organic compounds
3-[2-(3-Nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione
aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de
The title compound, C11H11N3O4, crystallizes with three independent but conformationally similar molecules in the 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 Carene—H⋯Onitro and Carene—H⋯O=C interactions into supramolecular sheets. Molecules of consecutive sheets are linked by Cmethyl—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 is reported here.
The ). Each molecule features an intramolecular N—H⋯O interaction (Table 1) that yields a six-membered hydrogen-bonded ring. In the 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.
contains three independent but conformationally similar molecules (Fig. 1In the crystal (Fig. 2), the molecules are connected by means of Carene—H⋯Onitro and Carene—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 Cmethyl—H⋯ Onitro 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.
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 .
details are summarized in Table 2
|
Structural data
CCDC reference: 1868829
https://doi.org/10.1107/S2414314618013445/hb4256sup1.cif
contains datablock I. DOI: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
Data collection: APEX2 (Bruker, 2014); cell
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).C11H11N3O4 | Z = 6 |
Mr = 249.23 | F(000) = 780 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII CCD area detector diffractometer | Rint = 0.033 |
φ and ω scans | θmax = 29.1°, θmin = 2.0° |
49810 measured reflections | h = −13→13 |
8881 independent reflections | k = −15→15 |
6440 reflections with I > 2σ(I) | l = −21→21 |
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(Fo2) + (0.0697P)2 + 0.3903P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
8881 reflections | Δρmax = 0.44 e Å−3 |
505 parameters | Δρmin = −0.30 e Å−3 |
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 Uiso(H) = 1.5 Ueq(C) for methyl and C—H = 0.95 Å and Uiso(H) = 1.2 Ueq(C) for aryl. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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···O1iv | 0.95 | 2.52 | 3.4114 (14) | 156 |
C9—H9···O3v | 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').
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