The crystal structures of the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide and of a tetra­nuclear copper(II) complex

The title tridentate ligand (HL1), crystallizes with three independent mol­ecules in the asymmetric unit. Its reaction with Cu(Ac)₂ produced a tetra­nuclear complex with a central tetra­kis­(μ-acetato)­dicopper paddle-wheel moiety linked on either side via bridging acetate anions to a mononuclear copper(II)–(L1) complex.

Key indicators

Structure: HL1

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.059
• wR factor = 0.134
• Data-to-parameter ratio = 7.9

Structure: I

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.083
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Datablock: HL1



Alert level B
PLAT340_ALERT_3_B Low Bond Precision on  C-C Bonds ...............    0.01547 Ang.
PLAT915_ALERT_3_B No Flack x Check Done: Low Friedel Pair Coverage         26 %

Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       6.33 Note
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21      ..O2       .       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H22      ..O2       .       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H44      ..O1       .       2.61 Ang.

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT112_ALERT_2_G ADDSYM Detects New (Pseudo) Symm. Elem       sub         85 %Fit
PLAT112_ALERT_2_G ADDSYM Detects New (Pseudo) Symm. Elem       sub         85 %Fit
PLAT115_ALERT_5_G ADDSYM Detects Noncrystallographic Inversion ...        89% Check
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3 Note
              C14 H10 N4 O
PLAT881_ALERT_1_G No Datum for _diffrn_reflns_av_R_equivalents ...     Please Do !
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

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




Datablock: I


Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full value Low .      0.937 Why?

Author Response: For compound <b>I</b>, data were measured at 173 K on a Stoe IPDS1; a one-circle image-plate diffractometer. For compound <b>I</b> a small cusp of data is missing. This is common with data measured using the IPDS1 for monoclinic and triclinic crystal systems.

Alert level B
PLAT911_ALERT_3_B Missing FCF Refl Between Thmin & STh/L=    0.600        282 Report

Alert level C
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4 Note

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT012_ALERT_1_G N.O.K.   _shelx_res_checksum Found in CIF ......     Please Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        6.0 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.22 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu2       (II)      .       2.11 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         63 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   1 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

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

---

Computing details

Data collection: STADI4 (Stoe & Cie, 1997) for HL1; EXPOSE in IPDS-I (Stoe & Cie, 2004) for (I). Cell refinement: STADI4 (Stoe & Cie, 1997) for HL1; CELL in IPDS-I (Stoe & Cie, 2004) for (I). Data reduction: X-RED (Stoe & Cie, 1997) for HL1; INTEGRATE in IPDS-I (Stoe & Cie, 2004) for (I). For both structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

N-(quinolin-8-yl)pyrazine-2-carboxamide (HL1)

Crystal data

C14H10N4O	F(000) = 1560
Mr = 250.26	Dx = 1.425 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 11.5047 (9) Å	Cell parameters from 38 reflections
b = 23.410 (3) Å	θ = 10.1–19.2°
c = 13.4115 (11) Å	µ = 0.10 mm^−1
β = 104.305 (8)°	T = 223 K
V = 3500.0 (6) Å^3	Block, colourless
Z = 12	0.50 × 0.40 × 0.30 mm

Data collection

STOE-Siemens AED2, 4-circle diffractometer	Rint = 0.0
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 2.0°
Plane graphite monochromator	h = −13→13
ω/\2q scans	k = 0→28
4090 measured reflections	l = −15→16
4090 independent reflections	2 standard reflections every 60 min
2851 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 4.6085P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max = 0.003
4090 reflections	Δρmax = 0.19 e Å^−3
515 parameters	Δρmin = −0.21 e Å^−3
2 restraints	Extinction correction: (SHELXL-2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (2)

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	0.7337 (5)	0.0790 (3)	0.8655 (4)	0.0463 (14)
N1	0.7597 (7)	0.1224 (4)	1.1248 (6)	0.0382 (19)
N2	0.6261 (8)	0.2143 (4)	1.0247 (7)	0.044 (2)
N3	0.8141 (6)	0.0339 (3)	1.0201 (5)	0.0360 (15)
H3N	0.822207	0.037888	1.085969	0.043*
N4	0.9191 (8)	−0.0366 (3)	1.1719 (7)	0.0331 (17)
C1	0.7234 (8)	0.1270 (4)	1.0203 (8)	0.034 (2)
C2	0.6608 (8)	0.1720 (4)	0.9717 (8)	0.037 (2)
H2	0.641206	0.173510	0.899409	0.044*
C3	0.6545 (8)	0.2114 (4)	1.1237 (8)	0.042 (2)
H3	0.627584	0.239705	1.162515	0.050*
C4	0.7270 (10)	0.1651 (5)	1.1748 (9)	0.045 (2)
H4	0.752016	0.165464	1.247046	0.055*
C5	0.7573 (6)	0.0775 (3)	0.9596 (6)	0.0320 (17)
C6	0.8616 (9)	−0.0171 (4)	0.9887 (7)	0.031 (2)
C7	0.8578 (10)	−0.0331 (5)	0.8907 (8)	0.042 (2)
H7	0.818655	−0.009305	0.836235	0.050*
C8	0.9096 (10)	−0.0833 (5)	0.8681 (9)	0.046 (3)
H8	0.906182	−0.092985	0.799415	0.055*
C9	0.9658 (10)	−0.1189 (5)	0.9464 (9)	0.046 (3)
H9	1.000005	−0.153289	0.931312	0.055*
C10	0.9724 (10)	−0.1040 (5)	1.0502 (9)	0.037 (2)
C11	1.0315 (11)	−0.1379 (5)	1.1327 (10)	0.056 (3)
H11	1.069668	−0.171833	1.120905	0.067*
C12	1.0335 (10)	−0.1216 (5)	1.2294 (9)	0.046 (3)
H12	1.073731	−0.143839	1.285804	0.055*
C13	0.9749 (9)	−0.0713 (5)	1.2449 (8)	0.038 (2)
H13	0.975561	−0.061557	1.313068	0.046*
C14	0.9177 (9)	−0.0536 (4)	1.0716 (8)	0.029 (2)
O2	1.1664 (6)	0.0867 (3)	1.2537 (5)	0.0469 (17)
N21	1.1428 (7)	0.0431 (3)	0.9977 (6)	0.0334 (19)
N22	1.2741 (9)	−0.0505 (4)	1.0996 (7)	0.047 (2)
N23	1.0843 (6)	0.1305 (3)	1.1025 (5)	0.0311 (16)
H23N	1.074944	0.126707	1.036416	0.037*
N24	0.9780 (7)	0.2026 (4)	0.9528 (6)	0.0359 (19)
C21	1.1773 (11)	0.0001 (5)	0.9463 (8)	0.041 (2)
H21	1.158817	0.001603	0.874010	0.049*
C22	1.2378 (11)	−0.0452 (5)	0.9946 (9)	0.049 (3)
H22	1.256284	−0.074972	0.954083	0.058*
C23	1.2382 (11)	−0.0062 (5)	1.1504 (9)	0.046 (3)
H23	1.256952	−0.006842	1.222691	0.055*
C24	1.1760 (8)	0.0391 (4)	1.1000 (7)	0.030 (2)
C25	1.1415 (7)	0.0869 (4)	1.1595 (6)	0.035 (2)
C26	1.0377 (8)	0.1811 (4)	1.1325 (7)	0.0267 (19)
C27	1.0415 (9)	0.1959 (4)	1.2346 (7)	0.033 (2)
H27	1.080413	0.172461	1.289764	0.040*
C28	0.9845 (10)	0.2474 (5)	1.2516 (9)	0.045 (3)
H28	0.987051	0.258236	1.319558	0.054*
C29	0.9267 (11)	0.2815 (4)	1.1738 (10)	0.046 (3)
H29	0.887722	0.314476	1.188833	0.056*
C30	0.9238 (10)	0.2689 (5)	1.0723 (10)	0.043 (3)
C31	0.8637 (10)	0.3020 (5)	0.9884 (9)	0.046 (3)
H31	0.822150	0.334769	1.000800	0.056*
C32	0.8633 (10)	0.2884 (5)	0.8881 (9)	0.051 (3)
H32	0.824502	0.311252	0.832158	0.061*
C33	0.9265 (10)	0.2366 (5)	0.8750 (9)	0.041 (3)
H33	0.931273	0.226477	0.808338	0.050*
C34	0.9778 (8)	0.2169 (4)	1.0483 (8)	0.030 (2)
O3	1.2338 (5)	0.2464 (3)	0.8676 (4)	0.0499 (15)
N31	1.2533 (7)	0.2882 (4)	1.1263 (6)	0.0357 (18)
N32	1.1316 (9)	0.3839 (4)	1.0267 (8)	0.056 (2)
N33	1.3101 (5)	0.2002 (3)	1.0212 (5)	0.0343 (14)
H33N	1.315150	0.203851	1.086711	0.041*
N34	1.4154 (7)	0.1285 (4)	1.1717 (6)	0.0351 (19)
C41	1.2238 (8)	0.2920 (4)	1.0237 (7)	0.032 (2)
C42	1.1626 (9)	0.3411 (4)	0.9757 (7)	0.040 (2)
H42	1.143118	0.343064	0.903457	0.048*
C43	1.1578 (10)	0.3785 (5)	1.1267 (9)	0.055 (3)
H43	1.132327	0.406954	1.165939	0.066*
C44	1.2214 (9)	0.3326 (4)	1.1769 (8)	0.041 (2)
H44	1.243254	0.332380	1.249264	0.050*
C45	1.2556 (6)	0.2439 (3)	0.9620 (6)	0.0337 (17)
C46	1.3596 (9)	0.1501 (4)	0.9928 (8)	0.035 (2)
C47	1.3526 (9)	0.1366 (4)	0.8925 (7)	0.036 (2)
H47	1.310731	0.160484	0.839348	0.043*
C48	1.4091 (10)	0.0861 (5)	0.8688 (9)	0.043 (3)
H48	1.406998	0.077855	0.799766	0.052*
C49	1.4661 (11)	0.0493 (5)	0.9437 (10)	0.048 (3)
H49	1.499598	0.015108	0.926739	0.057*
C50	1.4738 (9)	0.0637 (4)	1.0481 (9)	0.034 (2)
C51	1.5356 (10)	0.0298 (5)	1.1340 (10)	0.052 (3)
H51	1.576831	−0.003515	1.123746	0.062*
C52	1.5333 (10)	0.0465 (4)	1.2297 (10)	0.048 (3)
H52	1.573714	0.024722	1.286647	0.058*
C53	1.4737 (10)	0.0941 (5)	1.2445 (9)	0.044 (3)
H53	1.473984	0.103532	1.312724	0.053*
C54	1.4176 (9)	0.1133 (5)	1.0717 (8)	0.034 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.062 (4)	0.052 (4)	0.024 (3)	0.008 (3)	0.009 (3)	0.003 (2)
N1	0.038 (4)	0.041 (5)	0.033 (4)	0.001 (3)	0.004 (3)	−0.002 (3)
N2	0.047 (5)	0.031 (4)	0.052 (6)	0.005 (3)	0.011 (4)	0.010 (4)
N3	0.044 (4)	0.039 (4)	0.026 (3)	0.003 (3)	0.009 (3)	0.000 (3)
N4	0.037 (4)	0.032 (4)	0.028 (4)	0.004 (3)	0.004 (3)	0.001 (3)
C1	0.025 (4)	0.040 (5)	0.039 (5)	0.001 (3)	0.010 (4)	−0.002 (4)
C2	0.032 (5)	0.040 (5)	0.033 (5)	0.005 (4)	−0.002 (4)	0.014 (4)
C3	0.031 (5)	0.033 (5)	0.059 (7)	0.007 (4)	0.008 (4)	0.001 (4)
C4	0.043 (5)	0.037 (5)	0.048 (6)	0.005 (4)	−0.004 (4)	0.002 (4)
C5	0.030 (4)	0.028 (4)	0.040 (5)	0.001 (3)	0.013 (3)	0.000 (3)
C6	0.033 (5)	0.026 (4)	0.032 (5)	−0.007 (3)	0.004 (4)	0.001 (3)
C7	0.041 (5)	0.060 (6)	0.024 (5)	−0.007 (4)	0.008 (4)	0.010 (4)
C8	0.050 (6)	0.051 (6)	0.037 (5)	−0.008 (5)	0.015 (5)	−0.015 (5)
C9	0.057 (6)	0.042 (5)	0.043 (6)	−0.002 (5)	0.020 (5)	−0.015 (5)
C10	0.036 (5)	0.033 (5)	0.041 (6)	0.006 (4)	0.011 (4)	0.005 (4)
C11	0.058 (7)	0.043 (6)	0.075 (8)	0.017 (5)	0.031 (6)	0.013 (5)
C12	0.042 (5)	0.040 (6)	0.053 (7)	0.001 (5)	0.007 (5)	0.024 (5)
C13	0.035 (5)	0.057 (6)	0.021 (4)	−0.005 (4)	0.004 (4)	0.002 (4)
C14	0.031 (5)	0.031 (4)	0.027 (5)	−0.009 (4)	0.011 (4)	0.001 (4)
O2	0.055 (4)	0.052 (4)	0.034 (4)	0.009 (3)	0.011 (3)	0.010 (3)
N21	0.039 (4)	0.025 (4)	0.035 (5)	0.005 (3)	0.007 (4)	0.004 (3)
N22	0.059 (6)	0.038 (5)	0.043 (5)	0.009 (4)	0.011 (4)	0.010 (4)
N23	0.038 (4)	0.033 (4)	0.021 (4)	0.007 (3)	0.005 (3)	0.000 (3)
N24	0.032 (4)	0.043 (5)	0.031 (4)	−0.006 (4)	0.005 (3)	0.000 (4)
C21	0.059 (6)	0.034 (5)	0.032 (5)	−0.005 (5)	0.015 (5)	−0.005 (4)
C22	0.074 (8)	0.032 (6)	0.042 (6)	−0.005 (5)	0.019 (6)	−0.003 (5)
C23	0.054 (6)	0.042 (6)	0.045 (7)	−0.005 (5)	0.020 (5)	0.010 (5)
C24	0.033 (5)	0.027 (5)	0.029 (5)	−0.008 (4)	0.006 (4)	0.004 (4)
C25	0.025 (4)	0.055 (6)	0.022 (4)	−0.004 (4)	−0.001 (3)	0.016 (4)
C26	0.020 (4)	0.033 (5)	0.027 (5)	−0.002 (4)	0.004 (3)	0.004 (4)
C27	0.039 (5)	0.029 (5)	0.031 (5)	−0.014 (4)	0.010 (4)	−0.009 (4)
C28	0.053 (7)	0.044 (6)	0.046 (6)	−0.015 (5)	0.025 (5)	−0.009 (5)
C29	0.054 (6)	0.025 (5)	0.068 (8)	−0.004 (4)	0.031 (6)	−0.008 (5)
C30	0.038 (6)	0.041 (6)	0.054 (7)	−0.005 (5)	0.019 (5)	−0.006 (5)
C31	0.050 (6)	0.034 (5)	0.055 (7)	−0.002 (5)	0.015 (5)	0.002 (5)
C32	0.043 (6)	0.058 (8)	0.049 (7)	−0.001 (6)	0.006 (5)	−0.005 (5)
C33	0.043 (6)	0.036 (6)	0.042 (6)	0.001 (4)	0.006 (5)	0.013 (5)
C34	0.022 (4)	0.025 (4)	0.038 (5)	−0.003 (3)	0.001 (4)	−0.009 (4)
O3	0.062 (4)	0.064 (4)	0.024 (3)	0.007 (3)	0.011 (3)	0.009 (3)
N31	0.036 (4)	0.038 (4)	0.032 (4)	−0.001 (3)	0.005 (3)	0.002 (3)
N32	0.061 (5)	0.046 (5)	0.061 (6)	0.009 (4)	0.015 (5)	0.010 (5)
N33	0.035 (3)	0.043 (4)	0.026 (3)	0.000 (3)	0.008 (3)	0.002 (3)
N34	0.038 (4)	0.039 (4)	0.028 (4)	−0.007 (3)	0.008 (3)	0.000 (3)
C41	0.026 (4)	0.035 (5)	0.036 (5)	−0.002 (3)	0.008 (4)	0.009 (4)
C42	0.041 (5)	0.043 (6)	0.033 (5)	0.007 (4)	0.006 (4)	0.008 (4)
C43	0.054 (6)	0.053 (7)	0.056 (7)	0.012 (5)	0.009 (5)	0.009 (5)
C44	0.047 (5)	0.040 (5)	0.038 (5)	0.012 (4)	0.013 (4)	−0.001 (4)
C45	0.038 (4)	0.026 (4)	0.036 (4)	0.001 (3)	0.007 (3)	0.003 (3)
C46	0.039 (5)	0.033 (5)	0.038 (5)	−0.006 (4)	0.018 (4)	−0.013 (4)
C47	0.039 (5)	0.042 (5)	0.030 (5)	−0.005 (4)	0.014 (4)	−0.003 (4)
C48	0.045 (6)	0.047 (6)	0.045 (6)	−0.017 (5)	0.024 (5)	−0.021 (5)
C49	0.050 (6)	0.043 (6)	0.056 (7)	−0.008 (5)	0.024 (5)	−0.023 (5)
C50	0.036 (5)	0.024 (5)	0.045 (6)	−0.008 (4)	0.015 (4)	0.000 (4)
C51	0.044 (5)	0.037 (5)	0.082 (9)	0.005 (4)	0.032 (6)	0.013 (5)
C52	0.039 (5)	0.042 (6)	0.063 (7)	0.010 (4)	0.012 (5)	0.036 (5)
C53	0.037 (5)	0.056 (6)	0.035 (5)	−0.009 (4)	0.002 (4)	0.001 (4)
C54	0.035 (5)	0.040 (5)	0.027 (5)	−0.007 (4)	0.013 (4)	−0.001 (4)

Geometric parameters (Å, º)

O1—C5	1.224 (9)	C26—C27	1.403 (13)
N1—C4	1.311 (14)	C26—C34	1.439 (14)
N1—C1	1.364 (12)	C27—C28	1.418 (15)
N2—C3	1.289 (13)	C27—H27	0.9400
N2—C2	1.337 (13)	C28—C29	1.351 (17)
N3—C5	1.366 (10)	C28—H28	0.9400
N3—C6	1.419 (11)	C29—C30	1.385 (17)
N3—H3N	0.8700	C29—H29	0.9400
N4—C13	1.312 (14)	C30—C31	1.400 (16)
N4—C14	1.398 (13)	C30—C34	1.438 (15)
C1—C2	1.349 (14)	C31—C32	1.380 (16)
C1—C5	1.521 (11)	C31—H31	0.9400
C2—H2	0.9400	C32—C33	1.447 (16)
C3—C4	1.435 (15)	C32—H32	0.9400
C3—H3	0.9400	C33—H33	0.9400
C4—H4	0.9400	O3—C45	1.230 (9)
C6—C7	1.358 (13)	N31—C41	1.337 (12)
C6—C14	1.424 (14)	N31—C44	1.340 (12)
C7—C8	1.385 (15)	N32—C43	1.306 (14)
C7—H7	0.9400	N32—C42	1.312 (13)
C8—C9	1.371 (17)	N33—C45	1.350 (10)
C8—H8	0.9400	N33—C46	1.399 (11)
C9—C10	1.419 (16)	N33—H33N	0.8700
C9—H9	0.9400	N34—C53	1.314 (14)
C10—C11	1.395 (16)	N34—C54	1.395 (13)
C10—C14	1.400 (11)	C41—C42	1.417 (14)
C11—C12	1.347 (17)	C41—C45	1.494 (12)
C11—H11	0.9400	C42—H42	0.9400
C12—C13	1.398 (15)	C43—C44	1.378 (16)
C12—H12	0.9400	C43—H43	0.9400
C13—H13	0.9400	C44—H44	0.9400
O2—C25	1.224 (11)	C46—C47	1.366 (13)
N21—C24	1.333 (12)	C46—C54	1.398 (15)
N21—C21	1.334 (13)	C47—C48	1.422 (13)
N22—C23	1.360 (15)	C47—H47	0.9400
N22—C22	1.372 (15)	C48—C49	1.362 (17)
N23—C25	1.347 (11)	C48—H48	0.9400
N23—C26	1.399 (11)	C49—C50	1.421 (16)
N23—H23N	0.8700	C49—H49	0.9400
N24—C34	1.324 (13)	C50—C54	1.403 (11)
N24—C33	1.329 (13)	C50—C51	1.435 (16)
C21—C22	1.344 (17)	C51—C52	1.348 (16)
C21—H21	0.9400	C51—H51	0.9400
C22—H22	0.9400	C52—C53	1.350 (15)
C23—C24	1.362 (16)	C52—H52	0.9400
C23—H23	0.9400	C53—H53	0.9400
C24—C25	1.484 (13)
C4—N1—C1	114.3 (10)	C26—C27—C28	117.5 (10)
C3—N2—C2	118.4 (9)	C26—C27—H27	121.2
C5—N3—C6	128.0 (7)	C28—C27—H27	121.2
C5—N3—H3N	116.0	C29—C28—C27	122.5 (11)
C6—N3—H3N	116.0	C29—C28—H28	118.7
C13—N4—C14	115.5 (8)	C27—C28—H28	118.7
C2—C1—N1	123.4 (9)	C28—C29—C30	121.4 (10)
C2—C1—C5	120.8 (9)	C28—C29—H29	119.3
N1—C1—C5	115.8 (9)	C30—C29—H29	119.3
N2—C2—C1	121.0 (9)	C29—C30—C31	124.0 (11)
N2—C2—H2	119.5	C29—C30—C34	119.5 (12)
C1—C2—H2	119.5	C31—C30—C34	116.3 (11)
N2—C3—C4	120.1 (9)	C32—C31—C30	122.5 (11)
N2—C3—H3	120.0	C32—C31—H31	118.8
C4—C3—H3	120.0	C30—C31—H31	118.8
N1—C4—C3	122.6 (10)	C31—C32—C33	115.5 (11)
N1—C4—H4	118.7	C31—C32—H32	122.2
C3—C4—H4	118.7	C33—C32—H32	122.2
O1—C5—N3	125.8 (7)	N24—C33—C32	123.1 (11)
O1—C5—C1	120.6 (8)	N24—C33—H33	118.4
N3—C5—C1	113.5 (7)	C32—C33—H33	118.4
C7—C6—N3	126.7 (9)	N24—C34—C30	122.3 (11)
C7—C6—C14	119.3 (9)	N24—C34—C26	119.8 (8)
N3—C6—C14	114.0 (8)	C30—C34—C26	117.9 (10)
C6—C7—C8	122.3 (10)	C41—N31—C44	116.1 (9)
C6—C7—H7	118.9	C43—N32—C42	116.0 (10)
C8—C7—H7	118.9	C45—N33—C46	129.6 (7)
C9—C8—C7	119.7 (10)	C45—N33—H33N	115.2
C9—C8—H8	120.2	C46—N33—H33N	115.2
C7—C8—H8	120.2	C53—N34—C54	115.5 (9)
C8—C9—C10	120.2 (10)	N31—C41—C42	119.5 (9)
C8—C9—H9	119.9	N31—C41—C45	119.1 (8)
C10—C9—H9	119.9	C42—C41—C45	121.4 (8)
C11—C10—C14	118.2 (9)	N32—C42—C41	123.5 (9)
C11—C10—C9	122.4 (10)	N32—C42—H42	118.3
C14—C10—C9	119.4 (9)	C41—C42—H42	118.3
C12—C11—C10	119.5 (10)	N32—C43—C44	122.5 (11)
C12—C11—H11	120.3	N32—C43—H43	118.7
C10—C11—H11	120.3	C44—C43—H43	118.7
C11—C12—C13	119.2 (10)	N31—C44—C43	122.3 (10)
C11—C12—H12	120.4	N31—C44—H44	118.8
C13—C12—H12	120.4	C43—C44—H44	118.8
N4—C13—C12	125.1 (10)	O3—C45—N33	126.1 (7)
N4—C13—H13	117.4	O3—C45—C41	121.2 (8)
C12—C13—H13	117.4	N33—C45—C41	112.7 (7)
N4—C14—C10	122.5 (8)	C47—C46—C54	120.3 (9)
N4—C14—C6	118.4 (9)	C47—C46—N33	122.3 (9)
C10—C14—C6	119.1 (8)	C54—C46—N33	117.5 (8)
C24—N21—C21	115.7 (9)	C46—C47—C48	119.6 (10)
C23—N22—C22	113.1 (10)	C46—C47—H47	120.2
C25—N23—C26	130.3 (8)	C48—C47—H47	120.2
C25—N23—H23N	114.9	C49—C48—C47	121.6 (10)
C26—N23—H23N	114.9	C49—C48—H48	119.2
C34—N24—C33	120.0 (9)	C47—C48—H48	119.2
N21—C21—C22	122.0 (11)	C48—C49—C50	118.6 (10)
N21—C21—H21	119.0	C48—C49—H49	120.7
C22—C21—H21	119.0	C50—C49—H49	120.7
C21—C22—N22	123.8 (11)	C54—C50—C49	119.9 (9)
C21—C22—H22	118.1	C54—C50—C51	116.2 (8)
N22—C22—H22	118.1	C49—C50—C51	123.9 (10)
N22—C23—C24	122.1 (11)	C52—C51—C50	118.8 (10)
N22—C23—H23	118.9	C52—C51—H51	120.6
C24—C23—H23	118.9	C50—C51—H51	120.6
N21—C24—C23	123.2 (9)	C51—C52—C53	120.7 (10)
N21—C24—C25	117.0 (8)	C51—C52—H52	119.7
C23—C24—C25	119.8 (9)	C53—C52—H52	119.7
O2—C25—N23	123.1 (9)	N34—C53—C52	125.5 (11)
O2—C25—C24	121.8 (9)	N34—C53—H53	117.2
N23—C25—C24	115.1 (8)	C52—C53—H53	117.2
N23—C26—C27	124.6 (9)	N34—C54—C46	116.9 (9)
N23—C26—C34	114.2 (8)	N34—C54—C50	123.2 (8)
C27—C26—C34	121.1 (9)	C46—C54—C50	120.0 (7)
C4—N1—C1—C2	1.0 (13)	C27—C28—C29—C30	−2.4 (17)
C4—N1—C1—C5	−178.7 (8)	C28—C29—C30—C31	178.9 (11)
C3—N2—C2—C1	0.3 (14)	C28—C29—C30—C34	3.3 (17)
N1—C1—C2—N2	−2.7 (14)	C29—C30—C31—C32	179.5 (11)
C5—C1—C2—N2	177.0 (8)	C34—C30—C31—C32	−4.8 (16)
C2—N2—C3—C4	3.3 (14)	C30—C31—C32—C33	1.6 (16)
C1—N1—C4—C3	2.7 (14)	C34—N24—C33—C32	−3.1 (16)
N2—C3—C4—N1	−5.1 (16)	C31—C32—C33—N24	2.6 (16)
C6—N3—C5—O1	2.7 (13)	C33—N24—C34—C30	−0.4 (15)
C6—N3—C5—C1	−177.2 (8)	C33—N24—C34—C26	−177.6 (9)
C2—C1—C5—O1	3.8 (12)	C29—C30—C34—N24	−179.8 (8)
N1—C1—C5—O1	−176.5 (8)	C31—C30—C34—N24	4.3 (16)
C2—C1—C5—N3	−176.2 (8)	C29—C30—C34—C26	−2.6 (16)
N1—C1—C5—N3	3.4 (10)	C31—C30—C34—C26	−178.5 (7)
C5—N3—C6—C7	−1.3 (14)	N23—C26—C34—N24	−4.6 (12)
C5—N3—C6—C14	178.9 (7)	C27—C26—C34—N24	178.4 (9)
N3—C6—C7—C8	178.4 (9)	N23—C26—C34—C30	178.1 (9)
C14—C6—C7—C8	−1.8 (15)	C27—C26—C34—C30	1.1 (14)
C6—C7—C8—C9	0.8 (17)	C44—N31—C41—C42	0.0 (12)
C7—C8—C9—C10	−0.9 (17)	C44—N31—C41—C45	−179.6 (8)
C8—C9—C10—C11	−178.2 (11)	C43—N32—C42—C41	−1.7 (15)
C8—C9—C10—C14	2.1 (15)	N31—C41—C42—N32	−0.5 (14)
C14—C10—C11—C12	0.5 (15)	C45—C41—C42—N32	179.1 (9)
C9—C10—C11—C12	−179.3 (11)	C42—N32—C43—C44	4.3 (17)
C10—C11—C12—C13	0.7 (17)	C41—N31—C44—C43	2.5 (14)
C14—N4—C13—C12	1.7 (15)	N32—C43—C44—N31	−5.0 (18)
C11—C12—C13—N4	−1.9 (18)	C46—N33—C45—O3	3.7 (13)
C13—N4—C14—C10	−0.3 (12)	C46—N33—C45—C41	−175.4 (8)
C13—N4—C14—C6	−178.2 (9)	N31—C41—C45—O3	−177.5 (8)
C11—C10—C14—N4	−0.7 (12)	C42—C41—C45—O3	2.9 (12)
C9—C10—C14—N4	179.0 (11)	N31—C41—C45—N33	1.6 (10)
C11—C10—C14—C6	177.2 (11)	C42—C41—C45—N33	−178.0 (8)
C9—C10—C14—C6	−3.1 (12)	C45—N33—C46—C47	−3.9 (14)
C7—C6—C14—N4	−179.1 (9)	C45—N33—C46—C54	176.2 (7)
N3—C6—C14—N4	0.8 (12)	C54—C46—C47—C48	−2.6 (14)
C7—C6—C14—C10	2.9 (12)	N33—C46—C47—C48	177.4 (9)
N3—C6—C14—C10	−177.2 (7)	C46—C47—C48—C49	2.8 (15)
C24—N21—C21—C22	2.4 (16)	C47—C48—C49—C50	−3.2 (16)
N21—C21—C22—N22	−3.1 (19)	C48—C49—C50—C54	3.5 (14)
C23—N22—C22—C21	2.7 (17)	C48—C49—C50—C51	−177.4 (10)
C22—N22—C23—C24	−2.0 (16)	C54—C50—C51—C52	1.6 (13)
C21—N21—C24—C23	−1.8 (15)	C49—C50—C51—C52	−177.6 (10)
C21—N21—C24—C25	178.6 (9)	C50—C51—C52—C53	0.3 (16)
N22—C23—C24—N21	1.8 (16)	C54—N34—C53—C52	−0.3 (15)
N22—C23—C24—C25	−178.6 (9)	C51—C52—C53—N34	−1.0 (18)
C26—N23—C25—O2	−3.2 (15)	C53—N34—C54—C46	−178.0 (9)
C26—N23—C25—C24	178.6 (8)	C53—N34—C54—C50	2.4 (12)
N21—C24—C25—O2	178.9 (9)	C47—C46—C54—N34	−176.6 (9)
C23—C24—C25—O2	−0.7 (13)	N33—C46—C54—N34	3.4 (13)
N21—C24—C25—N23	−2.8 (11)	C47—C46—C54—C50	3.0 (13)
C23—C24—C25—N23	177.5 (9)	N33—C46—C54—C50	−177.0 (7)
C25—N23—C26—C27	−0.7 (15)	C49—C50—C54—N34	176.2 (11)
C25—N23—C26—C34	−177.6 (8)	C51—C50—C54—N34	−3.0 (11)
N23—C26—C27—C28	−176.8 (8)	C49—C50—C54—C46	−3.4 (11)
C34—C26—C27—C28	−0.2 (14)	C51—C50—C54—C46	177.4 (11)
C26—C27—C28—C29	0.8 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.87	2.21	2.661 (10)	112
N3—H3N···N4	0.87	2.23	2.667 (10)	111
C7—H7···O1	0.94	2.36	2.967 (13)	122
N23—H23N···N21	0.87	2.22	2.662 (10)	112
N23—H23N···N24	0.87	2.24	2.675 (11)	110
C21—H21···O2^i	0.94	2.64	3.264 (12)	125
C22—H22···O2^i	0.94	2.64	3.278 (13)	125
C27—H27···O2	0.94	2.34	2.912 (13)	119
N33—H33N···N31	0.87	2.21	2.667 (10)	113
N33—H33N···N34	0.87	2.26	2.674 (11)	109
C44—H44···O1^ii	0.94	2.61	3.244 (11)	125
C47—H47···O3	0.94	2.27	2.893 (12)	123

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

Hexa-µ-acetato-1:2κ²O:O';2:3κ⁸O:O'; 3:4κ²O:O'-dimethanol-1κO,2κO-bis[N-(quinolin-8-yl)pyrazine-2-carboxamide]-1κ³N,N',N''; 4κ³N,N',N''-tetracopper(II) methanol disolvate (I)

Crystal data

[Cu4(C42H44N8O16)]·2CH4O	Z = 1
Mr = 1235.09	F(000) = 632
Triclinic, P1	Dx = 1.645 Mg m^−3
a = 8.1485 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2132 (9) Å	Cell parameters from 8000 reflections
c = 14.2662 (12) Å	θ = 2.2–25.9°
α = 98.352 (9)°	µ = 1.76 mm^−1
β = 93.668 (10)°	T = 153 K
γ = 103.578 (9)°	Block, green
V = 1247.11 (19) Å^3	0.50 × 0.30 × 0.25 mm

Data collection

STOE IPDS 1 diffractometer	4499 independent reflections
Radiation source: fine-focus sealed tube	3906 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.050
φ rotation scans	θmax = 25.9°, θmin = 2.2°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −10→10
Tmin = 0.564, Tmax = 1.000	k = −13→13
9825 measured reflections	l = −17→17

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)] = 0.031	Hydrogen site location: mixed
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0579P)^2] where P = (Fo^2 + 2Fc^2)/3
4499 reflections	(Δ/σ)max = 0.001
344 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.39598 (3)	0.31687 (2)	0.17585 (2)	0.01373 (9)
O2	0.1648 (2)	0.37443 (17)	0.10360 (12)	0.0196 (4)
H2O	0.208 (3)	0.440 (3)	0.081 (2)	0.020 (7)*
C15	0.0276 (3)	0.3951 (3)	0.15486 (19)	0.0295 (6)
H15C	−0.070186	0.391617	0.109933	0.044*
H15B	0.061424	0.477100	0.195227	0.044*
H15A	−0.003095	0.330750	0.194798	0.044*
N1	0.5500 (2)	0.49209 (19)	0.19753 (13)	0.0158 (4)
N2	0.7940 (2)	0.7145 (2)	0.20796 (15)	0.0220 (4)
N3	0.5020 (2)	0.30915 (19)	0.05748 (13)	0.0143 (4)
N4	0.2904 (2)	0.13793 (19)	0.12373 (13)	0.0151 (4)
O1	0.6953 (2)	0.42282 (17)	−0.02929 (12)	0.0214 (4)
C1	0.6469 (3)	0.5128 (2)	0.12584 (15)	0.0145 (4)
C2	0.7678 (3)	0.6243 (2)	0.13166 (17)	0.0193 (5)
H2	0.834295	0.637233	0.080020	0.023*
C3	0.6944 (3)	0.6927 (2)	0.27740 (17)	0.0221 (5)
H3	0.707511	0.755074	0.331961	0.027*
C4	0.5719 (3)	0.5817 (2)	0.27251 (16)	0.0193 (5)
H4	0.503163	0.569718	0.323337	0.023*
C5	0.6164 (3)	0.4088 (2)	0.04218 (15)	0.0145 (5)
C6	0.4453 (3)	0.1982 (2)	−0.00583 (15)	0.0142 (4)
C7	0.4895 (3)	0.1676 (2)	−0.09636 (15)	0.0174 (5)
H7	0.568342	0.227202	−0.122700	0.021*
C8	0.4187 (3)	0.0487 (2)	−0.14995 (16)	0.0209 (5)
H8	0.450487	0.029735	−0.212245	0.025*
C9	0.3049 (3)	−0.0406 (2)	−0.11458 (16)	0.0209 (5)
H9	0.258555	−0.120132	−0.152212	0.025*
C10	0.2569 (3)	−0.0133 (2)	−0.02131 (16)	0.0172 (5)
C11	0.1416 (3)	−0.0996 (2)	0.02149 (18)	0.0212 (5)
H11	0.088973	−0.180113	−0.012911	0.025*
C12	0.1067 (3)	−0.0660 (2)	0.11283 (17)	0.0221 (5)
H12	0.030098	−0.123070	0.142415	0.027*
C13	0.1849 (3)	0.0530 (2)	0.16210 (16)	0.0183 (5)
H13	0.161656	0.074312	0.225945	0.022*
C14	0.3277 (3)	0.1054 (2)	0.03234 (15)	0.0141 (4)
Cu2	0.44706 (3)	0.08030 (3)	0.45535 (2)	0.01311 (9)
O3	0.3072 (2)	0.34649 (16)	0.29775 (11)	0.0178 (3)
O4	0.3848 (2)	0.19608 (16)	0.36021 (11)	0.0195 (4)
O5	0.5820 (2)	0.21036 (16)	0.55744 (12)	0.0220 (4)
O6	0.6575 (2)	0.08152 (17)	0.39303 (11)	0.0208 (4)
O7	0.3245 (2)	−0.07186 (17)	0.36824 (12)	0.0250 (4)
O8	0.25541 (19)	0.05939 (17)	0.53366 (12)	0.0214 (4)
C16	0.3260 (3)	0.2889 (2)	0.36657 (15)	0.0144 (4)
C17	0.2738 (4)	0.3410 (3)	0.46051 (17)	0.0300 (6)
H17A	0.225199	0.411380	0.452304	0.045*
H17B	0.373388	0.369265	0.507758	0.045*
H17C	0.188966	0.276304	0.482413	0.045*
C18	0.6718 (3)	0.1805 (2)	0.62131 (16)	0.0179 (5)
C19	0.7880 (3)	0.2856 (3)	0.69104 (19)	0.0294 (6)
H19A	0.736862	0.295786	0.751097	0.044*
H19B	0.804464	0.362812	0.664396	0.044*
H19C	0.897884	0.266140	0.702785	0.044*
C20	0.7617 (3)	0.0184 (2)	0.40933 (15)	0.0159 (5)
C21	0.9158 (3)	0.0332 (3)	0.35565 (17)	0.0227 (5)
H21C	1.015191	0.034582	0.398686	0.034*
H21B	0.934162	0.111348	0.330169	0.034*
H21A	0.898758	−0.036643	0.303063	0.034*
O9	0.7083 (3)	0.2935 (2)	0.28288 (15)	0.0402 (5)
H9O	0.646942	0.230274	0.299405	0.060*
C22	0.7910 (4)	0.3767 (3)	0.3638 (2)	0.0457 (8)
H22A	0.853986	0.453730	0.344812	0.069*
H22B	0.869998	0.339429	0.397142	0.069*
H22C	0.707048	0.395299	0.406157	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01849 (15)	0.01031 (18)	0.01175 (14)	0.00192 (11)	0.00404 (10)	0.00134 (11)
O2	0.0199 (8)	0.0199 (11)	0.0213 (8)	0.0052 (7)	0.0047 (6)	0.0088 (8)
C15	0.0202 (12)	0.0357 (18)	0.0291 (13)	0.0058 (11)	0.0026 (10)	−0.0044 (12)
N1	0.0172 (9)	0.0165 (12)	0.0143 (9)	0.0048 (7)	0.0002 (7)	0.0042 (8)
N2	0.0228 (10)	0.0146 (12)	0.0249 (10)	−0.0001 (8)	−0.0024 (8)	0.0016 (9)
N3	0.0158 (8)	0.0126 (11)	0.0137 (9)	0.0013 (7)	0.0013 (7)	0.0028 (8)
N4	0.0155 (8)	0.0142 (11)	0.0158 (9)	0.0044 (7)	0.0020 (7)	0.0021 (8)
O1	0.0257 (8)	0.0193 (10)	0.0188 (8)	0.0015 (7)	0.0093 (7)	0.0052 (7)
C1	0.0143 (10)	0.0146 (13)	0.0165 (10)	0.0061 (8)	−0.0003 (8)	0.0055 (9)
C2	0.0171 (10)	0.0168 (14)	0.0228 (11)	0.0019 (9)	0.0007 (9)	0.0040 (10)
C3	0.0273 (12)	0.0150 (14)	0.0212 (12)	0.0032 (9)	−0.0031 (9)	−0.0008 (10)
C4	0.0238 (11)	0.0187 (14)	0.0151 (10)	0.0059 (9)	0.0003 (9)	0.0016 (9)
C5	0.0141 (10)	0.0141 (14)	0.0163 (10)	0.0049 (8)	−0.0006 (8)	0.0044 (9)
C6	0.0149 (9)	0.0134 (13)	0.0151 (10)	0.0055 (8)	−0.0014 (8)	0.0029 (9)
C7	0.0208 (10)	0.0206 (14)	0.0123 (10)	0.0068 (9)	0.0020 (8)	0.0045 (9)
C8	0.0265 (12)	0.0248 (15)	0.0126 (10)	0.0108 (10)	0.0014 (9)	0.0002 (10)
C9	0.0277 (12)	0.0164 (14)	0.0162 (11)	0.0061 (9)	−0.0031 (9)	−0.0036 (9)
C10	0.0174 (10)	0.0158 (14)	0.0172 (11)	0.0047 (9)	−0.0030 (8)	0.0002 (9)
C11	0.0209 (11)	0.0125 (14)	0.0264 (12)	0.0009 (9)	−0.0027 (9)	−0.0015 (10)
C12	0.0198 (11)	0.0177 (15)	0.0258 (12)	−0.0026 (9)	0.0035 (9)	0.0049 (10)
C13	0.0201 (11)	0.0165 (14)	0.0176 (11)	0.0021 (9)	0.0050 (8)	0.0034 (9)
C14	0.0149 (9)	0.0147 (13)	0.0135 (10)	0.0057 (8)	−0.0001 (8)	0.0019 (9)
Cu2	0.01474 (14)	0.01284 (18)	0.01143 (14)	0.00311 (10)	0.00007 (10)	0.00198 (11)
O3	0.0262 (8)	0.0157 (10)	0.0141 (7)	0.0083 (6)	0.0048 (6)	0.0043 (7)
O4	0.0279 (8)	0.0187 (10)	0.0140 (7)	0.0094 (7)	0.0004 (6)	0.0046 (7)
O5	0.0240 (8)	0.0170 (10)	0.0218 (8)	0.0028 (7)	−0.0047 (7)	−0.0003 (7)
O6	0.0231 (8)	0.0236 (11)	0.0198 (8)	0.0098 (7)	0.0079 (6)	0.0081 (7)
O7	0.0314 (9)	0.0198 (11)	0.0204 (8)	0.0039 (7)	−0.0073 (7)	0.0006 (7)
O8	0.0191 (8)	0.0252 (11)	0.0234 (8)	0.0077 (7)	0.0059 (6)	0.0103 (8)
C16	0.0140 (10)	0.0149 (14)	0.0133 (10)	0.0022 (8)	−0.0002 (8)	0.0026 (9)
C17	0.0464 (15)	0.0338 (18)	0.0164 (12)	0.0196 (13)	0.0102 (11)	0.0066 (11)
C18	0.0141 (10)	0.0203 (15)	0.0165 (11)	0.0023 (9)	0.0021 (8)	−0.0028 (9)
C19	0.0265 (12)	0.0227 (17)	0.0313 (14)	0.0005 (10)	−0.0082 (11)	−0.0064 (11)
C20	0.0174 (10)	0.0140 (14)	0.0131 (10)	0.0011 (8)	−0.0002 (8)	−0.0030 (9)
C21	0.0198 (11)	0.0244 (16)	0.0234 (12)	0.0041 (9)	0.0048 (9)	0.0037 (10)
O9	0.0560 (13)	0.0284 (14)	0.0405 (11)	0.0107 (10)	0.0252 (10)	0.0108 (10)
C22	0.0507 (18)	0.033 (2)	0.053 (2)	0.0066 (14)	0.0113 (15)	0.0083 (16)

Geometric parameters (Å, º)

Cu1—N1	2.037 (2)	C11—C12	1.370 (4)
Cu1—N3	1.9457 (18)	C11—H11	0.9500
Cu1—N4	1.998 (2)	C12—C13	1.397 (4)
Cu1—O2	2.3541 (16)	C12—H12	0.9500
Cu1—O3	1.9401 (15)	C13—H13	0.9500
O2—C15	1.420 (3)	Cu2—Cu2^i	2.6202 (6)
O2—H2O	0.85 (3)	Cu2—O4	2.1255 (16)
C15—H15C	0.9800	Cu2—O5	1.9703 (17)
C15—H15B	0.9800	Cu2—O6	1.9793 (15)
C15—H15A	0.9800	Cu2—O7	1.9692 (18)
N1—C4	1.328 (3)	Cu2—O8	1.9671 (16)
N1—C1	1.345 (3)	O3—C16	1.271 (3)
N2—C3	1.334 (3)	O4—C16	1.238 (3)
N2—C2	1.343 (3)	O5—C18	1.264 (3)
N3—C5	1.331 (3)	O6—C20	1.258 (3)
N3—C6	1.388 (3)	O7—C18^i	1.256 (3)
N4—C13	1.332 (3)	O8—C20^i	1.267 (3)
N4—C14	1.375 (3)	C16—C17	1.510 (3)
O1—C5	1.249 (3)	C17—H17A	0.9800
C1—C2	1.386 (3)	C17—H17B	0.9800
C1—C5	1.506 (3)	C17—H17C	0.9800
C2—H2	0.9500	C18—C19	1.513 (3)
C3—C4	1.391 (3)	C19—H19A	0.9800
C3—H3	0.9500	C19—H19B	0.9800
C4—H4	0.9500	C19—H19C	0.9800
C6—C7	1.380 (3)	C20—C21	1.501 (3)
C6—C14	1.436 (3)	C21—H21C	0.9800
C7—C8	1.407 (4)	C21—H21B	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.375 (4)	O9—C22	1.396 (4)
C8—H8	0.9500	O9—H9O	0.8400
C9—C10	1.422 (3)	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
C10—C14	1.406 (3)	C22—H22C	0.9800
C10—C11	1.418 (3)
O3—Cu1—N3	172.66 (8)	C11—C12—H12	120.3
O3—Cu1—N4	105.05 (7)	C13—C12—H12	120.3
N3—Cu1—N4	82.29 (8)	N4—C13—C12	123.0 (2)
O3—Cu1—N1	91.72 (7)	N4—C13—H13	118.5
N3—Cu1—N1	80.94 (8)	C12—C13—H13	118.5
N4—Cu1—N1	162.67 (8)	N4—C14—C10	122.1 (2)
O3—Cu1—O2	88.87 (6)	N4—C14—C6	116.8 (2)
N3—Cu1—O2	91.42 (7)	C10—C14—C6	121.1 (2)
N4—Cu1—O2	90.51 (7)	O8—Cu2—O7	88.94 (8)
N1—Cu1—O2	94.20 (7)	O8—Cu2—O5	89.35 (7)
C15—O2—Cu1	121.65 (14)	O7—Cu2—O5	169.04 (7)
C15—O2—H2O	109.0 (19)	O8—Cu2—O6	168.74 (7)
Cu1—O2—H2O	105.5 (18)	O7—Cu2—O6	91.16 (7)
O2—C15—H15C	109.5	O5—Cu2—O6	88.42 (7)
O2—C15—H15B	109.5	O8—Cu2—O4	102.95 (6)
H15C—C15—H15B	109.5	O7—Cu2—O4	92.05 (7)
O2—C15—H15A	109.5	O5—Cu2—O4	98.88 (7)
H15C—C15—H15A	109.5	O6—Cu2—O4	88.31 (6)
H15B—C15—H15A	109.5	O8—Cu2—Cu2^i	86.81 (5)
C4—N1—C1	118.3 (2)	O7—Cu2—Cu2^i	82.29 (5)
C4—N1—Cu1	129.20 (16)	O5—Cu2—Cu2^i	86.81 (5)
C1—N1—Cu1	112.44 (15)	O6—Cu2—Cu2^i	82.04 (5)
C3—N2—C2	116.5 (2)	O4—Cu2—Cu2^i	168.68 (5)
C5—N3—C6	125.59 (19)	C16—O3—Cu1	124.70 (15)
C5—N3—Cu1	118.94 (16)	C16—O4—Cu2	135.91 (14)
C6—N3—Cu1	115.44 (14)	C18—O5—Cu2	119.47 (16)
C13—N4—C14	118.3 (2)	C20—O6—Cu2	125.71 (15)
C13—N4—Cu1	129.49 (17)	C18^i—O7—Cu2	125.03 (15)
C14—N4—Cu1	112.08 (15)	C20^i—O8—Cu2	120.48 (15)
N1—C1—C2	120.3 (2)	O4—C16—O3	123.9 (2)
N1—C1—C5	116.22 (19)	O4—C16—C17	120.1 (2)
C2—C1—C5	123.5 (2)	O3—C16—C17	116.0 (2)
N2—C2—C1	122.1 (2)	C16—C17—H17A	109.5
N2—C2—H2	118.9	C16—C17—H17B	109.5
C1—C2—H2	118.9	H17A—C17—H17B	109.5
N2—C3—C4	122.2 (2)	C16—C17—H17C	109.5
N2—C3—H3	118.9	H17A—C17—H17C	109.5
C4—C3—H3	118.9	H17B—C17—H17C	109.5
N1—C4—C3	120.7 (2)	O7^i—C18—O5	126.2 (2)
N1—C4—H4	119.6	O7^i—C18—C19	116.8 (2)
C3—C4—H4	119.6	O5—C18—C19	117.0 (2)
O1—C5—N3	128.5 (2)	C18—C19—H19A	109.5
O1—C5—C1	120.2 (2)	C18—C19—H19B	109.5
N3—C5—C1	111.34 (18)	H19A—C19—H19B	109.5
C7—C6—N3	128.8 (2)	C18—C19—H19C	109.5
C7—C6—C14	118.3 (2)	H19A—C19—H19C	109.5
N3—C6—C14	112.89 (19)	H19B—C19—H19C	109.5
C6—C7—C8	120.5 (2)	O6—C20—O8^i	124.8 (2)
C6—C7—H7	119.8	O6—C20—C21	118.0 (2)
C8—C7—H7	119.8	O8^i—C20—C21	117.2 (2)
C9—C8—C7	121.8 (2)	C20—C21—H21C	109.5
C9—C8—H8	119.1	C20—C21—H21B	109.5
C7—C8—H8	119.1	H21C—C21—H21B	109.5
C8—C9—C10	119.6 (2)	C20—C21—H21A	109.5
C8—C9—H9	120.2	H21C—C21—H21A	109.5
C10—C9—H9	120.2	H21B—C21—H21A	109.5
C14—C10—C11	117.6 (2)	C22—O9—H9O	109.5
C14—C10—C9	118.7 (2)	O9—C22—H22A	109.5
C11—C10—C9	123.6 (2)	O9—C22—H22B	109.5
C12—C11—C10	119.5 (2)	H22A—C22—H22B	109.5
C12—C11—H11	120.3	O9—C22—H22C	109.5
C10—C11—H11	120.3	H22A—C22—H22C	109.5
C11—C12—C13	119.4 (2)	H22B—C22—H22C	109.5
C4—N1—C1—C2	1.0 (3)	C8—C9—C10—C11	−179.5 (2)
Cu1—N1—C1—C2	−175.58 (16)	C14—C10—C11—C12	−1.5 (3)
C4—N1—C1—C5	−179.55 (19)	C9—C10—C11—C12	178.1 (2)
Cu1—N1—C1—C5	3.9 (2)	C10—C11—C12—C13	0.3 (4)
C3—N2—C2—C1	−1.6 (3)	C14—N4—C13—C12	−2.0 (3)
N1—C1—C2—N2	0.5 (3)	Cu1—N4—C13—C12	173.02 (17)
C5—C1—C2—N2	−178.9 (2)	C11—C12—C13—N4	1.5 (4)
C2—N2—C3—C4	1.3 (3)	C13—N4—C14—C10	0.7 (3)
C1—N1—C4—C3	−1.4 (3)	Cu1—N4—C14—C10	−175.18 (16)
Cu1—N1—C4—C3	174.59 (16)	C13—N4—C14—C6	−178.42 (19)
N2—C3—C4—N1	0.2 (4)	Cu1—N4—C14—C6	5.8 (2)
C6—N3—C5—O1	−0.8 (4)	C11—C10—C14—N4	1.0 (3)
Cu1—N3—C5—O1	−178.55 (18)	C9—C10—C14—N4	−178.6 (2)
C6—N3—C5—C1	179.67 (18)	C11—C10—C14—C6	−179.94 (19)
Cu1—N3—C5—C1	1.9 (2)	C9—C10—C14—C6	0.4 (3)
N1—C1—C5—O1	176.57 (19)	C7—C6—C14—N4	178.15 (19)
C2—C1—C5—O1	−4.0 (3)	N3—C6—C14—N4	−0.7 (3)
N1—C1—C5—N3	−3.8 (3)	C7—C6—C14—C10	−0.9 (3)
C2—C1—C5—N3	175.59 (19)	N3—C6—C14—C10	−179.77 (18)
C5—N3—C6—C7	−1.5 (4)	Cu2—O4—C16—O3	176.52 (15)
Cu1—N3—C6—C7	176.32 (18)	Cu2—O4—C16—C17	−2.7 (3)
C5—N3—C6—C14	177.16 (19)	Cu1—O3—C16—O4	−9.5 (3)
Cu1—N3—C6—C14	−5.0 (2)	Cu1—O3—C16—C17	169.72 (17)
N3—C6—C7—C8	179.5 (2)	Cu2—O5—C18—O7^i	−6.0 (3)
C14—C6—C7—C8	0.8 (3)	Cu2—O5—C18—C19	173.09 (16)
C6—C7—C8—C9	−0.3 (4)	Cu2—O6—C20—O8^i	2.5 (3)
C7—C8—C9—C10	−0.2 (4)	Cu2—O6—C20—C21	−179.18 (15)
C8—C9—C10—C14	0.1 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1^ii	0.86 (3)	1.84 (3)	2.689 (3)	178 (3)
O9—H9O···O4	0.84	2.33	2.955 (3)	132
O9—H9O···O6	0.84	2.30	3.000 (3)	141
C3—H3···O8^iii	0.95	2.56	3.508 (3)	174
C7—H7···O1	0.95	2.36	2.943 (3)	119
C9—H9···O9^iv	0.95	2.57	3.415 (3)	149
C13—H13···O4	0.95	2.54	3.175 (3)	124
C21—H21C···O8^v	0.98	2.59	3.563 (3)	170

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z; (v) x+1, y, z.