2,3-Dimeth­oxy-10-oxostrychnidinium hydrogen oxalate dihydrate

Krishnan, P.; Gayathri, K.; Sivakumar, N.; Chakkaravarthi, G.; Anbalagan, G.

doi:10.1107/S1600536813008623

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o659

https://doi.org/10.1107/S1600536813008623

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2,3-Dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate

P. Krishnan,^a K. Gayathri,^a N. Sivakumar,^a G. Chakkaravarthi ^b ^* and G. Anbalagan ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, anbu_24663@yahoo.co.in

(Received 15 February 2013; accepted 28 March 2013; online 5 April 2013)

In the cation of the title salt, C₂₃H₂₇N₂O₄⁺·C₂HO₄⁻·2H₂O, both fused pyrrolidine rings exhibit twisted conformations, while the piperidine rings adopt screw-boat and boat conformations. In the crystal, the three components are linked via O—H⋯O and N—H⋯O interactions, forming a tape along the b axis. The tapes are further linked by weak C—H⋯O hydrogen bonds. forming a three-dimensional network.

Related literature

For related structures, see: Smith et al. (2005 , 2006 ).

Experimental

Crystal data

C₂₃H₂₇N₂O₄⁺·C₂HO₄⁻·2H₂O
M_r = 520.53
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6110 (2) Å
b = 10.7375 (3) Å
c = 29.4990 (7) Å
V = 2410.75 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.28 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.978
13171 measured reflections
5805 independent reflections
5363 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.05
5805 reflections
354 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O8	0.88 (1)	1.87 (1)	2.712 (2)	159 (2)
O5—H5A⋯O7ⁱ	0.83 (1)	1.83 (1)	2.652 (2)	170 (4)
O9—H9A⋯O3ⁱⁱ	0.85 (1)	2.04 (2)	2.832 (3)	155 (5)
O9—H9B⋯O10	0.84 (1)	2.40 (3)	3.161 (4)	151 (5)
O10—H10D⋯O8	0.82 (1)	2.04 (1)	2.854 (3)	173 (5)
C7—H7⋯O9ⁱⁱⁱ	0.98	2.50	3.456 (3)	166
C11—H11⋯O9^iv	0.98	2.56	3.519 (3)	168
C17—H17A⋯O1ⁱⁱ	0.97	2.56	3.518 (2)	168
C21—H21A⋯O6^v	0.97	2.43	3.188 (3)	135
C21—H21B⋯O5^vi	0.97	2.59	3.293 (3)	130
C14—H14B⋯O1^vii	0.97	2.49	3.291 (2)	139
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) x, y-1, z; (iv) x+1, y-1, z; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813008623/is5247sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008623/is5247Isup2.hkl

checkCIF report

Comment top

The strychnos alkaloids strychnine and brucine have mostly been used to resolve enantiomorphic mixtures of chiral compounds, and the number of crystal structures of both salts and adducts of strychnine (Smith et al., 2006).

The geometric parameters of the title compound (Fig. 1) agree well with reported similar structure (Smith et al., 2005,2006). In the cation, both the pyrrolidine rings exhibit twisted conformations. The sum of bond angles around N1 [354.9 (2)°] and N2 [330.4 (2)°] indicates the sp² and sp³ hybridized state of N1 and N2 atoms, respectively. The crystal packing is influenced by intermolecular N—H···O, O—H···O and C—H···O interactions (Table 1 & Fig. 2).

Related literature top

For related structures, see: Smith et al. (2005, 2006).

Experimental top

The title compound was synthesized by mixing brucine (3.94 g, 0.01 mol) and oxalic acid dihydrate in 50 ml of 50% ethanol/water under reflux for 10 min. The partial room temperature evaporation of the filtered solution gave colorless single crystals in a week.

Structure description top

For related structures, see: Smith et al. (2005, 2006).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

2,3-Dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate top

Crystal data top

C₂₃H₂₇N₂O₄⁺·C₂HO₄⁻·2H₂O	F(000) = 1104
M_r = 520.53	D_x = 1.434 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5990 reflections
a = 7.6110 (2) Å	θ = 2.0–28.2°
b = 10.7375 (3) Å	µ = 0.11 mm⁻¹
c = 29.4990 (7) Å	T = 295 K
V = 2410.75 (11) Å³	Block, colourless
Z = 4	0.28 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	5805 independent reflections
Radiation source: fine-focus sealed tube	5363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω and φ scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→9
T_min = 0.970, T_max = 0.978	k = −10→14
13171 measured reflections	l = −39→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0708P)² + 0.4586P] where P = (F_o² + 2F_c²)/3
5805 reflections	(Δ/σ)_max < 0.001
354 parameters	Δρ_max = 0.33 e Å⁻³
7 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₃H₂₇N₂O₄⁺·C₂HO₄⁻·2H₂O	V = 2410.75 (11) Å³
M_r = 520.53	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.6110 (2) Å	µ = 0.11 mm⁻¹
b = 10.7375 (3) Å	T = 295 K
c = 29.4990 (7) Å	0.28 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	5805 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5363 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.978	R_int = 0.020
13171 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	7 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.33 e Å⁻³
5805 reflections	Δρ_min = −0.32 e Å⁻³
354 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8167 (2)	0.10403 (15)	0.04553 (5)	0.0273 (3)
C2	0.7938 (2)	0.22682 (15)	0.03194 (5)	0.0300 (3)
H2	0.7733	0.2890	0.0532	0.036*
C3	0.8019 (2)	0.25510 (14)	−0.01380 (5)	0.0281 (3)
C4	0.8270 (2)	0.16002 (15)	−0.04610 (5)	0.0283 (3)
C5	0.8518 (2)	0.03741 (15)	−0.03262 (5)	0.0277 (3)
H5	0.8702	−0.0256	−0.0537	0.033*
C6	0.8480 (2)	0.01221 (14)	0.01373 (5)	0.0262 (3)
C7	0.8725 (2)	−0.08541 (14)	0.08561 (5)	0.0240 (3)
H7	0.7940	−0.1469	0.0995	0.029*
C8	0.7954 (2)	0.04770 (14)	0.09221 (5)	0.0255 (3)
C9	0.9615 (3)	−0.20278 (15)	0.01824 (6)	0.0331 (4)
C10	1.0233 (3)	−0.29667 (16)	0.05273 (6)	0.0407 (4)
H10A	1.1123	−0.3482	0.0385	0.049*
H10B	0.9249	−0.3505	0.0600	0.049*
C11	1.0995 (2)	−0.24681 (16)	0.09759 (6)	0.0330 (4)
H11	1.2270	−0.2597	0.0978	0.040*
C12	1.0603 (2)	−0.10686 (15)	0.10212 (5)	0.0263 (3)
H12	1.1366	−0.0652	0.0801	0.032*
C13	1.0974 (2)	−0.04399 (16)	0.14785 (6)	0.0287 (3)
H13	1.2200	−0.0594	0.1563	0.034*
C14	1.0718 (2)	0.09617 (16)	0.14006 (6)	0.0331 (4)
H14A	1.1111	0.1422	0.1665	0.040*
H14B	1.1406	0.1230	0.1142	0.040*
C15	0.8791 (2)	0.12124 (15)	0.13160 (5)	0.0288 (3)
H2A	0.8636	0.2104	0.1258	0.035*
C16	0.6084 (2)	0.0154 (2)	0.15679 (6)	0.0371 (4)
H16A	0.6202	−0.0731	0.1625	0.045*
H16B	0.5032	0.0455	0.1718	0.045*
C17	0.6010 (2)	0.04159 (18)	0.10656 (6)	0.0346 (4)
H17A	0.5420	0.1199	0.1006	0.042*
H17B	0.5400	−0.0245	0.0906	0.042*
C18	1.0805 (4)	−0.30313 (19)	0.17721 (7)	0.0494 (5)
H18A	1.2029	−0.2779	0.1768	0.059*
H18B	1.0718	−0.3800	0.1943	0.059*
C19	0.9727 (3)	−0.20421 (18)	0.19990 (6)	0.0387 (4)
H19	0.9001	−0.2256	0.2240	0.046*
C20	0.9792 (2)	−0.08679 (16)	0.18616 (5)	0.0296 (3)
C21	0.8705 (3)	0.01255 (17)	0.20833 (6)	0.0329 (4)
H21A	0.9465	0.0685	0.2251	0.040*
H21B	0.7893	−0.0254	0.2296	0.040*
C22	0.8296 (3)	0.47074 (16)	−0.00029 (7)	0.0383 (4)
H22A	0.7379	0.4784	0.0219	0.057*
H22B	0.8411	0.5477	−0.0166	0.057*
H22C	0.9385	0.4518	0.0146	0.057*
C23	0.8254 (4)	0.1045 (2)	−0.12426 (7)	0.0518 (6)
H23A	0.9309	0.0558	−0.1224	0.078*
H23B	0.8183	0.1428	−0.1536	0.078*
H23C	0.7253	0.0515	−0.1198	0.078*
C24	0.6076 (2)	0.36823 (15)	0.23109 (6)	0.0334 (4)
C25	0.6212 (3)	0.51090 (15)	0.23589 (6)	0.0337 (4)
N1	0.8757 (2)	−0.10346 (12)	0.03567 (4)	0.0277 (3)
N2	0.7689 (2)	0.08528 (14)	0.17329 (5)	0.0309 (3)
H2B	0.728 (3)	0.1521 (16)	0.1869 (8)	0.046*
O1	0.8278 (2)	0.19783 (12)	−0.09044 (4)	0.0388 (3)
O2	0.7871 (2)	0.37348 (11)	−0.03112 (4)	0.0376 (3)
O3	0.9853 (3)	−0.21823 (13)	−0.02266 (5)	0.0509 (4)
O4	1.0205 (2)	−0.32384 (12)	0.13148 (5)	0.0432 (3)
O5	0.4765 (2)	0.57002 (13)	0.22834 (7)	0.0586 (5)
H5A	0.470 (5)	0.6456 (12)	0.2345 (12)	0.088*
O6	0.7510 (3)	0.56036 (16)	0.24876 (10)	0.0912 (9)
O7	0.5180 (3)	0.31491 (13)	0.25994 (6)	0.0654 (6)
O8	0.6928 (2)	0.32090 (14)	0.19997 (5)	0.0524 (4)
O9	0.5505 (4)	0.7048 (3)	0.11705 (8)	0.0835 (6)
H9A	0.565 (6)	0.709 (5)	0.0885 (4)	0.125*
H9B	0.609 (6)	0.647 (3)	0.1290 (16)	0.125*
O10	0.7913 (4)	0.4655 (3)	0.12287 (7)	0.0885 (8)
H10C	0.8980 (17)	0.462 (5)	0.1196 (15)	0.133*
H10D	0.758 (5)	0.429 (4)	0.1460 (10)	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0343 (8)	0.0252 (7)	0.0223 (7)	0.0027 (6)	−0.0002 (6)	0.0020 (6)
C2	0.0409 (9)	0.0237 (7)	0.0255 (7)	0.0035 (6)	−0.0005 (7)	−0.0003 (6)
C3	0.0350 (8)	0.0222 (7)	0.0271 (7)	0.0006 (6)	−0.0029 (6)	0.0033 (6)
C4	0.0333 (8)	0.0287 (8)	0.0228 (7)	−0.0018 (6)	−0.0025 (6)	0.0023 (6)
C5	0.0357 (8)	0.0249 (7)	0.0226 (7)	0.0009 (6)	−0.0023 (6)	−0.0018 (6)
C6	0.0325 (8)	0.0206 (7)	0.0254 (7)	0.0007 (6)	−0.0011 (6)	0.0011 (5)
C7	0.0295 (7)	0.0202 (6)	0.0224 (6)	−0.0010 (6)	0.0007 (6)	0.0010 (5)
C8	0.0331 (8)	0.0204 (7)	0.0229 (7)	0.0035 (6)	0.0010 (6)	0.0023 (5)
C9	0.0472 (10)	0.0236 (7)	0.0285 (8)	0.0034 (7)	−0.0008 (7)	−0.0012 (6)
C10	0.0663 (12)	0.0236 (7)	0.0323 (9)	0.0115 (8)	−0.0008 (9)	−0.0030 (6)
C11	0.0396 (9)	0.0279 (8)	0.0314 (8)	0.0098 (7)	0.0000 (7)	0.0013 (6)
C12	0.0283 (7)	0.0251 (7)	0.0255 (7)	−0.0002 (6)	0.0022 (6)	0.0004 (6)
C13	0.0259 (7)	0.0318 (8)	0.0283 (8)	−0.0029 (6)	−0.0018 (6)	−0.0003 (6)
C14	0.0399 (9)	0.0283 (8)	0.0310 (8)	−0.0122 (7)	0.0024 (7)	−0.0029 (6)
C15	0.0433 (9)	0.0205 (7)	0.0225 (7)	−0.0008 (7)	0.0041 (7)	0.0005 (5)
C16	0.0312 (8)	0.0506 (11)	0.0294 (8)	−0.0005 (8)	0.0047 (7)	0.0042 (8)
C17	0.0328 (8)	0.0428 (9)	0.0283 (8)	0.0081 (7)	0.0010 (7)	0.0028 (7)
C18	0.0812 (16)	0.0349 (9)	0.0321 (9)	0.0151 (10)	−0.0075 (10)	0.0069 (8)
C19	0.0514 (11)	0.0378 (9)	0.0270 (8)	−0.0005 (8)	−0.0003 (8)	0.0044 (7)
C20	0.0323 (8)	0.0326 (8)	0.0239 (7)	−0.0007 (7)	−0.0021 (6)	0.0003 (6)
C21	0.0397 (9)	0.0360 (9)	0.0231 (7)	0.0019 (7)	0.0019 (7)	0.0015 (6)
C22	0.0549 (11)	0.0242 (8)	0.0357 (9)	−0.0015 (8)	−0.0059 (8)	−0.0002 (7)
C23	0.0891 (17)	0.0400 (10)	0.0264 (8)	0.0080 (11)	−0.0042 (10)	−0.0017 (8)
C24	0.0441 (9)	0.0212 (7)	0.0350 (8)	0.0023 (7)	0.0045 (7)	0.0003 (6)
C25	0.0417 (9)	0.0229 (7)	0.0366 (9)	−0.0005 (7)	0.0056 (8)	0.0019 (6)
N1	0.0382 (7)	0.0221 (6)	0.0229 (6)	0.0002 (6)	−0.0022 (5)	0.0005 (5)
N2	0.0378 (7)	0.0315 (7)	0.0233 (6)	0.0054 (6)	0.0036 (6)	−0.0006 (5)
O1	0.0630 (9)	0.0298 (6)	0.0236 (6)	0.0004 (6)	−0.0020 (6)	0.0036 (5)
O2	0.0614 (8)	0.0229 (5)	0.0285 (6)	−0.0004 (6)	−0.0094 (6)	0.0038 (5)
O3	0.0907 (12)	0.0356 (7)	0.0264 (6)	0.0144 (8)	0.0030 (7)	−0.0031 (5)
O4	0.0689 (10)	0.0273 (6)	0.0333 (7)	0.0015 (6)	−0.0040 (7)	0.0054 (5)
O5	0.0460 (8)	0.0263 (6)	0.1035 (14)	0.0053 (6)	0.0038 (9)	0.0004 (8)
O6	0.0656 (12)	0.0400 (9)	0.168 (3)	−0.0093 (9)	−0.0456 (15)	0.0125 (12)
O7	0.1001 (14)	0.0238 (6)	0.0724 (12)	−0.0072 (8)	0.0471 (11)	−0.0007 (7)
O8	0.0770 (11)	0.0329 (7)	0.0473 (8)	0.0084 (7)	0.0221 (8)	−0.0039 (6)
O9	0.0839 (15)	0.0941 (17)	0.0725 (14)	−0.0141 (14)	−0.0099 (12)	0.0102 (13)
O10	0.1118 (19)	0.0983 (17)	0.0553 (11)	−0.0444 (16)	0.0036 (12)	0.0131 (11)

Geometric parameters (Å, º) top

C1—C6	1.382 (2)	C15—H2A	0.9800
C1—C2	1.389 (2)	C16—C17	1.509 (2)
C1—C8	1.513 (2)	C16—N2	1.514 (2)
C2—C3	1.384 (2)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—O2	1.3745 (19)	C17—H17A	0.9700
C3—C4	1.410 (2)	C17—H17B	0.9700
C4—O1	1.3694 (19)	C18—O4	1.441 (2)
C4—C5	1.388 (2)	C18—C19	1.499 (3)
C5—C6	1.394 (2)	C18—H18A	0.9700
C5—H5	0.9300	C18—H18B	0.9700
C6—N1	1.4162 (19)	C19—C20	1.325 (2)
C7—N1	1.4861 (19)	C19—H19	0.9300
C7—C12	1.528 (2)	C20—C21	1.500 (2)
C7—C8	1.557 (2)	C21—N2	1.509 (2)
C7—H7	0.9800	C21—H21A	0.9700
C8—C17	1.540 (2)	C21—H21B	0.9700
C8—C15	1.543 (2)	C22—O2	1.422 (2)
C9—O3	1.231 (2)	C22—H22A	0.9600
C9—N1	1.352 (2)	C22—H22B	0.9600
C9—C10	1.508 (2)	C22—H22C	0.9600
C10—C11	1.541 (3)	C23—O1	1.414 (2)
C10—H10A	0.9700	C23—H23A	0.9600
C10—H10B	0.9700	C23—H23B	0.9600
C11—O4	1.430 (2)	C23—H23C	0.9600
C11—C12	1.538 (2)	C24—O7	1.232 (2)
C11—H11	0.9800	C24—O8	1.234 (2)
C12—C13	1.535 (2)	C24—C25	1.542 (2)
C12—H12	0.9800	C25—O6	1.184 (3)
C13—C20	1.515 (2)	C25—O5	1.291 (3)
C13—C14	1.535 (2)	N2—H2B	0.880 (10)
C13—H13	0.9800	O5—H5A	0.833 (10)
C14—C15	1.512 (3)	O9—H9A	0.850 (10)
C14—H14A	0.9700	O9—H9B	0.836 (10)
C14—H14B	0.9700	O10—H10C	0.818 (10)
C15—N2	1.537 (2)	O10—H10D	0.824 (10)

C6—C1—C2	120.21 (15)	C14—C15—H2A	108.6
C6—C1—C8	110.56 (13)	N2—C15—H2A	108.6
C2—C1—C8	128.96 (14)	C8—C15—H2A	108.6
C3—C2—C1	118.94 (15)	C17—C16—N2	104.69 (14)
C3—C2—H2	120.5	C17—C16—H16A	110.8
C1—C2—H2	120.5	N2—C16—H16A	110.8
O2—C3—C2	124.15 (15)	C17—C16—H16B	110.8
O2—C3—C4	115.44 (14)	N2—C16—H16B	110.8
C2—C3—C4	120.40 (14)	H16A—C16—H16B	108.9
O1—C4—C5	123.65 (14)	C16—C17—C8	104.00 (13)
O1—C4—C3	115.56 (14)	C16—C17—H17A	111.0
C5—C4—C3	120.78 (14)	C8—C17—H17A	111.0
C4—C5—C6	117.53 (14)	C16—C17—H17B	111.0
C4—C5—H5	121.2	C8—C17—H17B	111.0
C6—C5—H5	121.2	H17A—C17—H17B	109.0
C1—C6—C5	122.07 (14)	O4—C18—C19	110.72 (17)
C1—C6—N1	109.96 (14)	O4—C18—H18A	109.5
C5—C6—N1	127.97 (14)	C19—C18—H18A	109.5
N1—C7—C12	106.32 (13)	O4—C18—H18B	109.5
N1—C7—C8	104.47 (12)	C19—C18—H18B	109.5
C12—C7—C8	116.82 (13)	H18A—C18—H18B	108.1
N1—C7—H7	109.6	C20—C19—C18	121.13 (18)
C12—C7—H7	109.6	C20—C19—H19	119.4
C8—C7—H7	109.6	C18—C19—H19	119.4
C1—C8—C17	111.72 (13)	C19—C20—C21	121.50 (16)
C1—C8—C15	115.90 (13)	C19—C20—C13	122.60 (16)
C17—C8—C15	102.20 (13)	C21—C20—C13	115.90 (14)
C1—C8—C7	102.29 (12)	C20—C21—N2	110.60 (13)
C17—C8—C7	110.93 (13)	C20—C21—H21A	109.5
C15—C8—C7	114.10 (13)	N2—C21—H21A	109.5
O3—C9—N1	123.36 (16)	C20—C21—H21B	109.5
O3—C9—C10	121.68 (16)	N2—C21—H21B	109.5
N1—C9—C10	114.94 (15)	H21A—C21—H21B	108.1
C9—C10—C11	117.69 (14)	O2—C22—H22A	109.5
C9—C10—H10A	107.9	O2—C22—H22B	109.5
C11—C10—H10A	107.9	H22A—C22—H22B	109.5
C9—C10—H10B	107.9	O2—C22—H22C	109.5
C11—C10—H10B	107.9	H22A—C22—H22C	109.5
H10A—C10—H10B	107.2	H22B—C22—H22C	109.5
O4—C11—C12	115.02 (14)	O1—C23—H23A	109.5
O4—C11—C10	103.96 (15)	O1—C23—H23B	109.5
C12—C11—C10	109.95 (14)	H23A—C23—H23B	109.5
O4—C11—H11	109.2	O1—C23—H23C	109.5
C12—C11—H11	109.2	H23A—C23—H23C	109.5
C10—C11—H11	109.2	H23B—C23—H23C	109.5
C7—C12—C13	112.69 (13)	O7—C24—O8	127.87 (17)
C7—C12—C11	107.52 (13)	O7—C24—C25	115.82 (16)
C13—C12—C11	118.08 (14)	O8—C24—C25	116.25 (16)
C7—C12—H12	105.9	O6—C25—O5	123.14 (17)
C13—C12—H12	105.9	O6—C25—C24	122.07 (18)
C11—C12—H12	105.9	O5—C25—C24	114.56 (17)
C20—C13—C12	114.40 (13)	C9—N1—C6	126.16 (14)
C20—C13—C14	109.49 (14)	C9—N1—C7	119.19 (13)
C12—C13—C14	106.05 (13)	C6—N1—C7	109.64 (12)
C20—C13—H13	108.9	C21—N2—C16	112.17 (14)
C12—C13—H13	108.9	C21—N2—C15	113.49 (14)
C14—C13—H13	108.9	C16—N2—C15	107.91 (13)
C15—C14—C13	108.81 (13)	C21—N2—H2B	106.9 (16)
C15—C14—H14A	109.9	C16—N2—H2B	105.2 (17)
C13—C14—H14A	109.9	C15—N2—H2B	110.8 (17)
C15—C14—H14B	109.9	C4—O1—C23	117.63 (14)
C13—C14—H14B	109.9	C3—O2—C22	115.02 (13)
H14A—C14—H14B	108.3	C11—O4—C18	115.61 (16)
C14—C15—N2	110.62 (13)	C25—O5—H5A	120 (3)
C14—C15—C8	115.71 (14)	H9A—O9—H9B	113 (5)
N2—C15—C8	104.41 (13)	H10C—O10—H10D	112 (3)

C6—C1—C2—C3	0.4 (3)	C17—C8—C15—C14	153.36 (14)
C8—C1—C2—C3	−173.02 (16)	C7—C8—C15—C14	33.55 (18)
C1—C2—C3—O2	−177.73 (17)	C1—C8—C15—N2	153.27 (13)
C1—C2—C3—C4	2.1 (3)	C17—C8—C15—N2	31.53 (15)
O2—C3—C4—O1	−2.0 (2)	C7—C8—C15—N2	−88.28 (15)
C2—C3—C4—O1	178.14 (16)	N2—C16—C17—C8	34.94 (18)
O2—C3—C4—C5	177.02 (16)	C1—C8—C17—C16	−165.99 (14)
C2—C3—C4—C5	−2.9 (3)	C15—C8—C17—C16	−41.43 (17)
O1—C4—C5—C6	179.91 (16)	C7—C8—C17—C16	80.57 (17)
C3—C4—C5—C6	1.0 (2)	O4—C18—C19—C20	−67.2 (3)
C2—C1—C6—C5	−2.3 (3)	C18—C19—C20—C21	179.35 (18)
C8—C1—C6—C5	172.24 (15)	C18—C19—C20—C13	−1.5 (3)
C2—C1—C6—N1	177.02 (16)	C12—C13—C20—C19	60.4 (2)
C8—C1—C6—N1	−8.48 (19)	C14—C13—C20—C19	179.25 (17)
C4—C5—C6—C1	1.6 (2)	C12—C13—C20—C21	−120.38 (16)
C4—C5—C6—N1	−177.60 (16)	C14—C13—C20—C21	−1.5 (2)
C6—C1—C8—C17	−102.75 (17)	C19—C20—C21—N2	−128.70 (18)
C2—C1—C8—C17	71.1 (2)	C13—C20—C21—N2	52.1 (2)
C6—C1—C8—C15	140.73 (15)	O7—C24—C25—O6	106.6 (3)
C2—C1—C8—C15	−45.4 (2)	O8—C24—C25—O6	−70.8 (3)
C6—C1—C8—C7	15.96 (18)	O7—C24—C25—O5	−68.1 (3)
C2—C1—C8—C7	−170.16 (17)	O8—C24—C25—O5	114.5 (2)
N1—C7—C8—C1	−16.91 (15)	O3—C9—N1—C6	−20.4 (3)
C12—C7—C8—C1	100.19 (15)	C10—C9—N1—C6	161.06 (17)
N1—C7—C8—C17	102.36 (14)	O3—C9—N1—C7	−172.66 (18)
C12—C7—C8—C17	−140.54 (14)	C10—C9—N1—C7	8.8 (2)
N1—C7—C8—C15	−142.87 (13)	C1—C6—N1—C9	−157.88 (17)
C12—C7—C8—C15	−25.77 (19)	C5—C6—N1—C9	21.4 (3)
O3—C9—C10—C11	141.4 (2)	C1—C6—N1—C7	−3.42 (19)
N1—C9—C10—C11	−40.0 (3)	C5—C6—N1—C7	175.81 (16)
C9—C10—C11—O4	135.72 (18)	C12—C7—N1—C9	45.57 (19)
C9—C10—C11—C12	12.1 (2)	C8—C7—N1—C9	169.70 (15)
N1—C7—C12—C13	157.39 (12)	C12—C7—N1—C6	−110.93 (14)
C8—C7—C12—C13	41.30 (18)	C8—C7—N1—C6	13.20 (17)
N1—C7—C12—C11	−70.77 (15)	C20—C21—N2—C16	78.03 (17)
C8—C7—C12—C11	173.15 (13)	C20—C21—N2—C15	−44.60 (19)
O4—C11—C12—C7	−75.91 (18)	C17—C16—N2—C21	−140.63 (14)
C10—C11—C12—C7	41.01 (19)	C17—C16—N2—C15	−14.89 (18)
O4—C11—C12—C13	52.9 (2)	C14—C15—N2—C21	−10.95 (19)
C10—C11—C12—C13	169.84 (15)	C8—C15—N2—C21	114.17 (15)
C7—C12—C13—C20	59.13 (18)	C14—C15—N2—C16	−135.90 (15)
C11—C12—C13—C20	−67.24 (19)	C8—C15—N2—C16	−10.78 (17)
C7—C12—C13—C14	−61.65 (17)	C5—C4—O1—C23	10.6 (3)
C11—C12—C13—C14	171.98 (14)	C3—C4—O1—C23	−170.48 (19)
C20—C13—C14—C15	−55.45 (18)	C2—C3—O2—C22	23.2 (3)
C12—C13—C14—C15	68.45 (17)	C4—C3—O2—C22	−156.72 (17)
C13—C14—C15—N2	62.41 (18)	C12—C11—O4—C18	−64.4 (2)
C13—C14—C15—C8	−56.03 (18)	C10—C11—O4—C18	175.37 (16)
C1—C8—C15—C14	−84.91 (17)	C19—C18—O4—C11	88.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O8	0.88 (1)	1.87 (1)	2.712 (2)	159 (2)
O5—H5A···O7ⁱ	0.83 (1)	1.83 (1)	2.652 (2)	170 (4)
O9—H9A···O3ⁱⁱ	0.85 (1)	2.04 (2)	2.832 (3)	155 (5)
O9—H9B···O10	0.84 (1)	2.40 (3)	3.161 (4)	151 (5)
O10—H10D···O8	0.82 (1)	2.04 (1)	2.854 (3)	173 (5)
C7—H7···O9ⁱⁱⁱ	0.98	2.50	3.456 (3)	166
C11—H11···O9^iv	0.98	2.56	3.519 (3)	168
C17—H17A···O1ⁱⁱ	0.97	2.56	3.518 (2)	168
C21—H21A···O6^v	0.97	2.43	3.188 (3)	135
C21—H21B···O5^vi	0.97	2.59	3.293 (3)	130
C14—H14B···O1^vii	0.97	2.49	3.291 (2)	139

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

Experimental details

Crystal data
Chemical formula	C₂₃H₂₇N₂O₄⁺·C₂HO₄⁻·2H₂O
M_r	520.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	7.6110 (2), 10.7375 (3), 29.4990 (7)
V (Å³)	2410.75 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	13171, 5805, 5363
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.05
No. of reflections	5805
No. of parameters	354
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.32

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O8	0.880 (10)	1.872 (13)	2.712 (2)	159 (2)
O5—H5A···O7ⁱ	0.833 (10)	1.827 (12)	2.652 (2)	170 (4)
O9—H9A···O3ⁱⁱ	0.850 (10)	2.04 (2)	2.832 (3)	155 (5)
O9—H9B···O10	0.836 (10)	2.40 (3)	3.161 (4)	151 (5)
O10—H10D···O8	0.824 (10)	2.035 (12)	2.854 (3)	173 (5)
C7—H7···O9ⁱⁱⁱ	0.98	2.50	3.456 (3)	166
C11—H11···O9^iv	0.98	2.56	3.519 (3)	168
C17—H17A···O1ⁱⁱ	0.97	2.56	3.518 (2)	168
C21—H21A···O6^v	0.97	2.43	3.188 (3)	135
C21—H21B···O5^vi	0.97	2.59	3.293 (3)	130
C14—H14B···O1^vii	0.97	2.49	3.291 (2)	139

Acknowledgements

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

References

Bruker (2003). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G., Wermuth, U. D., Healy, P. C., Young, D. J. & White, J. M. (2005). Acta Cryst. E61, o2646–o2648. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Smith, G., Wermuth, U. D., Young, D. J. & White, J. M. (2006). Acta Cryst. E62, o1553–o1555. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar