Download citation
Download citation
link to html
Structures having the unusual protonated 4-arsonoanilinium species, namely in the hydro­chloride salt, C6H9AsNO3+·Cl, (I), and the complex salts formed from the reaction of (4-amino­phenyl)­arsonic acid (p-arsanilic acid) with copper(II) sulfate, i.e. hexa­aqua­copper(II) bis­(4-arsonoanilinium) di­sulfate dihydrate, (C6H9AsNO3)2[Cu(H2O)6](SO4)2·2H2O, (II), with copper(II) chloride, i.e. poly[bis­(4-arsonoanilinium) [tetra-μ-chlorido-cuprate(II)]], {(C6H9AsNO3)2[CuCl4]}n, (III), and with cadmium chloride, i.e. poly[bis­(4-arsonoanilinium) [tetra-μ-chlorido-cadmate(II)]], {(C6H9AsNO3)2[CdCl4]}n, (IV), have been determined. In (II), the two 4-arsonoanilinium cations are accompanied by [Cu(H2O)6]2+ cations with sulfate anions. In the isotypic complex salts (III) and (IV), they act as counter-cations to the {[CuCl4]2−}n or {[CdCl4]2−}n anionic polymer sheets, respectively. In (II), the [Cu(H2O)6]2+ ion sits on a crystallographic centre of symmetry and displays a slightly distorted octahedral coordination geometry. The asymmetric unit for (II) contains, in addition to half the [Cu(H2O)6]2+ ion, one 4-arsonoanilinium cation, a sulfate dianion and a solvent water molecule. Extensive O—H...O and N—H...O hydrogen bonds link all the species, giving an overall three-dimensional structure. In (III), four of the chloride ligands are related by inversion [Cu—Cl = 2.2826 (8) and 2.2990 (9) Å], with the other two sites of the tetra­gonally distorted octa­hedral CuCl6 unit occupied by symmetry-generated Cl-atom donors [Cu—Cl = 2.9833 (9) Å], forming a two-dimensional coordination polymer network substructure lying parallel to (001). In the crystal, the polymer layers are linked across [001] by a number of bridging hydrogen bonds involving N—H...Cl inter­actions from head-to-head-linked As—O—H...O 4-arsonoanilinium cations. A three-dimensional network structure is formed. CdII compound (IV) is isotypic with CuII complex (III), but with the central CdCl6 complex repeat unit having a more regular M—Cl bond-length range [2.5232 (12)–2.6931 (10) Å] compared to that in (III). This series of compounds represents the first reported crystal structures having the protonated 4-arsono­anilinium species.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961700314X/ky3114sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961700314X/ky3114Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961700314X/ky3114IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961700314X/ky3114IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961700314X/ky3114IVsup5.hkl
Contains datablock IV

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S205322961700314X/ky3114Isup6.cml
Supplementary material

CCDC references: 1534722; 1534721; 1534720; 1534719

Computing details top

For all compounds, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015). Program(s) used to solve structure: SIR 92 (Altomare et al., 1993) for (I); SHELXS97 (Sheldrick, 2008) for (II), (III); SIR92 (Altomare et al., 1993) for (IV). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

(I) 4-Arsonoanilinium chloride top
Crystal data top
C6H9AsNO3+·ClF(000) = 504
Mr = 253.51Dx = 1.810 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1528 reflections
a = 16.6534 (8) Åθ = 4.4–29.2°
b = 7.4129 (3) ŵ = 3.91 mm1
c = 7.6073 (4) ÅT = 200 K
β = 97.795 (4)°Plate, colourless
V = 930.44 (8) Å30.40 × 0.40 × 0.15 mm
Z = 4
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
1820 independent reflections
Radiation source: Enhance (Mo) X-ray source1601 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.7°
ω scansh = 209
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
k = 89
Tmin = 0.66, Tmax = 0.98l = 99
3922 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0304P)2 + 0.3689P]
where P = (Fo2 + 2Fc2)/3
1820 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 0.44 e Å3
5 restraintsΔρmin = 0.48 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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 (Å2) top
xyzUiso*/Ueq
As10.37111 (2)0.53013 (4)0.52946 (4)0.0235 (1)
O110.43235 (13)0.4083 (3)0.6799 (3)0.0387 (8)
O120.41875 (13)0.6107 (3)0.3702 (3)0.0345 (7)
O130.32856 (15)0.6985 (3)0.6375 (3)0.0454 (8)
N40.08067 (16)0.0693 (3)0.2459 (3)0.0218 (8)
C10.28113 (17)0.3841 (4)0.4442 (3)0.0200 (8)
C20.28676 (18)0.1973 (4)0.4548 (4)0.0263 (9)
C30.22080 (19)0.0936 (4)0.3897 (4)0.0252 (9)
C40.15124 (17)0.1775 (3)0.3126 (3)0.0178 (8)
C50.14488 (18)0.3635 (3)0.2991 (4)0.0225 (8)
C60.21088 (18)0.4666 (4)0.3665 (4)0.0246 (9)
Cl10.05319 (5)0.22825 (9)0.51606 (9)0.0245 (2)
H20.335700.141600.506600.0310*
H30.223300.034200.398000.0300*
H50.096300.418600.244800.0270*
H60.208000.594400.359500.0300*
H110.4836 (13)0.400 (5)0.664 (5)0.0580*
H130.363 (2)0.748 (5)0.720 (4)0.0680*
H410.090 (2)0.014 (3)0.171 (3)0.0260*
H420.0631 (19)0.008 (3)0.330 (3)0.0260*
H430.0432 (15)0.135 (3)0.185 (3)0.0260*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
As10.0114 (2)0.0300 (2)0.0279 (2)0.0011 (1)0.0019 (1)0.0005 (1)
O110.0152 (12)0.0649 (15)0.0346 (12)0.0039 (11)0.0017 (10)0.0195 (11)
O120.0170 (12)0.0419 (12)0.0441 (13)0.0039 (10)0.0024 (10)0.0197 (11)
O130.0187 (13)0.0528 (15)0.0621 (16)0.0012 (11)0.0035 (11)0.0324 (13)
N40.0249 (15)0.0208 (13)0.0189 (12)0.0069 (11)0.0001 (10)0.0011 (10)
C10.0163 (15)0.0247 (14)0.0188 (13)0.0008 (12)0.0015 (11)0.0004 (12)
C20.0206 (17)0.0280 (15)0.0297 (15)0.0080 (12)0.0016 (13)0.0041 (13)
C30.0295 (18)0.0159 (13)0.0300 (15)0.0026 (12)0.0037 (13)0.0018 (12)
C40.0200 (15)0.0188 (13)0.0146 (12)0.0040 (11)0.0027 (11)0.0026 (11)
C50.0180 (15)0.0214 (14)0.0261 (14)0.0030 (12)0.0039 (12)0.0027 (12)
C60.0186 (16)0.0177 (13)0.0363 (16)0.0016 (12)0.0005 (13)0.0016 (12)
Cl10.0315 (4)0.0200 (3)0.0212 (3)0.0009 (3)0.0009 (3)0.0032 (3)
Geometric parameters (Å, º) top
As1—O111.688 (2)C1—C21.390 (4)
As1—O121.648 (2)C1—C61.380 (4)
As1—O131.701 (2)C2—C31.377 (4)
As1—C11.891 (3)C3—C41.374 (4)
O11—H110.88 (2)C4—C51.386 (3)
O13—H130.87 (3)C5—C61.379 (4)
N4—C41.456 (4)C2—H20.9500
N4—H410.87 (2)C3—H30.9500
N4—H420.87 (2)C5—H50.9500
N4—H430.87 (2)C6—H60.9500
O11—As1—O12112.68 (11)C2—C1—C6120.9 (3)
O11—As1—O13108.54 (11)C1—C2—C3119.4 (3)
O11—As1—C1107.71 (11)C2—C3—C4119.1 (3)
O12—As1—O13111.29 (11)N4—C4—C3119.6 (2)
O12—As1—C1113.18 (11)N4—C4—C5118.2 (2)
O13—As1—C1102.89 (12)C3—C4—C5122.2 (3)
As1—O11—H11117 (2)C4—C5—C6118.4 (3)
As1—O13—H13112 (2)C1—C6—C5120.0 (3)
H42—N4—H43113 (3)C1—C2—H2120.00
H41—N4—H42103 (2)C3—C2—H2120.00
H41—N4—H43103 (2)C2—C3—H3120.00
C4—N4—H41114 (2)C4—C3—H3120.00
C4—N4—H42111.6 (18)C4—C5—H5121.00
C4—N4—H43111.3 (15)C6—C5—H5121.00
As1—C1—C2120.4 (2)C1—C6—H6120.00
As1—C1—C6118.7 (2)C5—C6—H6120.00
O11—As1—C1—C222.9 (2)As1—C1—C6—C5178.4 (2)
O11—As1—C1—C6159.1 (2)C2—C1—C6—C50.4 (4)
O12—As1—C1—C2102.3 (2)C1—C2—C3—C41.2 (4)
O12—As1—C1—C675.7 (2)C2—C3—C4—N4179.0 (3)
O13—As1—C1—C2137.5 (2)C2—C3—C4—C50.5 (4)
O13—As1—C1—C644.5 (2)N4—C4—C5—C6178.3 (3)
As1—C1—C2—C3179.1 (2)C3—C4—C5—C60.3 (4)
C6—C1—C2—C31.2 (4)C4—C5—C6—C10.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O12i0.88 (2)1.68 (2)2.563 (3)178 (5)
O13—H13···O12ii0.87 (3)1.73 (3)2.582 (3)167 (4)
N4—H41···Cl1iii0.87 (2)2.29 (2)3.073 (2)151 (3)
N4—H42···Cl10.87 (2)2.27 (2)3.091 (2)158 (2)
N4—H43···Cl1iv0.87 (2)2.30 (2)3.160 (3)170 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+3/2, z+1/2; (iii) x, y1/2, z1/2; (iv) x, y+1/2, z+1/2.
(II) Hexaaquacopper(II) bis(4-arsonoanilinium) disulfate dihydrate top
Crystal data top
(C6H9AsNO3)2[Cu(H2O)6](SO4)2·2H2OF(000) = 846
Mr = 835.92Dx = 1.915 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2421 reflections
a = 15.0784 (6) Åθ = 3.8–29.0°
b = 11.2302 (4) ŵ = 3.26 mm1
c = 8.6756 (4) ÅT = 200 K
β = 99.305 (4)°Plate, colourless
V = 1449.74 (10) Å30.30 × 0.25 × 0.08 mm
Z = 2
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
2846 independent reflections
Radiation source: Enhance (Mo) X-ray source2518 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.3°
ω scansh = 1817
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
k = 1312
Tmin = 0.670, Tmax = 0.980l = 910
6196 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0274P)2 + 0.3694P]
where P = (Fo2 + 2Fc2)/3
2846 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.36 e Å3
13 restraintsΔρmin = 0.51 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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 (Å2) top
xyzUiso*/Ueq
As10.33980 (2)0.10571 (2)0.24157 (3)0.0172 (1)
O110.36399 (14)0.0443 (2)0.4232 (2)0.0276 (7)
O120.26786 (13)0.02573 (18)0.1225 (2)0.0249 (6)
O130.30451 (14)0.24789 (18)0.2623 (3)0.0305 (7)
N40.71564 (17)0.1526 (2)0.0761 (3)0.0174 (7)
C10.45558 (19)0.1223 (2)0.1863 (3)0.0165 (8)
C20.4777 (2)0.2222 (2)0.1063 (3)0.0205 (8)
C30.5634 (2)0.2323 (2)0.0701 (3)0.0213 (9)
C40.62545 (18)0.1425 (2)0.1130 (3)0.0158 (8)
C50.6026 (2)0.0410 (2)0.1881 (3)0.0218 (9)
C60.5178 (2)0.0313 (3)0.2253 (3)0.0222 (9)
Cu10.000000.000000.000000.0135 (1)
O1W0.01471 (14)0.10426 (18)0.2269 (2)0.0210 (6)
O2W0.10719 (14)0.0857 (2)0.0346 (2)0.0246 (7)
O3W0.07864 (16)0.13263 (18)0.1006 (2)0.0251 (7)
S10.83825 (5)0.41681 (6)0.01779 (7)0.0152 (2)
O10.89949 (14)0.33415 (17)0.0779 (2)0.0255 (7)
O20.85590 (14)0.53998 (16)0.0346 (2)0.0229 (6)
O30.74402 (14)0.38634 (16)0.0044 (2)0.0222 (6)
O40.84847 (14)0.40444 (18)0.1831 (2)0.0232 (6)
O4W0.13231 (15)0.30042 (17)0.2021 (2)0.0217 (7)
H20.434500.282900.076600.0250*
H30.579700.300600.016200.0260*
H50.645200.021300.213600.0260*
H60.501600.037700.277700.0270*
H110.3229 (18)0.001 (2)0.445 (4)0.0330*
H130.2483 (13)0.260 (3)0.246 (4)0.0330*
H410.7543 (18)0.137 (3)0.163 (3)0.0270*
H420.724 (2)0.2267 (18)0.044 (3)0.0270*
H430.720 (2)0.102 (2)0.002 (3)0.0270*
H11W0.0329 (16)0.105 (3)0.263 (4)0.0330*
H12W0.0537 (19)0.082 (3)0.296 (3)0.0330*
H21W0.110 (2)0.116 (3)0.123 (3)0.0330*
H22W0.155 (2)0.063 (3)0.018 (3)0.0330*
H31W0.073 (2)0.195 (2)0.050 (3)0.0330*
H32W0.084 (2)0.146 (3)0.197 (2)0.0330*
H41W0.0939 (18)0.249 (2)0.182 (4)0.0330*
H42W0.126 (2)0.343 (3)0.125 (3)0.0330*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
As10.0116 (2)0.0185 (2)0.0209 (2)0.0023 (1)0.0008 (1)0.0012 (1)
O110.0194 (12)0.0386 (13)0.0240 (11)0.0124 (10)0.0014 (9)0.0042 (10)
O120.0132 (11)0.0298 (11)0.0300 (11)0.0017 (9)0.0012 (9)0.0078 (9)
O130.0149 (11)0.0217 (11)0.0546 (15)0.0006 (10)0.0050 (11)0.0056 (10)
N40.0141 (13)0.0190 (12)0.0186 (12)0.0008 (11)0.0010 (10)0.0005 (10)
C10.0126 (14)0.0174 (14)0.0185 (14)0.0032 (11)0.0009 (12)0.0011 (11)
C20.0153 (15)0.0178 (14)0.0275 (15)0.0040 (12)0.0012 (12)0.0040 (12)
C30.0205 (16)0.0170 (14)0.0259 (15)0.0008 (12)0.0021 (13)0.0075 (12)
C40.0115 (14)0.0209 (14)0.0138 (13)0.0037 (12)0.0016 (11)0.0017 (11)
C50.0172 (16)0.0189 (14)0.0282 (16)0.0049 (12)0.0003 (13)0.0061 (12)
C60.0212 (17)0.0186 (14)0.0261 (16)0.0037 (12)0.0021 (13)0.0057 (12)
Cu10.0118 (2)0.0143 (2)0.0142 (2)0.0003 (2)0.0012 (2)0.0011 (2)
O1W0.0153 (11)0.0313 (12)0.0162 (10)0.0020 (10)0.0017 (8)0.0031 (9)
O2W0.0157 (11)0.0363 (13)0.0212 (11)0.0046 (10)0.0013 (9)0.0084 (9)
O3W0.0355 (14)0.0204 (11)0.0165 (10)0.0043 (10)0.0043 (10)0.0003 (9)
S10.0142 (4)0.0175 (3)0.0140 (3)0.0002 (3)0.0022 (3)0.0002 (3)
O10.0300 (13)0.0258 (11)0.0191 (10)0.0114 (10)0.0010 (9)0.0011 (9)
O20.0261 (12)0.0175 (10)0.0227 (10)0.0056 (9)0.0028 (9)0.0019 (8)
O30.0172 (11)0.0192 (10)0.0321 (12)0.0013 (9)0.0099 (9)0.0017 (8)
O40.0169 (11)0.0391 (12)0.0138 (10)0.0023 (9)0.0027 (8)0.0027 (8)
O4W0.0212 (12)0.0193 (11)0.0239 (11)0.0019 (9)0.0012 (9)0.0001 (9)
Geometric parameters (Å, º) top
Cu1—O3W2.013 (2)O2W—H21W0.85 (3)
Cu1—O1W2.2702 (18)O3W—H31W0.82 (2)
Cu1—O2W1.946 (2)O3W—H32W0.841 (18)
Cu1—O3Wi2.013 (2)O4W—H42W0.82 (3)
Cu1—O1Wi2.2702 (18)O4W—H41W0.82 (3)
Cu1—O2Wi1.946 (2)N4—C41.451 (4)
As1—O111.7046 (18)N4—H420.89 (2)
As1—O121.6395 (19)N4—H430.90 (2)
As1—O131.702 (2)N4—H410.89 (3)
As1—C11.893 (3)C1—C21.388 (3)
S1—O41.4736 (19)C1—C61.392 (4)
S1—O21.4668 (19)C2—C31.383 (4)
S1—O31.484 (2)C3—C41.385 (4)
S1—O11.468 (2)C4—C51.384 (3)
O11—H110.83 (3)C5—C61.373 (4)
O13—H130.85 (2)C2—H20.9500
O1W—H12W0.81 (3)C3—H30.9500
O1W—H11W0.83 (3)C5—H50.9500
O2W—H22W0.83 (3)C6—H60.9500
O11—As1—O12112.44 (10)H31W—O3W—H32W111 (3)
O11—As1—O13107.80 (11)Cu1—O3W—H32W121 (2)
O11—As1—C1101.87 (11)Cu1—O3W—H31W113.3 (19)
O12—As1—O13113.22 (11)H41W—O4W—H42W105 (3)
O12—As1—C1115.95 (10)H42—N4—H43109 (2)
O13—As1—C1104.56 (10)H41—N4—H42110 (3)
O2W—Cu1—O3W90.74 (9)H41—N4—H43113 (3)
O1Wi—Cu1—O2W95.08 (8)C4—N4—H41107.8 (17)
O2W—Cu1—O2Wi180.00C4—N4—H42109.0 (19)
O2W—Cu1—O3Wi89.26 (9)C4—N4—H43107.7 (19)
O1Wi—Cu1—O3W92.15 (7)As1—C1—C2120.8 (2)
O3W—Cu1—O3Wi180.00As1—C1—C6118.6 (2)
O1W—Cu1—O1Wi180.00C2—C1—C6120.5 (3)
O1W—Cu1—O2W84.92 (8)C1—C2—C3119.3 (2)
O1W—Cu1—O3W87.85 (7)C2—C3—C4119.7 (2)
O3—S1—O4107.85 (11)N4—C4—C3120.0 (2)
O2—S1—O4110.38 (11)N4—C4—C5118.8 (2)
O1—S1—O3109.42 (11)C3—C4—C5121.2 (3)
O1—S1—O4109.60 (12)C4—C5—C6119.2 (3)
O1—S1—O2110.79 (11)C1—C6—C5120.1 (3)
O2—S1—O3108.74 (12)C1—C2—H2120.00
As1—O11—H11113 (2)C3—C2—H2120.00
As1—O13—H13117 (2)C2—C3—H3120.00
H11W—O1W—H12W107 (3)C4—C3—H3120.00
Cu1—O1W—H12W116 (2)C4—C5—H5120.00
Cu1—O1W—H11W111 (2)C6—C5—H5120.00
H21W—O2W—H22W117 (3)C1—C6—H6120.00
Cu1—O2W—H22W116 (2)C5—C6—H6120.00
Cu1—O2W—H21W120 (2)
O11—As1—C1—C2140.8 (2)As1—C1—C6—C5179.4 (2)
O11—As1—C1—C640.3 (2)C2—C1—C6—C51.6 (4)
O12—As1—C1—C296.8 (2)C1—C2—C3—C40.5 (4)
O12—As1—C1—C682.2 (2)C2—C3—C4—N4179.7 (2)
O13—As1—C1—C228.6 (2)C2—C3—C4—C51.7 (4)
O13—As1—C1—C6152.4 (2)N4—C4—C5—C6179.2 (2)
As1—C1—C2—C3178.93 (19)C3—C4—C5—C62.3 (4)
C6—C1—C2—C32.1 (4)C4—C5—C6—C10.6 (4)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O3ii0.83 (3)1.76 (3)2.582 (3)167 (3)
O13—H13···O4W0.85 (2)1.79 (2)2.631 (3)174 (3)
O1W—H11W···O4iii0.83 (3)1.92 (3)2.745 (3)171 (4)
O1W—H12W···O2ii0.81 (3)1.90 (3)2.703 (3)176 (3)
O2W—H21W···O4Wiv0.85 (3)1.86 (3)2.698 (3)170 (3)
O2W—H22W···O120.83 (3)1.84 (3)2.667 (3)173 (3)
O3W—H31W···O1v0.82 (2)2.00 (2)2.792 (3)161 (3)
O3W—H32W···O1vi0.84 (2)1.94 (2)2.780 (2)176 (4)
O4W—H41W···O1W0.82 (3)2.09 (3)2.858 (3)157 (3)
O4W—H42W···O2vii0.82 (3)1.96 (3)2.753 (3)164 (3)
N4—H41···O4viii0.89 (3)1.85 (3)2.726 (3)169 (3)
N4—H42···O30.89 (2)1.88 (2)2.767 (3)175 (2)
N4—H43···O12ix0.90 (2)1.80 (2)2.680 (3)166 (2)
C2—H2···O11iv0.952.493.385 (3)157
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iii) x1, y+1/2, z+1/2; (iv) x, y+1/2, z1/2; (v) x1, y, z; (vi) x1, y+1/2, z1/2; (vii) x+1, y+1, z; (viii) x, y+1/2, z+1/2; (ix) x+1, y, z.
(III) Poly[bis(4-arsonoanilinium) [tetra-µ-chlorido-cuprate(II)]] top
Crystal data top
(C6H9AsNO3)2[CuCl4]F(000) = 1260
Mr = 641.47Dx = 2.057 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1633 reflections
a = 7.6315 (4) Åθ = 3.9–29.0°
b = 7.1244 (4) ŵ = 4.77 mm1
c = 38.0925 (15) ÅT = 200 K
V = 2071.08 (18) Å3Plate, green
Z = 40.25 × 0.25 × 0.04 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
2028 independent reflections
Radiation source: Enhance (Mo) X-ray source1715 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = 99
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
k = 38
Tmin = 0.544, Tmax = 0.980l = 4628
6065 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.0415P)2 + 0.2932P]
where P = (Fo2 + 2Fc2)/3
2028 reflections(Δ/σ)max = 0.001
139 parametersΔρmax = 0.42 e Å3
5 restraintsΔρmin = 0.57 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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 (Å2) top
xyzUiso*/Ueq
Cu10.500000.500000.500000.0224 (2)
Cl10.54832 (12)0.52358 (15)0.44103 (2)0.0294 (3)
Cl20.70111 (12)0.73489 (12)0.50945 (3)0.0288 (3)
As11.05548 (5)0.75093 (6)0.29143 (1)0.0228 (1)
O111.2663 (3)0.8193 (4)0.28480 (7)0.0352 (9)
O120.9644 (3)0.6341 (4)0.25899 (6)0.0336 (9)
O130.9462 (4)0.9566 (4)0.29820 (8)0.0363 (10)
N40.9665 (5)0.4774 (5)0.44152 (9)0.0291 (11)
C11.0413 (4)0.6402 (6)0.33687 (9)0.0226 (11)
C21.1575 (5)0.6990 (6)0.36228 (9)0.0318 (14)
C31.1353 (5)0.6432 (6)0.39646 (9)0.0296 (11)
C40.9985 (5)0.5270 (5)0.40483 (10)0.0244 (11)
C50.8857 (5)0.4604 (6)0.37931 (10)0.0360 (13)
C60.9080 (5)0.5174 (6)0.34507 (10)0.0334 (13)
H21.252900.778100.356100.0380*
H31.214000.684700.414100.0360*
H50.793900.376300.385300.0430*
H60.832000.472300.327200.0400*
H111.321 (5)0.750 (5)0.2708 (11)0.0530*
H130.961 (6)1.033 (6)0.2812 (10)0.0550*
H410.985 (5)0.356 (3)0.4438 (11)0.0350*
H421.046 (4)0.530 (6)0.4545 (10)0.0350*
H430.859 (3)0.506 (5)0.4486 (10)0.0350*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0255 (3)0.0225 (4)0.0191 (3)0.0066 (3)0.0005 (3)0.0006 (3)
Cl10.0326 (5)0.0355 (6)0.0200 (5)0.0028 (4)0.0018 (4)0.0006 (4)
Cl20.0300 (5)0.0261 (5)0.0302 (5)0.0094 (4)0.0015 (4)0.0001 (4)
As10.0241 (2)0.0295 (3)0.0149 (2)0.0019 (2)0.0007 (1)0.0009 (2)
O110.0292 (15)0.0446 (19)0.0319 (15)0.0032 (14)0.0086 (12)0.0056 (14)
O120.0379 (15)0.0431 (19)0.0198 (14)0.0001 (13)0.0064 (11)0.0016 (13)
O130.0402 (16)0.0367 (19)0.0321 (15)0.0121 (13)0.0116 (13)0.0076 (14)
N40.0339 (18)0.033 (2)0.0204 (17)0.0044 (16)0.0026 (14)0.0052 (16)
C10.0260 (18)0.024 (2)0.0177 (18)0.0011 (15)0.0012 (14)0.0035 (16)
C20.033 (2)0.039 (3)0.0234 (19)0.0129 (18)0.0010 (16)0.0047 (18)
C30.033 (2)0.034 (2)0.0219 (18)0.0086 (18)0.0082 (16)0.0007 (18)
C40.0273 (19)0.025 (2)0.0208 (19)0.0033 (16)0.0045 (15)0.0024 (16)
C50.036 (2)0.048 (3)0.0240 (18)0.020 (2)0.0017 (18)0.0030 (19)
C60.032 (2)0.047 (3)0.0212 (18)0.0145 (19)0.0070 (17)0.0005 (19)
Geometric parameters (Å, º) top
Cu1—Cl2i2.2990 (9)N4—H410.88 (2)
Cu1—Cl2ii2.9833 (9)N4—H420.87 (4)
Cu1—Cl1i2.2826 (8)N4—H430.89 (3)
Cu1—Cl12.2826 (8)C1—C21.378 (5)
Cu1—Cl22.2990 (9)C1—C61.378 (5)
Cu1—Cl2iii2.9833 (9)C2—C31.372 (5)
As1—O121.644 (2)C3—C41.370 (5)
As1—O131.706 (3)C4—C51.383 (5)
As1—C11.905 (4)C5—C61.377 (5)
As1—O111.700 (2)C2—H20.9500
O11—H110.84 (4)C3—H30.9500
O13—H130.85 (4)C5—H50.9500
N4—C41.462 (5)C6—H60.9500
O11—As1—C1107.90 (13)C4—N4—H42109 (2)
O11—As1—O12115.70 (12)C4—N4—H43113 (2)
O11—As1—O13103.83 (14)As1—C1—C2118.4 (3)
O13—As1—C1100.98 (16)As1—C1—C6120.7 (3)
O12—As1—O13109.99 (14)C2—C1—C6120.6 (3)
O12—As1—C1116.69 (15)C1—C2—C3119.9 (4)
Cl1—Cu1—Cl289.58 (4)C2—C3—C4119.4 (4)
Cl2—Cu1—Cl2i180.00N4—C4—C3119.7 (3)
Cl2—Cu1—Cl2ii86.07 (3)N4—C4—C5119.0 (3)
Cl1i—Cu1—Cl2iii92.40 (3)C3—C4—C5121.2 (4)
Cl2i—Cu1—Cl2ii93.93 (3)C4—C5—C6119.2 (4)
Cl1—Cu1—Cl2i90.42 (4)C1—C6—C5119.6 (4)
Cl1—Cu1—Cl2iii87.60 (3)C1—C2—H2120.00
Cl1—Cu1—Cl1i180.00C3—C2—H2120.00
Cu1—Cl2—Cu1iv162.25 (5)C2—C3—H3120.00
As1—O11—H11113 (3)C4—C3—H3120.00
As1—O13—H13112 (3)C4—C5—H5120.00
H42—N4—H43112 (3)C6—C5—H5120.00
H41—N4—H42105 (4)C1—C6—H6120.00
H41—N4—H43110 (3)C5—C6—H6120.00
C4—N4—H41108 (3)
O11—As1—C1—C228.1 (4)As1—C1—C6—C5170.7 (3)
O11—As1—C1—C6157.8 (3)C2—C1—C6—C53.2 (6)
O12—As1—C1—C2160.4 (3)C1—C2—C3—C40.9 (6)
O12—As1—C1—C625.6 (4)C2—C3—C4—N4175.7 (4)
O13—As1—C1—C280.4 (3)C2—C3—C4—C52.0 (6)
O13—As1—C1—C693.6 (3)N4—C4—C5—C6175.5 (4)
As1—C1—C2—C3170.5 (3)C3—C4—C5—C62.3 (6)
C6—C1—C2—C33.5 (6)C4—C5—C6—C10.3 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y1/2, z; (iii) x1/2, y+3/2, z+1; (iv) x+1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O12v0.84 (4)1.78 (4)2.609 (4)170 (3)
O13—H13···O12vi0.85 (4)1.79 (4)2.610 (4)162 (4)
N4—H41···Cl1ii0.88 (2)2.38 (2)3.235 (4)163 (4)
N4—H42···Cl2iv0.87 (4)2.47 (4)3.301 (4)161 (3)
N4—H43···Cl10.89 (3)2.39 (2)3.208 (4)153 (3)
C6—H6···O13ii0.952.403.268 (5)152
Symmetry codes: (ii) x+3/2, y1/2, z; (iv) x+1/2, y+3/2, z+1; (v) x+1/2, y, z+1/2; (vi) x+2, y+1/2, z+1/2.
(IV) Poly[bis(4-arsonoanilinium) [tetra-µ-chlorido-cadmate(II)]] top
Crystal data top
(C6H9AsNO3)2[CdCl4]F(000) = 1336
Mr = 690.32Dx = 2.168 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1959 reflections
a = 7.5525 (4) Åθ = 3.9–28.7°
b = 7.2578 (3) ŵ = 4.67 mm1
c = 38.5872 (17) ÅT = 200 K
V = 2115.14 (17) Å3Plate, colourless
Z = 40.41 × 0.25 × 0.10 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
2070 independent reflections
Radiation source: ENHANCE (Mo) X-ray source1778 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = 96
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015
k = 87
Tmin = 0.485, Tmax = 0.980l = 4447
5452 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0265P)2]
where P = (Fo2 + 2Fc2)/3
2070 reflections(Δ/σ)max = 0.001
139 parametersΔρmax = 0.62 e Å3
5 restraintsΔρmin = 0.50 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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 (Å2) top
xyzUiso*/Ueq
Cd10.500000.500000.500000.0145 (1)
Cl10.55662 (14)0.52125 (14)0.43568 (3)0.0211 (3)
Cl20.70634 (14)0.79615 (13)0.50986 (3)0.0194 (3)
As11.05703 (6)0.75535 (6)0.29043 (1)0.0155 (1)
O111.2690 (4)0.8254 (4)0.28422 (7)0.0237 (10)
O120.9688 (4)0.6397 (4)0.25798 (7)0.0222 (9)
O130.9450 (4)0.9568 (4)0.29732 (8)0.0251 (10)
N40.9693 (5)0.4583 (5)0.43687 (9)0.0203 (11)
C11.0425 (6)0.6420 (6)0.33478 (9)0.0161 (11)
C21.1509 (6)0.7069 (6)0.36094 (10)0.0227 (14)
C31.1299 (6)0.6438 (6)0.39430 (10)0.0213 (12)
C41.0021 (5)0.5170 (5)0.40065 (10)0.0160 (12)
C50.8963 (6)0.4450 (6)0.37506 (11)0.0253 (16)
C60.9169 (6)0.5087 (6)0.34161 (10)0.0233 (14)
H21.240100.795200.355900.0270*
H31.203300.688000.412500.0260*
H50.810700.353200.380300.0310*
H60.845300.461300.323400.0280*
H111.331 (6)0.758 (5)0.2703 (10)0.0360*
H130.952 (6)1.034 (5)0.2798 (9)0.0380*
H410.974 (6)0.337 (3)0.4383 (12)0.0240*
H421.048 (5)0.515 (5)0.4508 (10)0.0240*
H430.858 (3)0.492 (5)0.4422 (11)0.0240*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0138 (2)0.0150 (2)0.0146 (2)0.0006 (2)0.0006 (2)0.0013 (2)
Cl10.0220 (6)0.0257 (6)0.0155 (5)0.0001 (4)0.0018 (4)0.0001 (4)
Cl20.0191 (5)0.0182 (5)0.0210 (5)0.0071 (4)0.0016 (4)0.0006 (4)
As10.0148 (2)0.0205 (2)0.0112 (2)0.0011 (2)0.0003 (2)0.0006 (2)
O110.0169 (17)0.0326 (18)0.0215 (15)0.0013 (14)0.0061 (13)0.0052 (14)
O120.0217 (17)0.0261 (16)0.0187 (15)0.0003 (14)0.0056 (13)0.0027 (13)
O130.0287 (19)0.0232 (17)0.0233 (16)0.0094 (14)0.0066 (15)0.0043 (13)
N40.019 (2)0.027 (2)0.0149 (18)0.0003 (17)0.0016 (16)0.0017 (16)
C10.020 (2)0.017 (2)0.0113 (19)0.0024 (18)0.0014 (17)0.0020 (16)
C20.024 (3)0.027 (2)0.017 (2)0.011 (2)0.0014 (19)0.0017 (18)
C30.025 (2)0.025 (2)0.014 (2)0.006 (2)0.0034 (18)0.0014 (18)
C40.016 (2)0.015 (2)0.017 (2)0.0051 (17)0.0032 (18)0.0002 (16)
C50.021 (3)0.033 (3)0.022 (2)0.014 (2)0.001 (2)0.002 (2)
C60.021 (2)0.034 (3)0.015 (2)0.007 (2)0.0064 (19)0.0040 (19)
Geometric parameters (Å, º) top
Cd1—Cl2i2.6820 (10)N4—H410.88 (2)
Cd1—Cl2ii2.6931 (10)N4—H420.90 (4)
Cd1—Cl1i2.5232 (12)N4—H430.90 (3)
Cd1—Cl12.5232 (12)C1—C21.382 (6)
Cd1—Cl22.6820 (10)C1—C61.380 (6)
Cd1—Cl2iii2.6931 (10)C2—C31.376 (6)
As1—O111.697 (3)C3—C41.356 (6)
As1—O121.648 (3)C4—C51.374 (6)
As1—O131.710 (3)C5—C61.380 (6)
As1—C11.902 (4)C2—H20.9500
O11—H110.86 (4)C3—H30.9500
O13—H130.88 (4)C5—H50.9500
N4—C41.482 (5)C6—H60.9500
Cl1—Cd1—Cl289.55 (3)C4—N4—H41110 (3)
Cl1—Cd1—Cl2iii88.11 (3)C4—N4—H42109 (2)
Cl1—Cd1—Cl1i180.00C4—N4—H43107 (3)
Cl1—Cd1—Cl2i90.45 (3)As1—C1—C2118.4 (3)
Cl1—Cd1—Cl2ii91.89 (3)As1—C1—C6121.0 (3)
Cl2—Cd1—Cl2iii93.34 (3)C2—C1—C6120.4 (4)
Cl1i—Cd1—Cl290.45 (3)C1—C2—C3120.1 (4)
Cl2—Cd1—Cl2i180.00C2—C3—C4118.5 (4)
Cl2—Cd1—Cl2ii86.66 (3)N4—C4—C3119.0 (3)
O11—As1—C1108.13 (17)N4—C4—C5118.1 (3)
O11—As1—O12115.27 (14)C3—C4—C5122.9 (4)
O11—As1—O13103.45 (14)C4—C5—C6118.7 (4)
O13—As1—C1101.62 (17)C1—C6—C5119.4 (4)
O12—As1—O13110.70 (15)C1—C2—H2120.00
O12—As1—C1116.10 (16)C3—C2—H2120.00
Cd1—Cl2—Cd1iv154.00 (4)C2—C3—H3121.00
As1—O11—H11115 (3)C4—C3—H3121.00
As1—O13—H13113 (3)C4—C5—H5121.00
H42—N4—H43111 (3)C6—C5—H5121.00
H41—N4—H42113 (4)C1—C6—H6120.00
H41—N4—H43107 (4)C5—C6—H6120.00
Cl1—Cd1—Cl2—Cd1iv45.92 (10)As1—C1—C6—C5172.4 (3)
O11—As1—C1—C232.4 (4)C2—C1—C6—C52.2 (7)
O11—As1—C1—C6152.9 (3)C1—C2—C3—C40.4 (7)
O12—As1—C1—C2163.8 (3)C2—C3—C4—N4175.5 (4)
O12—As1—C1—C621.6 (4)C2—C3—C4—C52.0 (6)
O13—As1—C1—C276.1 (4)N4—C4—C5—C6175.3 (4)
O13—As1—C1—C698.6 (4)C3—C4—C5—C62.2 (6)
As1—C1—C2—C3172.3 (3)C4—C5—C6—C10.1 (6)
C6—C1—C2—C32.4 (7)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y1/2, z; (iii) x1/2, y+3/2, z+1; (iv) x+1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O12v0.86 (4)1.74 (4)2.597 (4)175 (3)
O13—H13···O12vi0.88 (4)1.75 (4)2.596 (4)160 (4)
N4—H41···Cl1ii0.88 (2)2.31 (2)3.178 (4)170 (5)
N4—H42···Cl2iv0.90 (4)2.37 (4)3.257 (4)168 (3)
N4—H43···Cl10.90 (3)2.30 (2)3.150 (4)158 (4)
C6—H6···O13ii0.952.413.246 (5)146
Symmetry codes: (ii) x+3/2, y1/2, z; (iv) x+1/2, y+3/2, z+1; (v) x+1/2, y, z+1/2; (vi) x+2, y+1/2, z+1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds