6,7-Dihydro-5H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium tris­(thio­cyanato-κN)cuprate(I)

Xu, N.; Niu, Y.-Y.; Ng, S.W.

doi:10.1107/S1600536810036779

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1280

doi:10.1107/S1600536810036779

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6,7-Dihydro-5H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium tris(thiocyanato-κN)cuprate(I)

Na Xu,^a Yun-Yin Niu ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 September 2010; accepted 14 September 2010; online 18 September 2010)

The title copper(I) salt, (C₁₅H₁₄N₂)[Cu(NCS)₃], exists as non-interacting cations and trigonal–planar anions. The cation is buckled, the r.m.s. deviation of the atoms passing through the phenanthroline portion being 0.16 Å. The Cu^I atom is displaced by 0.019 (2) Å out of the N₃ triangle. The crystal studied was a non-merohedral twin with twin domains in an approximate ratio of 55:45.

Related literature

For a three-coordinate tris(thiocyanato)cuprate(I) system, see: Song et al. (2008 ). For a study of the title cation, see: Liu et al. (2007 ).

Experimental

Crystal data

(C₁₅H₁₄N₂)[Cu(NCS)₃]
M_r = 460.06
Monoclinic, P 2₁ /n
a = 17.2687 (4) Å
b = 6.5825 (2) Å
c = 17.2702 (4) Å
β = 107.803 (2)°
V = 1869.12 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 100 K
0.25 × 0.02 × 0.02 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.703, T_max = 0.970
15488 measured reflections
4303 independent reflections
3657 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.075
S = 0.99
4303 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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/S1600536810036779/zs2065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036779/zs2065Isup2.hkl

checkCIF report

Comment top

There is no report on a free, three-coordinate tris(thiocyanato)cuprate(I or II) ion in the structural literature. The potassium–benzene-18-crown-6 salt has the copper(I) atom in a three-coordinate environment but the sulfur ends of the thiocyanate ligands are also engaged in coordination (Song et al., 2008). The title salt (Scheme I, Fig. 1) represents the first example of a three-coordinate trithiocyanatocuprate(I) system; the salt exists as discrete cations and anions. On the other hand, the cation has also been documented only once in the structural literature (Liu et al., 2007). In the present salt, the phenanthroline portion is severely buckled (r.m.s. deviation of the plane passing through the atoms comprising the phenanthroline portion being 0.16 Å), with the nitrogen atoms deviating the largest distances (0.30, 0.30 Å).

Related literature top

For a three-coordinate tris(thiocyanato)cuprate(I) system, see: Song et al. (2008). For a study of the title cation, see: Liu et al. (2007).

Experimental top

6,7-Dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium] dibromide was synthesized by reacting 1,3-dibromopropane with 1,10-phenanthroline monohydrate. A methanol solution (10 ml) of the salt (0.40 g, 1 mmol) was mixed with a water/DMF (1:4) solution (10 ml) of colorless copper(I) thiocyanate (0.12 g, 1 mmol). An excess of potassium thiocyanate (0.50 g, 5 mmol) was added. The solution was filtered and the solvent allow to evaporate slowly to furnish dark brown crystals of the cuprate salt.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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. Displacement ellipsoid plot (Barbour, 2001) of [C₁₅H₁₄N₂]²⁺ [Cu(NCS)₃]^2- at the 70% probability level.

6,7-Dihydro-5H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline- 4,8-diium tris(thiocyanato-κN)cuprate(I) top

Crystal data top

(C₁₅H₁₄N₂)[Cu(NCS)₃]	F(000) = 936
M_r = 460.06	D_x = 1.635 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2549 reflections
a = 17.2687 (4) Å	θ = 2.5–27.3°
b = 6.5825 (2) Å	µ = 1.52 mm⁻¹
c = 17.2702 (4) Å	T = 100 K
β = 107.803 (2)°	Prism, brown
V = 1869.12 (8) Å³	0.25 × 0.02 × 0.02 mm
Z = 4

Data collection top

Bruker SMART APEX CCD-detector diffractometer	4303 independent reflections
Radiation source: fine-focus sealed tube	3657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 27.5°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→21
T_min = 0.703, T_max = 0.970	k = −8→8
15488 measured reflections	l = −22→21

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0347P)²] where P = (F_o² + 2F_c²)/3
4303 reflections	(Δ/σ)_max = 0.001
245 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

(C₁₅H₁₄N₂)[Cu(NCS)₃]	V = 1869.12 (8) Å³
M_r = 460.06	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 17.2687 (4) Å	µ = 1.52 mm⁻¹
b = 6.5825 (2) Å	T = 100 K
c = 17.2702 (4) Å	0.25 × 0.02 × 0.02 mm
β = 107.803 (2)°

Data collection top

Bruker SMART APEX CCD-detector diffractometer	4303 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3657 reflections with I > 2σ(I)
T_min = 0.703, T_max = 0.970	R_int = 0.048
15488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 0.99	Δρ_max = 0.38 e Å⁻³
4303 reflections	Δρ_min = −0.37 e Å⁻³
245 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.58165 (3)	0.28784 (6)	0.33388 (3)	0.01689 (10)
S1	0.30831 (6)	0.32947 (13)	0.33202 (7)	0.0244 (2)
S2	0.81220 (7)	0.20364 (14)	0.55830 (7)	0.0380 (2)
S3	0.57925 (7)	0.23791 (13)	0.06016 (7)	0.0262 (2)
N1	0.06515 (15)	0.3406 (4)	0.21244 (15)	0.0115 (5)
N2	−0.03925 (18)	0.2372 (4)	0.31533 (17)	0.0138 (6)
N3	0.47097 (19)	0.3174 (4)	0.33561 (18)	0.0180 (6)
N4	0.67485 (17)	0.2767 (4)	0.42593 (16)	0.0194 (5)
N5	0.58441 (19)	0.2614 (4)	0.2234 (2)	0.0184 (7)
C1	0.1136 (2)	0.3304 (4)	0.1650 (2)	0.0181 (7)
H1	0.1702	0.3554	0.1879	0.022*
C2	0.0825 (3)	0.2840 (5)	0.0826 (2)	0.0215 (9)
H2	0.1181	0.2658	0.0508	0.026*
C3	0.0010 (3)	0.2649 (5)	0.0479 (2)	0.0222 (9)
H3	−0.0208	0.2456	−0.0091	0.027*
C4	−0.0516 (2)	0.2736 (4)	0.0965 (2)	0.0158 (8)
C5	−0.1377 (3)	0.2680 (4)	0.0618 (3)	0.0219 (8)
H5	−0.1611	0.2509	0.0048	0.026*
C6	−0.1863 (3)	0.2870 (5)	0.1097 (3)	0.0224 (8)
H6	−0.2434	0.2995	0.0856	0.027*
C7	−0.1528 (2)	0.2885 (4)	0.1957 (2)	0.0181 (8)
C8	−0.2032 (2)	0.2962 (5)	0.2473 (2)	0.0216 (9)
H8	−0.2604	0.3089	0.2240	0.026*
C9	−0.1704 (2)	0.2855 (5)	0.3296 (3)	0.0223 (9)
H9	−0.2035	0.3044	0.3640	0.027*
C10	−0.0880 (2)	0.2466 (4)	0.3622 (2)	0.0176 (8)
H10	−0.0656	0.2261	0.4192	0.021*
C11	−0.0685 (2)	0.2773 (4)	0.2317 (2)	0.0122 (7)
C12	−0.0164 (2)	0.2952 (4)	0.1818 (2)	0.0136 (7)
C13	0.09703 (17)	0.4419 (4)	0.29339 (17)	0.0145 (6)
H13A	0.0576	0.5464	0.2984	0.017*
H13B	0.1487	0.5116	0.2965	0.017*
C14	0.11182 (19)	0.2948 (5)	0.3639 (2)	0.0163 (6)
H14A	0.1165	0.3712	0.4145	0.020*
H14B	0.1637	0.2221	0.3711	0.020*
C15	0.04293 (18)	0.1418 (5)	0.34912 (18)	0.0143 (7)
H15A	0.0499	0.0369	0.3107	0.017*
H15B	0.0460	0.0735	0.4011	0.017*
C16	0.4032 (2)	0.3236 (4)	0.3330 (2)	0.0137 (7)
C17	0.7321 (2)	0.2479 (5)	0.4813 (2)	0.0168 (6)
C18	0.5820 (2)	0.2508 (4)	0.1556 (2)	0.0164 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0175 (3)	0.01500 (17)	0.0177 (3)	0.00063 (19)	0.00476 (13)	0.00035 (18)
S1	0.0145 (5)	0.0330 (5)	0.0246 (5)	0.0017 (4)	0.0041 (4)	−0.0004 (4)
S2	0.0355 (7)	0.0243 (5)	0.0366 (7)	0.0063 (4)	−0.0149 (4)	−0.0040 (4)
S3	0.0273 (6)	0.0356 (5)	0.0150 (5)	0.0062 (4)	0.0055 (4)	0.0010 (4)
N1	0.0122 (14)	0.0123 (12)	0.0096 (14)	0.0015 (10)	0.0027 (11)	0.0013 (10)
N2	0.0158 (15)	0.0101 (12)	0.0168 (15)	−0.0002 (10)	0.0068 (12)	−0.0003 (10)
N3	0.0205 (18)	0.0194 (15)	0.0140 (16)	−0.0013 (12)	0.0049 (13)	−0.0032 (11)
N4	0.024 (2)	0.0187 (14)	0.017 (2)	0.0009 (11)	0.0080 (9)	−0.0017 (11)
N5	0.0189 (17)	0.0179 (14)	0.0194 (18)	0.0047 (11)	0.0074 (14)	0.0004 (11)
C1	0.0185 (19)	0.0161 (17)	0.023 (2)	0.0050 (13)	0.0118 (15)	0.0040 (13)
C2	0.032 (2)	0.0166 (18)	0.021 (2)	0.0041 (15)	0.0149 (18)	0.0035 (13)
C3	0.040 (3)	0.0152 (15)	0.012 (2)	0.0002 (14)	0.0082 (18)	0.0010 (12)
C4	0.021 (2)	0.0113 (14)	0.0119 (19)	0.0009 (12)	0.0012 (15)	0.0008 (11)
C5	0.028 (3)	0.0134 (14)	0.014 (2)	−0.0009 (13)	−0.0087 (16)	0.0001 (13)
C6	0.018 (2)	0.0174 (14)	0.023 (3)	−0.0020 (14)	−0.0053 (16)	0.0002 (14)
C7	0.015 (2)	0.0088 (13)	0.029 (2)	−0.0001 (12)	0.0046 (16)	−0.0001 (13)
C8	0.013 (2)	0.0176 (15)	0.034 (2)	−0.0019 (13)	0.0062 (17)	−0.0001 (14)
C9	0.021 (2)	0.0186 (18)	0.034 (3)	−0.0001 (14)	0.0197 (19)	−0.0021 (15)
C10	0.023 (2)	0.0155 (16)	0.0165 (19)	−0.0054 (13)	0.0086 (16)	−0.0009 (12)
C11	0.0148 (19)	0.0092 (15)	0.0106 (18)	0.0025 (12)	0.0009 (14)	−0.0002 (12)
C12	0.0182 (19)	0.0094 (15)	0.0121 (18)	0.0014 (12)	0.0030 (14)	0.0031 (11)
C13	0.0133 (16)	0.0156 (15)	0.0133 (16)	−0.0012 (11)	0.0022 (12)	−0.0015 (11)
C14	0.0136 (19)	0.0207 (16)	0.0139 (19)	−0.0030 (12)	0.0032 (10)	0.0031 (12)
C15	0.0132 (15)	0.0165 (15)	0.0130 (16)	0.0020 (12)	0.0038 (13)	0.0043 (12)
C16	0.017 (2)	0.0129 (16)	0.0096 (17)	0.0021 (12)	0.0022 (13)	−0.0002 (11)
C17	0.019 (2)	0.0116 (17)	0.022 (2)	0.0000 (12)	0.0097 (11)	−0.0038 (13)
C18	0.0095 (18)	0.0114 (15)	0.027 (2)	0.0013 (11)	0.0027 (15)	0.0000 (12)

Geometric parameters (Å, º) top

Cu1—N4	1.886 (2)	C4—C5	1.423 (5)
Cu1—N3	1.930 (3)	C5—C6	1.353 (4)
Cu1—N5	1.930 (3)	C5—H5	0.9500
S1—C16	1.634 (4)	C6—C7	1.419 (6)
S2—C17	1.626 (3)	C6—H6	0.9500
S3—C18	1.637 (4)	C7—C11	1.400 (5)
N1—C1	1.340 (4)	C7—C8	1.424 (5)
N1—C12	1.378 (4)	C8—C9	1.361 (6)
N1—C13	1.494 (4)	C8—H8	0.9500
N2—C10	1.336 (4)	C9—C10	1.385 (6)
N2—C11	1.401 (4)	C9—H9	0.9500
N2—C15	1.497 (4)	C10—H10	0.9500
N3—C16	1.158 (4)	C11—C12	1.429 (4)
N4—C17	1.161 (3)	C13—C14	1.515 (4)
N5—C18	1.161 (5)	C13—H13A	0.9900
C1—C2	1.393 (5)	C13—H13B	0.9900
C1—H1	0.9500	C14—C15	1.519 (4)
C2—C3	1.356 (6)	C14—H14A	0.9900
C2—H2	0.9500	C14—H14B	0.9900
C3—C4	1.413 (5)	C15—H15A	0.9900
C3—H3	0.9500	C15—H15B	0.9900
C4—C12	1.418 (5)

N4—Cu1—N3	125.77 (14)	C7—C8—H8	119.6
N4—Cu1—N5	123.83 (15)	C8—C9—C10	118.9 (3)
N3—Cu1—N5	110.37 (9)	C8—C9—H9	120.6
C1—N1—C12	120.7 (3)	C10—C9—H9	120.6
C1—N1—C13	118.3 (3)	N2—C10—C9	121.4 (4)
C12—N1—C13	119.9 (2)	N2—C10—H10	119.3
C10—N2—C11	121.4 (3)	C9—C10—H10	119.3
C10—N2—C15	118.7 (3)	C7—C11—N2	117.8 (3)
C11—N2—C15	118.7 (3)	C7—C11—C12	119.2 (4)
C16—N3—Cu1	175.2 (3)	N2—C11—C12	122.9 (4)
C17—N4—Cu1	172.8 (2)	N1—C12—C4	119.0 (3)
C18—N5—Cu1	176.2 (3)	N1—C12—C11	122.9 (3)
N1—C1—C2	121.2 (3)	C4—C12—C11	118.0 (4)
N1—C1—H1	119.4	N1—C13—C14	113.0 (2)
C2—C1—H1	119.4	N1—C13—H13A	109.0
C3—C2—C1	119.7 (3)	C14—C13—H13A	109.0
C3—C2—H2	120.1	N1—C13—H13B	109.0
C1—C2—H2	120.1	C14—C13—H13B	109.0
C2—C3—C4	120.2 (3)	H13A—C13—H13B	107.8
C2—C3—H3	119.9	C13—C14—C15	110.9 (2)
C4—C3—H3	119.9	C13—C14—H14A	109.4
C3—C4—C12	118.1 (3)	C15—C14—H14A	109.4
C3—C4—C5	121.8 (3)	C13—C14—H14B	109.4
C12—C4—C5	120.1 (3)	C15—C14—H14B	109.4
C6—C5—C4	120.2 (5)	H14A—C14—H14B	108.0
C6—C5—H5	119.9	N2—C15—C14	112.8 (2)
C4—C5—H5	119.9	N2—C15—H15A	109.0
C5—C6—C7	120.7 (5)	C14—C15—H15A	109.0
C5—C6—H6	119.7	N2—C15—H15B	109.0
C7—C6—H6	119.7	C14—C15—H15B	109.0
C11—C7—C6	120.0 (3)	H15A—C15—H15B	107.8
C11—C7—C8	118.4 (3)	N3—C16—S1	178.3 (3)
C6—C7—C8	121.6 (3)	N4—C17—S2	179.0 (3)
C9—C8—C7	120.8 (3)	N5—C18—S3	179.4 (3)
C9—C8—H8	119.6

C12—N1—C1—C2	3.3 (5)	C15—N2—C11—C7	155.2 (3)
C13—N1—C1—C2	−164.4 (3)	C10—N2—C11—C12	171.5 (3)
N1—C1—C2—C3	5.5 (5)	C15—N2—C11—C12	−21.0 (4)
C1—C2—C3—C4	−5.8 (5)	C1—N1—C12—C4	−11.3 (4)
C2—C3—C4—C12	−2.2 (4)	C13—N1—C12—C4	156.1 (3)
C2—C3—C4—C5	175.7 (3)	C1—N1—C12—C11	171.5 (3)
C3—C4—C5—C6	−176.6 (3)	C13—N1—C12—C11	−21.1 (4)
C12—C4—C5—C6	1.2 (4)	C3—C4—C12—N1	10.7 (4)
C4—C5—C6—C7	−7.5 (4)	C5—C4—C12—N1	−167.2 (3)
C5—C6—C7—C11	2.2 (4)	C3—C4—C12—C11	−172.0 (3)
C5—C6—C7—C8	−176.2 (3)	C5—C4—C12—C11	10.1 (4)
C11—C7—C8—C9	−2.4 (5)	C7—C11—C12—N1	162.0 (3)
C6—C7—C8—C9	176.1 (3)	N2—C11—C12—N1	−21.8 (4)
C7—C8—C9—C10	−6.4 (5)	C7—C11—C12—C4	−15.2 (4)
C11—N2—C10—C9	3.6 (4)	N2—C11—C12—C4	161.0 (3)
C15—N2—C10—C9	−163.9 (3)	C1—N1—C13—C14	−111.1 (3)
C8—C9—C10—N2	5.9 (5)	C12—N1—C13—C14	81.2 (3)
C6—C7—C11—N2	−167.1 (3)	N1—C13—C14—C15	−42.1 (4)
C8—C7—C11—N2	11.4 (4)	C10—N2—C15—C14	−110.8 (3)
C6—C7—C11—C12	9.3 (4)	C11—N2—C15—C14	81.4 (3)
C8—C7—C11—C12	−172.2 (3)	C13—C14—C15—N2	−43.3 (4)
C10—N2—C11—C7	−12.3 (4)

Experimental details

Crystal data
Chemical formula	(C₁₅H₁₄N₂)[Cu(NCS)₃]
M_r	460.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	17.2687 (4), 6.5825 (2), 17.2702 (4)
β (°)	107.803 (2)
V (Å³)	1869.12 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.25 × 0.02 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.703, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	15488, 4303, 3657
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.075, 0.99
No. of reflections	4303
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.37

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the National Natural Science Foundation of China (No. 20671083) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Y., Li, Q., Guo, G.-S. & Chen, K. (2007). Cryst. Growth Des. 7, 1672–1675. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, X.-M., Huang, X.-Q., Dou, J.-M. & Li, D.-C. (2008). Acta Cryst. E64, m489. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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