Crystal structure of 2-methyl-piperazine-1,4-diium bis-(hydrogen maleate).

In the title salt, C5H14N2 (2+)·2C4H3O4 (-), the asymmetric unit contains two independent 2-methyl-piperazinium dications, which comprise a racemic pair, and four hydrogen maleate monoanions. In the roughly planar hydrogen maleate anions, intra-molecular O-H⋯O hydrogen bonds generate S(7) rings. In the crystal, the four independent anions are linked to the 2-methyl-piperazinium cations through N-H⋯O hydrogen bonds, forming two-dimensional layered structures lying parallel to (001).

Related literature

For maleate geometry and its S(7) ring formation, see: Anitha et al. (2012 ▸). For background on 2-methyl­piperazine salts, see: Hajlaoui et al. (2011 ▸); Wilkinson & Harrison (2007 ▸). For a similar structure, see: Mathlouthi et al. (2014 ▸). For puckering parameters, see: Cremer & Pople (1975 ▸).

Experimental

Crystal data

C5H14N2 2+·2C4H3O4 −

M = 332.31

Triclinic,

a = 11.4678 (9) Å

b = 11.4919 (9) Å

c = 13.3404 (13) Å

α = 71.692 (8)°

β = 75.572 (8)°

γ = 74.303 (7)°

V = 1580.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 170 K

0.33 × 0.14 × 0.07 mm

Data collection

Agilent SuperNova (single source at offset, Eos) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▸) T min = 0.970, T max = 0.990

10102 measured reflections

6990 independent reflections

5127 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.133

S = 1.06

6990 reflections

451 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2011 (Burla et al., 2012 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▸, 2015 ▸) within WinGX (Farrugia, 2012 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, General. DOI: 10.1107/S2056989015003102/zs2325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003102/zs2325Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015003102/zs2325Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015003102/zs2325fig1.tif

The two dications and the four anions in the asymmetric unit of the title salt, with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015003102/zs2325fig2.tif

A view of a layerered structure of the title compound along the c axis showing the two-dimensional layers lying parallel to the (001) plane. Hydrogen bonds are denoted by dashed lines.

Click here for additional data file.

b . DOI: 10.1107/S2056989015003102/zs2325fig3.tif

The structure of the title compound viewed along the b axis.

CCDC reference: 1049285

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

C5H14N22+·2C4H3O4−	Z = 4
Mr = 332.31	F(000) = 704
Triclinic, P1	Dx = 1.396 Mg m−3
a = 11.4678 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4919 (9) Å	Cell parameters from 3309 reflections
c = 13.3404 (13) Å	θ = 2.2–28.5°
α = 71.692 (8)°	µ = 0.12 mm−1
β = 75.572 (8)°	T = 170 K
γ = 74.303 (7)°	Prism, colourless
V = 1580.7 (2) Å3	0.33 × 0.14 × 0.07 mm

Agilent SuperNova (single source at offset, Eos) diffractometer	6990 independent reflections
Mirror monochromator	5127 reflections with I > 2σ(I)
Detector resolution: 16.0107 pixels mm-1	Rint = 0.020
ω scans	θmax = 29.0°, θmin = 1.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −14→14
Tmin = 0.970, Tmax = 0.990	k = −15→11
10102 measured reflections	l = −17→18

Refinement on F2	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133	w = 1/[σ2(Fo2) + (0.0497P)2 + 0.2961P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
6990 reflections	Δρmax = 0.27 e Å−3
451 parameters	Δρmin = −0.23 e Å−3

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
N1	0.47112 (14)	−0.07313 (15)	0.24023 (13)	0.0264 (3)
H1C	0.4636 (18)	−0.1306 (16)	0.2079 (15)	0.032*
H1D	0.5432 (16)	−0.0963 (18)	0.2683 (15)	0.032*
N2	0.24684 (15)	0.10974 (15)	0.21164 (13)	0.0289 (4)
H2E	0.2571 (19)	0.1670 (17)	0.2438 (15)	0.035*
H2F	0.1734 (16)	0.1357 (18)	0.1822 (15)	0.035*
C1	0.36652 (17)	−0.06564 (18)	0.33304 (15)	0.0285 (4)
H1	0.3764	−0.0068	0.3704	0.034*
C2	0.24641 (17)	−0.01499 (18)	0.29123 (16)	0.0303 (4)
H2A	0.2339	−0.0745	0.2569	0.036*
H2B	0.1773	−0.0068	0.3519	0.036*
C3	0.35045 (17)	0.10233 (19)	0.11976 (16)	0.0317 (4)
H3A	0.3505	0.1868	0.0698	0.038*
H3B	0.3398	0.0471	0.0803	0.038*
C4	0.47168 (17)	0.05140 (18)	0.15914 (16)	0.0306 (4)
H4A	0.5394	0.0420	0.0977	0.037*
H4B	0.4863	0.1112	0.1919	0.037*
C5	0.3686 (2)	−0.19420 (19)	0.41174 (17)	0.0389 (5)
H5A	0.4474	−0.2245	0.4372	0.058*
H5B	0.3588	−0.2526	0.3759	0.058*
H5C	0.3011	−0.1885	0.4729	0.058*
N1A	0.94928 (15)	0.40524 (14)	0.23662 (13)	0.0261 (3)
H1E	0.9556 (18)	0.3171 (14)	0.2709 (15)	0.031*
H1F	1.0225 (15)	0.4310 (18)	0.2052 (15)	0.031*
N2A	0.78144 (15)	0.64376 (15)	0.20796 (14)	0.0290 (4)
H2G	0.7075 (15)	0.6198 (19)	0.2407 (16)	0.035*
H2H	0.7684 (19)	0.7327 (14)	0.1807 (15)	0.035*
C1A	0.89052 (18)	0.46035 (17)	0.32972 (15)	0.0294 (4)
H1A	0.8112	0.4321	0.3635	0.035*
C2A	0.86258 (18)	0.60249 (17)	0.28913 (16)	0.0306 (4)
H2C	0.8216	0.6396	0.3500	0.037*
H2D	0.9404	0.6322	0.2567	0.037*
C3A	0.83774 (19)	0.58864 (17)	0.11580 (15)	0.0319 (4)
H3C	0.9137	0.6198	0.0775	0.038*
H3D	0.7798	0.6150	0.0650	0.038*
C4A	0.86848 (18)	0.44718 (17)	0.15408 (15)	0.0289 (4)
H4C	0.7916	0.4155	0.1853	0.035*
H4D	0.9110	0.4120	0.0924	0.035*
C5A	0.9731 (2)	0.4155 (2)	0.41267 (18)	0.0428 (5)
H5D	0.9892	0.3237	0.4373	0.064*
H5E	0.9325	0.4506	0.4738	0.064*
H5F	1.0511	0.4429	0.3807	0.064*
O1	0.66248 (13)	−0.15326 (13)	0.35791 (11)	0.0348 (3)
O2	0.66093 (13)	0.04943 (13)	0.30938 (12)	0.0395 (4)
H2	0.720 (2)	0.116 (2)	0.3089 (19)	0.059*
O3	0.79597 (13)	0.18044 (12)	0.30752 (11)	0.0354 (3)
O4	0.97246 (13)	0.15407 (12)	0.35879 (11)	0.0326 (3)
C6	0.70396 (18)	−0.06453 (18)	0.35806 (15)	0.0296 (4)
C7	0.80662 (18)	−0.09258 (18)	0.41811 (15)	0.0319 (4)
H7	0.8216	−0.1751	0.4640	0.038*
C8	0.88045 (18)	−0.02073 (18)	0.41771 (15)	0.0306 (4)
H8	0.9404	−0.0603	0.4626	0.037*
C9	0.88357 (18)	0.11290 (17)	0.35741 (15)	0.0276 (4)
O1A	0.26932 (14)	0.25263 (14)	0.33171 (12)	0.0416 (4)
O2A	0.42635 (13)	0.33042 (13)	0.22241 (11)	0.0342 (3)
H2I	0.493 (2)	0.398 (2)	0.2194 (18)	0.051*
O3A	0.55889 (13)	0.46177 (13)	0.22439 (11)	0.0342 (3)
O4A	0.58356 (13)	0.55559 (14)	0.33715 (12)	0.0396 (4)
C6A	0.35063 (19)	0.31324 (18)	0.31199 (16)	0.0311 (4)
C7A	0.3585 (2)	0.36602 (19)	0.39852 (16)	0.0355 (5)
H7A	0.3016	0.3453	0.4632	0.043*
C8A	0.43201 (19)	0.43722 (19)	0.40013 (16)	0.0334 (5)
H8A	0.4193	0.4589	0.4657	0.040*
C9A	0.53077 (18)	0.48811 (18)	0.31542 (16)	0.0300 (4)
O1B	0.73978 (12)	−0.10379 (12)	0.10276 (11)	0.0303 (3)
O2B	0.91092 (12)	−0.12659 (12)	0.16097 (11)	0.0346 (3)
H2J	0.980 (2)	−0.060 (2)	0.1591 (18)	0.052*
O3B	1.04304 (13)	0.00525 (12)	0.16145 (11)	0.0340 (3)
O4B	1.05050 (12)	0.20575 (12)	0.10410 (11)	0.0294 (3)
C6B	0.82359 (17)	−0.05937 (17)	0.11055 (15)	0.0258 (4)
C7B	0.81991 (18)	0.07654 (17)	0.05890 (16)	0.0307 (4)
H7B	0.7552	0.1182	0.0193	0.037*
C8B	0.89284 (18)	0.14906 (17)	0.05930 (16)	0.0307 (4)
H8B	0.8715	0.2341	0.0201	0.037*
C9B	1.00213 (16)	0.11871 (17)	0.11108 (14)	0.0243 (4)
O1C	0.16316 (13)	0.47339 (14)	0.10385 (12)	0.0409 (4)
O2C	0.18351 (13)	0.57671 (13)	0.21065 (11)	0.0367 (3)
H2K	0.250 (2)	0.640 (2)	0.2150 (18)	0.055*
O3C	0.31604 (13)	0.70898 (14)	0.20988 (11)	0.0373 (3)
O4C	0.47555 (14)	0.78285 (14)	0.10389 (12)	0.0417 (4)
C6C	0.21839 (17)	0.53961 (18)	0.12438 (15)	0.0295 (4)
C7C	0.32705 (17)	0.57784 (17)	0.04445 (15)	0.0282 (4)
H7C	0.3474	0.5450	−0.0162	0.034*
C8C	0.40062 (17)	0.65074 (17)	0.04398 (15)	0.0279 (4)
H8C	0.4646	0.6614	−0.0169	0.033*
C9C	0.39798 (18)	0.71797 (18)	0.12411 (16)	0.0299 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0202 (8)	0.0294 (8)	0.0316 (9)	−0.0010 (7)	−0.0068 (7)	−0.0129 (7)
N2	0.0219 (8)	0.0305 (9)	0.0368 (9)	−0.0005 (7)	−0.0096 (7)	−0.0133 (7)
C1	0.0240 (10)	0.0335 (10)	0.0285 (10)	−0.0021 (8)	−0.0043 (8)	−0.0126 (8)
C2	0.0242 (10)	0.0337 (10)	0.0330 (11)	−0.0051 (8)	−0.0030 (8)	−0.0115 (9)
C3	0.0263 (10)	0.0364 (11)	0.0326 (11)	−0.0048 (8)	−0.0070 (8)	−0.0096 (9)
C4	0.0251 (10)	0.0321 (10)	0.0349 (11)	−0.0045 (8)	−0.0061 (8)	−0.0098 (9)
C5	0.0362 (12)	0.0397 (12)	0.0357 (12)	−0.0023 (9)	−0.0057 (10)	−0.0083 (10)
N1A	0.0256 (8)	0.0214 (8)	0.0313 (9)	−0.0044 (7)	−0.0039 (7)	−0.0084 (7)
N2A	0.0267 (9)	0.0212 (8)	0.0373 (10)	−0.0047 (7)	−0.0024 (7)	−0.0082 (7)
C1A	0.0339 (11)	0.0275 (10)	0.0278 (10)	−0.0070 (8)	−0.0033 (8)	−0.0099 (8)
C2A	0.0314 (10)	0.0274 (10)	0.0347 (11)	−0.0053 (8)	−0.0043 (9)	−0.0126 (8)
C3A	0.0361 (11)	0.0268 (10)	0.0311 (11)	−0.0056 (8)	−0.0049 (9)	−0.0071 (8)
C4A	0.0304 (10)	0.0263 (10)	0.0322 (10)	−0.0046 (8)	−0.0079 (8)	−0.0102 (8)
C5A	0.0502 (14)	0.0408 (12)	0.0428 (13)	−0.0060 (10)	−0.0181 (11)	−0.0137 (10)
O1	0.0325 (8)	0.0370 (8)	0.0390 (8)	−0.0134 (6)	−0.0114 (6)	−0.0064 (6)
O2	0.0367 (8)	0.0336 (8)	0.0508 (9)	−0.0078 (7)	−0.0212 (7)	−0.0039 (7)
O3	0.0345 (8)	0.0281 (7)	0.0428 (8)	−0.0056 (6)	−0.0155 (7)	−0.0026 (6)
O4	0.0360 (8)	0.0271 (7)	0.0389 (8)	−0.0095 (6)	−0.0129 (6)	−0.0074 (6)
C6	0.0275 (10)	0.0338 (11)	0.0275 (10)	−0.0095 (8)	−0.0040 (8)	−0.0060 (8)
C7	0.0343 (11)	0.0312 (10)	0.0310 (11)	−0.0114 (9)	−0.0124 (9)	−0.0003 (8)
C8	0.0323 (11)	0.0313 (10)	0.0280 (10)	−0.0071 (8)	−0.0123 (9)	−0.0021 (8)
C9	0.0309 (10)	0.0287 (10)	0.0245 (10)	−0.0066 (8)	−0.0058 (8)	−0.0082 (8)
O1A	0.0520 (10)	0.0429 (9)	0.0386 (8)	−0.0252 (8)	−0.0034 (7)	−0.0133 (7)
O2A	0.0387 (8)	0.0358 (8)	0.0315 (8)	−0.0115 (6)	−0.0028 (6)	−0.0131 (6)
O3A	0.0295 (7)	0.0452 (8)	0.0301 (7)	−0.0117 (6)	0.0009 (6)	−0.0142 (6)
O4A	0.0345 (8)	0.0514 (9)	0.0414 (8)	−0.0197 (7)	−0.0025 (7)	−0.0184 (7)
C6A	0.0373 (11)	0.0271 (10)	0.0301 (11)	−0.0092 (9)	−0.0068 (9)	−0.0063 (8)
C7A	0.0437 (12)	0.0416 (12)	0.0248 (10)	−0.0203 (10)	−0.0005 (9)	−0.0085 (9)
C8A	0.0390 (12)	0.0409 (12)	0.0253 (10)	−0.0163 (9)	−0.0037 (9)	−0.0104 (9)
C9A	0.0263 (10)	0.0320 (10)	0.0322 (11)	−0.0040 (8)	−0.0075 (8)	−0.0092 (9)
O1B	0.0281 (7)	0.0263 (7)	0.0397 (8)	−0.0068 (6)	−0.0095 (6)	−0.0099 (6)
O2B	0.0296 (7)	0.0244 (7)	0.0501 (9)	−0.0057 (6)	−0.0167 (7)	−0.0026 (6)
O3B	0.0320 (8)	0.0244 (7)	0.0487 (9)	−0.0039 (6)	−0.0201 (7)	−0.0057 (6)
O4B	0.0255 (7)	0.0275 (7)	0.0369 (8)	−0.0070 (6)	−0.0064 (6)	−0.0091 (6)
C6B	0.0253 (10)	0.0259 (9)	0.0266 (10)	−0.0043 (7)	−0.0031 (8)	−0.0094 (8)
C7B	0.0295 (10)	0.0258 (10)	0.0372 (11)	−0.0042 (8)	−0.0155 (9)	−0.0028 (8)
C8B	0.0314 (11)	0.0222 (9)	0.0374 (11)	−0.0042 (8)	−0.0151 (9)	−0.0004 (8)
C9B	0.0216 (9)	0.0262 (9)	0.0255 (9)	−0.0046 (7)	−0.0022 (7)	−0.0091 (8)
O1C	0.0358 (8)	0.0560 (10)	0.0394 (8)	−0.0223 (7)	−0.0057 (7)	−0.0146 (7)
O2C	0.0316 (8)	0.0453 (9)	0.0355 (8)	−0.0138 (7)	0.0037 (6)	−0.0167 (7)
O3C	0.0392 (8)	0.0422 (8)	0.0353 (8)	−0.0133 (7)	0.0011 (7)	−0.0189 (7)
O4C	0.0528 (10)	0.0419 (9)	0.0391 (8)	−0.0253 (8)	−0.0023 (7)	−0.0140 (7)
C6C	0.0253 (10)	0.0316 (10)	0.0311 (10)	−0.0040 (8)	−0.0086 (8)	−0.0067 (8)
C7C	0.0287 (10)	0.0294 (10)	0.0258 (10)	−0.0027 (8)	−0.0063 (8)	−0.0079 (8)
C8C	0.0273 (10)	0.0295 (10)	0.0253 (10)	−0.0046 (8)	−0.0037 (8)	−0.0070 (8)
C9C	0.0322 (11)	0.0266 (10)	0.0314 (11)	−0.0059 (8)	−0.0075 (9)	−0.0071 (8)

N1—C4	1.499 (2)	O2—C6	1.287 (2)
N1—C1	1.500 (2)	O2—H2	1.15 (3)
N1—H1C	0.926 (14)	O3—C9	1.281 (2)
N1—H1D	0.932 (15)	O3—H2	1.28 (3)
N2—C3	1.485 (2)	O4—C9	1.241 (2)
N2—C2	1.492 (2)	C6—C7	1.495 (3)
N2—H2E	0.936 (15)	C7—C8	1.331 (3)
N2—H2F	0.953 (15)	C7—H7	0.9500
C1—C2	1.514 (3)	C8—C9	1.499 (3)
C1—C5	1.518 (3)	C8—H8	0.9500
C1—H1	1.0000	O1A—C6A	1.240 (2)
C2—H2A	0.9900	O2A—C6A	1.284 (2)
C2—H2B	0.9900	O2A—H2I	1.21 (2)
C3—C4	1.510 (3)	O3A—C9A	1.286 (2)
C3—H3A	0.9900	O3A—H2I	1.22 (2)
C3—H3B	0.9900	O4A—C9A	1.239 (2)
C4—H4A	0.9900	C6A—C7A	1.493 (3)
C4—H4B	0.9900	C7A—C8A	1.332 (3)
C5—H5A	0.9800	C7A—H7A	0.9500
C5—H5B	0.9800	C8A—C9A	1.486 (3)
C5—H5C	0.9800	C8A—H8A	0.9500
N1A—C4A	1.496 (2)	O1B—C6B	1.242 (2)
N1A—C1A	1.498 (2)	O2B—C6B	1.282 (2)
N1A—H1E	0.962 (14)	O2B—H2J	1.24 (2)
N1A—H1F	0.921 (15)	O3B—C9B	1.284 (2)
N2A—C3A	1.484 (2)	O3B—H2J	1.18 (2)
N2A—C2A	1.485 (2)	O4B—C9B	1.238 (2)
N2A—H2G	0.923 (15)	C6B—C7B	1.490 (3)
N2A—H2H	0.954 (15)	C7B—C8B	1.333 (2)
C1A—C5A	1.512 (3)	C7B—H7B	0.9500
C1A—C2A	1.520 (3)	C8B—C9B	1.488 (3)
C1A—H1A	1.0000	C8B—H8B	0.9500
C2A—H2C	0.9900	O1C—C6C	1.238 (2)
C2A—H2D	0.9900	O2C—C6C	1.286 (2)
C3A—C4A	1.512 (3)	O2C—H2K	1.20 (2)
C3A—H3C	0.9900	O3C—C9C	1.283 (2)
C3A—H3D	0.9900	O3C—H2K	1.22 (2)
C4A—H4C	0.9900	O4C—C9C	1.238 (2)
C4A—H4D	0.9900	C6C—C7C	1.491 (3)
C5A—H5D	0.9800	C7C—C8C	1.338 (2)
C5A—H5E	0.9800	C7C—H7C	0.9500
C5A—H5F	0.9800	C8C—C9C	1.493 (3)
O1—C6	1.237 (2)	C8C—H8C	0.9500
C4—N1—C1	111.81 (14)	C4A—C3A—H3D	109.6
C4—N1—H1C	109.4 (12)	H3C—C3A—H3D	108.1
C1—N1—H1C	108.5 (13)	N1A—C4A—C3A	110.55 (15)
C4—N1—H1D	107.7 (12)	N1A—C4A—H4C	109.5
C1—N1—H1D	106.4 (12)	C3A—C4A—H4C	109.5
H1C—N1—H1D	113.1 (17)	N1A—C4A—H4D	109.5
C3—N2—C2	111.34 (15)	C3A—C4A—H4D	109.5
C3—N2—H2E	107.0 (13)	H4C—C4A—H4D	108.1
C2—N2—H2E	110.0 (12)	C1A—C5A—H5D	109.5
C3—N2—H2F	106.1 (12)	C1A—C5A—H5E	109.5
C2—N2—H2F	108.9 (12)	H5D—C5A—H5E	109.5
H2E—N2—H2F	113.4 (17)	C1A—C5A—H5F	109.5
N1—C1—C2	109.12 (15)	H5D—C5A—H5F	109.5
N1—C1—C5	109.79 (15)	H5E—C5A—H5F	109.5
C2—C1—C5	111.37 (16)	C6—O2—H2	111.4 (12)
N1—C1—H1	108.8	C9—O3—H2	111.6 (11)
C2—C1—H1	108.8	O1—C6—O2	122.17 (17)
C5—C1—H1	108.8	O1—C6—C7	118.00 (17)
N2—C2—C1	110.87 (16)	O2—C6—C7	119.83 (17)
N2—C2—H2A	109.5	C8—C7—C6	130.47 (18)
C1—C2—H2A	109.5	C8—C7—H7	114.8
N2—C2—H2B	109.5	C6—C7—H7	114.8
C1—C2—H2B	109.5	C7—C8—C9	129.97 (18)
H2A—C2—H2B	108.1	C7—C8—H8	115.0
N2—C3—C4	110.34 (15)	C9—C8—H8	115.0
N2—C3—H3A	109.6	O4—C9—O3	122.40 (17)
C4—C3—H3A	109.6	O4—C9—C8	117.61 (17)
N2—C3—H3B	109.6	O3—C9—C8	119.99 (17)
C4—C3—H3B	109.6	C6A—O2A—H2I	111.0 (11)
H3A—C3—H3B	108.1	C9A—O3A—H2I	111.4 (11)
N1—C4—C3	110.65 (16)	O1A—C6A—O2A	122.80 (18)
N1—C4—H4A	109.5	O1A—C6A—C7A	116.90 (18)
C3—C4—H4A	109.5	O2A—C6A—C7A	120.29 (18)
N1—C4—H4B	109.5	C8A—C7A—C6A	130.79 (19)
C3—C4—H4B	109.5	C8A—C7A—H7A	114.6
H4A—C4—H4B	108.1	C6A—C7A—H7A	114.6
C1—C5—H5A	109.5	C7A—C8A—C9A	130.13 (18)
C1—C5—H5B	109.5	C7A—C8A—H8A	114.9
H5A—C5—H5B	109.5	C9A—C8A—H8A	114.9
C1—C5—H5C	109.5	O4A—C9A—O3A	122.54 (19)
H5A—C5—H5C	109.5	O4A—C9A—C8A	116.96 (17)
H5B—C5—H5C	109.5	O3A—C9A—C8A	120.50 (17)
C4A—N1A—C1A	111.40 (14)	C6B—O2B—H2J	109.4 (11)
C4A—N1A—H1E	110.4 (12)	C9B—O3B—H2J	109.6 (11)
C1A—N1A—H1E	101.4 (12)	O1B—C6B—O2B	122.06 (17)
C4A—N1A—H1F	108.5 (12)	O1B—C6B—C7B	117.68 (16)
C1A—N1A—H1F	108.9 (12)	O2B—C6B—C7B	120.26 (16)
H1E—N1A—H1F	116.1 (18)	C8B—C7B—C6B	130.34 (17)
C3A—N2A—C2A	111.72 (15)	C8B—C7B—H7B	114.8
C3A—N2A—H2G	109.8 (13)	C6B—C7B—H7B	114.8
C2A—N2A—H2G	108.4 (13)	C7B—C8B—C9B	130.62 (17)
C3A—N2A—H2H	107.6 (12)	C7B—C8B—H8B	114.7
C2A—N2A—H2H	109.1 (12)	C9B—C8B—H8B	114.7
H2G—N2A—H2H	110.3 (18)	O4B—C9B—O3B	122.09 (16)
N1A—C1A—C5A	110.46 (16)	O4B—C9B—C8B	117.92 (16)
N1A—C1A—C2A	109.13 (15)	O3B—C9B—C8B	119.99 (16)
C5A—C1A—C2A	111.50 (16)	C6C—O2C—H2K	111.3 (11)
N1A—C1A—H1A	108.6	C9C—O3C—H2K	111.7 (11)
C5A—C1A—H1A	108.6	O1C—C6C—O2C	121.98 (18)
C2A—C1A—H1A	108.6	O1C—C6C—C7C	117.87 (17)
N2A—C2A—C1A	110.29 (15)	O2C—C6C—C7C	120.14 (17)
N2A—C2A—H2C	109.6	C8C—C7C—C6C	130.72 (18)
C1A—C2A—H2C	109.6	C8C—C7C—H7C	114.6
N2A—C2A—H2D	109.6	C6C—C7C—H7C	114.6
C1A—C2A—H2D	109.6	C7C—C8C—C9C	130.18 (18)
H2C—C2A—H2D	108.1	C7C—C8C—H8C	114.9
N2A—C3A—C4A	110.50 (15)	C9C—C8C—H8C	114.9
N2A—C3A—H3C	109.6	O4C—C9C—O3C	122.04 (18)
C4A—C3A—H3C	109.6	O4C—C9C—C8C	117.88 (18)
N2A—C3A—H3D	109.6	O3C—C9C—C8C	120.08 (17)
C4—N1—C1—C2	56.7 (2)	C6—C7—C8—C9	0.8 (4)
C4—N1—C1—C5	179.01 (15)	C7—C8—C9—O4	−170.0 (2)
C3—N2—C2—C1	58.3 (2)	C7—C8—C9—O3	10.4 (3)
N1—C1—C2—N2	−57.02 (19)	O1A—C6A—C7A—C8A	−177.6 (2)
C5—C1—C2—N2	−178.38 (15)	O2A—C6A—C7A—C8A	2.9 (3)
C2—N2—C3—C4	−57.0 (2)	C6A—C7A—C8A—C9A	0.2 (4)
C1—N1—C4—C3	−56.6 (2)	C7A—C8A—C9A—O4A	178.0 (2)
N2—C3—C4—N1	55.7 (2)	C7A—C8A—C9A—O3A	−2.2 (3)
C4A—N1A—C1A—C5A	179.32 (16)	O1B—C6B—C7B—C8B	176.1 (2)
C4A—N1A—C1A—C2A	−57.8 (2)	O2B—C6B—C7B—C8B	−3.9 (3)
C3A—N2A—C2A—C1A	−58.2 (2)	C6B—C7B—C8B—C9B	0.1 (4)
N1A—C1A—C2A—N2A	57.7 (2)	C7B—C8B—C9B—O4B	−176.0 (2)
C5A—C1A—C2A—N2A	−179.99 (16)	C7B—C8B—C9B—O3B	3.6 (3)
C2A—N2A—C3A—C4A	56.7 (2)	O1C—C6C—C7C—C8C	177.83 (19)
C1A—N1A—C4A—C3A	57.0 (2)	O2C—C6C—C7C—C8C	−1.2 (3)
N2A—C3A—C4A—N1A	−55.4 (2)	C6C—C7C—C8C—C9C	0.1 (3)
O1—C6—C7—C8	167.9 (2)	C7C—C8C—C9C—O4C	−178.34 (19)
O2—C6—C7—C8	−12.7 (3)	C7C—C8C—C9C—O3C	0.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O4Ci	0.93 (1)	1.91 (2)	2.802 (2)	162 (2)
N1—H1D···O1	0.93 (2)	1.89 (2)	2.801 (2)	166 (2)
N2—H2E···O1A	0.94 (2)	1.80 (2)	2.723 (2)	168 (2)
N2—H2F···O3Bii	0.95 (2)	2.50 (2)	3.187 (2)	129 (2)
N2—H2F···O4Bii	0.95 (2)	1.82 (2)	2.760 (2)	169 (2)
N1A—H1E···O3	0.96 (1)	2.59 (2)	3.279 (2)	129 (2)
N1A—H1E···O4	0.96 (1)	1.86 (2)	2.811 (2)	169 (2)
N1A—H1F···O1Ciii	0.92 (2)	1.90 (2)	2.787 (2)	162 (2)
N2A—H2G···O4A	0.92 (2)	1.81 (2)	2.710 (2)	164 (2)
N2A—H2H···O1Biv	0.95 (2)	1.82 (2)	2.764 (2)	168 (2)
N2A—H2H···O2Biv	0.95 (2)	2.51 (2)	3.191 (2)	128 (2)
O2—H2···O3	1.15 (3)	1.28 (3)	2.4258 (19)	174 (2)
O2A—H2I···O3A	1.21 (2)	1.22 (2)	2.4240 (19)	175 (2)
O3B—H2J···O2B	1.18 (2)	1.24 (2)	2.4174 (18)	177 (2)
O2C—H2K···O3C	1.20 (2)	1.22 (2)	2.4192 (19)	174 (2)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1CO4C i	0.93(1)	1.91(2)	2.802(2)	162(2)
N1H1DO1	0.93(2)	1.89(2)	2.801(2)	166(2)
N2H2EO1A	0.94(2)	1.80(2)	2.723(2)	168(2)
N2H2FO3B ii	0.95(2)	2.50(2)	3.187(2)	129(2)
N2H2FO4B ii	0.95(2)	1.82(2)	2.760(2)	169(2)
N1AH1EO3	0.96(1)	2.59(2)	3.279(2)	129(2)
N1AH1EO4	0.96(1)	1.86(2)	2.811(2)	169(2)
N1AH1FO1C iii	0.92(2)	1.90(2)	2.787(2)	162(2)
N2AH2GO4A	0.92(2)	1.81(2)	2.710(2)	164(2)
N2AH2HO1B iv	0.95(2)	1.82(2)	2.764(2)	168(2)
N2AH2HO2B iv	0.95(2)	2.51(2)	3.191(2)	128(2)
O2H2O3	1.15(3)	1.28(3)	2.4258(19)	174(2)
O2AH2IO3A	1.21(2)	1.22(2)	2.4240(19)	175(2)
O3BH2JO2B	1.18(2)	1.24(2)	2.4174(18)	177(2)
O2CH2KO3C	1.20(2)	1.22(2)	2.4192(19)	174(2)

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