Tetra­amminediaqua­copper(II) 4-amino-2,5-dichloro­benzene­sulfonate

In the title compound, [Cu(H₂O)₂(NH₃)₄](C₆H₄Cl₂NO₃S)₂, the Cu^II cation lies on an inversion centre and is six-coordinated by four NH₃ mol­ecules and two water mol­ecules in an enlongated octa­hedral coordination geometry. The anion is free from coordination but is linked to the Cu^II complex cation via O—H...O and N—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.076
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   O1W     ..      17.43 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N2      ..       5.72 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N3      ..       6.24 su

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.09

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

As metal sulfonates are a class of novel materials showing interesting properties, such as exchange, guest sorption (Côté & Shimizu, 2003; Yang et al., 2006), several studies on the coordination chemistry of transition metal sulfonates and their solid-state properties have been reported. In some cases, sulfonate group can compete with water molecule and coordinate to metal ion (Markku & Reijo, 1993). As part of an investigation of the structure of transition metal sulfonate compounds, we present here the structure of the title compound.

The crystal of the compound is composed of [Cu(NH₃)₄(H₂O)₂]²⁺ cations and 4-amino-2,5-dichlorobenzenesulfonate anions (Fig. 1). The Cu^II cation lies on an inversion center and is six-coordinated by four NH₃ molecules and two water molecules. The Cu—O1W bond in the axial direction is much longer than Cu—N bonds in the equatorial plane (Table 1), showing the typical Jahn-Teller distortion. The anions act as counterions and are hydrogen-bonded to the complex cations, forming a three dimensional supra-molecular structure (Fig. 2).

Related literature

For general background, see: Côté & Shimizu (2003); Markku & Reijo (1993); Yang et al. (2006).

S2. Experimental

A mixture of CuCl₂·2H₂O (0.171 g, 1 mmol) and NaOH (0.080 g, 2 mmol) in water (10 ml) was stirred for 10 min at room temperature, then the Cu(OH)₂ precipitate was collected by filtration and washed with water. 4-Amino-2,5-dichlorobenzenesulfonic acid (0.484 g, 2 mmol) was added to the Cu(OH)₂ suspension in water (10 ml) with stirring, and a blue precipitate was obtained. A minimum amount of ammonia solution (14 M) was added to give a blue, clear solution. Suitable crystals of the title compound were obtained after several days.

S3. Refinement

H atoms bonded to N and O atoms were located in a difference Fourier map and refined as riding in their as-found relative positions, U_iso(H) = 1.5U_eq(N,O). Aromatic H atoms were poisitioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (i) -x + 2, -y, -z + 2].
	Fig. 2. View of the two-dimensional network formed by the L^- anions and [Cu(NH3)4(H2O)2]^2+ cations. The hydrogen bonds are drawn as dashed lines.

Tetraamminediaquacopper(II) 4-amino-2,5-dichlorobenzenesulfonate

Crystal data

[Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2	Z = 1
Mr = 649.83	F(000) = 331
Triclinic, P1	Dx = 1.808 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.367 (6) Å	Cell parameters from 5673 reflections
b = 7.380 (5) Å	θ = 3.2–27.5°
c = 12.689 (10) Å	µ = 1.59 mm^−1
α = 96.22 (4)°	T = 293 K
β = 94.62 (4)°	Block, blue
γ = 118.33 (3)°	0.44 × 0.37 × 0.27 mm
V = 596.8 (8) Å^3

Data collection

Rigaku R-AXIS RAPID IP diffractometer	2715 independent reflections
Radiation source: rotor target	2518 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
Tmin = 0.521, Tmax = 0.650	l = −16→16
5849 measured 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 0.1532P] where P = (Fo^2 + 2Fc^2)/3
2715 reflections	(Δ/σ)max = 0.001
151 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.42 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
Cu1	1.0000	0.0000	1.0000	0.02605 (10)
Cl1	0.12744 (6)	0.22744 (8)	0.68358 (3)	0.03803 (12)
Cl2	0.80402 (7)	0.27818 (7)	0.40904 (3)	0.03640 (12)
S1	0.57643 (6)	0.30274 (6)	0.80181 (3)	0.02445 (11)
C1	0.5153 (2)	0.2819 (2)	0.66165 (12)	0.0231 (3)
C2	0.3236 (2)	0.2471 (2)	0.61119 (13)	0.0248 (3)
C3	0.2789 (2)	0.2209 (3)	0.50137 (13)	0.0279 (3)
H3	0.1496	0.1983	0.4704	0.033*
C4	0.4238 (3)	0.2275 (3)	0.43586 (12)	0.0270 (3)
C5	0.6171 (2)	0.2647 (2)	0.48716 (13)	0.0256 (3)
C6	0.6623 (2)	0.2912 (2)	0.59713 (12)	0.0246 (3)
H6	0.7921	0.3155	0.6284	0.030*
N1	0.3790 (3)	0.1971 (3)	0.32678 (12)	0.0384 (4)
H1N	0.2620	0.1798	0.2962	0.058*
H2N	0.4689	0.2039	0.2910	0.058*
O1	0.4554 (2)	0.0939 (2)	0.82788 (10)	0.0357 (3)
O2	0.79984 (18)	0.3761 (2)	0.82209 (10)	0.0357 (3)
O1W	1.0063 (2)	−0.1798 (2)	0.81528 (12)	0.0445 (3)
H1A	0.9705	−0.3136	0.8054	0.067*
H1B	1.1262	−0.1150	0.8014	0.067*
N2	0.6962 (2)	−0.0932 (2)	0.95054 (12)	0.0317 (3)
H2A	0.6650	−0.0215	0.9104	0.048*
H2B	0.6300	−0.1033	1.0089	0.048*
H2C	0.6394	−0.2209	0.9211	0.048*
O3	0.5222 (2)	0.4502 (2)	0.85509 (10)	0.0362 (3)
N3	1.0992 (2)	0.2790 (2)	0.95026 (11)	0.0314 (3)
H3A	1.0038	0.2791	0.9115	0.047*
H3B	1.1447	0.3759	1.0025	0.047*
H3C	1.1979	0.3035	0.9140	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02468 (15)	0.02976 (17)	0.02568 (15)	0.01440 (12)	0.00308 (11)	0.00729 (11)
Cl1	0.0261 (2)	0.0597 (3)	0.0322 (2)	0.0231 (2)	0.00693 (16)	0.01044 (19)
Cl2	0.0330 (2)	0.0446 (3)	0.0305 (2)	0.01790 (19)	0.01035 (16)	0.00277 (17)
S1	0.02302 (18)	0.0277 (2)	0.02057 (18)	0.01111 (15)	0.00088 (14)	0.00409 (14)
C1	0.0238 (7)	0.0231 (7)	0.0216 (7)	0.0110 (6)	0.0017 (6)	0.0046 (5)
C2	0.0227 (7)	0.0256 (8)	0.0270 (7)	0.0116 (6)	0.0045 (6)	0.0074 (6)
C3	0.0238 (7)	0.0302 (8)	0.0286 (8)	0.0127 (6)	−0.0011 (6)	0.0062 (6)
C4	0.0301 (8)	0.0242 (8)	0.0236 (7)	0.0110 (6)	0.0015 (6)	0.0047 (6)
C5	0.0264 (7)	0.0242 (8)	0.0256 (7)	0.0115 (6)	0.0065 (6)	0.0045 (6)
C6	0.0220 (6)	0.0251 (7)	0.0264 (7)	0.0115 (6)	0.0015 (6)	0.0046 (6)
N1	0.0371 (8)	0.0530 (10)	0.0225 (7)	0.0205 (7)	0.0008 (6)	0.0062 (6)
O1	0.0392 (7)	0.0336 (7)	0.0297 (6)	0.0128 (5)	0.0042 (5)	0.0122 (5)
O2	0.0250 (6)	0.0494 (8)	0.0300 (6)	0.0167 (5)	−0.0017 (5)	0.0074 (5)
O1W	0.0394 (7)	0.0418 (8)	0.0477 (8)	0.0143 (6)	0.0165 (6)	0.0087 (6)
N2	0.0298 (7)	0.0364 (8)	0.0317 (7)	0.0185 (6)	0.0024 (6)	0.0062 (6)
O3	0.0378 (6)	0.0382 (7)	0.0310 (6)	0.0198 (6)	0.0014 (5)	−0.0042 (5)
N3	0.0328 (7)	0.0339 (8)	0.0286 (7)	0.0169 (6)	0.0028 (6)	0.0073 (6)

Geometric parameters (Å, º)

Cu1—N2	2.024 (2)	C3—H3	0.9300
Cu1—N2^i	2.024 (2)	C4—N1	1.365 (2)
Cu1—N3	2.025 (2)	C4—C5	1.403 (3)
Cu1—N3^i	2.025 (2)	C5—C6	1.379 (2)
Cu1—O1W	2.580 (2)	C6—H6	0.9300
Cl1—C2	1.731 (2)	N1—H1N	0.8605
Cl2—C5	1.732 (2)	N1—H2N	0.8179
S1—O3	1.4482 (15)	O1W—H1A	0.8836
S1—O2	1.4574 (17)	O1W—H1B	0.8260
S1—O1	1.4608 (17)	N2—H2A	0.8642
S1—C1	1.771 (2)	N2—H2B	0.9089
C1—C6	1.390 (2)	N2—H2C	0.8531
C1—C2	1.395 (2)	N3—H3A	0.8251
C2—C3	1.377 (2)	N3—H3B	0.8346
C3—C4	1.391 (3)	N3—H3C	0.8488
N2—Cu1—N2^i	180.000 (1)	C3—C4—C5	116.84 (15)
N2—Cu1—N3	92.99 (7)	C6—C5—C4	122.08 (15)
N2^i—Cu1—N3	87.01 (7)	C6—C5—Cl2	119.39 (13)
N2—Cu1—N3^i	87.01 (7)	C4—C5—Cl2	118.53 (14)
N2^i—Cu1—N3^i	92.99 (7)	C5—C6—C1	120.52 (15)
N3—Cu1—N3^i	180.000 (1)	C5—C6—H6	119.7
O3—S1—O2	112.05 (9)	C1—C6—H6	119.7
O3—S1—O1	112.11 (10)	C4—N1—H1N	120.9
O2—S1—O1	111.67 (9)	C4—N1—H2N	118.6
O3—S1—C1	108.15 (8)	H1N—N1—H2N	120.3
O2—S1—C1	105.56 (8)	H1A—O1W—H1B	107.3
O1—S1—C1	106.89 (9)	Cu1—N2—H2A	119.1
C6—C1—C2	117.67 (15)	Cu1—N2—H2B	109.0
C6—C1—S1	118.57 (12)	H2A—N2—H2B	108.1
C2—C1—S1	123.70 (12)	Cu1—N2—H2C	106.8
C3—C2—C1	121.70 (15)	H2A—N2—H2C	111.0
C3—C2—Cl1	116.75 (13)	H2B—N2—H2C	101.4
C1—C2—Cl1	121.53 (13)	Cu1—N3—H3A	110.6
C2—C3—C4	121.18 (15)	Cu1—N3—H3B	110.9
C2—C3—H3	119.4	H3A—N3—H3B	109.9
C4—C3—H3	119.4	Cu1—N3—H3C	110.4
N1—C4—C3	121.51 (16)	H3A—N3—H3C	107.6
N1—C4—C5	121.65 (16)	H3B—N3—H3C	107.4
O3—S1—C1—C6	133.25 (13)	Cl1—C2—C3—C4	−178.05 (13)
O2—S1—C1—C6	13.16 (15)	C2—C3—C4—N1	178.56 (16)
O1—S1—C1—C6	−105.86 (14)	C2—C3—C4—C5	−0.8 (2)
O3—S1—C1—C2	−49.74 (16)	N1—C4—C5—C6	−178.61 (16)
O2—S1—C1—C2	−169.83 (14)	C3—C4—C5—C6	0.7 (2)
O1—S1—C1—C2	71.15 (16)	N1—C4—C5—Cl2	1.6 (2)
C6—C1—C2—C3	0.6 (2)	C3—C4—C5—Cl2	−179.06 (12)
S1—C1—C2—C3	−176.48 (13)	C4—C5—C6—C1	0.0 (3)
C6—C1—C2—Cl1	178.68 (12)	Cl2—C5—C6—C1	179.77 (12)
S1—C1—C2—Cl1	1.6 (2)	C2—C1—C6—C5	−0.6 (2)
C1—C2—C3—C4	0.2 (3)	S1—C1—C6—C5	176.58 (13)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2^ii	0.88	2.07	2.900 (3)	156
O1W—H1B···O1^iii	0.83	2.14	2.925 (3)	159
N1—H1N···O1W^iv	0.86	2.34	3.179 (4)	166
N1—H2N···Cl2	0.82	2.56	2.967 (3)	112
N2—H2A···O1	0.86	2.32	3.134 (3)	157
N2—H2B···O1^v	0.91	2.22	3.108 (3)	166
N2—H2C···O3^ii	0.85	2.19	3.038 (3)	174
N3—H3A···O2	0.82	2.23	3.033 (3)	164
N3—H3B···O2^vi	0.84	2.59	3.412 (3)	166
N3—H3B···O3^vi	0.84	2.59	3.226 (3)	133
N3—H3C···O3^iii	0.85	2.33	3.157 (3)	164

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