Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615015818/lf3019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015818/lf30191sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015818/lf30192sup3.hkl |
CCDC references: 1420090; 1420089
Much attention has been concentrated on the crystal engineering of new dielectric and ferroelectric materials in recent years, owing to their novel structural characteristics and potential applications, for instance as filters, capacitors, resonators, switchable nonlinear optical devices or solid-state transducer components in microwave communication systems (Vanderah, 2002; Fu et al., 2008; Ye et al., 2013; Shi et al., 2015). In the search for potential ferroelectric materials, molecular-based one-, two- and three-dimensional metal organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature. Many reports have been devoted to the formation of infinite polymeric frameworks through N-donor bridging ligands (Olenyuk et al., 1999; Rosi et al., 2003; Li, 2015). In contrast to the cyanamide ligands [N(CN)Y]- [Y = Ph2P(S), Ph2P(NCN) or NO2], the pseudohalide ligand dicyanamide [dca, N(CN)2-] is a remarkably versatile building block for the construction of metal–organic architectures since it may act as a mono-, bi- and tridentate ligand, yielding a variety of novel structures (Sun et al., 2001).
A notable feature of metal–dca coordination polymers is the ability of cations to template anionic [M(dca)3]- networks (Biswas et al., 2006). The prime cases of previously reported three-dimensional metal–dca networks are neutral binary systems. The series MX2 with X = [N(CN)2]- (M = Cr2+, Mn2+, Co2+, Ni2+ or Cu2+ ) and related complexes have attracted increased interest because of their rutile-like structures containing chains of doubly-bridged metal atoms with M(NCNCN)M units (Li & Wang, 2014). According to previous reports, the pseudohalide ligand dicyanamide plays an instructive role in building coordination polymers. In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, we report here the use of tetramethylammonium and butyltriphenylphosphonium cations as templates for the formation of two different coordination polymers, namely {(Me4N)[Mn2(dca)5]}n, (I), and {(BuPh3P)2[Mn(dca)4]}n, (II), which exhibit interesting structural features.
A solution of sodium dicyanamide (0.801 g, 9 mmol) in water was added to a solution of tetramethylammonium chloride (0.329 g, 3 mmol) in water. Mn(NO3)2·4H2O (1.073 g, 3 mmol) was then added, affording a colourless solution. Upon standing at room temperature for several days, suitable colourless single crystals of (I) were obtained by slow solvent evaporation.
For the synthesis of (II), n-butyltriphenylphosphonium bromide was used instead of tetramethylammonium chloride. Using the same method as for the preparation of (I), suitable colourless single crystals of (II) were obtained.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were refined isotropically. H atoms on C atoms were included in calculated positions and were refined as riding, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and with Uiso(H) = 1.5UUeq(C) for methyl H atoms or 1.2UUeq(C) otherwise.
The asymmetric unit of complex (I) contains two independent MnII cations, five anionic dicyanamide (dca) ligands, complemented by a tetramethylammonium counter-ion (Fig. 1). As shown in Fig. 1, there are two unique octahedrally coordinated MnII cations with similar coordination models. The central Mn1 cation is six-coordinated by six nitrile N atoms from six anionic dca ligands, adopting a distorted octahedral coordination geometry, with the N1, N3, N4 and N6 atoms in the basal plane and atoms N2 and N5 in apical positions. The Mn2 cation also adopts a distorted octahedral coordination geometry, with the N7, N8, N11i and N15ii atoms in the basal plane, and atoms N9ii and N13iii in the apical position (symmetry codes are as in Table 2), and is surrounded by four nitrile N atoms from four anionic dca ligands and two amide N atoms from dca ligands. Each MnII cation is joined to neighbouring MnII cations through µ-1,5- and µ-1,3,5-bridging dicyanamide ligands. The Mn—N(nitrile) bond lengths range from 2.152 (2) to 2.389 (2) Å and the Mn—N(amide) bond lengths vary between 2.397 (2) and 2.421 (2) Å (Table 2). There are two sorts of angles around each MnII centre, namely orthogonal cis angles [81.61 (8)–98.47 (9)°] and linear trans angles [167.69 (8)–174.12 (8)°]. The Mn—N(nitrile) [2.203 (2)–2.389 (2) Å] bond lengths of the µ-1,3,5-bridging dicyanamide ligands are significantly longer than those of the µ-1,5-bridging dicyanamide ligands [2.152 (2)–2.198 (2) Å]. And the Mn—N(amide) bond lengths of the µ-1,3,5-bridging dicyanamide ligands are consistent with those of other reported manganese–dicyanamide compounds (Luo et al., 2005). The N4—C5, C5—N10 and N11—C6 bond lengths (Table 2) indicate triple- and single-bond character, as is typical for bridging [N(CN)2]- ligands. All bond lengths and angles within the dicyanamide ligands are almost typical of the M—N···C—N—C···N—M and M—N···C—N(Mn)—C···N—M bridging modes.
Compound (I) is a new coordination polymer in which both of the six-coordinated MnII centres adopt a distorted octahedral coordination geometry. It displays a novel coordination architecture compared with the similar compound, [Mn(dmpz){N(CN)2}2]2, (III) (dmpz is 3,5-dimethylpyrazole; Luo et al., 2005), in which the central Mn1 cation is coordinated by four dicyanamide nitrile N atoms and two atoms of dmpz molecules, rather than six nitrile N atoms from six anionic dca ligands, as for atom Mn1 in (I). In (I), the overall crystal structure motif exhibits linear M—dca—M bridging mode, which consists of µ-1,5- and µ-1,3,5-bridging dicyanamide anions, forming a three-dimensional anionic network (Fig. 3a). This is also different from what was found in our previous work. In [(CH3)4P][Cd(NCNCN)2Cl], one type of dca ligand is involved in the formation of [Cd(dca)Cl]2 building blocks and the other links these building blocks into a three-dimensional structure (Li & Wang, 2014). The amide N atom of the µ-1,3,5-bridging dicyanamide anions connects adjacent the MnII cations into an eight-membered [Mn2(dca)] ring; meanwhile, the amide N atom of the µ-1,3,5-bridging dicyanamide ligands and the nitrile N atom of µ-1,5-bridging dicyanamide ligands are bonded to adjacent MnII cations, forming a large 20-membered [Mn4(dca)4] ring (Fig. 2). The Mn···Mn distance across the µ-1,3,5-bridging dca is 8.533 (3) Å, while the shortest Mn···Mn contact across the µ-1,3-bridging dca ligand is 5.716 (3) Å. This phenomenon in (I) is different from the two-dimensional compound [Mn(dca)2(pydz)]n (Wriedt & Näther, 2011), where the metal atoms are connected in one direction by double M(dca)2M bridges and in the other by the amide N atom of the µ-1,3,5-bridging dca ligand, forming a two-dimensional layer structure.
It should be pointed out that the three-dimensional anionic framework in (I) exhibits a void space of 289.8 Å3, which amounts to 28.0% of the unit-cell volume. Additionally, each of the cavities in (I) accommodates only one tetramethylammonium cation, but the orientations of the cations in adjacent cages are different (Fig. 3b). The distances of between the two cations is 8.691 (4) Å. This marks a difference with regard to the related (Ph4E)[Mn(dca)3] (E = P or As) structures, where two-dimensional anionic [Mn(dca)3]- sheets are separated by layers of Ph4E+ cations (van der Werff et al., 2001). In addition, in these compounds, the cations lie in pairs within cavities in the anionic network. The tetramethylammonium cations do not participate in any significant supramolecular interactions, though they are obviously important for stabilizing the structure.
The asymmetric unit of complex (II) contains half MnII cation, four half anionic dicyanamide (dca) ligands, complemented by a noncoordinating n-butyltriphenylphosphonium [(n-butyl)PPh3] counter-ion (Fig. 4). As shown in Fig. 4, the central MnII cation is six-coordinated by six terminal N atoms from six different dca ligands, four of which are bridging, adopting a slightly distorted octahedral coordinated geometry, with the N1, N1i, N3 and N3i atoms in the basal plane, and the N4 and N4i atoms in the apical position [symmetry code: (i) -x+1, -y+2, -z]. Each MnII cation is connected to two neighbouring MnII cations through bridging double dca ligands. The Mn—N bond lengths (Table 2) and cis-N—Mn—N angles range from 87.17 (12) to 92.83 (12)°, with a trans angle of 180.0 (2)°, which are all in good agreement with values found in other MnII complexes with a six-coordinated geometry (van der Werff et al., 2001). All bond lengths and angles within the n-butyltriphenylphosphonium ligand are typical and the benzene ring is strictly planar.
In contrast with the structure of (I), in (II), double dca bridges exist between adjacent MnII cations to give a chain structure, with an Mn··· Mn distance of 7.6050 (15) Å. In addition, the one-dimensional anionic framework is filled by n-butyltriphenylphosphonium cations through electrostatic and hydrogen-bonding interactions (C19—H19B···N6 and C19—H19A···N5; Table 3). Intermolecular hydrogen-bonding interactions between the cations and the bridging thiocyanate ligands further stabilize the one-dimensional layer structure (Fig. 5).
Our original interest in (I) and (II) lay mainly in their potential as phase-transition materials (Ye et al., 2013; Fu et al., 2013; Shi et al., 2014; Liao et al., 2014). The variable-temperature dielectric response, especially in the relatively high frequency range, is treated as an effective indicator of a structural phase transition. However, measurement of theirs dielectric properties with varying temperature did not observe dielectric anomalies within the temperature range 90–380 K. This reveals that the two compounds might not undergo a distinct structural phase transition within this temperature range and so both of them are not ferroelectric materials like those reported earlier (Ye et al., 2009; Fu et al., 2008). Further phase-transition materials still need to be sought and explored, and other related materials are currently being investigated for dielectric properties and ferroelectric activity.
For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(C4H12N)[Mn2(C2N3)5] | Z = 2 |
Mr = 514.28 | F(000) = 516 |
Triclinic, P1 | Dx = 1.650 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.368 (2) Å | Cell parameters from 4723 reflections |
b = 10.377 (2) Å | θ = 3.5–27.5° |
c = 11.898 (2) Å | µ = 1.26 mm−1 |
α = 65.64 (3)° | T = 293 K |
β = 82.28 (3)° | Block, colourless |
γ = 62.83 (3)° | 0.30 × 0.25 × 0.20 mm |
V = 1035.1 (3) Å3 |
Rigaku SCXmini diffractometer | 4245 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 27.5°, θmin = 3.5° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −13→13 |
Tmin = 0.704, Tmax = 0.787 | l = −15→15 |
10736 measured reflections | 3 standard reflections every 180 reflections |
4723 independent reflections | intensity decay: none |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0377P)2 + 0.8558P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
4723 reflections | Δρmax = 0.61 e Å−3 |
289 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0819 (12) |
(C4H12N)[Mn2(C2N3)5] | γ = 62.83 (3)° |
Mr = 514.28 | V = 1035.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.368 (2) Å | Mo Kα radiation |
b = 10.377 (2) Å | µ = 1.26 mm−1 |
c = 11.898 (2) Å | T = 293 K |
α = 65.64 (3)° | 0.30 × 0.25 × 0.20 mm |
β = 82.28 (3)° |
Rigaku SCXmini diffractometer | 4245 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.029 |
Tmin = 0.704, Tmax = 0.787 | 3 standard reflections every 180 reflections |
10736 measured reflections | intensity decay: none |
4723 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.61 e Å−3 |
4723 reflections | Δρmin = −0.51 e Å−3 |
289 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn2 | 0.15430 (3) | 0.77945 (4) | 0.73446 (3) | 0.02088 (9) | |
Mn1 | 0.45551 (3) | 1.14431 (4) | 0.73319 (3) | 0.02105 (9) | |
N1 | 0.3662 (2) | 1.0750 (3) | 0.61795 (19) | 0.0368 (5) | |
N3 | 0.2807 (2) | 1.4121 (2) | 0.62898 (19) | 0.0355 (5) | |
N4 | 0.5090 (2) | 1.2376 (3) | 0.84650 (19) | 0.0381 (5) | |
N6 | 0.6323 (2) | 0.9083 (2) | 0.8239 (2) | 0.0379 (5) | |
N7 | 0.1864 (2) | 1.0001 (2) | 0.58237 (17) | 0.0283 (4) | |
N8 | 0.0182 (2) | 1.1541 (3) | 0.39690 (19) | 0.0373 (5) | |
N11 | 0.6630 (2) | 1.2544 (2) | 1.17046 (19) | 0.0349 (5) | |
N15 | 0.8366 (2) | 0.4475 (2) | 1.14708 (18) | 0.0309 (4) | |
N13 | 0.0045 (2) | 1.0823 (3) | 1.1730 (2) | 0.0387 (5) | |
N9 | 0.6950 (2) | 1.3521 (2) | 0.39593 (17) | 0.0303 (4) | |
N10 | 0.5053 (3) | 1.3484 (3) | 0.9922 (2) | 0.0408 (5) | |
N5 | 0.2942 (3) | 1.1001 (3) | 0.8620 (2) | 0.0405 (5) | |
N2 | 0.5898 (2) | 1.2214 (3) | 0.5791 (2) | 0.0378 (5) | |
N12 | 0.1520 (2) | 0.9928 (3) | 1.0187 (2) | 0.0395 (5) | |
N14 | 0.8310 (2) | 0.6742 (2) | 0.9648 (2) | 0.0400 (5) | |
C1 | 0.2814 (2) | 1.0441 (2) | 0.59740 (19) | 0.0251 (4) | |
C2 | 0.1000 (2) | 1.0866 (2) | 0.4808 (2) | 0.0254 (4) | |
C6 | 0.5945 (2) | 1.2896 (2) | 1.0857 (2) | 0.0246 (4) | |
C5 | 0.5144 (2) | 1.2812 (3) | 0.9192 (2) | 0.0274 (5) | |
C10 | 0.8246 (2) | 0.5586 (3) | 1.0610 (2) | 0.0250 (4) | |
C3 | 0.6385 (2) | 1.2853 (3) | 0.4957 (2) | 0.0260 (4) | |
C9 | 0.7197 (3) | 0.7957 (3) | 0.8947 (2) | 0.0283 (5) | |
C8 | 0.0765 (2) | 1.0476 (3) | 1.0984 (2) | 0.0278 (5) | |
C4 | 0.2941 (2) | 1.5225 (3) | 0.61405 (19) | 0.0257 (4) | |
C7 | 0.2257 (2) | 1.0559 (3) | 0.9383 (2) | 0.0291 (5) | |
N16 | 0.1781 (2) | 0.5460 (2) | 0.26852 (19) | 0.0367 (5) | |
C11 | 0.1565 (4) | 0.6144 (4) | 0.1308 (3) | 0.0633 (9) | |
H11A | 0.2212 | 0.5365 | 0.1000 | 0.095* | |
H11B | 0.1765 | 0.7045 | 0.0962 | 0.095* | |
H11C | 0.0579 | 0.6464 | 0.1077 | 0.095* | |
C14 | 0.1499 (12) | 0.4125 (9) | 0.3200 (5) | 0.208 (5) | |
H14A | 0.1640 | 0.3689 | 0.4085 | 0.312* | |
H14B | 0.2150 | 0.3346 | 0.2893 | 0.312* | |
H14C | 0.0514 | 0.4435 | 0.2972 | 0.312* | |
C13 | 0.0815 (10) | 0.6616 (7) | 0.3168 (5) | 0.177 (4) | |
H13A | 0.0965 | 0.6161 | 0.4053 | 0.265* | |
H13B | −0.0174 | 0.6937 | 0.2944 | 0.265* | |
H13C | 0.1011 | 0.7519 | 0.2829 | 0.265* | |
C12 | 0.3210 (6) | 0.5052 (12) | 0.3027 (4) | 0.195 (5) | |
H12A | 0.3346 | 0.4611 | 0.3912 | 0.293* | |
H12B | 0.3369 | 0.5978 | 0.2685 | 0.293* | |
H12C | 0.3888 | 0.4288 | 0.2717 | 0.293* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn2 | 0.02375 (17) | 0.02298 (17) | 0.01556 (16) | −0.01156 (13) | −0.00151 (12) | −0.00519 (13) |
Mn1 | 0.02544 (17) | 0.02405 (17) | 0.01714 (16) | −0.01521 (13) | 0.00159 (12) | −0.00659 (13) |
N1 | 0.0471 (12) | 0.0424 (12) | 0.0319 (11) | −0.0306 (10) | −0.0054 (9) | −0.0103 (9) |
N3 | 0.0472 (12) | 0.0294 (10) | 0.0321 (11) | −0.0192 (9) | 0.0043 (9) | −0.0121 (9) |
N4 | 0.0436 (12) | 0.0432 (12) | 0.0328 (11) | −0.0179 (10) | −0.0065 (9) | −0.0188 (10) |
N6 | 0.0393 (12) | 0.0279 (10) | 0.0340 (11) | −0.0121 (9) | −0.0050 (9) | −0.0019 (9) |
N7 | 0.0341 (10) | 0.0294 (10) | 0.0226 (9) | −0.0200 (8) | −0.0089 (8) | −0.0015 (8) |
N8 | 0.0412 (12) | 0.0371 (11) | 0.0306 (11) | −0.0242 (10) | −0.0135 (9) | 0.0017 (9) |
N11 | 0.0404 (11) | 0.0342 (11) | 0.0315 (11) | −0.0175 (9) | −0.0101 (9) | −0.0097 (9) |
N15 | 0.0302 (10) | 0.0258 (10) | 0.0273 (10) | −0.0105 (8) | 0.0005 (8) | −0.0040 (8) |
N13 | 0.0419 (12) | 0.0427 (12) | 0.0379 (12) | −0.0227 (10) | 0.0155 (10) | −0.0211 (10) |
N9 | 0.0429 (11) | 0.0301 (10) | 0.0246 (10) | −0.0228 (9) | 0.0126 (8) | −0.0123 (8) |
N10 | 0.0468 (13) | 0.0333 (11) | 0.0398 (12) | −0.0075 (9) | −0.0209 (10) | −0.0169 (10) |
N5 | 0.0467 (13) | 0.0468 (13) | 0.0352 (12) | −0.0282 (11) | 0.0165 (10) | −0.0185 (10) |
N2 | 0.0439 (12) | 0.0400 (12) | 0.0342 (11) | −0.0261 (10) | 0.0152 (10) | −0.0144 (10) |
N12 | 0.0435 (12) | 0.0463 (13) | 0.0501 (13) | −0.0327 (11) | 0.0265 (10) | −0.0309 (11) |
N14 | 0.0285 (10) | 0.0280 (10) | 0.0403 (12) | −0.0110 (8) | 0.0011 (9) | 0.0060 (9) |
C1 | 0.0328 (11) | 0.0243 (10) | 0.0191 (10) | −0.0146 (9) | −0.0021 (8) | −0.0062 (8) |
C2 | 0.0302 (11) | 0.0247 (10) | 0.0250 (11) | −0.0181 (9) | −0.0005 (9) | −0.0058 (9) |
C6 | 0.0272 (10) | 0.0238 (10) | 0.0254 (11) | −0.0133 (9) | −0.0006 (9) | −0.0093 (9) |
C5 | 0.0254 (11) | 0.0276 (11) | 0.0264 (11) | −0.0121 (9) | −0.0056 (9) | −0.0059 (9) |
C10 | 0.0231 (10) | 0.0253 (11) | 0.0258 (11) | −0.0106 (8) | 0.0015 (8) | −0.0099 (9) |
C3 | 0.0263 (11) | 0.0272 (11) | 0.0269 (11) | −0.0134 (9) | 0.0052 (9) | −0.0122 (9) |
C9 | 0.0343 (12) | 0.0265 (11) | 0.0266 (11) | −0.0182 (10) | 0.0062 (9) | −0.0088 (9) |
C8 | 0.0288 (11) | 0.0262 (11) | 0.0304 (12) | −0.0162 (9) | 0.0046 (9) | −0.0093 (9) |
C4 | 0.0295 (11) | 0.0280 (11) | 0.0184 (10) | −0.0131 (9) | 0.0052 (8) | −0.0089 (9) |
C7 | 0.0282 (11) | 0.0322 (12) | 0.0310 (12) | −0.0140 (10) | 0.0061 (9) | −0.0166 (10) |
N16 | 0.0452 (12) | 0.0358 (11) | 0.0289 (11) | −0.0233 (10) | −0.0032 (9) | −0.0050 (9) |
C11 | 0.094 (3) | 0.063 (2) | 0.0319 (15) | −0.041 (2) | −0.0114 (16) | −0.0069 (15) |
C14 | 0.460 (15) | 0.194 (7) | 0.065 (3) | −0.268 (10) | −0.018 (6) | 0.014 (4) |
C13 | 0.254 (9) | 0.092 (4) | 0.064 (3) | 0.027 (5) | −0.018 (4) | −0.032 (3) |
C12 | 0.071 (3) | 0.437 (14) | 0.055 (3) | −0.116 (6) | 0.012 (2) | −0.076 (5) |
Mn2—N11i | 2.152 (2) | N9—C3 | 1.318 (3) |
Mn2—N15ii | 2.154 (2) | N9—Mn2v | 2.421 (2) |
Mn2—N13iii | 2.154 (2) | N10—C6 | 1.291 (3) |
Mn2—N8iv | 2.203 (2) | N10—C5 | 1.291 (3) |
Mn2—N7 | 2.397 (2) | N5—C7 | 1.149 (3) |
Mn2—N9v | 2.421 (2) | N2—C3 | 1.144 (3) |
Mn1—N6 | 2.185 (2) | N12—C7 | 1.293 (3) |
Mn1—N5 | 2.188 (2) | N12—C8 | 1.293 (3) |
Mn1—N4 | 2.198 (2) | N14—C10 | 1.293 (3) |
Mn1—N1 | 2.240 (2) | N14—C9 | 1.296 (3) |
Mn1—N2 | 2.250 (2) | C4—N9vi | 1.314 (3) |
Mn1—N3 | 2.389 (2) | N16—C12 | 1.409 (5) |
N1—C1 | 1.148 (3) | N16—C14 | 1.414 (5) |
N3—C4 | 1.155 (3) | N16—C13 | 1.446 (6) |
N4—C5 | 1.147 (3) | N16—C11 | 1.494 (3) |
N6—C9 | 1.150 (3) | C11—H11A | 0.9600 |
N7—C2 | 1.315 (3) | C11—H11B | 0.9600 |
N7—C1 | 1.317 (3) | C11—H11C | 0.9600 |
N8—C2 | 1.146 (3) | C14—H14A | 0.9600 |
N8—Mn2iv | 2.203 (2) | C14—H14B | 0.9600 |
N11—C6 | 1.143 (3) | C14—H14C | 0.9600 |
N11—Mn2i | 2.152 (2) | C13—H13A | 0.9600 |
N15—C10 | 1.150 (3) | C13—H13B | 0.9600 |
N15—Mn2ii | 2.154 (2) | C13—H13C | 0.9600 |
N13—C8 | 1.147 (3) | C12—H12A | 0.9600 |
N13—Mn2iii | 2.154 (2) | C12—H12B | 0.9600 |
N9—C4vi | 1.314 (3) | C12—H12C | 0.9600 |
N11i—Mn2—N15ii | 94.74 (9) | C7—N5—Mn1 | 170.1 (2) |
N11i—Mn2—N13iii | 94.13 (9) | C3—N2—Mn1 | 168.4 (2) |
N15ii—Mn2—N13iii | 98.47 (9) | C7—N12—C8 | 124.2 (2) |
N11i—Mn2—N8iv | 167.94 (8) | C10—N14—C9 | 124.9 (2) |
N15ii—Mn2—N8iv | 95.82 (8) | N1—C1—N7 | 175.6 (2) |
N13iii—Mn2—N8iv | 90.08 (9) | N8—C2—N7 | 174.0 (2) |
N11i—Mn2—N7 | 83.03 (8) | N11—C6—N10 | 171.6 (3) |
N15ii—Mn2—N7 | 167.69 (8) | N4—C5—N10 | 172.1 (3) |
N13iii—Mn2—N7 | 93.77 (8) | N15—C10—N14 | 171.9 (2) |
N8iv—Mn2—N7 | 85.42 (8) | N2—C3—N9 | 175.9 (2) |
N11i—Mn2—N9v | 93.46 (8) | N6—C9—N14 | 172.2 (3) |
N15ii—Mn2—N9v | 85.32 (7) | N13—C8—N12 | 171.9 (2) |
N13iii—Mn2—N9v | 171.20 (8) | N3—C4—N9vi | 176.1 (2) |
N8iv—Mn2—N9v | 81.61 (8) | N5—C7—N12 | 172.7 (3) |
N7—Mn2—N9v | 82.74 (7) | C12—N16—C14 | 110.9 (6) |
N6—Mn1—N5 | 95.02 (9) | C12—N16—C13 | 106.9 (5) |
N6—Mn1—N4 | 92.71 (9) | C14—N16—C13 | 109.2 (6) |
N5—Mn1—N4 | 89.91 (9) | C12—N16—C11 | 109.7 (3) |
N6—Mn1—N1 | 94.57 (9) | C14—N16—C11 | 109.7 (3) |
N5—Mn1—N1 | 84.82 (9) | C13—N16—C11 | 110.4 (3) |
N4—Mn1—N1 | 171.36 (8) | N16—C11—H11A | 109.5 |
N6—Mn1—N2 | 93.68 (9) | N16—C11—H11B | 109.5 |
N5—Mn1—N2 | 170.61 (9) | H11A—C11—H11B | 109.5 |
N4—Mn1—N2 | 93.21 (9) | N16—C11—H11C | 109.5 |
N1—Mn1—N2 | 90.97 (8) | H11A—C11—H11C | 109.5 |
N6—Mn1—N3 | 174.12 (8) | H11B—C11—H11C | 109.5 |
N5—Mn1—N3 | 89.89 (9) | N16—C14—H14A | 109.5 |
N4—Mn1—N3 | 84.04 (8) | N16—C14—H14B | 109.5 |
N1—Mn1—N3 | 89.10 (8) | H14A—C14—H14B | 109.5 |
N2—Mn1—N3 | 81.64 (8) | N16—C14—H14C | 109.5 |
C1—N1—Mn1 | 151.2 (2) | H14A—C14—H14C | 109.5 |
C4—N3—Mn1 | 125.72 (19) | H14B—C14—H14C | 109.5 |
C5—N4—Mn1 | 166.1 (2) | N16—C13—H13A | 109.5 |
C9—N6—Mn1 | 163.5 (2) | N16—C13—H13B | 109.5 |
C2—N7—C1 | 118.04 (19) | H13A—C13—H13B | 109.5 |
C2—N7—Mn2 | 118.34 (14) | N16—C13—H13C | 109.5 |
C1—N7—Mn2 | 123.55 (14) | H13A—C13—H13C | 109.5 |
C2—N8—Mn2iv | 162.10 (18) | H13B—C13—H13C | 109.5 |
C6—N11—Mn2i | 155.2 (2) | N16—C12—H12A | 109.5 |
C10—N15—Mn2ii | 162.25 (19) | N16—C12—H12B | 109.5 |
C8—N13—Mn2iii | 161.7 (2) | H12A—C12—H12B | 109.5 |
C4vi—N9—C3 | 117.33 (19) | N16—C12—H12C | 109.5 |
C4vi—N9—Mn2v | 115.55 (14) | H12A—C12—H12C | 109.5 |
C3—N9—Mn2v | 124.20 (15) | H12B—C12—H12C | 109.5 |
C6—N10—C5 | 125.6 (2) | ||
N6—Mn1—N1—C1 | 103.6 (4) | N4—Mn1—N5—C7 | −90.2 (12) |
N5—Mn1—N1—C1 | 9.0 (4) | N1—Mn1—N5—C7 | 96.6 (12) |
N4—Mn1—N1—C1 | −43.7 (8) | N2—Mn1—N5—C7 | 160.3 (10) |
N2—Mn1—N1—C1 | −162.6 (4) | N3—Mn1—N5—C7 | −174.3 (12) |
N3—Mn1—N1—C1 | −81.0 (4) | N6—Mn1—N2—C3 | −171.4 (10) |
N6—Mn1—N3—C4 | −23.7 (9) | N5—Mn1—N2—C3 | 30.7 (13) |
N5—Mn1—N3—C4 | 122.8 (2) | N4—Mn1—N2—C3 | −78.5 (10) |
N4—Mn1—N3—C4 | 32.9 (2) | N1—Mn1—N2—C3 | 93.9 (10) |
N1—Mn1—N3—C4 | −152.4 (2) | N3—Mn1—N2—C3 | 5.0 (10) |
N2—Mn1—N3—C4 | −61.3 (2) | Mn1—N1—C1—N7 | −56 (4) |
N6—Mn1—N4—C5 | −98.8 (8) | C2—N7—C1—N1 | 173 (3) |
N5—Mn1—N4—C5 | −3.8 (8) | Mn2—N7—C1—N1 | −4 (4) |
N1—Mn1—N4—C5 | 48.5 (11) | Mn2iv—N8—C2—N7 | −14 (3) |
N2—Mn1—N4—C5 | 167.3 (8) | C1—N7—C2—N8 | −171 (2) |
N3—Mn1—N4—C5 | 86.1 (8) | Mn2—N7—C2—N8 | 6 (3) |
N5—Mn1—N6—C9 | −63.0 (7) | Mn2i—N11—C6—N10 | −101.0 (18) |
N4—Mn1—N6—C9 | 27.1 (7) | C5—N10—C6—N11 | 179 (100) |
N1—Mn1—N6—C9 | −148.2 (7) | Mn1—N4—C5—N10 | −80 (2) |
N2—Mn1—N6—C9 | 120.5 (7) | C6—N10—C5—N4 | −174.9 (18) |
N3—Mn1—N6—C9 | 83.4 (11) | Mn2ii—N15—C10—N14 | −98.7 (18) |
N11i—Mn2—N7—C2 | 178.26 (19) | C9—N14—C10—N15 | 173.8 (17) |
N15ii—Mn2—N7—C2 | 98.1 (4) | Mn1—N2—C3—N9 | −119 (3) |
N13iii—Mn2—N7—C2 | −88.03 (19) | C4vi—N9—C3—N2 | 174 (4) |
N8iv—Mn2—N7—C2 | 1.75 (18) | Mn2v—N9—C3—N2 | −26 (4) |
N9v—Mn2—N7—C2 | 83.85 (18) | Mn1—N6—C9—N14 | −109.8 (19) |
N11i—Mn2—N7—C1 | −5.01 (19) | C10—N14—C9—N6 | −173.9 (18) |
N15ii—Mn2—N7—C1 | −85.2 (4) | Mn2iii—N13—C8—N12 | −132.0 (17) |
N13iii—Mn2—N7—C1 | 88.7 (2) | C7—N12—C8—N13 | 176.1 (18) |
N8iv—Mn2—N7—C1 | 178.5 (2) | Mn1—N3—C4—N9vi | −92 (4) |
N9v—Mn2—N7—C1 | −99.43 (19) | Mn1—N5—C7—N12 | −63 (3) |
N6—Mn1—N5—C7 | 2.5 (12) | C8—N12—C7—N5 | −175 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+2; (iii) −x, −y+2, −z+2; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1; (vi) −x+1, −y+3, −z+1. |
(C22H24P)2[Mn(C2N3)4] | F(000) = 998 |
Mr = 957.90 | Dx = 1.270 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5687 reflections |
a = 15.711 (3) Å | θ = 3.0–27.5° |
b = 7.6050 (15) Å | µ = 0.38 mm−1 |
c = 21.499 (4) Å | T = 293 K |
β = 102.86 (3)° | Block, colourless |
V = 2504.3 (9) Å3 | 0.30 × 0.28 × 0.25 mm |
Z = 2 |
Rigaku SCXmini diffractometer | 2956 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.078 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −16→20 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −9→9 |
Tmin = 0.896, Tmax = 0.912 | l = −24→27 |
15859 measured reflections | 3 standard reflections every 180 reflections |
5687 independent reflections | intensity decay: none |
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)] = 0.070 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.193 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0885P)2] where P = (Fo2 + 2Fc2)/3 |
5687 reflections | (Δ/σ)max = 0.018 |
305 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
(C22H24P)2[Mn(C2N3)4] | V = 2504.3 (9) Å3 |
Mr = 957.90 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.711 (3) Å | µ = 0.38 mm−1 |
b = 7.6050 (15) Å | T = 293 K |
c = 21.499 (4) Å | 0.30 × 0.28 × 0.25 mm |
β = 102.86 (3)° |
Rigaku SCXmini diffractometer | 2956 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.078 |
Tmin = 0.896, Tmax = 0.912 | 3 standard reflections every 180 reflections |
15859 measured reflections | intensity decay: none |
5687 independent reflections |
R[F2 > 2σ(F2)] = 0.070 | 0 restraints |
wR(F2) = 0.193 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.37 e Å−3 |
5687 reflections | Δρmin = −0.37 e Å−3 |
305 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.5000 | 1.0000 | 0.0000 | 0.0369 (2) | |
P1 | 0.98034 (6) | 0.31631 (12) | 0.18127 (5) | 0.0384 (3) | |
C1 | 0.9210 (2) | 0.1715 (5) | 0.12067 (17) | 0.0409 (9) | |
C23 | 0.6199 (3) | 0.6691 (5) | 0.0626 (2) | 0.0522 (11) | |
C13 | 0.9085 (2) | 0.4607 (4) | 0.21230 (17) | 0.0381 (9) | |
N1 | 0.5958 (2) | 0.8112 (4) | 0.06046 (17) | 0.0547 (9) | |
C18 | 0.8580 (3) | 0.5834 (5) | 0.17119 (19) | 0.0487 (10) | |
H18 | 0.8592 | 0.5838 | 0.1281 | 0.058* | |
N4 | 0.4247 (2) | 1.0155 (5) | 0.07382 (18) | 0.0620 (10) | |
C25 | 0.3791 (3) | 1.0114 (5) | 0.1080 (2) | 0.0469 (10) | |
C19 | 1.0446 (3) | 0.1836 (5) | 0.24372 (19) | 0.0494 (10) | |
H19A | 1.0927 | 0.1330 | 0.2283 | 0.059* | |
H19B | 1.0694 | 0.2594 | 0.2794 | 0.059* | |
C14 | 0.9073 (3) | 0.4616 (5) | 0.27653 (19) | 0.0462 (10) | |
H14 | 0.9407 | 0.3811 | 0.3042 | 0.055* | |
N3 | 0.5785 (2) | 1.2368 (4) | 0.04030 (17) | 0.0539 (9) | |
C15 | 0.8559 (3) | 0.5830 (6) | 0.2995 (2) | 0.0606 (12) | |
H15 | 0.8550 | 0.5842 | 0.3426 | 0.073* | |
C2 | 0.8313 (2) | 0.1797 (5) | 0.09785 (18) | 0.0472 (10) | |
H2 | 0.7990 | 0.2657 | 0.1130 | 0.057* | |
N5 | 0.3353 (3) | 0.9923 (6) | 0.15235 (19) | 0.0762 (12) | |
C6 | 0.9684 (3) | 0.0395 (5) | 0.0976 (2) | 0.0555 (11) | |
H6 | 1.0285 | 0.0312 | 0.1129 | 0.067* | |
C24 | 0.6096 (3) | 1.3704 (5) | 0.0520 (2) | 0.0525 (11) | |
C20 | 0.9950 (3) | 0.0351 (6) | 0.2677 (2) | 0.0670 (14) | |
H20A | 0.9683 | −0.0394 | 0.2321 | 0.080* | |
H20B | 0.9487 | 0.0847 | 0.2855 | 0.080* | |
C17 | 0.8068 (3) | 0.7029 (6) | 0.1939 (2) | 0.0575 (11) | |
H17 | 0.7732 | 0.7832 | 0.1663 | 0.069* | |
N2 | 0.6550 (3) | 0.5137 (5) | 0.0674 (3) | 0.110 (2) | |
C7 | 1.0580 (3) | 0.4417 (6) | 0.0837 (2) | 0.0672 (13) | |
H7 | 1.0233 | 0.3617 | 0.0566 | 0.081* | |
C3 | 0.7895 (3) | 0.0601 (6) | 0.0525 (2) | 0.0591 (12) | |
H3 | 0.7294 | 0.0656 | 0.0373 | 0.071* | |
C16 | 0.8055 (3) | 0.7032 (6) | 0.2580 (2) | 0.0601 (12) | |
H16 | 0.7709 | 0.7840 | 0.2735 | 0.072* | |
C26 | 0.2628 (3) | 1.0763 (6) | 0.1507 (2) | 0.0580 (12) | |
C5 | 0.9263 (3) | −0.0765 (6) | 0.0528 (2) | 0.0663 (13) | |
H5 | 0.9581 | −0.1632 | 0.0375 | 0.080* | |
C4 | 0.8376 (3) | −0.0671 (6) | 0.0299 (2) | 0.0633 (13) | |
H4 | 0.8098 | −0.1466 | −0.0009 | 0.076* | |
C11 | 1.1020 (4) | 0.5746 (7) | 0.1848 (2) | 0.0814 (16) | |
H11 | 1.0975 | 0.5879 | 0.2269 | 0.098* | |
C21 | 1.0552 (4) | −0.0768 (6) | 0.3188 (3) | 0.0907 (18) | |
H21A | 1.0223 | −0.1780 | 0.3278 | 0.109* | |
H21B | 1.1027 | −0.1204 | 0.3010 | 0.109* | |
C8 | 1.1166 (4) | 0.5498 (8) | 0.0605 (3) | 0.0869 (17) | |
H8 | 1.1215 | 0.5401 | 0.0183 | 0.104* | |
C10 | 1.1609 (4) | 0.6794 (8) | 0.1609 (3) | 0.104 (2) | |
H10 | 1.1971 | 0.7580 | 0.1876 | 0.125* | |
C9 | 1.1649 (4) | 0.6655 (7) | 0.0990 (3) | 0.0866 (17) | |
H9 | 1.2023 | 0.7388 | 0.0831 | 0.104* | |
C22 | 1.0917 (4) | 0.0086 (8) | 0.3774 (3) | 0.107 (2) | |
H22A | 1.1321 | 0.0971 | 0.3705 | 0.160* | |
H22B | 1.1216 | −0.0761 | 0.4076 | 0.160* | |
H22C | 1.0459 | 0.0625 | 0.3938 | 0.160* | |
N6 | 0.1989 (3) | 1.1341 (6) | 0.1550 (3) | 0.1090 (18) | |
C12 | 1.0516 (3) | 0.4543 (5) | 0.1471 (2) | 0.0467 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0394 (5) | 0.0244 (4) | 0.0471 (5) | 0.0001 (3) | 0.0101 (4) | −0.0043 (4) |
P1 | 0.0339 (5) | 0.0373 (5) | 0.0436 (6) | −0.0010 (4) | 0.0081 (4) | −0.0026 (4) |
C1 | 0.038 (2) | 0.042 (2) | 0.043 (2) | −0.0033 (17) | 0.0096 (17) | −0.0004 (17) |
C23 | 0.040 (2) | 0.033 (2) | 0.073 (3) | −0.0076 (18) | −0.010 (2) | −0.007 (2) |
C13 | 0.038 (2) | 0.036 (2) | 0.039 (2) | −0.0030 (16) | 0.0064 (16) | −0.0019 (16) |
N1 | 0.051 (2) | 0.0312 (18) | 0.076 (3) | 0.0011 (16) | 0.0026 (18) | −0.0024 (17) |
C18 | 0.055 (3) | 0.052 (2) | 0.039 (2) | 0.008 (2) | 0.0108 (19) | −0.0033 (19) |
N4 | 0.067 (3) | 0.058 (2) | 0.069 (3) | −0.001 (2) | 0.033 (2) | −0.005 (2) |
C25 | 0.049 (2) | 0.040 (2) | 0.049 (2) | −0.001 (2) | 0.005 (2) | −0.004 (2) |
C19 | 0.052 (2) | 0.046 (2) | 0.046 (2) | 0.0041 (19) | 0.0004 (19) | −0.0011 (19) |
C14 | 0.046 (2) | 0.051 (2) | 0.042 (2) | −0.0005 (19) | 0.0103 (18) | −0.0005 (18) |
N3 | 0.062 (2) | 0.0261 (17) | 0.069 (2) | −0.0046 (16) | 0.0046 (18) | −0.0071 (16) |
C15 | 0.069 (3) | 0.074 (3) | 0.040 (3) | −0.001 (3) | 0.014 (2) | −0.014 (2) |
C2 | 0.039 (2) | 0.054 (2) | 0.049 (2) | −0.0014 (19) | 0.0105 (18) | −0.007 (2) |
N5 | 0.070 (3) | 0.096 (3) | 0.072 (3) | 0.024 (2) | 0.036 (2) | 0.025 (2) |
C6 | 0.044 (2) | 0.060 (3) | 0.064 (3) | 0.002 (2) | 0.014 (2) | −0.015 (2) |
C24 | 0.047 (2) | 0.031 (2) | 0.068 (3) | 0.0077 (19) | −0.010 (2) | −0.001 (2) |
C20 | 0.075 (3) | 0.053 (3) | 0.066 (3) | −0.016 (2) | −0.001 (2) | 0.011 (2) |
C17 | 0.059 (3) | 0.053 (3) | 0.056 (3) | 0.013 (2) | 0.005 (2) | 0.000 (2) |
N2 | 0.059 (3) | 0.036 (2) | 0.200 (6) | 0.0019 (19) | −0.044 (3) | −0.022 (3) |
C7 | 0.069 (3) | 0.071 (3) | 0.064 (3) | −0.013 (3) | 0.021 (2) | −0.006 (2) |
C3 | 0.046 (3) | 0.065 (3) | 0.062 (3) | −0.011 (2) | 0.003 (2) | −0.012 (2) |
C16 | 0.057 (3) | 0.057 (3) | 0.069 (3) | 0.009 (2) | 0.019 (2) | −0.020 (2) |
C26 | 0.054 (3) | 0.058 (3) | 0.066 (3) | 0.007 (2) | 0.022 (2) | 0.008 (2) |
C5 | 0.070 (3) | 0.058 (3) | 0.072 (3) | 0.002 (2) | 0.019 (3) | −0.019 (2) |
C4 | 0.080 (4) | 0.056 (3) | 0.052 (3) | −0.011 (3) | 0.010 (2) | −0.015 (2) |
C11 | 0.104 (4) | 0.084 (4) | 0.061 (3) | −0.041 (3) | 0.030 (3) | −0.003 (3) |
C21 | 0.138 (5) | 0.045 (3) | 0.080 (4) | −0.004 (3) | 0.004 (4) | 0.013 (3) |
C8 | 0.095 (4) | 0.100 (4) | 0.074 (4) | −0.020 (4) | 0.036 (3) | 0.008 (3) |
C10 | 0.113 (5) | 0.107 (5) | 0.086 (4) | −0.061 (4) | 0.008 (4) | 0.008 (4) |
C9 | 0.083 (4) | 0.098 (4) | 0.079 (4) | −0.029 (3) | 0.019 (3) | 0.018 (3) |
C22 | 0.142 (6) | 0.087 (4) | 0.080 (4) | −0.004 (4) | 0.001 (4) | 0.016 (4) |
N6 | 0.091 (4) | 0.105 (4) | 0.152 (5) | 0.038 (3) | 0.071 (3) | 0.026 (3) |
C12 | 0.046 (2) | 0.044 (2) | 0.052 (3) | −0.0024 (18) | 0.0139 (19) | −0.0043 (19) |
Mn1—N4i | 2.183 (4) | C6—H6 | 0.9300 |
Mn1—N4 | 2.183 (4) | C24—N2ii | 1.304 (5) |
Mn1—N3 | 2.245 (3) | C20—C21 | 1.536 (6) |
Mn1—N3i | 2.245 (3) | C20—H20A | 0.9700 |
Mn1—N1 | 2.268 (3) | C20—H20B | 0.9700 |
Mn1—N1i | 2.268 (3) | C17—C16 | 1.382 (6) |
P1—C19 | 1.799 (4) | C17—H17 | 0.9300 |
P1—C1 | 1.800 (4) | N2—C24iii | 1.304 (5) |
P1—C13 | 1.806 (4) | C7—C12 | 1.392 (6) |
P1—C12 | 1.806 (4) | C7—C8 | 1.405 (7) |
C1—C2 | 1.386 (5) | C7—H7 | 0.9300 |
C1—C6 | 1.405 (5) | C3—C4 | 1.380 (6) |
C23—N1 | 1.143 (4) | C3—H3 | 0.9300 |
C23—N2 | 1.299 (5) | C16—H16 | 0.9300 |
C13—C14 | 1.385 (5) | C26—N6 | 1.118 (6) |
C13—C18 | 1.404 (5) | C5—C4 | 1.372 (6) |
C18—C17 | 1.373 (5) | C5—H5 | 0.9300 |
C18—H18 | 0.9300 | C4—H4 | 0.9300 |
N4—C25 | 1.136 (5) | C11—C12 | 1.355 (6) |
C25—N5 | 1.302 (6) | C11—C10 | 1.402 (7) |
C19—C20 | 1.526 (5) | C11—H11 | 0.9300 |
C19—H19A | 0.9700 | C21—C22 | 1.421 (7) |
C19—H19B | 0.9700 | C21—H21A | 0.9700 |
C14—C15 | 1.388 (6) | C21—H21B | 0.9700 |
C14—H14 | 0.9300 | C8—C9 | 1.325 (7) |
N3—C24 | 1.131 (4) | C8—H8 | 0.9300 |
C15—C16 | 1.394 (6) | C10—C9 | 1.350 (7) |
C15—H15 | 0.9300 | C10—H10 | 0.9300 |
C2—C3 | 1.388 (5) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C22—H22A | 0.9600 |
N5—C26 | 1.299 (6) | C22—H22B | 0.9600 |
C6—C5 | 1.365 (6) | C22—H22C | 0.9600 |
N4—Mn1—N4i | 180.0 | N3—C24—N2ii | 172.7 (4) |
N4i—Mn1—N3 | 89.07 (13) | C19—C20—C21 | 111.9 (4) |
N4—Mn1—N3 | 90.93 (13) | C19—C20—H20A | 109.2 |
N4i—Mn1—N3i | 90.93 (13) | C21—C20—H20A | 109.2 |
N4—Mn1—N3i | 89.07 (13) | C19—C20—H20B | 109.2 |
N3—Mn1—N3i | 180.0 | C21—C20—H20B | 109.2 |
N4i—Mn1—N1 | 89.13 (14) | H20A—C20—H20B | 107.9 |
N4—Mn1—N1 | 90.87 (14) | C18—C17—C16 | 119.7 (4) |
N3—Mn1—N1 | 92.83 (12) | C18—C17—H17 | 120.1 |
N3i—Mn1—N1 | 87.17 (12) | C16—C17—H17 | 120.1 |
N4i—Mn1—N1i | 90.87 (14) | C23—N2—C24iii | 122.8 (4) |
N4—Mn1—N1i | 89.13 (14) | C12—C7—C8 | 120.1 (5) |
N3—Mn1—N1i | 87.17 (12) | C12—C7—H7 | 119.9 |
N3i—Mn1—N1i | 92.83 (12) | C8—C7—H7 | 119.9 |
N1—Mn1—N1i | 180.0 | C4—C3—C2 | 119.8 (4) |
C19—P1—C1 | 108.15 (18) | C4—C3—H3 | 120.1 |
C19—P1—C13 | 111.02 (18) | C2—C3—H3 | 120.1 |
C1—P1—C13 | 111.93 (17) | C17—C16—C15 | 120.3 (4) |
C19—P1—C12 | 109.49 (19) | C17—C16—H16 | 119.9 |
C1—P1—C12 | 109.21 (18) | C15—C16—H16 | 119.9 |
C13—P1—C12 | 107.02 (18) | N6—C26—N5 | 171.3 (5) |
C2—C1—C6 | 119.0 (4) | C6—C5—C4 | 120.9 (4) |
C2—C1—P1 | 123.4 (3) | C6—C5—H5 | 119.5 |
C6—C1—P1 | 117.5 (3) | C4—C5—H5 | 119.5 |
N1—C23—N2 | 174.3 (4) | C5—C4—C3 | 120.1 (4) |
C14—C13—C18 | 119.5 (3) | C5—C4—H4 | 119.9 |
C14—C13—P1 | 121.3 (3) | C3—C4—H4 | 119.9 |
C18—C13—P1 | 119.0 (3) | C12—C11—C10 | 120.7 (5) |
C23—N1—Mn1 | 142.5 (3) | C12—C11—H11 | 119.7 |
C17—C18—C13 | 120.6 (4) | C10—C11—H11 | 119.7 |
C17—C18—H18 | 119.7 | C22—C21—C20 | 116.3 (5) |
C13—C18—H18 | 119.7 | C22—C21—H21A | 108.2 |
C25—N4—Mn1 | 172.4 (4) | C20—C21—H21A | 108.2 |
N4—C25—N5 | 171.8 (5) | C22—C21—H21B | 108.2 |
C20—C19—P1 | 115.0 (3) | C20—C21—H21B | 108.2 |
C20—C19—H19A | 108.5 | H21A—C21—H21B | 107.4 |
P1—C19—H19A | 108.5 | C9—C8—C7 | 119.8 (5) |
C20—C19—H19B | 108.5 | C9—C8—H8 | 120.1 |
P1—C19—H19B | 108.5 | C7—C8—H8 | 120.1 |
H19A—C19—H19B | 107.5 | C9—C10—C11 | 119.7 (5) |
C15—C14—C13 | 119.7 (4) | C9—C10—H10 | 120.2 |
C15—C14—H14 | 120.1 | C11—C10—H10 | 120.2 |
C13—C14—H14 | 120.1 | C8—C9—C10 | 121.5 (5) |
C24—N3—Mn1 | 168.4 (3) | C8—C9—H9 | 119.3 |
C14—C15—C16 | 120.1 (4) | C10—C9—H9 | 119.3 |
C14—C15—H15 | 120.0 | C21—C22—H22A | 109.5 |
C16—C15—H15 | 120.0 | C21—C22—H22B | 109.5 |
C1—C2—C3 | 120.2 (4) | H22A—C22—H22B | 109.5 |
C1—C2—H2 | 119.9 | C21—C22—H22C | 109.5 |
C3—C2—H2 | 119.9 | H22A—C22—H22C | 109.5 |
C26—N5—C25 | 121.9 (4) | H22B—C22—H22C | 109.5 |
C5—C6—C1 | 119.9 (4) | C11—C12—C7 | 118.2 (4) |
C5—C6—H6 | 120.0 | C11—C12—P1 | 118.8 (3) |
C1—C6—H6 | 120.0 | C7—C12—P1 | 123.0 (3) |
C19—P1—C1—C2 | 126.8 (3) | N1—Mn1—N3—C24 | 164.2 (18) |
C13—P1—C1—C2 | 4.2 (4) | N1i—Mn1—N3—C24 | −15.8 (18) |
C12—P1—C1—C2 | −114.1 (3) | C13—C14—C15—C16 | 0.2 (6) |
C19—P1—C1—C6 | −50.6 (4) | C6—C1—C2—C3 | −0.6 (6) |
C13—P1—C1—C6 | −173.2 (3) | P1—C1—C2—C3 | −178.0 (3) |
C12—P1—C1—C6 | 68.5 (4) | N4—C25—N5—C26 | 175 (3) |
C19—P1—C13—C14 | 0.3 (4) | C2—C1—C6—C5 | 0.9 (6) |
C1—P1—C13—C14 | 121.2 (3) | P1—C1—C6—C5 | 178.4 (4) |
C12—P1—C13—C14 | −119.2 (3) | Mn1—N3—C24—N2ii | −139 (3) |
C19—P1—C13—C18 | 175.3 (3) | P1—C19—C20—C21 | 177.5 (4) |
C1—P1—C13—C18 | −63.7 (3) | C13—C18—C17—C16 | 0.5 (6) |
C12—P1—C13—C18 | 55.9 (3) | N1—C23—N2—C24iii | 178 (100) |
N2—C23—N1—Mn1 | 142 (6) | C1—C2—C3—C4 | −0.2 (6) |
N4i—Mn1—N1—C23 | −67.0 (6) | C18—C17—C16—C15 | 0.0 (7) |
N4—Mn1—N1—C23 | 113.0 (6) | C14—C15—C16—C17 | −0.3 (7) |
N3—Mn1—N1—C23 | −156.0 (6) | C25—N5—C26—N6 | 165 (4) |
N3i—Mn1—N1—C23 | 24.0 (6) | C1—C6—C5—C4 | −0.4 (7) |
N1i—Mn1—N1—C23 | 78 (20) | C6—C5—C4—C3 | −0.4 (8) |
C14—C13—C18—C17 | −0.7 (6) | C2—C3—C4—C5 | 0.7 (7) |
P1—C13—C18—C17 | −175.8 (3) | C19—C20—C21—C22 | 66.0 (7) |
N4i—Mn1—N4—C25 | 35 (100) | C12—C7—C8—C9 | −1.0 (8) |
N3—Mn1—N4—C25 | 164 (3) | C12—C11—C10—C9 | 2.8 (10) |
N3i—Mn1—N4—C25 | −16 (3) | C7—C8—C9—C10 | 1.8 (10) |
N1—Mn1—N4—C25 | −103 (3) | C11—C10—C9—C8 | −2.7 (10) |
N1i—Mn1—N4—C25 | 77 (3) | C10—C11—C12—C7 | −2.1 (8) |
Mn1—N4—C25—N5 | 106 (4) | C10—C11—C12—P1 | 177.3 (5) |
C1—P1—C19—C20 | −49.3 (4) | C8—C7—C12—C11 | 1.2 (7) |
C13—P1—C19—C20 | 73.9 (4) | C8—C7—C12—P1 | −178.2 (4) |
C12—P1—C19—C20 | −168.2 (3) | C19—P1—C12—C11 | −62.3 (4) |
C18—C13—C14—C15 | 0.3 (6) | C1—P1—C12—C11 | 179.5 (4) |
P1—C13—C14—C15 | 175.3 (3) | C13—P1—C12—C11 | 58.1 (4) |
N4i—Mn1—N3—C24 | 75.1 (18) | C19—P1—C12—C7 | 117.1 (4) |
N4—Mn1—N3—C24 | −104.9 (18) | C1—P1—C12—C7 | −1.1 (4) |
N3i—Mn1—N3—C24 | −66.7 (18) | C13—P1—C12—C7 | −122.5 (4) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···N6iv | 0.97 | 2.54 | 3.424 (7) | 152 |
C19—H19B···N5v | 0.97 | 2.56 | 3.491 (6) | 161 |
Symmetry codes: (iv) x+1, y−1, z; (v) −x+3/2, y−1/2, −z+1/2. |
Experimental details
(1) | (2) | |
Crystal data | ||
Chemical formula | (C4H12N)[Mn2(C2N3)5] | (C22H24P)2[Mn(C2N3)4] |
Mr | 514.28 | 957.90 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.368 (2), 10.377 (2), 11.898 (2) | 15.711 (3), 7.6050 (15), 21.499 (4) |
α, β, γ (°) | 65.64 (3), 82.28 (3), 62.83 (3) | 90, 102.86 (3), 90 |
V (Å3) | 1035.1 (3) | 2504.3 (9) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.26 | 0.38 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 | 0.30 × 0.28 × 0.25 |
Data collection | ||
Diffractometer | Rigaku SCXmini diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.704, 0.787 | 0.896, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10736, 4723, 4245 | 15859, 5687, 2956 |
Rint | 0.029 | 0.078 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.094, 1.09 | 0.070, 0.193, 1.02 |
No. of reflections | 4723 | 5687 |
No. of parameters | 289 | 305 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.51 | 0.37, −0.37 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
Mn2—N11i | 2.152 (2) | N1—C1 | 1.148 (3) |
Mn2—N15ii | 2.154 (2) | N3—C4 | 1.155 (3) |
Mn2—N13iii | 2.154 (2) | N6—C9 | 1.150 (3) |
Mn2—N8iv | 2.203 (2) | N7—C1 | 1.317 (3) |
Mn2—N7 | 2.397 (2) | N11—C6 | 1.143 (3) |
Mn2—N9v | 2.421 (2) | N15—C10 | 1.150 (3) |
Mn1—N6 | 2.185 (2) | N13—C8 | 1.147 (3) |
Mn1—N5 | 2.188 (2) | N10—C6 | 1.291 (3) |
Mn1—N4 | 2.198 (2) | N10—C5 | 1.291 (3) |
Mn1—N1 | 2.240 (2) | N2—C3 | 1.144 (3) |
Mn1—N2 | 2.250 (2) | N16—C12 | 1.409 (5) |
Mn1—N3 | 2.389 (2) | N16—C14 | 1.414 (5) |
N15ii—Mn2—N13iii | 98.47 (9) | N4—Mn1—N1 | 171.36 (8) |
N11i—Mn2—N8iv | 167.94 (8) | N6—Mn1—N3 | 174.12 (8) |
N15ii—Mn2—N7 | 167.69 (8) | C1—N1—Mn1 | 151.2 (2) |
N8iv—Mn2—N9v | 81.61 (8) | C4—N3—Mn1 | 125.72 (19) |
N6—Mn1—N1 | 94.57 (9) | C9—N6—Mn1 | 163.5 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+2; (iii) −x, −y+2, −z+2; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1. |
Mn1—N4 | 2.183 (4) | Mn1—N1 | 2.268 (3) |
Mn1—N3 | 2.245 (3) | ||
N4—Mn1—N4i | 180.0 | N4i—Mn1—N1 | 89.13 (14) |
N4—Mn1—N3 | 90.93 (13) | N3—Mn1—N1 | 92.83 (12) |
N3—Mn1—N3i | 180.0 |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···N6ii | 0.97 | 2.54 | 3.424 (7) | 151.8 |
C19—H19B···N5iii | 0.97 | 2.56 | 3.491 (6) | 161.0 |
Symmetry codes: (ii) x+1, y−1, z; (iii) −x+3/2, y−1/2, −z+1/2. |
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