3-[2-(3-Nitro­phen­yl)hydrazin-1-ylidene]pentane-2,4-dione

Marten, J.; Seichter, W.; Weber, E.

doi:10.1107/S2414314618013445

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181344

https://doi.org/10.1107/S2414314618013445

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3-[2-(3-Nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione

Jan Marten,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 August 2018; accepted 20 September 2018; online 28 September 2018)

The title compound, C₁₁H₁₁N₃O₄, crystallizes with three independent but conformationally similar molecules in the asymmetric unit. The plane through the pentane-2,4-dione moiety of the molecule is inclined at angles of 10.1 (1), 10.6 (1) and 17.4 (1)° with regard to the respective arene ring. In the crystal, the molecules are connected via C_arene—H⋯O_nitro and C_arene—H⋯O=C interactions into supramolecular sheets. Molecules of consecutive sheets are linked by C_methyl—H⋯O bonds.

Keywords: crystal structure; arylhydrazone; pentane-2,4-dione derivative; C—H⋯O interactions; π–π stacking.

CCDC reference: 1868829

Structure description

Arylhydrazones of β-diketones have recently become interesting objects of scientific study with regard to complex formation (Marten et al., 2005 ) and hydrogen bonding, exerting an active influence both on the spectroscopic and electrochemical as well as the structural properties of the β-ketone derivative (Marten et al., 2007 , 2011 ; Sethukumar et al., 2010 ), including the research question of resonance-assisted hydrogen bonding (RAHB) (Gilli et al., 1989 ; Alkorta et al., 2004 ). The title compound belongs to this category of promising molecules and its crystal structure is reported here.

The asymmetric unit contains three independent but conformationally similar molecules (Fig. 1). Each molecule features an intramolecular N—H⋯O interaction (Table 1) that yields a six-membered hydrogen-bonded ring. In the crystal structure, the molecules exist in an EZE configuration which – in this order – represents the alignment of the non-H-bridged O2x—C4x fragment, the hydrogen-bonded O1x—C2x fragment, and the aryl group with respect to the N1x=C3x double bond (x = -,A,B) (Gómez-Sánchez et al., 1987 ). This geometry agrees with that found in the solid-state structures of other compounds of this kind (Bertolasi et al. 1994 ; Marten et al. 2005, 2007). The molecules deviate slightly from planarity, showing tilt angles of 9.0 (2), 6.6 (2) and 9.7 (1)° between the mean planes of the hydrogen-bonded ring and the arene ring. The molecules exhibit a highly distorted geometry along the pentane-2,4-dione fragment, which can be seen from the enlarged torsion angles of the atomic sequences N1x—C3x—C2x—O1x and C2x—C3x—C4x—O2x being −10.0 (2) and −5.1 (2)° for molecule A, −10.0 (2) and −5.1 (2)° for molecule B and 18.5 (2) and 9.7 (2)° for molecule C. The six-membered hydrogen-bonded rings, however, are less affected by the distortion. The largest atomic distances from the mean plane are found to be 0.076 (1) and −0.102 (1) Å for atoms O1B and C2B of molecule C. In addition, the nitro groups are tilted slightly with respect to the benzene ring, showing inclination angles of 11.9 (1), 10.7 (1) and 7.8 (1)° for molecules A, B and C, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11B—H11B⋯O1Aⁱ	0.95	2.63	3.4824 (15)	150
C9B—H9B⋯O3Aⁱⁱ	0.95	2.53	3.4837 (16)	178
N2B—H2B⋯O1B	0.90 (1)	1.90 (1)	2.5952 (13)	133 (1)
C11A—H11A⋯O1Bⁱ	0.95	2.53	3.4347 (15)	158
C9A—H9A⋯O3Bⁱⁱ	0.95	2.59	3.5227 (15)	168
C5A—H5A2⋯N1ⁱ	0.98	2.65	3.5230 (16)	149
C5A—H5A1⋯O1Aⁱⁱⁱ	0.98	2.51	3.4424 (15)	158
C1A—H1A2⋯O4ⁱ	0.98	2.49	3.4674 (16)	173
N2A—H2A⋯O1A	0.90 (1)	1.91 (1)	2.5873 (13)	131 (1)
C11—H11⋯O1^iv	0.95	2.52	3.4114 (14)	156
C9—H9⋯O3^v	0.95	2.63	3.5450 (15)	163
C5—H5B⋯N1Aⁱ	0.98	2.69	3.5445 (16)	146
C1—H1B⋯O4Aⁱ	0.98	2.47	3.4237 (18)	165
N2—H2⋯O1	0.89 (1)	1.89 (1)	2.5834 (12)	134 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+2; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) -x+1, -y+2, -z+1.

Figure 1
Perspective view of the molecular structure of the title compound with the atom labelling. Displacement ellipsoids of non-H atoms are shown at the 50% probability level.

In the crystal (Fig. 2), the molecules are connected by means of C_arene—H⋯O_nitro and C_arene—H⋯O=C interactions (Desiraju & Steiner, 1999 ) giving rise to sheets that extend parallel to the bc plane. In the stacking direction of these two-dimensional-supramolecular aggregates, the molecules are linked by C_methyl—H⋯ O_nitro hydrogen bonds (Table 1, Fig. 3). Moreover, the crystal is stabilized by π–π stacking interactions between the aromatic rings and the six-membered hydrogen-bonded rings with centroid–centroid distances of 4.1043 (8)–4.4867 (8) Å.

Figure 2
Structure of the molecular sheets including the mode of intermolecular bonding in the crystal of the title compound. Dashed lines represent hydrogen bonds. Particular ring systems of intermolecular interactions are specified by colour highlighting. Specification of the ring pattern corresponds to the graph-set notation introduced by M. C. Etter (Etter et al., 1990

Figure 3
Packing diagram of the title compound viewed along the c axis. The intermolecular contacts are shown as dashed lines.

Synthesis and crystallization

The title compound was prepared from pentane-2,4-dione and 3-nitrophenyldiazonium chloride (diazotization of 3-nitroaniline) via a Japp–Klingemann route (Phillips, 1959 ) following a described protocol (Sethukumar et al., 2010) to yield yellow crystals (78%, m.p. 412 K) and spectroscopic data correspond to the literature (Bülow & Schlotterbeck, 1902 ; Sethukumar et al., 2010). Crystals were grown by the slow evaporation technique using ethanol as solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₁N₃O₄
M_r	249.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	93
a, b, c (Å)	10.1251 (5), 11.1335 (6), 15.9006 (8)
α, β, γ (°)	102.745 (3), 101.100 (3), 101.520 (3)
V (Å³)	1659.74 (15)
Z	6
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.28 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area detector
No. of measured, independent and observed [I > 2σ(I)] reflections	49810, 8881, 6440
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.127, 1.00
No. of reflections	8881
No. of parameters	505
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1868829

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013445/hb4256sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013445/hb4256Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618013445/hb4256Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

3-[2-(3-Nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione top

Crystal data top

C₁₁H₁₁N₃O₄	Z = 6
M_r = 249.23	F(000) = 780
Triclinic, P1	D_x = 1.496 Mg m⁻³
a = 10.1251 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1335 (6) Å	Cell parameters from 9958 reflections
c = 15.9006 (8) Å	θ = 2.5–38.8°
α = 102.745 (3)°	µ = 0.12 mm⁻¹
β = 101.100 (3)°	T = 93 K
γ = 101.520 (3)°	Irregular, yellow
V = 1659.74 (15) Å³	0.28 × 0.20 × 0.10 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	R_int = 0.033
φ and ω scans	θ_max = 29.1°, θ_min = 2.0°
49810 measured reflections	h = −13→13
8881 independent reflections	k = −15→15
6440 reflections with I > 2σ(I)	l = −21→21

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0697P)² + 0.3903P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
8881 reflections	Δρ_max = 0.44 e Å⁻³
505 parameters	Δρ_min = −0.30 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were positioned geometrically and refined isotropically using the riding model with C—H = 0.98 Å and U_iso(H) = 1.5 U_eq(C) for methyl and C—H = 0.95 Å and U_iso(H) = 1.2 U_eq(C) for aryl.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.50272 (9)	0.37266 (8)	0.01900 (6)	0.01728 (18)
O2	0.51679 (11)	0.09300 (8)	0.15551 (6)	0.0236 (2)
O3	0.43473 (10)	0.84492 (9)	0.50143 (6)	0.0226 (2)
O4	0.46928 (9)	0.65656 (9)	0.48900 (6)	0.0202 (2)
N1	0.49937 (10)	0.40849 (9)	0.19988 (6)	0.01255 (19)
N2	0.49547 (10)	0.50955 (9)	0.17125 (6)	0.0129 (2)
H2	0.4964 (19)	0.5041 (16)	0.1147 (7)	0.039 (5)*
N3	0.45970 (10)	0.74844 (10)	0.45984 (7)	0.0151 (2)
C1	0.55504 (17)	0.17248 (13)	0.00493 (9)	0.0269 (3)
H1A	0.4730	0.1000	−0.0146	0.040*
H1B	0.6303	0.1525	0.0439	0.040*
H1C	0.5853	0.1897	−0.0471	0.040*
C2	0.51931 (12)	0.28713 (11)	0.05460 (8)	0.0146 (2)
C3	0.50838 (12)	0.30180 (11)	0.14792 (7)	0.0124 (2)
C4	0.51293 (12)	0.19961 (11)	0.19419 (8)	0.0141 (2)
C5	0.51082 (13)	0.23092 (12)	0.29086 (8)	0.0166 (2)
H5A	0.4200	0.2448	0.2966	0.025*
H5B	0.5839	0.3083	0.3238	0.025*
H5C	0.5272	0.1601	0.3152	0.025*
C6	0.49515 (11)	0.62290 (11)	0.23101 (7)	0.0118 (2)
C7	0.47929 (11)	0.62682 (11)	0.31640 (8)	0.0126 (2)
H7	0.4698	0.5528	0.3375	0.015*
C8	0.47793 (12)	0.74318 (11)	0.36949 (7)	0.0128 (2)
C9	0.49204 (12)	0.85409 (11)	0.34252 (8)	0.0146 (2)
H9	0.4903	0.9320	0.3810	0.017*
C10	0.50894 (12)	0.84719 (11)	0.25684 (8)	0.0155 (2)
H10	0.5189	0.9214	0.2360	0.019*
C11	0.51135 (12)	0.73260 (11)	0.20173 (8)	0.0149 (2)
H11	0.5241	0.7290	0.1437	0.018*
O1A	0.16277 (9)	0.55721 (8)	0.38561 (6)	0.01764 (19)
O2A	0.18248 (10)	0.28004 (8)	0.52201 (6)	0.0236 (2)
O3A	0.18275 (12)	1.04571 (10)	0.88501 (6)	0.0330 (3)
O4A	0.14636 (10)	0.84097 (9)	0.85760 (6)	0.0255 (2)
N1A	0.16065 (10)	0.59407 (9)	0.56645 (7)	0.0140 (2)
N2A	0.15028 (11)	0.69368 (9)	0.53691 (7)	0.0141 (2)
H2A	0.1507 (17)	0.6910 (16)	0.4802 (7)	0.034 (5)*
N3A	0.16103 (11)	0.93940 (11)	0.83415 (7)	0.0200 (2)
C1A	0.22945 (14)	0.36347 (12)	0.37409 (8)	0.0185 (3)
H1A1	0.1526	0.2868	0.3575	0.028*
H1A2	0.3104	0.3507	0.4128	0.028*
H1A3	0.2538	0.3802	0.3203	0.028*
C2A	0.18617 (12)	0.47422 (11)	0.42247 (8)	0.0144 (2)
C3A	0.17495 (12)	0.48892 (11)	0.51580 (8)	0.0140 (2)
C4A	0.17907 (12)	0.38607 (11)	0.56176 (8)	0.0157 (2)
C5A	0.17481 (13)	0.41559 (12)	0.65827 (8)	0.0187 (3)
H5A1	0.0844	0.4311	0.6635	0.028*
H5A2	0.2490	0.4915	0.6924	0.028*
H5A3	0.1882	0.3433	0.6816	0.028*
C6A	0.14666 (12)	0.80636 (11)	0.59629 (8)	0.0135 (2)
C7A	0.15249 (12)	0.81389 (11)	0.68543 (8)	0.0146 (2)
H7A	0.1560	0.7424	0.7084	0.018*
C8A	0.15295 (12)	0.93022 (12)	0.73937 (8)	0.0150 (2)
C9A	0.14790 (12)	1.03754 (12)	0.70965 (8)	0.0170 (2)
H9A	0.1503	1.1161	0.7491	0.020*
C10A	0.13916 (13)	1.02583 (12)	0.61947 (8)	0.0175 (2)
H10A	0.1342	1.0971	0.5965	0.021*
C11A	0.13772 (12)	0.91090 (12)	0.56317 (8)	0.0161 (2)
H11A	0.1306	0.9035	0.5017	0.019*
O1B	0.85907 (9)	0.19177 (8)	0.65642 (6)	0.01866 (19)
O2B	0.85133 (10)	−0.09374 (8)	0.78295 (6)	0.0206 (2)
O3B	0.78511 (11)	0.66059 (9)	1.13961 (6)	0.0259 (2)
O4B	0.80431 (10)	0.46675 (9)	1.12265 (6)	0.0220 (2)
N1B	0.85135 (10)	0.22594 (9)	0.83719 (7)	0.0140 (2)
N2B	0.85919 (11)	0.33023 (9)	0.81086 (7)	0.0145 (2)
H2B	0.8644 (18)	0.3274 (16)	0.7549 (7)	0.036 (5)*
N3B	0.80267 (10)	0.56166 (10)	1.09587 (7)	0.0169 (2)
C1B	0.76785 (13)	−0.03138 (11)	0.61996 (8)	0.0179 (2)
H1B1	0.7221	−0.0223	0.5623	0.027*
H1B2	0.6996	−0.0821	0.6428	0.027*
H1B3	0.8423	−0.0741	0.6126	0.027*
C2B	0.82836 (12)	0.09774 (11)	0.68436 (8)	0.0142 (2)
C3B	0.84300 (12)	0.11612 (11)	0.78164 (8)	0.0137 (2)
C4B	0.84416 (12)	0.01022 (11)	0.82453 (8)	0.0150 (2)
C5B	0.83783 (14)	0.03443 (12)	0.92040 (8)	0.0205 (3)
H5B1	0.8525	−0.0389	0.9420	0.031*
H5B2	0.7464	0.0474	0.9254	0.031*
H5B3	0.9105	0.1106	0.9561	0.031*
C6B	0.85292 (12)	0.44227 (11)	0.86994 (8)	0.0137 (2)
C7B	0.82885 (12)	0.44323 (11)	0.95337 (8)	0.0140 (2)
H7B	0.8165	0.3682	0.9732	0.017*
C8B	0.82363 (12)	0.55825 (11)	1.00622 (8)	0.0142 (2)
C9B	0.83941 (12)	0.66991 (12)	0.98035 (8)	0.0172 (2)
H9B	0.8334	0.7465	1.0183	0.021*
C10B	0.86433 (13)	0.66630 (12)	0.89682 (8)	0.0185 (2)
H10B	0.8760	0.7415	0.8771	0.022*
C11B	0.87222 (12)	0.55351 (11)	0.84220 (8)	0.0164 (2)
H11B	0.8908	0.5520	0.7857	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0288 (5)	0.0129 (4)	0.0130 (4)	0.0094 (4)	0.0057 (3)	0.0050 (3)
O2	0.0433 (6)	0.0108 (4)	0.0197 (5)	0.0105 (4)	0.0104 (4)	0.0045 (4)
O3	0.0317 (5)	0.0184 (5)	0.0173 (4)	0.0075 (4)	0.0106 (4)	−0.0012 (4)
O4	0.0275 (5)	0.0209 (5)	0.0151 (4)	0.0076 (4)	0.0063 (4)	0.0084 (4)
N1	0.0153 (4)	0.0093 (5)	0.0139 (5)	0.0043 (4)	0.0036 (4)	0.0039 (4)
N2	0.0203 (5)	0.0089 (5)	0.0111 (5)	0.0057 (4)	0.0051 (4)	0.0029 (4)
N3	0.0167 (5)	0.0152 (5)	0.0118 (5)	0.0025 (4)	0.0036 (4)	0.0017 (4)
C1	0.0519 (9)	0.0226 (7)	0.0144 (6)	0.0233 (7)	0.0110 (6)	0.0066 (5)
C2	0.0192 (5)	0.0114 (6)	0.0121 (5)	0.0048 (4)	0.0022 (4)	0.0017 (4)
C3	0.0168 (5)	0.0096 (5)	0.0110 (5)	0.0044 (4)	0.0029 (4)	0.0024 (4)
C4	0.0158 (5)	0.0121 (6)	0.0150 (5)	0.0038 (4)	0.0039 (4)	0.0045 (4)
C5	0.0242 (6)	0.0134 (6)	0.0151 (5)	0.0066 (5)	0.0070 (5)	0.0060 (5)
C6	0.0139 (5)	0.0100 (5)	0.0115 (5)	0.0050 (4)	0.0032 (4)	0.0014 (4)
C7	0.0155 (5)	0.0100 (5)	0.0134 (5)	0.0041 (4)	0.0043 (4)	0.0041 (4)
C8	0.0146 (5)	0.0134 (6)	0.0102 (5)	0.0043 (4)	0.0033 (4)	0.0021 (4)
C9	0.0165 (5)	0.0109 (6)	0.0155 (5)	0.0050 (4)	0.0042 (4)	0.0005 (4)
C10	0.0211 (6)	0.0104 (6)	0.0177 (6)	0.0063 (5)	0.0063 (5)	0.0064 (5)
C11	0.0201 (6)	0.0139 (6)	0.0131 (5)	0.0068 (5)	0.0052 (4)	0.0054 (5)
O1A	0.0258 (5)	0.0146 (4)	0.0151 (4)	0.0090 (4)	0.0052 (3)	0.0055 (3)
O2A	0.0384 (5)	0.0135 (5)	0.0212 (5)	0.0094 (4)	0.0083 (4)	0.0057 (4)
O3A	0.0567 (7)	0.0226 (5)	0.0168 (5)	0.0114 (5)	0.0098 (5)	−0.0025 (4)
O4A	0.0373 (6)	0.0265 (5)	0.0191 (5)	0.0129 (4)	0.0111 (4)	0.0112 (4)
N1A	0.0154 (5)	0.0103 (5)	0.0165 (5)	0.0029 (4)	0.0036 (4)	0.0042 (4)
N2A	0.0209 (5)	0.0100 (5)	0.0125 (5)	0.0054 (4)	0.0057 (4)	0.0027 (4)
N3A	0.0256 (6)	0.0206 (6)	0.0151 (5)	0.0086 (4)	0.0059 (4)	0.0038 (4)
C1A	0.0274 (6)	0.0150 (6)	0.0162 (6)	0.0103 (5)	0.0075 (5)	0.0038 (5)
C2A	0.0157 (5)	0.0121 (6)	0.0143 (5)	0.0030 (4)	0.0024 (4)	0.0030 (4)
C3A	0.0156 (5)	0.0110 (6)	0.0153 (5)	0.0031 (4)	0.0031 (4)	0.0038 (4)
C4A	0.0162 (5)	0.0138 (6)	0.0167 (6)	0.0035 (4)	0.0028 (4)	0.0049 (5)
C5A	0.0238 (6)	0.0186 (6)	0.0156 (6)	0.0062 (5)	0.0050 (5)	0.0078 (5)
C6A	0.0153 (5)	0.0107 (6)	0.0139 (5)	0.0034 (4)	0.0047 (4)	0.0008 (4)
C7A	0.0172 (5)	0.0136 (6)	0.0152 (5)	0.0055 (4)	0.0051 (4)	0.0060 (5)
C8A	0.0163 (5)	0.0171 (6)	0.0127 (5)	0.0054 (5)	0.0055 (4)	0.0033 (5)
C9A	0.0187 (6)	0.0138 (6)	0.0180 (6)	0.0050 (5)	0.0056 (5)	0.0013 (5)
C10A	0.0216 (6)	0.0129 (6)	0.0207 (6)	0.0063 (5)	0.0066 (5)	0.0070 (5)
C11A	0.0207 (6)	0.0156 (6)	0.0139 (5)	0.0060 (5)	0.0057 (4)	0.0051 (5)
O1B	0.0287 (5)	0.0128 (4)	0.0163 (4)	0.0058 (4)	0.0083 (4)	0.0049 (3)
O2B	0.0322 (5)	0.0133 (4)	0.0183 (4)	0.0105 (4)	0.0074 (4)	0.0031 (4)
O3B	0.0384 (6)	0.0204 (5)	0.0207 (5)	0.0114 (4)	0.0138 (4)	0.0000 (4)
O4B	0.0302 (5)	0.0202 (5)	0.0191 (4)	0.0082 (4)	0.0088 (4)	0.0081 (4)
N1B	0.0164 (5)	0.0105 (5)	0.0159 (5)	0.0053 (4)	0.0035 (4)	0.0038 (4)
N2B	0.0219 (5)	0.0103 (5)	0.0121 (5)	0.0057 (4)	0.0054 (4)	0.0020 (4)
N3B	0.0178 (5)	0.0163 (5)	0.0154 (5)	0.0043 (4)	0.0047 (4)	0.0013 (4)
C1B	0.0236 (6)	0.0139 (6)	0.0148 (6)	0.0022 (5)	0.0063 (5)	0.0025 (5)
C2B	0.0161 (5)	0.0126 (6)	0.0154 (5)	0.0057 (4)	0.0055 (4)	0.0033 (5)
C3B	0.0164 (5)	0.0111 (6)	0.0146 (5)	0.0054 (4)	0.0043 (4)	0.0031 (4)
C4B	0.0159 (5)	0.0131 (6)	0.0165 (6)	0.0048 (4)	0.0040 (4)	0.0043 (5)
C5B	0.0326 (7)	0.0166 (6)	0.0154 (6)	0.0090 (5)	0.0082 (5)	0.0063 (5)
C6B	0.0148 (5)	0.0109 (6)	0.0143 (5)	0.0044 (4)	0.0026 (4)	0.0012 (4)
C7B	0.0158 (5)	0.0113 (6)	0.0152 (5)	0.0043 (4)	0.0034 (4)	0.0038 (5)
C8B	0.0146 (5)	0.0151 (6)	0.0128 (5)	0.0040 (4)	0.0039 (4)	0.0028 (4)
C9B	0.0199 (6)	0.0112 (6)	0.0188 (6)	0.0049 (5)	0.0052 (5)	−0.0005 (5)
C10B	0.0242 (6)	0.0121 (6)	0.0209 (6)	0.0052 (5)	0.0072 (5)	0.0057 (5)
C11B	0.0208 (6)	0.0146 (6)	0.0147 (5)	0.0056 (5)	0.0050 (5)	0.0045 (5)

Geometric parameters (Å, º) top

O1—C2	1.2331 (14)	C4A—C5A	1.5078 (16)
O2—C4	1.2224 (14)	C5A—H5A1	0.9800
O3—N3	1.2307 (13)	C5A—H5A2	0.9800
O4—N3	1.2258 (13)	C5A—H5A3	0.9800
N1—N2	1.3082 (13)	C6A—C7A	1.3904 (16)
N1—C3	1.3194 (14)	C6A—C11A	1.3907 (16)
N2—C6	1.4033 (14)	C7A—C8A	1.3853 (16)
N2—H2	0.890 (9)	C7A—H7A	0.9500
N3—C8	1.4733 (14)	C8A—C9A	1.3848 (17)
C1—C2	1.4945 (16)	C9A—C10A	1.3947 (17)
C1—H1A	0.9800	C9A—H9A	0.9500
C1—H1B	0.9800	C10A—C11A	1.3860 (17)
C1—H1C	0.9800	C10A—H10A	0.9500
C2—C3	1.4848 (15)	C11A—H11A	0.9500
C3—C4	1.4882 (16)	O1B—C2B	1.2323 (14)
C4—C5	1.5047 (16)	O2B—C4B	1.2234 (14)
C5—H5A	0.9800	O3B—N3B	1.2314 (13)
C5—H5B	0.9800	O4B—N3B	1.2251 (13)
C5—H5C	0.9800	N1B—N2B	1.3116 (14)
C6—C7	1.3899 (15)	N1B—C3B	1.3174 (15)
C6—C11	1.3913 (16)	N2B—C6B	1.4071 (15)
C7—C8	1.3857 (16)	N2B—H2B	0.896 (9)
C7—H7	0.9500	N3B—C8B	1.4746 (15)
C8—C9	1.3841 (16)	C1B—C2B	1.4992 (16)
C9—C10	1.3929 (16)	C1B—H1B1	0.9800
C9—H9	0.9500	C1B—H1B2	0.9800
C10—C11	1.3869 (16)	C1B—H1B3	0.9800
C10—H10	0.9500	C2B—C3B	1.4887 (16)
C11—H11	0.9500	C3B—C4B	1.4875 (16)
O1A—C2A	1.2355 (14)	C4B—C5B	1.5044 (16)
O2A—C4A	1.2205 (15)	C5B—H5B1	0.9800
O3A—N3A	1.2281 (14)	C5B—H5B2	0.9800
O4A—N3A	1.2242 (14)	C5B—H5B3	0.9800
N1A—N2A	1.3109 (14)	C6B—C7B	1.3924 (16)
N1A—C3A	1.3179 (15)	C6B—C11B	1.3943 (16)
N2A—C6A	1.4056 (14)	C7B—C8B	1.3850 (16)
N2A—H2A	0.897 (9)	C7B—H7B	0.9500
N3A—C8A	1.4730 (15)	C8B—C9B	1.3827 (17)
C1A—C2A	1.4937 (16)	C9B—C10B	1.3924 (17)
C1A—H1A1	0.9800	C9B—H9B	0.9500
C1A—H1A2	0.9800	C10B—C11B	1.3867 (17)
C1A—H1A3	0.9800	C10B—H10B	0.9500
C2A—C3A	1.4855 (16)	C11B—H11B	0.9500
C3A—C4A	1.4912 (16)

N2—N1—C3	121.67 (10)	C4A—C5A—H5A2	109.5
N1—N2—C6	119.22 (9)	H5A1—C5A—H5A2	109.5
N1—N2—H2	118.1 (11)	C4A—C5A—H5A3	109.5
C6—N2—H2	122.6 (11)	H5A1—C5A—H5A3	109.5
O4—N3—O3	123.81 (10)	H5A2—C5A—H5A3	109.5
O4—N3—C8	118.34 (9)	C7A—C6A—C11A	120.79 (11)
O3—N3—C8	117.84 (10)	C7A—C6A—N2A	121.34 (10)
C2—C1—H1A	109.5	C11A—C6A—N2A	117.87 (10)
C2—C1—H1B	109.5	C8A—C7A—C6A	117.09 (11)
H1A—C1—H1B	109.5	C8A—C7A—H7A	121.5
C2—C1—H1C	109.5	C6A—C7A—H7A	121.5
H1A—C1—H1C	109.5	C9A—C8A—C7A	123.98 (11)
H1B—C1—H1C	109.5	C9A—C8A—N3A	118.61 (10)
O1—C2—C3	119.25 (10)	C7A—C8A—N3A	117.40 (11)
O1—C2—C1	119.96 (11)	C8A—C9A—C10A	117.38 (11)
C3—C2—C1	120.74 (10)	C8A—C9A—H9A	121.3
N1—C3—C2	123.61 (10)	C10A—C9A—H9A	121.3
N1—C3—C4	112.75 (10)	C11A—C10A—C9A	120.42 (11)
C2—C3—C4	123.59 (10)	C11A—C10A—H10A	119.8
O2—C4—C3	121.77 (11)	C9A—C10A—H10A	119.8
O2—C4—C5	120.44 (11)	C10A—C11A—C6A	120.29 (11)
C3—C4—C5	117.78 (10)	C10A—C11A—H11A	119.9
C4—C5—H5A	109.5	C6A—C11A—H11A	119.9
C4—C5—H5B	109.5	N2B—N1B—C3B	121.30 (10)
H5A—C5—H5B	109.5	N1B—N2B—C6B	119.20 (10)
C4—C5—H5C	109.5	N1B—N2B—H2B	119.1 (11)
H5A—C5—H5C	109.5	C6B—N2B—H2B	121.6 (11)
H5B—C5—H5C	109.5	O4B—N3B—O3B	123.88 (11)
C7—C6—C11	120.66 (10)	O4B—N3B—C8B	118.42 (10)
C7—C6—N2	121.85 (10)	O3B—N3B—C8B	117.70 (10)
C11—C6—N2	117.49 (10)	C2B—C1B—H1B1	109.5
C8—C7—C6	117.19 (11)	C2B—C1B—H1B2	109.5
C8—C7—H7	121.4	H1B1—C1B—H1B2	109.5
C6—C7—H7	121.4	C2B—C1B—H1B3	109.5
C9—C8—C7	123.93 (11)	H1B1—C1B—H1B3	109.5
C9—C8—N3	118.30 (10)	H1B2—C1B—H1B3	109.5
C7—C8—N3	117.77 (10)	O1B—C2B—C3B	118.94 (10)
C8—C9—C10	117.47 (10)	O1B—C2B—C1B	119.82 (11)
C8—C9—H9	121.3	C3B—C2B—C1B	121.11 (10)
C10—C9—H9	121.3	N1B—C3B—C4B	113.72 (10)
C11—C10—C9	120.38 (11)	N1B—C3B—C2B	123.48 (10)
C11—C10—H10	119.8	C4B—C3B—C2B	122.76 (10)
C9—C10—H10	119.8	O2B—C4B—C3B	120.68 (11)
C10—C11—C6	120.37 (11)	O2B—C4B—C5B	120.87 (11)
C10—C11—H11	119.8	C3B—C4B—C5B	118.45 (10)
C6—C11—H11	119.8	C4B—C5B—H5B1	109.5
N2A—N1A—C3A	122.15 (10)	C4B—C5B—H5B2	109.5
N1A—N2A—C6A	119.27 (10)	H5B1—C5B—H5B2	109.5
N1A—N2A—H2A	120.0 (11)	C4B—C5B—H5B3	109.5
C6A—N2A—H2A	120.6 (11)	H5B1—C5B—H5B3	109.5
O4A—N3A—O3A	123.94 (11)	H5B2—C5B—H5B3	109.5
O4A—N3A—C8A	118.19 (10)	C7B—C6B—C11B	120.72 (11)
O3A—N3A—C8A	117.87 (11)	C7B—C6B—N2B	121.67 (11)
C2A—C1A—H1A1	109.5	C11B—C6B—N2B	117.61 (10)
C2A—C1A—H1A2	109.5	C8B—C7B—C6B	117.14 (11)
H1A1—C1A—H1A2	109.5	C8B—C7B—H7B	121.4
C2A—C1A—H1A3	109.5	C6B—C7B—H7B	121.4
H1A1—C1A—H1A3	109.5	C9B—C8B—C7B	123.82 (11)
H1A2—C1A—H1A3	109.5	C9B—C8B—N3B	118.40 (10)
O1A—C2A—C3A	118.99 (10)	C7B—C8B—N3B	117.77 (10)
O1A—C2A—C1A	119.89 (10)	C8B—C9B—C10B	117.76 (11)
C3A—C2A—C1A	121.09 (10)	C8B—C9B—H9B	121.1
N1A—C3A—C2A	123.52 (11)	C10B—C9B—H9B	121.1
N1A—C3A—C4A	113.14 (10)	C11B—C10B—C9B	120.33 (12)
C2A—C3A—C4A	123.34 (10)	C11B—C10B—H10B	119.8
O2A—C4A—C3A	121.08 (11)	C9B—C10B—H10B	119.8
O2A—C4A—C5A	120.79 (11)	C10B—C11B—C6B	120.20 (11)
C3A—C4A—C5A	118.11 (10)	C10B—C11B—H11B	119.9
C4A—C5A—H5A1	109.5	C6B—C11B—H11B	119.9

C3—N1—N2—C6	−175.82 (10)	N2A—C6A—C7A—C8A	177.91 (10)
N2—N1—C3—C2	1.98 (17)	C6A—C7A—C8A—C9A	0.05 (18)
N2—N1—C3—C4	179.36 (10)	C6A—C7A—C8A—N3A	−179.19 (10)
O1—C2—C3—N1	−9.03 (18)	O4A—N3A—C8A—C9A	170.20 (11)
C1—C2—C3—N1	168.77 (12)	O3A—N3A—C8A—C9A	−10.12 (17)
O1—C2—C3—C4	173.88 (11)	O4A—N3A—C8A—C7A	−10.52 (16)
C1—C2—C3—C4	−8.32 (18)	O3A—N3A—C8A—C7A	169.16 (11)
N1—C3—C4—O2	177.63 (11)	C7A—C8A—C9A—C10A	1.27 (18)
C2—C3—C4—O2	−5.00 (18)	N3A—C8A—C9A—C10A	−179.50 (11)
N1—C3—C4—C5	−1.62 (15)	C8A—C9A—C10A—C11A	−0.89 (18)
C2—C3—C4—C5	175.76 (10)	C9A—C10A—C11A—C6A	−0.77 (18)
N1—N2—C6—C7	−9.15 (16)	C7A—C6A—C11A—C10A	2.16 (18)
N1—N2—C6—C11	170.88 (10)	N2A—C6A—C11A—C10A	−177.53 (11)
C11—C6—C7—C8	1.12 (17)	C3B—N1B—N2B—C6B	173.25 (10)
N2—C6—C7—C8	−178.86 (10)	N2B—N1B—C3B—C4B	176.26 (10)
C6—C7—C8—C9	−0.34 (17)	N2B—N1B—C3B—C2B	−5.93 (17)
C6—C7—C8—N3	179.37 (10)	O1B—C2B—C3B—N1B	18.51 (17)
O4—N3—C8—C9	−168.61 (10)	C1B—C2B—C3B—N1B	−157.16 (11)
O3—N3—C8—C9	11.87 (15)	O1B—C2B—C3B—C4B	−163.87 (11)
O4—N3—C8—C7	11.66 (15)	C1B—C2B—C3B—C4B	20.45 (16)
O3—N3—C8—C7	−167.86 (10)	N1B—C3B—C4B—O2B	−172.49 (11)
C7—C8—C9—C10	−0.19 (17)	C2B—C3B—C4B—O2B	9.68 (17)
N3—C8—C9—C10	−179.90 (10)	N1B—C3B—C4B—C5B	6.87 (15)
C8—C9—C10—C11	−0.04 (17)	C2B—C3B—C4B—C5B	−170.96 (11)
C9—C10—C11—C6	0.82 (18)	N1B—N2B—C6B—C7B	−4.58 (17)
C7—C6—C11—C10	−1.38 (17)	N1B—N2B—C6B—C11B	175.21 (10)
N2—C6—C11—C10	178.60 (10)	C11B—C6B—C7B—C8B	0.68 (17)
C3A—N1A—N2A—C6A	−174.84 (10)	N2B—C6B—C7B—C8B	−179.55 (10)
N2A—N1A—C3A—C2A	2.44 (17)	C6B—C7B—C8B—C9B	0.68 (18)
N2A—N1A—C3A—C4A	−177.70 (10)	C6B—C7B—C8B—N3B	−178.10 (10)
O1A—C2A—C3A—N1A	−9.99 (18)	O4B—N3B—C8B—C9B	−171.93 (11)
C1A—C2A—C3A—N1A	168.04 (11)	O3B—N3B—C8B—C9B	7.75 (16)
O1A—C2A—C3A—C4A	170.15 (11)	O4B—N3B—C8B—C7B	6.92 (16)
C1A—C2A—C3A—C4A	−11.81 (17)	O3B—N3B—C8B—C7B	−173.40 (11)
N1A—C3A—C4A—O2A	175.02 (11)	C7B—C8B—C9B—C10B	−1.14 (18)
C2A—C3A—C4A—O2A	−5.11 (18)	N3B—C8B—C9B—C10B	177.64 (11)
N1A—C3A—C4A—C5A	−3.29 (15)	C8B—C9B—C10B—C11B	0.23 (18)
C2A—C3A—C4A—C5A	176.58 (11)	C9B—C10B—C11B—C6B	1.08 (19)
N1A—N2A—C6A—C7A	−0.64 (16)	C7B—C6B—C11B—C10B	−1.55 (18)
N1A—N2A—C6A—C11A	179.05 (10)	N2B—C6B—C11B—C10B	178.67 (11)
C11A—C6A—C7A—C8A	−1.77 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11B—H11B···O1Aⁱ	0.95	2.63	3.4824 (15)	150
C9B—H9B···O3Aⁱⁱ	0.95	2.53	3.4837 (16)	178
N2B—H2B···O1B	0.90 (1)	1.90 (1)	2.5952 (13)	133 (1)
C11A—H11A···O1Bⁱ	0.95	2.53	3.4347 (15)	158
C9A—H9A···O3Bⁱⁱ	0.95	2.59	3.5227 (15)	168
C5A—H5A2···N1ⁱ	0.98	2.65	3.5230 (16)	149
C5A—H5A1···O1Aⁱⁱⁱ	0.98	2.51	3.4424 (15)	158
C1A—H1A2···O4ⁱ	0.98	2.49	3.4674 (16)	173
N2A—H2A···O1A	0.90 (1)	1.91 (1)	2.5873 (13)	131 (1)
C11—H11···O1^iv	0.95	2.52	3.4114 (14)	156
C9—H9···O3^v	0.95	2.63	3.5450 (15)	163
C5—H5B···N1Aⁱ	0.98	2.69	3.5445 (16)	146
C1—H1B···O4Aⁱ	0.98	2.47	3.4237 (18)	165
N2—H2···O1	0.89 (1)	1.89 (1)	2.5834 (12)	134 (2)

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

Funding information

We acknowledge the financial support by the Deutsche Forschungsgemeinschaft (DFG Priority Program 1362 `Porous Metal-Organic Frameworks').

References

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