Alkali metal complexes of 6-methyl-2-pyridone: simple formulae, but not so simple structures

Reaction of 6-methyl-2-pyridone (Hmhp) with Na or K metal, or with Rb or Cs 2-ethylhexoxide, in an appropriate single or mixed solvent, yields a series of solvated polymeric complexes with the empirical formulae M(mhp)(H₂O)₂ [(1), M = Na; (2), M = K], M(mhp)(H₂O) [(3), M = Rb; (4), M = Cs] and Cs(mhp)(ROH) [(5), R = Me; (6), R = Et]. All of the products have been crystallographically characterized and show sheet polymeric structures, except for a double-chain structure for (2). In all of the structures, mhp⁻ and solvent molecules function as bridging ligands; two metal ions are bridged (μ₂) by each solvent molecule in (1), (5) and (6), while (2) contains both μ₂ and μ₃ triple bridges, and (3) and (4) display highly unusual μ₄ quadruple bridging of metal ions by water molecules. The pyridonate O atom bridges two or three metal ions in each case. Nitrogen is also involved in coordination to the heavier metals; it bonds to a single ion in (3) and (4), but has an almost unprecedented bridging role in (5) and (6). As a result of the extensive bridging by ligands, coordination numbers between 6 and 8 are achieved for the metal ions. In each structure, all solvent OH groups form hydrogen bonds to pyridonate O and, in some cases, N atoms. With one exception, these are the first reported pyridonate complexes of the alkali metals Na–Cs that do not also include transition metals.

Computing details

For all compounds, data collection: Bruker SMART; cell refinement: Bruker APEX2; data reduction: Bruker APEX2; program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: SHELXL2013; molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL and local programs.

Figures

(dmt34_1)

Crystal data

Na^+·C6H6NO^−·2H2O	F(000) = 352
Mr = 167.14	Dx = 1.386 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.8784 (15) Å	Cell parameters from 3850 reflections
b = 8.3444 (9) Å	θ = 2.4–28.2°
c = 6.9228 (7) Å	µ = 0.15 mm^−1
β = 92.8320 (13)°	T = 160 K
V = 800.73 (15) Å^3	Plate, colourless
Z = 4	0.80 × 0.80 × 0.05 mm

Data collection

Bruker SMART 1K CCD diffractometer	1684 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.021
thin–slice ω scans	θmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan SADABS	h = −18→18
Tmin = 0.810, Tmax = 0.942	k = −11→11
6593 measured reflections	l = −9→9
1950 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: mixed
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0549P)^2 + 0.2218P] where P = (Fo^2 + 2Fc^2)/3
1950 reflections	(Δ/σ)max = 0.001
117 parameters	Δρmax = 0.42 e Å^−3
4 restraints	Δρmin = −0.18 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.51314 (4)	0.50189 (6)	0.25045 (7)	0.02154 (15)
O1	0.38878 (6)	0.44159 (11)	0.47268 (12)	0.0214 (2)
N1	0.26454 (7)	0.52877 (11)	0.27246 (14)	0.0170 (2)
C1	0.29655 (8)	0.45057 (13)	0.43520 (15)	0.0153 (2)
C2	0.22908 (9)	0.37894 (15)	0.55688 (17)	0.0215 (3)
H2	0.2506	0.3287	0.6743	0.026*
C3	0.13281 (9)	0.38312 (15)	0.50318 (19)	0.0253 (3)
H3	0.0875	0.3326	0.5816	0.030*
C4	0.10108 (9)	0.46142 (16)	0.33346 (19)	0.0236 (3)
H4	0.0345	0.4643	0.2946	0.028*
C5	0.16881 (9)	0.53453 (15)	0.22350 (17)	0.0205 (3)
C6	0.14139 (11)	0.6258 (2)	0.0418 (2)	0.0373 (4)
H6A	0.1660	0.7356	0.0532	0.056*
H6B	0.0710	0.6281	0.0226	0.056*
H6C	0.1693	0.5730	−0.0689	0.056*
O2	0.59557 (6)	0.61178 (11)	−0.00336 (12)	0.0216 (2)
H2A	0.6001 (13)	0.7125 (11)	−0.003 (3)	0.040 (5)*
H2B	0.6463 (9)	0.582 (2)	−0.053 (2)	0.041 (5)*
O3	0.41000 (7)	0.74206 (11)	0.18535 (17)	0.0326 (3)
H3A	0.3994 (19)	0.780 (3)	0.076 (2)	0.085 (9)*
H3B	0.3591 (9)	0.693 (2)	0.206 (3)	0.047 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0247 (3)	0.0226 (3)	0.0177 (3)	−0.00667 (19)	0.00552 (18)	−0.00368 (17)
O1	0.0159 (4)	0.0287 (5)	0.0194 (4)	0.0007 (3)	0.0004 (3)	0.0053 (3)
N1	0.0185 (5)	0.0160 (4)	0.0164 (5)	−0.0003 (4)	0.0006 (3)	0.0016 (4)
C1	0.0178 (5)	0.0130 (5)	0.0151 (5)	0.0004 (4)	0.0022 (4)	−0.0006 (4)
C2	0.0241 (6)	0.0200 (6)	0.0211 (6)	0.0037 (5)	0.0071 (4)	0.0059 (4)
C3	0.0216 (6)	0.0210 (6)	0.0343 (7)	−0.0001 (5)	0.0114 (5)	0.0028 (5)
C4	0.0158 (5)	0.0236 (6)	0.0314 (7)	0.0010 (4)	0.0003 (5)	−0.0048 (5)
C5	0.0218 (6)	0.0192 (5)	0.0201 (6)	0.0030 (4)	−0.0018 (4)	−0.0027 (4)
C6	0.0324 (8)	0.0483 (9)	0.0303 (7)	0.0070 (7)	−0.0080 (6)	0.0107 (6)
O2	0.0229 (5)	0.0210 (5)	0.0216 (4)	−0.0058 (3)	0.0074 (3)	−0.0048 (3)
O3	0.0281 (5)	0.0201 (5)	0.0491 (7)	−0.0071 (4)	−0.0039 (5)	0.0107 (4)

Geometric parameters (Å, º)

Na1—Na1^i	3.4689 (10)	C2—H2	0.950
Na1—Na1^ii	3.4924 (10)	C2—C3	1.3695 (17)
Na1—Na1^iii	4.1881 (5)	C3—H3	0.950
Na1—Na1^iv	4.1881 (5)	C3—C4	1.3964 (19)
Na1—O1	2.4210 (10)	C4—H4	0.950
Na1—O1^ii	2.3433 (10)	C4—C5	1.3806 (18)
Na1—O2	2.3313 (10)	C5—C6	1.5031 (18)
Na1—O2^i	2.4180 (10)	C6—H6A	0.980
Na1—O3	2.4909 (11)	C6—H6B	0.980
Na1—O3^iv	2.4472 (11)	C6—H6C	0.980
Na1—H3B	2.671 (19)	O2—Na1^i	2.4180 (10)
O1—Na1^ii	2.3433 (10)	O2—H2A	0.842 (9)
O1—C1	1.2956 (14)	O2—H2B	0.836 (9)
N1—C1	1.3575 (14)	O3—Na1^iii	2.4473 (11)
N1—C5	1.3556 (15)	O3—H3A	0.828 (10)
C1—C2	1.4218 (15)	O3—H3B	0.836 (9)
O1—Na1—O1^ii	85.73 (3)	C1—C2—C3	119.39 (11)
O1—Na1—O2	162.25 (4)	H2—C2—C3	120.3
O1^ii—Na1—O2	104.51 (4)	C2—C3—H3	119.9
O1^ii—Na1—O2^i	167.03 (4)	C2—C3—C4	120.21 (11)
O1—Na1—O2^i	85.90 (3)	H3—C3—C4	119.9
O1—Na1—O3	82.00 (4)	C3—C4—H4	120.8
O1^ii—Na1—O3^iv	78.43 (4)	C3—C4—C5	118.41 (11)
O1—Na1—O3^iv	91.06 (4)	H4—C4—C5	120.8
O1^ii—Na1—O3	106.94 (4)	N1—C5—C4	122.14 (11)
O1—Na1—H3B	66.8 (3)	N1—C5—C6	115.58 (11)
O1^ii—Na1—H3B	113.8 (4)	C4—C5—C6	122.28 (11)
O2—Na1—O2^i	86.18 (3)	C5—C6—H6A	109.5
O2—Na1—O3	81.15 (4)	C5—C6—H6B	109.5
O2—Na1—O3^iv	105.05 (4)	C5—C6—H6C	109.5
O2^i—Na1—O3^iv	91.84 (4)	H6A—C6—H6B	109.5
O2^i—Na1—O3	81.65 (4)	H6A—C6—H6C	109.5
O2—Na1—H3B	95.6 (3)	H6B—C6—H6C	109.5
O2^i—Na1—H3B	71.6 (4)	Na1—O2—Na1^i	93.82 (3)
O3—Na1—O3^iv	170.77 (3)	Na1—O2—H2A	115.5 (13)
O3—Na1—H3B	18.2 (2)	Na1^i—O2—H2A	115.8 (13)
O3^iv—Na1—H3B	152.6 (3)	Na1—O2—H2B	130.3 (13)
Na1—O1—Na1^ii	94.27 (3)	Na1^i—O2—H2B	95.9 (13)
Na1—O1—C1	126.09 (7)	H2A—O2—H2B	103.4 (18)
Na1^ii—O1—C1	132.87 (7)	Na1—O3—Na1^iii	116.01 (4)
C1—N1—C5	120.07 (10)	Na1—O3—H3A	123 (2)
O1—C1—N1	118.26 (10)	Na1^iii—O3—H3A	83 (2)
O1—C1—C2	122.02 (10)	Na1—O3—H3B	93.2 (14)
N1—C1—C2	119.71 (10)	Na1^iii—O3—H3B	140.3 (14)
C1—C2—H2	120.3	H3A—O3—H3B	103 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^iii	0.84 (1)	1.93 (1)	2.7680 (13)	174 (2)
O2—H2B···N1^i	0.84 (1)	2.21 (1)	2.9955 (13)	157 (2)
O3—H3A···O1^v	0.83 (1)	2.43 (2)	3.0298 (13)	130 (2)
O3—H3B···N1	0.84 (1)	1.97 (1)	2.7798 (14)	164 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2; (v) x, −y+3/2, z−1/2.

(dmt39_2)

Crystal data

K^+·C6H6NO^−·2H2O	Dx = 1.411 Mg m^−3
Mr = 183.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 2899 reflections
a = 8.2804 (14) Å	θ = 2.8–28.2°
b = 28.818 (5) Å	µ = 0.58 mm^−1
c = 7.2304 (12) Å	T = 150 K
V = 1725.3 (5) Å^3	Plate, colourless
Z = 8	0.40 × 0.40 × 0.10 mm
F(000) = 768

Data collection

Bruker SMART 1K CCD diffractometer	1607 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.039
thin–slice ω scans	θmax = 28.2°, θmin = 2.6°
Absorption correction: multi-scan SADABS	h = −9→10
Tmin = 0.832, Tmax = 0.959	k = −38→26
7578 measured reflections	l = −9→9
2048 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0196P)^2 + 3.0798P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2048 reflections	Δρmax = 0.35 e Å^−3
118 parameters	Δρmin = −0.65 e Å^−3
4 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (8)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
K1	0.48146 (6)	0.26225 (2)	0.19978 (7)	0.01862 (17)
O1	0.5224 (2)	0.17990 (6)	0.0000 (2)	0.0178 (4)
N1	0.4660 (2)	0.12636 (7)	0.2234 (3)	0.0179 (4)
C1	0.5328 (3)	0.13713 (8)	0.0569 (3)	0.0155 (5)
C2	0.6118 (3)	0.10226 (9)	−0.0478 (3)	0.0223 (6)
H2	0.6602	0.1097	−0.1632	0.027*
C3	0.6179 (3)	0.05770 (9)	0.0183 (4)	0.0275 (6)
H3	0.6715	0.0342	−0.0507	0.033*
C4	0.5458 (3)	0.04688 (9)	0.1863 (4)	0.0263 (6)
H4	0.5480	0.0160	0.2327	0.032*
C5	0.4708 (3)	0.08191 (9)	0.2843 (4)	0.0239 (5)
C6	0.3889 (4)	0.07304 (11)	0.4673 (4)	0.0391 (8)
H6A	0.4351	0.0935	0.5617	0.059*
H6B	0.4055	0.0406	0.5037	0.059*
H6C	0.2730	0.0792	0.4556	0.059*
O2	0.6641 (2)	0.29757 (6)	−0.0786 (3)	0.0228 (4)
H2A	0.7600 (17)	0.3057 (10)	−0.058 (4)	0.035 (9)*
H2B	0.626 (4)	0.3228 (7)	−0.115 (5)	0.044 (10)*
O3	0.2978 (2)	0.30218 (6)	−0.0918 (3)	0.0209 (4)
H3A	0.336 (4)	0.3263 (7)	−0.140 (4)	0.040 (10)*
H3B	0.208 (2)	0.3110 (10)	−0.053 (4)	0.034 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0236 (3)	0.0209 (3)	0.0114 (2)	0.0008 (2)	0.0015 (2)	−0.00028 (19)
O1	0.0157 (9)	0.0197 (8)	0.0178 (8)	0.0002 (7)	0.0002 (7)	0.0023 (7)
N1	0.0184 (10)	0.0191 (10)	0.0163 (9)	0.0002 (8)	0.0009 (8)	0.0005 (8)
C1	0.0119 (11)	0.0184 (12)	0.0162 (10)	−0.0018 (9)	−0.0019 (9)	−0.0018 (9)
C2	0.0226 (13)	0.0242 (13)	0.0201 (12)	−0.0019 (11)	0.0030 (10)	−0.0043 (10)
C3	0.0272 (15)	0.0213 (14)	0.0339 (14)	0.0029 (11)	−0.0008 (12)	−0.0090 (11)
C4	0.0298 (14)	0.0167 (12)	0.0326 (13)	−0.0001 (10)	−0.0066 (12)	0.0012 (11)
C5	0.0261 (13)	0.0229 (13)	0.0228 (12)	−0.0037 (10)	−0.0038 (12)	0.0029 (10)
C6	0.055 (2)	0.0319 (16)	0.0305 (15)	−0.0018 (15)	0.0097 (15)	0.0119 (13)
O2	0.0182 (10)	0.0223 (10)	0.0278 (10)	−0.0033 (8)	−0.0049 (8)	0.0065 (8)
O3	0.0167 (9)	0.0210 (10)	0.0249 (10)	0.0007 (7)	0.0049 (7)	0.0024 (8)

Geometric parameters (Å, º)

K1—K1^i	3.6835 (6)	C2—C3	1.371 (4)
K1—K1^ii	3.6835 (6)	C3—H3	0.950
K1—K1^iii	3.8976 (12)	C3—C4	1.389 (4)
K1—K1^iv	4.5031 (13)	C4—H4	0.950
K1—O1	2.7989 (18)	C4—C5	1.381 (4)
K1—O1^i	2.7580 (17)	C5—C6	1.509 (4)
K1—O2	2.716 (2)	C6—H6A	0.980
K1—O2^i	2.7977 (19)	C6—H6B	0.980
K1—O3	2.8431 (19)	C6—H6C	0.980
K1—O3^i	2.8341 (19)	O2—K1^ii	2.7977 (19)
K1—O3^v	2.9899 (19)	O2—H2A	0.841 (10)
O1—K1^ii	2.7581 (17)	O2—H2B	0.837 (10)
O1—C1	1.302 (3)	O3—K1^ii	2.8341 (19)
N1—C1	1.361 (3)	O3—K1^vi	2.9899 (19)
N1—C5	1.355 (3)	O3—H3A	0.838 (10)
C1—C2	1.418 (3)	O3—H3B	0.839 (10)
C2—H2	0.950
O1—K1—O1^i	154.67 (6)	C2—C3—H3	120.0
O1—K1—O2	82.41 (5)	C2—C3—C4	119.9 (2)
O1^i—K1—O2	106.76 (6)	H3—C3—C4	120.0
O1^i—K1—O2^i	81.67 (5)	C3—C4—H4	120.7
O1—K1—O2^i	73.00 (5)	C3—C4—C5	118.6 (2)
O1—K1—O3	91.45 (5)	H4—C4—C5	120.7
O1^i—K1—O3^i	92.49 (5)	N1—C5—C4	122.5 (2)
O1—K1—O3^i	77.51 (5)	N1—C5—C6	115.6 (2)
O1^i—K1—O3	113.88 (5)	C4—C5—C6	121.9 (2)
O1^i—K1—O3^v	57.71 (5)	C5—C6—H6A	109.5
O1—K1—O3^v	132.85 (5)	C5—C6—H6B	109.5
O2—K1—O2^i	110.75 (7)	C5—C6—H6C	109.5
O2—K1—O3	66.21 (6)	H6A—C6—H6B	109.5
O2—K1—O3^i	159.81 (6)	H6A—C6—H6C	109.5
O2^i—K1—O3^i	65.29 (6)	H6B—C6—H6C	109.5
O2^i—K1—O3	164.45 (6)	K1—O2—K1^ii	83.83 (5)
O2—K1—O3^v	131.30 (6)	K1—O2—H2A	120 (2)
O2^i—K1—O3^v	111.50 (5)	K1^ii—O2—H2A	141 (2)
O3—K1—O3^i	111.86 (7)	K1—O2—H2B	110 (2)
O3^i—K1—O3^v	64.48 (7)	K1^ii—O2—H2B	99 (2)
O3—K1—O3^v	78.71 (3)	H2A—O2—H2B	100 (3)
K1—O1—K1^ii	83.03 (5)	K1—O3—K1^ii	80.91 (5)
K1—O1—C1	130.37 (14)	K1^ii—O3—K1^vi	83.97 (5)
K1^ii—O1—C1	145.98 (14)	K1—O3—K1^vi	129.17 (7)
C1—N1—C5	119.4 (2)	K1—O3—H3A	116 (2)
O1—C1—N1	117.9 (2)	K1^ii—O3—H3A	97 (2)
O1—C1—C2	122.2 (2)	K1^vi—O3—H3A	114 (2)
N1—C1—C2	119.9 (2)	K1—O3—H3B	110 (2)
C1—C2—H2	120.2	K1^ii—O3—H3B	149 (2)
C1—C2—C3	119.6 (2)	K1^vi—O3—H3B	66 (2)
H2—C2—C3	120.2	H3A—O3—H3B	103 (3)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1/2, −y+1/2, z; (iv) −x+3/2, −y+1/2, z; (v) −x+1/2, y, z+1/2; (vi) −x+1/2, y, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^iv	0.84 (1)	1.90 (1)	2.736 (2)	176 (3)
O2—H2B···N1^ii	0.84 (1)	2.29 (2)	3.090 (3)	159 (3)
O3—H3A···N1^ii	0.84 (1)	2.00 (1)	2.823 (3)	167 (3)
O3—H3B···O1^iii	0.84 (1)	1.96 (1)	2.781 (2)	166 (3)

Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) −x+1/2, −y+1/2, z; (iv) −x+3/2, −y+1/2, z.

(dmt45_3)

Crystal data

Rb^+·C6H6NO^−·H2O	F(000) = 416
Mr = 211.60	Dx = 1.851 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9109 (16) Å	Cell parameters from 4247 reflections
b = 7.8661 (9) Å	θ = 3.0–28.2°
c = 7.0235 (8) Å	µ = 6.46 mm^−1
β = 98.8733 (15)°	T = 150 K
V = 759.35 (15) Å^3	Plate, colourless
Z = 4	0.80 × 0.20 × 0.05 mm

Data collection

Bruker SMART 1K CCD diffractometer	1623 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.045
thin–slice ω scans	θmax = 28.3°, θmin = 3.0°
Absorption correction: multi-scan SADABS	h = −17→18
Tmin = 0.147, Tmax = 0.263	k = −10→10
6454 measured reflections	l = −9→9
1854 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: mixed
wR(F^2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0394P)^2 + 0.5119P] where P = (Fo^2 + 2Fc^2)/3
1854 reflections	(Δ/σ)max = 0.011
100 parameters	Δρmax = 0.66 e Å^−3
2 restraints	Δρmin = −0.61 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.42923 (2)	0.41085 (3)	0.22194 (3)	0.01794 (11)
O1	0.37561 (15)	0.4459 (2)	0.6218 (3)	0.0225 (4)
N1	0.27157 (16)	0.5266 (3)	0.8276 (3)	0.0175 (5)
C1	0.2880 (2)	0.4483 (3)	0.6626 (4)	0.0167 (5)
C2	0.2092 (2)	0.3709 (4)	0.5405 (4)	0.0222 (6)
H2	0.2203	0.3122	0.4277	0.027*
C3	0.1169 (2)	0.3813 (4)	0.5861 (4)	0.0248 (6)
H3	0.0639	0.3303	0.5044	0.030*
C4	0.1009 (2)	0.4668 (4)	0.7525 (4)	0.0221 (6)
H4	0.0372	0.4773	0.7844	0.027*
C5	0.1799 (2)	0.5355 (3)	0.8692 (4)	0.0197 (5)
C6	0.1683 (3)	0.6275 (4)	1.0531 (5)	0.0311 (7)
H6A	0.2080	0.5713	1.1626	0.047*
H6B	0.0998	0.6252	1.0707	0.047*
H6C	0.1896	0.7457	1.0453	0.047*
O2	0.57754 (14)	0.2583 (3)	0.0206 (3)	0.0239 (4)
H2A	0.598 (2)	0.168 (3)	−0.023 (5)	0.033 (10)*
H2B	0.622 (2)	0.326 (5)	0.066 (6)	0.059 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.01860 (16)	0.01551 (15)	0.02034 (16)	0.00074 (9)	0.00497 (10)	0.00007 (9)
O1	0.0209 (10)	0.0161 (9)	0.0328 (11)	0.0003 (8)	0.0115 (9)	−0.0014 (8)
N1	0.0171 (11)	0.0139 (10)	0.0217 (11)	−0.0004 (9)	0.0036 (9)	−0.0002 (9)
C1	0.0199 (13)	0.0108 (11)	0.0202 (12)	0.0009 (10)	0.0060 (10)	0.0008 (10)
C2	0.0263 (15)	0.0183 (13)	0.0217 (13)	0.0001 (11)	0.0030 (11)	−0.0030 (10)
C3	0.0215 (15)	0.0213 (14)	0.0298 (15)	−0.0028 (11)	−0.0014 (12)	0.0012 (11)
C4	0.0169 (13)	0.0218 (13)	0.0288 (14)	0.0015 (11)	0.0072 (11)	0.0039 (11)
C5	0.0239 (14)	0.0134 (12)	0.0236 (13)	0.0024 (11)	0.0095 (11)	0.0024 (10)
C6	0.0343 (18)	0.0304 (16)	0.0323 (16)	0.0000 (14)	0.0171 (14)	−0.0093 (13)
O2	0.0187 (10)	0.0258 (11)	0.0278 (11)	−0.0017 (9)	0.0051 (8)	−0.0105 (9)

Geometric parameters (Å, º)

Rb1—Rb1^i	4.1782 (6)	N1—C5	1.353 (4)
Rb1—Rb1^ii	4.3275 (6)	C1—Rb1^v	3.429 (3)
Rb1—Rb1^iii	4.3285 (5)	C1—C2	1.421 (4)
Rb1—O1	3.027 (2)	C2—H2	0.950
Rb1—O1^iii	2.960 (2)	C2—C3	1.373 (4)
Rb1—O1^ii	2.988 (2)	C3—H3	0.950
Rb1—N1^iv	3.382 (2)	C3—C4	1.396 (4)
Rb1—C1^iii	3.429 (3)	C4—H4	0.950
Rb1—O2	2.9320 (19)	C4—C5	1.376 (4)
Rb1—O2^v	3.0152 (19)	C5—C6	1.511 (4)
Rb1—O2^i	3.104 (2)	C6—H6A	0.980
Rb1—O2^vi	3.287 (2)	C6—H6B	0.980
Rb1—H2B	3.13 (4)	C6—H6C	0.980
O1—Rb1^v	2.960 (2)	O2—Rb1^iii	3.0152 (19)
O1—Rb1^ii	2.988 (2)	O2—Rb1^i	3.104 (2)
O1—C1	1.294 (3)	O2—Rb1^viii	3.287 (2)
N1—Rb1^vii	3.382 (2)	O2—H2A	0.843 (10)
N1—C1	1.362 (3)	O2—H2B	0.841 (10)
O1^iii—Rb1—O1^ii	128.78 (5)	Rb1—O1—Rb1^ii	92.01 (6)
O1—Rb1—O1^iii	102.57 (6)	Rb1—O1—C1	125.60 (17)
O1—Rb1—O1^ii	87.99 (6)	Rb1^v—O1—C1	99.94 (15)
O1^iii—Rb1—N1^iv	87.29 (6)	Rb1^ii—O1—C1	138.26 (17)
O1^ii—Rb1—N1^iv	129.58 (6)	Rb1^vii—N1—C1	113.70 (16)
O1—Rb1—N1^iv	120.91 (6)	Rb1^vii—N1—C5	110.55 (16)
O1^iii—Rb1—C1^iii	21.82 (6)	C1—N1—C5	119.6 (2)
O1^ii—Rb1—C1^iii	145.73 (6)	Rb1^v—C1—O1	58.24 (13)
O1—Rb1—C1^iii	88.23 (6)	Rb1^v—C1—N1	115.94 (16)
O1—Rb1—O2	141.00 (6)	Rb1^v—C1—C2	95.44 (16)
O1^iii—Rb1—O2	70.60 (6)	O1—C1—N1	118.9 (2)
O1^ii—Rb1—O2	70.39 (5)	O1—C1—C2	121.7 (2)
O1^iii—Rb1—O2^v	82.37 (6)	N1—C1—C2	119.5 (2)
O1^ii—Rb1—O2^v	54.93 (6)	C1—C2—H2	120.1
O1—Rb1—O2^v	68.59 (5)	C1—C2—C3	119.8 (3)
O1^iii—Rb1—O2^i	132.78 (5)	H2—C2—C3	120.1
O1^ii—Rb1—O2^i	80.46 (5)	C2—C3—H3	120.0
O1—Rb1—O2^i	116.22 (5)	C2—C3—C4	120.0 (3)
O1^iii—Rb1—O2^vi	153.06 (5)	H3—C3—C4	120.0
O1^ii—Rb1—O2^vi	65.52 (5)	C3—C4—H4	120.9
O1—Rb1—O2^vi	51.82 (5)	C3—C4—C5	118.2 (3)
O1—Rb1—H2B	133.8 (7)	H4—C4—C5	120.9
O1^iii—Rb1—H2B	84.9 (5)	N1—C5—C4	123.0 (3)
O1^ii—Rb1—H2B	55.1 (4)	N1—C5—C6	116.0 (3)
N1^iv—Rb1—C1^iii	80.52 (6)	C4—C5—C6	121.1 (3)
N1^iv—Rb1—O2	97.52 (6)	C5—C6—H6A	109.5
N1^iv—Rb1—O2^v	167.49 (6)	C5—C6—H6B	109.5
N1^iv—Rb1—O2^i	50.49 (5)	C5—C6—H6C	109.5
N1^iv—Rb1—O2^vi	99.02 (5)	H6A—C6—H6B	109.5
N1^iv—Rb1—H2B	104.7 (7)	H6A—C6—H6C	109.5
C1^iii—Rb1—O2	92.11 (6)	H6B—C6—H6C	109.5
C1^iii—Rb1—O2^v	92.21 (6)	Rb1—O2—Rb1^iii	93.40 (6)
C1^iii—Rb1—O2^i	130.97 (6)	Rb1—O2—Rb1^i	87.57 (5)
C1^iii—Rb1—O2^vi	133.42 (6)	Rb1^iii—O2—Rb1^i	91.65 (5)
C1^iii—Rb1—H2B	106.7 (4)	Rb1—O2—Rb1^viii	89.59 (5)
O2—Rb1—O2^v	72.43 (4)	Rb1^iii—O2—Rb1^viii	86.62 (5)
O2—Rb1—O2^i	92.43 (5)	Rb1^i—O2—Rb1^viii	176.58 (7)
O2^v—Rb1—O2^i	135.35 (4)	Rb1—O2—H2A	146 (3)
O2—Rb1—O2^vi	133.45 (4)	Rb1^iii—O2—H2A	67 (2)
O2^v—Rb1—O2^vi	93.38 (5)	Rb1^i—O2—H2A	119 (3)
O2^i—Rb1—O2^vi	66.651 (10)	Rb1^viii—O2—H2A	63 (3)
O2—Rb1—H2B	15.5 (3)	Rb1—O2—H2B	95 (3)
O2^v—Rb1—H2B	67.4 (8)	Rb1^iii—O2—H2B	158 (3)
O2^i—Rb1—H2B	86.7 (8)	Rb1^i—O2—H2B	69 (3)
O2^vi—Rb1—H2B	118.1 (4)	Rb1^viii—O2—H2B	113 (3)
Rb1^v—O1—Rb1^ii	95.10 (6)	H2A—O2—H2B	113 (4)
Rb1—O1—Rb1^v	92.59 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^viii	0.84 (1)	1.93 (1)	2.769 (3)	171 (4)
O2—H2B···N1^ii	0.84 (1)	1.94 (1)	2.778 (3)	178 (5)

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

(dmt28_4)

Crystal data

Cs^+·C6H6NO^−·H2O	F(000) = 488
Mr = 259.04	Dx = 2.120 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.174 (3) Å	Cell parameters from 3289 reflections
b = 8.2056 (14) Å	θ = 2.9–28.5°
c = 7.0984 (12) Å	µ = 4.51 mm^−1
β = 100.605 (2)°	T = 160 K
V = 811.5 (2) Å^3	Plate, colourless
Z = 4	0.40 × 0.40 × 0.02 mm

Data collection

Bruker SMART 1K CCD diffractometer	1678 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.027
thin–slice ω scans	θmax = 28.5°, θmin = 2.9°
Absorption correction: multi-scan SADABS	h = −18→19
Tmin = 0.294, Tmax = 0.460	k = −10→10
4766 measured reflections	l = −9→9
1911 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0666P)^2 + 0.861P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1911 reflections	Δρmax = 2.61 e Å^−3
101 parameters	Δρmin = −1.83 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (10)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cs1	0.42228 (2)	0.41248 (3)	0.21030 (4)	0.01846 (15)
O1	0.3721 (2)	0.4540 (4)	0.6345 (5)	0.0232 (7)
N1	0.2634 (3)	0.5371 (4)	0.8171 (6)	0.0209 (7)
C1	0.2848 (3)	0.4545 (5)	0.6640 (6)	0.0185 (8)
C2	0.2105 (4)	0.3673 (5)	0.5409 (7)	0.0239 (9)
H2	0.2249	0.3073	0.4353	0.029*
C3	0.1172 (4)	0.3705 (6)	0.5759 (7)	0.0272 (10)
H3	0.0676	0.3127	0.4948	0.033*
C4	0.0972 (3)	0.4598 (6)	0.7322 (7)	0.0265 (9)
H4	0.0337	0.4652	0.7572	0.032*
C5	0.1711 (3)	0.5394 (5)	0.8484 (6)	0.0215 (9)
C6	0.1553 (4)	0.6375 (8)	1.0202 (9)	0.0404 (13)
H6A	0.1966	0.5953	1.1359	0.061*
H6B	0.0880	0.6289	1.0340	0.061*
H6C	0.1712	0.7520	1.0020	0.061*
O2	0.5869 (2)	0.2461 (4)	0.0335 (4)	0.0228 (7)
H2A	0.607 (5)	0.159 (5)	−0.007 (10)	0.052 (19)*
H2B	0.634 (3)	0.303 (6)	0.084 (8)	0.040 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0230 (2)	0.01205 (19)	0.0201 (2)	0.00008 (8)	0.00314 (12)	0.00001 (8)
O1	0.0230 (16)	0.0128 (12)	0.0354 (18)	0.0029 (12)	0.0094 (14)	0.0011 (13)
N1	0.0233 (19)	0.0130 (15)	0.0251 (19)	−0.0017 (14)	0.0010 (15)	−0.0015 (14)
C1	0.021 (2)	0.0109 (15)	0.023 (2)	0.0014 (16)	0.0030 (17)	0.0034 (15)
C2	0.030 (2)	0.0189 (18)	0.022 (2)	−0.0003 (18)	0.0030 (18)	−0.0041 (17)
C3	0.026 (2)	0.023 (2)	0.029 (2)	−0.0010 (19)	−0.0020 (19)	0.0031 (19)
C4	0.022 (2)	0.021 (2)	0.036 (3)	0.0020 (18)	0.006 (2)	0.005 (2)
C5	0.028 (2)	0.0161 (18)	0.021 (2)	0.0006 (17)	0.0066 (17)	0.0017 (16)
C6	0.043 (3)	0.040 (3)	0.042 (3)	0.001 (3)	0.019 (3)	−0.016 (3)
O2	0.0235 (16)	0.0200 (16)	0.0249 (17)	−0.0032 (13)	0.0046 (13)	−0.0063 (13)

Geometric parameters (Å, º)

Cs1—Cs1^i	4.2722 (7)	C1—Cs1^ii	3.569 (4)
Cs1—Cs1^ii	4.4392 (6)	C1—C2	1.430 (7)
Cs1—O1	3.237 (3)	C2—Cs1^ii	3.794 (5)
Cs1—O1^iii	3.114 (3)	C2—H2	0.950
Cs1—O1^iv	3.119 (3)	C2—C3	1.390 (7)
Cs1—N1^v	3.405 (4)	C3—H3	0.950
Cs1—C1^iii	3.569 (4)	C3—C4	1.401 (7)
Cs1—C2^iii	3.794 (5)	C4—H4	0.950
Cs1—O2	3.156 (3)	C4—C5	1.373 (7)
Cs1—O2^ii	3.230 (3)	C5—C6	1.511 (7)
Cs1—O2^i	3.283 (3)	C6—H6A	0.980
Cs1—O2^vi	3.302 (3)	C6—H6B	0.980
Cs1—H2B	3.41 (6)	C6—H6C	0.980
O1—Cs1^ii	3.114 (3)	O2—Cs1^iii	3.230 (3)
O1—Cs1^iv	3.119 (3)	O2—Cs1^i	3.283 (3)
O1—C1	1.292 (5)	O2—Cs1^viii	3.302 (3)
N1—Cs1^vii	3.405 (4)	O2—H2A	0.840 (10)
N1—C1	1.361 (6)	O2—H2B	0.842 (10)
N1—C5	1.367 (6)
O1^iii—Cs1—O1^iv	124.68 (8)	O2^i—Cs1—H2B	92.2 (10)
O1—Cs1—O1^iii	100.37 (9)	O2^vi—Cs1—H2B	119.3 (5)
O1—Cs1—O1^iv	89.17 (8)	Cs1^ii—O1—Cs1^iv	96.27 (9)
O1^iii—Cs1—N1^v	93.03 (9)	Cs1—O1—Cs1^ii	88.66 (8)
O1^iv—Cs1—N1^v	128.18 (9)	Cs1—O1—Cs1^iv	90.83 (8)
O1—Cs1—N1^v	120.36 (9)	Cs1—O1—C1	122.1 (3)
O1^iii—Cs1—C1^iii	20.91 (9)	Cs1^ii—O1—C1	99.8 (2)
O1^iv—Cs1—C1^iii	141.98 (9)	Cs1^iv—O1—C1	143.3 (3)
O1—Cs1—C1^iii	87.98 (9)	Cs1^vii—N1—C1	107.1 (3)
O1^iii—Cs1—C2^iii	38.63 (9)	Cs1^vii—N1—C5	112.3 (3)
O1^iv—Cs1—C2^iii	163.29 (9)	C1—N1—C5	119.8 (4)
O1—Cs1—C2^iii	93.56 (9)	Cs1^ii—C1—O1	59.3 (2)
O1—Cs1—O2	136.10 (8)	Cs1^ii—C1—N1	123.0 (3)
O1^iii—Cs1—O2	71.07 (8)	Cs1^ii—C1—C2	87.8 (3)
O1^iv—Cs1—O2	65.23 (8)	O1—C1—N1	119.4 (4)
O1^iii—Cs1—O2^ii	81.14 (9)	O1—C1—C2	121.2 (4)
O1^iv—Cs1—O2^ii	52.01 (8)	N1—C1—C2	119.3 (4)
O1—Cs1—O2^ii	68.62 (8)	Cs1^ii—C2—C1	70.0 (3)
O1^iii—Cs1—O2^i	138.37 (8)	Cs1^ii—C2—H2	70.4
O1^iv—Cs1—O2^i	80.23 (8)	Cs1^ii—C2—C3	132.7 (3)
O1—Cs1—O2^i	113.97 (8)	C1—C2—H2	120.0
O1^iii—Cs1—O2^vi	149.84 (8)	C1—C2—C3	119.9 (4)
O1^iv—Cs1—O2^vi	69.11 (8)	H2—C2—C3	120.0
O1—Cs1—O2^vi	50.40 (8)	C2—C3—H3	120.4
O1—Cs1—H2B	128.8 (9)	C2—C3—C4	119.3 (4)
O1^iii—Cs1—H2B	83.3 (7)	H3—C3—C4	120.4
O1^iv—Cs1—H2B	51.3 (5)	C3—C4—H4	120.6
N1^v—Cs1—C1^iii	84.86 (9)	C3—C4—C5	118.8 (4)
N1^v—Cs1—C2^iii	63.68 (9)	H4—C4—C5	120.6
N1^v—Cs1—O2	103.29 (9)	N1—C5—C4	122.8 (4)
N1^v—Cs1—O2^ii	170.29 (9)	N1—C5—C6	115.2 (4)
N1^v—Cs1—O2^i	49.87 (8)	C4—C5—C6	121.9 (5)
N1^v—Cs1—O2^vi	96.62 (8)	C5—C6—H6A	109.5
N1^v—Cs1—H2B	110.2 (10)	C5—C6—H6B	109.5
C1^iii—Cs1—C2^iii	22.13 (10)	C5—C6—H6C	109.5
C1^iii—Cs1—O2	91.69 (9)	H6A—C6—H6B	109.5
C1^iii—Cs1—O2^ii	92.09 (9)	H6A—C6—H6C	109.5
C1^iii—Cs1—O2^i	134.71 (9)	H6B—C6—H6C	109.5
C1^iii—Cs1—O2^vi	132.36 (9)	Cs1—O2—Cs1^iii	88.07 (8)
C1^iii—Cs1—H2B	104.2 (6)	Cs1—O2—Cs1^i	83.10 (7)
C2^iii—Cs1—O2	102.23 (9)	Cs1^iii—O2—Cs1^i	90.91 (8)
C2^iii—Cs1—O2^ii	114.05 (9)	Cs1—O2—Cs1^viii	91.87 (8)
C2^iii—Cs1—O2^i	113.38 (9)	Cs1^iii—O2—Cs1^viii	87.75 (7)
C2^iii—Cs1—O2^vi	124.53 (9)	Cs1^i—O2—Cs1^viii	174.83 (11)
C2^iii—Cs1—H2B	116.1 (5)	Cs1—O2—H2A	146 (5)
O2—Cs1—O2^ii	67.53 (5)	Cs1^iii—O2—H2A	70 (5)
O2—Cs1—O2^i	96.90 (7)	Cs1^i—O2—H2A	122 (5)
O2^ii—Cs1—O2^i	132.19 (6)	Cs1^viii—O2—H2A	62 (5)
O2—Cs1—O2^vi	133.21 (6)	Cs1—O2—H2B	101 (4)
O2^ii—Cs1—O2^vi	92.25 (7)	Cs1^iii—O2—H2B	160 (4)
O2^i—Cs1—O2^vi	65.236 (14)	Cs1^i—O2—H2B	73 (4)
O2—Cs1—H2B	14.0 (5)	Cs1^viii—O2—H2B	109 (4)
O2^ii—Cs1—H2B	61.6 (10)	H2A—O2—H2B	109 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^viii	0.84 (1)	1.96 (2)	2.785 (4)	168 (7)
O2—H2B···N1^iv	0.84 (1)	1.99 (1)	2.822 (5)	172 (6)

Symmetry codes: (iv) −x+1, −y+1, −z+1; (viii) −x+1, y−1/2, −z+1/2.

(dmt49_5)

Crystal data

Cs^+·C6H6NO^−·CH4O	F(000) = 520
Mr = 273.07	Dx = 1.942 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.764 (2) Å	Cell parameters from 1848 reflections
b = 12.106 (2) Å	θ = 2.5–28.2°
c = 7.1736 (13) Å	µ = 3.92 mm^−1
β = 92.363 (3)°	T = 150 K
V = 934.0 (3) Å^3	Plate, colourless
Z = 4	0.30 × 0.30 × 0.05 mm

Data collection

Bruker SMART 1K CCD diffractometer	1654 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.045
thin–slice ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan SADABS	h = −14→13
Tmin = 0.458, Tmax = 0.563	k = −15→15
4570 measured reflections	l = −7→9
2234 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0436P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
2234 reflections	Δρmax = 1.29 e Å^−3
107 parameters	Δρmin = −1.24 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0056 (7)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cs1	0.06440 (3)	0.85798 (3)	0.23256 (5)	0.02218 (14)
O1	0.0497 (4)	0.5887 (3)	0.3081 (6)	0.0241 (9)
N1	0.2198 (4)	0.6326 (4)	0.1428 (7)	0.0192 (9)
C1	0.1653 (5)	0.5722 (4)	0.2764 (8)	0.0209 (11)
C2	0.2367 (6)	0.4947 (5)	0.3828 (9)	0.0260 (13)
H2	0.1985	0.4523	0.4761	0.031*
C3	0.3610 (6)	0.4803 (5)	0.3523 (9)	0.0278 (13)
H3	0.4087	0.4277	0.4229	0.033*
C4	0.4159 (6)	0.5438 (5)	0.2165 (9)	0.0274 (13)
H4	0.5018	0.5362	0.1938	0.033*
C5	0.3424 (6)	0.6186 (5)	0.1151 (9)	0.0252 (13)
C6	0.3959 (6)	0.6902 (6)	−0.0319 (10)	0.0338 (15)
H6A	0.3687	0.6630	−0.1556	0.051*
H6B	0.4869	0.6880	−0.0195	0.051*
H6C	0.3672	0.7663	−0.0166	0.051*
C7	−0.2282 (6)	0.6579 (6)	0.1116 (11)	0.0371 (16)
H7A	−0.2856	0.6899	0.0169	0.056*
H7B	−0.2357	0.6976	0.2297	0.056*
H7C	−0.2486	0.5798	0.1295	0.056*
O2	−0.1060 (4)	0.6670 (5)	0.0528 (7)	0.0398 (12)
H2A	−0.080 (9)	0.632 (7)	0.147 (8)	0.07 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0273 (2)	0.0212 (2)	0.0182 (2)	0.00323 (16)	0.00207 (12)	0.00059 (15)
O1	0.021 (2)	0.027 (2)	0.025 (2)	−0.0002 (17)	0.0048 (16)	0.0017 (18)
N1	0.023 (2)	0.016 (2)	0.019 (2)	0.0015 (18)	0.0023 (18)	0.0035 (18)
C1	0.026 (3)	0.015 (2)	0.022 (3)	0.003 (2)	0.004 (2)	−0.002 (2)
C2	0.032 (3)	0.027 (3)	0.020 (3)	−0.001 (2)	0.000 (2)	0.002 (2)
C3	0.032 (3)	0.021 (3)	0.030 (3)	0.005 (2)	−0.007 (3)	0.003 (2)
C4	0.021 (3)	0.028 (3)	0.033 (4)	0.006 (2)	0.001 (2)	0.001 (3)
C5	0.029 (3)	0.028 (3)	0.019 (3)	−0.004 (2)	0.001 (2)	−0.001 (2)
C6	0.028 (3)	0.036 (3)	0.038 (4)	0.003 (3)	0.010 (3)	0.009 (3)
C7	0.024 (3)	0.045 (4)	0.043 (4)	−0.001 (3)	0.002 (3)	0.002 (3)
O2	0.030 (3)	0.065 (3)	0.025 (3)	−0.006 (2)	0.002 (2)	0.008 (2)

Geometric parameters (Å, º)

Cs1—O1	3.310 (4)	C1—Cs1^iii	3.591 (6)
Cs1—O1^i	3.060 (4)	C1—C2	1.416 (8)
Cs1—O1^ii	3.110 (4)	C2—Cs1^iii	3.647 (6)
Cs1—N1	3.278 (4)	C2—Cs1^iv	3.703 (6)
Cs1—N1^iii	3.326 (5)	C2—H2	0.950
Cs1—C1	3.636 (5)	C2—C3	1.375 (9)
Cs1—C1^i	3.582 (6)	C3—H3	0.950
Cs1—C1^ii	3.591 (6)	C3—C4	1.392 (9)
Cs1—C2^ii	3.647 (6)	C4—H4	0.950
Cs1—C2^i	3.703 (6)	C4—C5	1.389 (8)
Cs1—O2	3.190 (5)	C5—C6	1.498 (9)
Cs1—O2^iii	3.013 (5)	C6—H6A	0.980
Cs1—H2A	3.20 (10)	C6—H6B	0.980
O1—Cs1^iv	3.060 (4)	C6—H6C	0.980
O1—Cs1^iii	3.110 (4)	C7—H7A	0.980
O1—C1	1.290 (7)	C7—H7B	0.980
N1—Cs1^ii	3.326 (5)	C7—H7C	0.980
N1—C1	1.359 (7)	C7—O2	1.402 (8)
N1—C5	1.353 (7)	O2—Cs1^ii	3.013 (5)
C1—Cs1^iv	3.582 (6)	O2—H2A	0.838 (10)
O1^i—Cs1—O1^ii	73.33 (12)	C2^i—Cs1—O2^iii	70.16 (14)
O1—Cs1—O1^i	153.24 (3)	C2^i—Cs1—O2	75.53 (13)
O1—Cs1—O1^ii	111.34 (11)	C2^ii—Cs1—H2A	122.9 (13)
O1—Cs1—N1	40.60 (10)	C2^i—Cs1—H2A	85.8 (13)
O1^i—Cs1—N1	161.24 (11)	O2—Cs1—O2^iii	82.96 (13)
O1^ii—Cs1—N1	89.21 (11)	O2—Cs1—H2A	15.1 (3)
O1^i—Cs1—N1^iii	103.79 (11)	O2^iii—Cs1—H2A	75.8 (16)
O1^ii—Cs1—N1^iii	149.60 (11)	Cs1^iv—O1—Cs1^iii	106.67 (12)
O1—Cs1—N1^iii	85.10 (10)	Cs1—O1—Cs1^iv	154.85 (14)
O1—Cs1—C1	20.73 (11)	Cs1—O1—Cs1^iii	87.42 (10)
O1^i—Cs1—C1^i	20.53 (11)	Cs1—O1—C1	94.0 (3)
O1^ii—Cs1—C1^i	79.91 (12)	Cs1^iv—O1—C1	103.2 (3)
O1—Cs1—C1^i	132.72 (11)	Cs1^iii—O1—C1	101.2 (3)
O1^i—Cs1—C1^ii	80.42 (12)	Cs1—N1—Cs1^ii	84.45 (10)
O1^ii—Cs1—C1^ii	20.64 (11)	Cs1—N1—C1	94.1 (3)
O1—Cs1—C1^ii	113.54 (11)	Cs1^ii—N1—C1	115.2 (4)
O1^i—Cs1—C1	173.71 (11)	Cs1—N1—C5	130.0 (3)
O1^ii—Cs1—C1	106.57 (12)	Cs1^ii—N1—C5	109.4 (3)
O1^i—Cs1—C2^ii	72.64 (12)	C1—N1—C5	119.2 (5)
O1^ii—Cs1—C2^ii	39.81 (12)	Cs1^iv—C1—Cs1^iii	87.27 (13)
O1—Cs1—C2^ii	128.57 (12)	Cs1—C1—Cs1^iv	118.94 (15)
O1^i—Cs1—C2^i	39.34 (12)	Cs1—C1—Cs1^iii	75.78 (11)
O1^ii—Cs1—C2^i	71.31 (12)	Cs1—C1—O1	65.2 (3)
O1—Cs1—C2^i	115.43 (12)	Cs1^iv—C1—O1	56.3 (3)
O1—Cs1—O2	47.29 (12)	Cs1^iii—C1—O1	58.2 (3)
O1^i—Cs1—O2^iii	84.84 (13)	Cs1—C1—N1	64.1 (3)
O1^ii—Cs1—O2^iii	139.39 (12)	Cs1^iv—C1—N1	134.1 (4)
O1^i—Cs1—O2	113.65 (12)	Cs1^iii—C1—N1	132.2 (3)
O1^ii—Cs1—O2	75.49 (12)	Cs1—C1—C2	146.2 (4)
O1—Cs1—O2^iii	75.01 (13)	Cs1^iv—C1—C2	83.6 (3)
O1—Cs1—H2A	33.0 (7)	Cs1^iii—C1—C2	80.9 (4)
O1^i—Cs1—H2A	125.1 (13)	O1—C1—N1	119.3 (5)
O1^ii—Cs1—H2A	89.1 (8)	O1—C1—C2	120.9 (5)
N1—Cs1—N1^iii	87.71 (12)	N1—C1—C2	119.8 (5)
N1—Cs1—C1	21.89 (12)	Cs1^iii—C2—Cs1^iv	84.66 (13)
N1—Cs1—C1^i	163.05 (13)	Cs1^iii—C2—C1	76.5 (3)
N1^iii—Cs1—C1^i	108.23 (12)	Cs1^iv—C2—C1	74.0 (3)
N1—Cs1—C1^ii	80.84 (12)	Cs1^iii—C2—H2	62.1
N1^iii—Cs1—C1^ii	129.65 (12)	Cs1^iv—C2—H2	61.0
N1^iii—Cs1—C1	79.54 (12)	Cs1^iii—C2—C3	134.2 (4)
N1—Cs1—C2^ii	89.63 (13)	Cs1^iv—C2—C3	139.1 (4)
N1^iii—Cs1—C2^ii	109.90 (12)	C1—C2—H2	119.7
N1—Cs1—C2^i	141.01 (12)	C1—C2—C3	120.6 (6)
N1^iii—Cs1—C2^i	125.89 (12)	H2—C2—C3	119.7
N1—Cs1—O2	66.86 (12)	C2—C3—H3	120.5
N1—Cs1—O2^iii	113.44 (13)	C2—C3—C4	119.0 (6)
N1^iii—Cs1—O2^iii	68.20 (12)	H3—C3—C4	120.5
N1^iii—Cs1—O2	129.95 (12)	C3—C4—H4	120.7
N1—Cs1—H2A	59.7 (16)	C3—C4—C5	118.5 (6)
N1^iii—Cs1—H2A	115.0 (4)	H4—C4—C5	120.7
C1^i—Cs1—C1^ii	92.73 (13)	N1—C5—C4	122.9 (5)
C1—Cs1—C1^i	153.38 (9)	N1—C5—C6	115.9 (5)
C1—Cs1—C1^ii	101.68 (14)	C4—C5—C6	121.2 (6)
C1^i—Cs1—C2^ii	90.22 (13)	C5—C6—H6A	109.5
C1^ii—Cs1—C2^ii	22.55 (13)	C5—C6—H6B	109.5
C1—Cs1—C2^ii	111.49 (13)	C5—C6—H6C	109.5
C1^i—Cs1—C2^i	22.34 (13)	H6A—C6—H6B	109.5
C1^ii—Cs1—C2^i	89.19 (13)	H6A—C6—H6C	109.5
C1—Cs1—C2^i	134.45 (13)	H6B—C6—H6C	109.5
C1—Cs1—O2	60.66 (13)	H7A—C7—H7B	109.5
C1^i—Cs1—O2^iii	69.21 (14)	H7A—C7—H7C	109.5
C1^i—Cs1—O2	97.61 (13)	H7A—C7—O2	109.5
C1^ii—Cs1—O2^iii	159.20 (14)	H7B—C7—H7C	109.5
C1^ii—Cs1—O2	89.58 (13)	H7B—C7—O2	109.5
C1—Cs1—O2^iii	91.57 (14)	H7C—C7—O2	109.5
C1—Cs1—H2A	48.8 (12)	Cs1—O2—Cs1^ii	91.33 (13)
C1^i—Cs1—H2A	106.7 (15)	Cs1—O2—C7	117.8 (4)
C1^ii—Cs1—H2A	100.9 (12)	Cs1^ii—O2—C7	146.1 (4)
C2^ii—Cs1—C2^i	95.34 (13)	Cs1—O2—H2A	83 (7)
C2^ii—Cs1—O2^iii	156.42 (15)	Cs1^ii—O2—H2A	111 (7)
C2^ii—Cs1—O2	112.12 (13)	C7—O2—H2A	90 (7)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.84 (1)	1.85 (5)	2.609 (6)	150 (9)

(dmt29_6)

Crystal data

Cs^+·C6H6NO^−·C2H6O	F(000) = 1104
Mr = 574.19	Dx = 1.844 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.6376 (10) Å	Cell parameters from 9973 reflections
b = 24.980 (2) Å	θ = 2.4–28.2°
c = 7.2431 (6) Å	µ = 3.54 mm^−1
β = 100.7564 (11)°	T = 160 K
V = 2068.7 (3) Å^3	Needle, colourless
Z = 4	0.40 × 0.10 × 0.02 mm

Data collection

Bruker SMART 1K CCD diffractometer	4243 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.033
thin–slice ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan SADABS	h = −15→15
Tmin = 0.435, Tmax = 0.563	k = −32→32
18269 measured reflections	l = −9→9
5014 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0236P)^2 + 3.5254P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5014 reflections	Δρmax = 0.76 e Å^−3
226 parameters	Δρmin = −0.86 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00039 (8)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cs1	0.56862 (2)	0.42740 (2)	0.25243 (3)	0.02436 (7)
Cs2	0.60813 (2)	0.32213 (2)	0.77849 (3)	0.02667 (7)
O1	0.6394 (2)	0.30188 (9)	0.3731 (3)	0.0270 (5)
N1	0.7738 (2)	0.33596 (10)	0.2112 (4)	0.0210 (5)
C1	0.7479 (3)	0.30827 (11)	0.3595 (5)	0.0212 (6)
C2	0.8394 (3)	0.28671 (14)	0.4963 (5)	0.0286 (7)
H2	0.8212	0.2671	0.5996	0.034*
C3	0.9532 (3)	0.29390 (15)	0.4803 (5)	0.0342 (8)
H3	1.0144	0.2796	0.5724	0.041*
C4	0.9791 (3)	0.32247 (15)	0.3278 (5)	0.0312 (8)
H4	1.0579	0.3281	0.3142	0.037*
C5	0.8877 (3)	0.34230 (13)	0.1974 (5)	0.0246 (7)
C6	0.9098 (4)	0.37228 (16)	0.0273 (5)	0.0378 (9)
H6A	0.8889	0.3496	−0.0843	0.057*
H6B	0.9928	0.3819	0.0445	0.057*
H6C	0.8622	0.4049	0.0110	0.057*
O2	0.5462 (2)	0.45504 (9)	0.8236 (3)	0.0260 (5)
N2	0.7094 (2)	0.45109 (10)	0.6888 (4)	0.0210 (5)
C7	0.6507 (3)	0.47158 (12)	0.8187 (4)	0.0202 (6)
C8	0.7060 (3)	0.51065 (13)	0.9495 (5)	0.0247 (7)
H8	0.6655	0.5252	1.0403	0.030*
C9	0.8175 (3)	0.52716 (13)	0.9439 (5)	0.0276 (7)
H9	0.8544	0.5531	1.0310	0.033*
C10	0.8765 (3)	0.50583 (13)	0.8106 (5)	0.0259 (7)
H10	0.9540	0.5167	0.8051	0.031*
C11	0.8190 (3)	0.46827 (12)	0.6863 (5)	0.0222 (6)
C12	0.8786 (3)	0.44357 (15)	0.5390 (6)	0.0343 (8)
H12A	0.8650	0.4048	0.5348	0.051*
H12B	0.9628	0.4506	0.5707	0.051*
H12C	0.8467	0.4592	0.4161	0.051*
O3	0.4632 (3)	0.30977 (13)	0.0943 (4)	0.0425 (7)
H3A	0.525 (2)	0.3090 (18)	0.174 (5)	0.043 (14)*
C13	0.3681 (5)	0.2973 (3)	0.1800 (9)	0.093 (2)
H13A	0.3847	0.2623	0.2431	0.112*
H13B	0.3664	0.3242	0.2799	0.112*
C14	0.2593 (6)	0.2948 (4)	0.0752 (11)	0.103 (3)
H14A	0.2368	0.3301	0.0214	0.154*
H14B	0.2040	0.2836	0.1546	0.154*
H14C	0.2581	0.2687	−0.0263	0.154*
O4	0.4236 (3)	0.40245 (14)	0.5464 (4)	0.0449 (7)
H4A	0.465 (4)	0.4193 (18)	0.635 (5)	0.062 (17)*
C15	0.3039 (4)	0.4137 (2)	0.5399 (7)	0.0552 (13)
H15A	0.2612	0.4103	0.4088	0.066*
H15B	0.2955	0.4512	0.5804	0.066*
C16	0.2525 (6)	0.3782 (3)	0.6587 (9)	0.086 (2)
H16A	0.2532	0.3415	0.6110	0.128*
H16B	0.1716	0.3892	0.6587	0.128*
H16C	0.2976	0.3798	0.7871	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.02773 (12)	0.02366 (10)	0.02224 (11)	0.00389 (8)	0.00609 (8)	0.00135 (8)
Cs2	0.03420 (13)	0.02574 (11)	0.02137 (11)	0.00334 (8)	0.00851 (8)	0.00167 (8)
O1	0.0269 (13)	0.0278 (12)	0.0284 (13)	−0.0034 (10)	0.0110 (10)	−0.0002 (10)
N1	0.0265 (15)	0.0165 (12)	0.0204 (13)	−0.0013 (10)	0.0051 (11)	0.0001 (10)
C1	0.0293 (18)	0.0135 (13)	0.0220 (16)	−0.0011 (12)	0.0082 (13)	−0.0035 (11)
C2	0.036 (2)	0.0233 (15)	0.0279 (18)	0.0047 (14)	0.0108 (15)	0.0077 (14)
C3	0.035 (2)	0.0335 (19)	0.033 (2)	0.0126 (16)	0.0035 (16)	0.0080 (15)
C4	0.0243 (19)	0.0330 (18)	0.038 (2)	0.0027 (14)	0.0107 (15)	0.0014 (15)
C5	0.0306 (19)	0.0185 (14)	0.0259 (17)	−0.0019 (13)	0.0087 (14)	−0.0019 (12)
C6	0.037 (2)	0.043 (2)	0.035 (2)	−0.0050 (17)	0.0123 (17)	0.0110 (17)
O2	0.0228 (12)	0.0295 (12)	0.0268 (12)	−0.0019 (9)	0.0076 (9)	−0.0047 (10)
N2	0.0209 (14)	0.0201 (12)	0.0226 (14)	0.0010 (10)	0.0054 (11)	−0.0008 (10)
C7	0.0220 (16)	0.0184 (14)	0.0203 (15)	0.0006 (12)	0.0040 (12)	0.0020 (12)
C8	0.0304 (19)	0.0217 (15)	0.0224 (16)	0.0029 (13)	0.0065 (14)	−0.0039 (13)
C9	0.034 (2)	0.0229 (16)	0.0238 (17)	−0.0032 (14)	−0.0006 (14)	−0.0020 (13)
C10	0.0218 (17)	0.0261 (16)	0.0288 (18)	−0.0029 (13)	0.0025 (13)	−0.0002 (13)
C11	0.0234 (17)	0.0198 (14)	0.0237 (16)	0.0011 (12)	0.0048 (13)	0.0032 (12)
C12	0.030 (2)	0.0335 (19)	0.042 (2)	−0.0040 (15)	0.0132 (17)	−0.0102 (16)
O3	0.0315 (17)	0.065 (2)	0.0331 (16)	−0.0077 (14)	0.0103 (13)	−0.0011 (14)
C13	0.046 (4)	0.172 (8)	0.065 (4)	−0.038 (4)	0.019 (3)	−0.005 (4)
C14	0.051 (4)	0.175 (9)	0.087 (5)	−0.006 (4)	0.027 (4)	0.001 (5)
O4	0.0295 (16)	0.070 (2)	0.0359 (16)	−0.0066 (14)	0.0077 (13)	−0.0188 (15)
C15	0.050 (3)	0.047 (3)	0.061 (3)	0.004 (2)	−0.010 (2)	0.006 (2)
C16	0.083 (5)	0.094 (5)	0.090 (5)	−0.036 (4)	0.041 (4)	−0.030 (4)

Geometric parameters (Å, º)

Cs1—O1	3.317 (2)	C6—Cs2^i	3.845 (4)
Cs1—N1	3.358 (3)	C6—H6A	0.980
Cs1—C1	3.634 (3)	C6—H6B	0.980
Cs1—O2^i	3.145 (2)	C6—H6C	0.980
Cs1—O2^ii	3.231 (2)	O2—Cs1^iv	3.145 (2)
Cs1—N2	3.330 (3)	O2—Cs1^ii	3.231 (2)
Cs1—C7^ii	3.558 (3)	O2—C7	1.291 (4)
Cs1—C7^i	3.622 (3)	N2—C7	1.361 (4)
Cs1—C8^i	3.606 (3)	N2—C11	1.349 (4)
Cs1—C8^ii	3.606 (3)	C7—Cs1^ii	3.558 (3)
Cs1—O3	3.306 (3)	C7—Cs1^iv	3.622 (3)
Cs1—H3A	3.04 (4)	C7—C8	1.427 (4)
Cs1—O4	3.019 (3)	C8—Cs1^iv	3.606 (3)
Cs1—H4A	3.23 (5)	C8—Cs1^ii	3.606 (3)
Cs2—O1	3.067 (2)	C8—H8	0.950
Cs2—O1^iii	3.179 (2)	C8—C9	1.368 (5)
Cs2—N1^iv	3.377 (3)	C9—H9	0.950
Cs2—C1	3.718 (3)	C9—C10	1.392 (5)
Cs2—C1^iii	3.639 (3)	C10—H10	0.950
Cs2—C2	3.776 (4)	C10—C11	1.384 (5)
Cs2—C6^iv	3.845 (4)	C11—C12	1.508 (5)
Cs2—O2	3.426 (2)	C12—H12A	0.980
Cs2—N2	3.532 (3)	C12—H12B	0.980
Cs2—C7	3.770 (3)	C12—H12C	0.980
Cs2—O3^iv	3.100 (3)	O3—Cs2^i	3.100 (3)
Cs2—O4	3.180 (3)	O3—H3A	0.835 (10)
Cs2—H4A	3.02 (5)	O3—C13	1.401 (6)
O1—Cs2^v	3.179 (2)	C13—H13A	0.990
O1—C1	1.295 (4)	C13—H13B	0.990
N1—Cs2^i	3.377 (3)	C13—C14	1.351 (9)
N1—C1	1.358 (4)	C14—H14A	0.980
N1—C5	1.356 (4)	C14—H14B	0.980
C1—Cs2^v	3.639 (3)	C14—H14C	0.980
C1—C2	1.418 (5)	O4—H4A	0.839 (10)
C2—H2	0.950	O4—C15	1.414 (6)
C2—C3	1.363 (5)	C15—H15A	0.990
C3—H3	0.950	C15—H15B	0.990
C3—C4	1.395 (5)	C15—C16	1.441 (8)
C4—H4	0.950	C16—H16A	0.980
C4—C5	1.377 (5)	C16—H16B	0.980
C5—C6	1.504 (5)	C16—H16C	0.980
O1—Cs1—N1	40.08 (6)	O2—Cs2—O4	46.04 (7)
O1—Cs1—C1	20.84 (7)	O2—Cs2—H4A	30.8 (2)
O1—Cs1—O2^i	116.00 (6)	N2—Cs2—C7	21.16 (6)
O1—Cs1—O2^ii	168.08 (6)	N2—Cs2—O3^iv	118.21 (7)
O1—Cs1—N2	82.19 (6)	N2—Cs2—O4	62.80 (7)
O1—Cs1—C7^ii	147.63 (7)	N2—Cs2—H4A	52.0 (8)
O1—Cs1—C7^i	115.07 (6)	C7—Cs2—O3^iv	97.09 (8)
O1—Cs1—C8^i	126.08 (7)	C7—Cs2—O4	58.82 (7)
O1—Cs1—C8^ii	132.07 (7)	C7—Cs2—H4A	44.4 (4)
O1—Cs1—O3	46.28 (7)	O3^iv—Cs2—O4	92.65 (8)
O1—Cs1—H3A	32.1 (3)	O3^iv—Cs2—H4A	89.6 (10)
O1—Cs1—O4	76.29 (8)	O4—Cs2—H4A	15.3 (2)
O1—Cs1—H4A	80.1 (9)	Cs1—O1—Cs2	91.62 (6)
N1—Cs1—C1	21.94 (7)	Cs1—O1—Cs2^v	148.38 (9)
N1—Cs1—O2^i	89.46 (6)	Cs1—O1—C1	93.49 (17)
N1—Cs1—O2^ii	151.83 (6)	Cs2—O1—Cs2^v	109.75 (7)
N1—Cs1—N2	88.47 (6)	Cs2—O1—C1	110.1 (2)
N1—Cs1—C7^ii	166.53 (7)	Cs2^v—O1—C1	100.24 (17)
N1—Cs1—C7^i	79.80 (7)	Cs1—N1—Cs2^i	81.94 (6)
N1—Cs1—C8^i	86.25 (7)	Cs1—N1—C1	90.54 (18)
N1—Cs1—C8^ii	147.89 (7)	Cs1—N1—C5	130.37 (19)
N1—Cs1—O3	65.71 (7)	Cs2^i—N1—C1	120.6 (2)
N1—Cs1—H3A	54.4 (6)	Cs2^i—N1—C5	109.9 (2)
N1—Cs1—O4	115.01 (8)	C1—N1—C5	118.8 (3)
N1—Cs1—H4A	114.8 (9)	Cs1—C1—Cs2	77.09 (6)
C1—Cs1—O2^i	109.20 (7)	Cs1—C1—Cs2^v	118.49 (9)
C1—Cs1—O2^ii	169.56 (7)	Cs1—C1—O1	65.67 (16)
C1—Cs1—N2	77.41 (7)	Cs1—C1—N1	67.52 (17)
C1—Cs1—C7^ii	168.39 (7)	Cs1—C1—C2	141.8 (2)
C1—Cs1—C7^i	101.57 (7)	Cs2—C1—Cs2^v	87.96 (7)
C1—Cs1—C8^i	107.45 (7)	Cs2—C1—O1	50.78 (17)
C1—Cs1—C8^ii	150.23 (7)	Cs2^v—C1—O1	59.26 (15)
C1—Cs1—O3	60.47 (8)	Cs2—C1—N1	142.6 (2)
C1—Cs1—H3A	46.5 (3)	Cs2^v—C1—N1	119.1 (2)
C1—Cs1—O4	93.14 (8)	Cs2—C1—C2	81.4 (2)
C1—Cs1—H4A	93.3 (9)	Cs2^v—C1—C2	91.6 (2)
O2^i—Cs1—O2^ii	71.14 (7)	O1—C1—N1	119.1 (3)
O2^i—Cs1—N2	146.49 (6)	O1—C1—C2	121.0 (3)
O2^ii—Cs1—N2	96.60 (6)	N1—C1—C2	119.8 (3)
O2^i—Cs1—C7^ii	77.07 (7)	Cs2—C2—C1	76.79 (19)
O2^ii—Cs1—C7^ii	21.23 (6)	Cs2—C2—H2	53.7
O2^i—Cs1—C7^i	20.47 (7)	Cs2—C2—C3	144.8 (3)
O2^ii—Cs1—C7^i	75.10 (6)	C1—C2—H2	119.8
O2^i—Cs1—C8^i	40.26 (7)	C1—C2—C3	120.4 (3)
O2^ii—Cs1—C8^i	65.70 (7)	H2—C2—C3	119.8
O2^i—Cs1—C8^ii	66.51 (7)	C2—C3—H3	120.3
O2^ii—Cs1—C8^ii	39.97 (7)	C2—C3—C4	119.5 (3)
O2^i—Cs1—O3	84.03 (7)	H3—C3—C4	120.3
O2^ii—Cs1—O3	129.34 (7)	C3—C4—H4	120.9
O2^i—Cs1—H3A	92.8 (7)	C3—C4—C5	118.3 (3)
O2^ii—Cs1—H3A	143.5 (3)	H4—C4—C5	120.9
O2^i—Cs1—O4	141.99 (7)	N1—C5—C4	123.2 (3)
O2^ii—Cs1—O4	92.29 (8)	N1—C5—C6	115.9 (3)
O2^i—Cs1—H4A	152.4 (8)	C4—C5—C6	120.8 (3)
O2^ii—Cs1—H4A	89.7 (9)	Cs2^i—C6—C5	86.6 (2)
N2—Cs1—C7^ii	102.94 (7)	Cs2^i—C6—H6A	50.2
N2—Cs1—C7^i	127.33 (7)	Cs2^i—C6—H6B	158.6
N2—Cs1—C8^i	106.24 (7)	Cs2^i—C6—H6C	76.6
N2—Cs1—C8^ii	123.39 (7)	C5—C6—H6A	109.5
N2—Cs1—O3	124.88 (7)	C5—C6—H6B	109.5
N2—Cs1—H3A	112.7 (5)	C5—C6—H6C	109.5
N2—Cs1—O4	66.91 (7)	H6A—C6—H6B	109.5
N2—Cs1—H4A	52.6 (5)	H6A—C6—H6C	109.5
C7^ii—Cs1—C7^i	87.51 (7)	H6B—C6—H6C	109.5
C7^ii—Cs1—C8^i	83.72 (7)	Cs1^iv—O2—Cs1^ii	108.86 (7)
C7^ii—Cs1—C8^ii	22.97 (7)	Cs1^iv—O2—Cs2	84.34 (6)
C7^i—Cs1—C8^i	22.77 (7)	Cs1^ii—O2—Cs2	162.21 (8)
C7^i—Cs1—C8^ii	82.81 (7)	Cs1^iv—O2—C7	101.11 (19)
C7^ii—Cs1—O3	111.75 (8)	Cs1^ii—O2—C7	93.79 (18)
C7^i—Cs1—O3	96.38 (7)	Cs2—O2—C7	95.26 (18)
C7^ii—Cs1—H3A	125.0 (4)	Cs1—N2—Cs2	83.72 (6)
C7^i—Cs1—H3A	101.3 (9)	Cs1—N2—C7	120.1 (2)
C7^ii—Cs1—O4	76.60 (8)	Cs1—N2—C11	110.0 (2)
C7^i—Cs1—O4	161.34 (8)	Cs2—N2—C7	89.33 (17)
C7^ii—Cs1—H4A	78.2 (9)	Cs2—N2—C11	129.89 (19)
C7^i—Cs1—H4A	164.8 (9)	C7—N2—C11	119.1 (3)
C8^i—Cs1—C8^ii	88.05 (8)	Cs1^ii—C7—Cs1^iv	92.49 (7)
C8^i—Cs1—O3	118.67 (7)	Cs1^ii—C7—Cs2	127.64 (9)
C8^ii—Cs1—O3	89.85 (8)	Cs1^iv—C7—Cs2	73.33 (6)
C8^i—Cs1—H3A	121.7 (9)	Cs1^ii—C7—O2	64.98 (16)
C8^ii—Cs1—H3A	103.8 (3)	Cs1^iv—C7—O2	58.42 (16)
C8^i—Cs1—O4	156.64 (8)	Cs1^ii—C7—N2	127.2 (2)
C8^ii—Cs1—O4	78.75 (8)	Cs1^iv—C7—N2	137.1 (2)
C8^i—Cs1—H4A	146.9 (7)	Cs1^ii—C7—C8	80.43 (18)
C8^ii—Cs1—H4A	86.0 (8)	Cs1^iv—C7—C8	77.99 (19)
O3—Cs1—H3A	14.3 (3)	Cs2—C7—O2	64.80 (16)
O3—Cs1—O4	80.83 (8)	Cs2—C7—N2	69.51 (16)
O3—Cs1—H4A	93.9 (6)	Cs2—C7—C8	139.9 (2)
H3A—Cs1—O4	80.5 (9)	O2—C7—N2	119.7 (3)
H3A—Cs1—H4A	91.4 (11)	O2—C7—C8	120.7 (3)
O4—Cs1—H4A	15.0 (4)	N2—C7—C8	119.6 (3)
O1—Cs2—O1^iii	90.94 (5)	Cs1^iv—C8—Cs1^ii	91.95 (8)
O1—Cs2—N1^iv	139.12 (7)	Cs1^iv—C8—C7	79.24 (19)
O1^iii—Cs2—N1^iv	82.95 (6)	Cs1^ii—C8—C7	76.61 (19)
O1—Cs2—C1	19.09 (7)	Cs1^iv—C8—H8	57.7
O1—Cs2—C1^iii	82.95 (7)	Cs1^ii—C8—H8	66.4
O1^iii—Cs2—C1^iii	20.50 (7)	Cs1^iv—C8—C9	136.2 (2)
O1^iii—Cs2—C1	92.03 (6)	Cs1^ii—C8—C9	129.2 (2)
O1—Cs2—C2	38.68 (7)	C7—C8—H8	120.0
O1^iii—Cs2—C2	79.86 (7)	C7—C8—C9	119.9 (3)
O1—Cs2—C6^iv	103.98 (7)	H8—C8—C9	120.0
O1^iii—Cs2—C6^iv	99.14 (8)	C8—C9—H9	120.0
O1—Cs2—O2	108.41 (6)	C8—C9—C10	119.9 (3)
O1^iii—Cs2—O2	160.30 (6)	H9—C9—C10	120.0
O1—Cs2—N2	82.60 (6)	C9—C10—H10	121.0
O1^iii—Cs2—N2	154.14 (6)	C9—C10—C11	118.0 (3)
O1—Cs2—C7	101.53 (6)	H10—C10—C11	121.0
O1^iii—Cs2—C7	160.09 (7)	N2—C11—C10	123.4 (3)
O1—Cs2—O3^iv	150.21 (7)	N2—C11—C12	116.1 (3)
O1^iii—Cs2—O3^iv	78.46 (7)	C10—C11—C12	120.4 (3)
O1—Cs2—O4	77.71 (7)	Cs1—C12—C11	85.1 (2)
O1^iii—Cs2—O4	140.12 (7)	Cs1—C12—H12A	75.4
O1—Cs2—H4A	87.6 (8)	Cs1—C12—H12B	160.9
O1^iii—Cs2—H4A	153.1 (6)	Cs1—C12—H12C	52.5
N1^iv—Cs2—C1^iii	77.37 (7)	C11—C12—H12A	109.5
N1^iv—Cs2—C1	120.40 (7)	C11—C12—H12B	109.5
N1^iv—Cs2—C2	100.67 (7)	C11—C12—H12C	109.5
N1^iv—Cs2—C6^iv	38.58 (7)	H12A—C12—H12B	109.5
N1^iv—Cs2—O2	84.61 (6)	H12A—C12—H12C	109.5
N1^iv—Cs2—N2	85.70 (6)	H12B—C12—H12C	109.5
N1^iv—Cs2—C7	77.46 (6)	Cs1—O3—Cs2^i	87.10 (7)
N1^iv—Cs2—O3^iv	67.70 (7)	Cs1—O3—H3A	64 (3)
N1^iv—Cs2—O4	129.66 (7)	Cs1—O3—C13	108.4 (4)
N1^iv—Cs2—H4A	114.9 (3)	Cs2^i—O3—H3A	90 (3)
C1—Cs2—C1^iii	78.33 (7)	Cs2^i—O3—C13	158.8 (3)
C1—Cs2—C2	21.80 (7)	H3A—O3—C13	110 (3)
C1^iii—Cs2—C2	62.30 (7)	O3—C13—H13A	107.4
C1^iii—Cs2—C6^iv	82.79 (8)	O3—C13—H13B	107.4
C1—Cs2—C6^iv	84.99 (8)	O3—C13—C14	119.8 (6)
C1—Cs2—O2	107.46 (6)	H13A—C13—H13B	106.9
C1^iii—Cs2—O2	161.38 (7)	H13A—C13—C14	107.4
C1—Cs2—N2	73.92 (6)	H13B—C13—C14	107.4
C1^iii—Cs2—N2	133.76 (7)	C13—C14—H14A	109.5
C1—Cs2—C7	94.82 (6)	C13—C14—H14B	109.5
C1^iii—Cs2—C7	145.64 (7)	C13—C14—H14C	109.5
C1^iii—Cs2—O3^iv	94.61 (8)	H14A—C14—H14B	109.5
C1—Cs2—O3^iv	166.97 (7)	H14A—C14—H14C	109.5
C1—Cs2—O4	88.99 (7)	H14B—C14—H14C	109.5
C1^iii—Cs2—O4	152.52 (8)	Cs1—O4—Cs2	95.27 (8)
C1—Cs2—H4A	95.2 (9)	Cs1—O4—H4A	97 (4)
C1^iii—Cs2—H4A	167.7 (3)	Cs1—O4—C15	127.8 (3)
C2—Cs2—C6^iv	69.48 (8)	Cs2—O4—H4A	71 (4)
C2—Cs2—O2	117.55 (7)	Cs2—O4—C15	135.0 (3)
C2—Cs2—N2	79.53 (7)	H4A—O4—C15	110 (4)
C2—Cs2—C7	100.21 (7)	O4—C15—H15A	109.2
C2—Cs2—O3^iv	156.48 (8)	O4—C15—H15B	109.2
C2—Cs2—O4	109.93 (7)	O4—C15—C16	111.9 (5)
C2—Cs2—H4A	113.9 (10)	H15A—C15—H15B	107.9
C6^iv—Cs2—O2	80.17 (8)	H15A—C15—C16	109.2
C6^iv—Cs2—N2	58.82 (7)	H15B—C15—C16	109.2
C6^iv—Cs2—C7	62.98 (8)	C15—C16—H16A	109.5
C6^iv—Cs2—O3^iv	105.16 (8)	C15—C16—H16B	109.5
C6^iv—Cs2—O4	120.64 (8)	C15—C16—H16C	109.5
C6^iv—Cs2—H4A	107.2 (5)	H16A—C16—H16B	109.5
O2—Cs2—N2	38.45 (6)	H16A—C16—H16C	109.5
O2—Cs2—C7	19.94 (6)	H16B—C16—H16C	109.5
O2—Cs2—O3^iv	82.71 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.84 (1)	1.78 (1)	2.603 (4)	169 (5)
O4—H4A···O2	0.84 (1)	1.76 (1)	2.593 (4)	177 (6)