2,2′-(Biphenyl-2,2′-diyldi­oxy)diaceto­hydrazide

Ibad, F.; Mustafa, A.; Shah, M.R.; VanDerveer, D.

doi:10.1107/S1600536808014864

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1130-o1131

doi:10.1107/S1600536808014864

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2,2′-(Biphenyl-2,2′-diyldioxy)diacetohydrazide

Farooq Ibad,^a Asra Mustafa,^a Muhammad Raza Shah ^a ^* and Donald VanDerveer ^b

^aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bChemistry Department, Clemson University, Clemson, SC 29634-0973, USA
^*Correspondence e-mail: raza_shahm@yahoo.com

(Received 5 May 2008; accepted 16 May 2008; online 21 May 2008)

In the molecule of the title compound, C₁₆H₁₈N₄O₄, the dihedral angle between the mean planes of the two benzene rings is 56.76 (5)°. The crystal structure reveals extensive intermolecular hydrogen bonds between carbonyl O atoms and primary amines, as well as between primary and secondary amines of hydrazide, forming rings of R₂²(10) and R₂²(6) motifs, respectively. The structure is further stabilized by intramolecular and non-classical hydrogen bonds of the types N—H⋯O and C—H⋯O, respectively. The structure does not show any π–π interactions.

Related literature

For related literature see: Dekeyser et al. (2003 ); Ali et al. (2008 ); Baudry et al. (2006 ); Bhat et al. (1974 ); Etter (1990 ); Kakefuda et al. (2002 ); Litvinchuk et al. (2004 ); Priebe et al. (2008 ); Sisson et al. (2006 ); Thaker & Patel (2008 ); Yan et al. (1993 ).

Experimental

Crystal data

C₁₆H₁₈N₄O₄
M_r = 330.34
Triclinic, $[P \overline 1]$
a = 8.4041 (17) Å
b = 9.7148 (19) Å
c = 10.465 (2) Å
α = 99.27 (3)°
β = 92.50 (3)°
γ = 113.85 (3)°
V = 765.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 (2) K
0.31 × 0.29 × 0.22 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.968, T_max = 0.977
5673 measured reflections
2695 independent reflections
2440 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.05
2695 reflections
237 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.924 (14)	2.192 (15)	3.059 (2)	155.7 (15)
N1—H1B⋯O4ⁱⁱ	0.930 (14)	2.510 (17)	3.0112 (18)	114.1 (13)
N3—H3⋯N4ⁱⁱⁱ	0.900 (13)	2.191 (15)	2.9524 (18)	141.9 (14)
N4—H4B⋯O1^iv	0.936 (14)	2.267 (16)	2.9873 (18)	133.3 (14)
N1—H1B⋯O1	0.930 (14)	2.348 (17)	2.7873 (18)	108.6 (13)
N2—H2⋯O2	0.906 (14)	2.118 (17)	2.5375 (16)	107.1 (13)
N3—H3⋯O3	0.900 (13)	2.230 (16)	2.5977 (17)	103.9 (12)
C5—H5A⋯N1^v	0.95	2.53	3.359 (2)	146
C11—H11A⋯O1^vi	0.95	2.47	3.292 (2)	145
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y-1, z-1; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z+1; (v) x, y+1, z; (vi) x, y, z+1.

Data collection: CrystalClear (Rigaku/MSC, 2006 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014864/pv2081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014864/pv2081Isup2.hkl

checkCIF report

Comment top

Biphenyl hydrazides are of crucial importance in the design and synthesis of novel advanced functional materials (Thaker & Patel, 2008) and compounds of biological importance (Kakefuda et al., 2002; Dekeyser et al., 2003). Our interest in the synthesis of biphenyl dihydrazide arose from the fact that we wanted to attach macrocycles like porphyrin to diphenyl dicarboxylic acid and carboxylic substituted oligo(p-phenylene)s (Litvinchuk et al., 2004) to form functionalized pores (Sisson et al., 2006; Baudry et al., 2006). The coupling of amino-substituted macrocycles gave poor yields so we changed the strategy and synthesized carboxylic substituted macrocycles and hydrazide substituted biphenyls. Studies on the coupling of these biphenyl hydrazides and macrocycles are in progress. In this paper, we report the synthesis and crystal structure of the title compound, (I).

The molecules of the title compound (Fig. 1) are held together by intermolecular hydrogen bonds involving carbonyl O-atoms and primary amines as well as primary amines and secondary amines of the type N—H···O and N—H···H, respectively, which stabilize the crystal structure (Fig. 2) resulting in ten and six membered which may be described in the graph set notation as R₂²(10) and R₂²(6) (Etter, 1990). There are three intramolecular hydrogen bonds in addition to non-classical hydrogen bonds involving phenyl H-atoms and a carbonyl oxygen and a primary amine; details of hydrogen bonding geometry have been provided in Table 1.

The C1—O1 and C16—O4 distances in (I) are 1.2284 (17)Å and 1.2338 (16) Å, respectively, typical of double bonds (Yan et al., 1993), whereas the distances C1—N2 and C16—N3 at 1.3320 (18)Å and 1.3291 (18)Å are consistent with those reported (Priebe et al., 2008), suggesting partial double bond character. Similarly, the distances N1—N2 and N3—N4, 1.4198 (17)Å and 1.4196 (17) Å, respectively, are typical for a single bond, which are in agreement with those of the analogous compound (Bhat et al., 1974), suggesting that the title compound exists as resonance hybrid between a polar and a neutral form.

Related literature top

For related literature see: Dekeyser et al. (2003); Ali et al. (2008).

For related literature, see: Baudry et al. (2006); Bhat et al. (1974); Etter (1990); Kakefuda et al. (2002); Litvinchuk et al. (2004); Priebe et al. (2008); Sisson et al. (2006); Thaker & Patel (2008); Yan et al. (1993).

Experimental top

Diethyl 2,2'-(biphenyl-2,2'-diylbis(oxy))diacetate (500 mg, 1.4 mmol) was refluxed in the presence of hydrazine hydrate (5 ml, 103 mmol) in ethanol (10 ml) at 353 K for 2 h, the reaction mixture was cooled down to room temperature and then poured into 10 ml of water. The reaction mixture was extracted three times with ethyl acetate. The combined organic phases were concentrated under reduced pressure. The crude residue was dissolved in ethanol and slow evaporation of ethanol afforded colorless crystals (276 mg, 60% yield) suitable for XRD analysis.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the the title compound showing 50% probability displacement ellipsoids with arbitrary shperes for H atoms.
	Fig. 2. Packing diagram of (I) with hydrogen bonds viewed along the b axis. Symmetry codes for A through D are: 1 - x,1 - y,1 - z; x,1 + y,z; 1 - x,-y,1 - z; and 1 - x,1 - y,2 - z, respectively.

2,2'-(Biphenyl-2,2'-diyldioxy)diacetohydrazide top

Crystal data top

C₁₆H₁₈N₄O₄	Z = 2
M_r = 330.34	F(000) = 348
Triclinic, P1	D_x = 1.433 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4041 (17) Å	Cell parameters from 2518 reflections
b = 9.7148 (19) Å	θ = 2.7–26.4°
c = 10.465 (2) Å	µ = 0.11 mm⁻¹
α = 99.27 (3)°	T = 153 K
β = 92.50 (3)°	Chip, colorless
γ = 113.85 (3)°	0.31 × 0.29 × 0.22 mm
V = 765.7 (3) Å³

Data collection top

Rigaku Mercury CCD diffractometer	2695 independent reflections
Radiation source: Sealed Tube	2440 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.009
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.2°, θ_min = 2.0°
ω scans	h = −10→9
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −10→11
T_min = 0.968, T_max = 0.977	l = −12→12
5673 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0447P)² + 0.3477P] where P = (F_o² + 2F_c²)/3
2695 reflections	(Δ/σ)_max = 0.001
237 parameters	Δρ_max = 0.20 e Å⁻³
6 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₈N₄O₄	γ = 113.85 (3)°
M_r = 330.34	V = 765.7 (3) Å³
Triclinic, P1	Z = 2
a = 8.4041 (17) Å	Mo Kα radiation
b = 9.7148 (19) Å	µ = 0.11 mm⁻¹
c = 10.465 (2) Å	T = 153 K
α = 99.27 (3)°	0.31 × 0.29 × 0.22 mm
β = 92.50 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2695 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2440 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.977	R_int = 0.009
5673 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	6 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.20 e Å⁻³
2695 reflections	Δρ_min = −0.20 e Å⁻³
237 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
O1	0.32268 (15)	−0.23766 (13)	−0.20890 (9)	0.0317 (3)
O2	0.26996 (14)	−0.02884 (11)	0.08294 (9)	0.0263 (2)
O3	0.33765 (13)	0.10884 (10)	0.50896 (8)	0.0242 (2)
O4	0.41183 (15)	0.35080 (12)	0.81794 (9)	0.0313 (3)
N1	0.28627 (18)	−0.42946 (14)	−0.03033 (12)	0.0282 (3)
H1A	0.389 (2)	−0.419 (2)	0.0137 (16)	0.034*
H1B	0.293 (2)	−0.452 (2)	−0.1191 (14)	0.034*
N2	0.28707 (16)	−0.28115 (14)	−0.00437 (11)	0.0253 (3)
H2	0.253 (2)	−0.254 (2)	0.0732 (15)	0.035 (5)*
N3	0.41999 (16)	0.39435 (13)	0.61151 (11)	0.0236 (3)
H3	0.428 (2)	0.362 (2)	0.5272 (14)	0.038 (5)*
N4	0.46353 (18)	0.55390 (14)	0.64554 (12)	0.0271 (3)
H4A	0.544 (2)	0.5916 (19)	0.7182 (15)	0.032*
H4B	0.364 (2)	0.565 (2)	0.6732 (16)	0.032*
C1	0.29940 (17)	−0.19832 (16)	−0.09628 (12)	0.0216 (3)
C2	0.28191 (18)	−0.04884 (16)	−0.05358 (12)	0.0217 (3)
H2B	0.3851	0.0379	−0.0726	0.026*
H2C	0.1756	−0.0523	−0.1013	0.026*
C3	0.21044 (17)	0.07599 (15)	0.14010 (12)	0.0196 (3)
C4	0.20643 (18)	0.19491 (15)	0.08338 (13)	0.0224 (3)
H4C	0.2437	0.2059	−0.0002	0.027*
C5	0.14735 (18)	0.29724 (16)	0.15019 (14)	0.0253 (3)
H5A	0.1430	0.3779	0.1116	0.030*
C6	0.09474 (18)	0.28244 (15)	0.27275 (14)	0.0246 (3)
H6A	0.0544	0.3527	0.3181	0.029*
C7	0.10118 (17)	0.16440 (15)	0.32919 (13)	0.0212 (3)
H7A	0.0664	0.1557	0.4137	0.025*
C8	0.15766 (16)	0.05875 (14)	0.26424 (12)	0.0187 (3)
C9	0.15926 (17)	−0.07024 (15)	0.32413 (12)	0.0187 (3)
C10	0.25033 (17)	−0.04279 (15)	0.44785 (12)	0.0189 (3)
C11	0.25260 (18)	−0.16331 (16)	0.50320 (13)	0.0229 (3)
H11A	0.3164	−0.1431	0.5864	0.028*
C12	0.1608 (2)	−0.31304 (16)	0.43565 (14)	0.0261 (3)
H12A	0.1631	−0.3956	0.4724	0.031*
C13	0.0658 (2)	−0.34330 (16)	0.31497 (14)	0.0271 (3)
H13A	0.0014	−0.4462	0.2700	0.033*
C14	0.06546 (18)	−0.22235 (15)	0.26023 (13)	0.0229 (3)
H14A	0.0000	−0.2436	0.1776	0.028*
C15	0.36921 (19)	0.14095 (16)	0.64783 (12)	0.0242 (3)
H15A	0.4720	0.1228	0.6757	0.029*
H15B	0.2663	0.0717	0.6837	0.029*
C16	0.40281 (17)	0.30626 (16)	0.69949 (12)	0.0218 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0463 (7)	0.0413 (6)	0.0184 (5)	0.0285 (5)	0.0086 (4)	0.0069 (4)
O2	0.0425 (6)	0.0299 (5)	0.0148 (5)	0.0231 (5)	0.0048 (4)	0.0048 (4)
O3	0.0358 (6)	0.0189 (5)	0.0135 (4)	0.0073 (4)	0.0008 (4)	0.0026 (4)
O4	0.0438 (6)	0.0325 (6)	0.0156 (5)	0.0157 (5)	0.0017 (4)	0.0004 (4)
N1	0.0377 (7)	0.0248 (6)	0.0259 (6)	0.0165 (6)	0.0055 (5)	0.0054 (5)
N2	0.0358 (7)	0.0251 (6)	0.0193 (6)	0.0164 (5)	0.0066 (5)	0.0051 (5)
N3	0.0307 (6)	0.0196 (6)	0.0179 (6)	0.0087 (5)	0.0049 (5)	0.0008 (4)
N4	0.0358 (7)	0.0210 (6)	0.0224 (6)	0.0111 (5)	0.0055 (5)	0.0004 (5)
C1	0.0205 (6)	0.0282 (7)	0.0173 (6)	0.0112 (6)	0.0020 (5)	0.0045 (5)
C2	0.0250 (7)	0.0252 (7)	0.0150 (6)	0.0103 (6)	0.0024 (5)	0.0051 (5)
C3	0.0210 (6)	0.0182 (6)	0.0184 (6)	0.0079 (5)	−0.0007 (5)	0.0016 (5)
C4	0.0239 (7)	0.0216 (7)	0.0204 (6)	0.0071 (5)	0.0010 (5)	0.0075 (5)
C5	0.0266 (7)	0.0184 (7)	0.0311 (7)	0.0081 (6)	−0.0006 (6)	0.0094 (6)
C6	0.0265 (7)	0.0183 (7)	0.0300 (7)	0.0116 (6)	0.0013 (6)	0.0026 (5)
C7	0.0215 (7)	0.0202 (7)	0.0208 (6)	0.0080 (5)	0.0014 (5)	0.0032 (5)
C8	0.0197 (6)	0.0159 (6)	0.0185 (6)	0.0058 (5)	−0.0006 (5)	0.0029 (5)
C9	0.0217 (6)	0.0187 (7)	0.0179 (6)	0.0101 (5)	0.0051 (5)	0.0044 (5)
C10	0.0222 (6)	0.0173 (6)	0.0169 (6)	0.0080 (5)	0.0051 (5)	0.0025 (5)
C11	0.0281 (7)	0.0259 (7)	0.0183 (6)	0.0138 (6)	0.0036 (5)	0.0071 (5)
C12	0.0351 (8)	0.0219 (7)	0.0271 (7)	0.0154 (6)	0.0063 (6)	0.0102 (6)
C13	0.0337 (8)	0.0175 (7)	0.0289 (7)	0.0102 (6)	0.0016 (6)	0.0030 (5)
C14	0.0279 (7)	0.0207 (7)	0.0200 (6)	0.0105 (6)	0.0003 (5)	0.0028 (5)
C15	0.0325 (7)	0.0252 (7)	0.0134 (6)	0.0104 (6)	0.0021 (5)	0.0041 (5)
C16	0.0204 (6)	0.0251 (7)	0.0176 (6)	0.0080 (5)	0.0017 (5)	0.0019 (5)

Geometric parameters (Å, º) top

O1—C1	1.2284 (17)	C4—H4C	0.9500
O2—C3	1.3736 (16)	C5—C6	1.385 (2)
O2—C2	1.4242 (15)	C5—H5A	0.9500
O3—C10	1.3779 (17)	C6—C7	1.3901 (19)
O3—C15	1.4259 (15)	C6—H6A	0.9500
O4—C16	1.2338 (16)	C7—C8	1.3922 (19)
N1—N2	1.4198 (17)	C7—H7A	0.9500
N1—H1A	0.925 (14)	C8—C9	1.4931 (18)
N1—H1B	0.930 (14)	C9—C14	1.3949 (19)
N2—C1	1.3320 (18)	C9—C10	1.4037 (19)
N2—H2	0.907 (14)	C10—C11	1.3937 (19)
N3—C16	1.3291 (18)	C11—C12	1.387 (2)
N3—N4	1.4196 (17)	C11—H11A	0.9500
N3—H3	0.904 (14)	C12—C13	1.386 (2)
N4—H4A	0.914 (14)	C12—H12A	0.9500
N4—H4B	0.936 (14)	C13—C14	1.3888 (19)
C1—C2	1.5164 (19)	C13—H13A	0.9500
C2—H2B	0.9900	C14—H14A	0.9500
C2—H2C	0.9900	C15—C16	1.514 (2)
C3—C4	1.3924 (19)	C15—H15A	0.9900
C3—C8	1.4046 (18)	C15—H15B	0.9900
C4—C5	1.389 (2)

C3—O2—C2	119.52 (10)	C7—C6—H6A	120.1
C10—O3—C15	117.33 (10)	C6—C7—C8	121.29 (12)
N2—N1—H1A	105.6 (11)	C6—C7—H7A	119.4
N2—N1—H1B	106.5 (11)	C8—C7—H7A	119.4
H1A—N1—H1B	107.7 (15)	C7—C8—C3	117.98 (12)
C1—N2—N1	122.76 (12)	C7—C8—C9	120.86 (11)
C1—N2—H2	119.5 (11)	C3—C8—C9	121.16 (12)
N1—N2—H2	116.3 (11)	C14—C9—C10	117.93 (12)
C16—N3—N4	123.00 (11)	C14—C9—C8	120.81 (11)
C16—N3—H3	121.4 (12)	C10—C9—C8	121.23 (12)
N4—N3—H3	114.3 (12)	O3—C10—C11	122.79 (11)
N3—N4—H4A	106.8 (11)	O3—C10—C9	116.07 (11)
N3—N4—H4B	107.6 (11)	C11—C10—C9	121.13 (12)
H4A—N4—H4B	105.1 (15)	C12—C11—C10	119.35 (12)
O1—C1—N2	123.62 (13)	C12—C11—H11A	120.3
O1—C1—C2	120.88 (12)	C10—C11—H11A	120.3
N2—C1—C2	115.50 (11)	C13—C12—C11	120.59 (13)
O2—C2—C1	108.04 (11)	C13—C12—H12A	119.7
O2—C2—H2B	110.1	C11—C12—H12A	119.7
C1—C2—H2B	110.1	C12—C13—C14	119.61 (13)
O2—C2—H2C	110.1	C12—C13—H13A	120.2
C1—C2—H2C	110.1	C14—C13—H13A	120.2
H2B—C2—H2C	108.4	C13—C14—C9	121.34 (12)
O2—C3—C4	123.65 (12)	C13—C14—H14A	119.3
O2—C3—C8	115.15 (11)	C9—C14—H14A	119.3
C4—C3—C8	121.17 (12)	O3—C15—C16	109.67 (11)
C5—C4—C3	119.38 (13)	O3—C15—H15A	109.7
C5—C4—H4C	120.3	C16—C15—H15A	109.7
C3—C4—H4C	120.3	O3—C15—H15B	109.7
C6—C5—C4	120.42 (12)	C16—C15—H15B	109.7
C6—C5—H5A	119.8	H15A—C15—H15B	108.2
C4—C5—H5A	119.8	O4—C16—N3	124.25 (13)
C5—C6—C7	119.76 (13)	O4—C16—C15	119.25 (12)
C5—C6—H6A	120.1	N3—C16—C15	116.49 (11)

N1—N2—C1—O1	−5.0 (2)	C7—C8—C9—C10	−55.87 (18)
N1—N2—C1—C2	174.76 (12)	C3—C8—C9—C10	125.09 (14)
C3—O2—C2—C1	−163.98 (11)	C15—O3—C10—C11	−25.80 (18)
O1—C1—C2—O2	−175.55 (12)	C15—O3—C10—C9	155.02 (12)
N2—C1—C2—O2	4.71 (16)	C14—C9—C10—O3	−178.44 (11)
C2—O2—C3—C4	−18.76 (19)	C8—C9—C10—O3	−0.38 (18)
C2—O2—C3—C8	163.23 (12)	C14—C9—C10—C11	2.38 (19)
O2—C3—C4—C5	−178.61 (12)	C8—C9—C10—C11	−179.57 (12)
C8—C3—C4—C5	−0.7 (2)	O3—C10—C11—C12	179.79 (12)
C3—C4—C5—C6	0.7 (2)	C9—C10—C11—C12	−1.1 (2)
C4—C5—C6—C7	0.0 (2)	C10—C11—C12—C13	−0.8 (2)
C5—C6—C7—C8	−0.8 (2)	C11—C12—C13—C14	1.2 (2)
C6—C7—C8—C3	0.82 (19)	C12—C13—C14—C9	0.1 (2)
C6—C7—C8—C9	−178.24 (12)	C10—C9—C14—C13	−1.9 (2)
O2—C3—C8—C7	178.01 (11)	C8—C9—C14—C13	−179.96 (13)
C4—C3—C8—C7	−0.05 (19)	C10—O3—C15—C16	−159.34 (11)
O2—C3—C8—C9	−2.93 (18)	N4—N3—C16—O4	4.7 (2)
C4—C3—C8—C9	179.01 (12)	N4—N3—C16—C15	−175.62 (12)
C7—C8—C9—C14	122.12 (14)	O3—C15—C16—O4	171.27 (12)
C3—C8—C9—C14	−56.91 (18)	O3—C15—C16—N3	−8.42 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.92 (1)	2.19 (2)	3.059 (2)	156 (2)
N1—H1B···O4ⁱⁱ	0.93 (1)	2.51 (2)	3.0112 (18)	114 (1)
N3—H3···N4ⁱⁱⁱ	0.90 (1)	2.19 (2)	2.9524 (18)	142 (1)
N4—H4B···O1^iv	0.94 (1)	2.27 (2)	2.9873 (18)	133 (1)
N1—H1B···O1	0.93 (1)	2.35 (2)	2.7873 (18)	109 (1)
N2—H2···O2	0.91 (1)	2.12 (2)	2.5375 (16)	107 (1)
N3—H3···O3	0.90 (1)	2.23 (2)	2.5977 (17)	104 (1)
C5—H5A···N1^v	0.95	2.53	3.359 (2)	146
C11—H11A···O1^vi	0.95	2.47	3.292 (2)	145

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₄O₄
M_r	330.34
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	8.4041 (17), 9.7148 (19), 10.465 (2)
α, β, γ (°)	99.27 (3), 92.50 (3), 113.85 (3)
V (Å³)	765.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.29 × 0.22

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.968, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	5673, 2695, 2440
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.05
No. of reflections	2695
No. of parameters	237
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20

Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXS (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.924 (14)	2.192 (15)	3.059 (2)	155.7 (15)
N1—H1B···O4ⁱⁱ	0.930 (14)	2.510 (17)	3.0112 (18)	114.1 (13)
N3—H3···N4ⁱⁱⁱ	0.900 (13)	2.191 (15)	2.9524 (18)	141.9 (14)
N4—H4B···O1^iv	0.936 (14)	2.267 (16)	2.9873 (18)	133.3 (14)
N1—H1B···O1	0.930 (14)	2.348 (17)	2.7873 (18)	108.6 (13)
N2—H2···O2	0.906 (14)	2.118 (17)	2.5375 (16)	107.1 (13)
N3—H3···O3	0.900 (13)	2.230 (16)	2.5977 (17)	103.9 (12)
C5—H5A···N1^v	0.95	2.53	3.359 (2)	146.3
C11—H11A···O1^vi	0.95	2.47	3.292 (2)	144.8

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

Acknowledgements

The authors thank the Higher Education Commission of Pakistan for financial support.

References

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