(Benzoato-κO)bis-(1,10-phenanthroline-κN,N')copper(II) chloride benzoic acid disolvate.

In the title complex, [Cu(C(7)H(5)O(2))(C(12)H(8)N(2))(2)]Cl·2C(6)H(5)CO-OH, the Cu(II) ion is coordinated by one carboxyl-ate O atom from a benzoate anion and four N atoms from two phenantroline ligands in a distorted five-coordinate trigonal-bipyramidal CuON(4) chromophore. The Cu(2+) and the Cl(-) ion are imposed by a twofold rotation axiss which also bisects the equally disordered benzoate anion. In the crystal, the mol-ecules are assembled into chains along [010] by C-H⋯Cl, O-H⋯Cl and C-H⋯O hydrogen-bonding inter-actions. The resulting chains are further connected into two-dimensional supra-molecular layers parallel to [100] by inter-chain π⋯π stacking inter-actions [centroid-centroid distance = 3.823 (5) Å] between the phenanthroline ligands and the benzoic acid mol-ecules, and by C-H⋯O hydrogen-bonding inter-actions. Strong π⋯π stacking inter-actions between adjacent phenantroline ligands [3.548 (4) Å] assemble the layers into a three-dimensional supra-molecular architecture.

Related literature

For copper–aromatic acid coordination polymers, see: Li et al. (2006 ▶); Devereux et al. (2007 ▶). For related structures, see: Mao et al. (2001 ▶). For the τ parameter, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(C7H5O2)(C12H8N2)2]Cl·2C7H6O2

M = 824.74

Monoclinic,

a = 16.724 (3) Å

b = 19.288 (4) Å

c = 13.295 (3) Å

β = 113.86 (3)°

V = 3922.1 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.68 mm−1

T = 293 K

0.35 × 0.31 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.710, T max = 0.750

15193 measured reflections

3449 independent reflections

2623 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.101

S = 1.08

3449 reflections

286 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.45 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011487/zq2032sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011487/zq2032Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C7H5O2)(C12H8N2)2]Cl·2C7H6O2	F(000) = 1700
Mr = 824.74	Dx = 1.397 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 15193 reflections
a = 16.724 (3) Å	θ = 3.2–25.0°
b = 19.288 (4) Å	µ = 0.68 mm−1
c = 13.295 (3) Å	T = 293 K
β = 113.86 (3)°	Block, blue
V = 3922.1 (14) Å3	0.35 × 0.31 × 0.28 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	3449 independent reflections
Radiation source: fine-focus sealed tube	2623 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 0 pixels mm-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −19→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
Tmin = 0.710, Tmax = 0.750	l = −15→15
15193 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0393P)2 + 3.5087P] where P = (Fo2 + 2Fc2)/3
3449 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.5000	0.26282 (3)	0.2500	0.05651 (17)
N1	0.40747 (13)	0.19982 (11)	0.12871 (18)	0.0554 (5)
N2	0.40438 (13)	0.26263 (12)	0.30525 (18)	0.0565 (5)
O1	0.4521 (4)	0.3849 (3)	0.1410 (5)	0.090 (2)	0.50
O2	0.5351 (3)	0.3568 (3)	0.3129 (5)	0.0600 (12)	0.50
C1	0.5000	0.4012 (3)	0.2500	0.0678 (11)
C2	0.5084 (4)	0.47718 (18)	0.2698 (3)	0.0556 (17)	0.50
C3	0.4829 (4)	0.5284 (3)	0.1894 (2)	0.0788 (19)	0.50
H3A	0.4598	0.5159	0.1131	0.095*	0.50
C4	0.4907 (5)	0.5979 (2)	0.2196 (3)	0.075 (3)	0.50
H4A	0.4731	0.6333	0.1641	0.090*	0.50
C5	0.5240 (5)	0.61615 (16)	0.3302 (4)	0.084 (3)	0.50
H5A	0.5295	0.6641	0.3511	0.100*	0.50
C6	0.5495 (3)	0.5649 (2)	0.4106 (3)	0.0794 (18)	0.50
H6A	0.5726	0.5775	0.4869	0.095*	0.50
C7	0.5417 (3)	0.49540 (19)	0.3803 (3)	0.0639 (15)	0.50
H7A	0.5593	0.4600	0.4358	0.077*	0.50
C8	0.4095 (2)	0.16743 (16)	0.0414 (2)	0.0694 (8)
H8A	0.4614	0.1678	0.0313	0.083*
C9	0.3373 (2)	0.13300 (16)	−0.0355 (3)	0.0791 (9)
H9A	0.3417	0.1106	−0.0950	0.095*
C10	0.2608 (2)	0.13242 (17)	−0.0231 (3)	0.0794 (9)
H10A	0.2123	0.1097	−0.0742	0.095*
C11	0.25483 (17)	0.16598 (14)	0.0667 (2)	0.0620 (7)
C12	0.17667 (18)	0.16982 (17)	0.0868 (3)	0.0790 (9)
H12A	0.1260	0.1485	0.0379	0.095*
C13	0.17515 (18)	0.20324 (17)	0.1738 (3)	0.0773 (9)
H13A	0.1231	0.2055	0.1835	0.093*
C14	0.25144 (16)	0.23560 (14)	0.2524 (2)	0.0596 (7)
C15	0.25428 (19)	0.27038 (17)	0.3459 (3)	0.0726 (8)
H15A	0.2041	0.2741	0.3596	0.087*
C16	0.3303 (2)	0.29866 (18)	0.4164 (3)	0.0773 (9)
H16A	0.3330	0.3211	0.4796	0.093*
C17	0.40467 (19)	0.29405 (17)	0.3938 (3)	0.0728 (8)
H17A	0.4565	0.3138	0.4430	0.087*
C18	0.32904 (15)	0.23281 (13)	0.2352 (2)	0.0502 (6)
C19	0.33051 (15)	0.19836 (13)	0.1411 (2)	0.0509 (6)
C20	0.6442 (2)	0.89663 (16)	0.5209 (3)	0.0723 (8)
C21	0.6652 (2)	0.94046 (15)	0.6202 (3)	0.0673 (8)
C22	0.7514 (2)	0.9571 (2)	0.6830 (3)	0.0868 (10)
H22A	0.7949	0.9405	0.6626	0.104*
C23	0.7738 (3)	0.9976 (2)	0.7744 (3)	0.1056 (12)
H23A	0.8322	1.0083	0.8157	0.127*
C24	0.7114 (3)	1.0223 (2)	0.8054 (4)	0.1033 (12)
H24A	0.7268	1.0498	0.8680	0.124*
C25	0.6259 (3)	1.0067 (2)	0.7445 (4)	0.1094 (14)
H25A	0.5833	1.0236	0.7662	0.131*
C26	0.6014 (2)	0.96621 (18)	0.6513 (3)	0.0901 (11)
H26A	0.5427	0.9564	0.6100	0.108*
Cl	0.5000	0.80270 (7)	0.2500	0.0916 (4)
O4	0.69924 (15)	0.87024 (14)	0.4972 (2)	0.1004 (8)
O3	0.55968 (17)	0.88975 (14)	0.4593 (2)	0.0977 (8)
H31	0.544 (3)	0.867 (2)	0.400 (3)	0.117*

	U11	U22	U33	U12	U13	U23
Cu	0.0442 (3)	0.0686 (3)	0.0647 (3)	0.000	0.0303 (2)	0.000
N1	0.0514 (12)	0.0577 (13)	0.0631 (13)	0.0028 (10)	0.0293 (11)	−0.0023 (11)
N2	0.0457 (11)	0.0689 (14)	0.0605 (13)	−0.0025 (10)	0.0274 (11)	−0.0060 (11)
O1	0.074 (3)	0.099 (5)	0.066 (4)	0.006 (3)	−0.003 (3)	−0.021 (3)
O2	0.048 (3)	0.066 (3)	0.065 (3)	−0.003 (2)	0.021 (3)	−0.001 (2)
C1	0.043 (2)	0.069 (3)	0.090 (4)	0.000	0.025 (2)	0.000
C2	0.036 (3)	0.071 (3)	0.057 (5)	0.001 (4)	0.015 (4)	0.008 (3)
C3	0.051 (4)	0.108 (6)	0.068 (4)	0.009 (4)	0.014 (3)	0.018 (4)
C4	0.066 (5)	0.059 (4)	0.099 (10)	0.010 (5)	0.031 (7)	0.030 (4)
C5	0.066 (5)	0.062 (4)	0.118 (8)	0.009 (4)	0.033 (6)	−0.016 (5)
C6	0.086 (4)	0.067 (4)	0.077 (4)	0.000 (3)	0.025 (4)	−0.008 (4)
C7	0.065 (4)	0.060 (4)	0.062 (4)	0.000 (3)	0.020 (3)	−0.004 (3)
C8	0.0703 (18)	0.071 (2)	0.077 (2)	0.0054 (16)	0.0401 (17)	−0.0067 (16)
C9	0.088 (2)	0.071 (2)	0.075 (2)	−0.0002 (18)	0.0290 (18)	−0.0246 (17)
C10	0.0640 (19)	0.075 (2)	0.085 (2)	−0.0066 (16)	0.0146 (17)	−0.0168 (18)
C11	0.0550 (16)	0.0535 (16)	0.0726 (19)	−0.0011 (13)	0.0207 (14)	−0.0038 (14)
C12	0.0483 (16)	0.078 (2)	0.105 (3)	−0.0131 (15)	0.0248 (17)	−0.009 (2)
C13	0.0491 (16)	0.081 (2)	0.108 (3)	−0.0054 (15)	0.0388 (18)	0.000 (2)
C14	0.0462 (14)	0.0615 (17)	0.0778 (18)	0.0016 (13)	0.0322 (14)	0.0083 (15)
C15	0.0616 (18)	0.086 (2)	0.090 (2)	0.0066 (16)	0.0514 (18)	0.0042 (18)
C16	0.071 (2)	0.097 (2)	0.080 (2)	0.0014 (18)	0.0474 (18)	−0.0120 (18)
C17	0.0627 (17)	0.093 (2)	0.0726 (19)	−0.0080 (16)	0.0373 (16)	−0.0174 (17)
C18	0.0423 (13)	0.0502 (14)	0.0619 (15)	0.0033 (11)	0.0248 (12)	0.0061 (13)
C19	0.0450 (13)	0.0464 (15)	0.0629 (16)	0.0042 (11)	0.0237 (13)	0.0044 (12)
C20	0.080 (2)	0.0680 (19)	0.093 (2)	0.0097 (16)	0.061 (2)	0.0170 (17)
C21	0.083 (2)	0.0550 (17)	0.088 (2)	0.0119 (15)	0.0592 (19)	0.0123 (15)
C22	0.073 (2)	0.106 (3)	0.093 (3)	0.0252 (19)	0.044 (2)	0.014 (2)
C23	0.089 (3)	0.132 (4)	0.093 (3)	0.011 (2)	0.034 (2)	−0.005 (3)
C24	0.115 (3)	0.106 (3)	0.105 (3)	−0.002 (3)	0.061 (3)	−0.014 (2)
C25	0.115 (3)	0.105 (3)	0.146 (4)	−0.003 (3)	0.093 (3)	−0.031 (3)
C26	0.084 (2)	0.085 (2)	0.129 (3)	−0.0038 (18)	0.072 (2)	−0.016 (2)
Cl	0.0794 (8)	0.0839 (8)	0.1148 (10)	0.000	0.0425 (7)	0.000
O4	0.0964 (16)	0.121 (2)	0.1100 (18)	0.0257 (15)	0.0688 (15)	−0.0062 (15)
O3	0.0869 (17)	0.113 (2)	0.118 (2)	−0.0093 (14)	0.0673 (17)	−0.0255 (16)

Cu—O2	1.984 (5)	C11—C19	1.399 (4)
Cu—O2i	1.984 (5)	C11—C12	1.438 (4)
Cu—N2i	2.012 (2)	C12—C13	1.334 (4)
Cu—N2	2.012 (2)	C12—H12A	0.9300
Cu—N1	2.110 (2)	C13—C14	1.425 (4)
Cu—N1i	2.110 (2)	C13—H13A	0.9300
N1—C8	1.330 (3)	C14—C15	1.396 (4)
N1—C19	1.362 (3)	C14—C18	1.407 (3)
N2—C17	1.322 (3)	C15—C16	1.352 (4)
N2—C18	1.355 (3)	C15—H15A	0.9300
O1—C1	1.378 (6)	C16—C17	1.395 (4)
O2—C1	1.174 (6)	C16—H16A	0.9300
C1—C2	1.486 (6)	C17—H17A	0.9300
C2—C3	1.3900	C18—C19	1.425 (3)
C2—C7	1.3900	C20—O4	1.200 (3)
C3—C4	1.3900	C20—O3	1.323 (4)
C3—H3A	0.9600	C20—C21	1.485 (4)
C4—C5	1.3900	C21—C22	1.380 (5)
C4—H4A	0.9600	C21—C26	1.384 (4)
C5—C6	1.3900	C22—C23	1.363 (5)
C5—H5A	0.9601	C22—H22A	0.9300
C6—C7	1.3900	C23—C24	1.355 (5)
C6—H6A	0.9599	C23—H23A	0.9300
C7—H7A	0.9601	C24—C25	1.361 (5)
C8—C9	1.395 (4)	C24—H24A	0.9300
C8—H8A	0.9300	C25—C26	1.379 (5)
C9—C10	1.356 (4)	C25—H25A	0.9300
C9—H9A	0.9300	C26—H26A	0.9300
C10—C11	1.395 (4)	Cl—Cli	0.000 (3)
C10—H10A	0.9300	O3—H31	0.85 (4)
O2—Cu—O2i	47.8 (3)	C11—C10—H10A	120.1
O2—Cu—N2i	90.69 (16)	C10—C11—C19	117.1 (3)
O2i—Cu—N2i	89.49 (16)	C10—C11—C12	124.5 (3)
O2—Cu—N2	89.49 (16)	C19—C11—C12	118.4 (3)
O2i—Cu—N2	90.69 (16)	C13—C12—C11	121.6 (3)
N2i—Cu—N2	179.80 (13)	C13—C12—H12A	119.2
O2—Cu—N1	148.10 (18)	C11—C12—H12A	119.2
O2i—Cu—N1	101.76 (18)	C12—C13—C14	121.5 (3)
N2i—Cu—N1	99.53 (8)	C12—C13—H13A	119.3
N2—Cu—N1	80.35 (8)	C14—C13—H13A	119.3
O2—Cu—N1i	101.76 (18)	C15—C14—C18	117.5 (3)
O2i—Cu—N1i	148.10 (18)	C15—C14—C13	124.1 (3)
N2i—Cu—N1i	80.35 (8)	C18—C14—C13	118.4 (3)
N2—Cu—N1i	99.53 (8)	C16—C15—C14	119.7 (2)
N1—Cu—N1i	109.69 (12)	C16—C15—H15A	120.2
C8—N1—C19	117.0 (2)	C14—C15—H15A	120.2
C8—N1—Cu	131.86 (18)	C15—C16—C17	119.7 (3)
C19—N1—Cu	110.87 (16)	C15—C16—H16A	120.2
C17—N2—C18	118.3 (2)	C17—C16—H16A	120.2
C17—N2—Cu	127.38 (19)	N2—C17—C16	122.6 (3)
C18—N2—Cu	113.88 (16)	N2—C17—H17A	118.7
C1—O2—Cu	112.8 (4)	C16—C17—H17A	118.7
O2—C1—O1	119.6 (6)	N2—C18—C14	122.3 (2)
O2—C1—C2	127.5 (4)	N2—C18—C19	117.4 (2)
O1—C1—C2	112.6 (4)	C14—C18—C19	120.3 (2)
C3—C2—C7	120.0	N1—C19—C11	123.5 (2)
C3—C2—C1	126.0 (3)	N1—C19—C18	116.7 (2)
C7—C2—C1	113.9 (3)	C11—C19—C18	119.8 (2)
C4—C3—C2	120.0	O4—C20—O3	122.4 (3)
C4—C3—H3A	120.0	O4—C20—C21	122.9 (3)
C2—C3—H3A	120.0	O3—C20—C21	114.6 (3)
C3—C4—C5	120.0	C22—C21—C26	118.6 (3)
C3—C4—H4A	120.0	C22—C21—C20	119.0 (3)
C5—C4—H4A	120.0	C26—C21—C20	122.5 (3)
C4—C5—C6	120.0	C23—C22—C21	121.1 (3)
C4—C5—H5A	120.0	C23—C22—H22A	119.5
C6—C5—H5A	120.0	C21—C22—H22A	119.5
C7—C6—C5	120.0	C24—C23—C22	120.3 (4)
C7—C6—H6A	120.0	C24—C23—H23A	119.8
C5—C6—H6A	120.0	C22—C23—H23A	119.8
C6—C7—C2	120.0	C23—C24—C25	119.6 (4)
C6—C7—H7A	120.0	C23—C24—H24A	120.2
C2—C7—H7A	120.0	C25—C24—H24A	120.2
N1—C8—C9	122.9 (3)	C24—C25—C26	121.3 (3)
N1—C8—H8A	118.5	C24—C25—H25A	119.4
C9—C8—H8A	118.5	C26—C25—H25A	119.4
C10—C9—C8	119.6 (3)	C25—C26—C21	119.2 (4)
C10—C9—H9A	120.2	C25—C26—H26A	120.4
C8—C9—H9A	120.2	C21—C26—H26A	120.4
C9—C10—C11	119.9 (3)	C20—O3—H31	119 (3)
C9—C10—H10A	120.1

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cl	0.96	2.94	3.728 (4)	140
O3—H31···Cl	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
O3—H31···Cli	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
C24—H24A···O4ii	0.93	2.49	3.355 (5)	155
C8—H8A···O3iii	0.93	2.47	3.307 (4)	149
C10—H10A···O1iv	0.93	2.53	3.275 (7)	138
C12—H12A···O1iv	0.93	2.30	3.106 (7)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cl	0.96	2.94	3.728 (4)	140
O3—H31⋯Cl	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
O3—H31⋯Cli	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
C24—H24A⋯O4ii	0.93	2.49	3.355 (5)	155
C8—H8A⋯O3iii	0.93	2.47	3.307 (4)	149
C10—H10A⋯O1iv	0.93	2.53	3.275 (7)	138
C12—H12A⋯O1iv	0.93	2.30	3.106 (7)	146

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .