069	0.583253	0.043949	0.029*
C4AD	0.5183 (2)	0.61625 (8)	0.1619 (2)	0.0195 (5)
C5D	0.5367 (2)	0.65910 (9)	0.1239 (2)	0.0212 (5)
H5D	0.592342	0.664130	0.076469	0.025*
C6D	0.4763 (2)	0.69410 (8)	0.1533 (2)	0.0204 (5)
C7D	0.3958 (2)	0.68667 (8)	0.2267 (2)	0.0201 (5)
C8D	0.3764 (2)	0.64453 (8)	0.2628 (2)	0.0194 (5)
H8D	0.320784	0.639469	0.310247	0.023*
C8AD	0.4372 (2)	0.60898 (8)	0.2310 (2)	0.0183 (5)
C9D	0.5655 (2)	0.74504 (9)	0.0392 (3)	0.0302 (6)
H9DA	0.643226	0.734014	0.086790	0.045*
H9DB	0.569281	0.776624	0.024304	0.045*
H9DC	0.535748	0.730216	−0.049524	0.045*
C10D	0.2825 (2)	0.71885 (9)	0.3572 (3)	0.0255 (6)
H10D	0.217398	0.698505	0.324162	0.038*
H10E	0.253126	0.747532	0.374325	0.038*
H10F	0.335976	0.707603	0.442593	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0323 (10)	0.0149 (9)	0.0302 (10)	0.0031 (8)	0.0143 (8)	−0.0012 (7)
O2A	0.0305 (11)	0.0214 (10)	0.0332 (10)	0.0007 (8)	0.0141 (8)	0.0066 (8)
N2A	0.0300 (14)	0.0233 (13)	0.0330 (13)	0.0081 (11)	0.0007 (11)	−0.0073 (10)
C1A	0.0246 (14)	0.0246 (15)	0.0249 (13)	0.0071 (11)	0.0044 (11)	−0.0041 (11)
C3A	0.0201 (13)	0.0132 (13)	0.0406 (16)	0.0001 (10)	0.0026 (11)	−0.0004 (11)
C4A	0.0317 (16)	0.0188 (15)	0.062 (2)	0.0022 (12)	0.0240 (14)	0.0060 (14)
C4AA	0.0230 (14)	0.0164 (13)	0.0300 (14)	−0.0015 (10)	0.0087 (11)	−0.0013 (10)
C5A	0.0211 (13)	0.0190 (14)	0.0282 (13)	−0.0004 (10)	0.0099 (11)	−0.0024 (10)
C6A	0.0225 (13)	0.0167 (13)	0.0191 (12)	0.0018 (10)	0.0043 (10)	−0.0018 (10)
C7A	0.0210 (13)	0.0187 (13)	0.0186 (12)	−0.0018 (10)	0.0020 (10)	0.0003 (10)
C8A	0.0198 (13)	0.0282 (15)	0.0185 (12)	0.0000 (11)	0.0059 (10)	−0.0020 (10)
C8AA	0.0178 (13)	0.0182 (13)	0.0211 (12)	0.0019 (10)	0.0012 (10)	−0.0037 (10)
C9A	0.0342 (16)	0.0185 (14)	0.0335 (14)	0.0016 (11)	0.0160 (12)	−0.0029 (11)
C10A	0.0269 (15)	0.0306 (16)	0.0295 (14)	−0.0039 (12)	0.0083 (11)	0.0070 (12)
O1B	0.0429 (12)	0.0258 (11)	0.0258 (10)	0.0009 (9)	−0.0018 (9)	−0.0007 (8)
O2B	0.0413 (12)	0.0186 (10)	0.0306 (10)	0.0074 (8)	0.0055 (9)	−0.0055 (8)
O3B	0.0281 (11)	0.0208 (10)	0.0388 (11)	−0.0017 (8)	0.0111 (8)	0.0025 (8)
O4B	0.0316 (11)	0.0271 (11)	0.0418 (11)	0.0044 (9)	0.0140 (9)	0.0151 (9)
C1B	0.0373 (16)	0.0200 (14)	0.0270 (14)	−0.0027 (12)	0.0076 (12)	0.0039 (11)
C2B	0.0204 (13)	0.0208 (14)	0.0224 (13)	−0.0001 (10)	0.0063 (10)	0.0017 (10)
C3B	0.0208 (13)	0.0184 (13)	0.0195 (12)	0.0012 (10)	0.0041 (10)	−0.0006 (10)
C4B	0.0284 (14)	0.0168 (13)	0.0255 (13)	−0.0001 (11)	0.0067 (11)	−0.0029 (10)
C5B	0.0270 (15)	0.0120 (13)	0.0412 (16)	0.0042 (11)	0.0076 (12)	−0.0034 (11)
C6B	0.0325 (16)	0.0122 (13)	0.0373 (16)	0.0056 (11)	−0.0037 (12)	0.0031 (11)
C7B	0.0313 (15)	0.0170 (14)	0.0342 (15)	−0.0029 (11)	0.0085 (12)	0.0001 (11)
C8B	0.0235 (14)	0.0227 (14)	0.0211 (13)	0.0036 (11)	0.0078 (11)	−0.0018 (10)
C9B	0.0273 (15)	0.0184 (13)	0.0217 (12)	0.0032 (11)	0.0113 (11)	−0.0003 (10)
O1C	0.0456 (13)	0.0370 (13)	0.0479 (13)	−0.0240 (10)	0.0280 (10)	−0.0236 (10)
O2C	0.0358 (11)	0.0309 (11)	0.0354 (11)	−0.0043 (9)	0.0191 (9)	−0.0138 (9)
O3C	0.0249 (11)	0.0359 (12)	0.0300 (10)	0.0069 (8)	0.0124 (8)	0.0101 (8)
O4C	0.0214 (10)	0.0255 (11)	0.0368 (11)	0.0035 (8)	0.0085 (8)	0.0122 (8)
C1C	0.0324 (15)	0.0124 (13)	0.0246 (13)	−0.0028 (11)	0.0112 (11)	0.0005 (10)
C2C	0.0191 (13)	0.0157 (13)	0.0239 (12)	−0.0006 (10)	0.0079 (10)	0.0002 (10)
C3C	0.0231 (13)	0.0179 (13)	0.0167 (12)	−0.0002 (10)	0.0029 (10)	−0.0006 (10)
C4C	0.0354 (15)	0.0176 (14)	0.0275 (14)	0.0038 (11)	0.0140 (12)	−0.0004 (11)
C5C	0.0287 (15)	0.0214 (15)	0.0409 (16)	0.0072 (12)	0.0097 (13)	0.0132 (12)
C6C	0.0350 (15)	0.0194 (14)	0.0232 (13)	−0.0010 (11)	0.0034 (11)	0.0065 (10)
C7C	0.0408 (17)	0.0112 (13)	0.0303 (14)	−0.0020 (11)	0.0099 (12)	−0.0010 (11)
C8C	0.0269 (14)	0.0124 (12)	0.0238 (13)	0.0001 (10)	0.0099 (11)	0.0008 (10)
C9C	0.0220 (14)	0.0249 (14)	0.0172 (12)	0.0051 (11)	0.0040 (10)	−0.0014 (10)
O1D	0.0314 (11)	0.0163 (10)	0.0374 (11)	−0.0014 (8)	0.0141 (8)	0.0073 (8)
O2D	0.0310 (10)	0.0141 (9)	0.0323 (10)	0.0037 (8)	0.0140 (8)	0.0029 (7)
N2D	0.0263 (13)	0.0130 (12)	0.0284 (12)	−0.0007 (9)	0.0037 (10)	0.0008 (9)
C1D	0.0292 (14)	0.0154 (13)	0.0240 (13)	0.0018 (11)	0.0105 (11)	−0.0009 (10)
C3D	0.0218 (13)	0.0221 (14)	0.0254 (13)	0.0049 (11)	0.0040 (10)	−0.0041 (11)
C4D	0.0234 (14)	0.0220 (14)	0.0260 (13)	0.0029 (11)	0.0074 (11)	−0.0018 (11)
C4AD	0.0203 (13)	0.0191 (13)	0.0168 (11)	0.0004 (10)	0.0023 (10)	−0.0005 (10)
C5D	0.0182 (13)	0.0239 (14)	0.0221 (12)	−0.0023 (10)	0.0067 (10)	0.0009 (10)
C6D	0.0224 (13)	0.0152 (13)	0.0211 (12)	−0.0007 (10)	0.0026 (10)	0.0032 (10)
C7D	0.0234 (13)	0.0151 (13)	0.0201 (12)	0.0034 (10)	0.0040 (10)	0.0014 (10)
C8D	0.0209 (13)	0.0191 (13)	0.0191 (12)	−0.0009 (10)	0.0074 (10)	0.0010 (10)
C8AD	0.0218 (13)	0.0150 (13)	0.0165 (11)	−0.0004 (10)	0.0030 (10)	0.0008 (9)
C9D	0.0312 (15)	0.0227 (15)	0.0375 (16)	−0.0033 (12)	0.0115 (12)	0.0099 (12)
C10D	0.0324 (15)	0.0176 (13)	0.0291 (14)	0.0007 (11)	0.0131 (12)	−0.0010 (11)

Geometric parameters (Å, º)

O1A—C6A	1.371 (3)	O2C—C8C	1.303 (3)
O1A—C9A	1.431 (3)	O2C—H2OC	0.98 (4)
O2A—C7A	1.366 (3)	O3C—C9C	1.214 (3)
O2A—C10A	1.430 (3)	O4C—C9C	1.321 (3)
N2A—C1A	1.465 (4)	O4C—H4OC	1.09 (5)
N2A—C3A	1.511 (4)	C1C—C6C	1.515 (4)
N2A—H1NA	1.04 (4)	C1C—C7C	1.529 (4)
N2A—H2NA	0.93 (4)	C1C—C2C	1.573 (3)
C1A—C8AA	1.507 (3)	C1C—H1C	1.0000
C1A—H1AB	0.9900	C2C—C8C	1.512 (3)
C1A—H1AA	0.9900	C2C—C3C	1.561 (3)
C3A—C4A	1.497 (4)	C2C—H2C	1.0000
C3A—H3AB	0.9900	C3C—C9C	1.506 (4)
C3A—H3AA	0.9900	C3C—C4C	1.557 (4)
C4A—C4AA	1.507 (4)	C3C—H3C	1.0000
C4A—H4AB	0.9900	C4C—C5C	1.517 (4)
C4A—H4AA	0.9900	C4C—C7C	1.538 (4)
C4AA—C8AA	1.375 (4)	C4C—H4C	1.0000
C4AA—C5A	1.402 (4)	C5C—C6C	1.316 (4)
C5A—C6A	1.382 (4)	C5C—H5C	0.9500
C5A—H5A	0.9500	C6C—H6C	0.9500
C6A—C7A	1.404 (4)	C7C—H7CB	0.9900
C7A—C8A	1.380 (4)	C7C—H7CA	0.9900
C8A—C8AA	1.401 (4)	O1D—C6D	1.364 (3)
C8A—H8A	0.9500	O1D—C9D	1.431 (3)
C9A—H9AC	0.9800	O2D—C7D	1.366 (3)
C9A—H9AB	0.9800	O2D—C10D	1.429 (3)
C9A—H9AA	0.9800	N2D—C3D	1.484 (3)
C10A—H10A	0.9800	N2D—C1D	1.486 (3)
C10A—H10B	0.9800	N2D—H1ND	0.95 (3)
C10A—H10C	0.9800	N2D—H2ND	0.90 (4)
O1B—C8B	1.243 (3)	C1D—C8AD	1.509 (3)
O2B—C8B	1.278 (3)	C1D—H1DB	0.9900
O3B—C9B	1.237 (3)	C1D—H1DA	0.9900
O4B—C9B	1.300 (3)	C3D—C4D	1.516 (4)
C1B—C6B	1.506 (4)	C3D—H3DA	0.9900
C1B—C7B	1.534 (4)	C3D—H3DB	0.9900
C1B—C2B	1.558 (4)	C4D—C4AD	1.503 (4)
C1B—H1B	1.0000	C4D—H4DB	0.9900
C2B—C8B	1.516 (4)	C4D—H4DA	0.9900
C2B—C3B	1.571 (3)	C4AD—C8AD	1.385 (3)
C2B—H2B	1.0000	C4AD—C5D	1.402 (4)
C3B—C9B	1.522 (4)	C5D—C6D	1.377 (4)
C3B—C4B	1.565 (3)	C5D—H5D	0.9500
C3B—H3B	1.0000	C6D—C7D	1.410 (4)
C4B—C5B	1.515 (4)	C7D—C8D	1.378 (4)
C4B—C7B	1.541 (4)	C8D—C8AD	1.402 (3)
C4B—H4B	1.0000	C8D—H8D	0.9500
C5B—C6B	1.325 (4)	C9D—H9DA	0.9800
C5B—H5B	0.9500	C9D—H9DB	0.9800
C6B—H6B	0.9500	C9D—H9DC	0.9800
C7B—H7BB	0.9900	C10D—H10D	0.9800
C7B—H7BA	0.9900	C10D—H10E	0.9800
O1C—C8C	1.202 (3)	C10D—H10F	0.9800
C6A—O1A—C9A	117.07 (19)	C9C—O4C—H4OC	113 (2)
C7A—O2A—C10A	117.8 (2)	C6C—C1C—C7C	99.9 (2)
C1A—N2A—C3A	111.6 (2)	C6C—C1C—C2C	106.3 (2)
C1A—N2A—H1NA	111 (2)	C7C—C1C—C2C	101.5 (2)
C3A—N2A—H1NA	103 (2)	C6C—C1C—H1C	115.7
C1A—N2A—H2NA	111 (2)	C7C—C1C—H1C	115.7
C3A—N2A—H2NA	109 (2)	C2C—C1C—H1C	115.7
H1NA—N2A—H2NA	111 (3)	C8C—C2C—C3C	116.8 (2)
N2A—C1A—C8AA	111.9 (2)	C8C—C2C—C1C	109.9 (2)
N2A—C1A—H1AB	109.2	C3C—C2C—C1C	101.33 (19)
C8AA—C1A—H1AB	109.2	C8C—C2C—H2C	109.5
N2A—C1A—H1AA	109.2	C3C—C2C—H2C	109.5
C8AA—C1A—H1AA	109.2	C1C—C2C—H2C	109.5
H1AB—C1A—H1AA	107.9	C9C—C3C—C4C	117.4 (2)
C4A—C3A—N2A	108.7 (2)	C9C—C3C—C2C	116.5 (2)
C4A—C3A—H3AB	109.9	C4C—C3C—C2C	103.37 (19)
N2A—C3A—H3AB	109.9	C9C—C3C—H3C	106.2
C4A—C3A—H3AA	109.9	C4C—C3C—H3C	106.2
N2A—C3A—H3AA	109.9	C2C—C3C—H3C	106.2
H3AB—C3A—H3AA	108.3	C5C—C4C—C7C	100.1 (2)
C3A—C4A—C4AA	114.1 (2)	C5C—C4C—C3C	108.3 (2)
C3A—C4A—H4AB	108.7	C7C—C4C—C3C	98.4 (2)
C4AA—C4A—H4AB	108.7	C5C—C4C—H4C	115.9
C3A—C4A—H4AA	108.7	C7C—C4C—H4C	115.9
C4AA—C4A—H4AA	108.7	C3C—C4C—H4C	115.9
H4AB—C4A—H4AA	107.6	C6C—C5C—C4C	107.9 (2)
C8AA—C4AA—C5A	119.2 (2)	C6C—C5C—H5C	126.0
C8AA—C4AA—C4A	120.7 (2)	C4C—C5C—H5C	126.0
C5A—C4AA—C4A	120.2 (2)	C5C—C6C—C1C	107.4 (2)
C6A—C5A—C4AA	121.1 (2)	C5C—C6C—H6C	126.3
C6A—C5A—H5A	119.4	C1C—C6C—H6C	126.3
C4AA—C5A—H5A	119.4	C1C—C7C—C4C	93.6 (2)
O1A—C6A—C5A	124.9 (2)	C1C—C7C—H7CB	113.0
O1A—C6A—C7A	115.4 (2)	C4C—C7C—H7CB	113.0
C5A—C6A—C7A	119.6 (2)	C1C—C7C—H7CA	113.0
O2A—C7A—C8A	125.2 (2)	C4C—C7C—H7CA	113.0
O2A—C7A—C6A	115.8 (2)	H7CB—C7C—H7CA	110.4
C8A—C7A—C6A	119.0 (2)	O1C—C8C—O2C	123.3 (2)
C7A—C8A—C8AA	121.2 (2)	O1C—C8C—C2C	124.5 (2)
C7A—C8A—H8A	119.4	O2C—C8C—C2C	112.2 (2)
C8AA—C8A—H8A	119.4	O3C—C9C—O4C	124.3 (2)
C4AA—C8AA—C8A	119.9 (2)	O3C—C9C—C3C	125.0 (2)
C4AA—C8AA—C1A	121.4 (2)	O4C—C9C—C3C	110.4 (2)
C8A—C8AA—C1A	118.6 (2)	C6D—O1D—C9D	117.1 (2)
O1A—C9A—H9AC	109.5	C7D—O2D—C10D	117.25 (19)
O1A—C9A—H9AB	109.5	C3D—N2D—C1D	112.7 (2)
H9AC—C9A—H9AB	109.5	C3D—N2D—H1ND	108 (2)
O1A—C9A—H9AA	109.5	C1D—N2D—H1ND	108 (2)
H9AC—C9A—H9AA	109.5	C3D—N2D—H2ND	106 (2)
H9AB—C9A—H9AA	109.5	C1D—N2D—H2ND	107 (2)
O2A—C10A—H10A	109.5	H1ND—N2D—H2ND	116 (3)
O2A—C10A—H10B	109.5	N2D—C1D—C8AD	112.4 (2)
H10A—C10A—H10B	109.5	N2D—C1D—H1DB	109.1
O2A—C10A—H10C	109.5	C8AD—C1D—H1DB	109.1
H10A—C10A—H10C	109.5	N2D—C1D—H1DA	109.1
H10B—C10A—H10C	109.5	C8AD—C1D—H1DA	109.1
C6B—C1B—C7B	100.8 (2)	H1DB—C1D—H1DA	107.9
C6B—C1B—C2B	106.8 (2)	N2D—C3D—C4D	110.6 (2)
C7B—C1B—C2B	100.3 (2)	N2D—C3D—H3DA	109.5
C6B—C1B—H1B	115.6	C4D—C3D—H3DA	109.5
C7B—C1B—H1B	115.6	N2D—C3D—H3DB	109.5
C2B—C1B—H1B	115.6	C4D—C3D—H3DB	109.5
C8B—C2B—C1B	114.2 (2)	H3DA—C3D—H3DB	108.1
C8B—C2B—C3B	117.9 (2)	C4AD—C4D—C3D	112.6 (2)
C1B—C2B—C3B	102.5 (2)	C4AD—C4D—H4DB	109.1
C8B—C2B—H2B	107.2	C3D—C4D—H4DB	109.1
C1B—C2B—H2B	107.2	C4AD—C4D—H4DA	109.1
C3B—C2B—H2B	107.2	C3D—C4D—H4DA	109.1
C9B—C3B—C4B	115.3 (2)	H4DB—C4D—H4DA	107.8
C9B—C3B—C2B	116.2 (2)	C8AD—C4AD—C5D	119.0 (2)
C4B—C3B—C2B	102.26 (19)	C8AD—C4AD—C4D	120.7 (2)
C9B—C3B—H3B	107.5	C5D—C4AD—C4D	120.1 (2)
C4B—C3B—H3B	107.5	C6D—C5D—C4AD	121.8 (2)
C2B—C3B—H3B	107.5	C6D—C5D—H5D	119.1
C5B—C4B—C7B	99.8 (2)	C4AD—C5D—H5D	119.1
C5B—C4B—C3B	108.5 (2)	O1D—C6D—C5D	125.3 (2)
C7B—C4B—C3B	98.5 (2)	O1D—C6D—C7D	115.7 (2)
C5B—C4B—H4B	115.9	C5D—C6D—C7D	119.0 (2)
C7B—C4B—H4B	115.9	O2D—C7D—C8D	125.0 (2)
C3B—C4B—H4B	115.9	O2D—C7D—C6D	115.6 (2)
C6B—C5B—C4B	108.2 (3)	C8D—C7D—C6D	119.4 (2)
C6B—C5B—H5B	125.9	C7D—C8D—C8AD	121.3 (2)
C4B—C5B—H5B	125.9	C7D—C8D—H8D	119.3
C5B—C6B—C1B	107.1 (2)	C8AD—C8D—H8D	119.3
C5B—C6B—H6B	126.4	C4AD—C8AD—C8D	119.5 (2)
C1B—C6B—H6B	126.4	C4AD—C8AD—C1D	122.3 (2)
C1B—C7B—C4B	93.7 (2)	C8D—C8AD—C1D	118.3 (2)
C1B—C7B—H7BB	113.0	O1D—C9D—H9DA	109.5
C4B—C7B—H7BB	113.0	O1D—C9D—H9DB	109.5
C1B—C7B—H7BA	113.0	H9DA—C9D—H9DB	109.5
C4B—C7B—H7BA	113.0	O1D—C9D—H9DC	109.5
H7BB—C7B—H7BA	110.4	H9DA—C9D—H9DC	109.5
O1B—C8B—O2B	124.4 (2)	H9DB—C9D—H9DC	109.5
O1B—C8B—C2B	119.3 (2)	O2D—C10D—H10D	109.5
O2B—C8B—C2B	116.2 (2)	O2D—C10D—H10E	109.5
O3B—C9B—O4B	124.1 (2)	H10D—C10D—H10E	109.5
O3B—C9B—C3B	122.2 (2)	O2D—C10D—H10F	109.5
O4B—C9B—C3B	113.7 (2)	H10D—C10D—H10F	109.5
C8C—O2C—H2OC	111 (2)	H10E—C10D—H10F	109.5
C3A—N2A—C1A—C8AA	−51.4 (3)	C6C—C1C—C2C—C8C	52.6 (3)
C1A—N2A—C3A—C4A	64.1 (3)	C7C—C1C—C2C—C8C	156.7 (2)
N2A—C3A—C4A—C4AA	−45.8 (3)	C6C—C1C—C2C—C3C	−71.5 (2)
C3A—C4A—C4AA—C8AA	18.7 (4)	C7C—C1C—C2C—C3C	32.6 (2)
C3A—C4A—C4AA—C5A	−162.9 (3)	C8C—C2C—C3C—C9C	16.8 (3)
C8AA—C4AA—C5A—C6A	−0.5 (4)	C1C—C2C—C3C—C9C	136.1 (2)
C4A—C4AA—C5A—C6A	−179.0 (3)	C8C—C2C—C3C—C4C	−113.5 (2)
C9A—O1A—C6A—C5A	13.7 (3)	C1C—C2C—C3C—C4C	5.8 (2)
C9A—O1A—C6A—C7A	−168.1 (2)	C9C—C3C—C4C—C5C	−67.9 (3)
C4AA—C5A—C6A—O1A	−179.5 (2)	C2C—C3C—C4C—C5C	61.9 (3)
C4AA—C5A—C6A—C7A	2.3 (4)	C9C—C3C—C4C—C7C	−171.5 (2)
C10A—O2A—C7A—C8A	6.3 (3)	C2C—C3C—C4C—C7C	−41.8 (2)
C10A—O2A—C7A—C6A	−174.8 (2)	C7C—C4C—C5C—C6C	31.5 (3)
O1A—C6A—C7A—O2A	0.2 (3)	C3C—C4C—C5C—C6C	−71.0 (3)
C5A—C6A—C7A—O2A	178.6 (2)	C4C—C5C—C6C—C1C	2.4 (3)
O1A—C6A—C7A—C8A	179.2 (2)	C7C—C1C—C6C—C5C	−35.7 (3)
C5A—C6A—C7A—C8A	−2.4 (4)	C2C—C1C—C6C—C5C	69.5 (3)
O2A—C7A—C8A—C8AA	179.8 (2)	C6C—C1C—C7C—C4C	51.0 (2)
C6A—C7A—C8A—C8AA	0.9 (4)	C2C—C1C—C7C—C4C	−58.0 (2)
C5A—C4AA—C8AA—C8A	−1.0 (4)	C5C—C4C—C7C—C1C	−49.6 (2)
C4A—C4AA—C8AA—C8A	177.4 (2)	C3C—C4C—C7C—C1C	60.8 (2)
C5A—C4AA—C8AA—C1A	175.4 (2)	C3C—C2C—C8C—O1C	12.3 (4)
C4A—C4AA—C8AA—C1A	−6.1 (4)	C1C—C2C—C8C—O1C	−102.3 (3)
C7A—C8A—C8AA—C4AA	0.9 (4)	C3C—C2C—C8C—O2C	−169.8 (2)
C7A—C8A—C8AA—C1A	−175.7 (2)	C1C—C2C—C8C—O2C	75.6 (3)
N2A—C1A—C8AA—C4AA	22.5 (3)	C4C—C3C—C9C—O3C	3.9 (4)
N2A—C1A—C8AA—C8A	−161.0 (2)	C2C—C3C—C9C—O3C	−119.4 (3)
C6B—C1B—C2B—C8B	58.6 (3)	C4C—C3C—C9C—O4C	−170.2 (2)
C7B—C1B—C2B—C8B	163.3 (2)	C2C—C3C—C9C—O4C	66.5 (3)
C6B—C1B—C2B—C3B	−70.1 (2)	C3D—N2D—C1D—C8AD	−45.5 (3)
C7B—C1B—C2B—C3B	34.6 (2)	C1D—N2D—C3D—C4D	61.8 (3)
C8B—C2B—C3B—C9B	3.8 (3)	N2D—C3D—C4D—C4AD	−47.9 (3)
C1B—C2B—C3B—C9B	130.2 (2)	C3D—C4D—C4AD—C8AD	21.5 (3)
C8B—C2B—C3B—C4B	−122.7 (2)	C3D—C4D—C4AD—C5D	−162.5 (2)
C1B—C2B—C3B—C4B	3.7 (2)	C8AD—C4AD—C5D—C6D	−0.1 (4)
C9B—C3B—C4B—C5B	−63.9 (3)	C4D—C4AD—C5D—C6D	−176.1 (2)
C2B—C3B—C4B—C5B	63.1 (3)	C9D—O1D—C6D—C5D	5.8 (4)
C9B—C3B—C4B—C7B	−167.4 (2)	C9D—O1D—C6D—C7D	−176.3 (2)
C2B—C3B—C4B—C7B	−40.3 (2)	C4AD—C5D—C6D—O1D	179.4 (2)
C7B—C4B—C5B—C6B	32.8 (3)	C4AD—C5D—C6D—C7D	1.6 (4)
C3B—C4B—C5B—C6B	−69.6 (3)	C10D—O2D—C7D—C8D	15.2 (3)
C4B—C5B—C6B—C1B	0.3 (3)	C10D—O2D—C7D—C6D	−165.1 (2)
C7B—C1B—C6B—C5B	−33.7 (3)	O1D—C6D—C7D—O2D	−0.1 (3)
C2B—C1B—C6B—C5B	70.7 (3)	C5D—C6D—C7D—O2D	178.0 (2)
C6B—C1B—C7B—C4B	50.2 (2)	O1D—C6D—C7D—C8D	179.6 (2)
C2B—C1B—C7B—C4B	−59.4 (2)	C5D—C6D—C7D—C8D	−2.3 (4)
C5B—C4B—C7B—C1B	−49.4 (2)	O2D—C7D—C8D—C8AD	−178.7 (2)
C3B—C4B—C7B—C1B	61.2 (2)	C6D—C7D—C8D—C8AD	1.6 (4)
C1B—C2B—C8B—O1B	15.6 (3)	C5D—C4AD—C8AD—C8D	−0.7 (3)
C3B—C2B—C8B—O1B	136.1 (3)	C4D—C4AD—C8AD—C8D	175.3 (2)
C1B—C2B—C8B—O2B	−168.7 (2)	C5D—C4AD—C8AD—C1D	177.3 (2)
C3B—C2B—C8B—O2B	−48.2 (3)	C4D—C4AD—C8AD—C1D	−6.6 (4)
C4B—C3B—C9B—O3B	49.1 (3)	C7D—C8D—C8AD—C4AD	0.0 (4)
C2B—C3B—C9B—O3B	−70.5 (3)	C7D—C8D—C8AD—C1D	−178.2 (2)
C4B—C3B—C9B—O4B	−129.3 (2)	N2D—C1D—C8AD—C4AD	18.1 (3)
C2B—C3B—C9B—O4B	111.1 (3)	N2D—C1D—C8AD—C8D	−163.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2D—H1ND···O1B	0.95 (3)	1.78 (4)	2.694 (3)	161 (3)
N2D—H2ND···O3B^i	0.90 (4)	2.08 (4)	2.891 (3)	150 (3)
N2A—H1NA···O4B^ii	1.04 (4)	1.83 (4)	2.847 (3)	167 (3)
N2A—H2NA···O4B^iii	0.93 (4)	2.26 (4)	2.995 (3)	135 (3)
N2A—H2NA···O2B^iii	0.93 (4)	2.38 (4)	2.985 (3)	122 (3)
O2C—H2OC···O2B^i	0.98 (4)	1.52 (4)	2.491 (3)	174 (4)
O4C—H4OC···O4B^iv	1.09 (5)	1.41 (5)	2.495 (3)	173 (4)

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