(μ-Naphthalene-1,5-disulfonato-κ2O1:O5)bis­[triaqua­(glycinato-κ2N,O)copper(II)]

Gao, S.; Ng, S.W.

doi:10.1107/S1600536812019332

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m730

doi:10.1107/S1600536812019332

Open

access

(μ-Naphthalene-1,5-disulfonato-κ²O¹:O⁵)bis[triaqua(glycinato-κ²N,O)copper(II)]

Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 24 April 2012; accepted 30 April 2012; online 5 May 2012)

In the title compound, [Cu₂(C₂H₄NO₂)₂(C₁₀H₆O₆S₂)(H₂O)₆], the naphthalenedisulfonate group lies on a center of inversion and bridges two glycinate-chelated Cu^II atoms. The Cu^II atom exists in a CuNO₄ square-pyramidal geometry that is distorted towards an octahedron owing to a long Cu—O_sulfonate bond [2.636 (2) Å]. In the crystal, extensive N—H⋯O and O—H⋯O hydrogen bonds link adjacent molecules into a three-dimensional network

Related literature

For a review of metal arenesulfonates, see: Cai (2004 ).

Experimental

Crystal data

[Cu₂(C₂H₄NO₂)₂(C₁₀H₆O₆S₂)(H₂O)₆]
M_r = 669.57
Monoclinic, P 2₁ /c
a = 5.802 (3) Å
b = 11.341 (6) Å
c = 17.613 (8) Å
β = 99.793 (18)°
V = 1142.1 (9) Å³
Z = 2
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 293 K
0.38 × 0.26 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.498, T_max = 0.688
10939 measured reflections
2615 independent reflections
2482 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.073
S = 1.07
2615 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O2ⁱ	0.84	2.02	2.741 (2)	143
O1w—H12⋯O5ⁱⁱ	0.84	2.10	2.785 (2)	139
O2w—H21⋯O4ⁱⁱⁱ	0.84	2.00	2.773 (2)	152
O2w—H22⋯O4^iv	0.84	2.02	2.823 (2)	158
O3w—H31⋯O2ⁱⁱ	0.84	1.91	2.676 (2)	151
O3w—H32⋯O3^iv	0.84	1.93	2.691 (2)	150
N1—H1⋯O5	0.88	2.53	3.079 (3)	121
N1—H2⋯O2ⁱⁱ	0.88	2.50	3.194 (3)	137
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812019332/xu5523sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019332/xu5523Isup2.hkl

checkCIF report

Comment top

Metal arenesulfonates are generally crystalline compounds; in some, the metal is connected to the arenesulfonate by a covalent bond whereas in others, the arenesulfonate interacts indirectly with the metal center in an outer-sphere type of coordination (Cai, 2004). In the title compound (Scheme I), the Cu^II atom exists in a CuNO₄ square-pyramidal geometry that is distorted towards an octahedron owing to the long Cu–O_sulfonate bond (2.636 (2) Å). The atom lies above the square plane (r.m.s. deviation 0.082 Å) and the apical water molecule lies 2.371 (2) Å above the plane (Fig.1). Extensive N–H···O and O–H···O hydrogen bonds link adjacent molecules into a three-dimensional network (Table 1).

Related literature top

For a review of metal arenesulfonates, see: Cai (2004).

Experimental top

Dicopper carbonate dihydroxide (1 mmol, 221 mg), glycine (2 mmol, 150 mg) 1,5-naphthalenedisulfonic acid tetrahydrate (2 mmol, 720 mg) were dissolved in water (10 ml). The solution was heated for 5 h and then filtered. Blue crystals separated from the solution after several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the title compound at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry-related atoms are not labeled.

(µ-Naphthalene-1,5-disulfonato- κ²O¹:O⁵)bis[triaqua(glycinato- κ²N,O)copper(II)] top

Crystal data top

[Cu₂(C₂H₄NO₂)₂(C₁₀H₆O₆S₂)(H₂O)₆]	F(000) = 684
M_r = 669.57	D_x = 1.947 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10177 reflections
a = 5.802 (3) Å	θ = 3.6–27.5°
b = 11.341 (6) Å	µ = 2.13 mm⁻¹
c = 17.613 (8) Å	T = 293 K
β = 99.793 (18)°	Prism, blue
V = 1142.1 (9) Å³	0.38 × 0.26 × 0.19 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2615 independent reflections
Radiation source: fine-focus sealed tube	2482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scan	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→6
T_min = 0.498, T_max = 0.688	k = −14→14
10939 measured reflections	l = −21→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0429P)² + 0.6921P] where P = (F_o² + 2F_c²)/3
2615 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Cu₂(C₂H₄NO₂)₂(C₁₀H₆O₆S₂)(H₂O)₆]	V = 1142.1 (9) Å³
M_r = 669.57	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.802 (3) Å	µ = 2.13 mm⁻¹
b = 11.341 (6) Å	T = 293 K
c = 17.613 (8) Å	0.38 × 0.26 × 0.19 mm
β = 99.793 (18)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2615 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2482 reflections with I > 2σ(I)
T_min = 0.498, T_max = 0.688	R_int = 0.022
10939 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	Δρ_max = 0.47 e Å⁻³
2615 reflections	Δρ_min = −0.63 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.35965 (4)	0.51409 (2)	0.341914 (12)	0.02354 (9)
S1	0.70836 (8)	0.73372 (4)	0.44741 (2)	0.02159 (11)
O1	0.1995 (2)	0.64747 (12)	0.28644 (8)	0.0287 (3)
O2	0.2226 (3)	0.77425 (13)	0.19250 (8)	0.0343 (3)
O1w	0.1638 (3)	0.37202 (15)	0.26192 (9)	0.0397 (4)
H11	0.0956	0.3256	0.2879	0.060*
H12	0.2599	0.3342	0.2407	0.060*
O2w	0.1040 (3)	0.50030 (11)	0.40277 (8)	0.0265 (3)
H21	0.0939	0.5633	0.4271	0.040*
H22	0.1325	0.4441	0.4340	0.040*
O3w	0.5629 (3)	0.39956 (14)	0.40378 (8)	0.0369 (3)
H31	0.5917	0.3436	0.3756	0.055*
H32	0.4956	0.3734	0.4389	0.055*
O3	0.4994 (2)	0.66501 (11)	0.45410 (7)	0.0270 (3)
O4	0.9218 (3)	0.67519 (12)	0.48533 (8)	0.0327 (3)
O5	0.7143 (3)	0.76531 (13)	0.36808 (8)	0.0345 (3)
N1	0.5974 (3)	0.53828 (15)	0.27352 (9)	0.0280 (3)
H1	0.7251	0.5697	0.2999	0.034*
H2	0.6344	0.4702	0.2548	0.034*
C1	0.2931 (3)	0.68561 (16)	0.23169 (10)	0.0236 (3)
C2	0.4970 (3)	0.61731 (17)	0.21047 (11)	0.0279 (4)
H2A	0.4444	0.5714	0.1643	0.033*
H2B	0.6160	0.6719	0.1996	0.033*
C3	0.6918 (3)	0.86710 (14)	0.49908 (9)	0.0200 (3)
C4	0.8728 (3)	0.89338 (16)	0.55662 (10)	0.0258 (4)
H4	0.9958	0.8404	0.5691	0.031*
C5	0.8744 (4)	1.00050 (17)	0.59723 (12)	0.0275 (4)
H5	0.9982	1.0174	0.6366	0.033*
C6	0.6966 (3)	1.07958 (16)	0.57946 (10)	0.0239 (3)
H6	0.7024	1.1507	0.6060	0.029*
C7	0.5021 (3)	1.05448 (14)	0.52074 (9)	0.0186 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02546 (13)	0.02263 (14)	0.02478 (14)	0.00560 (8)	0.01067 (9)	0.00671 (8)
S1	0.0305 (2)	0.01428 (19)	0.0221 (2)	0.00179 (15)	0.01062 (16)	−0.00129 (14)
O1	0.0311 (6)	0.0273 (7)	0.0307 (7)	0.0076 (5)	0.0134 (5)	0.0098 (5)
O2	0.0379 (7)	0.0294 (7)	0.0378 (8)	0.0054 (6)	0.0131 (6)	0.0152 (6)
O1w	0.0462 (9)	0.0409 (9)	0.0350 (8)	−0.0102 (7)	0.0153 (7)	−0.0150 (7)
O2w	0.0324 (7)	0.0199 (6)	0.0310 (7)	0.0022 (5)	0.0162 (6)	0.0001 (5)
O3w	0.0491 (8)	0.0386 (8)	0.0266 (7)	0.0221 (7)	0.0162 (6)	0.0093 (6)
O3	0.0362 (7)	0.0196 (6)	0.0270 (6)	−0.0049 (5)	0.0107 (5)	−0.0012 (5)
O4	0.0352 (7)	0.0224 (6)	0.0420 (8)	0.0107 (6)	0.0106 (6)	−0.0027 (6)
O5	0.0529 (9)	0.0306 (7)	0.0241 (6)	−0.0039 (6)	0.0187 (6)	−0.0018 (5)
N1	0.0273 (8)	0.0283 (8)	0.0302 (8)	0.0054 (6)	0.0103 (6)	0.0031 (6)
C1	0.0254 (8)	0.0210 (8)	0.0246 (8)	−0.0019 (7)	0.0046 (7)	0.0005 (6)
C2	0.0325 (9)	0.0286 (9)	0.0247 (8)	0.0019 (7)	0.0113 (7)	0.0021 (7)
C3	0.0266 (8)	0.0145 (7)	0.0202 (7)	0.0013 (6)	0.0076 (6)	−0.0006 (6)
C4	0.0259 (8)	0.0224 (8)	0.0282 (9)	0.0057 (7)	0.0021 (7)	0.0003 (7)
C5	0.0274 (9)	0.0269 (9)	0.0255 (9)	−0.0008 (7)	−0.0033 (7)	−0.0042 (7)
C6	0.0288 (8)	0.0194 (8)	0.0226 (8)	−0.0018 (7)	0.0023 (7)	−0.0037 (6)
C7	0.0239 (8)	0.0142 (7)	0.0183 (7)	0.0001 (6)	0.0051 (6)	0.0000 (6)

Geometric parameters (Å, º) top

Cu1—O1	1.9485 (15)	O3w—H32	0.8400
Cu1—O3w	1.9566 (15)	N1—C2	1.468 (2)
Cu1—O2w	1.9783 (16)	N1—H1	0.8800
Cu1—N1	1.9988 (18)	N1—H2	0.8800
Cu1—O1w	2.3081 (17)	C1—C2	1.513 (3)
Cu1—O3	2.636 (2)	C2—H2A	0.9700
S1—O5	1.4486 (15)	C2—H2B	0.9700
S1—O4	1.4626 (15)	C3—C4	1.363 (3)
S1—O3	1.4629 (15)	C3—C7ⁱ	1.430 (2)
S1—C3	1.7763 (18)	C4—C5	1.409 (3)
O1—C1	1.261 (2)	C4—H4	0.9300
O2—C1	1.248 (2)	C5—C6	1.362 (3)
O1w—H11	0.8400	C5—H5	0.9300
O1w—H12	0.8400	C6—C7	1.424 (2)
O2w—H21	0.8400	C6—H6	0.9300
O2w—H22	0.8400	C7—C3ⁱ	1.430 (2)
O3w—H31	0.8400	C7—C7ⁱ	1.434 (3)

O1—Cu1—O3w	170.20 (7)	Cu1—N1—H1	110.0
O1—Cu1—O2w	89.75 (6)	C2—N1—H2	110.0
O3w—Cu1—O2w	94.72 (7)	Cu1—N1—H2	110.0
O1—Cu1—N1	84.86 (6)	H1—N1—H2	108.4
O3w—Cu1—N1	90.81 (7)	O2—C1—O1	123.76 (17)
O2w—Cu1—N1	174.45 (6)	O2—C1—C2	118.17 (16)
O1—Cu1—O1w	95.31 (7)	O1—C1—C2	118.03 (16)
O3w—Cu1—O1w	93.67 (8)	N1—C2—C1	110.61 (15)
O2w—Cu1—O1w	86.50 (6)	N1—C2—H2A	109.5
N1—Cu1—O1w	92.67 (7)	C1—C2—H2A	109.5
O5—S1—O4	113.29 (9)	N1—C2—H2B	109.5
O5—S1—O3	111.43 (9)	C1—C2—H2B	109.5
O4—S1—O3	111.76 (9)	H2A—C2—H2B	108.1
O5—S1—C3	107.21 (9)	C4—C3—C7ⁱ	121.37 (15)
O4—S1—C3	105.54 (8)	C4—C3—S1	117.72 (13)
O3—S1—C3	107.12 (8)	C7ⁱ—C3—S1	120.89 (13)
C1—O1—Cu1	114.77 (12)	C3—C4—C5	120.24 (16)
Cu1—O1w—H11	109.5	C3—C4—H4	119.9
Cu1—O1w—H12	109.5	C5—C4—H4	119.9
H11—O1w—H12	109.5	C6—C5—C4	120.77 (17)
Cu1—O2w—H21	109.5	C6—C5—H5	119.6
Cu1—O2w—H22	109.5	C4—C5—H5	119.6
H21—O2w—H22	109.5	C5—C6—C7	120.72 (17)
Cu1—O3w—H31	109.5	C5—C6—H6	119.6
Cu1—O3w—H32	109.5	C7—C6—H6	119.6
H31—O3w—H32	109.5	C6—C7—C3ⁱ	123.13 (15)
C2—N1—Cu1	108.28 (12)	C6—C7—C7ⁱ	119.03 (19)
C2—N1—H1	110.0	C3ⁱ—C7—C7ⁱ	117.83 (18)

O2w—Cu1—O1—C1	−174.25 (13)	O4—S1—C3—C4	4.06 (16)
N1—Cu1—O1—C1	4.42 (13)	O3—S1—C3—C4	123.29 (15)
O1w—Cu1—O1—C1	−87.80 (14)	O5—S1—C3—C7ⁱ	61.24 (16)
O1—Cu1—N1—C2	−13.65 (13)	O4—S1—C3—C7ⁱ	−177.71 (14)
O3w—Cu1—N1—C2	175.17 (13)	O3—S1—C3—C7ⁱ	−58.48 (16)
O1w—Cu1—N1—C2	81.45 (13)	C7ⁱ—C3—C4—C5	−1.1 (3)
Cu1—O1—C1—O2	−175.95 (15)	S1—C3—C4—C5	177.09 (15)
Cu1—O1—C1—C2	6.4 (2)	C3—C4—C5—C6	−0.4 (3)
Cu1—N1—C2—C1	19.48 (19)	C4—C5—C6—C7	1.6 (3)
O2—C1—C2—N1	164.25 (17)	C5—C6—C7—C3ⁱ	178.49 (18)
O1—C1—C2—N1	−18.0 (2)	C5—C6—C7—C7ⁱ	−1.3 (3)
O5—S1—C3—C4	−116.99 (15)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2ⁱⁱ	0.84	2.02	2.741 (2)	143
O1w—H12···O5ⁱⁱⁱ	0.84	2.10	2.785 (2)	139
O2w—H21···O4^iv	0.84	2.00	2.773 (2)	152
O2w—H22···O4^v	0.84	2.02	2.823 (2)	158
O3w—H31···O2ⁱⁱⁱ	0.84	1.91	2.676 (2)	151
O3w—H32···O3^v	0.84	1.93	2.691 (2)	150
N1—H1···O5	0.88	2.53	3.079 (3)	121
N1—H2···O2ⁱⁱⁱ	0.88	2.50	3.194 (3)	137

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂H₄NO₂)₂(C₁₀H₆O₆S₂)(H₂O)₆]
M_r	669.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.802 (3), 11.341 (6), 17.613 (8)
β (°)	99.793 (18)
V (Å³)	1142.1 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.38 × 0.26 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.498, 0.688
No. of measured, independent and observed [I > 2σ(I)] reflections	10939, 2615, 2482
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.073, 1.07
No. of reflections	2615
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.63

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2ⁱ	0.84	2.02	2.741 (2)	143
O1w—H12···O5ⁱⁱ	0.84	2.10	2.785 (2)	139
O2w—H21···O4ⁱⁱⁱ	0.84	2.00	2.773 (2)	152
O2w—H22···O4^iv	0.84	2.02	2.823 (2)	158
O3w—H31···O2ⁱⁱ	0.84	1.91	2.676 (2)	151
O3w—H32···O3^iv	0.84	1.93	2.691 (2)	150
N1—H1···O5	0.88	2.53	3.079 (3)	121
N1—H2···O2ⁱⁱ	0.88	2.50	3.194 (3)	137

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

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Key Project of the Education Bureau of Heilongjiang Province (Nos. 12511z023 and 2011CJHB006), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang University (Hdtd2010–04) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Cai, J. (2004). Coord. Chem. Rev. 248, 1061–1083. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.