Isostructural rubidium and caesium 4-(3,5-di­nitro­pyrazol-4-yl)-3,5-di­nitro­pyrazolates: crystal engineering with polynitro energetic species

Domasevitch, K.V.; Ponomarova, V.V.

doi:10.1107/S2056989021010227

research communications

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ISSN: 2056-9890

Volume 77| Part 11| November 2021| Pages 1109-1115

https://doi.org/10.1107/S2056989021010227

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Isostructural rubidium and caesium 4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazolates: crystal engineering with polynitro energetic species

Kostiantyn V. Domasevitch ^a ^* and Vira V. Ponomarova ^a

^aInorganic Chemistry Department, National Taras Shevchenko University of Kyiv, Volodymyrska Str. 64/13, 01601 Kyiv, Ukraine
^*Correspondence e-mail: dk@univ.kiev.ua

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 1 October 2021; accepted 3 October 2021; online 13 October 2021)

In the structures of the title salts, poly[[μ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium], [Rb(C₆HN₈O₈)]_n, (1), and its isostructural caesium analogue [Cs(C₆HN₈O₈)_n, (2), two independent cations M1 and M2 (M = Rb, Cs) are situated on a crystallographic twofold axis and on a center of inversion, respectively. Mutual intermolecular hydrogen bonding between the conjugate 3,5-dinitopyrazole NH-donor and 3,5-dinitropyrazole N-acceptor sites of the anions [N⋯N = 2.785 (2) Å for (1) and 2.832 (3) Å for (2)] governs the self-assembly of the translation-related anions in a predictable fashion. Such one-component modular construction of the organic subtopology supports the utility of the crystal-engineering approach towards designing the structures of polynitro energetic materials. The anionic chains are further linked by multiple ion–dipole interactions involving the 12-coordinate cations bonded to two pyrazole N-atoms [Rb—N = 3.1285 (16), 3.2261 (16) Å; Cs—N = 3.369 (2), 3.401 (2) Å] and all of the eight nitro O-atoms [Rb—O = 2.8543 (15)–3.6985 (16) Å; Cs—O = 3.071 (2)–3.811 (2) Å]. The resulting ionic networks follow the CsCl topological archetype, with either metal or organic ions residing in an environment of eight counter-ions. Weak lone pair–π-hole interactions [pyrazole-N atoms to NO₂ groups; N⋯N = 2.990 (3)–3.198 (3) Å] are also relevant to the packing. The Hirshfeld surfaces and percentage two-dimensional fingerprint plots for (1) and (2) are described.

Keywords: crystal structure; rubidium; caesium; nitropyrazoles; energetic materials; hydrogen bonding.

CCDC references: 2113578; 2113577

1. Chemical context

Many issues of crystal engineering, in regard to control over bonding patterns, supramolecular topologies, molecular packing, and crystal morphologies are highly relevant to the area of energetic materials. In particular, non-covalent contacts involving common explosophore nitro groups (Bauzá et al., 2017 ) establish pathways to transmit intermolecular interactions and they are often responsible for higher densities of the solids (Zhang et al., 2000 ). The layered architectures of the energetic solids provide better buffering against external mechanical stimuli, which is essential for developing insensitive materials (Zhang et al., 2008 ). At the same time, incorporation of specific coordination geometries for the assembly of metal–organic solids offers potential for the synthesis of new perchlorate-free flame colorants and pyrotechnics (Glück et al., 2017 ). However, successful applications of the crystal-engineering methodology toward designing the structures of polynitro compounds are relatively rare, so far (Domasevitch et al., 2020 ). This is predetermined by a lack of reliable supramolecular synthons comprising the nitro groups, which are only weak acceptors of conventional hydrogen bonds (Robinson et al., 2000 ) and are only weak donors with respect to the metal ions. A more severe limitation is associated with the need for direct bonding between the nitro-rich functionalities only, since the incorporation of any low-energetic component or solvent molecules is an inevitable penalty to the performance. Such dilution of the energetic moieties in the crystals is relevant, for example, to a series of hydrogen-bonded solids prepared by Aakeröy et al. (2015 ) with acidic ethylenedinitramine and common bitopic pyridine-N bases.

Recently, we have reported a new strategy for the construction of energetic salts, which offers higher degree of control over the structure. Double functionality of the well-performing material 3,3′,5,5′-tetranitro-4,4′-bipyrazole [H₂(TNBP)] (Domasevitch et al., 2019 ) grants synthetic access either to singly or doubly anionic species [{H(TNBP)}⁻ and {TNBP}²⁻, respectively]. The former combine conjugate dinitropyrazole donor and dinitropyrazolate acceptor sites for sustaining particularly strong N—H⋯N bonding. In fact, such bonding of two explosophores dominated the self-assembly in a very predictable fashion and it was traced in all of the previously examined salts with a range of nitrogen-rich cations (Gospodinov et al., 2020 ). That the resulting networks are ionic may find further applications to the synthesis of inorganic nitro-rich salts, based upon Li⁺, Rb⁺, Cs⁺, Sr²⁺, Ba²⁺ and other s- and p-block cations, which are a new generation of `green' pyrotechnic formulations (Steinhauser & Klapötke, 2008 ).

Following the above findings, we now describe the synthesis and structure of rubidium and caesium 4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazolates M{H(TNBP)} [M = Rb (1) and Cs (2)], incorporating the peculiar half-deprotonated bipyrazole tectons. These materials may give an insight into the development of flame colorants in pyrotechnics: rubidium and caesium compounds exhibit, respectively, purple and orange colors when burned.

2. Structural commentary

The title compounds are isostructural, crystallizing in space group C2/c. The molecular structure of the rubidium salt (1) is shown in Fig. 1, with the unique part comprising one organic anion {H(TNBP)}⁻ (or C₆HN₈O₈⁻) and two cations situated on a crystallographic twofold axis [Rb1] or on a center of inversion [Rb2]. The easy formation of such salts is conditioned by the appreciable acidity of polynitropyrazoles, c.f. pK_a = 3.14 for 3,5-dinitropyrazole versus 14.63 for the parent pyrazole (Janssen et al., 1973 ), while for the crystallization of singly charged hydrogen bipyrazolate derivatives, the weakly polarizing, large Rb⁺ and Cs⁺ cations are important.

Figure 1
The molecular structure and the atom-labeling scheme for (1) [the atom labeling for (2) is identical, with Cs1 and Cs2 instead of Rb1 and Rb2], with displacement ellipsoids drawn at the 50% probability level and the N—H⋯N hydrogen bond shown as a dashed line. [Symmetry code: (i) x, y + 1, z.]

Both unique metal ions exhibit exceptionally high coordination numbers of twelve, which are completed with ten O atoms [Rb—O = 2.8543 (15)–3.6985 (16) Å; Cs—O 3.071 (2)–3.811 (2) Å] and two N atoms of the pyrazole rings [Rb—N = 3.1285 (16) and 3.2261 (16) Å; Cs—N = 3.369 (2) and 3.401 (2) Å] (Tables 1 and 2). Most of these separations slightly exceed the sum of the corresponding ionic radii [which are M—O = 3.13 and 3.28 Å; M—N = 3.18 and 3.34 Å for 12-coordinate Rb and Cs ions, respectively (Shannon, 1976 )], indicating the weakness of these relatively distal ion–dipole interactions. This may be best related to the bonding in the ionic salts with polynitro anions lacking conventional donor sites. For example, in caesium picrate, the cations display a comparable 12-fold coordination and a wide spread of Cs—O separations of 3.028 (3)–3.847 (2) Å (Schouten et al., 1990 ). The coordination polyhedra of the two unique cations are very similar and represent essentially distorted icosahedra (Fig. 2). These are completed with a twofold axis [for M1] or inversion [for M2] related pairs of chelating nitropyrazole-N,O groups, pseudo-chelating NO₂ groups and two singly coordinated NO₂ groups. Both kinds of cations reside in a closest environment of eight {H(TNBP)}⁻ anions, which maintain supramolecular boxes with a small internal cavity for the cation (Fig. 3). It is notable that all of the eight O atoms present and the two pyrazole N atoms coordinate to the metal ions.

Table 1
Selected bond lengths (Å) for (1)

Rb1—O1ⁱ	2.8543 (15)	Rb2—O5ⁱⁱⁱ	2.9616 (17)
Rb1—O5	2.9673 (16)	Rb2—O7	2.9690 (15)
Rb1—N3	3.1285 (16)	Rb2—O3ⁱ	3.0743 (17)
Rb1—O8ⁱⁱ	3.3074 (16)	Rb2—N2ⁱ	3.2261 (16)
Rb1—O3ⁱⁱⁱ	3.424 (2)	Rb2—O6ⁱⁱⁱ	3.2275 (16)
Rb1—O4ⁱⁱⁱ	3.4942 (16)	Rb2—O2ⁱⁱ	3.6985 (16)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Selected bond lengths (Å) for (2)

Cs1—O1ⁱ	3.071 (2)	Cs2—O7	3.109 (2)
Cs1—O5	3.177 (2)	Cs2—O5ⁱⁱ	3.159 (2)
Cs1—O3ⁱⁱ	3.351 (3)	Cs2—O3ⁱ	3.297 (2)
Cs1—N3	3.369 (2)	Cs2—O6ⁱⁱ	3.396 (2)
Cs1—O4ⁱⁱ	3.464 (2)	Cs2—N2ⁱ	3.401 (2)
Cs1—O8ⁱⁱⁱ	3.514 (2)	Cs2—O2^iv	3.811 (2)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
Twelvefold coordination environments adopted by the Rb1 and Rb2 ions in (1), in the form of distorted icosahedra. The coordination of the two Cs ions in (2) is almost identical. [Symmetry codes: (i) x, y + 1, z; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z; (iv) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (v) −x + 1, y + 1, −z + $[{1\over 2}]$ ; (vi) −x + 1, y, −z + $[{1\over 2}]$ ; (vii) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (viii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ix) −x, −y + 1, −z; (x) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (xi) −x, −y, −z.]

Figure 3
The Rb2 ion resides inside a supramolecular prism (represented here as a gray box) adopted by eight anions, which complete the coordination environment. The vertices of the prism are built through the mid-points of the central C—C bonds of the molecules. The environments of Rb1 and the respective Cs ions in the structure of (2) are similar. [Symmetry codes: (i) x, y + 1, z; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (ix) −x, −y + 1, −z.]

The main geometrical parameters of the organic anions are very similar to those of the parent [H₂(TNBP)] (Domasevitch et al., 2019). In the case of (1), the protolytic inequivalency of two pyrazole halves is reflected by the ring C—N distances, which are almost the same for anionic ring A (atoms C4/C5/C6/N3/N4) [N3—C4 = 1.343 (2) and N4—C6 1.348 (2) Å] and are slightly differentiated for the neutral ring B (C1/C2/C3/N1/N2) [N1—C1 1.348 (2) and N2—C3 1.331 (2) Å] (Fig. 1). In addition, the deprotonation causes slight elongation of the N—N bond, which is 1.336 (2) Å for ring B and 1.347 (2) Å for ring A. Even more sensitive parameters are the bond angles at the N atoms, which are perceptibly different for the former fragment [N2—N1—C1 = 110.67 (15); C3—N2—N1 = 104.29 (15)°], being much closer for the latter [106.38 (15) and 107.59 (15)°]. In the case of (2), the corresponding geometries are nearly identical for rings A and B [C—N = 1.340 (3)–1.346 (3) Å; N2—N1—C1 = 109.8 (2); N3—N4—C6 = 109.6 (2)° and N1—N2—C3 = 104.9 (2); N4—N3—C4 = 105.1 (2)°]. This situation agrees with the disorder of the H atoms between two positions [at the N1 or N4 carrier atoms] within the N—H⋯N hydrogen bond in (2) as discussed below.

In both structures, the {H(TNBP)}⁻ anions display twisted conformations, with the dihedral angles between the rings being 42.99 (8) and 44.86 (10)° for (1) and (2), respectively. These angles, however, are unusually small. For example, typical parameters for the structurally similar 3,3′,5,5′-tetramethyl-4,4′-bipyrazole unit are 65–90° (Ponomarova et al., 2013 ). The flattening of the {H(TNBP)}⁻ anion suggests certain attractivity in steric interactions of the NO₂ groups, which generates a set of short intramolecular O⋯N contacts, the shortest being O2⋯N7 at 2.786 (3) Å observed for (2). Indeed, the nitro/nitro stackings are energetically favorable, as a special kind of lone pair–π-hole bond (Bauzá et al., 2017).

3. Supramolecular features

The ionic structures of the title compounds may be regarded as three-dimensional networks, which are related to the structure of CsCl. The metal ions themselves constitute a distorted primitive cubic framework with the cells representing elongated prisms [the M⋯M edges are 5.2560 (3), 6.5962 (3), 8.8395 (8) and 5.4775 (4), 6.3932 (5), 9.1482 (12) Å for (1) and (2), respectively]. Every such cell is populated with the organic anion and, conversely, every cation resides inside the distorted prismatic box of eight anions (Figs. 3 and 4).

Figure 4
Fragment of the crystal structure of (1), showing the polar hydrogen-bonded anionic chains propagating along the b-axis direction, in the environment of the Rb cations. Blue lines indicate a pseudo-primitive cubic net arrangement of the cations, with every cell populated by a single anion (c.f. the structure of CsCl). [Symmetry codes: (i) x, y + 1, z; (vi) −x + 1, y, −z + $[{1\over 2}]$ ; (xiv) x, y − 1, z.]

Beyond Coulombic attraction, the principal supramolecular interaction is strong and directional N—H⋯N hydrogen bonding between the pyrazole and pyrazolate halves of translation-related anions [N1⋯N4^xiv = 2.785 (2) and 2.832 (3) Å; H⋯N^xiv = 1.93 and 1.99 Å; N1H⋯N4^xiv = 166 and 163° for (1) and (2), respectively; symmetry code: (xiv) x, y − 1, z], arranging the latter into linear polar chains propagating along the b-axis direction (Fig. 4). Such bonding involving the conjugate acid (pyrazole-NH) and base (pyrazolate-N) sites is a very rare, if not the only, example of a highly reliable supramolecular synthon for crystal engineering with energetic polynitro derivatives. In fact, the conjugate interactions are relevant for many organic species, e.g. carboxylates (Speakman, 1972 ) and oximes (Domasevitch et al., 1998 ), being often the most crucial bonding for the crystal patterns. With the aid of such a synthon, the assembly of the organic subtopology of lower dimensionality is possible in a very rational and predictable fashion and the title structures exactly follow the motifs of previously examined NH₃OH⁺ and 3,3′,5,5′-tetramethyl-4,4′-bipyrazolium {H(TNBP)}⁻ salts (Gospodinov et al., 2020).

The above hydrogen-bonded chains associate to yield layers lying parallel to the ac plane and the latter are separated by the layers of metal cations (Fig. 5). There are two kinds of weaker interactions, which facilitate close packing of the chains. The first of these is identified by close N3⋯N6ⁱⁱ and N2⋯N7^xii contacts [the shortest of 2.990 (3) Å] originating in situation of the pyrazole N atoms almost exactly above the NO₂ N atoms (Table 3). This peculiar lone pair–π-hole interaction occurs instead of the more common NO₂/NO₂ bonding (Bauzá et al., 2017), which is also relevant for the structure of [H₂(TNBP)] itself (Domasevitch et al., 2019). One can note that extensive ion-dipole interactions M⋯O₂N in (1) and (2) mitigate against mutual interactions of nitro groups, which are totally eliminated from the suite of supramolecular bonds. The second type of interchain interaction is stacking between pairs of inversion-related pyrazole and pyrazolate rings (Fig. 6), with the O7 and N5 atoms situated nearly above the centroids of the rings Aⁱⁱⁱ and B^xiii, respectively [symmetry codes: (iii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z; (xiii) −x + $[{1\over 2}]$ , −y − $[{1\over 2}]$ , −z.] (Table 4). As a result of the inversion symmetry of the stacks, the alignment of two polar hydrogen-bonded chains in (1) is antiparallel, while the above lone pair–π-hole interactions support coherent alignment of the contributing chains (Fig. 6). This results in pairing of the chains possessing identical polarities (Fig. 5). In the structure of (2), the polarity of the chains is eliminated because of the disorder of the H atoms in the N—H⋯N/N⋯H—N bonds.

Table 3
Geometry of lone pair–π-hole interactions (Å, °) in (1) and (2)

N⋯plane is a distance of an N-donor to the mean plane of a nitro group and φ is an angle of the N⋯N axis to the plane of the nitro group.

Compound	N-Donor	Group	N⋯N	N⋯plane	φ
(1)	N2	(C4N7O5O6)^xii	2.997 (3)	2.980 (2)	83.9 (2)
	N3	(C3N6O3O4)ⁱⁱ	3.198 (3)	3.093 (2)	75.3 (2)
(2)	N2	(C4N7O5O6)^xii	2.990 (3)	2.976 (3)	84.5 (2)
	N3	(C3N6O3O4)ⁱⁱ	3.186 (3)	3.083 (3)	75.4 (2)
Symmetry codes: (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (xii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

Table 4
Geometry of stacking interactions involving nitro and pyrazole groups (Å, °) in (1) and (2)

Atom⋯Cg is the shortest distance from the nitro group atom to the centroid of the ring; Atom⋯plane is the deviation of the given atom from the mean plane of the ring and φ is the angle of the atom⋯Cg axis to the plane of the ring.

Compound	Atom	Ring	Atom⋯Cg	Atom⋯plane	φ
(1)	O7	(C4C5C6N3N4)ⁱⁱⁱ	3.265 (3)	3.262 (2)	87.5 (2)
	N5	(C1C2C3N1N2)^xiii	3.541 (3)	3.526 (3)	84.7 (2)
(2)	O7	(C4C5C6N3N4)ⁱⁱⁱ	3.240 (3)	3.232 (3)	86.0 (3)
	N5	(C1C2C3N1N2)^xiii	3.448 (3)	3.389 (3)	79.4 (3)
Symmetry codes: (iii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z; (xiii) −x + $[{1\over 2}]$ , −y − $[{1\over 2}]$ , −z.

Figure 5
Structure of (1) viewed in projection on the ac plane (down the direction of the anionic chains) showing the organic layers, which are separated by layers of the cations. The chains of opposite polarity are identified by blue and red colors. [Symmetry codes: (iv) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (v) −x + 1, y + 1, −z + $[{1\over 2}]$ .]

Figure 6
A suite of non-covalent interactions of the {H(TNBP)}⁻ anions, with two kinds of lone pair–π-hole bonds (marked in red) and two kinds of nitro/pyrazole stacks (marked in blue) complementing the conventional hydrogen bonding. [Symmetry codes: (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (v) −x + 1, y + 1, −z + $[{1\over 2}]$ ; (vi) −x + 1, y, −z + $[{1\over 2}]$ ; (xiii) −x + $[{1\over 2}]$ , −y − $[{1\over 2}]$ , −z; (xiv) x, y − 1, z.]

4. Hirshfeld analysis

The supramolecular interactions in the title structures were also assessed by Hirshfeld surface analysis (Spackman & Byrom, 1997 ; McKinnon et al., 2004 ; Hirshfeld, 1977 ; Spackman & McKinnon, 2002 ) performed with CrystalExplorer17 (Turner et al., 2017 ). The contributions of different kinds of interatomic contacts to the Hirshfeld surfaces of the individual anions are listed in Table 5 and the fingerprint plots for (1) are shown in Fig. 7. The most significant contributors are O⋯O contacts (37.4%), while the fraction of O,N⋯Rb (15.4%) is relatively modest due to the larger lengths of the ion–dipole interactions. The shortest O⋯O separation on the plot of ∼2.8 Å corresponds to the contact O1⋯O8^xiii = 2.741 (2) Å [2.732 (3) Å in (2); symmetry code (xiii) −x + $[{1\over 2}]$ , −y − $[{1\over 2}]$ , −z]. We note that slight contraction of the O⋯M fraction in the case of M = Rb [13.6% for (1) and 13.0% for (2)] coincides with a larger contribution of less favorable O⋯O contacts [37.4% for (1) and 35.5% for (2)]. This may be an additional factor destabilizing the structure: the crystals of (1) eventually decompose under the mother solution, unlike the stable Cs analogue. The lone pair–π-hole pyrazole-NO₂ interactions generate 5.3% (1) and 6.3% (2) of the contacts of the Hirshfeld surfaces, with the shortest N⋯N = 2.9 Å. The nature of the O⋯N/N⋯O and N⋯C/C⋯N contacts [in total 23.3% (1) and 22.8% (2)] is similar, since they correspond to the stacking of pyrazole and NO₂ groups with shortest O⋯N and N⋯C distances of 3.2 and 3.3 Å, respectively. However, there are no pairs of the features that are characteristic for the mutual O⋯N/N⋯O interactions of NO₂ groups themselves (Domasevitch et al., 2020). The contributions of the O⋯H/H⋯O and N⋯H/H⋯N contacts are comparable and perceptible [5.4 and 6.9% for (1) and 5.2 and 6.6% for (2)], but only the latter correspond to hydrogen bonding, as is reflected in the plots. These bonds are responsible for a pair of very sharp features pointing to the lower left, with a shortest contact of 1.9 Å, whereas O⋯H/H⋯O contacts are identified only with a diffuse collection of points between the above features and with a shortest contact of 2.8 Å.

Table 5
Contributions of the different kinds of the contacts (%) to the Hirshfeld surfaces of individual anions in (1)^a and (2)

M = Rb (1) and Cs (2)

Contact	(1)	(2)
O⋯M	13.0	13.6
N⋯M	2.4	2.2
O⋯O	37.4	35.5
N⋯N	5.3	6.3
C⋯C	1.0	0.7
O⋯N/N⋯O	15.8	16.2
O⋯C/C⋯O	3.8	5.4
N⋯C/C⋯N	7.5	6.6
N⋯H/H⋯N	6.9	6.6
O⋯H/H⋯O	5.4	5.2
C⋯H/H⋯C	1.5	1.7
Note: (a) For the two-dimensional plots for (1), see Fig. 7.

Figure 7
Two-dimensional fingerprint plots for the individual anions in (1), and delineated into the principal contributions of O,N⋯Rb, O⋯O, N⋯N, O⋯N/N⋯O, O⋯C/C⋯O, N⋯C/C⋯C, N⋯H/H⋯N and O⋯H/H⋯O contacts. Other contacts are C⋯H/H⋯C (1.5%) and C⋯C (1.0%).

5. Synthesis and crystallization

3,3′,5,5′-Tetranitro-4,4′-bipyrazole [H₂(TNBP)] was synthesized in 92% yield by nitration of 4,4′-bipyrazole in mixed acids and then crystallized from water as a monohydrate (Domasevitch et al., 2019).

To prepare the Rb salt (1), 0.332 g (1.0 mmol) of H₂(TNBP)·H₂O was added to a solution of 0.116 g (0.5 mmol) of Rb₂CO₃ in 8 ml of water and the mixture was heated at 353–363 K until total dissolution was observed. The solution was cooled to room temperature and left for a few hours for crystallization. Pale-yellow crystals of Rb{H(TNBP)} were isolated in a yield of 0.325 g (82%) and dried in air. The compound is unstable when stored under the reaction solution as the initially formed crystals dissolve in a period of 10–15 d and colorless H₂(TNBP)·H₂O deposits. In a similar way, the reaction of 0.332 g (1.0 mmol) of H₂(TNBP)·H₂O and 0.163 g (0.5 mmol) of Cs₂CO₃ in 8 ml of water gives 0.415 g (93%) of pale-yellow Cs{H(TNBP)} (2). Unlike (1), this material is stable under the mother solution. Similar reactions with Na₂CO₃ and K₂CO₃ did not afford any hydrogen bipyrazolates and led to soluble M₂{TNBP} (M = Na, K) and precipitation of the excess amount of H₂(TNBP)·H₂O.

Analysis (%) calculated for (1), C₆HN₈O₈Rb: C 18.08, H 0.25, N 28.12; found: C 17.93, H 0.44, N 28.49. IR (KBr, cm⁻¹): 590 w, 708 w, 838 m, 854 s, 996 m, 1024 m, 1308 s, 1352 vs, 1398 vs, 1432 m, 1490 vs, 1500 m, 1556 vs, 1636 w, 3448 br.

Analysis (%) calculated for (2), C₆HCsN₈O₈: C 16.15, H 0.23, N 25.13; found: C 16.01, H 0.38, N 28.11. IR (KBr, cm⁻¹): 516 w, 586 m, 708 m, 838 s, 852 s, 994 s, 1022 m, 1170 w, 1306 s, 1324 s, 1350 vs, 1396 vs, 1432 s, 1488 vs, 1512 vs, 1544 vs, 1634 m, 3024 br, 3442 br.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. The hydrogen atoms were located and then refined as riding with N—H = 0.87 Å and U_iso(H) = 1.5U_eq(N). For (2), the H atom is equally disordered over two positions corresponding to the N1 and N4 carrier atoms.

Table 6
Experimental details

	(1)	(2)
Crystal data
Chemical formula	[Rb(C₆HN₈O₈)]	[Cs(C₆HN₈O₈)]
M_r	398.62	446.06
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	213	213
a, b, c (Å)	19.4400 (15), 8.6070 (4), 16.0977 (10)	19.944 (2), 8.6307 (7), 16.2083 (17)
β (°)	115.264 (7)	113.766 (8)
V (Å³)	2435.8 (3)	2553.4 (5)
Z	8	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	4.13	2.97
Crystal size (mm)	0.20 × 0.16 × 0.14	0.20 × 0.16 × 0.14

Data collection
Diffractometer	Stoe IPDS	Stoe IPDS
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001 ) and X-SHAPE (Stoe & Cie, 1999 )]	Numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
T_min, T_max	0.672, 0.789	0.677, 0.772
No. of measured, independent and observed [I > 2σ(I)] reflections	9925, 2890, 2186	9014, 2990, 2686
R_int	0.033	0.042
(sin θ/λ)_max (Å⁻¹)	0.658	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.055, 0.89	0.027, 0.060, 1.21
No. of reflections	2890	2990
No. of parameters	210	211
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.39	0.67, −0.77
Computer programs: IPDS Software (Stoe & Cie, 2000 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/1 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC references: 2113578; 2113577

Crystal structure: contains datablocks global, 1, 2. DOI: https://doi.org/10.1107/S2056989021010227/hb7988sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989021010227/hb79881sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989021010227/hb79882sup3.hkl

checkCIF report

Computing details top

For both structures, data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) top

Crystal data top

[Rb(C₆HN₈O₈)]	F(000) = 1552
M_r = 398.62	D_x = 2.174 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.4400 (15) Å	Cell parameters from 8000 reflections
b = 8.6070 (4) Å	θ = 2.3–27.9°
c = 16.0977 (10) Å	µ = 4.13 mm⁻¹
β = 115.264 (7)°	T = 213 K
V = 2435.8 (3) Å³	Prism, yellow
Z = 8	0.20 × 0.16 × 0.14 mm

Data collection top

Stoe IPDS diffractometer	2186 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
φ oscillation scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −25→25
T_min = 0.672, T_max = 0.789	k = −10→11
9925 measured reflections	l = −20→20
2890 independent 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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0326P)²] where P = (F_o² + 2F_c²)/3
2890 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.39 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.

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

	x	y	z	U_iso*/U_eq
Rb1	0.500000	0.39279 (3)	0.250000	0.02840 (9)
Rb2	0.000000	0.500000	0.000000	0.03230 (9)
O1	0.38330 (9)	−0.38304 (18)	0.16106 (14)	0.0422 (5)
O2	0.38489 (9)	−0.14611 (18)	0.11639 (13)	0.0344 (4)
O3	0.03697 (9)	−0.16032 (19)	0.06215 (16)	0.0490 (5)
O4	0.10681 (9)	0.03244 (17)	0.13792 (13)	0.0347 (4)
O5	0.45319 (8)	0.09854 (18)	0.30718 (12)	0.0329 (4)
O6	0.37797 (9)	−0.09294 (16)	0.29580 (11)	0.0301 (4)
O7	0.13123 (9)	0.34370 (17)	−0.01293 (13)	0.0344 (4)
O8	0.12218 (8)	0.09417 (17)	−0.03095 (11)	0.0280 (3)
N1	0.23222 (9)	−0.36612 (17)	0.10737 (13)	0.0199 (4)
H1	0.247444	−0.461154	0.107308	0.030*
N2	0.16218 (9)	−0.32601 (19)	0.09532 (13)	0.0210 (4)
N3	0.33470 (9)	0.27100 (18)	0.19547 (13)	0.0207 (4)
N4	0.26946 (9)	0.31935 (17)	0.12643 (13)	0.0200 (4)
N5	0.35387 (9)	−0.25662 (18)	0.13349 (12)	0.0212 (4)
N6	0.09790 (10)	−0.0935 (2)	0.10011 (14)	0.0266 (4)
N7	0.39083 (9)	0.03467 (19)	0.27152 (13)	0.0218 (4)
N8	0.15509 (9)	0.21089 (19)	0.01062 (13)	0.0206 (4)
C1	0.27606 (10)	−0.2391 (2)	0.11965 (14)	0.0175 (4)
C2	0.23545 (10)	−0.1061 (2)	0.11814 (14)	0.0161 (4)
C3	0.16475 (10)	−0.1719 (2)	0.10251 (15)	0.0181 (4)
C4	0.32927 (10)	0.1159 (2)	0.19966 (14)	0.0177 (4)
C5	0.26131 (10)	0.0553 (2)	0.13416 (14)	0.0158 (4)
C6	0.22651 (10)	0.1926 (2)	0.08941 (14)	0.0167 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.01707 (13)	0.01962 (14)	0.0442 (2)	0.000	0.00897 (13)	0.000
Rb2	0.02226 (15)	0.03355 (17)	0.0307 (2)	0.00090 (12)	0.00132 (12)	−0.01165 (14)
O1	0.0311 (8)	0.0188 (8)	0.0702 (14)	0.0128 (6)	0.0153 (9)	0.0038 (8)
O2	0.0284 (8)	0.0279 (8)	0.0533 (12)	−0.0005 (6)	0.0234 (8)	0.0034 (8)
O3	0.0212 (8)	0.0283 (9)	0.0941 (17)	−0.0011 (7)	0.0214 (9)	0.0036 (9)
O4	0.0411 (9)	0.0214 (8)	0.0519 (12)	0.0071 (7)	0.0299 (9)	−0.0003 (7)
O5	0.0206 (7)	0.0336 (8)	0.0327 (10)	−0.0044 (6)	0.0001 (7)	0.0048 (7)
O6	0.0375 (8)	0.0155 (7)	0.0272 (10)	−0.0001 (6)	0.0040 (7)	0.0046 (6)
O7	0.0313 (8)	0.0190 (7)	0.0470 (12)	0.0121 (6)	0.0111 (8)	0.0127 (7)
O8	0.0225 (7)	0.0231 (8)	0.0305 (10)	−0.0046 (6)	0.0037 (6)	0.0008 (7)
N1	0.0231 (8)	0.0089 (7)	0.0267 (11)	0.0004 (6)	0.0098 (7)	−0.0010 (7)
N2	0.0222 (8)	0.0127 (8)	0.0283 (11)	−0.0004 (6)	0.0109 (7)	0.0020 (7)
N3	0.0220 (8)	0.0141 (8)	0.0230 (10)	−0.0016 (6)	0.0067 (7)	−0.0010 (7)
N4	0.0213 (8)	0.0103 (7)	0.0277 (11)	−0.0001 (6)	0.0098 (7)	0.0009 (7)
N5	0.0211 (8)	0.0164 (8)	0.0230 (10)	0.0031 (6)	0.0064 (7)	−0.0051 (7)
N6	0.0256 (9)	0.0174 (9)	0.0423 (13)	0.0030 (7)	0.0198 (8)	0.0077 (8)
N7	0.0241 (9)	0.0176 (9)	0.0196 (10)	0.0010 (6)	0.0053 (7)	−0.0014 (7)
N8	0.0187 (8)	0.0180 (8)	0.0263 (11)	0.0031 (6)	0.0108 (7)	0.0057 (7)
C1	0.0203 (9)	0.0115 (9)	0.0193 (12)	0.0001 (7)	0.0070 (8)	0.0000 (7)
C2	0.0187 (9)	0.0104 (8)	0.0188 (11)	0.0010 (7)	0.0075 (8)	0.0008 (8)
C3	0.0203 (9)	0.0122 (9)	0.0223 (12)	0.0008 (7)	0.0095 (8)	0.0019 (8)
C4	0.0206 (9)	0.0119 (8)	0.0192 (11)	0.0007 (7)	0.0070 (8)	−0.0003 (7)
C5	0.0177 (9)	0.0109 (8)	0.0202 (12)	0.0014 (7)	0.0094 (8)	0.0003 (7)
C6	0.0185 (9)	0.0126 (8)	0.0198 (11)	0.0016 (7)	0.0089 (8)	0.0011 (7)

Geometric parameters (Å, º) top

Rb1—O1ⁱ	2.8543 (15)	O1—N5	1.221 (2)
Rb1—O1ⁱⁱ	2.8543 (15)	O2—N5	1.219 (2)
Rb1—O5	2.9673 (16)	O3—N6	1.220 (2)
Rb1—O5ⁱⁱⁱ	2.9673 (16)	O4—N6	1.219 (2)
Rb1—N3	3.1285 (16)	O5—N7	1.228 (2)
Rb1—N3ⁱⁱⁱ	3.1285 (16)	O6—N7	1.227 (2)
Rb1—O8^iv	3.3074 (16)	O7—N8	1.231 (2)
Rb1—O8^v	3.3074 (16)	O8—N8	1.225 (2)
Rb1—O3^vi	3.424 (2)	N1—N2	1.336 (2)
Rb1—O3^vii	3.424 (2)	N1—C1	1.348 (2)
Rb1—O4^vi	3.4942 (16)	N1—H1	0.8700
Rb1—O4^vii	3.4942 (16)	N2—C3	1.331 (2)
Rb2—O5^viii	2.9616 (17)	N3—C4	1.343 (2)
Rb2—O5^vii	2.9616 (17)	N3—N4	1.347 (2)
Rb2—O7^ix	2.9690 (15)	N4—C6	1.348 (2)
Rb2—O7	2.9690 (15)	N5—C1	1.440 (2)
Rb2—O3^x	3.0743 (17)	N6—C3	1.450 (2)
Rb2—O3ⁱⁱ	3.0743 (17)	N7—C4	1.441 (2)
Rb2—N2^x	3.2261 (16)	N8—C6	1.435 (3)
Rb2—N2ⁱⁱ	3.2261 (16)	C1—C2	1.384 (3)
Rb2—O6^viii	3.2275 (16)	C2—C3	1.406 (3)
Rb2—O6^vii	3.2275 (16)	C2—C5	1.462 (2)
Rb2—O2^v	3.6985 (16)	C4—C5	1.393 (3)
Rb2—O2^xi	3.6985 (16)	C5—C6	1.399 (3)

O1ⁱ—Rb1—O1ⁱⁱ	94.94 (7)	O5^vii—Rb2—O6^viii	139.46 (4)
O1ⁱ—Rb1—O5	134.80 (5)	O7^ix—Rb2—O6^viii	71.28 (5)
O1ⁱⁱ—Rb1—O5	116.69 (4)	O7—Rb2—O6^viii	108.72 (5)
O1ⁱ—Rb1—O5ⁱⁱⁱ	116.69 (4)	O3^x—Rb2—O6^viii	86.34 (5)
O1ⁱⁱ—Rb1—O5ⁱⁱⁱ	134.80 (5)	O3ⁱⁱ—Rb2—O6^viii	93.66 (5)
O5—Rb1—O5ⁱⁱⁱ	62.80 (7)	N2^x—Rb2—O6^viii	59.09 (4)
O1ⁱ—Rb1—N3	150.29 (5)	N2ⁱⁱ—Rb2—O6^viii	120.91 (4)
O1ⁱⁱ—Rb1—N3	65.44 (5)	O5^viii—Rb2—O6^vii	139.46 (4)
O5—Rb1—N3	52.18 (4)	O5^vii—Rb2—O6^vii	40.54 (4)
O5ⁱⁱⁱ—Rb1—N3	92.36 (4)	O7^ix—Rb2—O6^vii	108.72 (5)
O1ⁱ—Rb1—N3ⁱⁱⁱ	65.44 (5)	O7—Rb2—O6^vii	71.28 (5)
O1ⁱⁱ—Rb1—N3ⁱⁱⁱ	150.29 (5)	O3^x—Rb2—O6^vii	93.66 (5)
O5—Rb1—N3ⁱⁱⁱ	92.36 (4)	O3ⁱⁱ—Rb2—O6^vii	86.34 (5)
O5ⁱⁱⁱ—Rb1—N3ⁱⁱⁱ	52.18 (4)	N2^x—Rb2—O6^vii	120.91 (4)
N3—Rb1—N3ⁱⁱⁱ	140.85 (6)	N2ⁱⁱ—Rb2—O6^vii	59.09 (4)
O1ⁱ—Rb1—O8^iv	52.19 (5)	O6^viii—Rb2—O6^vii	180.00 (7)
O1ⁱⁱ—Rb1—O8^iv	124.56 (5)	O5^viii—Rb2—O2^v	63.14 (4)
O5—Rb1—O8^iv	82.76 (4)	O5^vii—Rb2—O2^v	116.86 (4)
O5ⁱⁱⁱ—Rb1—O8^iv	100.60 (4)	O7^ix—Rb2—O2^v	127.24 (4)
N3—Rb1—O8^iv	119.65 (4)	O7—Rb2—O2^v	52.75 (4)
N3ⁱⁱⁱ—Rb1—O8^iv	61.84 (4)	O3^x—Rb2—O2^v	105.45 (5)
O1ⁱ—Rb1—O8^v	124.56 (5)	O3ⁱⁱ—Rb2—O2^v	74.55 (5)
O1ⁱⁱ—Rb1—O8^v	52.19 (5)	N2^x—Rb2—O2^v	126.63 (4)
O5—Rb1—O8^v	100.60 (4)	N2ⁱⁱ—Rb2—O2^v	53.37 (4)
O5ⁱⁱⁱ—Rb1—O8^v	82.76 (4)	O6^viii—Rb2—O2^v	74.96 (4)
N3—Rb1—O8^v	61.84 (4)	O6^vii—Rb2—O2^v	105.04 (4)
N3ⁱⁱⁱ—Rb1—O8^v	119.65 (4)	O5^viii—Rb2—O2^xi	116.86 (4)
O8^iv—Rb1—O8^v	176.11 (5)	O5^vii—Rb2—O2^xi	63.14 (4)
O1ⁱ—Rb1—O3^vi	96.42 (5)	O7^ix—Rb2—O2^xi	52.76 (4)
O1ⁱⁱ—Rb1—O3^vi	93.94 (5)	O7—Rb2—O2^xi	127.25 (4)
O5—Rb1—O3^vi	111.58 (4)	O3^x—Rb2—O2^xi	74.55 (5)
O5ⁱⁱⁱ—Rb1—O3^vi	53.44 (4)	O3ⁱⁱ—Rb2—O2^xi	105.45 (5)
N3—Rb1—O3^vi	106.56 (4)	N2^x—Rb2—O2^xi	53.37 (4)
N3ⁱⁱⁱ—Rb1—O3^vi	68.00 (4)	N2ⁱⁱ—Rb2—O2^xi	126.63 (4)
O8^iv—Rb1—O3^vi	128.33 (4)	O6^viii—Rb2—O2^xi	105.04 (4)
O8^v—Rb1—O3^vi	52.33 (4)	O6^vii—Rb2—O2^xi	74.96 (4)
O1ⁱ—Rb1—O3^vii	93.94 (5)	O2^v—Rb2—O2^xi	180.00 (3)
O1ⁱⁱ—Rb1—O3^vii	96.42 (5)	N5—O1—Rb1^xii	158.96 (13)
O5—Rb1—O3^vii	53.44 (4)	N6—O3—Rb2^xii	130.77 (13)
O5ⁱⁱⁱ—Rb1—O3^vii	111.58 (4)	N6—O3—Rb1^xiii	91.12 (15)
N3—Rb1—O3^vii	68.00 (4)	Rb2^xii—O3—Rb1^xiii	107.84 (5)
N3ⁱⁱⁱ—Rb1—O3^vii	106.56 (4)	N6—O4—Rb1^xiii	87.86 (12)
O8^iv—Rb1—O3^vii	52.33 (4)	N7—O5—Rb2^xiv	99.33 (12)
O8^v—Rb1—O3^vii	128.33 (4)	N7—O5—Rb1	127.55 (12)
O3^vi—Rb1—O3^vii	164.66 (6)	Rb2^xiv—O5—Rb1	124.88 (5)
O1ⁱ—Rb1—O4^vi	60.41 (5)	N7—O6—Rb2^xiv	86.64 (11)
O1ⁱⁱ—Rb1—O4^vi	91.65 (5)	N8—O7—Rb2	128.40 (13)
O5—Rb1—O4^vi	141.47 (4)	N8—O8—Rb1^v	121.64 (12)
O5ⁱⁱⁱ—Rb1—O4^vi	78.75 (4)	N2—N1—C1	110.67 (15)
N3—Rb1—O4^vi	137.39 (5)	N2—N1—H1	124.7
N3ⁱⁱⁱ—Rb1—O4^vi	59.64 (4)	C1—N1—H1	124.7
O8^iv—Rb1—O4^vi	102.96 (4)	C3—N2—N1	104.29 (15)
O8^v—Rb1—O4^vi	75.66 (4)	C3—N2—Rb2^xii	119.80 (12)
O3^vi—Rb1—O4^vi	36.38 (4)	N1—N2—Rb2^xii	132.66 (12)
O3^vii—Rb1—O4^vi	153.75 (4)	C4—N3—N4	106.38 (15)
O1ⁱ—Rb1—O4^vii	91.65 (5)	C4—N3—Rb1	114.35 (12)
O1ⁱⁱ—Rb1—O4^vii	60.41 (5)	N4—N3—Rb1	128.37 (12)
O5—Rb1—O4^vii	78.75 (4)	N3—N4—C6	107.59 (15)
O5ⁱⁱⁱ—Rb1—O4^vii	141.47 (4)	O2—N5—O1	125.25 (17)
N3—Rb1—O4^vii	59.64 (4)	O2—N5—C1	118.13 (15)
N3ⁱⁱⁱ—Rb1—O4^vii	137.39 (5)	O1—N5—C1	116.61 (16)
O8^iv—Rb1—O4^vii	75.66 (4)	O4—N6—O3	124.73 (18)
O8^v—Rb1—O4^vii	102.96 (4)	O4—N6—C3	117.74 (17)
O3^vi—Rb1—O4^vii	153.75 (4)	O3—N6—C3	117.50 (18)
O3^vii—Rb1—O4^vii	36.38 (4)	O4—N6—Rb1^xiii	72.68 (11)
O4^vi—Rb1—O4^vii	139.76 (5)	O3—N6—Rb1^xiii	69.40 (14)
O5^viii—Rb2—O5^vii	180.00 (8)	C3—N6—Rb1^xiii	132.87 (13)
O5^viii—Rb2—O7^ix	108.32 (4)	O6—N7—O5	123.15 (18)
O5^vii—Rb2—O7^ix	71.68 (4)	O6—N7—C4	118.54 (16)
O5^viii—Rb2—O7	71.68 (4)	O5—N7—C4	118.29 (16)
O5^vii—Rb2—O7	108.32 (4)	O6—N7—Rb2^xiv	72.15 (11)
O7^ix—Rb2—O7	180.0	O5—N7—Rb2^xiv	59.69 (11)
O5^viii—Rb2—O3^x	57.45 (5)	C4—N7—Rb2^xiv	146.67 (12)
O5^vii—Rb2—O3^x	122.55 (5)	O8—N8—O7	123.57 (18)
O7^ix—Rb2—O3^x	111.42 (4)	O8—N8—C6	118.40 (15)
O7—Rb2—O3^x	68.58 (4)	O7—N8—C6	118.00 (17)
O5^viii—Rb2—O3ⁱⁱ	122.55 (5)	N1—C1—C2	110.36 (16)
O5^vii—Rb2—O3ⁱⁱ	57.45 (5)	N1—C1—N5	119.62 (15)
O7^ix—Rb2—O3ⁱⁱ	68.58 (4)	C2—C1—N5	130.01 (16)
O7—Rb2—O3ⁱⁱ	111.42 (4)	C1—C2—C3	100.20 (16)
O3^x—Rb2—O3ⁱⁱ	180.00 (10)	C1—C2—C5	129.17 (17)
O5^viii—Rb2—N2^x	64.39 (4)	C3—C2—C5	130.53 (17)
O5^vii—Rb2—N2^x	115.61 (4)	N2—C3—C2	114.47 (16)
O7^ix—Rb2—N2^x	63.20 (4)	N2—C3—N6	117.47 (16)
O7—Rb2—N2^x	116.80 (4)	C2—C3—N6	127.90 (17)
O3^x—Rb2—N2^x	50.09 (4)	N3—C4—C5	113.82 (17)
O3ⁱⁱ—Rb2—N2^x	129.91 (4)	N3—C4—N7	117.80 (17)
O5^viii—Rb2—N2ⁱⁱ	115.61 (4)	C5—C4—N7	128.31 (17)
O5^vii—Rb2—N2ⁱⁱ	64.39 (4)	C4—C5—C6	99.63 (15)
O7^ix—Rb2—N2ⁱⁱ	116.80 (4)	C4—C5—C2	129.27 (17)
O7—Rb2—N2ⁱⁱ	63.20 (4)	C6—C5—C2	131.10 (17)
O3^x—Rb2—N2ⁱⁱ	129.91 (4)	N4—C6—C5	112.57 (17)
O3ⁱⁱ—Rb2—N2ⁱⁱ	50.09 (4)	N4—C6—N8	119.01 (16)
N2^x—Rb2—N2ⁱⁱ	180.0	C5—C6—N8	128.38 (16)
O5^viii—Rb2—O6^viii	40.54 (4)

C1—N1—N2—C3	−1.3 (2)	C1—C2—C3—N2	0.0 (2)
C1—N1—N2—Rb2^xii	157.43 (14)	C5—C2—C3—N2	−176.6 (2)
C4—N3—N4—C6	−1.0 (2)	C1—C2—C3—N6	175.2 (2)
Rb1—N3—N4—C6	140.39 (14)	C5—C2—C3—N6	−1.4 (4)
Rb1^xii—O1—N5—O2	26.7 (6)	O4—N6—C3—N2	154.3 (2)
Rb1^xii—O1—N5—C1	−153.8 (4)	O3—N6—C3—N2	−24.1 (3)
Rb1^xiii—O4—N6—O3	48.3 (2)	Rb1^xiii—N6—C3—N2	62.6 (3)
Rb1^xiii—O4—N6—C3	−129.88 (17)	O4—N6—C3—C2	−20.8 (3)
Rb2^xii—O3—N6—O4	−164.56 (17)	O3—N6—C3—C2	160.8 (2)
Rb1^xiii—O3—N6—O4	−49.6 (2)	Rb1^xiii—N6—C3—C2	−112.5 (2)
Rb2^xii—O3—N6—C3	13.7 (3)	N4—N3—C4—C5	0.3 (2)
Rb1^xiii—O3—N6—C3	128.59 (17)	Rb1—N3—C4—C5	−147.15 (14)
Rb2^xii—O3—N6—Rb1^xiii	−114.92 (19)	N4—N3—C4—N7	−177.06 (17)
Rb2^xiv—O6—N7—O5	32.5 (2)	Rb1—N3—C4—N7	35.5 (2)
Rb2^xiv—O6—N7—C4	−145.49 (16)	O6—N7—C4—N3	156.77 (19)
Rb2^xiv—O5—N7—O6	−36.3 (2)	O5—N7—C4—N3	−21.3 (3)
Rb1—O5—N7—O6	174.67 (14)	Rb2^xiv—N7—C4—N3	55.7 (3)
Rb2^xiv—O5—N7—C4	141.67 (15)	O6—N7—C4—C5	−20.2 (3)
Rb1—O5—N7—C4	−7.3 (3)	O5—N7—C4—C5	161.7 (2)
Rb1—O5—N7—Rb2^xiv	−149.01 (17)	Rb2^xiv—N7—C4—C5	−121.3 (2)
Rb1^v—O8—N8—O7	22.7 (3)	N3—C4—C5—C6	0.4 (2)
Rb1^v—O8—N8—C6	−155.32 (13)	N7—C4—C5—C6	177.5 (2)
Rb2—O7—N8—O8	72.4 (3)	N3—C4—C5—C2	−179.85 (19)
Rb2—O7—N8—C6	−109.63 (17)	N7—C4—C5—C2	−2.8 (4)
N2—N1—C1—C2	1.4 (2)	C1—C2—C5—C4	−41.0 (4)
N2—N1—C1—N5	−179.72 (17)	C3—C2—C5—C4	134.7 (2)
O2—N5—C1—N1	157.8 (2)	C1—C2—C5—C6	138.7 (2)
O1—N5—C1—N1	−21.7 (3)	C3—C2—C5—C6	−45.6 (4)
O2—N5—C1—C2	−23.6 (3)	N3—N4—C6—C5	1.3 (2)
O1—N5—C1—C2	156.9 (2)	N3—N4—C6—N8	−176.64 (16)
N1—C1—C2—C3	−0.8 (2)	C4—C5—C6—N4	−1.0 (2)
N5—C1—C2—C3	−179.5 (2)	C2—C5—C6—N4	179.2 (2)
N1—C1—C2—C5	175.8 (2)	C4—C5—C6—N8	176.7 (2)
N5—C1—C2—C5	−2.9 (4)	C2—C5—C6—N8	−3.1 (4)
N1—N2—C3—C2	0.8 (2)	O8—N8—C6—N4	168.87 (18)
Rb2^xii—N2—C3—C2	−161.31 (14)	O7—N8—C6—N4	−9.2 (3)
N1—N2—C3—N6	−174.94 (18)	O8—N8—C6—C5	−8.7 (3)
Rb2^xii—N2—C3—N6	23.0 (2)	O7—N8—C6—C5	173.2 (2)

Symmetry codes: (i) −x+1, y+1, −z+1/2; (ii) x, y+1, z; (iii) −x+1, y, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+1/2, −y+1/2, −z; (vi) x+1/2, y+1/2, z; (vii) −x+1/2, y+1/2, −z+1/2; (viii) x−1/2, −y+1/2, z−1/2; (ix) −x, −y+1, −z; (x) −x, −y, −z; (xi) x−1/2, y+1/2, z; (xii) x, y−1, z; (xiii) x−1/2, y−1/2, z; (xiv) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4^xii	0.87	1.93	2.785 (2)	166

Symmetry code: (xii) x, y−1, z.

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) top

Crystal data top

[Cs(C₆HN₈O₈)]	F(000) = 1696
M_r = 446.06	D_x = 2.321 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.944 (2) Å	Cell parameters from 8000 reflections
b = 8.6307 (7) Å	θ = 2.2–27.8°
c = 16.2083 (17) Å	µ = 2.97 mm⁻¹
β = 113.766 (8)°	T = 213 K
V = 2553.4 (5) Å³	Prism, yellow
Z = 8	0.20 × 0.16 × 0.14 mm

Data collection top

Stoe IPDS diffractometer	2686 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
φ oscillation scans	θ_max = 27.8°, θ_min = 2.2°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −20→26
T_min = 0.677, T_max = 0.772	k = −11→11
9014 measured reflections	l = −21→21
2990 independent reflections

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0214P)² + 3.932P] where P = (F_o² + 2F_c²)/3
S = 1.21	(Δ/σ)_max < 0.001
2990 reflections	Δρ_max = 0.67 e Å⁻³
211 parameters	Δρ_min = −0.77 e Å⁻³
0 restraints	Extinction correction: SHELXL2018/1 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00151 (14)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cs1	0.500000	0.42703 (3)	0.250000	0.03031 (9)
Cs2	0.000000	0.500000	0.000000	0.04080 (10)
O1	0.36906 (14)	−0.3754 (3)	0.1294 (2)	0.0536 (7)
O2	0.38087 (12)	−0.1274 (2)	0.12176 (15)	0.0369 (5)
O3	0.04269 (12)	−0.1420 (3)	0.07349 (18)	0.0460 (6)
O4	0.11168 (14)	0.0488 (2)	0.14521 (17)	0.0391 (5)
O5	0.44367 (12)	0.1085 (2)	0.29706 (15)	0.0379 (5)
O6	0.36857 (13)	−0.0765 (2)	0.29226 (14)	0.0351 (5)
O7	0.13940 (12)	0.3610 (2)	−0.01257 (15)	0.0391 (5)
O8	0.12142 (13)	0.1123 (2)	−0.02282 (14)	0.0370 (5)
N1	0.22944 (13)	−0.3511 (2)	0.10259 (15)	0.0260 (5)
H1A	0.243307	−0.445633	0.099377	0.039*	0.5
N2	0.16260 (13)	−0.3095 (2)	0.09520 (15)	0.0267 (5)
N3	0.32972 (13)	0.2858 (2)	0.19322 (15)	0.0266 (5)
N4	0.26741 (13)	0.3309 (2)	0.12597 (15)	0.0252 (5)
H1B	0.256042	0.426103	0.108253	0.038*	0.5
N5	0.34581 (13)	−0.2427 (2)	0.12310 (15)	0.0260 (5)
N6	0.10201 (14)	−0.0772 (3)	0.10736 (17)	0.0304 (5)
N7	0.38266 (14)	0.0482 (3)	0.26693 (15)	0.0268 (5)
N8	0.15723 (13)	0.2273 (2)	0.01333 (15)	0.0253 (5)
C1	0.27188 (15)	−0.2249 (3)	0.11572 (17)	0.0228 (5)
C2	0.23398 (15)	−0.0903 (3)	0.11868 (16)	0.0216 (5)
C3	0.16581 (15)	−0.1553 (3)	0.10518 (17)	0.0236 (5)
C4	0.32386 (15)	0.1316 (3)	0.19768 (17)	0.0230 (5)
C5	0.25873 (14)	0.0703 (3)	0.13417 (16)	0.0208 (5)
C6	0.22504 (15)	0.2064 (3)	0.08996 (17)	0.0230 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.02186 (13)	0.02958 (13)	0.03945 (15)	0.000	0.01232 (10)	0.000
Cs2	0.02484 (14)	0.04935 (19)	0.03776 (16)	−0.00107 (11)	0.00175 (11)	−0.01535 (12)
O1	0.0407 (13)	0.0213 (10)	0.095 (2)	0.0120 (10)	0.0230 (14)	−0.0019 (12)
O2	0.0366 (12)	0.0257 (10)	0.0524 (13)	0.0006 (9)	0.0220 (10)	0.0023 (9)
O3	0.0277 (11)	0.0353 (11)	0.0727 (16)	−0.0002 (10)	0.0177 (11)	0.0033 (11)
O4	0.0456 (13)	0.0234 (10)	0.0604 (14)	0.0040 (9)	0.0339 (12)	−0.0020 (9)
O5	0.0276 (11)	0.0354 (11)	0.0418 (12)	−0.0014 (8)	0.0047 (9)	0.0046 (9)
O6	0.0440 (13)	0.0198 (9)	0.0305 (10)	−0.0020 (8)	0.0035 (9)	0.0055 (8)
O7	0.0395 (12)	0.0224 (9)	0.0488 (12)	0.0106 (9)	0.0107 (10)	0.0125 (9)
O8	0.0369 (12)	0.0276 (10)	0.0369 (11)	−0.0045 (9)	0.0048 (9)	0.0035 (8)
N1	0.0305 (11)	0.0154 (9)	0.0310 (11)	0.0029 (9)	0.0113 (9)	0.0008 (9)
N2	0.0312 (12)	0.0172 (10)	0.0313 (11)	−0.0004 (9)	0.0121 (10)	0.0011 (9)
N3	0.0305 (12)	0.0187 (10)	0.0282 (11)	−0.0016 (9)	0.0095 (9)	−0.0018 (9)
N4	0.0311 (12)	0.0127 (9)	0.0306 (11)	0.0031 (8)	0.0111 (9)	0.0014 (8)
N5	0.0272 (12)	0.0207 (10)	0.0283 (11)	0.0053 (9)	0.0094 (9)	−0.0017 (8)
N6	0.0314 (13)	0.0229 (11)	0.0427 (14)	0.0025 (10)	0.0208 (11)	0.0070 (10)
N7	0.0299 (12)	0.0211 (10)	0.0254 (11)	0.0028 (9)	0.0069 (9)	−0.0004 (8)
N8	0.0268 (12)	0.0206 (10)	0.0296 (11)	0.0045 (9)	0.0123 (9)	0.0048 (9)
C1	0.0282 (13)	0.0143 (10)	0.0232 (12)	0.0035 (9)	0.0076 (10)	0.0018 (9)
C2	0.0288 (13)	0.0131 (10)	0.0214 (11)	0.0013 (10)	0.0085 (10)	0.0011 (8)
C3	0.0284 (13)	0.0163 (11)	0.0279 (12)	0.0015 (10)	0.0134 (11)	0.0023 (9)
C4	0.0274 (13)	0.0171 (11)	0.0227 (11)	0.0022 (10)	0.0082 (10)	0.0010 (9)
C5	0.0267 (13)	0.0130 (10)	0.0232 (11)	0.0020 (9)	0.0105 (10)	0.0021 (9)
C6	0.0265 (13)	0.0162 (11)	0.0260 (12)	0.0052 (9)	0.0101 (10)	0.0026 (9)

Geometric parameters (Å, º) top

Cs1—O1ⁱ	3.071 (2)	O2—N5	1.222 (3)
Cs1—O1ⁱⁱ	3.071 (2)	O3—N6	1.221 (3)
Cs1—O5ⁱⁱⁱ	3.177 (2)	O4—N6	1.225 (3)
Cs1—O5	3.177 (2)	O5—N7	1.229 (3)
Cs1—O3^iv	3.351 (3)	O6—N7	1.224 (3)
Cs1—O3^v	3.351 (3)	O7—N8	1.230 (3)
Cs1—N3	3.369 (2)	O8—N8	1.225 (3)
Cs1—N3ⁱⁱⁱ	3.369 (2)	N1—N2	1.338 (3)
Cs1—O4^iv	3.464 (2)	N1—C1	1.342 (3)
Cs1—O4^v	3.464 (2)	N1—H1A	0.8700
Cs1—O8^vi	3.514 (2)	N2—C3	1.340 (3)
Cs1—O8^vii	3.514 (2)	N3—N4	1.339 (3)
Cs2—O7^viii	3.109 (2)	N3—C4	1.340 (3)
Cs2—O7	3.109 (2)	N4—C6	1.346 (3)
Cs2—O5^ix	3.159 (2)	N4—H1B	0.8700
Cs2—O5^v	3.159 (2)	N5—C1	1.439 (4)
Cs2—O3^x	3.297 (2)	N6—C3	1.453 (3)
Cs2—O3ⁱⁱ	3.297 (2)	N7—C4	1.447 (3)
Cs2—O6^ix	3.396 (2)	N8—C6	1.432 (3)
Cs2—O6^v	3.396 (2)	C1—C2	1.398 (3)
Cs2—N2^x	3.401 (2)	C2—C3	1.404 (4)
Cs2—N2ⁱⁱ	3.401 (2)	C2—C5	1.458 (3)
Cs2—O2^xi	3.811 (2)	C4—C5	1.396 (4)
Cs2—O2^vi	3.811 (2)	C5—C6	1.399 (3)
O1—N5	1.224 (3)

O1ⁱ—Cs1—O1ⁱⁱ	112.57 (9)	O5^ix—Cs2—N2^x	60.69 (6)
O1ⁱ—Cs1—O5ⁱⁱⁱ	109.94 (6)	O5^v—Cs2—N2^x	119.31 (6)
O1ⁱⁱ—Cs1—O5ⁱⁱⁱ	128.30 (6)	O3^x—Cs2—N2^x	47.39 (5)
O1ⁱ—Cs1—O5	128.30 (6)	O3ⁱⁱ—Cs2—N2^x	132.61 (5)
O1ⁱⁱ—Cs1—O5	109.94 (6)	O6^ix—Cs2—N2^x	55.26 (5)
O5ⁱⁱⁱ—Cs1—O5	60.14 (9)	O6^v—Cs2—N2^x	124.74 (5)
O1ⁱ—Cs1—O3^iv	101.47 (7)	O7^viii—Cs2—N2ⁱⁱ	119.87 (6)
O1ⁱⁱ—Cs1—O3^iv	89.92 (7)	O7—Cs2—N2ⁱⁱ	60.13 (6)
O5ⁱⁱⁱ—Cs1—O3^iv	53.49 (6)	O5^ix—Cs2—N2ⁱⁱ	119.31 (6)
O5—Cs1—O3^iv	106.69 (6)	O5^v—Cs2—N2ⁱⁱ	60.69 (6)
O1ⁱ—Cs1—O3^v	89.92 (7)	O3^x—Cs2—N2ⁱⁱ	132.61 (5)
O1ⁱⁱ—Cs1—O3^v	101.47 (7)	O3ⁱⁱ—Cs2—N2ⁱⁱ	47.39 (5)
O5ⁱⁱⁱ—Cs1—O3^v	106.69 (6)	O6^ix—Cs2—N2ⁱⁱ	124.74 (5)
O5—Cs1—O3^v	53.49 (6)	O6^v—Cs2—N2ⁱⁱ	55.26 (5)
O3^iv—Cs1—O3^v	159.51 (8)	N2^x—Cs2—N2ⁱⁱ	180.0
O1ⁱ—Cs1—N3	151.61 (7)	O7^viii—Cs2—O2^xi	46.92 (5)
O1ⁱⁱ—Cs1—N3	61.45 (6)	O7—Cs2—O2^xi	133.09 (5)
O5ⁱⁱⁱ—Cs1—N3	92.08 (6)	O5^ix—Cs2—O2^xi	114.79 (5)
O5—Cs1—N3	48.49 (5)	O5^v—Cs2—O2^xi	65.21 (5)
O3^iv—Cs1—N3	106.11 (6)	O3^x—Cs2—O2^xi	78.04 (6)
O3^v—Cs1—N3	66.04 (6)	O3ⁱⁱ—Cs2—O2^xi	101.96 (6)
O1ⁱ—Cs1—N3ⁱⁱⁱ	61.45 (6)	O6^ix—Cs2—O2^xi	100.16 (5)
O1ⁱⁱ—Cs1—N3ⁱⁱⁱ	151.61 (7)	O6^v—Cs2—O2^xi	79.84 (5)
O5ⁱⁱⁱ—Cs1—N3ⁱⁱⁱ	48.49 (5)	N2^x—Cs2—O2^xi	54.28 (5)
O5—Cs1—N3ⁱⁱⁱ	92.08 (6)	N2ⁱⁱ—Cs2—O2^xi	125.72 (5)
O3^iv—Cs1—N3ⁱⁱⁱ	66.03 (6)	O7^viii—Cs2—O2^vi	133.08 (5)
O3^v—Cs1—N3ⁱⁱⁱ	106.11 (6)	O7—Cs2—O2^vi	46.91 (5)
N3—Cs1—N3ⁱⁱⁱ	137.57 (8)	O5^ix—Cs2—O2^vi	65.21 (5)
O1ⁱ—Cs1—O4^iv	66.05 (7)	O5^v—Cs2—O2^vi	114.79 (5)
O1ⁱⁱ—Cs1—O4^iv	93.97 (7)	O3^x—Cs2—O2^vi	101.96 (6)
O5ⁱⁱⁱ—Cs1—O4^iv	77.60 (6)	O3ⁱⁱ—Cs2—O2^vi	78.04 (6)
O5—Cs1—O4^iv	137.70 (5)	O6^ix—Cs2—O2^vi	79.84 (5)
O3^iv—Cs1—O4^iv	36.92 (6)	O6^v—Cs2—O2^vi	100.16 (5)
O3^v—Cs1—O4^iv	155.15 (6)	N2^x—Cs2—O2^vi	125.72 (5)
N3—Cs1—O4^iv	138.81 (6)	N2ⁱⁱ—Cs2—O2^vi	54.28 (5)
N3ⁱⁱⁱ—Cs1—O4^iv	57.79 (6)	O2^xi—Cs2—O2^vi	180.00 (6)
O1ⁱ—Cs1—O4^v	93.97 (7)	N5—O1—Cs1^xii	140.2 (2)
O1ⁱⁱ—Cs1—O4^v	66.05 (7)	N6—O3—Cs2^xii	130.86 (18)
O5ⁱⁱⁱ—Cs1—O4^v	137.70 (6)	N6—O3—Cs1^xiii	93.91 (18)
O5—Cs1—O4^v	77.60 (6)	Cs2^xii—O3—Cs1^xiii	110.96 (7)
O3^iv—Cs1—O4^v	155.15 (6)	N6—O4—Cs1^xiii	88.50 (16)
O3^v—Cs1—O4^v	36.92 (6)	N7—O5—Cs2^xiv	99.67 (16)
N3—Cs1—O4^v	57.79 (6)	N7—O5—Cs1	131.31 (16)
N3ⁱⁱⁱ—Cs1—O4^v	138.81 (6)	Cs2^xiv—O5—Cs1	119.65 (7)
O4^iv—Cs1—O4^v	144.69 (7)	N7—O6—Cs2^xiv	88.38 (14)
O1ⁱ—Cs1—O8^vi	140.41 (6)	N8—O7—Cs2	118.85 (17)
O1ⁱⁱ—Cs1—O8^vi	48.43 (6)	N8—O8—Cs1^vi	127.02 (16)
O5ⁱⁱⁱ—Cs1—O8^vi	79.97 (5)	N2—N1—C1	109.8 (2)
O5—Cs1—O8^vi	90.40 (5)	N2—N1—H1A	125.1
O3^iv—Cs1—O8^vi	52.64 (6)	C1—N1—H1A	125.1
O3^v—Cs1—O8^vi	124.92 (6)	N1—N2—C3	104.9 (2)
N3—Cs1—O8^vi	59.05 (6)	N1—N2—Cs2^xii	130.12 (15)
N3ⁱⁱⁱ—Cs1—O8^vi	116.39 (6)	C3—N2—Cs2^xii	121.71 (17)
O4^iv—Cs1—O8^vi	79.82 (6)	N4—N3—C4	105.1 (2)
O4^v—Cs1—O8^vi	103.61 (6)	N4—N3—Cs1	128.32 (16)
O1ⁱ—Cs1—O8^vii	48.43 (6)	C4—N3—Cs1	116.41 (17)
O1ⁱⁱ—Cs1—O8^vii	140.41 (6)	N3—N4—C6	109.6 (2)
O5ⁱⁱⁱ—Cs1—O8^vii	90.40 (5)	N3—N4—H1B	125.2
O5—Cs1—O8^vii	79.97 (5)	C6—N4—H1B	125.2
O3^iv—Cs1—O8^vii	124.92 (6)	O2—N5—O1	124.3 (3)
O3^v—Cs1—O8^vii	52.64 (6)	O2—N5—C1	119.1 (2)
N3—Cs1—O8^vii	116.39 (6)	O1—N5—C1	116.6 (2)
N3ⁱⁱⁱ—Cs1—O8^vii	59.05 (6)	O3—N6—O4	124.1 (3)
O4^iv—Cs1—O8^vii	103.61 (6)	O3—N6—C3	118.4 (2)
O4^v—Cs1—O8^vii	79.82 (6)	O4—N6—C3	117.5 (2)
O8^vi—Cs1—O8^vii	168.92 (7)	O3—N6—Cs1^xiii	66.57 (17)
O7^viii—Cs2—O7	180.0	O4—N6—Cs1^xiii	71.87 (15)
O7^viii—Cs2—O5^ix	103.32 (6)	C3—N6—Cs1^xiii	137.60 (16)
O7—Cs2—O5^ix	76.68 (6)	O6—N7—O5	124.3 (2)
O7^viii—Cs2—O5^v	76.68 (6)	O6—N7—C4	118.3 (2)
O7—Cs2—O5^v	103.32 (6)	O5—N7—C4	117.4 (2)
O5^ix—Cs2—O5^v	180.00 (11)	O6—N7—Cs2^xiv	71.61 (14)
O7^viii—Cs2—O3^x	106.12 (6)	O5—N7—Cs2^xiv	60.53 (14)
O7—Cs2—O3^x	73.88 (6)	C4—N7—Cs2^xiv	149.11 (16)
O5^ix—Cs2—O3^x	54.16 (6)	O8—N8—O7	124.3 (2)
O5^v—Cs2—O3^x	125.84 (6)	O8—N8—C6	118.5 (2)
O7^viii—Cs2—O3ⁱⁱ	73.88 (6)	O7—N8—C6	117.1 (2)
O7—Cs2—O3ⁱⁱ	106.12 (6)	N1—C1—C2	111.4 (2)
O5^ix—Cs2—O3ⁱⁱ	125.84 (6)	N1—C1—N5	119.1 (2)
O5^v—Cs2—O3ⁱⁱ	54.16 (6)	C2—C1—N5	129.5 (2)
O3^x—Cs2—O3ⁱⁱ	180.00 (10)	C1—C2—C3	99.5 (2)
O7^viii—Cs2—O6^ix	68.69 (6)	C1—C2—C5	130.2 (3)
O7—Cs2—O6^ix	111.31 (6)	C3—C2—C5	130.2 (2)
O5^ix—Cs2—O6^ix	38.43 (5)	N2—C3—C2	114.3 (2)
O5^v—Cs2—O6^ix	141.57 (5)	N2—C3—N6	117.7 (2)
O3^x—Cs2—O6^ix	80.81 (5)	C2—C3—N6	127.8 (2)
O3ⁱⁱ—Cs2—O6^ix	99.19 (5)	N3—C4—C5	114.3 (2)
O7^viii—Cs2—O6^v	111.31 (6)	N3—C4—N7	118.3 (2)
O7—Cs2—O6^v	68.69 (6)	C5—C4—N7	127.3 (2)
O5^ix—Cs2—O6^v	141.57 (5)	C4—C5—C6	99.9 (2)
O5^v—Cs2—O6^v	38.43 (5)	C4—C5—C2	129.6 (2)
O3^x—Cs2—O6^v	99.19 (5)	C6—C5—C2	130.6 (2)
O3ⁱⁱ—Cs2—O6^v	80.81 (5)	N4—C6—C5	111.1 (2)
O6^ix—Cs2—O6^v	180.00 (9)	N4—C6—N8	119.0 (2)
O7^viii—Cs2—N2^x	60.13 (6)	C5—C6—N8	129.8 (2)
O7—Cs2—N2^x	119.87 (6)

C1—N1—N2—C3	−0.7 (3)	C1—C2—C3—N2	−0.1 (3)
C1—N1—N2—Cs2^xii	158.78 (16)	C5—C2—C3—N2	−178.3 (2)
C4—N3—N4—C6	−0.6 (3)	C1—C2—C3—N6	175.2 (2)
Cs1—N3—N4—C6	142.57 (18)	C5—C2—C3—N6	−3.1 (4)
Cs1^xii—O1—N5—O2	53.4 (5)	O3—N6—C3—N2	−22.2 (4)
Cs1^xii—O1—N5—C1	−127.5 (3)	O4—N6—C3—N2	156.2 (2)
Cs2^xii—O3—N6—O4	−167.5 (2)	Cs1^xiii—N6—C3—N2	63.3 (3)
Cs1^xiii—O3—N6—O4	−45.3 (3)	O3—N6—C3—C2	162.7 (3)
Cs2^xii—O3—N6—C3	10.7 (4)	O4—N6—C3—C2	−18.9 (4)
Cs1^xiii—O3—N6—C3	132.9 (2)	Cs1^xiii—N6—C3—C2	−111.8 (3)
Cs2^xii—O3—N6—Cs1^xiii	−122.2 (2)	N4—N3—C4—C5	0.4 (3)
Cs1^xiii—O4—N6—O3	43.4 (3)	Cs1—N3—C4—C5	−147.90 (19)
Cs1^xiii—O4—N6—C3	−134.9 (2)	N4—N3—C4—N7	−178.0 (2)
Cs2^xiv—O6—N7—O5	31.4 (3)	Cs1—N3—C4—N7	33.7 (3)
Cs2^xiv—O6—N7—C4	−148.0 (2)	O6—N7—C4—N3	155.1 (3)
Cs2^xiv—O5—N7—O6	−34.6 (3)	O5—N7—C4—N3	−24.4 (4)
Cs1—O5—N7—O6	−179.42 (19)	Cs2^xiv—N7—C4—N3	53.4 (4)
Cs2^xiv—O5—N7—C4	144.81 (19)	O6—N7—C4—C5	−23.1 (4)
Cs1—O5—N7—C4	0.0 (4)	O5—N7—C4—C5	157.4 (3)
Cs1—O5—N7—Cs2^xiv	−144.8 (2)	Cs2^xiv—N7—C4—C5	−124.8 (3)
Cs1^vi—O8—N8—O7	26.7 (4)	N3—C4—C5—C6	−0.1 (3)
Cs1^vi—O8—N8—C6	−152.15 (18)	N7—C4—C5—C6	178.2 (3)
Cs2—O7—N8—O8	66.2 (3)	N3—C4—C5—C2	179.4 (3)
Cs2—O7—N8—C6	−114.9 (2)	N7—C4—C5—C2	−2.3 (5)
N2—N1—C1—C2	0.7 (3)	C1—C2—C5—C4	−43.6 (4)
N2—N1—C1—N5	−178.4 (2)	C3—C2—C5—C4	134.1 (3)
O2—N5—C1—N1	169.4 (2)	C1—C2—C5—C6	135.7 (3)
O1—N5—C1—N1	−9.8 (4)	C3—C2—C5—C6	−46.5 (4)
O2—N5—C1—C2	−9.5 (4)	N3—N4—C6—C5	0.5 (3)
O1—N5—C1—C2	171.4 (3)	N3—N4—C6—N8	−176.5 (2)
N1—C1—C2—C3	−0.4 (3)	C4—C5—C6—N4	−0.3 (3)
N5—C1—C2—C3	178.5 (2)	C2—C5—C6—N4	−179.8 (3)
N1—C1—C2—C5	177.9 (2)	C4—C5—C6—N8	176.4 (3)
N5—C1—C2—C5	−3.2 (5)	C2—C5—C6—N8	−3.1 (5)
N1—N2—C3—C2	0.5 (3)	O8—N8—C6—N4	175.1 (2)
Cs2^xii—N2—C3—C2	−161.16 (16)	O7—N8—C6—N4	−3.9 (4)
N1—N2—C3—N6	−175.3 (2)	O8—N8—C6—C5	−1.4 (4)
Cs2^xii—N2—C3—N6	23.1 (3)	O7—N8—C6—C5	179.6 (3)

Symmetry codes: (i) −x+1, y+1, −z+1/2; (ii) x, y+1, z; (iii) −x+1, y, −z+1/2; (iv) x+1/2, y+1/2, z; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, −y+1/2, −z; (vii) x+1/2, −y+1/2, z+1/2; (viii) −x, −y+1, −z; (ix) x−1/2, −y+1/2, z−1/2; (x) −x, −y, −z; (xi) x−1/2, y+1/2, z; (xii) x, y−1, z; (xiii) x−1/2, y−1/2, z; (xiv) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4^xii	0.87	1.99	2.832 (3)	162
N4—H1B···N1ⁱⁱ	0.87	1.99	2.832 (3)	163

Symmetry codes: (ii) x, y+1, z; (xii) x, y−1, z.

Geometry of lone pair–π-hole interactions (Å, °) in (1) and (2) top

N···plane is a distance of an N-donor to the mean plane of a nitro group and φ is an angle of the N···N axis to the plane of the nitro group.

Compound	N-Donor	Group	N···N	N···plane	φ
(1)	N2	(C4N7O5O6)^xii	2.997 (3)	2.980 (2)	83.9 (2)
	N3	(C3N6O3O4)ⁱⁱ	3.198 (3)	3.093 (2)	75.3 (2)
(2)	N2	(C4N7O5O6)^xii	2.990 (3)	2.976 (3)	84.5 (2)
	N3	(C3N6O3O4)ⁱⁱ	3.186 (3)	3.083 (3)	75.4 (2)

Symmetry codes: (ii) -x + 1/2, y + 1/2, -z + 1/2; (xii) -x + 1/2, y - 1/2, -z + 1/2.

Geometry of stacking interactions involving nitro and pyrazole groups (Å, °) in (1) and (2) top

Atom···Cg is the shortest distance from the nitro group atom to the centroid of the ring; Atom···plane is the deviation of the given atom from the mean plane of the ring and φ is the angle of the atom···Cg axis to the plane of the ring.

Compound	Atom	Ring	Atom···Cg	Atom···plane	φ
(1)	O7	(C4C5C6N3N4)ⁱⁱⁱ	3.265 (3)	3.262 (2)	87.5 (2)
	N5	(C1C2C3N1N2)^xiii	3.541 (3)	3.526 (3)	84.7 (2)
(2)	O7	(C4C5C6N3N4)ⁱⁱⁱ	3.240 (3)	3.232 (3)	86.0 (3)
	N5	(C1C2C3N1N2)^xiii	3.448 (3)	3.389 (3)	79.4 (3)

Symmetry codes: (iii) -x + 1/2, -y + 1/2, -z; (xiii) -x + 1/2, -y - 1/2, -z.

Contributions of the different kinds of the contacts (%) to the Hirshfeld surfaces of individual anions in (1)^a and (2) top

M = Rb (1) and Cs (2)

Contact	(1)	(2)
O···M	13.0	13.6
N···M	2.4	2.2
O···O	37.4	35.5
N···N	5.3	6.3
C···C	1.0	0.7
O···N/N···O	15.8	16.2
O···C/C···O	3.8	5.4
N···C/C···N	7.5	6.6
N···H/H···N	6.9	6.6
O···H/H···O	5.4	5.2
C···H/H···C	1.5	1.7

Note: (a) For the 2D plots for (1), see Fig. 7.

Funding information

This work was supported by the Ministry of Education and Science of Ukraine (project No. 19BF037–05).

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Volume 77| Part 11| November 2021| Pages 1109-1115

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Isostructural rubidium and caesium 4-(3,5-di­nitro­pyrazol-4-yl)-3,5-di­nitro­pyrazolates: crystal engineering with polynitro energetic species

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld analysis

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Isostructural rubidium and caesium 4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazolates: crystal engineering with polynitro energetic species

3. Supramolecular features