Poly[[chlorido­(1,10-phenanthroline-[kappa]²N,N')copper(II)]-[mu]₃-1,1,3,3-tetra­cyano-2-eth­oxy­propenido-[kappa]³N:N':N'']: coordination polymer sheets linked into bilayers by hydrogen bonds

In the title compound, [Cu(C₉H₅N₄O)Cl(C₁₂H₈N₂)]_n or [Cu(tcnoet)Cl(phen)]_n, where phen is 1,10-phenanthroline and tcnoet is 1,1,3,3-tetra­cyano-2-eth­oxy­propenide, the axially elongated (4 + 2) coordination polyhedron around the Cu^II centre contains N atoms from three different tcnoet ligands. The resulting coordination polymer takes the form of sheets which are linked in pairs by a single C-H...N hydrogen bond to form bilayers. The bond lengths provide evidence for significant bond fixation in the phen ligand and extensive electronic delocalization in the tcnoet ligand, where the two -C(CN)₂ units are rotated, in conrotatory fashion, out of the plane of the central C₃O fragment.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and 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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Poly[[chlorido(1,10-phenanthroline-κ²N,N')copper(II)]-µ₃-1,1,3,3-tetracyano-2-ethoxypropenido-κ³N:N':N'']

Crystal data

[Cu(C9H5N4O)Cl(C12H8N2)]	F(000) = 1880
Mr = 464.37	Dx = 1.544 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6366 reflections
a = 31.79 (3) Å	θ = 2.6–31.0°
b = 7.925 (6) Å	µ = 1.25 mm^−1
c = 16.005 (13) Å	T = 296 K
β = 97.69 (3)°	Plate, green
V = 3996 (6) Å^3	0.27 × 0.23 × 0.14 mm
Z = 8

Data collection

Bruker X8 APEXII area-detector diffractometer	4596 independent reflections
Radiation source: fine-focus sealed tube	3188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
φ and ω scans	h = −41→41
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.722, Tmax = 0.804	l = −20→20
34518 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 0.7334P] where P = (Fo^2 + 2Fc^2)/3
4596 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.109132 (10)	0.30029 (4)	0.695410 (18)	0.03960 (12)
Cl1	0.05105 (2)	0.44903 (10)	0.64741 (5)	0.0578 (2)
N1	0.16459 (7)	0.1941 (2)	0.75086 (13)	0.0384 (5)
C2	0.19716 (9)	0.1342 (4)	0.71602 (18)	0.0504 (7)
H2	0.1960	0.1372	0.6577	0.061*
C3	0.23308 (9)	0.0670 (4)	0.7640 (2)	0.0601 (8)
H3	0.2552	0.0249	0.7374	0.072*
C4	0.23586 (9)	0.0630 (4)	0.8496 (2)	0.0586 (8)
H4	0.2600	0.0195	0.8818	0.070*
C4A	0.20220 (8)	0.1247 (3)	0.88875 (17)	0.0442 (6)
C4B	0.16713 (8)	0.1896 (3)	0.83635 (15)	0.0365 (5)
C5	0.20146 (10)	0.1260 (4)	0.97815 (18)	0.0565 (8)
H5	0.2248	0.0849	1.0136	0.068*
C6	0.16767 (10)	0.1857 (3)	1.01196 (17)	0.0526 (7)
H6	0.1681	0.1853	1.0702	0.063*
C6A	0.13105 (9)	0.2496 (3)	0.95917 (15)	0.0428 (6)
C6B	0.13112 (8)	0.2516 (3)	0.87180 (15)	0.0355 (5)
C7	0.09436 (10)	0.3073 (3)	0.98932 (17)	0.0507 (7)
H7	0.0929	0.3090	1.0470	0.061*
C8	0.06066 (10)	0.3611 (4)	0.93366 (19)	0.0558 (7)
H8	0.0359	0.3976	0.9531	0.067*
C9	0.06358 (9)	0.3610 (3)	0.84764 (18)	0.0483 (7)
H9	0.0405	0.3988	0.8105	0.058*
N10	0.09806 (6)	0.3090 (2)	0.81664 (13)	0.0370 (5)
C11	0.14488 (9)	0.2787 (3)	0.43121 (16)	0.0421 (6)
C12	0.11597 (8)	0.2046 (3)	0.36808 (16)	0.0411 (6)
C13	0.11784 (9)	0.2112 (3)	0.28176 (15)	0.0423 (6)
C111	0.13474 (9)	0.2791 (3)	0.51440 (17)	0.0448 (6)
N111	0.12696 (8)	0.2807 (3)	0.58229 (15)	0.0523 (6)
C112	0.18515 (11)	0.3424 (4)	0.41863 (17)	0.0564 (8)
N112	0.21808 (10)	0.3930 (5)	0.41061 (18)	0.0888 (10)
O121	0.08607 (6)	0.1140 (3)	0.39883 (12)	0.0552 (5)
C121	0.04102 (10)	0.1324 (5)	0.3638 (2)	0.0801 (11)
H21A	0.0377	0.2240	0.3233	0.096*
H21B	0.0309	0.0294	0.3352	0.096*
C122	0.01714 (14)	0.1667 (7)	0.4313 (4)	0.130 (2)
H22A	−0.0118	0.1891	0.4088	0.196*
H22B	0.0289	0.2634	0.4622	0.196*
H22C	0.0183	0.0709	0.4682	0.196*
C131	0.09473 (10)	0.0948 (3)	0.22534 (17)	0.0503 (7)
N131	0.07748 (10)	−0.0037 (3)	0.18067 (17)	0.0710 (8)
C132	0.14346 (9)	0.3290 (3)	0.24406 (17)	0.0450 (6)
N132	0.16247 (9)	0.4237 (3)	0.21067 (16)	0.0617 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0404 (2)	0.0556 (2)	0.02246 (18)	0.00481 (14)	0.00309 (13)	0.00303 (12)
Cl1	0.0434 (4)	0.0846 (5)	0.0444 (4)	0.0096 (3)	0.0016 (3)	0.0217 (3)
N1	0.0375 (12)	0.0507 (11)	0.0273 (11)	0.0018 (9)	0.0053 (9)	−0.0002 (9)
C2	0.0427 (16)	0.0718 (17)	0.0386 (16)	0.0057 (13)	0.0122 (13)	−0.0008 (13)
C3	0.0394 (16)	0.084 (2)	0.059 (2)	0.0145 (14)	0.0147 (15)	−0.0004 (16)
C4	0.0384 (16)	0.080 (2)	0.055 (2)	0.0130 (14)	−0.0019 (14)	0.0055 (15)
C4A	0.0388 (15)	0.0538 (14)	0.0378 (15)	0.0010 (11)	−0.0030 (12)	0.0010 (11)
C4B	0.0371 (14)	0.0428 (12)	0.0293 (14)	−0.0028 (10)	0.0032 (11)	0.0001 (9)
C5	0.0547 (19)	0.0720 (18)	0.0375 (17)	0.0061 (15)	−0.0133 (14)	0.0058 (13)
C6	0.062 (2)	0.0689 (17)	0.0241 (14)	0.0041 (14)	−0.0038 (13)	0.0008 (12)
C6A	0.0544 (17)	0.0492 (13)	0.0243 (13)	0.0007 (12)	0.0034 (12)	−0.0006 (10)
C6B	0.0371 (14)	0.0436 (12)	0.0251 (13)	−0.0007 (10)	0.0023 (11)	0.0003 (9)
C7	0.0625 (19)	0.0647 (16)	0.0267 (14)	0.0034 (14)	0.0128 (13)	−0.0029 (12)
C8	0.0533 (18)	0.0749 (18)	0.0432 (18)	0.0107 (15)	0.0216 (15)	−0.0007 (14)
C9	0.0416 (16)	0.0652 (16)	0.0393 (16)	0.0104 (13)	0.0097 (13)	0.0023 (12)
N10	0.0341 (11)	0.0495 (11)	0.0275 (11)	0.0042 (9)	0.0045 (9)	0.0012 (8)
C11	0.0451 (15)	0.0578 (15)	0.0235 (13)	0.0059 (12)	0.0053 (11)	−0.0010 (10)
C12	0.0412 (15)	0.0497 (14)	0.0321 (14)	0.0105 (11)	0.0036 (12)	0.0009 (10)
C13	0.0506 (16)	0.0495 (14)	0.0255 (14)	0.0084 (12)	0.0003 (12)	−0.0033 (10)
C111	0.0448 (16)	0.0580 (15)	0.0301 (15)	0.0084 (12)	−0.0005 (12)	−0.0010 (11)
N111	0.0539 (15)	0.0763 (16)	0.0267 (13)	0.0026 (12)	0.0051 (11)	−0.0015 (11)
C112	0.061 (2)	0.083 (2)	0.0246 (15)	−0.0050 (16)	0.0019 (14)	−0.0071 (13)
N112	0.068 (2)	0.153 (3)	0.0455 (18)	−0.040 (2)	0.0069 (15)	−0.0122 (18)
O121	0.0469 (12)	0.0730 (12)	0.0453 (12)	−0.0016 (10)	0.0050 (9)	0.0058 (9)
C121	0.046 (2)	0.121 (3)	0.071 (3)	−0.0071 (19)	−0.0003 (18)	−0.016 (2)
C122	0.062 (3)	0.190 (5)	0.142 (5)	0.014 (3)	0.024 (3)	−0.022 (4)
C131	0.0620 (19)	0.0557 (15)	0.0317 (15)	0.0120 (13)	0.0003 (14)	0.0000 (12)
N131	0.089 (2)	0.0700 (17)	0.0493 (17)	0.0026 (15)	−0.0084 (15)	−0.0145 (13)
C132	0.0503 (17)	0.0567 (15)	0.0261 (14)	0.0137 (13)	−0.0022 (12)	−0.0038 (11)
N132	0.0654 (17)	0.0765 (17)	0.0425 (15)	0.0009 (14)	0.0045 (13)	0.0103 (13)

Geometric parameters (Å, º)

Cu1—Cl1	2.2383 (16)	C9—H9	0.9300
Cu1—N1	2.046 (2)	N10—C6B	1.358 (3)
Cu1—N10	2.019 (3)	C6B—C4B	1.431 (4)
Cu1—N111	1.974 (3)	C4B—N1	1.360 (3)
Cu1—N131^i	2.555 (3)	C4A—C4B	1.400 (4)
Cu1—N132^ii	2.758 (4)	C6A—C6B	1.399 (4)
N1—C2	1.328 (3)	C11—C12	1.401 (4)
C2—C3	1.394 (4)	C11—C111	1.411 (4)
C2—H2	0.9300	C11—C112	1.416 (4)
C3—C4	1.362 (4)	C12—O121	1.337 (3)
C3—H3	0.9300	C12—C13	1.392 (4)
C4—C4A	1.399 (4)	C13—C131	1.424 (4)
C4—H4	0.9300	C13—C132	1.425 (4)
C4A—C5	1.434 (4)	C111—N111	1.146 (4)
C5—C6	1.351 (4)	C112—N112	1.144 (4)
C5—H5	0.9300	O121—C121	1.474 (4)
C6—C6A	1.436 (4)	C121—C122	1.426 (5)
C6—H6	0.9300	C121—H21A	0.9700
C6A—C7	1.398 (4)	C121—H21B	0.9700
C7—C8	1.367 (4)	C122—H22A	0.9600
C7—H7	0.9300	C122—H22B	0.9600
C8—C9	1.392 (4)	C122—H22C	0.9600
C8—H8	0.9300	C131—N131	1.147 (4)
C9—N10	1.328 (3)	C132—N132	1.140 (4)
Cl1—Cu1—N1	171.50 (6)	N10—C6B—C6A	123.3 (2)
Cl1—Cu1—N10	94.00 (7)	N10—C6B—C4B	116.6 (2)
Cl1—Cu1—N111	92.95 (8)	C6A—C6B—C4B	120.1 (2)
N1—Cu1—N10	81.27 (9)	C8—C7—C6A	119.7 (3)
N1—Cu1—N111	91.66 (10)	C8—C7—H7	120.2
N10—Cu1—N111	172.91 (9)	C6A—C7—H7	120.2
N131^i—Cu1—Cl1	98.99 (8)	C7—C8—C9	119.6 (3)
N131^i—Cu1—N1	88.14 (9)	C7—C8—H8	120.2
N131^i—Cu1—N10	90.17 (8)	C9—C8—H8	120.2
N131^i—Cu1—N111	90.05 (10)	N10—C9—C8	122.5 (3)
N132^ii—Cu1—Cl1	94.70 (7)	N10—C9—H9	118.7
N132^ii—Cu1—N1	78.69 (8)	C8—C9—H9	118.7
N132^ii—Cu1—N10	94.13 (8)	C9—N10—C6B	117.8 (2)
N132^ii—Cu1—N111	83.98 (10)	C9—N10—Cu1	128.95 (18)
N131^i—Cu1—N132^ii	165.34 (10)	C6B—N10—Cu1	113.20 (17)
C2—N1—C4B	117.9 (2)	C12—C11—C111	118.1 (3)
C2—N1—Cu1	129.80 (19)	C12—C11—C112	124.5 (2)
C4B—N1—Cu1	112.27 (16)	C111—C11—C112	117.3 (2)
N1—C2—C3	122.2 (3)	O121—C12—C13	120.8 (2)
N1—C2—H2	118.9	O121—C12—C11	113.0 (2)
C3—C2—H2	118.9	C13—C12—C11	126.1 (3)
C4—C3—C2	120.1 (3)	C12—C13—C131	121.2 (3)
C4—C3—H3	120.0	C12—C13—C132	123.2 (2)
C2—C3—H3	120.0	C131—C13—C132	115.6 (2)
C3—C4—C4A	119.5 (3)	N111—C111—C11	179.1 (3)
C3—C4—H4	120.3	C111—N111—Cu1	174.3 (2)
C4A—C4—H4	120.3	N112—C112—C11	178.2 (3)
C4—C4A—C4B	117.1 (3)	C12—O121—C121	120.7 (2)
C4—C4A—C5	124.4 (3)	C122—C121—O121	108.7 (3)
C4B—C4A—C5	118.5 (2)	C122—C121—H21A	110.0
N1—C4B—C4A	123.2 (2)	O121—C121—H21A	110.0
N1—C4B—C6B	116.5 (2)	C122—C121—H21B	110.0
C4A—C4B—C6B	120.3 (2)	O121—C121—H21B	110.0
C6—C5—C4A	121.5 (3)	H21A—C121—H21B	108.3
C6—C5—H5	119.3	C121—C122—H22A	109.5
C4A—C5—H5	119.3	C121—C122—H22B	109.5
C5—C6—C6A	120.9 (3)	H22A—C122—H22B	109.5
C5—C6—H6	119.6	C121—C122—H22C	109.5
C6A—C6—H6	119.6	H22A—C122—H22C	109.5
C7—C6A—C6B	117.0 (2)	H22B—C122—H22C	109.5
C7—C6A—C6	124.1 (3)	N131—C131—C13	177.1 (3)
C6B—C6A—C6	118.8 (3)	N132—C132—C13	176.7 (3)
N111—Cu1—N1—C2	−2.0 (2)	C4A—C4B—C6B—N10	−178.6 (2)
N10—Cu1—N1—C2	178.4 (2)	N1—C4B—C6B—C6A	179.3 (2)
N111—Cu1—N1—C4B	176.87 (17)	C4A—C4B—C6B—C6A	0.8 (4)
N10—Cu1—N1—C4B	−2.66 (16)	C6B—C6A—C7—C8	0.4 (4)
C4B—N1—C2—C3	0.4 (4)	C6—C6A—C7—C8	−178.0 (3)
Cu1—N1—C2—C3	179.3 (2)	C6A—C7—C8—C9	−1.2 (4)
N1—C2—C3—C4	−0.8 (5)	C7—C8—C9—N10	0.5 (5)
C2—C3—C4—C4A	0.8 (5)	C8—C9—N10—C6B	1.1 (4)
C3—C4—C4A—C4B	−0.6 (4)	C8—C9—N10—Cu1	−179.4 (2)
C3—C4—C4A—C5	179.6 (3)	C6A—C6B—N10—C9	−2.1 (4)
C2—N1—C4B—C4A	−0.2 (4)	C4B—C6B—N10—C9	177.4 (2)
Cu1—N1—C4B—C4A	−179.24 (19)	C6A—C6B—N10—Cu1	178.4 (2)
C2—N1—C4B—C6B	−178.6 (2)	C4B—C6B—N10—Cu1	−2.2 (3)
Cu1—N1—C4B—C6B	2.3 (3)	N1—Cu1—N10—C9	−176.9 (2)
C4—C4A—C4B—N1	0.2 (4)	Cl1—Cu1—N10—C9	10.2 (2)
C5—C4A—C4B—N1	−179.9 (2)	N1—Cu1—N10—C6B	2.62 (16)
C4—C4A—C4B—C6B	178.6 (2)	Cl1—Cu1—N10—C6B	−170.27 (16)
C5—C4A—C4B—C6B	−1.5 (4)	C111—C11—C12—O121	−12.4 (3)
C4—C4A—C5—C6	−179.2 (3)	C112—C11—C12—O121	162.7 (3)
C4B—C4A—C5—C6	1.0 (4)	C111—C11—C12—C13	171.3 (2)
C4A—C5—C6—C6A	0.2 (4)	C112—C11—C12—C13	−13.6 (4)
C5—C6—C6A—C7	177.5 (3)	O121—C12—C13—C131	−14.2 (4)
C5—C6—C6A—C6B	−0.9 (4)	C11—C12—C13—C131	161.8 (3)
C7—C6A—C6B—N10	1.3 (4)	O121—C12—C13—C132	167.7 (2)
C6—C6A—C6B—N10	179.8 (2)	C11—C12—C13—C132	−16.2 (4)
C7—C6A—C6B—C4B	−178.1 (2)	C13—C12—O121—C121	−50.1 (4)
C6—C6A—C6B—C4B	0.4 (4)	C11—C12—O121—C121	133.4 (3)
N1—C4B—C6B—N10	−0.1 (3)	C12—O121—C121—C122	−126.9 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N112^iii	0.93	2.55	3.450 (6)	163

Symmetry code: (iii) −x+1/2, y−1/2, −z+3/2.