Bis(2-hy­droxy­eth­yl)ammonium picrate

Nagapandiselvi, P.; Gopalakrishnan, R.

doi:10.1107/S1600536813021697

organic compounds

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Volume 69| Part 9| September 2013| Page o1455

doi:10.1107/S1600536813021697

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Bis(2-hydroxyethyl)ammonium picrate

Perumal Nagapandiselvi ^a and Rengasamy Gopalakrishnan ^a ^*

^aDepartment of Physics, Anna University, Chennai 600 025, India
^*Correspondence e-mail: krgkrishnan@annauniv.edu

(Received 8 July 2013; accepted 3 August 2013; online 21 August 2013)

The asymmetric unit of the title salt, C₄H₁₂NO₂⁺·C₆H₂N₃O₇⁻, contain two bis(2-hydroxyethyl)ammonium cations and two picrate anions. An intramolecular N—H⋯O hydrogen bond occurs in each cation. In the crystal, molecules are linked via O—H⋯O and N—H⋯O hydrogen bonds, which generate two R₂¹(6), an R₂²(10) and an R₂²(13) graph-set ring motifs. There are also a number of C—H⋯O hydrogen bonds present. The sum of these interactions leads to the formation a three-dimensional structure.

Related literature

For general background to picrate complexes, see: In et al. (1997 ); Zaderenko et al. 1997 ); Ashwell et al. (1995 ); Owen & White (1976 ); Shakir et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₄H₁₂NO₂⁺·C₆H₂N₃O₇⁻
M_r = 334.25
Monoclinic, P 2₁ /c
a = 24.9396 (6) Å
b = 6.9158 (2) Å
c = 16.2974 (5) Å
β = 94.608 (1)°
V = 2801.85 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.882, T_max = 0.966
31581 measured reflections
7194 independent reflections
5200 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.03
7194 reflections
436 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7A⋯O15	0.91 (1)	2.48 (2)	2.8235 (19)	103 (1)
N7—H7A⋯O17ⁱ	0.91 (1)	2.43 (2)	2.9853 (18)	120 (1)
N7—H7A⋯O18ⁱⁱ	0.91 (1)	2.21 (1)	2.9272 (18)	136 (2)
N7—H7B⋯O8ⁱ	0.91 (2)	1.97 (2)	2.8359 (18)	157 (2)
N7—H7B⋯O14ⁱ	0.91 (2)	2.36 (2)	2.969 (2)	125 (1)
N8—H8A⋯O15ⁱⁱⁱ	0.91 (2)	2.05 (2)	2.9076 (18)	157 (1)
N8—H8B⋯O18	0.91 (2)	2.56 (2)	2.898 (2)	103 (1)
N8—H8B⋯O16^iv	0.91 (2)	1.96 (2)	2.8523 (18)	170 (2)
O15—H15⋯O1	0.82	2.12	2.7891 (16)	139
O15—H15⋯O2	0.82	2.41	3.138 (2)	149
O16—H16⋯O17ⁱ	0.82	2.24	2.9822 (18)	150
O17—H17⋯O8	0.82	2.00	2.7323 (14)	148
O17—H17⋯O9	0.82	2.27	2.9079 (19)	134
O18—H18⋯O1^iv	0.82	1.96	2.7453 (18)	161
C3—H3⋯O7^iv	0.93	2.59	3.502 (2)	167
C9—H9⋯O13ⁱ	0.93	2.50	3.425 (2)	176
C17—H17A⋯O12^v	0.97	2.50	3.359 (2)	147
C19—H19A⋯O7ⁱⁱⁱ	0.97	2.45	3.319 (3)	148
C19—H19B⋯O5^vi	0.97	2.44	3.224 (2)	138
C21—H21B⋯O1ⁱⁱⁱ	0.97	2.33	3.195 (2)	148
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) -x, -y+1, -z+1; (vi) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813021697/su2621sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021697/su2621Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021697/su2621Isup3.cml

checkCIF report

Comment top

It is well known that picric acid forms charge transfer molecular complexes with a number of aromatic compounds such as aromatic hydrocarbons and amines, through electrostatic or hydrogen bonding interactions (In et al., 1997; Zaderenko et al., 1997). The bonding of donor-acceptor picric acid complexes strongly depends on the nature of partners. Some of the picric acid complexes crystallize in centrosymmetric space groups but have non-linear optical properties (NLO) [Shakir et al., 2009]. This is due to the aggregation of the donor-acceptor molecules in a non-centrosymmetric manner which contributes to the bulk susceptibility from intermolecular charge transfer (Ashwell et al., 1995; Owen & White, 1976). We report herein on the crystal structure of the title salt.

The asymmetric unit of the title salt, Fig. 1, contains two picrate anions and two bis(2-hydroxyethyl)ammonium cations. The amine molecule exists as ammonium ion due to protonation. The picric acid exists as a picrate anion since the proton is transferred to the amine.

The picrate benzene rings (C1-C6 and C7-C12) are inclined to one another by 39.47 (7) °.

In the crystal, molecules are linked via O—H···O and N—H···O hydrogen bonds, which generate two R₂¹(6), an R₂²(10) and an R₂²(13) graph-set ring motifs (Bernstein et al., 1995), forming a three-dimensional structure (Table 1 and Fig. 2). There are also C-H···O hydrogen bonds present (Table 1).

Related literature top

For general background to picrate complexes, see: In et al. (1997); Zaderenko et al. 1997); Ashwell et al. (1995); Owen & White (1976); Shakir et al. (2009). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

An equimolar mixture of 2,2'-azanediylbis(ethan-1-ol) (1.05 mmol) and picric acid (2.29 mmol) in an ethanol solution was stirred over 4 h to attain a saturated homogeneous mixture. The light yellow coloured solution turned a dark yellow and product formation was confirmed using TLC. The saturated solution was filtered into a clean beaker and kept in a constant temperature bath at 303 K. Yellow coloured prism-like crystals suitable for X-ray diffraction analysis were harvested in 2 days.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details). H-atoms not involved in hydrogen bonding have been omitted for clarity.

Bis(2-hydroxyethyl)ammonium picrate top

Crystal data top

C₄H₁₂NO₂⁺·C₆H₂N₃O₇⁻	F(000) = 1392
M_r = 334.25	D_x = 1.585 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8443 reflections
a = 24.9396 (6) Å	θ = 2.5–28.2°
b = 6.9158 (2) Å	µ = 0.14 mm⁻¹
c = 16.2974 (5) Å	T = 293 K
β = 94.608 (1)°	Block, yellow
V = 2801.85 (14) Å³	0.35 × 0.30 × 0.25 mm
Z = 8

Data collection top

Bruker SMART APEXII area-detector diffractometer	7194 independent reflections
Radiation source: fine-focus sealed tube	5200 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scans	θ_max = 28.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −33→33
T_min = 0.882, T_max = 0.966	k = −8→9
31581 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0578P)² + 0.8326P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
7194 reflections	Δρ_max = 0.52 e Å⁻³
436 parameters	Δρ_min = −0.33 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (5)

Crystal data top

C₄H₁₂NO₂⁺·C₆H₂N₃O₇⁻	V = 2801.85 (14) Å³
M_r = 334.25	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 24.9396 (6) Å	µ = 0.14 mm⁻¹
b = 6.9158 (2) Å	T = 293 K
c = 16.2974 (5) Å	0.35 × 0.30 × 0.25 mm
β = 94.608 (1)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	7194 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5200 reflections with I > 2σ(I)
T_min = 0.882, T_max = 0.966	R_int = 0.032
31581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	4 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.52 e Å⁻³
7194 reflections	Δρ_min = −0.33 e Å⁻³
436 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O1	0.36588 (4)	0.55080 (17)	0.35068 (7)	0.0376 (4)
O2	0.31475 (5)	0.6612 (3)	0.48109 (9)	0.0732 (6)
O3	0.36173 (6)	0.6189 (3)	0.59420 (9)	0.0770 (7)
O4	0.54463 (5)	0.8458 (2)	0.60986 (8)	0.0524 (5)
O5	0.58962 (5)	0.8254 (2)	0.50363 (8)	0.0539 (5)
O6	0.50603 (8)	0.4989 (3)	0.26298 (10)	0.0854 (7)
O7	0.42846 (7)	0.6218 (3)	0.22486 (8)	0.0879 (8)
N1	0.35824 (6)	0.6443 (2)	0.52065 (9)	0.0414 (5)
N2	0.54771 (5)	0.81045 (19)	0.53708 (8)	0.0343 (4)
N3	0.46430 (7)	0.5815 (3)	0.27694 (9)	0.0492 (5)
C1	0.40616 (6)	0.6139 (2)	0.39305 (9)	0.0286 (4)
C2	0.40723 (6)	0.6641 (2)	0.47915 (9)	0.0301 (4)
C3	0.45221 (6)	0.7261 (2)	0.52603 (9)	0.0298 (4)
C4	0.49989 (6)	0.7465 (2)	0.48898 (9)	0.0287 (4)
C5	0.50313 (6)	0.6991 (2)	0.40681 (9)	0.0314 (4)
C6	0.45820 (6)	0.6370 (2)	0.36189 (9)	0.0311 (4)
O8	0.14146 (4)	0.04467 (19)	0.63223 (7)	0.0408 (4)
O9	0.17482 (5)	0.1133 (3)	0.48253 (9)	0.0708 (6)
O10	0.11402 (5)	0.0955 (2)	0.38420 (8)	0.0597 (5)
O11	−0.05810 (5)	0.3536 (2)	0.41733 (7)	0.0477 (4)
O12	−0.09095 (5)	0.3430 (2)	0.53515 (8)	0.0551 (5)
O13	0.02107 (7)	0.1656 (3)	0.77418 (9)	0.0919 (8)
O14	0.08393 (6)	−0.0338 (3)	0.76020 (9)	0.0722 (6)
N4	0.12787 (5)	0.1159 (2)	0.45685 (8)	0.0371 (4)
N5	−0.05404 (5)	0.3196 (2)	0.49110 (8)	0.0335 (4)
N6	0.05233 (6)	0.0868 (3)	0.73232 (8)	0.0467 (5)
C7	0.09722 (6)	0.1020 (2)	0.59992 (9)	0.0286 (4)
C8	0.08651 (6)	0.1477 (2)	0.51350 (9)	0.0280 (4)
C9	0.03840 (6)	0.2168 (2)	0.47875 (9)	0.0286 (4)
C10	−0.00312 (6)	0.2474 (2)	0.52799 (9)	0.0282 (4)
C11	0.00245 (6)	0.2070 (2)	0.61143 (9)	0.0321 (4)
C12	0.05015 (6)	0.1339 (2)	0.64497 (9)	0.0316 (4)
O15	0.25842 (5)	0.43596 (19)	0.33076 (8)	0.0432 (4)
O16	0.23692 (4)	0.95252 (18)	0.11889 (8)	0.0398 (4)
N7	0.19095 (5)	0.7158 (2)	0.24951 (8)	0.0332 (4)
C15	0.17130 (7)	0.9075 (3)	0.21928 (11)	0.0423 (6)
C16	0.18137 (6)	0.9372 (3)	0.13031 (11)	0.0394 (5)
C17	0.19148 (7)	0.6884 (3)	0.34013 (10)	0.0407 (5)
C18	0.20910 (7)	0.4870 (3)	0.36335 (11)	0.0456 (6)
O17	0.24822 (4)	−0.02326 (19)	0.61782 (8)	0.0424 (4)
O18	0.30269 (5)	0.6577 (2)	0.78140 (10)	0.0560 (5)
N8	0.30854 (5)	0.2811 (2)	0.70463 (8)	0.0318 (4)
C19	0.32980 (6)	0.1541 (3)	0.64123 (11)	0.0396 (5)
C20	0.28589 (7)	0.0922 (3)	0.57860 (10)	0.0396 (5)
C21	0.35099 (7)	0.3627 (3)	0.76446 (11)	0.0409 (5)
C22	0.32629 (8)	0.4956 (3)	0.82332 (12)	0.0505 (6)
H3	0.45060	0.75380	0.58160	0.0360*
H5	0.53560	0.70980	0.38280	0.0380*
H9	0.03390	0.24270	0.42260	0.0340*
H11	−0.02580	0.22930	0.64410	0.0390*
H7A	0.2259 (4)	0.703 (3)	0.2383 (12)	0.048 (5)*
H7B	0.1700 (6)	0.623 (2)	0.2236 (11)	0.045 (5)*
H15	0.28350	0.48610	0.35860	0.0650*
H15A	0.18940	1.00830	0.25240	0.0510*
H15B	0.13300	0.91760	0.22540	0.0510*
H16	0.24850	0.84640	0.10650	0.0600*
H16A	0.16630	0.82940	0.09810	0.0470*
H16B	0.16320	1.05400	0.11020	0.0470*
H17A	0.15580	0.71130	0.35760	0.0490*
H17B	0.21590	0.78100	0.36800	0.0490*
H18A	0.21330	0.47650	0.42290	0.0550*
H18B	0.18140	0.39650	0.34320	0.0550*
H8A	0.2849 (6)	0.214 (2)	0.7332 (10)	0.041 (5)*
H8B	0.2887 (7)	0.377 (2)	0.6794 (11)	0.045 (5)*
H17	0.21760	0.01330	0.60360	0.0640*
H18	0.32190	0.75280	0.79060	0.0840*
H19A	0.34630	0.04070	0.66760	0.0480*
H19B	0.35720	0.22300	0.61400	0.0480*
H20A	0.26800	0.20500	0.55390	0.0470*
H20B	0.30100	0.01840	0.53540	0.0470*
H21A	0.37710	0.43310	0.73500	0.0490*
H21B	0.36960	0.25850	0.79470	0.0490*
H22A	0.29900	0.42650	0.85090	0.0610*
H22B	0.35370	0.53900	0.86480	0.0610*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0327 (6)	0.0383 (7)	0.0405 (6)	−0.0014 (5)	−0.0049 (5)	−0.0058 (5)
O2	0.0330 (7)	0.1269 (15)	0.0599 (9)	0.0037 (8)	0.0055 (6)	−0.0091 (9)
O3	0.0550 (9)	0.1382 (16)	0.0394 (8)	−0.0213 (10)	0.0137 (6)	0.0033 (9)
O4	0.0448 (7)	0.0731 (10)	0.0374 (7)	−0.0020 (7)	−0.0075 (5)	−0.0136 (6)
O5	0.0322 (6)	0.0742 (10)	0.0553 (8)	−0.0116 (6)	0.0039 (5)	−0.0109 (7)
O6	0.1145 (14)	0.0906 (13)	0.0560 (10)	0.0195 (12)	0.0371 (10)	−0.0135 (9)
O7	0.0681 (10)	0.1635 (19)	0.0303 (7)	−0.0470 (11)	−0.0073 (7)	0.0040 (9)
N1	0.0341 (7)	0.0495 (9)	0.0412 (8)	−0.0036 (6)	0.0071 (6)	−0.0049 (7)
N2	0.0324 (7)	0.0306 (7)	0.0388 (7)	0.0015 (5)	−0.0041 (5)	−0.0019 (6)
N3	0.0614 (10)	0.0577 (10)	0.0291 (7)	−0.0219 (8)	0.0074 (7)	−0.0032 (7)
C1	0.0299 (7)	0.0227 (7)	0.0322 (7)	0.0029 (6)	−0.0031 (6)	0.0021 (6)
C2	0.0301 (7)	0.0285 (8)	0.0319 (7)	0.0031 (6)	0.0032 (6)	0.0016 (6)
C3	0.0351 (8)	0.0270 (8)	0.0269 (7)	0.0037 (6)	0.0005 (6)	0.0002 (6)
C4	0.0305 (7)	0.0251 (8)	0.0298 (7)	0.0018 (6)	−0.0026 (6)	0.0016 (6)
C5	0.0303 (7)	0.0315 (8)	0.0326 (8)	−0.0014 (6)	0.0041 (6)	0.0011 (6)
C6	0.0370 (8)	0.0310 (8)	0.0251 (7)	−0.0019 (6)	0.0015 (6)	0.0014 (6)
O8	0.0284 (5)	0.0552 (8)	0.0391 (6)	0.0067 (5)	0.0040 (4)	0.0128 (5)
O9	0.0300 (7)	0.1358 (16)	0.0478 (8)	0.0092 (8)	0.0099 (6)	0.0189 (9)
O10	0.0523 (8)	0.0944 (12)	0.0335 (7)	0.0120 (8)	0.0109 (6)	−0.0077 (7)
O11	0.0392 (6)	0.0665 (9)	0.0364 (7)	0.0055 (6)	−0.0039 (5)	0.0083 (6)
O12	0.0319 (6)	0.0845 (11)	0.0499 (8)	0.0147 (7)	0.0087 (5)	0.0086 (7)
O13	0.0803 (11)	0.164 (2)	0.0331 (7)	0.0529 (12)	0.0147 (7)	0.0004 (10)
O14	0.0509 (8)	0.1207 (15)	0.0461 (8)	0.0241 (9)	0.0109 (6)	0.0377 (9)
N4	0.0325 (7)	0.0452 (8)	0.0347 (7)	0.0036 (6)	0.0090 (5)	0.0046 (6)
N5	0.0285 (6)	0.0351 (8)	0.0362 (7)	−0.0009 (5)	−0.0008 (5)	0.0006 (6)
N6	0.0336 (7)	0.0782 (12)	0.0285 (7)	0.0044 (8)	0.0030 (6)	0.0045 (7)
C7	0.0268 (7)	0.0283 (8)	0.0306 (7)	−0.0015 (6)	0.0019 (5)	0.0008 (6)
C8	0.0274 (7)	0.0281 (8)	0.0292 (7)	−0.0020 (6)	0.0063 (5)	−0.0004 (6)
C9	0.0311 (7)	0.0284 (8)	0.0261 (7)	−0.0036 (6)	0.0014 (5)	−0.0004 (6)
C10	0.0252 (7)	0.0285 (8)	0.0304 (7)	−0.0011 (6)	−0.0003 (5)	−0.0015 (6)
C11	0.0272 (7)	0.0384 (9)	0.0309 (7)	−0.0013 (6)	0.0037 (6)	−0.0041 (6)
C12	0.0310 (7)	0.0390 (9)	0.0249 (7)	−0.0014 (6)	0.0025 (6)	−0.0009 (6)
O15	0.0363 (6)	0.0448 (7)	0.0475 (7)	−0.0010 (5)	−0.0023 (5)	−0.0025 (6)
O16	0.0305 (6)	0.0399 (7)	0.0488 (7)	−0.0030 (5)	0.0021 (5)	−0.0031 (6)
N7	0.0286 (6)	0.0364 (8)	0.0349 (7)	0.0015 (6)	0.0044 (5)	−0.0043 (6)
C15	0.0371 (9)	0.0378 (10)	0.0528 (10)	0.0087 (7)	0.0083 (7)	−0.0007 (8)
C16	0.0281 (8)	0.0405 (10)	0.0484 (10)	0.0033 (7)	−0.0036 (7)	0.0052 (8)
C17	0.0384 (9)	0.0521 (11)	0.0324 (8)	−0.0010 (8)	0.0077 (7)	−0.0044 (7)
C18	0.0436 (10)	0.0525 (11)	0.0413 (9)	−0.0077 (8)	0.0078 (7)	0.0075 (8)
O17	0.0297 (6)	0.0469 (7)	0.0504 (7)	−0.0026 (5)	0.0015 (5)	0.0081 (6)
O18	0.0441 (7)	0.0416 (8)	0.0780 (10)	0.0070 (6)	−0.0221 (7)	−0.0157 (7)
N8	0.0267 (6)	0.0302 (7)	0.0381 (7)	0.0011 (5)	−0.0001 (5)	0.0000 (6)
C19	0.0273 (7)	0.0413 (10)	0.0512 (10)	0.0021 (7)	0.0092 (7)	−0.0068 (8)
C20	0.0393 (9)	0.0429 (10)	0.0374 (9)	−0.0037 (7)	0.0086 (7)	−0.0053 (7)
C21	0.0363 (8)	0.0320 (9)	0.0515 (10)	0.0001 (7)	−0.0134 (7)	0.0015 (7)
C22	0.0609 (12)	0.0408 (11)	0.0476 (10)	−0.0075 (9)	−0.0098 (9)	−0.0069 (8)

Geometric parameters (Å, º) top

O1—C1	1.2510 (18)	C1—C2	1.444 (2)
O2—N1	1.222 (2)	C1—C6	1.440 (2)
O3—N1	1.208 (2)	C2—C3	1.374 (2)
O4—N2	1.2195 (18)	C3—C4	1.383 (2)
O5—N2	1.2214 (18)	C4—C5	1.387 (2)
O6—N3	1.224 (3)	C5—C6	1.358 (2)
O7—N3	1.215 (2)	C3—H3	0.9300
O8—C7	1.2484 (18)	C5—H5	0.9300
O9—N4	1.2115 (18)	C7—C8	1.447 (2)
O10—N4	1.2147 (18)	C7—C12	1.451 (2)
O11—N5	1.2212 (17)	C8—C9	1.371 (2)
O12—N5	1.2228 (18)	C9—C10	1.376 (2)
O13—N6	1.207 (2)	C10—C11	1.384 (2)
O14—N6	1.211 (3)	C11—C12	1.366 (2)
O15—C18	1.423 (2)	C9—H9	0.9300
O16—C16	1.4166 (18)	C11—H11	0.9300
O15—H15	0.8200	C15—C16	1.505 (3)
O16—H16	0.8200	C17—C18	1.500 (3)
O17—C20	1.423 (2)	C15—H15A	0.9700
O18—C22	1.416 (2)	C15—H15B	0.9700
O17—H17	0.8200	C16—H16A	0.9700
O18—H18	0.8200	C16—H16B	0.9700
N1—C2	1.450 (2)	C17—H17B	0.9700
N2—C4	1.443 (2)	C17—H17A	0.9700
N3—C6	1.456 (2)	C18—H18A	0.9700
N4—C8	1.455 (2)	C18—H18B	0.9700
N5—C10	1.449 (2)	C19—C20	1.498 (2)
N6—C12	1.457 (2)	C21—C22	1.497 (3)
N7—C15	1.484 (2)	C19—H19A	0.9700
N7—C17	1.488 (2)	C19—H19B	0.9700
N7—H7A	0.909 (11)	C20—H20A	0.9700
N7—H7B	0.910 (15)	C20—H20B	0.9700
N8—C21	1.491 (2)	C21—H21A	0.9700
N8—C19	1.486 (2)	C21—H21B	0.9700
N8—H8B	0.906 (16)	C22—H22A	0.9700
N8—H8A	0.908 (15)	C22—H22B	0.9700

C18—O15—H15	109.00	N5—C10—C9	119.09 (13)
C16—O16—H16	109.00	C9—C10—C11	121.39 (14)
C20—O17—H17	109.00	N5—C10—C11	119.50 (13)
C22—O18—H18	109.00	C10—C11—C12	118.90 (14)
O3—N1—C2	118.72 (14)	N6—C12—C7	119.49 (13)
O2—N1—C2	119.37 (14)	N6—C12—C11	115.90 (13)
O2—N1—O3	121.85 (16)	C7—C12—C11	124.61 (13)
O4—N2—C4	118.42 (13)	C10—C9—H9	120.00
O5—N2—C4	118.88 (13)	C8—C9—H9	120.00
O4—N2—O5	122.69 (13)	C12—C11—H11	121.00
O6—N3—O7	124.47 (17)	C10—C11—H11	121.00
O6—N3—C6	117.06 (15)	N7—C15—C16	111.44 (15)
O7—N3—C6	118.47 (17)	O16—C16—C15	112.17 (14)
O9—N4—C8	119.85 (13)	N7—C17—C18	110.35 (15)
O9—N4—O10	121.75 (14)	O15—C18—C17	112.38 (15)
O10—N4—C8	118.39 (12)	C16—C15—H15A	109.00
O11—N5—O12	123.07 (14)	N7—C15—H15B	109.00
O11—N5—C10	118.38 (13)	C16—C15—H15B	109.00
O12—N5—C10	118.55 (13)	H15A—C15—H15B	108.00
O13—N6—O14	121.99 (15)	N7—C15—H15A	109.00
O14—N6—C12	119.52 (15)	O16—C16—H16B	109.00
O13—N6—C12	118.45 (16)	C15—C16—H16A	109.00
C15—N7—C17	114.82 (14)	C15—C16—H16B	109.00
H7A—N7—H7B	111.2 (16)	H16A—C16—H16B	108.00
C17—N7—H7B	109.3 (11)	O16—C16—H16A	109.00
C15—N7—H7B	108.3 (10)	N7—C17—H17A	110.00
C17—N7—H7A	104.8 (12)	N7—C17—H17B	110.00
C15—N7—H7A	108.5 (13)	C18—C17—H17B	110.00
C19—N8—C21	113.83 (12)	H17A—C17—H17B	108.00
H8A—N8—H8B	104.7 (14)	C18—C17—H17A	110.00
C21—N8—H8B	110.7 (10)	C17—C18—H18A	109.00
C19—N8—H8A	109.7 (9)	O15—C18—H18A	109.00
C19—N8—H8B	109.2 (11)	C17—C18—H18B	109.00
C21—N8—H8A	108.3 (10)	H18A—C18—H18B	108.00
O1—C1—C2	124.87 (14)	O15—C18—H18B	109.00
C2—C1—C6	111.67 (13)	N8—C19—C20	111.13 (13)
O1—C1—C6	123.41 (13)	O17—C20—C19	109.09 (14)
C1—C2—C3	124.47 (14)	N8—C21—C22	110.14 (14)
N1—C2—C1	118.70 (13)	O18—C22—C21	110.70 (16)
N1—C2—C3	116.81 (13)	N8—C19—H19A	109.00
C2—C3—C4	118.76 (14)	N8—C19—H19B	109.00
N2—C4—C3	119.74 (13)	C20—C19—H19A	109.00
N2—C4—C5	119.15 (13)	C20—C19—H19B	109.00
C3—C4—C5	121.06 (14)	H19A—C19—H19B	108.00
C4—C5—C6	119.05 (14)	O17—C20—H20A	110.00
N3—C6—C5	116.82 (14)	O17—C20—H20B	110.00
N3—C6—C1	118.16 (13)	C19—C20—H20A	110.00
C1—C6—C5	124.96 (14)	C19—C20—H20B	110.00
C2—C3—H3	121.00	H20A—C20—H20B	108.00
C4—C3—H3	121.00	N8—C21—H21A	110.00
C6—C5—H5	120.00	N8—C21—H21B	110.00
C4—C5—H5	120.00	C22—C21—H21A	110.00
O8—C7—C8	124.58 (14)	C22—C21—H21B	110.00
C8—C7—C12	111.45 (13)	H21A—C21—H21B	108.00
O8—C7—C12	123.96 (13)	O18—C22—H22A	109.00
N4—C8—C9	115.60 (13)	O18—C22—H22B	109.00
C7—C8—C9	124.41 (14)	C21—C22—H22A	110.00
N4—C8—C7	119.97 (13)	C21—C22—H22B	109.00
C8—C9—C10	119.16 (14)	H22A—C22—H22B	108.00

O2—N1—C2—C3	152.93 (17)	C6—C1—C2—C3	−0.1 (2)
O2—N1—C2—C1	−28.5 (2)	O1—C1—C6—C5	−177.78 (14)
O3—N1—C2—C1	154.31 (17)	C2—C1—C6—C5	−0.3 (2)
O3—N1—C2—C3	−24.2 (2)	C6—C1—C2—N1	−178.52 (12)
O5—N2—C4—C3	179.11 (14)	C1—C2—C3—C4	1.4 (2)
O4—N2—C4—C3	−0.3 (2)	N1—C2—C3—C4	179.82 (13)
O4—N2—C4—C5	−177.73 (14)	C2—C3—C4—C5	−2.3 (2)
O5—N2—C4—C5	1.6 (2)	C2—C3—C4—N2	−179.68 (13)
O6—N3—C6—C5	37.1 (2)	N2—C4—C5—C6	179.31 (13)
O7—N3—C6—C1	40.8 (3)	C3—C4—C5—C6	1.9 (2)
O7—N3—C6—C5	−141.99 (19)	C4—C5—C6—N3	−177.52 (14)
O6—N3—C6—C1	−140.14 (18)	C4—C5—C6—C1	−0.5 (2)
O9—N4—C8—C7	−24.1 (2)	C8—C7—C12—C11	−3.1 (2)
O9—N4—C8—C9	157.43 (17)	C12—C7—C8—C9	1.4 (2)
O10—N4—C8—C9	−21.5 (2)	O8—C7—C8—N4	4.0 (2)
O10—N4—C8—C7	157.01 (14)	C8—C7—C12—N6	177.03 (14)
O11—N5—C10—C11	−179.74 (14)	O8—C7—C12—N6	−3.8 (2)
O12—N5—C10—C9	178.72 (14)	C12—C7—C8—N4	−176.87 (12)
O12—N5—C10—C11	0.0 (2)	O8—C7—C12—C11	176.07 (15)
O11—N5—C10—C9	−1.0 (2)	O8—C7—C8—C9	−177.71 (15)
O14—N6—C12—C11	155.08 (17)	N4—C8—C9—C10	178.84 (13)
O14—N6—C12—C7	−25.0 (2)	C7—C8—C9—C10	0.5 (2)
O13—N6—C12—C11	−22.5 (2)	C8—C9—C10—N5	−179.71 (13)
O13—N6—C12—C7	157.36 (17)	C8—C9—C10—C11	−1.0 (2)
C17—N7—C15—C16	169.65 (14)	C9—C10—C11—C12	−0.5 (2)
C15—N7—C17—C18	176.94 (14)	N5—C10—C11—C12	178.17 (13)
C21—N8—C19—C20	−174.64 (15)	C10—C11—C12—C7	2.8 (2)
C19—N8—C21—C22	177.33 (15)	C10—C11—C12—N6	−177.37 (14)
C2—C1—C6—N3	176.61 (14)	N7—C15—C16—O16	−67.6 (2)
O1—C1—C2—C3	177.31 (14)	N7—C17—C18—O15	52.13 (19)
O1—C1—C6—N3	−0.8 (2)	N8—C19—C20—O17	−64.2 (2)
O1—C1—C2—N1	−1.1 (2)	N8—C21—C22—O18	−64.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···O15	0.91 (1)	2.48 (2)	2.8235 (19)	103 (1)
N7—H7A···O17ⁱ	0.91 (1)	2.43 (2)	2.9853 (18)	120 (1)
N7—H7A···O18ⁱⁱ	0.91 (1)	2.21 (1)	2.9272 (18)	136 (2)
N7—H7B···O8ⁱ	0.91 (2)	1.97 (2)	2.8359 (18)	157 (2)
N7—H7B···O14ⁱ	0.91 (2)	2.36 (2)	2.969 (2)	125 (1)
N8—H8A···O15ⁱⁱⁱ	0.91 (2)	2.05 (2)	2.9076 (18)	157 (1)
N8—H8B···O18	0.91 (2)	2.56 (2)	2.898 (2)	103 (1)
N8—H8B···O16^iv	0.91 (2)	1.96 (2)	2.8523 (18)	170 (2)
O15—H15···O1	0.82	2.12	2.7891 (16)	139
O15—H15···O2	0.82	2.41	3.138 (2)	149
O16—H16···O17ⁱ	0.82	2.24	2.9822 (18)	150
O17—H17···O8	0.82	2.00	2.7323 (14)	148
O17—H17···O9	0.82	2.27	2.9079 (19)	134
O18—H18···O1^iv	0.82	1.96	2.7453 (18)	161
C3—H3···O7^iv	0.93	2.59	3.502 (2)	167
C9—H9···O13ⁱ	0.93	2.50	3.425 (2)	176
C17—H17A···O12^v	0.97	2.50	3.359 (2)	147
C19—H19A···O7ⁱⁱⁱ	0.97	2.45	3.319 (3)	148
C19—H19B···O5^vi	0.97	2.44	3.224 (2)	138
C21—H21B···O1ⁱⁱⁱ	0.97	2.33	3.195 (2)	148

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x, −y+1, −z+1; (vi) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···O15	0.909 (11)	2.48 (2)	2.8235 (19)	102.9 (14)
N7—H7A···O17ⁱ	0.909 (11)	2.426 (19)	2.9853 (18)	119.9 (14)
N7—H7A···O18ⁱⁱ	0.909 (11)	2.208 (14)	2.9272 (18)	135.6 (17)
N7—H7B···O8ⁱ	0.910 (15)	1.974 (16)	2.8359 (18)	157.4 (15)
N7—H7B···O14ⁱ	0.910 (15)	2.356 (15)	2.969 (2)	124.6 (13)
N8—H8A···O15ⁱⁱⁱ	0.908 (15)	2.051 (16)	2.9076 (18)	156.8 (14)
N8—H8B···O18	0.906 (16)	2.561 (16)	2.898 (2)	102.7 (12)
N8—H8B···O16^iv	0.906 (16)	1.956 (16)	2.8523 (18)	169.9 (15)
O15—H15···O1	0.82	2.12	2.7891 (16)	139
O15—H15···O2	0.82	2.41	3.138 (2)	149
O16—H16···O17ⁱ	0.82	2.24	2.9822 (18)	150
O17—H17···O8	0.82	2.00	2.7323 (14)	148
O17—H17···O9	0.82	2.27	2.9079 (19)	134
O18—H18···O1^iv	0.82	1.96	2.7453 (18)	161
C3—H3···O7^iv	0.93	2.59	3.502 (2)	167
C9—H9···O13ⁱ	0.93	2.50	3.425 (2)	176
C17—H17A···O12^v	0.97	2.50	3.359 (2)	147
C19—H19A···O7ⁱⁱⁱ	0.97	2.45	3.319 (3)	148
C19—H19B···O5^vi	0.97	2.44	3.224 (2)	138
C21—H21B···O1ⁱⁱⁱ	0.97	2.33	3.195 (2)	148

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x, −y+1, −z+1; (vi) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT Madras, Chennai, India, for the data collection and acknowledge the Council of Scientific and Industrial research (CSIR) Government of India, for funding this project [No. 03 (115)/10/EMR-II].

References

Ashwell, G. J., Jefferies, G., Hamilton, D. G., Lynch, D. E., Roberts, M. P. S., Bahra, G. S. & Brown, C. R. (1995). Nature (London), 375, 385–388. CrossRef CAS Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
In, Y., Nagata, H., Doi, M., Ishida, T. & Wakahara, A. (1997). Acta Cryst. C53, 367–369. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Owen, J. R. & White, E. A. D. (1976). J. Mater. Sci. 11, 2165–2169. CrossRef CAS Web of Science Google Scholar
Shakir, M., Kushwaha, S. K., Maurya, K. K., Arora, M. & Bhagavannarayana, G. (2009). J. Cryst. Growth, 311, 3871–3875. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zaderenko, P., Gil, M. S., López, P., Ballesteros, P., Fonseca, I. & Albert, A. (1997). Acta Cryst. B53, 961–967. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar