A second polymorph of aqua-(2,9-di-methyl-1,10-phenanthroline-κN,N')bis-(formato-κO)copper(II).

A new monoclinic polymorphic form of the title compound, [Cu(HCO(2))(2)(C(14)H(12)N(2))(H(2)O)], is described. It differs from the first ortho-rhom-bic polymorph [Pan, Lin & Zheng (2005 ▶). Z. Kristallogr. New Cryst. Struct.220, 495-496] in the deviation of the Cu atom relative to the plane of the 2,9-dimethyl-1,10-phenanthroline (dmp) ligand. In the present structure, the Cu atom is shifted from the mean plane of the dmp ligand by only 0.005 (1) Å, compared with 0.318 (6) Å in the ortho-rhom-bic form. Hydrogen-bonding and π-π stacking inter-actions (mean inter-planar distance of 3.59 Å in the title compound) in the two different polymorphs are both essential to the supra-molecular assembly.

Related literature

For the orthorhombic polymorph, see: Pan et al. (2005 ▶).

Experimental

Crystal data

[Cu(HCO2)2(C14H12N2)(H2O)]

M = 379.85

Monoclinic,

a = 10.669 (2) Å

b = 7.7677 (16) Å

c = 19.338 (4) Å

β = 94.22 (3)°

V = 1598.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.40 mm−1

T = 295 (2) K

0.26 × 0.17 × 0.09 mm

Data collection

Bruker P4 diffractometer

Absorption correction: multi-scan (XSCANS; Siemens, 1996 ▶) T min = 0.749, T max = 0.879

15099 measured reflections

3632 independent reflections

3202 reflections with I > 2σ(I)

R int = 0.019

3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.072

S = 1.06

3632 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.22 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022812/fj2128sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022812/fj2128Isup2.hkl

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

[Cu(HCO2)2(C14H12N2)(H2O)]	F000 = 780
Mr = 379.85	Dx = 1.579 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.669 (2) Å	θ = 5.0–12.5º
b = 7.7677 (16) Å	µ = 1.40 mm−1
c = 19.338 (4) Å	T = 295 (2) K
β = 94.22 (3)º	Plate, blue
V = 1598.3 (6) Å3	0.26 × 0.17 × 0.09 mm
Z = 4

Bruker P4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 27.5º
Monochromator: graphite	θmin = 3.3º
T = 295(2) K	h = −13→13
θ/2θ scans	k = −10→9
Absorption correction: multi-scan(XSCANS; Siemens, 1996)	l = −24→25
Tmin = 0.749, Tmax = 0.879	3 standard reflections
15099 measured reflections	every 97 reflections
3632 independent reflections	intensity decay: none
3202 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H-atom parameters constrained
wR(F2) = 0.072	w = 1/[σ2(Fo2) + (0.0413P)2 + 0.5201P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3632 reflections	Δρmax = 0.35 e Å−3
219 parameters	Δρmin = −0.22 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Cu	0.209657 (18)	0.90493 (2)	0.156116 (9)	0.02440 (7)
N1	0.21922 (12)	0.80402 (17)	0.05966 (6)	0.0257 (3)
N2	0.42113 (13)	0.89494 (17)	0.14606 (7)	0.0275 (3)
C1	0.11886 (17)	0.7632 (2)	0.01841 (9)	0.0325 (4)
C2	0.1317 (2)	0.6999 (3)	−0.04910 (10)	0.0472 (5)
H2A	0.0605	0.6741	−0.0778	0.057*
C3	0.2471 (2)	0.6765 (3)	−0.07224 (10)	0.0508 (5)
H3A	0.2552	0.6332	−0.1165	0.061*
C4	0.35505 (19)	0.7178 (3)	−0.02912 (9)	0.0393 (4)
C5	0.4803 (2)	0.6986 (3)	−0.04949 (11)	0.0541 (6)
H5A	0.4929	0.6540	−0.0931	0.065*
C6	0.5804 (2)	0.7435 (3)	−0.00711 (11)	0.0537 (6)
H6A	0.6609	0.7298	−0.0217	0.064*
C7	0.56433 (17)	0.8120 (3)	0.05998 (10)	0.0397 (4)
C8	0.66470 (19)	0.8661 (3)	0.10598 (12)	0.0511 (5)
H8A	0.7468	0.8577	0.0931	0.061*
C9	0.64241 (19)	0.9302 (3)	0.16884 (12)	0.0478 (5)
H9A	0.7091	0.9659	0.1992	0.057*
C10	0.51845 (17)	0.9430 (2)	0.18838 (9)	0.0350 (4)
C11	0.44274 (15)	0.8321 (2)	0.08260 (8)	0.0289 (3)
C12	0.33615 (16)	0.7831 (2)	0.03694 (8)	0.0281 (3)
C13	−0.00801 (18)	0.7856 (3)	0.04536 (10)	0.0438 (4)
H13A	−0.0302	0.6831	0.0694	0.066*
H13B	−0.0691	0.8066	0.0073	0.066*
H13C	−0.0062	0.8816	0.0767	0.066*
C14	0.4920 (2)	1.0068 (3)	0.25888 (10)	0.0537 (6)
H14A	0.4243	1.0884	0.2547	0.081*
H14B	0.5659	1.0614	0.2802	0.081*
H14C	0.4691	0.9116	0.2870	0.081*
O1	0.18364 (13)	0.98991 (18)	0.24857 (6)	0.0408 (3)
O2	−0.02000 (15)	1.0452 (3)	0.22488 (8)	0.0613 (4)
C15	0.0760 (2)	1.0407 (3)	0.26275 (10)	0.0471 (5)
O3	0.18495 (13)	1.12747 (15)	0.10994 (6)	0.0365 (3)
O4	0.18327 (18)	1.41073 (16)	0.10823 (8)	0.0530 (4)
C16	0.19793 (18)	1.2723 (2)	0.13792 (9)	0.0360 (4)
O5	0.19568 (12)	0.67025 (15)	0.19376 (6)	0.0344 (3)
H5B	0.1958	0.5834	0.1636	0.051*
H5C	0.1416	0.6452	0.2242	0.054*
H15	0.0751	1.0904	0.3111	0.052*
H16	0.2383	1.2705	0.1852	0.049*

	U11	U22	U33	U12	U13	U23
Cu	0.02683 (11)	0.02277 (11)	0.02410 (11)	0.00161 (7)	0.00524 (7)	−0.00126 (7)
N1	0.0280 (7)	0.0227 (6)	0.0263 (6)	−0.0003 (5)	0.0021 (5)	−0.0001 (5)
N2	0.0267 (7)	0.0283 (7)	0.0276 (6)	−0.0012 (5)	0.0032 (5)	0.0011 (5)
C1	0.0353 (9)	0.0304 (8)	0.0313 (8)	−0.0023 (7)	−0.0011 (7)	−0.0003 (7)
C2	0.0495 (12)	0.0554 (12)	0.0350 (9)	−0.0055 (10)	−0.0086 (8)	−0.0096 (9)
C3	0.0627 (14)	0.0601 (13)	0.0297 (9)	−0.0010 (11)	0.0040 (9)	−0.0158 (9)
C4	0.0467 (11)	0.0421 (10)	0.0300 (8)	0.0022 (8)	0.0093 (7)	−0.0060 (8)
C5	0.0587 (14)	0.0690 (15)	0.0373 (10)	0.0073 (11)	0.0227 (9)	−0.0110 (10)
C6	0.0430 (12)	0.0737 (15)	0.0474 (11)	0.0080 (10)	0.0234 (9)	−0.0016 (11)
C7	0.0319 (9)	0.0479 (11)	0.0408 (9)	0.0023 (8)	0.0126 (7)	0.0052 (9)
C8	0.0246 (9)	0.0722 (14)	0.0575 (12)	−0.0005 (9)	0.0102 (8)	0.0079 (11)
C9	0.0306 (10)	0.0592 (13)	0.0526 (12)	−0.0096 (9)	−0.0033 (8)	0.0047 (10)
C10	0.0323 (9)	0.0346 (9)	0.0374 (9)	−0.0041 (7)	−0.0018 (7)	0.0021 (7)
C11	0.0292 (8)	0.0288 (8)	0.0295 (7)	0.0007 (6)	0.0077 (6)	0.0020 (7)
C12	0.0327 (8)	0.0264 (7)	0.0258 (7)	0.0020 (6)	0.0070 (6)	0.0006 (6)
C13	0.0308 (9)	0.0564 (12)	0.0434 (10)	−0.0056 (9)	−0.0033 (8)	0.0005 (9)
C14	0.0484 (12)	0.0687 (15)	0.0426 (11)	−0.0057 (11)	−0.0066 (9)	−0.0160 (11)
O1	0.0475 (8)	0.0463 (8)	0.0293 (6)	0.0104 (6)	0.0073 (5)	−0.0055 (6)
O2	0.0465 (9)	0.0904 (13)	0.0485 (8)	0.0135 (9)	0.0128 (7)	−0.0072 (9)
C15	0.0577 (13)	0.0534 (12)	0.0319 (9)	0.0127 (10)	0.0159 (9)	−0.0061 (9)
O3	0.0529 (8)	0.0249 (6)	0.0319 (6)	0.0037 (5)	0.0045 (5)	0.0000 (5)
O4	0.0859 (12)	0.0259 (7)	0.0479 (8)	0.0012 (7)	0.0098 (8)	0.0004 (6)
C16	0.0443 (10)	0.0292 (9)	0.0346 (8)	−0.0012 (7)	0.0028 (7)	−0.0013 (7)
O5	0.0415 (7)	0.0271 (6)	0.0359 (6)	−0.0028 (5)	0.0122 (5)	0.0032 (5)

Cu—O1	1.9450 (12)	C7—C11	1.408 (2)
Cu—O3	1.9546 (12)	C8—C9	1.351 (3)
Cu—O5	1.9726 (12)	C8—H8A	0.9300
Cu—N1	2.0328 (13)	C9—C10	1.405 (3)
Cu—N2	2.2801 (15)	C9—H9A	0.9300
N1—C1	1.326 (2)	C10—C14	1.497 (3)
N1—C12	1.363 (2)	C11—C12	1.439 (2)
N2—C10	1.327 (2)	C13—H13A	0.9600
N2—C11	1.356 (2)	C13—H13B	0.9600
C1—C2	1.411 (2)	C13—H13C	0.9600
C1—C13	1.496 (3)	C14—H14A	0.9600
C2—C3	1.353 (3)	C14—H14B	0.9600
C2—H2A	0.9300	C14—H14C	0.9600
C3—C4	1.408 (3)	O1—C15	1.264 (2)
C3—H3A	0.9300	O2—C15	1.215 (3)
C4—C12	1.403 (2)	C15—H15	1.0122
C4—C5	1.429 (3)	O3—C16	1.252 (2)
C5—C6	1.343 (3)	O4—C16	1.223 (2)
C5—H5A	0.9300	C16—H16	0.9821
C6—C7	1.424 (3)	O5—H5B	0.8914
C6—H6A	0.9300	O5—H5C	0.8760
C7—C8	1.405 (3)
O1—Cu—O3	95.53 (6)	C9—C8—H8A	119.9
O1—Cu—O5	87.40 (6)	C7—C8—H8A	119.9
O1—Cu—N1	174.06 (6)	C8—C9—C10	119.97 (19)
O1—Cu—N2	107.40 (6)	C8—C9—H9A	120.0
O3—Cu—O5	167.05 (6)	C10—C9—H9A	120.0
O3—Cu—N1	86.33 (5)	N2—C10—C9	121.54 (18)
O3—Cu—N2	95.28 (6)	N2—C10—C14	117.62 (17)
O5—Cu—N1	89.57 (5)	C9—C10—C14	120.81 (18)
O5—Cu—N2	95.87 (5)	N2—C11—C7	122.89 (16)
N1—Cu—N2	77.98 (6)	N2—C11—C12	118.11 (14)
C1—N1—C12	119.71 (14)	C7—C11—C12	119.01 (15)
C1—N1—Cu	123.47 (11)	N1—C12—C4	122.22 (16)
C12—N1—Cu	116.80 (11)	N1—C12—C11	118.15 (14)
C10—N2—C11	118.80 (15)	C4—C12—C11	119.63 (16)
C10—N2—Cu	132.20 (12)	C1—C13—H13A	109.5
C11—N2—Cu	108.95 (11)	C1—C13—H13B	109.5
N1—C1—C2	120.71 (17)	H13A—C13—H13B	109.5
N1—C1—C13	118.29 (15)	C1—C13—H13C	109.5
C2—C1—C13	121.00 (17)	H13A—C13—H13C	109.5
C3—C2—C1	120.38 (18)	H13B—C13—H13C	109.5
C3—C2—H2A	119.8	C10—C14—H14A	109.5
C1—C2—H2A	119.8	C10—C14—H14B	109.5
C2—C3—C4	119.86 (17)	H14A—C14—H14B	109.5
C2—C3—H3A	120.1	C10—C14—H14C	109.5
C4—C3—H3A	120.1	H14A—C14—H14C	109.5
C12—C4—C3	117.10 (18)	H14B—C14—H14C	109.5
C12—C4—C5	119.28 (18)	C15—O1—Cu	119.93 (13)
C3—C4—C5	123.61 (18)	O2—C15—O1	128.13 (18)
C6—C5—C4	121.48 (18)	O2—C15—H15	118.8
C6—C5—H5A	119.3	O1—C15—H15	112.9
C4—C5—H5A	119.3	C16—O3—Cu	126.20 (12)
C5—C6—C7	120.61 (18)	O4—C16—O3	125.51 (17)
C5—C6—H6A	119.7	O4—C16—H16	118.8
C7—C6—H6A	119.7	O3—C16—H16	114.6
C8—C7—C11	116.55 (17)	Cu—O5—H5B	117.0
C8—C7—C6	123.44 (18)	Cu—O5—H5C	121.6
C11—C7—C6	119.99 (19)	H5B—O5—H5C	107.7
C9—C8—C7	120.23 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O2i	0.88	1.86	2.714 (2)	166
O5—H5B···O4ii	0.89	1.72	2.605 (2)	175

Cu—O1	1.9450 (12)
Cu—O3	1.9546 (12)
Cu—O5	1.9726 (12)
Cu—N1	2.0328 (13)
Cu—N2	2.2801 (15)

O1—Cu—O3	95.53 (6)
O1—Cu—O5	87.40 (6)
O1—Cu—N1	174.06 (6)
O1—Cu—N2	107.40 (6)
O3—Cu—O5	167.05 (6)
O3—Cu—N1	86.33 (5)
O3—Cu—N2	95.28 (6)
O5—Cu—N1	89.57 (5)
O5—Cu—N2	95.87 (5)
N1—Cu—N2	77.98 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5C⋯O2i	0.88	1.86	2.714 (2)	166
O5—H5B⋯O4ii	0.89	1.72	2.605 (2)	175

Symmetry codes: (i) ; (ii) .