Crystal structure of the bis-(cyclo-hexyl-ammonium) succinate succinic acid salt adduct.

The crystal structure of the title salt adduct, 2C6H14N(+)·C4H4O4 (2-)·C4H6O4, consists of two cyclo-hexyl-ammonium cations, one succcinate dianion and one neutral succinic acid mol-ecule. Succinate dianions and succinic acid mol-ecules are self-assembled head-to-tail through O-H⋯O hydrogen bonds and adopt a syn-syn configuration, leading to a strand-like arrangement along [101]. The cyclo-hexyl-ammonium cations have a chair conformation and act as multidentate hydrogen-bond donors linking adjacent strands through inter-molecular N-H⋯O inter-actions to both the succinate and the succinic acid components. This results in two-dimensional supra-molecular layered structures lying parallel to (010).

Chemical context

In the field of crystal engineering, di­carb­oxy­lic acids constitute very suitable building blocks which can act as polydirectional synthons and thus present numerous possibilities for mol­ecular assembly through the formation of hydrogen-bonded networks (Ivasenko & Perepichka, 2011 ▸). Furthermore, the additional involvement of amines, via the formation of ammonium cations, significantly increases the potential for linkage and the topological diversity (Yuge et al., 2008 ▸; Lemmerer, 2011 ▸). Some papers dealing with spectroscopic studies on quaternary ammonium hydrogenoxalates have been reported from our laboratory (Gueye & Diop, 1995 ▸). In the scope of our current studies on the inter­actions between quaternary ammonium salts of carb­oxy­lic acids and halogenidotin(IV) complexes (Gueye et al., 2014 ▸), the reaction involving cyclo­hexyl­amine and succinic acid was initiated and led to the isolation of the title organic salt adduct 2C6H14N+·C4H4O4 2−·C4H6O4, (I), the structure of which is reported herein.

Structural comments

The asymmetric unit of (I) contains two cyclo­hexyl­ammonium cations, one succinate dianion and one mol­ecule of succinic acid (Fig. 1 ▸). By comparison with previous examples (Büyükgüngör & Odabas˛ogˇlu, 2002 ▸; Bruno et al., 2004 ▸; Du et al., 2009 ▸; Zhang et al., 2011 ▸; Froschauer & Weil, 2012 ▸), it is inter­esting to note that the carbon–oxygen bond distances recorded for the succinic acid [C1—O1 = 1.2974 (17), C1—O2 = 1.2356 (17), C4—O3 = 1.2367 (17), C4—O4 = 1.2961 (16)] and the succinate dianion [C5—O5 = 1.2955 (17), C5—O6 = 1.2356 (18), C8—O7 = 1.2348 (18) and C8—O8 = 1.2894 (17)] are very similar. In general, a more pronounced difference in length is expected between the C=O bond and the C—OH bond of succinic acid (in the range of 0.1 Å), while for the succinate dianion the deviation between the C—O bonds is narrowed (in the range of 0.01 Å). Thus, to confirm more accurately the nature of the components of (I), namely the presence of distinct succinic acid and succinate species, electron-density mapping has been performed (Fig. 2 ▸). It follows that the location of the acidic protons is clearly established, confirming unambiguously the composition of (I). Moreover, the relative equalizing of the carbon–oxygen bonds can be explained by the contribution of concomitant N—H⋯O inter­actions involving all oxygen atoms of succinic acid and the succinate dianion with surrounding cyclo­hexyl­ammonium cations. The average C—C—C—O torsion angle, calculated on 616 succinic acids, is equal to 171 (12)° with a deviation of the mean equal to 0.4°, whereas the average torsion angle calculated on 964 succinate acids is equal to 167 (12)° with a deviation of the mean also equal to 0.4°. These results match the torsion angles found in (I) for succinic acid: 154.09 (16), 156.32 (12), 159.25 (17) and 161.07 (12)° but those found for the succinate anion are rather different: 121.41 (15), 121.78 (17), 151.8 (2) and 152.14 (13)°.

Figure 1

A view of the two cyclo­hexa­minum cations, the succinate dianion and the succinic acid adduct species in the asymmetric unit of (I), showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

Electron-density mapping around C4H6O4 and C4H4O4 2−, showing the precise location of acidic protons.

Supra­molecular features

From a supra­molecular point of view, the four components of (I) are involved in the self-assembly. The succinate dianion and succinic acid are linked head-to-tail through short O—H⋯O hydrogen bonds [2.4636 (13) and 2.4734 (13) Å] (Table 1 ▸) leading to infinite strands which extend along [101]. These inter­molecular distances are consistent with the mean of 2.52 Å with a sample standard deviation of 0.06 Å observed on a sample of 25 observations from the CSD on a set of structures containing both a succinic acid and a succinate anion. The cyclo­hexyl­ammonium cations operate as multidentate hydrogen-bond donors through N—H⋯O inter­actions linking the succinate–succinic acid strands, giving two-dimensional supra­molecular layers lying parallel to (010) (Fig. 3 ▸).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO5i	0.91	1.99	2.8923(16)	173
N1H1BO2ii	0.91	2.10	2.8969(16)	146
N1H1CO7iii	0.91	1.86	2.7279(15)	158
N2H2AO8iv	0.91	2.00	2.8746(16)	160
N2H2BO3i	0.91	2.17	2.9098(15)	138
N2H2CO6v	0.91	1.94	2.7485(15)	148
O1H1O8vi	0.84	1.64	2.4734(13)	175
O4H4O5	0.84	1.63	2.4636(13)	175

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 3

Crystal packing of (I) viewed along the a axis, showing the infinite strands based on succinate–succinic acid hydrogen-bonding inter­actions and linked through the cyclo­hexyl­ammoninum cations into sheets. Inter­molecular hydrogen bonds are shown as dashed blue lines. H atoms not involved in hydrogen bonding are omitted for clarity. Colour code: C dark grey, H light grey, O red, N blue.

Synthesis and crystallization

The title compound was obtained by reacting cyclo­hexyl­amine (5.76 mL) with succinic acid (5.0 g) in a molar ratio of 2:1, in 50 mL of water, at 298 K. The resulting clear solution was allowed to evaporate at 298 K leading after a few days to colourless block-like crystals suitable for an X-ray crystal structure determination.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms, on carbon, oxygen and nitro­gen atoms were placed at calculated positions using a riding model with C—H = 1.00 (methine) or 0.99 Å (methyl­ene) and with U iso(H) = 1.2U eq(C), or O—H = 0.84 Å (hydrox­yl), N—H = 0.91 Å (amine) with U iso(H) = 1.5U eq(O or N).

Table 2

Experimental details

Crystal data
Chemical formula	2C6H14N+C4H4O4 2C4H6O4
M r	434.52
Crystal system, space group	Triclinic, P
Temperature (K)	115
a, b, c ()	9.5147(5), 10.4479(6), 11.4082(6)
, , ()	96.789(2), 93.287(2), 90.945(2)
V (3)	1123.96(11)
Z	2
Radiation type	Mo K 1
(mm1)	0.10
Crystal size (mm)	0.5 0.3 0.25
Data collection
Diffractometer	Nonius Kappa APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.710, 0.746
No. of measured, independent and observed [I > 2(I)] reflections	30513, 5190, 4273
R int	0.030
(sin /)max (1)	0.652
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.043, 0.115, 1.03
No. of reflections	5190
No. of parameters	275
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.38, 0.52

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXS2014 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), OLEX2 (Dolomanov et al., 2009 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012621/zs2336sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012621/zs2336Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012621/zs2336Isup3.cml

CCDC reference: 1409738

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C6H14N+·C4H4O42−·C4H6O4	Z = 2
Mr = 434.52	F(000) = 472
Triclinic, P1	Dx = 1.284 Mg m−3
a = 9.5147 (5) Å	Mo Kα1 radiation, λ = 0.71073 Å
b = 10.4479 (6) Å	Cell parameters from 9937 reflections
c = 11.4082 (6) Å	θ = 2.5–27.6°
α = 96.789 (2)°	µ = 0.10 mm−1
β = 93.287 (2)°	T = 115 K
γ = 90.945 (2)°	Prism, colourless
V = 1123.96 (11) Å3	0.5 × 0.3 × 0.25 mm

Nonius Kappa APEXII diffractometer	5190 independent reflections
Radiation source: X-ray tube, Siemens KFF Mo 2K-180	4273 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −12→12
Tmin = 0.710, Tmax = 0.746	k = −13→13
30513 measured reflections	l = −14→14

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0536P)2 + 0.724P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
5190 reflections	Δρmax = 0.38 e Å−3
275 parameters	Δρmin = −0.52 e Å−3

Experimental. SADABS (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0455 before and 0.0417 after correction. The ratio of minimum to maximum transmission is 0.9524. The λ/2 correction factor is 0.0015.

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.

	x	y	z	Uiso*/Ueq
C1	0.04814 (14)	0.86382 (12)	0.43156 (12)	0.0110 (3)
C2	0.17149 (14)	0.86205 (13)	0.52171 (12)	0.0121 (3)
H2D	0.1609	0.7851	0.5637	0.015*
H2E	0.1672	0.9390	0.5809	0.015*
C3	0.31605 (14)	0.86030 (13)	0.47093 (12)	0.0123 (3)
H3A	0.3271	0.7759	0.4233	0.015*
H3B	0.3203	0.9277	0.4170	0.015*
C4	0.43892 (14)	0.88243 (12)	0.56279 (11)	0.0105 (3)
C5	0.64831 (14)	1.09068 (14)	0.85914 (12)	0.0136 (3)
C6	0.76641 (15)	1.09519 (14)	0.95460 (12)	0.0158 (3)
H6A	0.7804	1.1849	0.9931	0.019*
H6B	0.8548	1.0686	0.9180	0.019*
C7	0.73497 (15)	1.00706 (14)	1.04801 (12)	0.0166 (3)
H7A	0.6473	1.0346	1.0854	0.020*
H7B	0.7193	0.9177	1.0092	0.020*
C8	0.85386 (15)	1.00936 (14)	1.14279 (12)	0.0147 (3)
C9	0.19496 (14)	0.31479 (13)	0.29397 (12)	0.0137 (3)
H9	0.2923	0.3391	0.3279	0.016*
C10	0.18667 (19)	0.33296 (15)	0.16317 (13)	0.0240 (3)
H10A	0.0932	0.3024	0.1270	0.029*
H10B	0.2592	0.2806	0.1225	0.029*
C11	0.2096 (2)	0.47517 (16)	0.14622 (15)	0.0293 (4)
H11A	0.3081	0.5016	0.1719	0.035*
H11B	0.1955	0.4849	0.0611	0.035*
C12	0.11074 (19)	0.56320 (15)	0.21517 (15)	0.0263 (4)
H12A	0.0131	0.5463	0.1814	0.032*
H12B	0.1362	0.6541	0.2081	0.036 (5)*
C13	0.1185 (2)	0.54188 (15)	0.34496 (15)	0.0272 (4)
H13A	0.0479	0.5956	0.3868	0.033*
H13B	0.2129	0.5694	0.3811	0.039 (6)*
C14	0.09117 (17)	0.40034 (14)	0.36036 (14)	0.0205 (3)
H14A	0.1003	0.3893	0.4454	0.025*
H14B	−0.0060	0.3745	0.3302	0.025*
C15	0.31417 (15)	0.36301 (13)	0.71133 (12)	0.0143 (3)
H15	0.2123	0.3698	0.6867	0.017*
C16	0.40040 (18)	0.43583 (14)	0.63179 (14)	0.0208 (3)
H16A	0.3808	0.3989	0.5483	0.025*
H16B	0.5020	0.4267	0.6523	0.025*
C17	0.3636 (2)	0.57889 (15)	0.64653 (15)	0.0275 (4)
H17A	0.4231	0.6258	0.5966	0.033*
H17B	0.2640	0.5880	0.6191	0.033*
C18	0.38570 (19)	0.63880 (15)	0.77466 (15)	0.0264 (4)
H18A	0.3541	0.7291	0.7817	0.032*
H18B	0.4873	0.6399	0.7990	0.032*
C19	0.30447 (19)	0.56390 (15)	0.85661 (14)	0.0245 (3)
H19A	0.2023	0.5748	0.8406	0.029*
H19B	0.3290	0.5998	0.9397	0.029*
C20	0.33692 (17)	0.41964 (14)	0.84057 (13)	0.0196 (3)
H20A	0.4358	0.4075	0.8682	0.024*
H20B	0.2751	0.3734	0.8893	0.024*
N1	0.16561 (12)	0.17671 (11)	0.30888 (10)	0.0136 (2)
H1A	0.2281	0.1259	0.2689	0.020*
H1B	0.1743	0.1663	0.3870	0.020*
H1C	0.0765	0.1539	0.2798	0.020*
N2	0.35079 (12)	0.22343 (11)	0.69782 (10)	0.0130 (2)
H2A	0.2985	0.1808	0.7459	0.020*
H2B	0.3322	0.1890	0.6213	0.020*
H2C	0.4439	0.2157	0.7181	0.020*
O1	0.07729 (10)	0.90365 (10)	0.33203 (8)	0.0147 (2)
H1	0.0031	0.9042	0.2885	0.022*
O2	−0.07178 (10)	0.83211 (10)	0.45502 (9)	0.0148 (2)
O3	0.55754 (10)	0.84347 (9)	0.54021 (8)	0.0145 (2)
O4	0.41065 (10)	0.94748 (10)	0.66222 (8)	0.0139 (2)
H4	0.4842	0.9578	0.7069	0.021*
O5	0.61844 (10)	0.97769 (10)	0.80258 (9)	0.0159 (2)
O6	0.58720 (12)	1.19027 (11)	0.84010 (10)	0.0241 (3)
O7	0.93003 (13)	1.10688 (11)	1.16655 (11)	0.0292 (3)
O8	0.86738 (10)	0.90635 (10)	1.19411 (9)	0.0159 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0143 (6)	0.0071 (6)	0.0113 (6)	0.0018 (5)	−0.0007 (5)	0.0001 (5)
C2	0.0118 (6)	0.0142 (6)	0.0105 (6)	0.0015 (5)	−0.0020 (5)	0.0029 (5)
C3	0.0121 (6)	0.0137 (6)	0.0105 (6)	−0.0015 (5)	−0.0017 (5)	−0.0002 (5)
C4	0.0130 (6)	0.0074 (6)	0.0113 (6)	−0.0017 (5)	−0.0006 (5)	0.0031 (5)
C5	0.0138 (6)	0.0176 (7)	0.0093 (6)	0.0000 (5)	−0.0018 (5)	0.0017 (5)
C6	0.0165 (7)	0.0185 (7)	0.0119 (6)	−0.0021 (5)	−0.0059 (5)	0.0031 (5)
C7	0.0166 (7)	0.0190 (7)	0.0138 (7)	−0.0046 (5)	−0.0072 (5)	0.0048 (6)
C8	0.0153 (7)	0.0176 (7)	0.0111 (6)	−0.0014 (5)	−0.0031 (5)	0.0032 (5)
C9	0.0147 (6)	0.0109 (6)	0.0149 (7)	−0.0021 (5)	0.0003 (5)	0.0001 (5)
C10	0.0407 (9)	0.0163 (7)	0.0154 (7)	0.0000 (7)	0.0091 (7)	0.0005 (6)
C11	0.0479 (11)	0.0200 (8)	0.0221 (8)	−0.0010 (7)	0.0161 (8)	0.0054 (6)
C12	0.0346 (9)	0.0148 (7)	0.0316 (9)	0.0006 (6)	0.0066 (7)	0.0092 (6)
C13	0.0420 (10)	0.0125 (7)	0.0282 (9)	0.0022 (7)	0.0164 (7)	0.0003 (6)
C14	0.0277 (8)	0.0149 (7)	0.0202 (7)	0.0020 (6)	0.0111 (6)	0.0032 (6)
C15	0.0166 (7)	0.0105 (6)	0.0160 (7)	0.0019 (5)	0.0013 (5)	0.0020 (5)
C16	0.0311 (8)	0.0145 (7)	0.0183 (7)	0.0034 (6)	0.0094 (6)	0.0039 (6)
C17	0.0462 (10)	0.0143 (7)	0.0253 (8)	0.0067 (7)	0.0153 (7)	0.0089 (6)
C18	0.0382 (9)	0.0114 (7)	0.0307 (9)	−0.0004 (6)	0.0132 (7)	0.0016 (6)
C19	0.0376 (9)	0.0140 (7)	0.0222 (8)	0.0007 (6)	0.0119 (7)	−0.0007 (6)
C20	0.0316 (8)	0.0128 (7)	0.0150 (7)	−0.0003 (6)	0.0061 (6)	0.0017 (5)
N1	0.0130 (5)	0.0120 (6)	0.0153 (6)	−0.0004 (4)	−0.0031 (4)	0.0018 (4)
N2	0.0138 (6)	0.0105 (5)	0.0142 (6)	−0.0004 (4)	−0.0020 (4)	0.0004 (4)
O1	0.0121 (5)	0.0206 (5)	0.0120 (5)	−0.0005 (4)	−0.0039 (4)	0.0060 (4)
O2	0.0121 (5)	0.0173 (5)	0.0153 (5)	−0.0013 (4)	−0.0007 (4)	0.0039 (4)
O3	0.0123 (5)	0.0159 (5)	0.0146 (5)	0.0019 (4)	−0.0007 (4)	−0.0001 (4)
O4	0.0119 (5)	0.0177 (5)	0.0108 (5)	0.0013 (4)	−0.0039 (4)	−0.0014 (4)
O5	0.0162 (5)	0.0163 (5)	0.0138 (5)	0.0011 (4)	−0.0053 (4)	−0.0008 (4)
O6	0.0271 (6)	0.0190 (5)	0.0241 (6)	0.0059 (4)	−0.0117 (5)	−0.0001 (4)
O7	0.0322 (6)	0.0232 (6)	0.0313 (6)	−0.0134 (5)	−0.0216 (5)	0.0127 (5)
O8	0.0155 (5)	0.0179 (5)	0.0147 (5)	−0.0013 (4)	−0.0046 (4)	0.0064 (4)

C1—C2	1.5174 (18)	C12—H12B	0.9900
C1—O1	1.2974 (17)	C12—C13	1.521 (2)
C1—O2	1.2356 (17)	C13—H13A	0.9900
C2—H2D	0.9900	C13—H13B	0.9900
C2—H2E	0.9900	C13—C14	1.530 (2)
C2—C3	1.5224 (19)	C14—H14A	0.9900
C3—H3A	0.9900	C14—H14B	0.9900
C3—H3B	0.9900	C15—H15	1.0000
C3—C4	1.5204 (18)	C15—C16	1.518 (2)
C4—O3	1.2367 (17)	C15—C20	1.524 (2)
C4—O4	1.2961 (16)	C15—N2	1.4972 (17)
C5—C6	1.5155 (18)	C16—H16A	0.9900
C5—O5	1.2955 (17)	C16—H16B	0.9900
C5—O6	1.2356 (18)	C16—C17	1.533 (2)
C6—H6A	0.9900	C17—H17A	0.9900
C6—H6B	0.9900	C17—H17B	0.9900
C6—C7	1.527 (2)	C17—C18	1.522 (2)
C7—H7A	0.9900	C18—H18A	0.9900
C7—H7B	0.9900	C18—H18B	0.9900
C7—C8	1.5172 (18)	C18—C19	1.523 (2)
C8—O7	1.2348 (18)	C19—H19A	0.9900
C8—O8	1.2894 (17)	C19—H19B	0.9900
C9—H9	1.0000	C19—C20	1.535 (2)
C9—C10	1.524 (2)	C20—H20A	0.9900
C9—C14	1.517 (2)	C20—H20B	0.9900
C9—N1	1.4961 (17)	N1—H1A	0.9100
C10—H10A	0.9900	N1—H1B	0.9100
C10—H10B	0.9900	N1—H1C	0.9100
C10—C11	1.534 (2)	N2—H2A	0.9100
C11—H11A	0.9900	N2—H2B	0.9100
C11—H11B	0.9900	N2—H2C	0.9100
C11—C12	1.514 (2)	O1—H1	0.8400
C12—H12A	0.9900	O4—H4	0.8400
O1—C1—C2	115.61 (11)	C12—C13—H13B	109.3
O2—C1—C2	120.85 (12)	C12—C13—C14	111.59 (13)
O2—C1—O1	123.51 (12)	H13A—C13—H13B	108.0
C1—C2—H2D	108.5	C14—C13—H13A	109.3
C1—C2—H2E	108.5	C14—C13—H13B	109.3
C1—C2—C3	115.06 (11)	C9—C14—C13	110.61 (12)
H2D—C2—H2E	107.5	C9—C14—H14A	109.5
C3—C2—H2D	108.5	C9—C14—H14B	109.5
C3—C2—H2E	108.5	C13—C14—H14A	109.5
C2—C3—H3A	108.6	C13—C14—H14B	109.5
C2—C3—H3B	108.6	H14A—C14—H14B	108.1
H3A—C3—H3B	107.6	C16—C15—H15	108.4
C4—C3—C2	114.67 (11)	C16—C15—C20	111.50 (12)
C4—C3—H3A	108.6	C20—C15—H15	108.4
C4—C3—H3B	108.6	N2—C15—H15	108.4
O3—C4—C3	120.91 (12)	N2—C15—C16	110.23 (11)
O3—C4—O4	123.68 (12)	N2—C15—C20	109.86 (11)
O4—C4—C3	115.37 (11)	C15—C16—H16A	109.6
O5—C5—C6	115.35 (12)	C15—C16—H16B	109.6
O6—C5—C6	120.21 (13)	C15—C16—C17	110.12 (12)
O6—C5—O5	124.44 (12)	H16A—C16—H16B	108.2
C5—C6—H6A	109.2	C17—C16—H16A	109.6
C5—C6—H6B	109.2	C17—C16—H16B	109.6
C5—C6—C7	111.84 (12)	C16—C17—H17A	109.3
H6A—C6—H6B	107.9	C16—C17—H17B	109.3
C7—C6—H6A	109.2	H17A—C17—H17B	107.9
C7—C6—H6B	109.2	C18—C17—C16	111.69 (13)
C6—C7—H7A	109.2	C18—C17—H17A	109.3
C6—C7—H7B	109.2	C18—C17—H17B	109.3
H7A—C7—H7B	107.9	C17—C18—H18A	109.4
C8—C7—C6	112.13 (12)	C17—C18—H18B	109.4
C8—C7—H7A	109.2	C17—C18—C19	111.36 (14)
C8—C7—H7B	109.2	H18A—C18—H18B	108.0
O7—C8—C7	119.57 (13)	C19—C18—H18A	109.4
O7—C8—O8	124.26 (13)	C19—C18—H18B	109.4
O8—C8—C7	116.16 (12)	C18—C19—H19A	109.2
C10—C9—H9	108.7	C18—C19—H19B	109.2
C14—C9—H9	108.7	C18—C19—C20	112.09 (13)
C14—C9—C10	110.73 (12)	H19A—C19—H19B	107.9
N1—C9—H9	108.7	C20—C19—H19A	109.2
N1—C9—C10	110.22 (11)	C20—C19—H19B	109.2
N1—C9—C14	109.86 (11)	C15—C20—C19	111.06 (12)
C9—C10—H10A	109.4	C15—C20—H20A	109.4
C9—C10—H10B	109.4	C15—C20—H20B	109.4
C9—C10—C11	111.02 (13)	C19—C20—H20A	109.4
H10A—C10—H10B	108.0	C19—C20—H20B	109.4
C11—C10—H10A	109.4	H20A—C20—H20B	108.0
C11—C10—H10B	109.4	C9—N1—H1A	109.5
C10—C11—H11A	109.1	C9—N1—H1B	109.5
C10—C11—H11B	109.1	C9—N1—H1C	109.5
H11A—C11—H11B	107.8	H1A—N1—H1B	109.5
C12—C11—C10	112.56 (13)	H1A—N1—H1C	109.5
C12—C11—H11A	109.1	H1B—N1—H1C	109.5
C12—C11—H11B	109.1	C15—N2—H2A	109.5
C11—C12—H12A	109.5	C15—N2—H2B	109.5
C11—C12—H12B	109.5	C15—N2—H2C	109.5
C11—C12—C13	110.91 (14)	H2A—N2—H2B	109.5
H12A—C12—H12B	108.0	H2A—N2—H2C	109.5
C13—C12—H12A	109.5	H2B—N2—H2C	109.5
C13—C12—H12B	109.5	C1—O1—H1	109.5
C12—C13—H13A	109.3	C4—O4—H4	109.5
C1—C2—C3—C4	169.67 (11)	C16—C15—C20—C19	55.77 (17)
C2—C3—C4—O3	156.32 (12)	C16—C17—C18—C19	−54.8 (2)
C2—C3—C4—O4	−25.91 (16)	C17—C18—C19—C20	53.0 (2)
C5—C6—C7—C8	179.04 (12)	C18—C19—C20—C15	−53.40 (19)
C6—C7—C8—O7	28.2 (2)	C20—C15—C16—C17	−57.25 (17)
C6—C7—C8—O8	−152.14 (13)	N1—C9—C10—C11	177.34 (13)
C9—C10—C11—C12	−54.0 (2)	N1—C9—C14—C13	−179.35 (13)
C10—C9—C14—C13	−57.37 (17)	N2—C15—C16—C17	−179.55 (13)
C10—C11—C12—C13	53.3 (2)	N2—C15—C20—C19	178.28 (12)
C11—C12—C13—C14	−54.75 (19)	O1—C1—C2—C3	−20.75 (17)
C12—C13—C14—C9	57.21 (19)	O2—C1—C2—C3	161.07 (12)
C14—C9—C10—C11	55.57 (18)	O5—C5—C6—C7	−58.22 (17)
C15—C16—C17—C18	56.77 (19)	O6—C5—C6—C7	121.41 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5i	0.91	1.99	2.8923 (16)	173
N1—H1B···O2ii	0.91	2.10	2.8969 (16)	146
N1—H1C···O7iii	0.91	1.86	2.7279 (15)	158
N2—H2A···O8iv	0.91	2.00	2.8746 (16)	160
N2—H2B···O3i	0.91	2.17	2.9098 (15)	138
N2—H2C···O6v	0.91	1.94	2.7485 (15)	148
O1—H1···O8vi	0.84	1.64	2.4734 (13)	175
O4—H4···O5	0.84	1.63	2.4636 (13)	175