Bis[μ-4,5-dicyano-N,N′-bis­(p-tolyl­sulfon­yl)-o-phenyl­enediaminato]bis­[diamminecopper(II)] dihydrate

Yuksel, F.; Tuncel, S.; Gürek, A.G.; Jeanneau, E.; Luneau, D.; Ahsen, V.

doi:10.1107/S1600536807017643

Bis[μ-4,5-dicyano-N,N′-bis(p-tolylsulfonyl)-o-phenylenediaminato]bis[diamminecopper(II)] dihydrate

F. Yuksel, S. Tuncel, A. G. Gürek, E. Jeanneau, D. Luneau and V. Ahsen

The title complex, [Cu₂(C₂₂H₁₆N₄O₄S₂)₂(NH₃)₄]·2H₂O, is a centrosymmetric dimer. The two copper ions are bridged by two 4,5-dicyano-N,N′-bis(p-tolylsulfonyl)-o-phenylenediamine ligands; the Cu

Cu distance is 8.749 (1) Å. Each copper ion is in a distorted square-pyramidal geometry, defined by two N atoms from one ligand, two N atoms from two coordinated ammonia molecules and one CN from the other ligand apically. The hydrogen-bonding network leads to a layered structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017643/bq2007sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017643/bq2007Isup2.hkl Contains datablock I

CCDC reference: 646743

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.007 Å
R factor = 0.056
wR factor = 0.059
Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N3      ..       5.03 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N4      ..       6.84 su
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C17    -   C21    ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C18    -   C22    ...       1.43 Ang.

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           26.04
           From the CIF: _reflns_number_total               4827
           From the CIF: _diffrn_reflns_limit_ max hkl   17.   11.   21.
           From the CIF: _diffrn_reflns_limit_ min hkl  -17.  -12.  -21.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   17.   12.   23.
           Calculated minimum hkl  -17.  -12.  -23.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K

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

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: The synthesis of this compound is a result of a collaboration between a french research group and a turkish one. Sinem Tuncel did the synthesis of the ligand. Fatma Yuksel did the synthesis and crystallisation of the title compound Dominique Luneau is the French team leader. Vefa Ahsen and Ayse Gul Gurek are the Turksih team leaders. Erwann Jeanneau did the crystallographic work.


   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg & Putz, 1996); software used to prepare material for publication: CRYSTALS.

Bis[µ-4,5-dicyano-N,N'-bis(p-tolylsulfonyl)-o- phenylendiaminato]bis[diamminecopper(II)] dihydrate top

Crystal data top

[Cu₂(C₂₂H₁₆N₄O₄S₂)₂(NH₃)₄]·2H₂O	F(000) = 1196
M_r = 1160.32	D_x = 1.569 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 5073 reflections
a = 14.1946 (8) Å	θ = 0.4–26.0°
b = 10.1475 (7) Å	µ = 1.11 mm⁻¹
c = 19.267 (1) Å	T = 293 K
β = 118.117 (3)°	Block, green
V = 2447.7 (3) Å³	0.27 × 0.19 × 0.15 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	3315 reflections with I > 1.0σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	θ_max = 26.0°, θ_min = 2.2°
T_min = 0.670, T_max = 0.847	h = −17→17
8752 measured reflections	k = −12→11
4827 independent reflections	l = −21→21

Refinement top

Refinement on F	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.056	Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982) [weight] = 1/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /F_max Method = Robust Weighting (Prince, 1982) W = [weight] [1-(δF/6σF)²]² A_i are: 1.05 1.13 0.672
wR(F²) = 0.059	(Δ/σ)_max = 0.000385
S = 1.05	Δρ_max = 0.47 e Å⁻³
3315 reflections	Δρ_min = −0.47 e Å⁻³
325 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.36435 (4)	−0.12750 (5)	0.65107 (3)	0.0545
S2	0.33181 (8)	−0.33686 (9)	0.52017 (6)	0.0550
S1	0.25388 (8)	0.16060 (10)	0.60919 (6)	0.0544
O4	0.4078 (2)	−0.3876 (3)	0.49714 (19)	0.0671
O1	0.2153 (3)	0.1149 (3)	0.66210 (18)	0.0665
O2	0.3287 (2)	0.2686 (3)	0.63682 (19)	0.0701
N2	0.3557 (3)	−0.1886 (3)	0.5526 (2)	0.0548
O3	0.3204 (3)	−0.4119 (3)	0.57941 (18)	0.0680
C15	0.3270 (3)	0.0401 (4)	0.5246 (2)	0.0493
C18	0.3774 (3)	0.0208 (4)	0.4007 (2)	0.0519
N1	0.3001 (3)	0.0331 (3)	0.5857 (2)	0.0523
C17	0.3546 (3)	0.1438 (4)	0.4227 (2)	0.0499
O5	0.5070 (3)	0.3731 (4)	0.6165 (2)	0.0796
C1	0.1409 (3)	0.2161 (4)	0.5230 (2)	0.0536
N3	0.4634 (3)	−0.2680 (3)	0.71640 (18)	0.0544
N4	0.3405 (3)	−0.0851 (3)	0.73925 (18)	0.0533
C6	0.0640 (3)	0.1282 (4)	0.4760 (3)	0.0601
C16	0.3298 (3)	0.1520 (4)	0.4838 (2)	0.0528
C21	0.3571 (3)	0.2603 (4)	0.3815 (2)	0.0563
N5	0.3565 (3)	0.3540 (4)	0.3477 (3)	0.0719
C8	0.2076 (3)	−0.3298 (4)	0.4334 (3)	0.0549
C19	0.3778 (3)	−0.0930 (4)	0.4420 (2)	0.0529
C20	0.3539 (3)	−0.0834 (4)	0.5037 (2)	0.0513
C12	0.0932 (4)	−0.3982 (6)	0.3020 (3)	0.0798
C9	0.1251 (4)	−0.2560 (5)	0.4325 (3)	0.0680
C4	−0.0451 (4)	0.3048 (5)	0.3952 (3)	0.0687
C3	0.0352 (4)	0.3924 (5)	0.4427 (3)	0.0720
C22	0.4075 (3)	0.0129 (4)	0.3397 (3)	0.0583
C5	−0.0291 (4)	0.1727 (5)	0.4127 (3)	0.0683
N6	0.4342 (4)	0.0081 (4)	0.2923 (3)	0.0755
C13	0.1919 (4)	−0.4011 (5)	0.3683 (3)	0.0664
C10	0.0267 (4)	−0.2528 (5)	0.3652 (3)	0.0746
C2	0.1272 (4)	0.3499 (4)	0.5057 (3)	0.0652
C11	0.0104 (4)	−0.3232 (6)	0.2990 (3)	0.0785
C7	−0.1463 (4)	0.3563 (7)	0.3262 (4)	0.0964
C14	−0.0960 (5)	−0.3207 (9)	0.2250 (4)	0.1122
H61	0.0749	0.0389	0.4877	0.0711*
H161	0.3164	0.2337	0.4988	0.0594*
H191	0.3953	−0.1749	0.4281	0.0598*
H121	0.0834	−0.4486	0.2594	0.0861*
H91	0.1355	−0.2085	0.4765	0.0809*
H31	0.0259	0.4823	0.4317	0.0879*
H51	−0.0814	0.1118	0.3822	0.0840*
H131	0.2465	−0.4507	0.3687	0.0750*
H101	−0.0279	−0.2028	0.3649	0.0871*
H21	0.1799	0.4094	0.5366	0.0789*
H71	−0.1991	0.2883	0.3070	0.1291*
H72	−0.1745	0.4302	0.3410	0.1292*
H73	−0.1326	0.3828	0.2842	0.1291*
H141	−0.1515	−0.3121	0.2395	0.1500*
H142	−0.1062	−0.4011	0.1963	0.1499*
H143	−0.0992	−0.2481	0.1924	0.1500*
H6	0.3317	−0.1541	0.7575	0.0765*
H5	0.3951	−0.0481	0.7732	0.0760*
H4	0.2891	−0.0347	0.7265	0.0757*
H1	0.5190	−0.2365	0.7552	0.0701*
H2	0.4828	−0.3137	0.6886	0.0704*
H3	0.4325	−0.3195	0.7333	0.0704*
H7	0.4520	0.3990	0.6150	0.1100*
H8	0.5158	0.4275	0.5890	0.1102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0572 (3)	0.0547 (3)	0.0521 (3)	0.0005 (2)	0.0261 (2)	0.0026 (2)
S2	0.0536 (6)	0.0466 (5)	0.0607 (6)	0.0005 (4)	0.0237 (5)	−0.0004 (4)
S1	0.0505 (5)	0.0565 (6)	0.0569 (6)	0.0030 (4)	0.0259 (5)	−0.0029 (4)
O4	0.0562 (17)	0.0640 (18)	0.0761 (19)	0.0078 (14)	0.0270 (15)	−0.0081 (15)
O1	0.0687 (19)	0.079 (2)	0.0619 (18)	0.0137 (15)	0.0389 (15)	0.0039 (15)
O2	0.0594 (17)	0.0607 (18)	0.080 (2)	−0.0057 (14)	0.0243 (15)	−0.0143 (15)
N2	0.063 (2)	0.0464 (17)	0.059 (2)	−0.0024 (15)	0.0321 (17)	−0.0003 (15)
O3	0.0725 (19)	0.0561 (17)	0.0695 (19)	−0.0083 (14)	0.0286 (16)	0.0088 (14)
C15	0.041 (2)	0.057 (2)	0.050 (2)	−0.0002 (16)	0.0220 (17)	−0.0010 (17)
C18	0.046 (2)	0.057 (2)	0.052 (2)	−0.0004 (17)	0.0226 (18)	−0.0014 (17)
N1	0.0555 (19)	0.0494 (18)	0.0570 (19)	0.0045 (15)	0.0306 (16)	0.0056 (14)
C17	0.0419 (18)	0.055 (2)	0.051 (2)	−0.0017 (16)	0.0199 (16)	0.0027 (17)
O5	0.077 (2)	0.082 (2)	0.078 (2)	−0.0079 (18)	0.0354 (18)	0.0039 (18)
C1	0.046 (2)	0.055 (2)	0.060 (2)	0.0011 (17)	0.0246 (18)	0.0017 (18)
N3	0.0582 (19)	0.0484 (18)	0.0483 (18)	0.0042 (14)	0.0182 (15)	0.0048 (14)
N4	0.061 (2)	0.0598 (19)	0.0456 (17)	0.0095 (15)	0.0301 (15)	0.0053 (14)
C6	0.061 (2)	0.055 (2)	0.066 (3)	−0.0008 (19)	0.032 (2)	0.000 (2)
C16	0.049 (2)	0.051 (2)	0.058 (2)	0.0016 (16)	0.0248 (18)	−0.0055 (17)
C21	0.051 (2)	0.059 (3)	0.060 (2)	0.0013 (18)	0.0263 (19)	0.001 (2)
N5	0.077 (3)	0.065 (3)	0.076 (3)	−0.0040 (19)	0.038 (2)	0.009 (2)
C8	0.053 (2)	0.052 (2)	0.060 (2)	0.0019 (17)	0.0272 (19)	0.0030 (18)
C19	0.047 (2)	0.054 (2)	0.057 (2)	−0.0033 (16)	0.0243 (17)	−0.0010 (17)
C20	0.049 (2)	0.048 (2)	0.055 (2)	0.0011 (16)	0.0226 (18)	0.0012 (17)
C12	0.070 (3)	0.100 (4)	0.058 (3)	0.005 (3)	0.020 (2)	−0.010 (3)
C9	0.060 (3)	0.066 (3)	0.079 (3)	0.007 (2)	0.034 (2)	−0.006 (2)
C4	0.056 (3)	0.076 (3)	0.072 (3)	0.006 (2)	0.029 (2)	0.010 (2)
C3	0.071 (3)	0.059 (3)	0.084 (3)	0.005 (2)	0.036 (3)	0.009 (2)
C22	0.062 (3)	0.055 (2)	0.061 (3)	−0.0021 (19)	0.032 (2)	−0.0001 (19)
C5	0.060 (3)	0.076 (3)	0.066 (3)	−0.008 (2)	0.028 (2)	−0.004 (2)
N6	0.096 (3)	0.071 (3)	0.076 (3)	0.003 (2)	0.054 (3)	0.000 (2)
C13	0.058 (2)	0.072 (3)	0.068 (3)	0.007 (2)	0.028 (2)	−0.003 (2)
C10	0.053 (3)	0.078 (3)	0.093 (4)	0.013 (2)	0.034 (3)	0.012 (3)
C2	0.058 (2)	0.054 (2)	0.082 (3)	−0.0008 (19)	0.031 (2)	−0.004 (2)
C11	0.056 (3)	0.090 (4)	0.077 (3)	0.001 (2)	0.022 (2)	0.011 (3)
C7	0.060 (3)	0.114 (5)	0.096 (4)	0.014 (3)	0.021 (3)	0.026 (4)
C14	0.060 (3)	0.163 (7)	0.086 (4)	0.006 (4)	0.011 (3)	0.015 (4)

Geometric parameters (Å, º) top

Cu1—N1	1.998 (3)	C6—C5	1.385 (7)
Cu1—N2	1.944 (3)	C6—H61	0.929
Cu1—N3	1.981 (3)	C16—H161	0.927
Cu1—N4	1.931 (3)	C21—N5	1.151 (6)
Cu1—N6ⁱ	2.810 (5)	C8—C9	1.384 (6)
S2—O4	1.441 (3)	C8—C13	1.372 (6)
S2—N2	1.603 (3)	C19—C20	1.386 (6)
S2—O3	1.443 (3)	C19—H191	0.942
S2—C8	1.769 (4)	C12—C13	1.381 (7)
S1—O1	1.442 (3)	C12—C11	1.378 (8)
S1—O2	1.442 (3)	C12—H121	0.920
S1—N1	1.609 (3)	C9—C10	1.388 (7)
S1—C1	1.772 (4)	C9—H91	0.925
N2—C20	1.416 (5)	C4—C3	1.394 (7)
C15—N1	1.401 (5)	C4—C5	1.375 (7)
C15—C16	1.392 (6)	C4—C7	1.519 (7)
C15—C20	1.422 (6)	C3—C2	1.368 (7)
C18—C17	1.404 (6)	C3—H31	0.932
C18—C19	1.400 (6)	C22—N6	1.143 (5)
C18—C22	1.429 (6)	C5—H51	0.931
C17—C16	1.380 (6)	C13—H131	0.921
C17—C21	1.434 (6)	C10—C11	1.384 (8)
O5—H7	0.811	C10—H101	0.924
O5—H8	0.815	C2—H21	0.927
C1—C6	1.369 (6)	C11—C14	1.512 (7)
C1—C2	1.390 (6)	C7—H71	0.956
N3—H1	0.853	C7—H72	0.955
N3—H2	0.846	C7—H73	0.956
N3—H3	0.841	C14—H141	0.956
N4—H6	0.819	C14—H142	0.958
N4—H5	0.832	C14—H143	0.955
N4—H4	0.828

N1—Cu1—N2	81.07 (14)	C5—C6—H61	120.8
N1—Cu1—N3	164.55 (14)	C15—C16—C17	121.3 (4)
N1—Cu1—N4	98.94 (14)	C15—C16—H161	119.2
N1—Cu1—N6ⁱ	88.37 (14)	C17—C16—H161	119.5
N2—Cu1—N3	95.17 (15)	C17—C21—N5	178.4 (4)
N2—Cu1—N4	166.69 (15)	S2—C8—C9	119.6 (4)
N2—Cu1—N6ⁱ	95.79 (14)	S2—C8—C13	120.2 (3)
N3—Cu1—N4	88.15 (15)	C9—C8—C13	120.2 (4)
N3—Cu1—N6ⁱ	77.05 (14)	C18—C19—C20	119.5 (4)
N4—Cu1—N6ⁱ	97.51 (14)	C18—C19—H191	119.8
O4—S2—N2	113.82 (19)	C20—C19—H191	120.7
O4—S2—O3	115.7 (2)	C15—C20—N2	113.5 (3)
N2—S2—O3	105.62 (19)	C15—C20—C19	120.8 (4)
O4—S2—C8	106.3 (2)	N2—C20—C19	125.7 (4)
N2—S2—C8	105.29 (19)	C13—C12—C11	121.6 (5)
O3—S2—C8	109.64 (19)	C13—C12—H121	118.3
O1—S1—O2	116.3 (2)	C11—C12—H121	120.1
O1—S1—N1	106.33 (18)	C8—C9—C10	119.8 (5)
O2—S1—N1	112.81 (19)	C8—C9—H91	120.2
O1—S1—C1	106.72 (19)	C10—C9—H91	120.0
O2—S1—C1	106.8 (2)	C3—C4—C5	118.1 (5)
N1—S1—C1	107.52 (19)	C3—C4—C7	119.9 (5)
S2—N2—Cu1	125.7 (2)	C5—C4—C7	121.9 (5)
S2—N2—C20	120.9 (3)	C4—C3—C2	121.7 (4)
Cu1—N2—C20	112.5 (3)	C4—C3—H31	119.4
N1—C15—C16	127.4 (4)	C2—C3—H31	118.9
N1—C15—C20	114.1 (4)	C18—C22—N6	178.2 (5)
C16—C15—C20	118.4 (4)	C6—C5—C4	120.8 (4)
C17—C18—C19	120.1 (4)	C6—C5—H51	119.0
C17—C18—C22	119.9 (4)	C4—C5—H51	120.1
C19—C18—C22	119.8 (4)	C22—N6—Cu1ⁱ	109.3 (4)
C15—N1—S1	120.3 (3)	C12—C13—C8	119.4 (4)
C15—N1—Cu1	110.3 (2)	C12—C13—H131	120.1
S1—N1—Cu1	127.2 (2)	C8—C13—H131	120.4
C18—C17—C16	119.9 (4)	C9—C10—C11	120.4 (5)
C18—C17—C21	119.7 (4)	C9—C10—H101	119.4
C16—C17—C21	120.4 (4)	C11—C10—H101	120.2
H7—O5—H8	101.4	C1—C2—C3	119.1 (4)
S1—C1—C6	120.0 (3)	C1—C2—H21	120.3
S1—C1—C2	119.8 (3)	C3—C2—H21	120.6
C6—C1—C2	120.1 (4)	C10—C11—C12	118.5 (5)
Cu1—N3—H1	111.9	C10—C11—C14	121.3 (5)
Cu1—N3—H2	109.7	C12—C11—C14	120.2 (6)
H1—N3—H2	108.5	C4—C7—H71	109.7
Cu1—N3—H3	110.5	C4—C7—H72	111.4
H1—N3—H3	109.2	H71—C7—H72	108.7
H2—N3—H3	106.8	C4—C7—H73	110.6
Cu1—N4—H6	108.2	H71—C7—H73	108.1
Cu1—N4—H5	107.9	H72—C7—H73	108.2
H6—N4—H5	108.8	C11—C14—H141	108.7
Cu1—N4—H4	111.9	C11—C14—H142	110.0
H6—N4—H4	111.3	H141—C14—H142	109.0
H5—N4—H4	108.6	C11—C14—H143	110.5
C1—C6—C5	120.2 (4)	H141—C14—H143	109.4
C1—C6—H61	119.0	H142—C14—H143	109.3

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2···O3	0.85	2.48	2.860 (5)	108
N4—H4···O1	0.83	1.93	2.648 (5)	144
O5—H7···O2	0.81	2.38	2.934 (6)	126
C2—H21···O2	0.93	2.53	2.905 (7)	105
C13—H131···O4	0.92	2.54	2.900 (7)	104
O5ⁱ—H8ⁱ···O4	0.81	2.41	2.962 (6)	126
N3—H1···O2ⁱⁱ	0.85	2.18	2.993 (5)	159
N4—H5···O5ⁱⁱ	0.83	2.07	2.630 (5)	124
N3—H3···N6ⁱⁱⁱ	0.84	2.22	2.970 (6)	148
O5—H8···O4^iv	0.81	2.54	3.178 (5)	137
O5—H7···O3^iv	0.81	2.54	3.239 (6)	146
C2—H21···O3^iv	0.93	2.53	3.422 (7)	162

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

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Format		BIBTeX
		EndNote
		RefMan
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		Medline
		CIF
		SGML
		Text
		Plain Text

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Bis[μ-4,5-dicyano-N,N′-bis­(p-tolyl­sulfon­yl)-o-phenyl­enediaminato]bis­[diamminecopper(II)] dihydrate

Supporting information

Key indicators

checkCIF/PLATON results

Bis[μ-4,5-dicyano-N,N′-bis(p-tolylsulfonyl)-o-phenylenediaminato]bis[diamminecopper(II)] dihydrate